KR102078106B1 - Pyrene derivatives comprising heteroaryl amine group and organic light-emitting diode including the same - Google Patents

Abstract

The present invention relates to a pyrene derivative represented by the following [Formula A] and an organic light emitting device comprising the same, substituents Z, Ar ₁ , Ar ₂ , R ₁ to R ₅ , a linking group L ₁ and L ₂ and X, m, p and q are the same as defined in the detailed description of the invention.
[Formula A]

Description

Pyrene derivative comprising heteroaryl amine group and organic light emitting device comprising the same {Pyrene derivatives comprising heteroaryl amine group and organic light-emitting diode including the same}

The present invention relates to a pyrene derivative including a heteroaryl amine group and an organic light emitting device including the same, and more particularly, when used as an organic light emitting material, it is excellent in brightness and luminous efficiency, and can show excellent device characteristics of long life. It relates to a pyrene derivative and an organic light emitting device comprising the same.

Recently, as the size of a display device increases, the demand for a display device having a small space occupancy or a bendable display device is increasing due to a flat panel structure. A liquid crystal display, which is a typical flat display device, is lighter than a conventional cathode ray tube (CRT). Although there is an advantage in that it is possible, there are disadvantages in that the viewing angle is limited and the back light is necessary. In contrast, the organic light emitting diode (OLED), a new flat panel display device, is a display using a self-luminous phenomenon, and has a large viewing angle, can be thinner and shorter than a liquid crystal display, and has a fast response speed. In recent years, application to full-color display or lighting is expected.

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode, a cathode and an organic material layer therebetween. In this case, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode, and electrons are injected into the organic material layer, and excitons are formed when the injected holes and the electrons meet each other. When it falls back to the ground, it glows. Such organic light emitting devices are known to have characteristics such as self-luminous, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

The material used as the organic material layer in the organic light emitting device may be classified into a light emitting material and a charge transport material such as a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function. The light emitting material may be classified into a polymer type and a low molecular type according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. . In addition, the light emitting materials may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve better natural colors according to light emission colors.

When an electric current is applied to the organic light emitting diode, holes and electrons are injected from the anode and the cathode, respectively, and the injected holes and electrons are recombined in the emission layer through the respective hole transport layer and the electron transport layer to form light emission excitons. The light emitting excitons thus formed emit light while transitioning to the ground state. The light may be divided into fluorescence using singlet excitons and phosphorescence using triplet excitons, and the fluorescence and phosphorescence may be used as light emitting sources of organic light emitting devices.

On the other hand, when only one material is used as the light emitting material, there is a problem that the maximum light emission wavelength is shifted to a long wavelength due to intermolecular interaction, and the color purity decreases or the efficiency of the device decreases due to the light emission attenuation effect, thereby increasing color purity and energy. Host-dopant systems can be used as luminescent materials to increase luminous efficiency through transition.

The principle is that when a small amount of dopant having an energy band gap smaller than that of the host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transported to the dopant, thereby producing high efficiency light. At this time, since the wavelength of the host shifts to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.

Recently, there is an increasing need for organic light emitting materials having high brightness and high color purity for application to full-color displays or lighting. Patent Publication No. 10-2010-0097181 (2010.09.02) as the organic light emitting material discloses an organic light emitting device using a pyrene-based derivative bonded to an amine containing a benzofuran or a dibenzofuran group as a substituent, US Patent Publication US 5645948 (July 8, 1997) discloses an organic light emitting device using a pyrene-based derivative in which a benzoxazole group is directly bonded to pyrene.

However, despite the above efforts, the luminance and luminous efficiency are superior to those of the organic light emitting materials manufactured by the prior art including the prior art, and the necessity of developing new organic light emitting materials having long life characteristics is continuously. It is a required situation.

Publication No. 10-2010-0097181 (2010.09.02)

United States Patent Publication US 5645948 (July, 1997)

Therefore, the first technical problem to be achieved by the present invention can be used in the light emitting layer of organic light emitting diodes (OLEDs), excellent in brightness and luminous efficiency, and a novel organic that can show excellent long-life device characteristics It is to provide a light emitting material.

Another object of the present invention is to provide an organic light emitting device including the organic light emitting material.

The present invention provides a compound represented by the following [Formula A] to achieve the first technical problem.

[Formula A]

In [Formula A],

X is one selected from O, S and Se,

The linking groups L ₁ and L ₂ are the same or different and are each independently a single bond, a substituted or unsubstituted arylene group having 5 to 50 carbon atoms, or a substituted or unsubstituted and selected from heteroatoms O, N, S and Si. A heteroarylene group having 2 to 50 carbon atoms,

Ar ₁ and Ar ₂ are the same as or different from each other, and each independently, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, or at least one selected from substituted, unsubstituted and heteroatoms O, N, S and Si A heteroaryl group having 2 to 50 carbon atoms,

Each substituent M bonded to the nitrogen atom of the amine group may be the same or different,

_One of R ₁ to R ₄ in the substituent M is a single bond bonded to a nitrogen atom,

The substituents Z and R ₁ to R ₅ are the same as or different from each other, and independently of each other, hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, A substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl having 5 to 30 carbon atoms An alkenyl group, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having at least one selected from O, N, S and Si as a hetero atom, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted A substituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted carbon number 1 To 30 alkylamine group, substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl group having 5 to 30 carbon atoms, Any group selected from the group consisting of a no group, a nitro group, and a halogen group, and may be combined with a neighboring substituent to form a saturated or unsaturated ring;

Each carbon atom in the pyrene ring is bonded to hydrogen when not bonded to the nitrogen atom of the amine or the substituent Z;

m is an integer from 1 to 8, and when m is 2 or more, each Z is the same as or different from each other,

p and q are each the same or different integers of 1 to 3, each Ar ₁ is the same or different when p is 2 or more, and each Ar ₂ is the same or different when q is 2 or more.

The present invention also includes a first electrode, a second electrode opposed to the first electrode and an organic layer interposed between the first electrode and the second electrode in order to achieve the second object, the organic layer is Provided is an organic light emitting device comprising at least one organic light emitting compound represented by Formula A of the present invention.

According to the present invention, the compound represented by [Formula A] is excellent in brightness and luminous efficiency compared to the existing material, and can show excellent device characteristics of long life, and can be used in devices for manufacturing full color displays. .

1 is a schematic diagram 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 pyrene derivative represented by the following [Formula A] as an organic light emitting compound that can be used in the light emitting layer of the organic light emitting device.

 [Formula A]

In [Formula A],

X is one selected from O, S, Se,

The linking groups L ₁ and L ₂ are the same or different and are each independently a single bond, a substituted or unsubstituted arylene group having 5 to 50 carbon atoms, or a substituted or unsubstituted and selected from heteroatoms O, N, S and Si. A heteroarylene group having 2 to 50 carbon atoms,

Ar ₁ and Ar ₂ are the same as or different from each other, and each independently, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, or at least one selected from substituted, unsubstituted and heteroatoms O, N, S and Si A heteroaryl group having 2 to 50 carbon atoms,

Each substituent M bonded to the nitrogen atom of the amine group may be the same or different,

_One of R ₁ to R ₄ in the substituent M is a single bond bonded to a nitrogen atom,

The substituents Z and R ₁ to R ₅ are the same as or different from each other, and independently of each other, hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, A substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl having 5 to 30 carbon atoms An alkenyl group, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having at least one selected from O, N, S and Si as a hetero atom, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted A substituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted carbon number 1 To 30 alkylamine group, substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl group having 5 to 30 carbon atoms, Any group selected from the group consisting of a no group, a nitro group, and a halogen group, and may be combined with a neighboring substituent to form a saturated or unsaturated ring;

Each carbon atom in the pyrene ring is bonded to hydrogen when not bonded to the nitrogen atom of the amine or the substituent Z;

m is an integer from 1 to 8, and when m is 2 or more, each Z is the same as or different from each other,

p and q are each the same or different integers of 1 to 3, each Ar ₁ is the same or different when p is 2 or more, and each Ar ₂ is the same or different when q is 2 or more,

The 'substituted' in the 'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group of 1 to 24 carbon atoms, halogenated alkyl group of 1 to 24 carbon atoms, alkenyl group of 1 to 24 carbon atoms , Alkynyl group having 1 to 24 carbon atoms, heteroalkyl group having 1 to 24 carbon atoms, aryl group having 6 to 24 carbon atoms, arylalkyl group having 6 to 24 carbon atoms, heteroaryl group having 2 to 24 carbon atoms or heteroarylalkyl group having 2 to 24 carbon atoms , Alkoxy group having 1 to 24 carbon atoms, alkylamino group having 1 to 24 carbon atoms, arylamino group having 1 to 24 carbon atoms, heteroarylaryl group having 1 to 24 carbon atoms, alkylsilyl group having 1 to 24 carbon atoms, arylsilyl having 1 to 24 carbon atoms It means that the group is substituted with one or more substituents selected from the group consisting of aryloxy group having 1 to 24 carbon atoms.

