KR101920345B1 - aromatic compound having fused cyclic substituent in aromatic ring and organic light-emitting diode including the same - Google Patents

Abstract

상기 [화학식 A] 에서,
X는 하기 구조식 X를 갖는 치환기이며,
Y는 하기 구조식 Y1 의 치환기이며, n은 1 내지 4의 정수이고, 구조식 X 및 구조식 Y1 은 발명의 상세한 설명에 기재된 바와 같다. The present invention relates to a compound having a substituent of a ring fused to an aromatic ring and an organic light emitting device comprising the same, and more specifically to a compound for an organic light emitting device represented by the following formula (A) and an organic light emitting device .
(A)

In the above formula (A)
X is a substituent having the structure X,
Y is a substituent of the following structural formula Y1, n is an integer of 1 to 4, and the structural formula X and the structural formula Y1 are as described in the description of the invention.

Description

[0001] The present invention relates to an aromatic compound having a fused ring substituent and an organic light emitting device comprising the aromatic compound and a fused cyclic substituent,

The present invention relates to an aromatic compound having a fused ring substituent and an organic light emitting device comprising the same. More particularly, the present invention relates to a compound for an organic light emitting device having a longer life characteristic and excellent device characteristics such as luminous efficiency, Emitting device.

In recent years, the demand for a flat display device having a small space occupation has been increasing due to the enlargement of a display device. The liquid crystal display, which is a typical flat display device, has an advantage of being lighter than a conventional CRT (cathode ray tube) angle is limited and a back light is necessarily required. In contrast, an organic light emitting diode (OLED), a new flat display device, is a display using an auto-luminescent phenomenon and has advantages such as a large viewing angle, a light weight and a small size compared to a liquid crystal display, In recent years, application to a full-color display or illumination is expected.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy.

An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode, a cathode, and an organic material layer therebetween. Here, in order to enhance the efficiency and stability of the organic light emitting device, the organic material layer may have a multi-layered structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out. Such an organic light emitting device is known to have characteristics such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

A material used as an organic material layer in an organic light emitting device can be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. The light emitting material may be classified into a polymer type and a low molecular type depending on the molecular weight and may be classified into a fluorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons according to an emission mechanism . Further, the light emitting material can be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural color depending on the luminescent color.

On the other hand, when only one material is used as a light emitting material, there arises a problem that the maximum light emission wavelength shifts to a long wavelength due to intermolecular interaction, the color purity decreases, or the efficiency of the device decreases due to the light emission attenuating effect. A host-dopant system can be used as a light emitting material in order to increase the efficiency of light emission through the light emitting layer 13. When the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with a small amount of the light emitting layer, It is transported by trolleys to produce high efficiency light. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, the light of the desired wavelength can be obtained according to the type of the dopant used.

As a conventional technique for improving the efficiency of an organic light emitting device, Patent Document 10-1018547 discloses an organic light emitting device including a mixture of an arylamine and an anthracene derivative in a light emitting medium layer, [0008] Japanese Patent Application Laid-Open No. 10-2006-0113954 discloses a technique relating to an organic light emitting device including an asymmetric anthracene derivative having a specific structure in a light emitting medium layer.

However, despite the fact that various kinds of compounds for use in the light emitting medium layer have been prepared including the above-mentioned conventional arts, there is a continuing need to develop stable, efficient and long-life organic compound layer materials for organic light emitting devices It is true.

Patent Registration No. 10-1018547 (March 23, 2011)

Patent Document 10-2006-0113954 (November 3, 2006)

Accordingly, a first technical object of the present invention is to provide a compound for an organic light emitting device which can be used for an organic light emitting layer, has a long life and is excellent in device characteristics such as luminous efficiency.

A second object of the present invention is to provide an organic light emitting device comprising the compound.

In order to achieve the first technical object, the present invention provides an organic compound represented by the following formula (A) as a compound that can be used in a light emitting layer of an organic light emitting device.

  (A)

In the above formula (A)

X is a substituent having the structure X,

Y is a substituent of the following structural formula Y1, and n is an integer of 1 to 2;

[Structural formula X]

Where T ₁ And, an oxygen atom or a sulfur atom, - and T ₂ are each independently the same as or different from each other, and _{a, -C (R 11) (R} 12) -, -N (R 11)

Cy is a saturated or unsaturated ring having 2 to 6 carbon atoms, including T ₁ and T ₂ ,

P is an integer of 0 to 1,

Each of R, R ₁₁ and R ₁₂ independently represents a hydrogen atom, a substituted or unsubstituted C1 to C30 alkyl group, A substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having a hetero atom O, N or S, a halogen group, May form a condensed ring of aliphatic, aromatic, aliphatic hetero or aromatic hetero with groups adjacent to each other,

The linking group L is a single bond, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 60 carbon atoms, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms,

The 'substituted' in the 'substituted or unsubstituted' refers to a group selected from the group consisting of deuterium, cyano, halogen, alkyl having 1 to 24 carbon atoms, halogenated alkyl having 1 to 24 carbon atoms, aryl having 6 to 24 carbon atoms, An arylalkyl group having 1 to 24 carbon atoms, or an alkoxy group having 1 to 24 carbon atoms.

 [Structural formula Y1]

In the above formula Y1,

R ₂₁ to R ₃₀ are the same or different and each is a substituent group as defined in R, R ₁₁ and R ₁₂ in the structural formula X, wherein n in R ₂₁ to R ₃₀ is the same or different substituent to be.

According to another aspect of the present invention, there is provided an organic light emitting display comprising a first electrode, a second electrode facing the first electrode, and an organic layer interposed between the first electrode and the second electrode, And at least one compound represented by the formula (A).

According to the present invention, the compound represented by the formula (A) can be improved in heat resistance as compared with a conventional material, has a long life, and has an excellent device characteristic such as luminous efficiency.

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

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

The present invention provides a compound represented by the following formula (A) as an organic compound that can be used in a light emitting layer of an organic light emitting device.

(A)

In the above formula (A)

X is a substituent having the structure X,

Y is a substituent having any one of the structures Y1 to Y5, and n is an integer of 1 to 4;

[Structural formula X]

Where T ₁ And, an oxygen atom or a sulfur atom, - and T ₂ are each independently the same as or different from each other, and _{a, -C (R 11) (R} 12) -, -N (R 11)

The Cy is formed by fused and connected to each other, and T ₁ And a saturated or unsaturated ring having 2 to 6 carbon atoms including T ₂ ,

P is an integer of 0 to 3,

Each of R, R ₁₁ and R ₁₂ independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C3- A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, A substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, An amino group, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom, a substituted or unsubstituted silyl group, a substituted A substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, And an ester group, and may form a condensed ring of aliphatic, aromatic, aliphatic hetero or aromatic hetero with groups adjacent to each other,

The linking group L is a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 60 carbon atoms, A substituted or unsubstituted C2-C60 heterocycloalkylene group, a substituted or unsubstituted C6-C60 arylene group, or a substituted or unsubstituted C2-C60 hetero Lt; / RTI >

[Structural formula Y1]

In the above formula Y1,

R ₂₁ to R ₃₀ are the same or different and each is a substituent group as defined in R, R ₁₁ and R ₁₂ in the structural formula X, wherein n in R ₂₁ to R ₃₀ is the same or different substituent to be.

[Structural formula Y2]

In the above formula Y2, R ₃₁ To R ₄₀ are the same or different and each is composed of the same substituents as defined for R, R ₁₁ and R ₁₂ in the structural formula X, wherein n of R ₃₁ to R ₄₀ are the same or different substituent groups represented by the structural formula X.

[Structural formula Y3]

In the above formula Y3, R < _{41 >} To R ₅₂ are jidoe made of the same substituents as defined for each of the same or different and the structural formula of R X, R ₁₁ and R _12, R ₄₁ To R < ₅₂ > are the same or different substituent groups represented by the structural formula X. [

[Structural formula Y4]

In the above formula Y4, R ₆₁ To R ₇₄ are jidoe made of the same substituents as defined for each of the same or different and the structural formula of R X, R ₁₁ and R _12, R ₆₁ To R < ₇₂ > are the same or different substituents represented by the structural formula X

[Structural formula Y5]

In the structural formula Y5, R ₈₁ to R ₉₀ are the same or different and each is a substituent group as defined for R, R ₁₁ and R ₁₂ in the structural formula X, and R ₈₁ To R < ₉₀ > are the same or different substituent groups represented by the structural formula X,

The 'substituted' in the 'substituted or unsubstituted' refers to a group selected from the group consisting of deuterium, a cyano group, a halogen group, a hydroxy group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, An alkenyl group, an alkynyl group having 1 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, An alkyl group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 1 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, An aryloxy group having 1 to 24 carbon atoms, an arylsilyl group, and an aryloxy group having 1 to 24 carbon atoms.

An aryl group, which is a substituent used in the compound of the present invention, means a carbocyclic aromatic system containing at least one ring, and when the substituent is present, it can be fused with neighboring substituents to further form a ring.

Specific examples of the aryl group include aromatic groups such as phenyl, naphthyl, tetrahydronaphthyl and the like, and at least one hydrogen atom of the aryl group may be substituted with a substituent such as a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, An amino group (-NH 2, -NH (R), -N (R ') (R "), R' and R" are each independently an alkyl group having 1 to 10 carbon atoms, An alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms, an alkynyl group having 1 to 24 carbon atoms, a carbonyl group having 1 to 24 carbon atoms, A heteroaryl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, or a heteroarylalkyl group having 2 to 24 carbon atoms.