On the other hand, when considering the range of the alkyl group or the aryl group in the "substituted or unsubstituted C1-30 alkyl group", "substituted or unsubstituted C5-50 aryl group", and the like, The range of carbon number of the alkyl group having 1 to 30 carbon atoms and the aryl group having 5 to 50 carbon atoms means the total carbon number constituting the alkyl portion or the aryl portion when viewed as unsubstituted without considering the substituted portion. will be. For example, the phenyl group substituted with the butyl group in the para position should be regarded as corresponding to the aryl group having 6 carbon atoms substituted with the butyl group having 4 carbon atoms.

The aryl group, which is a substituent used in the compound of the present invention, means an aromatic system composed of a hydrocarbon including one or more rings, and in the case where the aryl group has a substituent, the aryl group may be fused to each other with neighboring substituents to further form a ring. Can be.

Specific examples of the aryl group may include aromatic groups such as phenyl, naphthyl, tetrahydronaphthyl, and the like, and at least one hydrogen atom of the aryl group may be a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, or a silyl group. , Amino group (-NH ₂ , -NH (R), -N (R ') (R''),R' and R "are independently of each other an alkyl group having 1 to 10 carbon atoms, in this case referred to as" alkylamino group " ), Amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, C1-C24 alkyl group, C1-C24 halogenated alkyl group, C1-C24 alkenyl group, C1-C24 alkynyl group It may be substituted with 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 or a heteroarylalkyl group having 2 to 24 carbon atoms.

Heteroaryl group which is a substituent used in the compound of the present invention means a ring aromatic system having 2 to 24 carbon atoms containing 1, 2 or 3 hetero atoms selected from N, O, P or S, the remaining ring atoms are carbon, The rings may be fused to form a ring. At least one hydrogen atom of the heteroaryl group may be substituted with the same substituent as in the case of the aryl group.

Specific examples of the alkyl group which is a substituent used in the present invention include methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl and the like, and at least one of the alkyl groups The hydrogen atom can be substituted by the same substituent as the case of the said aryl group.

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

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

The pyrene derivative of the present invention is characterized in that the compound represented by the formula (A).

More specifically, the formula (A) is characterized in that the nitrogen of the amine group bonded to the pyrene has a structure including the substituent M.

The substituent M may have a structure of a substituted or unsubstituted benzoxazole group, a substituted or unsubstituted benzthiazole group, or a substituted or unsubstituted benzelenazole group according to the atom X in the 5-membered ring. Since the substituent M is bonded to the nitrogen atom, the pyrene derivative in the present invention is a dopant material, and has superior luminance and luminous efficiency as compared to the existing material, and may have a long life effect.

At this time, by changing the type of the substituents R1 to R5 of the benzoxazole group, the benzthiazole group or the benz selenazole group of the substituent M, or by changing the type of other substituents bonded to the amine, it is possible to control the luminescence properties of the organic light emitting material have.

Meanwhile, in the present invention, Ar ₁ and Ar ₂ may each be an aryl group or a heteroaryl group.

When Ar ₁ and Ar ₂ are the same or different heteroaryl groups, the heteroaryl group may be any one selected from the following [substituent 101] to [substituent 117], but is not limited thereto.

[Substitution 101] [Substitution 102] [Substitution 103] [Substitution 104]

[Substitution 105] [Substitution 106] [Substitution 107]

[Substitution 108] [Substitution 109] [Substitution 110]

[Substitution 111] [Substitution 112] [Substitution 113]

[Substitution 114] [Substitution 115] [Substitution 116]

[Substituent 117]

Wherein R is the same or different and independently from each other, hydrogen, deuterium, 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 a salt thereof, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, substituted or unsubstituted carbon atoms 1 An alkoxy group of 30 to 30, substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, substituted Or an unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, substituted or non-substituted A substituted (alkyl) amino group having 1 to 30 carbon atoms, a di (substituted or unsubstituted alkyl) amino group having 1 to 30 carbon atoms, or a (substituted or unsubstituted aryl) amino group having 6 to 30 carbon atoms, di (substituted or unsubstituted) Aryl) amino group having 6 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl group having 5 to 30 carbon atoms, germanium, phosphorus and boron; Substituents may be combined with groups adjacent to each other to form a saturated or unsaturated ring,

n is an integer from 1 to 9,

When the substituent R is not bonded to the aromatic ring or the carbon in the saturated hydrocarbon ring in [substituent 101] to [substituent 117], hydrogen is bonded,

When the substituent R is 2 or more, each R may be the same or different from each other,

One of the substituents R in the [substituent 101] to the [substituent 117] is a single bond bonded to the linking group L ₁ or L ₂ in the formula (A),

'Substituted' in the 'substituted or unsubstituted' is the same as defined above.

In addition, when Ar ₁ and Ar ₂ are the same or different aryl groups, the aryl group may be any one selected from the following [substituent 201] to [substituent 210], but is not limited thereto.

[Substituent 201] [Substituent 202] [Substituent 203]

[Substituent 204] [Substituent 205] [Substituent 206]

[Substituent 207] [Substituent 208] [Substituent 209]

[Substituent 210]

Wherein n is an integer from 1 to 9,

When the substituent R is not bonded to the carbon in the aromatic ring in the [substituent 201] to the [substituent 210], hydrogen is bonded, and the substituent R is the same as defined above.

Meanwhile, in the present invention, the linking groups L ₁ and L ₂ may each be a single bond or any one selected from the following [Formula 101] to [Formula 210].

[Structure 101] [Structure 102] [Structure 103] [Structure 104]

[Structure 105] [Structure 106] [Structure 107]

[Structure 108] [Structure 109] [Structure 110]

[Formula 111] [Formula 112] [Formula 113]

[Structure 114] [Structure 115] [Structure 116]

[Structure 117]

[Structure 201] [Structure 202] [Structure 203]

[Structure 204] [Structure 205] [Structure 206]

[Structure 207] [Structure 208] [Structure 209]

[Formula 210]

Where n is an integer from 2 to 9,

When the substituent R is not bonded to the carbon in the aromatic ring or the saturated hydrocarbon ring in [Formula 101] to [Formula 210], hydrogen is bonded,

Two to four R of the substituents R included in [Formula 101] to [Formula 210] are each a single bond bonded to a nitrogen atom and a substituent Ar ₁ , or a single bond bonded to a nitrogen atom and a substituent Ar ₂ , respectively. ,

The substituent R is the same as defined above.

Meanwhile, the substituent Z substituted in the pyrene skeleton is more specifically, deuterium, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number 3 to It may be any one selected from 30 cycloalkyl groups.

In addition, in the present invention, the pyrene derivative of Formula A may be bonded to the amines at positions 1, 6 or 2, 7 in the pyrene structure described in Structural Formula a.

[Formula a]

In addition, the pyrene derivative in the present invention may be obtained by reacting the same kind of amine with halogenated pyrene such as dibromo pyrene when the two amine groups are the same or different, and when the two amine groups are the same. And when two amine groups are different, they can be obtained by sequentially reacting each different kind of amine.

As described above, when reacting different amines sequentially, a pyrene derivative having one amine group bonded as an intermediate may be reacted with a new amine in the next step. When the two amines are different as described above, the pyrene derivative obtained is obtained as an asymmetric compound.

Further, the substituents 'substituted' to the respective possible functional groups in M, L ₁ , L ₂ , Ar _1, and Ar ₂ may be a cyano group, a halogen group, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 18 carbon atoms. It may be any one selected from the group consisting of an arylalkyl group having 6 to 18 carbon atoms, a heteroaryl group having 3 to 18 carbon atoms, an alkylsilyl group having 1 to 12 carbon atoms, and an arylsilyl group having 6 to 18 carbon atoms.

Meanwhile, in the present invention, M or Ar ₁ or Ar ₂ bonded to the amine of [Formula A] may include deuterium. Deuterium may also be included in substituents substituted with M or Ar ₁ or Ar ₂ bonded to the amine.

Preferably, the hydrogen atoms bonded to the aromatic ring of M or Ar ₁ or Ar ₂ may be substituted with deuterium.

In general, the deuterium substituted compounds have twice the atomic mass of deuterium compared to hydrogen-bonded compounds, resulting in lower zero point energy and lower vibration energy levels. In addition, physicochemical properties such as chemical bond lengths associated with deuterium appear differently from hydrogen, and in particular, the elongation amplitude of CD bonds is smaller than that of CH bonds, so that the van der Waals radius of deuterium is smaller than hydrogen, and in general, CD The bond is shorter and stronger than the CH bond.

In addition, when deuterium is substituted, the energy of the ground state is lowered, and as the bond length of deuterium and carbon is shortened, the molecular hardcore volume is reduced, thereby reducing the electrical polarizability. It is known that the thin film volume can be increased by weakening the intermolecular interaction. Such characteristics may create an effect of lowering the crystallinity of the thin film, that is, an amorphous state, and generally may be effective to increase the lifespan and driving characteristics of the organic light emitting diode, and may further improve heat resistance.

In addition, the pyrene derivative of Formula A may be any one selected from the following [Compound 1] to [Compound 117].

[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]

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

[Compound 52] [Compound 53] [Compound 54]

[Compound 55] [Compound 56] [Compound 57]

[Compound 58] [Compound 59] [Compound 60]

[Compound 61] [Compound 62] [Compound 63]

[Compound 64] [Compound 65] [Compound 66]

[Compound 67] [Compound 68] [Compound 69]

[Compound 70] [Compound 71] [Compound 72]

[Compound 73] [Compound 74] [Compound 75]

[Compound 76] [Compound 77] [Compound 78]

[Compound 79] [Compound 80] [Compound 81]

[Compound 82] [Compound 83] [Compound 84]

[Compound 85] [Compound 86] [Compound 87]

[Compound 88] [Compound 89] [Compound 90]

[Compound 91] [Compound 92] [Compound 93]

[Compound 94] [Compound 95] [Compound 96]

[Compound 97] [Compound 98] [Compound 99]

[Compound 100] [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]

In addition, the present invention is a first electrode; A second electrode opposed to the first electrode; And an organic layer interposed between the first electrode and the second electrode, wherein the organic layer includes at least one organic light emitting compound of the present invention.

In the present invention, "(organic layer) contains at least one organic compound" means "(organic layer) one organic compound belonging to the scope of the present invention or two or more different compounds belonging to the category of the organic compound. May include. "

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

Meanwhile, in the present invention, a host material may be used as the dopant in the light emitting layer. When the light emitting layer includes a host and a dopant, the content of the dopant may be generally selected from about 0.01 to about 20 parts by weight based on about 100 parts by weight of the host, but is not limited thereto.

In the present invention, as the electron transport layer material, a known electron transport material may be used as a function of stably transporting electrons injected from an electron injection electrode. Examples of known electron transport materials include quinoline derivatives, especially tris (8-quinolinorate) aluminum (Alq3), TAZ, Balq, beryllium bis (benzoquinolin-10-noate). olate: Bebq2), ADN, compound 201, compound 202, BCP, oxadiazole derivatives such as PBD, BMD, BND and the like may be used, but is not limited thereto.

TAZ BAlq

<Compound 201> <Compound 202> BCP

In the electron transport layer used in the present invention, the organometallic compound represented by the formula (C) may be used alone or in combination with the electron transport layer material.

 [Formula C]

In [Formula C],

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

M is an alkali metal, alkaline earth metal, aluminum (Al) or boron (B) atom, the OA is a monovalent ligand capable of single bond or coordination with the M,

O is oxygen,

A is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon group having 2 to 20 carbon atoms An alkynyl group, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, and at least one selected from O, N, S and Si as a substituted or unsubstituted hetero atom It is any one selected from a heteroaryl group having 2 to 50 carbon atoms,

When M is one metal selected from alkali metals, m = 1, n = 0,

When M is one metal selected from alkaline earth metals, m = 1, n = 1, or m = 2, n = 0,

When M is boron or aluminum, one of m = 1 to 3, and n is any one of 0 to 2, and satisfies m + n = 3;

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

In the present invention, Y is the same as or different from each other, and may be any one selected from the following [formula C1] to [formula C39], but is not limited thereto.

[Structure C1] [Structure C2] [Structure C3]

[Structure C4] [Structure C5] [Structure C6]

[Structure C7] [Structure C8] [Structure C9] [Structure C10]

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

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

[Structure C17] [Structure C18] [Structure C19] [Structure C20]

[Structure C21] [Structure C22] [Structure C23]

[Structure C24] [Structure C25] [Structure C26]

[Structure C27] [Structure C28] [Structure C29] [Structure C30]

[Structure C31] [Structure C32] [Structure C33]

[Structure C34] [Structure C35] [Structure C36]

[Structure C37] [Structure C38] [Structure C39]

In [Formula C1] to [Formula C39],

R is the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted Heteroaryl group having 3 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, 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 Selected from the group and may be connected to an adjacent substituent with alkylene or alkenylene to form a spirogory or fused ring.

Hereinafter, the organic light emitting diode of the present invention will be described with reference to FIG. 1.

1 is a cross-sectional view showing the structure of an organic light emitting device of the present invention. The organic 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, if necessary, the hole injection layer 30 and the electron The injection layer 70 may be further included. In addition, an intermediate layer of one or two layers may be further formed, and a hole blocking layer or an electron blocking layer may be further formed.

Referring to FIG. 1, the organic light emitting diode and a method of manufacturing the same are as follows. FIG. First, the anode 20 is formed by coating an anode electrode material on the substrate 10. As the substrate 10, a substrate used in a conventional organic EL device is used. An organic substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling, and waterproofness is preferable. As the anode electrode material, transparent indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), and the like are used.

The hole injection layer 30 is formed by vacuum-heat deposition or spin coating the hole injection layer material on the anode 20 electrode. Next, the hole transport layer 40 is formed by vacuum thermal evaporation or spin coating of the hole transport layer material on the hole injection layer 30.

The hole injection layer material may be used without particular limitation as long as it is commonly used in the art, for example, 2-TNATA [4,4 ', 4 "-tris (2-naphthylphenyl-phenylamino) -triphenylamine] , NPD [N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine)], TPD [N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'- biphenyl-4,4'-diamine], DNTPD [N, N'-diphenyl-N, N'-bis- [4- (phenyl-m-tolyl-amino) -phenyl] -biphenyl-4,4'-diamine ] Etc. However, this invention is not necessarily limited to this.