The heteroaryl group, which is a substituent used in the compounds of the present invention, refers to a C 2 -C 24 ring aromatic system containing 1, 2 or 3 heteroatoms selected from N, O, P or S and the remaining ring atoms are carbon, The rings may be fused to form a ring. And at least one hydrogen atom of the heteroaryl group may be substituted with the same substituent as the aryl group.

Specific examples of the alkyl group as a substituent used in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl and the like. The atom may be substituted with the same substituent as in the case of the aryl group.

Specific examples of the alkoxy group used as the substituent in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, At least one hydrogen atom in the alkoxy group may be substituted with the same substituent as in the case of the aryl group.

Specific examples of the silyl group used as the substituent in the compound of the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, silyl, diphenylvinylsilyl, Butylsilyl, dimethylpurylsilyl and the like, and at least one hydrogen atom of the silyl group may be substituted with the same substituent as the aryl group.

More specifically, in the compounds of the present invention, R, R _{11 ,} R ₁₂ , R _{21 in} formula [A] To R _52, R ₆₁ To R _{74 ,} R ₈₁ to R ₉₀ are each, independently of one another, hydrogen; heavy hydrogen; A halogen atom; A hydroxyl group; Cyano; A nitro group; An amino group; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms; A substituted or unsubstituted C2-C20 alkynyl; A substituent of the following formulas (4A) to (4H); Lt; / RTI >

In the above general formulas (4A) to (4H)

Z ₁ To Z ₇ are, independently of each other, hydrogen; heavy hydrogen; A halogen atom; A hydroxyl group; Cyano; A nitro group; An amino group; An amidino group; Hydrazine; Hydrazone; A carboxyl group or a salt thereof; Sulfonic acid group or its salt; Phosphoric acid or its salts; An alkyl group having 1 to 10 carbon atoms; An alkoxy group having 1 to 10 carbon atoms; An alkylthio group having 1 to 10 carbon atoms; An alkyl group having 1 to 10 carbon atoms which is substituted with at least one of a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt thereof, An alkyl group having 1 to 10 carbon atoms and an alkylthio group having 1 to 10 carbon atoms; A phenyl group; Naphthyl group; A fluorenyl group; A phenanthrenyl group; Anthryl group; Pyrenyl; A crycenyl group; An alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, hydrazine, hydrazone, a salt of a carboxyl group or a salt thereof, A phenyl group, a naphthyl group, a fluorenyl group, a phenanthrenyl group, an anthryl group, a pyrenyl group, and a klycenyl group substituted with at least one of an alkoxy group having 1 to 10 carbon atoms and an alkylthio group having 1 to 10 carbon atoms; Indole diarrhea; A benzimidazolyl group; Carbazolyl group; Imidazolyl group; An imidazolinyl group; Imidazopyridinyl group; An imidazopyrimidinyl group; A pyridinyl group; A pyrimidinyl group; Triazinyl groups; A quinolinyl group; An alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, hydrazine, hydrazone, a salt of a carboxyl group or a salt thereof, An imidazolyl group, an imidazopyridinyl group, an imidazolyl group, an imidazolyl group, an imidazolyl group, an imidazolyl group, an imidazolyl group, an imidazolyl group, an imidazolyl group, , An imidazopyrimidinyl group, a pyridinyl group, a pyrimidinyl group, a triazinyl group and a quinolinyl group; Di (alkyl having 1 to 10 carbon atoms) amino group; And an aryl group having 1 to 10 carbon atoms, and the aryl group having 6 to 10 carbon atoms is selected from the group consisting of a phenyl group, a naphthyl group, a fluorenyl group, a phenanthrenyl group, an anthryl group, a pyrenyl group, and a klycenyl group . ≪ / RTI >

In the present invention, the structural formula X in the above formula (A) can be represented by the following formulas (1A-a) to (1A-c) -c]. < / RTI >

[Chemical Formula 1A-b] [Chemical Formula 1A-c]

[Chemical Formula 1B-a] [Chemical Formula 1B-b] [Chemical Formula 1B-c]

[Chemical Formula 1C-a] [Chemical Formula 1C-b] [Chemical Formula 1C-c]

At this time, the X ₁ To X ₆ is _{CR 9 R 10, CR 11 R} 12, CR 13 R 14, CR 15 R 16, CR 17 R 18, CR 19 R 20, NR 11, is selected from S, O, R, R ₁ to R ₂₀ is the same as defined for R, R ₁₁ and R ₁₂ in the structural formula X.

More specifically, the structural formula X in the formula (A) can be represented by the following formula (1A-a1) to (1A-c1), (1B-a1) 1C-c1].

 (1A-b1) < RTI ID = 0.0 > (1A-a1)

[Formula 1B-a1] [Chemical Formula 1B-b1] [Chemical Formula 1B-c1]

[Chemical formula 1C-al] [Chemical formula 1C-b1] [Chemical formula 1C-c1]

Wherein X ₁ to X ₆ are selected from CR ₉ R ₁₀ , CR ₁₁ R _{12 ,} CR ₁₃ R _{14 ,} CR ₁₅ R _{16 ,} CR ₁₇ R _{18 ,} CR ₁₉ R _{20 ,} NR ₁₁ , S, , R ₁ to R ₆ , and R ₉ to R ₂₀ are the same as defined in R, R _11, and R ₁₂ in the structural formula X, respectively.

In this case, the ring part (cyclic group) fused to the aromatic hexagonal ring of the structural formula X is located at a distance of two carbon atoms from the linking group L or the substituent group Y (any one selected from Y1 to Y5) (Cyclic group) fused to a hexagonal ring can be more advantageously prevented from associating with each other than with a linking group L or a substituent group Y (any one selected from Y1 to Y5) separated by a carbon number of 1 have.

The compound represented by the formula (A) of the present invention may be any one selected from the group consisting of the following compounds [1] to [52].

[Compound 1] [Compound 2] [Compound 3]

[Compound 4] [Compound 5] [Compound 6]

[Compound 7] [Compound 8] [Compound 9]

[Compound 10] [Compound 11] [Compound 12]

 [Compound 13] [Compound 14] [Compound 15]

 [Compound 16] [Compound 17] [Compound 18]

 [Compound 19] [Compound 20] [Compound 21]

 [Compound 22] [Compound 23] [Compound 24]

[Compound 25] [Compound 26] [Compound 27]

 [Compound 28] [Compound 29] [Compound 30]

 [Compound 31] [Compound 32] [Compound 33]

[Compound 34] [Compound 35] [Compound 36]

[Compound 37] [Compound 38] [Compound 39]

 [Compound 40] [Compound 41] [Compound 42]

 [Compound 43] [Compound 44] [Compound 45]

[Compound 46] [Compound 47] [Compound 48]

[화합물 49] [화합물 50] [화합물 51]

[Compound 49] [Compound 50] [Compound 51]

[Compound 52]

In the above-mentioned [Compounds 1] to [Compound 52]

The substituent R may be the same or different and each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C3- A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, A substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C1-C30 arylthio group, a substituted or unsubstituted C1-C30 alkylamine group, a substituted or unsubstituted C5-C30 arylamine group , A substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having a hetero atom O, N or S, a substituted or unsubstituted A substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, , An amide group and an ester group, x is an integer of 1 to 20, and each substituent R may form a condensed ring with adjacent groups.

More specifically, the compound represented by the formula (A) of the present invention may be any one selected from the group consisting of the following [1-1] to [52-1].

[Compound 1-1] [Compound 2-1] [Compound 3-1]

[Compound 4-1] [Compound 5-1] [Compound 6-1]

 [Compound 7-1] [Compound 8-1] [Compound 9-1]

[Compound 10-1] [Compound 11-1] [Compound 12-1]

[Compound 13-1] [Compound 14-1] [Compound 15-1]

[Compound 16-1] [Compound 17-1] [Compound 18-1]

[Compound 19-1] [Compound 20-1] [Compound 21-1]

[Compound 22-1] [Compound 23-1] [Compound 24-1]

[Compound 25-1] [Compound 26-1] [Compound 27-1]

[Compound 28-1] [Compound 29-1] [Compound 30-1]

[Compound 31-1] [Compound 32-1] [Compound 33-1]

[Compound 34-1] [Compound 35-1] [Compound 36-1]

[Compound 37-1] [Compound 38-1] [Compound 39-1]

[Compound 40-1] [Compound 41-1] [Compound 42-1]

[Compound 43-1] [Compound 44-1] [Compound 45-1]

[Compound 46-1] [Compound 47-1] [Compound 48-1]

[Compound 49-1] [Compound 50-1] [Compound 51-1]

[Compound 52-1]

In the above-mentioned [1-1] to [52-1], x and substituent R are the same as defined in [Compound 1] to [Compound 52].

In the present invention, when the compound represented by the above formula (A) is any one selected from the above [compound 1] to [compound 52], or [compound 1-1] to [compound 52-1] An alkyl group having 1 to 5 carbon atoms; A cycloalkyl group having 3 to 12 carbon atoms; An aryl group having 6 to 10 carbon atoms; A heteroaryl group having 1 to 2 nitrogen, oxygen, or sulfur atoms; A silyl group having a substituent selected from an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an aryl group having 6 to 10 carbon atoms; ≪ / RTI > and x may be an integer of 1 to 4.

In this case, the substituents R are the same or different and independently selected from the group consisting of a methyl group, an ethyl group, a propyl group, a butyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and a naphthyl group; x may be an integer of 1 or 2.

The above-mentioned formula (A) of the present invention may be any one selected from the group consisting of the following [compounds 101] to [136], but is not limited thereto.