In addition, it is not particularly limited as long as it is commonly used in the art as a material of the hole transport layer, 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 (a-NPD) and the like can be used. However, the present invention is not necessarily limited thereto.

Subsequently, the 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 a vacuum deposition method or a spin coating method. can do. The hole blocking layer prevents such a problem by using a material having a very low highest Occupied Molecular Orbital (HOMO) level because when the hole is introduced into the cathode through the organic light emitting layer is reduced the lifetime and efficiency of the device. . At this time, the hole used The blocking material is not particularly limited, but has an electron transporting ability and a higher ionization potential than the light emitting compound, and BAlq, BCP, TPBI, etc. may be used.

After the electron transport layer 60 is deposited 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 a cathode 80 electrode. The metal for forming the cathode may be lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lidium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver ( Mg-Ag), and the like, and a transmissive cathode using ITO and IZO can be used to obtain a front light emitting device.

In addition, the light emitting layer may be formed of a host and a dopant.

Moreover, according to the specific example of this invention, it is preferable that the thickness of the said light emitting layer is 50-2,000 GPa.

In this case, the host used in the emission layer may be a compound represented by Formula 1A to Formula 1D.

[Formula 1A]

In Chemical Formula 1A,

Ar _7, Ar ₈ and Ar ₉ are the same as or different from each other, and each independently, a single bond, a substituted or unsubstituted C ₅ -C ₆₀ aromatic linking group, or a substituted or unsubstituted C ₂ -C ₆₀ heteroaromatic linking group;

R ₂₁ to R ₃₀ are the same as or different from each other, and each independently hydrogen, deuterium, 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, a sulfonic acid group or Salts thereof, phosphoric acid or salts thereof, substituted or unsubstituted alkyl groups having 1 to 60 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 60 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 60 carbon atoms, substituted or unsubstituted Substituted alkoxy group having 1 to 60 carbon atoms, substituted or unsubstituted alkylthio group having 1 to 60 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, substituted or unsubstituted aryl having 6 to 60 carbon atoms A 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 (alkyl) amino group having 1 to 60 carbon atoms, di (substituted or unsubstituted alkyl group having 1 to 60 carbon atoms), or (substituted or unsubstituted aryl having 6 to 60 carbon atoms) amino group, di (substituted Or an unsubstituted aryl) amino 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 and boron. Each substituent may form a condensed ring with a group adjacent to each other;

E, f and g are the same as or different from each other, and each independently an integer of 0 or 1 to 4;

The two sites represented by * of the anthracene may be the same or different from each other, and may be independently bonded to the P or Q structure to form an anthracene-based derivative selected from the following Chemical Formulas 1Aa-1 to 1Aa-3.

[Formula 1Aa-1] [Formula 1Aa-2] [Formula 1Aa-3]

Here, the 'substituted' in the 'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group of 1 to 24 carbon atoms, halogenated alkyl group of 1 to 24 carbon atoms, of 1 to 24 carbon atoms Alkenyl group, C1-C24 alkynyl group, C1-C24 heteroalkyl group, C6-C24 aryl group, C6-C24 arylalkyl group, C2-C24 heteroaryl group, or C2-C24 hetero Arylalkyl group, a C1-C24 alkoxy group, C1-C24 alkylamino group, C1-C24 arylamino group, C1-C24 hetero arylamino group, C1-C24 alkylsilyl group, C1-C24 It means substituted with one or more substituents selected from the group consisting of an arylsilyl group, an aryloxy group having 1 to 24 carbon atoms.

[Formula 1B]

In Chemical Formula 1B,

Ar ₁₇ to Ar ₂₀ may be the same as or different from each other, and each independently the same substituent as defined in Ar ₇ to Ar ₈ in Formula 1A, and R ₆₀ to R ₆₃ may be defined in R ₂₁ to R ₃₀ of Formula 1A. And the same substituent as described above.

The w and ww are the same or different from each other, the x and xx are the same or different from each other, the w + ww and x + xx values are the same or different from each other and are each independently an integer of 0-3. In addition, y and yy are the same as or different from each other, z and zz are the same as or different from each other, and y + yy to z + zz are 2 or less, and are integers of 0 to 2, respectively.

[Formula 1C]

In Chemical Formula 1C,

Ar ₂₁ to Ar ₂₄ may be the same as or different from each other, and each independently the same substituent as defined in Ar ₇ to Ar ₈ of Formula 1A, and R ₆₄ to R ₆₇ may be selected from R ₂₁ to R ₃₀ of Formula 1A. It consists of the same substituent as defined.

In addition, ee to hh are the same as or different from each other and each independently an integer of 1 to 4, and ii to ll are the same or different from each other and each independently an integer of 0 to 4.

[Formula 1D]

In Chemical Formula 1D,

Ar ₂₅ to Ar ₂₇ are the same as or different from each other, and each independently include the same substituent as defined in Ar ₇ to Ar ₈ of Formula 1A, and R ₆₈ to R ₇₃ are the same as or different from each other, and each independently It consists of the same substituent as defined in R <_21> -R <_30> of 1A, and each substituent may form a saturated or unsaturated cyclic structure with adjacent ones. In addition, the mm to ss are the same as or different from each other and are each independently an integer of 0 to 4.

More specifically, the host may be represented by any one selected from the group represented by the following [Host 1] to [Host 56], but is not limited thereto.

[Host1] [Host2] [Host3] [Host4]

[Host5] [Host6] [Host7] [Host8]

[Host9] [Host10] [Host11] [Host12]

[호스트13] [호스트14] [호스트15] [호스트16]

[Host13] [Host14] [Host15] [Host16]

[Host17] [Host18] [Host19] [Host20]

[Host21] [Host22] [Host23] [Host24]

[Host 25] [Host 26] [Host 27] [Host 28]

[Host29] [Host30] [Host31] [Host32]

[Host33] [Host34] [Host35] [Host36]

[Host37] [Host38] [Host39] [Host40]

[Host41] [Host42] [Host43] [Host44]

[Host45] [Host46] [Host47] [Host48]

[Host 49] [Host 50] [Host 51] [Host 52]

[Host53] [Host54] [Host55] [Host56]

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

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

In addition, the organic light emitting device in the present invention is a flat panel display device; Flexible display devices; Monochrome or white flat lighting devices; And a solid or white flexible lighting device; can be used in any one device selected from.

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

(Example)

Synthesis Example  1: Synthesis of Chemical Formula 1

Synthesis Example 1- (1): Synthesis of [Intermediate 1-a]

[Intermediate 1-a] was synthesized according to Scheme 1 below.

<Scheme 1>

                        [Intermediate 1-a]

Benzyl alcohol (31.0 g, 0.286 mol), 2-bromo-6-nitrophenol (25.0 g, 0.115 mol), iron (III) chloride (0.93 g, 5.7 mmol), 1,1'- in a 100 ml round bottom flask Bis (diphenylphosphino) ferrocene (1.27 g, 2 mmol) and 25 ml of toluene were added thereto, and the mixture was stirred under reflux at 150 ° C. for 24 hours. After the reaction was completed, the mixture was cooled under normal temperature, concentrated under reduced pressure, and separated by column. Recrystallization from petroleum ether afforded [Intermediate 1-a]. (15.0g, 48%)

Synthesis Example 1- (2): Synthesis of [Intermediate 1-b]

[Intermediate 1-b] was synthesized according to Scheme 2 below.

<Scheme 2>

                               [Intermediate 1-b]

1-bromo-2,5-dimethylbenzene (25.0 g, 0.135 mol) and 200 ml of tetrahydrofuran were added to a 1 L round bottom flask, and the mixture was cooled to −78 ° C. under a nitrogen atmosphere. 1.6M normal butyllithium (101ml, 0.162mol) was added dropwise to the cooled solution. After stirring for 2 hours at the same temperature, trimethyl borate (18.2 g, 0.176 mol) was added dropwise. After stirring for 1 hour at room temperature, 1 normal hydrochloric acid was added to acidify the solution. Concentration under reduced pressure and recrystallization with normal hexane gave [Intermediate 1-b]. (12.5g, 62%)

Synthesis Example 1- (3): Synthesis of [Intermediate 1-c]

According to Scheme 3 below, Intermediate 1-c was synthesized.