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

[Compound 104] [Compound 105] [Compound 106]

[Compound 107] [Compound 108] [Compound 109]

[Compound 110] [Compound 111] [Compound 112]

[Compound 113] [Compound 114] [Compound 115]

[Compound 116] [Compound 117] [Compound 118]

[Compound 119] [Compound 120] [Compound 121]

[Compound 122] [Compound 123] [Compound 124]

[Compound 125] [Compound 126] [Compound 127]

[Compound 128] [Compound 129] [Compound 130]

[Compound 131] [Compound 132] [Compound 133]

[Compound 134] [Compound 135] [Compound 136]

When the compound of formula (A) in the present invention is employed between a pair of electrodes (anode and cathode), the compound of formula (A) is reacted with a compound of formula The excitons can be prevented, and the excitons formed in the light emitting layer can not interact with each other, thereby increasing the luminous efficiency.

In addition, it can have a high heat resistance and a long life characteristic for the line heat generated in the organic layer between the pair of electrodes, between the organic layers or between the organic layer and the electrode.

The present invention also provides a plasma display panel comprising: a first electrode; A second electrode facing the first electrode; And an organic layer interposed between the first electrode and the second electrode, wherein the organic layer comprises at least one compound of the present invention.

In the present invention, " (organic layer) includes one or more compounds ", " (organic layer) may include one kind of compound belonging to the scope of the present invention or two or more different compounds belonging to the category of the above compound Can be interpreted as "exist".

At this time, the organic layer containing the compound of the present invention may include at least one of a hole injection layer, a hole transport layer, a functional layer having both a hole injection function and a hole transport function, a light emitting layer, an electron transport layer, and an electron injection layer.

Also, in the present invention, the organic layer interposed between the first electrode and the second electrode may be a light emitting layer, and in this case, the light emitting layer may be composed of a host and a dopant.

In the present invention, the compound of formula (A) may be used as a host.

Specific examples of the dopant substance used in the light emitting layer include a pyrene-based compound, a deuterium-substituted pyrene-based compound, an arylamine, a deuterium-substituted arylamine, a peryl-based compound, a deuterium-substituted peryl- Substituted carbazole-based compounds, stilbene-based compounds, deuterated substituted stilbene-based compounds, starburst-based compounds, deuterium-substituted starburst-based compounds, deuterium- An oxadiazole-based compound, a deuterium-substituted oxadiazole-based compound, coumarine, deuterium-substituted coumarine, and the like, but the present invention is not limited thereto.

When the light emitting layer includes a host and a dopant, the dopant may be selected from the range of about 0.01 to about 20 parts by weight based on 100 parts by weight of the host, but is not limited thereto.

In the present invention, at least one layer selected from the hole injecting layer, the hole transporting layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transporting layer and the electron injecting layer may be formed by a single molecular deposition method or a solution process, The organic light emitting element can be used for a display element, a display element, or a monochromatic or white illumination element.

As a specific example of the present invention, a hole transport layer (HTL) is further stacked between the anode and the organic emission layer, and an electron transport layer (ETL) is added between the cathode and the organic emission layer The hole transport layer is laminated in order to facilitate injection of holes from the anode. As the material of the hole transport layer, an electron donor molecule having a low ionization potential is used, and mainly triphenylamine is used as a basic skeleton Triamine or tetraamine derivatives are widely used.

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'- , 1-biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine (a-NPD).

A hole injection layer (HIL) may be additionally formed on the lower portion of the hole transport layer. The material for the hole injection layer is not particularly limited as long as it is commonly used in the art. For example, (4,4 ', 4 "-tri (N-carbazolyl) triphenylamine), m-MTDATA (4,4', 4" -tris- (3-methylphenylphenyl amino) riphenylamine) and the like.

In addition, the electron transport layer used in the organic light emitting device according to the present invention has an opportunity to recombine in the light emitting layer by smoothly transporting electrons supplied from the cathode to the organic light emitting layer and suppressing the movement of holes which are not bonded in the organic light emitting layer .

The material of the electron transport layer is not particularly limited as long as it is commonly used in the art. For example, it is possible to use an oxadiazole derivative such as PBD, BMD, BND or Alq ₃ as described above .

Meanwhile, an electron injection layer (EIL) may be further formed on the electron transport layer to facilitate injection of electrons from the cathode to ultimately improve power efficiency. The electron injection layer material As long as it is commonly used in the related art, it can be used without any particular limitation. For example, materials such as LiF, NaCl, CsF, Li ₂ O, and BaO can be used.

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

1 is a cross-sectional view showing a structure of an organic light emitting device of the present invention. The organic light emitting 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, An injection layer 70 may be further formed. In addition, one or two intermediate layers may be further formed, or a hole blocking layer or an electron blocking layer may be further formed.

Referring to FIG. 1, the organic light emitting device of the present invention and a method of manufacturing the same will be described below. First, an anode electrode material is coated on the substrate 10 to form an anode 20. Here, as the substrate 10, an organic substrate or a transparent plastic substrate which is excellent in transparency, surface smoothness, ease of handling, and waterproofness is used as a substrate used in a conventional organic EL device. As the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity are used.

A hole injection layer 30 is formed on the anode 20 by vacuum thermal deposition or spin coating. Subsequently, a hole transport layer 40 is formed by vacuum thermal deposition or spin coating on the hole transport layer 30 above the hole injection layer 30.

A hole blocking layer (not shown) is selectively formed on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method to form a thin film on the organic light emitting layer 50 can do. In the case where holes are injected into the cathode through the organic light-emitting layer, the lifetime and the efficiency of the device are reduced, and thus 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 . In this case, the hole blocking material to be used is not particularly limited, but it is required to have an ionization potential higher than that of the light emitting compound while having electron transporting ability. Typically, BAlq, BCP, TPBI and the like can be used.

After the electron transport layer 60 is deposited on the hole blocking layer by a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a cathode forming metal is deposited on the electron injection layer 70 in a vacuum heat- And the cathode 80 is formed by vapor deposition to complete the organic EL device. Here, as the metal for forming the cathode, lithium, magnesium, aluminum, aluminum-lithium, calcium, magnesium-magnesium, Mg-Ag), and a transmissive cathode using ITO or IZO can be used to obtain a top light-emitting device.

In addition, according to a specific example of the present invention, the thickness of the light emitting layer is preferably 50 to 2,000 ANGSTROM, and the light emitting layer may be composed of a host and a dopant, and the compound of the present invention may be used as a host.

In this case, the dopant may be a compound represented by the following Chemical Formula 1 or Chemical Formula 2. At this time, the light emitting layer may further include various dopant materials.

     [Chemical Formula 1] < EMI ID =

Among the above-mentioned formulas (1) and (2)

A is a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom, an optionally substituted arylene group having 6 to 60 carbon atoms , A substituted or unsubstituted heteroarylene group having 3 to 50 carbon atoms having hetero atoms O, N or S;

More specifically, A is a substituted or unsubstituted arylene group having 6 to 60 carbon atoms or a single bond, preferably an anthracene, pyrene, phenanthrene, indenophenanthrene, klysene, naphthacene, Perylene, pentacene. At this time, A may be a compound represented by the following formulas (A1) to (A10).

[Formula A1] [Formula A2] [Formula A3]

[Chemical Formula A4] [Chemical Formula A5] [Chemical Formula A6]

[Chemical formula A7] [Chemical formula A8] [Chemical formula A9]

(A10)

Wherein Z1 to Z2 in the formula [A3] represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, a substituted or unsubstituted C2- A substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 60 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted alkynyl group, A substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms (Substituted or unsubstituted C1-C60 alkyl) amino group, or a substituted or unsubstituted C6-C60 aryl) amino group, a substituted or unsubstituted (alkyl) amino group having 1 to 60 carbon atoms, And at least one selected from the group consisting of (a substituted or unsubstituted aryl group having 6 to 60 carbon atoms), an amino group, Z ₁ To Z < ₂ > are the same as or different from each other and can form a condensed ring with the groups adjacent to each other.

In the above formula (1)

X ₁ to X ₂ each independently represent a substituted or unsubstituted arylene group having 6 to 30 carbon atoms or a single bond, X ₁ and X ₂ may be bonded to each other,

Each of Y ₁ to Y ₂ independently represents a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 24 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, a substituted Or a substituted or unsubstituted C1 to C24 heteroalkyl group, a substituted or unsubstituted C3 to C24 cycloalkyl group, a substituted or unsubstituted C1 to C24 alkoxy group, a cyano group, a halogen group, a substituted or unsubstituted carbon number A substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, germanium, phosphorus, boron, deuterium, and hydrogen. more selected species and, Y ₁ to Y ₂ each are the same or different from each other, to form a condensed ring of aliphatic group, an aromatic, aliphatic or hetero-aromatic heterocyclic group which are adjacent to each other And.

Each of l and m is an integer of 1 to 20, and n is an integer of 1 to 4.

In the above formula (2)

C _y is a substituted or unsubstituted cycloalkyl having 3 to 8 carbon atoms, b is an integer of 1 to 4, and when b is 2 or more, each cycloalkane may be in a fused form, Each of which may be substituted with deuterium or alkyl, and may be the same as or different from each other.