<Scheme 3>

                 [Intermediate 1-b] [Intermediate 1-c]

In a 250 ml round bottom flask, 1-amino-2-bromo-4-methylpyridine (10.0 g, 0.053 mol), [Intermediate 1-b] (9.6 g, 0.064 mol), tetrakis (triphenylphosphine) palladium ( 1.2 g, 0.001 mol), potassium carbonate (14.8 g, 0.107 mol), 50 ml of toluene, 50 ml of tetrahydrofuran, and 20 ml of water were added and stirred under reflux. After the reaction was completed, the mixture was cooled to room temperature, and the organic layer was separated and concentrated under reduced pressure. After column chromatography separation, the mixture was recrystallized from normal hexane to obtain [Intermediate 1-c]. (10.0g, 88%)

Synthesis Example 1- (4): Synthesis of [Intermediate 1-d]

[Intermediate 1-d] was synthesized according to Scheme 4 below.

<Scheme 4>

[Intermediate 1-c] [Intermediate 1-a] [Intermediate 1-d]

[Intermediate 1-c] (8.5g, 40mmol), [Intermediate 1-a] (10.0g, 36mmol) Tris (dibenzylideneacetone) palladium (0.67g, 0.7mmol), sodium tert-butoxide in a 100ml round bottom flask Side (7.01 g, 73 mmol), 2,2'-bis (diphenylphosphino) -1,1'-binaphthalene (0.45 g, 0.7 mmol), and 50 ml of toluene were added and stirred under reflux for 3 hours. Separation by column chromatography and recrystallization with methanol yielded [Intermediate 1-d]. (11g, 75%)

Synthesis Example 1- (5): Synthesis of [Formula 1]

[Scheme 1] was synthesized according to Scheme 5 below.

<Scheme 5>

[중간체 1-d] [화학식 1]

[Intermediate 1-d] [Formula 1]

1,6-dibromopyrene (3.0g, 8mmol), [Intermediate 1-d] (7.4g, 18mmol), Tris (dibenzylideneacetone) palladium (0.31g, 0.3mmol) in 250ml round bottom flask, Sodium tert-butoxide (2.4 g, 25 mmol), 2,2'-bis (diphenylphosphino) -1,1'-binaphthalene (0.21 g, 0.3 mmol) and 80 ml of toluene were added and stirred under reflux for 15 hours. . After separation by column chromatography was recrystallized with ethyl acetate and heptane to obtain [Formula 1]. (3.0g, 35%)

MS (MALDI-TOF): m / z 1008.42 [M ⁺ ]

Synthesis Example 2 Synthesis of Chemical Formula 21

Synthesis Example 2- (1): Synthesis of [Intermediate 2-a]

[Intermediate 2-a] was synthesized according to Scheme 6 below.

<Scheme 6>

                        [Intermediate 2-a]

The synthesis was carried out in the same manner as in Synthesis Example 1- (2) except that 1-bromo-2-methylbenzene (25.0 g, 0.146 mol) was used instead of 1-bromo-2,5-dimethylbenzene [Intermediate 2 -a]. (12.5g, 63%)

Synthesis Example 2- (2): Synthesis of [Intermediate 2-b]

[Intermediate 2-b] was synthesized according to the following Scheme 7.

Scheme 7

                               [Intermediate 2-b]

3-aminopyridine (25.0 g, 0.226 mol), dimethyl sulfoxide (250 ml) and water (5 ml) were added to a 500 ml round bottom flask, and N-bromosuccinimide (99.3 g, 0.558 mol) was slowly added at 0 ° C. . The reaction solution was stirred at room temperature for 24 hours and then recrystallized with acetonitrile to obtain [Intermediate 2-b]. (59g, 89%)

Synthesis Example 2- (3): Synthesis of [Intermediate 2-c]

[Intermediate 2-c] was synthesized according to Scheme 8 below.

Scheme 8

[Intermediate 2-b] [Intermediate 2-a] [Intermediate 2-c]

The same method as in Synthesis Example 1- (3) except that [Intermediate 2-b] was used instead of 1-amino-2-bromo-4-methylpyridine and [Intermediate 2-a] instead of [Intermediate 1-b]. Experiment was carried out to obtain [Intermediate 2-c]. (12g, 73%)

Synthesis Example 2- (4): Synthesis of [Intermediate 2-d]

[Intermediate 2-d] was synthesized according to Scheme 9 below.

Scheme 9

[중간체 2-c] [중간체 1-a] [중간체 2-d]

[Intermediate 2-c] [Intermediate 1-a] [Intermediate 2-d]

[Intermediate 2-d] was obtained in the same manner as in Synthesis Example 1- (4), except that [Intermediate 2-c] was used instead of [Intermediate 1-c]. (11g, 64%)

Synthesis Example 2- (5): Synthesis of Formula 21

To [formula 21] was synthesized according to Scheme 10 below.

Scheme 10

[중간체 2-d] [화학식 21] 상기 합성예 1-(5)에서 [중간체 1-d] 대신 [중간체 2-d]를 사용한 것을 제외하고 동일한 방법으로 실험하여 [화학식 21]을 얻었다. (2.8g, 30%)

Intermediate 2-d Chemical Formula 21 was obtained in the same manner as in Synthesis Example 1- (5), except that Intermediate 2-d was used instead of Intermediate 1-d. (2.8g, 30%)

MS (MALDI-TOF): m / z 1132.45 [M ⁺ ]

Synthesis Example 3 Synthesis of Chemical Formula 39

Synthesis Example 3- (1): Synthesis of [Intermediate 3-a]

[Intermediate 3-a] was synthesized according to the following Scheme 11.

Scheme 11

               [Intermediate 3-a]

[Intermediate 3-a] was obtained in the same manner as in Synthesis Example 1- (1), except that 2-nitro-4-bromophenol was used instead of 2-bromo-6-nitrophenol. (16.0g, 50%)

Synthesis Example 3- (2): Synthesis of [Intermediate 3-b]

[Intermediate 3-b] was synthesized according to Scheme 12 below.

Scheme 12

                 [Intermediate 3-b]

[Intermediate 3-b] was obtained in the same manner as in Synthesis Example 1- (2), except that bromobenzene (25.0 g, 0.159 mol) was used instead of 1-bromo-2,5-dimethylbenzene. (13g, 67%)

Synthesis Example 3- (3): Synthesis of [Intermediate 3-c]

[Intermediate 3-c] was synthesized according to Scheme 13 below.

Scheme 13

[3,5-dibromo-2-pyridylamine] [intermediate 3-b] [intermediate 3-c]

In Synthesis Example 1- (3), 3,5-dibromo-2-pyridylamine instead of 1-amino-2-bromo-4-methylpyridine was substituted for [Intermediate 1-b]. Experiment was carried out in the same manner except that [intermediate 3-c] was obtained. (8 g, 68%)

Synthesis Example 3- (4): Synthesis of [Intermediate 3-d]

[Intermediate 3-d] was synthesized according to Scheme 14 below.

Scheme 14

[Intermediate 3-c] [Intermediate 3-a] [Intermediate 3-d]

[Intermediate 3-c] instead of [Intermediate 1-c] in Synthesis Example 1- (4) was tested in the same manner except that [Intermediate 3-a] was used instead of [Intermediate 1-a]. d]. (11g, 72%)

Synthesis Example 3- (5): Synthesis of [Formula 39]

To [formula 39] was synthesized according to Scheme 15 below.