Wherein B represents a single bond or _{- [C (R 5) (} R 6)] p - and wherein p is, and are of 1 to 3 integer, not less than p 2 2 or R ₅ and R ₆ are equal to each other or different, ;

Wherein _{R 1, R 2, R 3} , R 5 and R ₆ are, each independently, hydrogen, deuterium, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, hydrazine, hydrazone, a carboxyl group or A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms , A substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 60 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted aryloxy group having 6 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, Or beach (Substituted or unsubstituted alkyl group having 1 to 60 carbon atoms), a di (substituted or unsubstituted alkyl group having 1 to 60 carbon atoms) amino group, a substituted or unsubstituted amino group having 6 to 60 carbon atoms, An aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 40 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, germanium, phosphorus, boron,

a is an integer of 1 to 4, and when a is 2 or more, R ₃ of 2 or more are the same or different, and when R ₃ is plural, each R ₃ may be in fused form, and n is 1 to 4 It is an integer.

The amine group bonded to A in the formulas (1) and (2) may be represented by any one selected from the group consisting of the following [substituents 1] to [52], but is not limited thereto.

[Substituent 1] [Substituent 2] [Substituent 3]

  [Substituent group 4] [Substituent group 5] [Substituent group 6]

[Substituent group 7] [Substituent group 8] [Substituent group 9]

 [Substituent group 10] [Substituent group 11] [Substituent group 12]

 [Substituent group 13] [Substituent group 14] [Substituent group 15]

 [Substituent group 16] [Substituent group 17] [Substituent group 18]

 [Substituent group 19] [Substituent group 20] [Substituent group 21]

 [Substituent group 22] [Substituent group 23] [Substituent group 24]

[Substituent group 25] [Substituent group 26] [Substituent group 27]

[Substituent group 28] [Substituent group 29] [Substituent group 30]

[Substituent group 31] [Substituent group 32] [Substituent group 33]

[Substituent group 34] [Substituent group 35] Substituent group 36]

[Substituent group 37] [Substituent group 38] [Substituent group 39]

[Substituent group 40] [Substituent group 41] [Substituent group 42]

[Substituent group 43] [Substituent group 44] [Substituent group 45]

[Substituent group 46] [Substituent group 47] [Substituent group 48]

[Substituent group 49] [Substituent group 50] [Substituent group 51]

[Substituent 52]

In the above substituents, R may be the same or different from each other and is selected from the group consisting of hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, a substituted or unsubstituted C1- A substituted or unsubstituted alkylthio group having 1 to 60 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted C1 to C60 alkoxy group, A substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, a substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, (Substituted or unsubstituted alkyl having 1 to 60 carbon atoms) amino group, or a substituted or unsubstituted aryl (having 6 to 60 carbon atoms) amino group, di (substituted or unsubstituted A substituted or unsubstituted alkylsilyl group having 1 to 40 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, germanium, phosphorus, and boron, and each has 1 To 12 carbon atoms, and each of the substituents may form a condensed ring with adjacent groups.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be apparent, however, to those skilled in the art that these embodiments are for further explanation of the present invention and that the scope of the present invention is not limited thereby.

<Examples>

Synthesis Example 1 . BH1 Synthesis of

Synthesis Example 1 -1. Of 6- bromo- 1,1,4,4- tetramethyl- 1,2,3,4 -tetrahydronaphthalene synthesis

The reactor was set at 0 DEG C under nitrogen purge, and aluminum chloride (7 g, 600 mmol) was added to a mixed solution of 2,5-dichloro-2,5-dimethylhexane (110 g, 600 mmol) and bromobenzene 52.5 mmol) is slowly added dropwise. After stirring for about 20 minutes, 1 L of a 1: 1 mixed solution of ether and hexane was added and the mixture was washed with ice water, 10% HCl and 100 mL of brine. Water was removed with magnesium sulfate and the organic layer was removed under reduced pressure to give brown Oil is obtained. Crystallization using methanol gave 120 g (yield 80%) of 6-bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene.

Synthetic example  1-2. Synthesis of Anthracene Derivatives

Synthetic example  1-2-a) 9- Phenyl  Synthesis of anthracene

9.7 g (79 mmol) of phenyl boronic acid, 17 g (66 mmol) of 9-bromoanthracene, 18.3 g (132 mmol) of potassium carbonate, Pd _{(PPh 3) 4 1.5g (1mmol} ), water 35 ml, of toluene and reacted under reflux into a 90 ml of tetrahydrofuran and 90ml.

After completion of the reaction, the layers were separated to remove the water layer, and the organic layer was concentrated under reduced pressure to obtain 13.6 g (yield: 81%) of 9-phenylanthracene by column chromatography.

Synthetic example  1-2-b) 9- Phenyl - 10 bromoanthracene  synthesis

13.6 g (0.054 mol) of 9-phenylanthracene prepared in Synthesis Example 1-2-a and 272 ml of dichloromethane were placed in a 1 L three-necked round bottom flask, and the crystals were dissolved at room temperature. 10.1 g (0.063 mol) of bromine was diluted in 50 ml of dichloromethane and allowed to react slowly. After the completion of the reaction, the layer was separated to remove the water layer, and the organic layer was concentrated under reduced pressure to precipitate crystals with methanol, and then recrystallized to obtain 13.4 g of yellow 9-phenyl-10-bromoanthracene crystals (yield 75.5%).

Synthetic example  1-2-c) 9- Phenyl -10- Anthracene boronic acid  synthesis

9-phenyl-10-bromoanthracene (13.4 g, 40 mmol) was dissolved in 110 mL of THF. The n-BuLi (30 mL) was added slowly while cooling to -78 ° C. After the addition, trimethylborate (5.9 g, 56 mmol) was added thereto at -78 ° C for about 1 hour. After stirring at -78 ° C for 1 hour, the mixture was stirred at room temperature for 2 hours, and 2N HCl was added to adjust the acidity. EA, and the solvent was removed to obtain 9.2 g of 9-phenyl-10-anthracene boronic acid (yield: 76.7%).

Synthesis Example 1 -3. BH1 Synthesis of

9-phenyl-10-anthraceneboronic acid (9.2 g, 31 mmol) prepared in Synthesis Example 1-2-c, 6-bromo-1,1, (8.3 g, 31 mmol), K ₂ CO ₃ (8.6 g, 62 mmol) and Pd (PPh ₃ ) ₄ (0.7 g, 1 mmol) were added to a solution of 4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene Was added to 100 mL of toluene, 100 mL of tetrahydrofuran and 40 mL of water, and the mixture was stirred under reflux.

After completion of the reaction, the resulting crystals were filtered and recrystallized several times with toluene and acetone to synthesize BH1 (5.1 g, yield 37%).

MS (MALDI-TOF): m / z 441 [M] ^&lt; ⁺ & gt ^; . ^{13 C} NMR (75 MHz, CDCl ₃ )?: 31.7, 33.0, 34.9, 35.2, 124.4, 125.6, 127.4, 127.6, 127.9, 129.2, 130.9, 133.0, 133.1, 137.2, 138.4, 140.5, 148.2 [

Synthesis Example 2 . BH2 Synthesis of

Synthesis Example 2-1 . 6- bromo- 1,1,4,4,7- pentamethyl- 1,2,3,4 -tetrahydronaphthalene synthesis

Dichloro-2,5-dimethylhexane (18.3 g, 100 mmol), 2-bromotoluene (17.1 g (100 mmol) and 200 ml of 1,2-dichloroethane were added to the reactor under nitrogen purge After the reaction was completed, water was added, and the mixture was extracted with dichloromethane, and then the organic layer was treated with magnesium sulfate, and water (0.5 ml) was added to the reaction mixture, and the mixture was stirred at room temperature for 30 minutes. And concentrated under reduced pressure. The residue was recrystallized from methanol to obtain a white solid of melting point 73 DEG C. 6-Bromo-1,1,4,4,7-pentamethyl-1,2,3,4-tetrahydronaphthalene 15 g (yield: 53%) was obtained.

Synthesis Example 2 -2. BH2 Synthesis of

In the same manner as in Synthesis Example 1-3 except that 6-bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene was used instead of 6-bromo-1,1,4,4- BH2 (4.8 g, yield 32%) was synthesized using the same procedure except that the mo-1, 1, 4,4,7-pentamethyl-1,2,3,4-tetrahydronaphthalene was used.

MS (MALDI-TOF): m / z 455 [M] ^&lt; ⁺ & gt ^; . ^{13 C-} NMR (75 MHz, CDCl ₃ )?: 19.0, 31.7, 33.0, 35.2, 35.2, 125.6, 126.3, 127.4, 127.6, 127.9, 129.0, 129.2, 130.1, 130.9, 133.1, 137.2, 138.4, 145.2,

Synthesis Example 3 . BH3 Synthesis of

Synthesis Example 3 -One. 5- Bromo -2,2- Dihydro -1,1,3,3- Tetramethyl - One H - Inden  synthesis

In Synthesis Example 1-1, except that 2,4-dichloro-2,4-dimethylpentane was used instead of 2,5-dichloro-2,5-dimethylhexane used, 5 -Bromo-2,2-dihydro-1,1,3,3-tetramethyl- 1H -indene (110 g, yield 75%).

Synthesis Example 3 -2. BH3 Synthesis of

Bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene used in Synthesis Example 1-3 was replaced by 5-bromo- BH3 (4.9 g, yield 35%) was synthesized using the same procedure except that 2,2-dihydro-1,1,3,3-tetramethyl- 1H -indene was used.