Scheme 15

[중간체 3-d] [화학식 39]

[Intermediate 3-d] [Formula 39]

[Formula 39] was obtained in the same manner as in Synthesis Example 1- (5) except that [Intermediate 3-d] was used instead of [Intermediate 1-d]. (2.6g, 28%)

MS (MALDI-TOF): m / z 1104.42 [M ⁺ ]

Synthesis Example 4 Synthesis of Chemical Formula 58

Synthesis Example 4- (1): Synthesis of [Intermediate 4-a]

[Intermediate 4-a] was synthesized according to Scheme 16 below.

Scheme 16

                        [Intermediate 4-a]

In the same manner as in Synthesis Example 1- (1) except that 4-tertylbutyl benzyl alcohol instead of 2-bromo-6-nitrophenol was used instead of 2-nitro-4-bromophenol To obtain [Intermediate 4-a]. (13.0g, 41%)

Synthesis Example 4- (2): Synthesis of [Intermediate 4-b]

[Intermediate 4-b] was synthesized according to Scheme 17 below.

Scheme 17

                        [Intermediate 4-b]

In the same manner as in Synthesis Example 1- (2) except that 3,5-dimethylbenzene (25.0g, 0.159mol) was used instead of 1-bromo-2,5-dimethylbenzene [Intermediate 4-b] Got. (13g, 64%)

Synthesis Example 4- (3): Synthesis of [Intermediate 4-c]

[Intermediate 4-c] was synthesized according to Scheme 18 below.

Scheme 18

              [Intermediate 4-b] [Intermediate 4-c]

In Synthesis Example 1- (3), 1-amino-3-bromo-5-fluorobenzene instead of 1-amino-2-bromo-4-methylpyridine was replaced with [Intermediate 4-b] instead of [Intermediate 1-b]. ] Was obtained in the same manner except that [intermediate 4-c] was used. (15g, 88%)

Synthesis Example 4- (4): Synthesis of [Intermediate 4-d]

[Intermediate 4-d] was synthesized according to Scheme 19 below.

Scheme 19

[중간체 4-c] [중간체 4-a] [중간체 4-d]

[Intermediate 4-c] [Intermediate 4-a] [Intermediate 4-d]

[Intermediate 4-c] instead of [Intermediate 1-c] in Synthesis Example 1- (4) was tested in the same manner except that [Intermediate 4-a] was used instead of [Intermediate 1-a]. d]. (10 g, 70%)

Synthesis Example 4- (5): Synthesis of [Formula 58]

To [Scheme 58] was synthesized according to Scheme 20 below.

Scheme 20

[중간체 4-d] [화학식 58]

[Intermediate 4-d] [Formula 58]

[Formula 58] was obtained in the same manner as in Synthesis Example 1- (5) except that [Intermediate 4-d] was used instead of [Intermediate 1-d]. (3.5g, 34%)

MS (MALDI-TOF): m / z 1126.50 [M ⁺ ]

Synthesis Example 5 Synthesis of Chemical Formula 80

Synthesis Example 5- (1): Synthesis of [Intermediate 5-a]

[Intermediate 5-a] was synthesized according to Scheme 21 below.

Scheme 21

                          [Intermediate 5-a]

[Intermediate 5-a] was obtained in the same manner as in Synthesis Example 1- (2), except that 2-bromo-biphenyl was used instead of 1-bromo-2,5-dimethylbenzene. (15 g, 60%)

Synthesis Example 5- (2): Synthesis of [Intermediate 5-b]

[Intermediate 5-b] was synthesized according to Scheme 22 below.

Scheme 22

                                  [Intermediate 5-b]

2-amino-5-bromobenzothiol (15.0 g, 73 mmol) and 1-naphthylaldehyde (10.3 g, 66 mmol) were dissolved in 1,4-dioxane and refluxed at 100 ° C. in a 100 ml round bottom flask for 12 hours. Stirred Extracted with dichloromethane, concentrated under reduced pressure and separated by column chromatography to give [Intermediate 5-b]. (12.3g, 49%)

Synthesis Example 5- (3): Synthesis of [Intermediate 5-c]

[Intermediate 5-c] was synthesized according to Scheme 23 below.

Scheme 23

       [Intermediate 5-a] [Intermediate 5-c]

[Intermediate 5-c] was obtained in the same manner as in Synthesis Example 1- (3), except that [Intermediate 5-a] was used instead of [Intermediate 1-b]. (13g, 75%)

Synthesis Example 5- (4): Synthesis of [Intermediate 5-d]

[Intermediate 5-d] was synthesized according to Scheme 24 below.

Scheme 24

 [Intermediate 5-b] [Intermediate 5-c] [Intermediate 5-d]

[Intermediate 5-c] instead of [Intermediate 1-c] in Synthesis Example 1- (4) was tested in the same manner except that [Intermediate 5-b] was used instead of [Intermediate 1-a]. d]. (11g, 75%)

Synthesis Example 5- (5): Synthesis of [Formula 80]

[Scheme 80] was synthesized according to the following Reaction Scheme 25.

Scheme 25

              [Intermediate 5-d] [Formula 80]

[Formula 80] was obtained in the same manner as in Synthesis Example 1- (5) except that [Intermediate 5-d] was used instead of [Intermediate 1-d]. (3.2g, 28%)

MS (MALDI-TOF): m / z 1136.37 [M ⁺ ]

Synthesis Example 6 Synthesis of Chemical Formula 89

Synthesis Example 6- (1): Synthesis of [Intermediate 6-a]

[Intermediate 6-a] was synthesized according to Scheme 26 below.

Scheme 26

[중간체 6-a]

[Intermediate 6-a]

[Intermediate 6-a] was obtained in the same manner as in Synthesis Example 1- (3), except that 4-methylbenzeneboronic acid was used instead of [Intermediate 1-b]. (13g, 75%)

Synthesis Example 6- (2): Synthesis of [Intermediate 6-b]

[Intermediate 6-b] was synthesized according to Scheme 27 below.

Scheme 27

[중간체 6-b]

[Intermediate 6-b]

[Intermediate 6-b] was obtained in the same manner as in Synthesis Example 1- (1), except that 4-fluorobenzyl alcohol was used instead of benzyl alcohol. (13.0g, 41%)

Synthesis Example 6- (3): Synthesis of [Intermediate 6-c]

[Intermediate 6-c] was synthesized according to Scheme 28 below.

Scheme 28

                  [Intermediate 3-b] [Intermediate 6-c]

1,6-dibromopyrene (70g, 0.194mol), [Intermediate 3-b] (52.2g, 0.428mol), tetrakis (triphenylphosphine) palladium (11.2g, 0.01mol) in a 2L round bottom flask ), Potassium carbonate (80.6 g, 0.583 mol), toluene 350 ml, tetrahydrofuran 350 ml and water 140 ml were added and stirred under reflux. After the reaction was completed, the mixture was cooled to room temperature, and the resulting solid was filtered and washed with ethanol. The solid was dissolved in toluene, and the solid produced after cooling to room temperature was filtered to obtain [Intermediate 6-c]. (60.0g, 87%)

Synthesis Example 6- (4): Synthesis of [Intermediate 6-d] [Intermediate 6-d] was synthesized according to Scheme 29.

Scheme 29

[Intermediate 6-c] [Intermediate 6-d]

[Intermediate 6-c] (30.0g, 0.085mol) was dissolved in 900ml of dimethylformamide in a 2L round bottom flask, and N-bromosuccinimide (33.1g, 0.186mol) was added thereto and stirred at 50 ° C for 8 hours. . After the reaction was completed, 500ml of water was added to the mixture, and the resulting solid was filtered and washed with water and methanol. It was dissolved in dichlorobenzene and cooled to room temperature, and the produced solid was filtered to obtain [Intermediate 6-d]. (30g, 69%)

Synthesis Example 6- (5): Synthesis of [Intermediate 6-e]

[Intermediate 6-e] was synthesized according to Scheme 30 below.