MS (MALDI-TOF): m / z 427 [M] ^&lt; ⁺ & gt ^; . _{^{13 CNMR (75MHz, CDCl 3)}} δ: 32.0, 41.0, 41.3, 57.3, 124.4, 125.6, 126.4, 127.4, 127.6, 127.9, 129.2, 130.9, 133.0, 133.1, 137.2, 138.4, 147.8, 149.4 [33C]

Synthesis Example 4 . BH4 Synthesis of

Synthesis Example 4 -One. 7- Bromo -1,2,3,4- Tetrahydro -1,1- Dimethyl - Synthesis of naphthalene

21.5 g (84 mmol) of 2-methyl-5- (4-bromophenyl) -2-pentanol was dissolved in 42 g of polyphosphoric acid and heated at 60 DEG C for 9 hours. After the reaction is completed, it is hydrolyzed and extracted with ethyl acetate. The organic layer is treated with saturated sodium carbonate and aqueous sodium chloride solution. This was subjected to column chromatography to obtain 17 g (yield 85%) of 7-bromo-1,2,3,4-tetrahydro-1,1-dimethyl-naphthalene.

Synthesis Example 4 -2. BH4 Synthesis of

Except that the 7-bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene prepared in Synthesis Example 4-1 was used instead of the 6-bromo-1,1,4,4- BH4 (4.5 g, yield 32%) was synthesized using the same method except 1,2,3,4-tetrahydro-1,1-dimethyl-naphthalene was used.

MS (MALDI-TOF): m / z 413 [M] ^&lt; ⁺ & gt ^; . ^{13 C-} NMR (75 MHz, CDCl ₃ )?: 19.4, 30.1, 31.7, 34.6, 38.0, 124.6, 125.6, 126.6, 127.6, 127.9, 129.2, 133.0, 133.1, 133.3, 137.2, 138.4, 151.3,

Synthesis Example 5 . BH5 Synthesis of

Synthesis Example 5-1 . 6-Bromo-1,2,3,4-tetrahydro-1,1-dimethyl-naphthalene sum of the castle

The reactor was charged with 7-bromo-4,4-dimethyl-3,4-dihydro-2H-naphthalen-1-one (prepared according to the procedures published in Journal of Medicinal Chemistry 1995,38, 4764-7) g, 208 mmol) and 500 mL of trifluoroacetic acid was added dropwise triethylsilane (241 g, 2080 mmol). The mixed solution is refluxed for about 8 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was extracted with 2 L of ice water. The reaction mixture was extracted with diethylether. The organic layer was treated with magnesium sulfate and concentrated under reduced pressure. Column chromatography was performed with hexane to obtain 38 g (yield 76%) of pale yellow oil.

Synthesis Example 5 -2. BH5 Synthesis of

Except that 6-bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene used in Synthesis Example 1-3 was used instead of 6-bromo- BH5 (5.2 g, 44% yield) was synthesized using the same method except 1,2,3,4-tetrahydro-1,1-dimethyl-naphthalene was used.

MS (MALDI-TOF): m / z 413 [M] ^&lt; ⁺ & gt ^; . _{^{13 CNMR (75MHz, CDCl 3)}} δ: 19.4, 30.4, 31.7, 34.3, 38.0, 124.7, 125.6, 127.6, 127.9, 129.2, 129.5, 130.9, 133.1, 133.2, 134.3, 137.2, 138.4, 144.7, [32C]

Synthesis Example 6 . BH6 Synthesis of

Synthesis Example 6 -One. 6- Bromo -2,3- Dihydro -1,1- Dimethyl -One H - Inden  Synthesis of

To the reactor is added a mixed solution of 246 mL (246 mmol) of 1 M titanium chloride and 200 mL of dichloromethane and 176 mL (351 mmol) of 2 M dimethyl zinc / toluene solution is slowly added dropwise at 40 ° C. After stirring for 20 minutes, 460 g (117 mmol) of 6-bromo-indan-1-one and 200 mL of dichloromethane are added. The reaction proceeds at room temperature for about 18 hours. After completion of the reaction, the reaction mixture was extracted with methanol at 0 ° C and then extracted with dichloromethane. The organic layer is treated with magnesium sulfate and then concentrated under reduced pressure. Column chromatography of the residue by hexane gave a colorless oil (24 g, yield 94%).

Synthesis Example 6 -2. BH6 Synthesis of

Except that 6-bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene used in Synthesis Example 1-3 was replaced by 6-bromo- BH5 (5.2 g, 44% yield) was synthesized using the same method except 2,3-dihydro-1,1-dimethyl- 1H -indene was used.

MS (MALDI-TOF): m / z 399 [M] ^&lt; ⁺ & gt ^; . ^{13 C-} NMR (75 MHz, CDCl ₃ )?: 28.8, 29.8, 41.4, 44.1, 124.6, 125.6, 126.6, 127.6, 127.9, 129.2, 130.9, 133.1, 133.3, 137.2, 138.4, 141.6,

Synthesis Example 7 . BH7 Synthesis of

Synthesis Example 7 -One. 5- Bromo -2,3- Dihydro -2,2- Dimethyl -One H - Inden  synthesis

To a solution of 6-bromo-2,3-dihydro-2,2-dimethyl- 1H -inden-l-one (12.4 g, 52 mmol) and trifluoroacetic acid (15.0 g) at room temperature. After stirring for about 2.5 days at room temperature, water is added to the reaction solution to stop the reaction. Wash with water and saturated aqueous sodium bicarbonate solution. The mixture was extracted with ethyl acetate, the organic layer was treated with anhydrous sodium sulfate, and the organic layer was concentrated under reduced pressure. Hexane to obtain 11 g (yield: 94%) of 5-bromo-2,3-dihydro-2,2-dimethyl- 1H -indene.

Synthesis Example 7 -2. BH7 Synthesis of

Bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene used in Synthesis Example 1-3 was used instead of 6-bromo-1,1,4,4-tetramethyl-1,2,3,4- BH7 (5.0 g, yield 48%) was synthesized using the same method except 2,3-dihydro-2,2-dimethyl- 1H -indene was used.

MS (MALDI-TOF): m / z 399 [M] ^&lt; ⁺ & gt ^; . ^{13 C-} NMR (75 MHz, CDCl ₃ )?: 29.4, 30.4, 47.9, 48.2, 123.8, 125.6, 127.6, 127.9, 129.2, 129.3, 130.6, 130.9, 132.4, 133.1, 137.2, 138.4, 143.2,

Synthesis Example 8 . BH8 Synthesis of

Synthesis Example 8 -One. One- Pyreneboronic acid  synthesis

1-bromopyrene (30 g, 107 mmol) was dissolved in 240 mL of THF in a round bottom flask. The n-BuLi in n-hexane (1.6M) (80 mL) was slowly added to the solution while cooling to -78 ° C. After the addition, trimethylborate (15.5 g, 149 mmol) was added at -78 ° C for about 1 hour. After stirring at -78 ° C for 1 hour, the mixture was stirred at room temperature for 2 hours, and 2N HCl was added to adjust the acidity. EA, and the solvent was removed to obtain crystals with hexane to obtain 19.5 g (yield: 74%) of 1-pyreneboronic acid.

Synthesis Example 8 -2. BH8 Synthesis of

Except that 1-pyreneboronic acid prepared in Synthesis Example 8-1 was used instead of 9-phenyl-10-anthraceneboronic acid used in Synthesis Example 7-2, BH8 (4.5 g, yield 46 %) Were synthesized.

MS (MALDI-TOF): m / z 347 [M] ^&lt; ⁺ & gt ^; . ^{13 C} NMR (75 MHz, CDCl ₃ )?: 29.4, 30.4, 47.9, 48.2, 115.5, 121.9, 123.3, 123.8, 125.1, 125.6, 126.3, 126.6, 128.8, 129.3, 130.6, 132.2, 133.3, 133.9, 138.0, 143.2, 147.5 [27C]

Synthesis Example 9 . 8  synthesis

Synthesis Example 9 -One. 4- Phenylnaphthaleneboronic acid  synthesis

(Yield 75%) of 4-phenylnaphthaleneboronic acid was obtained by using 1-bromo-4-phenylnaphthalene instead of 9-phenyl-10-bromoanthracene used in Synthesis Example 1-2-c.

Synthesis Example 9 -2. (10- (4- Phenyl naphthalene -1-yl) anthracene-9-yl) Boronic  synthesis

Except that 4-phenylnaphthaleneboronic acid prepared in Synthesis Example 9-1 was used instead of phenylboronic acid used in the synthesis of anthracene derivative of Synthesis Example 1-2, (10- (4-phenylnaphthalene- Yl) anthracene-9-yl) boronic acid (yield: 71%).

Synthesis Example 9 -3. 8  synthesis

(10- (4-phenylnaphthalen-1-yl) anthracene-9-yl) boronic acid prepared in Synthetic Example 9-2 was used instead of 9-phenyl-10-anthraceneboronic acid used in Synthesis Example 1-3 8 (3.3 g, yield 35%) was synthesized in the same way except that

* MS (MALDI-TOF): m / z 567 [M] ^&lt; ⁺ & gt ^; . ¹³ CNMR (75 MHz, CDCl ₃ )?: 31.7, 33, 34.9, 35.2, 124.4, 125.6, 126.3, 126.4, 127.4, 127.6, 127.9, 128.3, 129, 129.2, 129.6, 130.7, 130.9, 131.9, 135.4, 135.6, 137.2, 140.5, 142, 148.2 [44C]

Synthesis Example 10 . (10)  synthesis

Synthesis Example 10 -One. 4- Bromonaphthol  synthesis

20 g (139 mmol) of naphthol and 100 mL of acetonitrile were added to a round bottom flask of nitrogen atmosphere and dissolved. The reaction was cooled to 0 &lt; 0 &gt; C and 25.2 g (142 mmol) of N-bromosuccinimide was dissolved in 250 mL of acetonitrile and slowly added dropwise. After the dropwise addition, the reaction is carried out at room temperature. When the reaction is completed, the reaction mixture is concentrated under reduced pressure and dissolved in ethyl acetate. The separated organic layer was filtered through silica gel and then vacuum distilled. After dissolving in dichloroethane, hexane was added while cooling and stirring was conducted to obtain 4-bromonaphthol (24.2 g, yield 78%).

Synthesis Example 10 -2. 3- Of phenylnaphthol  synthesis

28.5 g (214 mmol) of aluminum chloride and 150 mL of benzene were placed in a round bottom flask of nitrogen atmosphere, and the mixture was heated under reflux and stirred. 27.6 g (124 mmol) of 4-bromonaphthol prepared in Synthesis Example 10-1 was dissolved in 200 mL of benzene by heating and then slowly added dropwise. After refluxing stirring for one hour, when the reaction is complete, cool to room temperature and pour the reaction slowly into a cold 6 M aqueous hydrochloric acid solution. Extract with ethyl acetate. The separated organic layer was washed with sodium bicarbonate aqueous solution and water, filtered through silica gel, concentrated under reduced pressure, and hexane was added thereto, followed by stirring and filtration. The filtered crystals were recrystallized from dichloromethane and hexane to obtain 3-phenylnaphthol (15.7 g, yield 58%).

Synthesis Example 10 -3. 3- Phenyl naphthalene -1 day Of trifluoromethanesulfonate  synthesis

15.7 g (71 mmol) of the 3-phenylnaphthol prepared in Synthesis Example 10-2 was added to a round bottom flask and 160 mL of dichloromethane was added. To this was added 7.3 g (93 mmol) of pyridine and the reaction was cooled to 0 &lt; 0 &gt; C. 22.1 g (78 mmol) of trifluoromethane sulfonic acid hydride was slowly added dropwise thereto, and the reaction was carried out at room temperature. After completion of the reaction, a 0.3 M aqueous hydrochloric acid solution was added to complete the reaction. The organic layer was extracted with dichloromethane. The separated organic layer was filtered through silica gel, concentrated under reduced pressure, separated by column chromatography and concentrated under reduced pressure to obtain 3-phenylnaphthalen-1-yl trifluoromethanesulfonate (24 g, yield 95%) .

Synthesis Example 10 -4. (10- (3- Phenyl naphthalene -1-yl) anthracene-9-yl) Boronic  synthesis

Except that 3-phenylnaphthalen-1-yl trifluoromethane sulfonate prepared in Synthesis Example 10-3 was used instead of phenylboronic acid used in the synthesis of the anthracene derivative of Synthesis Example 1-2 15 g (yield 65%) of 10- (3-phenylnaphthalen-1-yl) anthracen-9-yl) boronic acid was obtained.

Synthesis Example 10 -5. (10)  synthesis

(10- (3-phenylnaphthalen-1-yl) anthracene-9-yl) boronic acid prepared in Synthesis Example 10-4 instead of 9- (4.9 g, yield 35%) was synthesized by using the same method except that

MS (MALDI-TOF): m / z 581 [M] ^&lt; ⁺ & gt ^; . _{^{13 CNMR (75MHz, CDCl 3)}} δ:

129.3, 129.3, 127.3, 127.4, 127.6, 127.9, 128.3, 129, 129.2, 130.1, 130.9, 132.33, 134.6, 134.7, 134.9, 137, 137.2, 140.8, 145.2, 146.5 [45C]

Synthesis Example 11 . (11)  synthesis

Synthetic example  11-1. Synthesis of Anthracene Derivatives

(10- (6-phenylnaphthalen-2-yl) anthracene-9-yl) boronic acid was synthesized by the same method as the synthesis method of the anthracene derivative prepared in Synthesis Example 1-1.

Synthetic example  11-2. (11)  synthesis

Instead of 6-bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene used in Synthesis Example 1-3, 5-bromo-2,3-dihydro- (10- (6-phenylnaphthalen-2-yl) anthracene-9-yl) aniline prepared in Synthesis Example 11-1 was used instead of 9-phenyl-10-anthraceneboronic acid. ) Boronic acid, the compound of formula 11 (4.2 g, yield 39%) was synthesized in the same manner.

MS (MALDI-TOF): m / z 541 [M] ^&lt; ⁺ & gt ^; . _{^{13 CNMR (75MHz, CDCl 3)}} δ:

124.3, 124.9, 124.6, 123.3, 124.8, 125.6, 126.1, 127.3, 127.6, 127.9, 128.2, 129, 129.2, 130.1, 130.9, 131.9, 132.6, 133, 133.1, 134.2, 137.2,

Synthesis Example 12 . 16  synthesis

Synthetic example  12-1. Synthesis of Anthracene Derivatives

(5-phenyl-7- (phenyl-d5) naphthalen-1-yl) anthracene-9-yl) boronic acid was synthesized by the same method as the synthesis method of anthracene derivative prepared in Synthesis Example 1-1 Were synthesized.

Synthetic example  12-2. 16  synthesis

Bromo-3 - [(1-methyl-2-propen-l-yl) -lH-pyrazole instead of 5-bromo-2,3-dihydro-3,3,6-trimethylbenzofuran used in Synthesis Example 11 1-yl) anthracene-9-yl) oxy] -1H-indene was used as an anthracene derivative, and the anthracene derivative was replaced with 10- (5- ) Boronic acid, the compound of formula 16 (4.0 g, yield 37%) was synthesized in the same manner.

MS (MALDI-TOF): m / z 653 [M] ^&lt; ⁺ & gt ^; . _{^{13 CNMR (75MHz, CDCl 3)}} δ:

31.2, 31.3, 33.4, 35.2, 107.1, 115.5, 115.8, 121.9, 123.3, 125.1, 125.4, 125.6, 126.1, 126.2, 126.3, 126.6, 128.3, 128.4, 128.6, 128.8, 129, 129.2, 130.1,130.9,132,132.2,132.4,132.5,133.3,134.2,145.4,146.4,160.9 [49C]

Synthesis Example 13 . 18  synthesis

Synthetic example  13-1. Synthesis of Anthracene Derivatives

(10- (phenyl-d5) anthracene-9-yl) boronic acid was synthesized by the same method as the synthesis method of the anthracene derivative prepared in Synthesis Example 1-1.

Synthetic example  13-2. 18  synthesis

Instead of 5-bromo-2,3-dihydro-3,3,6-trimethylbenzofuran used in Synthesis Example 11, 7-bromo-1,2-dihydro-1,1,4- (3.5 g, yield 38%) was obtained in the same manner as in the synthesis example 13-1, except that naphthalene and anthracene derivatives prepared in Synthesis Example 13-1 were used instead of (10- (phenyl- d5) anthracene- %) Were synthesized.

MS (MALDI-TOF): m / z 646 [M] ^&lt; ⁺ & gt ^; . _{^{13 CNMR (75MHz, CDCl 3)}} δ:

128.5, 133.3, 134.5, 135.4, 135.6, 135.7, 136.7, 137.2, 142,

Synthesis Example 14 . The compound of formula  synthesis

Synthetic example  14-1. Synthesis of Anthracene Derivatives

(2-fluoro-10- (pyrene-1-yl) anthracene-9-yl) boronic acid was synthesized by the same method as the synthesis method of the anthracene derivative prepared in Synthesis Example 1-1.

Synthetic example  14-2. The compound of formula  synthesis

Bromo-1,2,3,4-tetrahydro-l, l, 5-dihydro-3,3,6-trimethylbenzofuran used in Synthesis Example 11 instead of 5- Tetramethyl-7-pentylnaphthalene was used as an anthracene derivative, and an anthracene derivative was obtained in the same manner as in Synthesis Example 14-1 except that (2-fluoro-10- (pyrene- (19) (4.5 g, yield 43%) was synthesized in the same way except that the acid was used.

MS (MALDI-TOF): m / z 430 [M] ^&lt; ⁺ & gt ^; . _{^{13 CNMR (75MHz, CDCl 3)}} δ:

133.6, 124.7, 125.6, 125.9, 126, 126.7, 127.5, 129, 130.9, 133.1, 134.5, 134.8, 135.3, 137.2, 139.5, 152.2 [33C]

Synthesis Example 15 . The compound of formula  synthesis

Synthetic example  15-1. Synthesis of Anthracene Derivatives

(10- (naphthalen-2-yl) -2,7-diphenylanthracene-9-yl) boronic acid was synthesized by the same method as the synthesis method of anthracene derivative prepared in Synthesis Example 1-1.

Synthetic example  15-2. The compound of formula  synthesis

Bromo-3,4-dihydro-2,2,4,4-tetrahydroisoquinoline was used in place of 5-bromo-2,3-dihydro-3,3,6- 2-yl) -2,7-diphenylanthracene-9-yl) tetramethyl-2H-1-benzothiopyran prepared in Synthesis Example 15-1, (4.0 g, 41% yield) was synthesized in the same manner except that boronic acid was used.

MS (MALDI-TOF): m / z 661 [M] ^&lt; ⁺ & gt ^; . _{^{13 CNMR (75MHz, CDCl 3)}} δ:

129.5, 129.3, 124.5, 125.2, 126.8, 126.1, 126.2, 126.5, 127.6, 127.7, 127.9, 128.1, 128.2, 129.2, 131.8, 132, 132.7, 133.1, 133.3, 134.2, 136.1, 137.2, 140.8, 156.6 [49C]

Synthesis Example 16 . 26  synthesis

Synthesis Example 16 -One. (10- Cyclohexylanthracene -9-yl) Boronic  synthesis

(10-cyclohexyl anthracene-9-yl) boronic acid was obtained in the same manner as in the synthesis of anthracene derivative of Synthesis Example 1-2, except that cyclohexylboronic acid was used instead of phenylboronic acid.