Scheme 30

[Intermediate 6-a] [Intermediate 6-b] [Intermediate 6-e]

[Intermediate 6-a] instead of [Intermediate 1-c] in Synthesis Example 1- (4) was tested in the same manner except that [Intermediate 6-b] was used instead of [Intermediate 1-a]. e]. (11g, 70%)

Synthesis Example 6- (6): Synthesis of [Formula 89]

To [Chemical Formula 89] was synthesized according to Scheme 31 below.

Scheme 31

[Intermediate 6-d] [Intermediate 6-e] [Formula 89]

Experimental Example 1- (5) [intermediate 6-d] instead of 1,6-dibromopyrene in the same manner except [intermediate 6-e] instead of [intermediate 1-d] [ Formula 89] was obtained. (3.3g, 28%)

MS (MALDI-TOF): m / z 1168.43 [M ⁺ ]

Synthesis Example 7 Synthesis of Chemical Formula 105

Synthesis Example 7- (1): Synthesis of [Intermediate 7-a]

[Intermediate 7-a] was synthesized according to Scheme 32 below.

Scheme 32

                                    [Intermediate 7-a]

[Intermediate 7-a] was obtained in the same manner as in Synthesis Example 1- (1), except that 2-nitro-3-chlorophenol was used instead of 2-bromo-6-nitrophenol. (13.0g, 30%)

Synthesis Example 7- (2): Synthesis of [Intermediate 7-b]

[Intermediate 7-b] was synthesized according to Scheme 33 below.

Scheme 33

           [Intermediate 7-a] [Intermediate 7-b]

[Intermediate 7-a] (10.0g, 44mmol), 4-aminobiphenyl (14.7, 87mmol) tris (dibenzylideneacetone) palladium (1.99g, 0.2mmol), sodium tert-butoxide ( 5.02 g, 52 mmol), 2- (dicyclohexylphosphino) -2 ', 4', 6'-triisopropylbiphenyl (2.08 g, 0.44 mmol) and 100 ml of toluene were added thereto, and the mixture was stirred under reflux for 3 hours under a nitrogen atmosphere. . After extraction, the residue was separated by column chromatography and recrystallized with methanol to obtain [Intermediate 7-b]. (11g, 69%)

Synthesis Example 7- (3): Synthesis of Formula 105

To [formula 105] was synthesized according to Scheme 34 below.

Scheme 34

               Intermediate 7-b Formula 105

[Formula 105] was obtained in the same manner as in Synthesis Example 1- (5) except that [Intermediate 7-b] was used instead of [Intermediate 1-d]. (2.7g, 29%)

MS (MALDI-TOF): m / z 922.33 [M ⁺ ]

Synthesis Example 8: Synthesis of Chemical Formula 109

Synthesis Example 8- (1): Synthesis of [Intermediate 8-a]

[Intermediate 8-a] was synthesized according to the following Reaction Scheme 35.

Scheme 35

                                       [Intermediate 8-a]

[Intermediate 8-a] was obtained in the same manner as in Synthesis Example 1- (4), except that benzeneamine was used instead of [Intermediate 1-c]. (9.3g, 76%)

Synthesis Example 8- (2): Synthesis of [Intermediate 8-b]

[Intermediate 8-b] was synthesized according to Scheme 36 below.

Scheme 36

             [Intermediate 8-a] [Intermediate 8-b]

Intermediate 8-a (7.7 g, 27 mmol), 1,6-dibromopyrene (8.1 g, 22.5 mmol), 2,2'-bis (diphenylphosphino) -1-1'-binaptyl (0.28 g, 0.45 mmol), sodium tert-butoxide (4.3 g, 45 mmol) and palladium acetate (0.1 g, 0.45 mmol) were added to 100 mL of toluene and refluxed for 24 hours. Extracted with ethyl acetate and washed with methanol. Separation by column chromatography afforded [Intermediate 8-b]. (4.9g, 40%)

Synthesis Example 8- (3): Synthesis of Formula 109

To [formula 109] was synthesized according to Scheme 37 below.

Scheme 37

[Intermediate 8-b] [Intermediate 1-d] [Formula 109]

In the synthesis example 8- (2) [Intermediate 1-d] instead of [Intermediate 8-a] was tested in the same manner except [Intermediate 8-b] instead of 1,6-dibromopyrene [Formula 109 ] Was obtained. (3.5g, 33%)

MS (MALDI-TOF): m / z 889.34 [M ⁺ ]

Synthesis Example 9 Synthesis of Formula 116

Synthesis Example 9- (1): Synthesis of [Intermediate 9-a]

[Intermediate 9-a] was synthesized according to Scheme 38 below.

Scheme 38

       [Intermediate 5-b] [Intermediate 9-a]

In the same manner as in Synthesis Example 1- (4) except that 4-methylbenzeneamine was used instead of [Intermediate 1-c] and [Intermediate 5-b] instead of [Intermediate 1-a]. ] Was obtained. (10.1 g, 73%)

Synthesis Example 9- (2): Synthesis of [Intermediate 9-b]

[Intermediate 9-b] was synthesized according to Scheme 39 below.

Scheme 39

            [Intermediate 9-a] [Intermediate 9-b]

[Intermediate 9-b] was obtained in the same manner as in Synthesis Example 8- (2), except that [Intermediate 9-a] was used instead of [Intermediate 8-a]. (3.9 g, 37%)

Synthesis Example 9- (3): Synthesis of [Intermediate 9-c]

[Intermediate 9-c] was synthesized according to Scheme 40 below.

Scheme 40

   [Intermediate 6-b] [Intermediate 9-c]

In the Synthesis Example 1- (4), 5-methyl-2-pyridinamine instead of [Intermediate 1-c] was tested in the same manner except that [Intermediate 6-b] was used instead of [Intermediate 1-a]. 9-c]. (11.4g, 74%)

Synthesis Example 9- (4): Synthesis of Formula 116

To [formula 116] was synthesized according to Scheme 41 below.

Scheme 41

[Intermediate 9-b] [Intermediate 9-c] [Formula 116]

[Intermediate 9-c] instead of [Intermediate 8-a] in Synthesis Example 8- (2) was tested in the same manner except that [Intermediate 9-b] was used instead of 1,6-dibromopyrene. ] Was obtained. (2.9g, 30%)

MS (MALDI-TOF): m / z 883.28 [M ⁺ ]

Example 1-7: Article of the organic EL device

The light emitting area of the ITO glass was patterned to have a size of 2 mm x 2 mm and then washed. After mounting the ITO glass in a vacuum chamber, the base pressure was 1 × 10 ⁻⁷ torr, and then DNTPD (700 kPa) and α-NPD (300 kPa) were deposited on the ITO, followed by [BH1] and the present invention. 3% of the compound obtained by mixing was formed into a film (250 kV), and then formed in the order of Alq ₃ (350 kPa), LiF (5 kPa) and Al (1000 kPa) to manufacture an organic light emitting device. The luminescence properties of the organic light emitting device were measured at 0.4 mA.

            [DNTPD] [α-NPD]

[BH1] [Alq ₃ ]

Comparative Examples 1 and 2

Used in Examples 1 to 7 above. The organic light emitting device was manufactured in the same manner as in the case of using [BD1] and [BD2] instead of the compound, and the emission characteristics of the organic light emitting device were measured at 0.4 mA. The structures of [BD1] and [BD2] are as follows.

         [BD1] [BD2]

For organic light emitting diodes manufactured according to Examples 1 to 7 and Comparative Examples 1 and 2, voltage, current, luminance, color coordinates, and lifetime were measured, and the results are shown in the following [Table 1]. T80 means the time taken for the luminance to decrease to 80% of the initial luminance.