Synthesis Example 16 -2. 26  synthesis

Except that the (10-cyclohexyl anthracene-9-yl) boronic acid prepared in Synthesis Example 16-1 was used instead of the 9-phenyl-10-anthraceneboronic acid used in Synthesis Example 2-2 (3.6 g, yield yield 31%) was synthesized.

MS (MALDI-TOF): m / z 461 [M] ^&lt; ⁺ & gt ^; . _{^{13 CNMR (75MHz, CDCl 3)}} δ:

135,131.1,145.2,146.5 [35C] &lt; / RTI &gt;

Synthesis Example 17 . 27  synthesis

(3.5 g, yield 32%) was synthesized using the same method except that B-2-thiazolylboronic acid was used instead of cyclohexylboronic acid used in Synthesis Example 16.

MS (MALDI-TOF): m / z 462 [M] ^&lt; ⁺ & gt ^; . _{^{13 CNMR (75MHz, CDCl 3)}} δ:

129.3, 127.8, 125.6, 126.3, 127, 127.4, 130.1, 130.9, 133.1, 145.2, 146.5, 169.3 [33C]

Synthesis Example 18 . (28)  synthesis

28 (3.0 g, yield 30%) was synthesized using the same method except that B-4-dibenzothienylboronic acid was used instead of cyclohexylboronic acid used in Synthesis Example 16.

MS (MALDI-TOF): m / z 561 [M] ^&lt; ⁺ & gt ^; . _{^{13 CNMR (75MHz, CDCl 3)}} δ:

124.3, 135.2, 124.9, 142.2, 124.3, 124.4, 124.8, 125.6, 126.3, 126.4, 127, 127.4, 129, 130.1, 130.9, 133.1, 137.1, 139.9, 142.4, 145.2,

Synthesis Example 19 . 29  synthesis

Except that B- (2,3,4,5,6-pentafluorophenyl) boronic acid was used in place of cyclohexylboronic acid used in Synthesis Example 16, 3.2 g (yield: 3.2 g, yield: 33%).

MS (MALDI-TOF): m / z 545 [M] ^&lt; ⁺ & gt ^; . _{^{13 CNMR (75MHz, CDCl 3)}} δ:

135.3, 127.6, 126.3, 127, 127.4, 129, 130.1, 130.9, 133.1, 136.6, 137.2, 142, 145.2,

Synthesis Example 20 . BH9 Synthesis of

Synthesis Example 20 -One. Synthesis of intermediate 20-a

<Reaction formula 20-1>

                                         Intermediate 20-a

50 g (194 mmol) of 9-bromophenanthrene was added to a round bottom flask containing 500 ml of tetrahydrofuran, and the temperature was adjusted to -78 DEG C under a nitrogen atmosphere. After 30 minutes, 146 ml (233 mmol) of n-butyllithium was slowly added dropwise. After 1 hour, 28.3 g (274 mmol) of trimethylborate was slowly added dropwise and the temperature was raised to room temperature. After stirring for about 12 hours at room temperature, 2N (normal) hydrochloric acid aqueous solution was added dropwise to the reaction solution until it became an acid, and then extracted, and the organic layer was collected and distilled under reduced pressure. Recrystallization with normal nucleic acid followed by filtration and drying yielded 35 g (81% yield) of intermediate 20-a as a white solid.

Synthesis Example 20 -2. Synthesis of intermediate 20-b

<Reaction formula 20-2>

                                                        Intermediate 20-b

To a round bottom flask was added methyl 2-bromo benzoate 24g (112mmol), intermediate 20-a 34.7g (0.156mmol), tetrakis (triphenylphosphine) palladium _{{Pd (PPh 3) 4}} 2.6g (2mmol), potassium carbonate 30.9 g (223 mmol) of water, 50 mL of water, 125 mL of toluene and 125 mL of tetrahydrofuran were added and refluxed for 12 hours. After the completion of the reaction, the reaction product was separated, and the organic layer was concentrated under reduced pressure, followed by column separation and drying to obtain Intermediate 20-b (25 g, yield 72%) as a white solid.

Synthesis Example 20 -3. Synthesis of intermediate 20-c

<Reaction formula 20-3>

                                              Intermediate 20-c

25 g (80 mmol) of Intermediate 20-b was added to a round bottom flask containing 250 ml of tetrahydrofuran, and then the temperature was lowered to -78 DEG C under a nitrogen atmosphere. After 30 minutes, 150 ml (240 mmol) of 1.6M phenyllithium was slowly added dropwise, and the temperature was elevated to room temperature after 1 hour. After stirring for about 2 hours at room temperature, an aqueous solution of ammonium chloride was added dropwise, and the mixture was extracted, and the organic layer was collected and distilled under reduced pressure. Recrystallization with normal nucleic acid followed by filtration and drying gave 29 g (83% yield) of intermediate 20-c as a white solid.

Synthesis Example 20 -4. Synthesis of intermediate 20-d

<Reaction formula 20-4>

                                            Intermediate 20-d

29 g (66 mmol) of Intermediate 20-c was placed in a round bottom flask containing 290 ml of acetic acid. Thereafter, the temperature was raised to 80 DEG C, and 1 to 2 drops of an aqueous hydrochloric acid solution were added. After refluxing for about 2 hours, the temperature was adjusted to room temperature. The resulting solid was filtered and dried to yield a white solid of intermediate 20-d (27 g, yield 93%) as a white solid.

Synthesis Example 20 -5. Synthesis of intermediate 20-e

<Reaction Formula 20-5>

                                           Intermediate 20-e

27 g (65 mmol) of Intermediate 20-d was added to a round bottom flask containing 216 ml of chloroform and stirred. 28.9 g (181 mmol) of bromine was diluted with 54 ml of chloroform, which was slowly added dropwise and stirred at room temperature for 48 hours. The resulting solid was filtered and dried to obtain Intermediate 20-e (27 g, yield 93%) which was a white solid.

Synthesis Example 20 -6. Synthesis of intermediate 20-f

<Reaction formula 20-6>

   Intermediate 20-e Intermediate 20-f

Intermediate 20-f was synthesized by using the intermediate 20-e prepared in Synthesis Example 7, in the same manner as Synthesis Example 1-2-c (15 g, yield 78%).

Synthesis Example 20 -7. BH9 Synthesis of

<Reaction formula 20-7>

                                                             BH9

An intermediate 20-f prepared in Synthesis Example 20-6 was used instead of 9-phenyl-10-anthraceneboronic acid used in Synthesis Example 1-3, and 6-bromo-1,1,4,4-tetra BH9 was synthesized in the same manner except that the intermediate 20-e prepared in Synthesis Example 20-5 was used instead of methyl-1,2,3,4-tetrahydronaphthalene (7 g, yield 45%).

MS (MALDI-TOF): m / z 707 [M] ^&lt; ⁺ & gt ^; . _{^{13 CNMR (75MHz, CDCl 3)}} δ:

129.4, 127.4, 122.4, 123.8, 124.7, 125.2, 126.2, 126.6, 128.3, 128.9, 129, 129.2, 129.3, 129.4, 130.5, 130.6, 131.3, 131.9, 132.1, 134.6, 137.6, 139.9, 145.1, 142.4, 143.2, 147.5, 147.7 [55C]

Synthesis Example 21 . BH10 Synthesis of

BH10 was synthesized using the same method except that 9,9'-spirobi [fluorene] -2-ylboronic acid was used instead of 9-phenyl-10-anthraceneboronic acid used in Synthesis Example 1-3 . (5.5 g, 48% yield)

MS (MALDI-TOF): m / z 503 [M] ^&lt; ⁺ & gt ^; . _{^{13 CNMR (75MHz, CDCl 3)}} δ:

138.7, 128.9, 130.5, 138.2, 139.9, 140.5, 141, 141.1, 141.9, 142.4, 148.2 [

Example

Device fabrication and evaluation: Example  1 to 41

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. After the ITO glass was mounted in a vacuum chamber and the base pressure was adjusted to 1 × 10 ^-7 torr, CuPc (800 Å) and α-NPD (300 Å) were sequentially deposited on the ITO, a choice of BH1 to BH10) and (8) to (29 to film formation in the order of film formation (250 Å), and then _{Alq 3 (350Å), LiF (} 5 Å), Al (500 Å) was prepared in an organic electroluminescent device. On the other hand, one of the compounds represented by the following formulas (5) to (7) was selected and used as a dopant substance. The compound [BH1] to [BH10], [Formula 8], [Formula 10], [Formula 11], [Formula 16], [Formula 18], [Formula 19], [Formula 23] (29) is as follows.

[BH1] [BH2] [BH3]

 [BH4] [BH5] [BH6]

[BH7] [BH8]

 [BH9] [BH10]

[Chemical Formula 10] &lt; EMI ID =

 [Chemical Formula 19] [Chemical Formula 23] [Chemical Formula 26]

[Chemical Formula 27]

Comparative Examples 1 to 3

The light emitting layer may further comprise an anthracene compound represented by the following formula (4) as a host compound, and the dopant material may be one of compounds represented by the following formulas (5) to (7) Respectively.

Wherein the formula (7) is a mixture in which the left structural formula and the right structural formula are mixed at a molar ratio of 30:70.

[Chemical Formula 4] &lt; EMI ID =

[화학식 7]

(7)

Evaluation example

The voltage, the current density, the luminance, the luminescent color, and the lifetime of the organic electroluminescent device fabricated according to Examples 1 to 41 and Comparative Examples 1 to 3 were measured, and the results are shown in Table 1 below. T97 means the time required for the luminance to be reduced to 97% of the initial luminance.

Host Dopant Voltage Current density
(MA / cm2) Luminance
( CD / M 2) Luminous color T97 Example 1 BH 1 Formula 5 4.2 10 610 blue 89 Example 2 BH 2 Formula 5 4.1 10 650 blue 96 Example 3 BH 3 Formula 5 4.2 10 580 blue 75 Example 4 BH 4 Formula 5 4.3 10 590 blue 69 Example 5 BH 5 Formula 5 4.2 10 630 blue 70 Example 6 BH 6 Formula 5 4.1 10 600 blue 85 Example 7 BH 7 Formula 5 4.2 10 620 blue 82 Example 8 BH 8 Formula 5 4.1 10 610 blue 88 Example 9 BH 9 Formula 5 4.1 10 610 blue 85 Example 10 BH 10 Formula 5 4.2 10 590 blue 80 Example 11 8 Formula 5 4.0 10 610 blue 91 Example 12 10 Formula 5 4.1 10 610 blue 87 Example 13 Formula 11 Formula 5 4.2 10 580 blue 80 Example 14 Formula 16 Formula 5 4.1 10 580 blue 80 Example 15 18 Formula 5 4.0 10 680 blue 92 Example 16 Formula 19 Formula 5 4.0 10 600 blue 86 Example 17 Formula 23 Formula 5 4.2 10 580 blue 79 Example 18 26 Formula 5 4.1 10 590 blue 87 Example 19 27 Formula 5 4.0 10 560 blue 86 Example 20 28 Formula 5 4.1 10 560 blue 85 Example 21 Formula 29 Formula 5 4.1 10 600 blue 86 Comparative Example 1 Formula 4 Formula 5 6.5 10 420 blue 20 Example 22 BH 1 6 4.2 10 530 green 86 Example 23 BH 2 6 4.1 10 550 green 90 Example 24 BH 3 6 4.2 10 540 green 75 Example 25 BH 4 6 4.1 10 530 green 80 Example 26 BH 5 6 4.2 10 570 green 69 Example 27 BH 6 6 4.2 10 540 green 82 Example 28 BH 7 6 4.2 10 530 green 64 Example 29 BH 8 6 4.0 10 520 green 73 Example 30 BH 9 6 4.1 10 530 green 78 Example 31 BH 10 6 4.2 10 520 green 69 Comparative Example 2 Formula 4 6 6.2 10 380 green 12 Example 32 BH 1 Formula 7 4.1 10 510 yellow 74 Example 33 BH 2 Formula 7 4.2 10 580 yellow 85 Example 34 BH 3 Formula 7 4.2 10 520 yellow 70 Example 35 BH 4 Formula 7 4.1 10 560 yellow 69 Example 36 BH 5 Formula 7 4.0 10 550 yellow 64 Example 37 BH 6 Formula 7 4.2 10 540 yellow 73 Example 38 BH 7 Formula 7 4.1 10 560 yellow 71 Example 39 BH 8 Formula 7 4.2 10 540 yellow 69 Example 40 BH 9 Formula 7 4.1 10 570 yellow 78 Example 41 BH 10 Formula 7 4.2 10 530 yellow 70 Comparative Example 3 Formula 4 Formula 7 6.4 10 410 yellow 15

As shown in Table 1, the organic electroluminescent device including the organic electroluminescent compound according to the present invention has a low driving voltage and is excellent in light emission characteristics such as brightness and longevity, and can be utilized in various display devices.

10: substrate 20: anode
30: Hole injection layer 40: Hole transport layer
50: organic light emitting layer 60: electron transporting layer
70: electron injection layer 80: cathode

Claims (13)

A first electrode;
A second electrode facing the first electrode; And
And a light emitting layer interposed between the first electrode and the second electrode,
Wherein the light emitting layer comprises a host and a dopant,
The host is a compound represented by the following formula (A)
Wherein the dopant is a compound represented by the following formula (1).
(A)

In the above formula (A)
X is a substituent having the structure X,
Y is a substituent of the following structural formula Y1, and n is an integer of 1 to 2;
[Structural formula X]

Wherein T ₁ and T ₂ are each independently the same or different and are -C (R ₁₁ ) (R ₁₂ ) -, -N (R ₁₁ ) -, an oxygen atom or a sulfur atom,
The Cy is formed by fused and connected to each other and is a saturated ring having 2 or 3 carbon atoms including T ₁ and T _{2. The} ring including T _1, T ₂ and Cy is a 5-membered ring,
P is an integer of 0 to 1,
Each of R, R ₁₁ and R ₁₂ independently represents a hydrogen atom, a substituted or unsubstituted C1 to C30 alkyl group, A substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having a hetero atom O, N or S, a halogen group, May form a condensed ring of aliphatic, aromatic, aliphatic hetero or aromatic hetero with groups adjacent to each other,
The linking group L is a single bond, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 60 carbon atoms, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms,
[Structural formula Y1]

In the above formula Y1,
R ₂₁ to R ₃₀ are the same or different and each is a substituent group as defined in R, R ₁₁ and R ₁₂ in the structural formula X, wherein n in R ₂₁ to R ₃₀ is the same or different substituent to be.
[Chemical Formula 1]

In the above formula (1)
A is a substituted or unsubstituted pyrene group;
X ₁ and X ₂ are each independently a substituted or unsubstituted arylene group having 6 to 30 carbon atoms or a single bond, X ₁ and X ₂ may be bonded to each other;
Y ₁ to Y ₂ each independently represent a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 24 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, A substituted or unsubstituted alkylsilyl group having 1 to 40 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, deuterium, and hydrogen. And,
Y ₁ to Y ₂ are the same or different from each other and are adjacent to each other and an aliphatic, Aromatic fused rings;
l and m are each an integer of 1 to 20, and n is an integer of 1 to 4.
The 'substituted' in the 'substituted or unsubstituted' refers to a group selected from the group consisting of deuterium, cyano, halogen, alkyl having 1 to 24 carbon atoms, halogenated alkyl having 1 to 24 carbon atoms, aryl having 6 to 24 carbon atoms, Means an aryl group substituted with at least one substituent selected from the group consisting of arylalkyl groups having 1 to 24 carbon atoms, alkoxy groups having 1 to 24 carbon atoms, alkylsilyl groups having 1 to 24 carbon atoms, and arylsilyl groups having 6 to 24 carbon atoms. The method according to claim 1,
Wherein the structural formula X is any one of the following formulas (1A-a) to (1A-c).
[Chemical Formula 1A-b] [Chemical Formula 1A-c]

At this time, the X ₁ to X ₂ is CR ₉ R _10, CR ₁₁ R _12, NR _11, S, O is selected from, R, R ₁ to R _6, R ₉ to R ₁₂ have the structural formula X in claim 1; Are the same as defined in R, R &lt; ₁₁ &gt; and R &lt; ₁₂ &gt; 3. The method of claim 2,
Wherein the structural formula X is any one of the following formulas (1A-a1) to (1A-c1).
(1A-b1) &lt; RTI ID = 0.0 &gt; (1A-a1)

Here, X ₁ to X _2, R, R ₁ to R ₄ are the same as defined in claim 2. The method according to claim 1,
Wherein the formula [A] is any one selected from the group consisting of [compound 1] to [compound 6], [compound 28] to [compound 32].
[Compound 1] [Compound 2] [Compound 3]

[Compound 4] [Compound 5] [Compound 6]

[Compound 28] [Compound 29] [Compound 30]

[Compound 31] [Compound 32]

In [Compound 1] to [Compound 6], [Compound 28] to [Compound 32]
The substituent R may be the same or different and each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C1- A substituted or unsubstituted aryl group having 5 to 50 carbon atoms, and a halogen group, x is an integer of 1 to 8, each substituent R forms a condensed ring with the adjacent groups . 5. The method of claim 4,
The above-mentioned [Formula A] can be prepared by reacting [Compound 1-1], [Compound 4-1] to [Compound 6-1], [Compound 29-1] to [Compound 30-1], [Compound 34-1] Lt; RTI ID = 0.0 &gt; 35-1]. &Lt; / RTI &gt;
[Compound 1-1]

[Compound 4-1] [Compound 5-1] [Compound 6-1]

[Compound 29-1] [Compound 30-1]

[Compound 34-1] [Compound 35-1]

[Compound 1-1], [Compound 4-1] to [Compound 6-1], [Compound 29-1] to [Compound 30-1], [Compound 34-1] to [Compound 35-1] ,
X and substituent R are the same as defined in [Compound 1] to [Compound 6], [Compound 28] to [Compound 32] 6. The method of claim 5,
The substituents R are the same or different and independently of each other, an alkyl group having 1 to 5 carbon atoms; A cycloalkyl group having 3 to 12 carbon atoms; An aryl group having 6 to 10 carbon atoms; &Lt; / RTI &gt;
and x is an integer of 1 to 4. The method according to claim 6,
The substituents R may be the same or different and independently of each other,
A methyl group, an ethyl group, a propyl group, a butyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, and a naphthyl group;
and x is an integer of 1 or 2. The method according to claim 1,
Wherein the above-mentioned formula (A) is any one selected from the group consisting of [Compound 102], [Compound 104] to [Compound 105], [Compound 107], [Compound 110]
[Compound 102] [Compound 104] [Compound 105]

[Compound 107] [Compound 110]

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