Voltage
(V) Current density
(mA / cm ² ) Luminance
(cd / m ² ) CIEx CIEy Quantum efficiency T80 Example 1
[Formula 1] 3.8 10 600 0.142 0.097 5.61 80 Example 2
[Formula 21] 3.8 10 633 0.141 0.110 5.77 95 Example 3
[Formula 39] 3.8 10 620 0.143 0.107 6.16 96 Example 4
[Formula 58] 3.7 10 610 0.140 0.099 6.09 85 Example 5
[Formula 80] 3.8 10 578 0.141 0.105 6.83 100 Example 6
[Formula 89] 3.7 10 717 0.142 0.124 5.43 75 Example 7
[Formula 105] 3.7 10 752 0.141 0.120 6.46 110 Comparative Example 1
[BD1] 6.4 10 515 0.143 0.160 4.96 42 Comparative Example 2
[BD2] 6.0 10 550 0.141 0.168 4.88 40

As shown in Table 1, the asymmetric pyrene derivative according to the present invention has much higher luminance and luminous efficiency than the case of using the compounds of Comparative Example 1 and Comparative Example 2 according to the prior art, and can show excellent device characteristics of long life. In addition, the present invention has high applicability as an organic light emitting device.

Claims (16)

A pyrene derivative represented by the following [Formula A].
[Formula A]

In [Formula A],
X is one selected from O, S and Se,
The linking groups L ₁ and L ₂ are the same or different and are each independently a single bond, a substituted or unsubstituted arylene group having 5 to 50 carbon atoms, or a substituted or unsubstituted and selected from heteroatoms O, N, S and Si. A heteroarylene group having 2 to 50 carbon atoms,
Ar ₁ and Ar ₂ are the same as or different from each other, and each independently, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, or at least one selected from substituted, unsubstituted and heteroatoms O, N, S and Si A heteroaryl group having 2 to 50 carbon atoms,
Each substituent M bonded to the nitrogen atom of the amine group may be the same or different,
_One of R ₁ to R ₄ in the substituent M is a single bond bonded to a nitrogen atom,
The substituents Z and R ₁ to R ₅ are the same as or different from each other, and independently of each other, hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, A substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl having 5 to 30 carbon atoms An alkenyl group, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having at least one selected from O, N, S and Si as a hetero atom, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted A substituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted carbon number 1 To 30 alkylamine group, substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl group having 5 to 30 carbon atoms, Any group selected from the group consisting of a no group, a nitro group, and a halogen group, and may be combined with a neighboring substituent to form a saturated or unsaturated ring;
Each carbon atom in the pyrene ring is bonded to hydrogen when not bonded to the nitrogen atom of the amine or the substituent Z;
m is an integer from 1 to 8, and when m is 2 or more, each Z is the same as or different from each other,
p and q are each the same or different integers of 1 to 3, each Ar ₁ is the same or different when p is 2 or more, and each Ar ₂ is the same or different when q is 2 or more,
The 'substituted' in the 'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group of 1 to 24 carbon atoms, halogenated alkyl group of 1 to 24 carbon atoms, alkenyl group of 1 to 24 carbon atoms , Alkynyl group having 1 to 24 carbon atoms, heteroalkyl group having 1 to 24 carbon atoms, aryl group having 6 to 24 carbon atoms, arylalkyl group having 6 to 24 carbon atoms, heteroaryl group having 2 to 24 carbon atoms or heteroarylalkyl group having 2 to 24 carbon atoms , Alkoxy group having 1 to 24 carbon atoms, alkylamino group having 1 to 24 carbon atoms, arylamino group having 1 to 24 carbon atoms, heteroaryl group having 1 to 24 carbon atoms, alkylsilyl group having 1 to 24 carbon atoms, arylsilyl having 1 to 24 carbon atoms It means that the group is substituted with one or more substituents selected from the group consisting of aryloxy group having 1 to 24 carbon atoms. The method of claim 1,
In the case where Ar ₁ and Ar ₂ are the same or different heteroaryl groups, the heteroaryl group is any one selected from the following [substituent 101] to [substituent 117].
[Substitution 101] [Substitution 102] [Substitution 103] [Substitution 104]

[Substitution 105] [Substitution 106] [Substitution 107]

[Substitution 108] [Substitution 109] [Substitution 110]

[Substitution 111] [Substitution 112] [Substitution 113]

[Substitution 114] [Substitution 115] [Substitution 116]

[Substituent 117]

Wherein R is the same or different and independently from each other, hydrogen, deuterium, 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 a salt thereof, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, substituted or unsubstituted carbon atoms 1 An alkoxy group of 30 to 30, substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, substituted Or an unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, substituted or non-substituted A substituted (alkyl) amino group having 1 to 30 carbon atoms, a di (substituted or unsubstituted alkyl) amino group having 1 to 30 carbon atoms, or a (substituted or unsubstituted aryl having 6 to 30 carbon atoms), di (substituted or unsubstituted groups) Aryl) amino group having 6 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl group having 5 to 30 carbon atoms, germanium, phosphorus and boron, each of which may be selected from Substituents may be combined with groups adjacent to each other to form a saturated or unsaturated ring,
n is an integer from 1 to 9,
When the substituent R is not bonded to the aromatic ring or the carbon in the saturated hydrocarbon ring in the [substituent 101] to the [substituent 117], hydrogen is bonded,
When the substituent R is 2 or more, each R may be the same or different from each other,
One of the substituents R in the [substituent 101] to the [substituent 117] is a single bond bonded to the linking group L ₁ or L ₂ in the formula (A),
'Substituted' in 'substituted or unsubstituted' is the same as defined in claim 1. The method of claim 1,
In the case where Ar ₁ and Ar ₂ are the same or different aryl groups, the aryl group may be any one selected from the following [substituents 201] to [substituents 210].
[Substituent 201] [Substituent 202] [Substituent 203]

[Substituent 204] [Substituent 205] [Substituent 206]

[Substituent 207] [Substituent 208] [Substituent 209]

[Substituent 210]

Wherein n is an integer from 1 to 9,
When the substituent R is not bonded to the carbon in the aromatic ring in [substituent 201] to [substituent 210], hydrogen is bonded,
Substituent R is the same as the definition of substituent R in the said 2nd term. The method of claim 1,
The linking group L1 and L2 are each a single bond, or a pyrene derivative, characterized in that any one selected from the following [formula 101] to [formula 210].
[Structure 101] [Structure 102] [Structure 103] [Structure 104]

[Structure 105] [Structure 106] [Structure 107]

[Structure 108] [Structure 109] [Structure 110]

[Formula 111] [Formula 112] [Formula 113]

[Structure 114] [Structure 115] [Structure 116]

[Structure 117]

[Structure 201] [Structure 202] [Structure 203]

[Structure 204] [Structure 205] [Structure 206]

[Structure 207] [Structure 208] [Structure 209]

[Formula 210]

Where n is an integer from 2 to 9,
When the substituent R is not bonded to the carbon in the aromatic ring or the saturated hydrocarbon ring in [Formula 101] to [Formula 210], hydrogen is bonded,
Two to four R of the substituents R included in [Formula 101] to [Formula 210] are each a single bond bonded to a nitrogen atom and a substituent Ar ₁ , or a single bond bonded to a nitrogen atom and a substituent Ar ₂ , respectively. ,
The substituent R is the same as defined in claim 2. The method of claim 1,
The substituent Z is any one selected from deuterium, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms Pyrene derivatives characterized by the above-mentioned. The method according to any one of claims 1 to 5,
The pyrene derivative of Formula (A) is a pyrene derivative, characterized in that the amines are bonded to positions 1, 6 or 2, 7, respectively. The method according to any one of claims 1 to 5,
M or Ar ₁ or Ar ₂ bonded to the amine of [Formula A] is a pyrene derivative, characterized in that it comprises deuterium. The method according to any one of claims 1 to 5,
The substituents substituted in M, L ₁ , L ₂ , Ar ₁ and Ar ₂ may be a cyano group, a halogen group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 6 to 18 carbon atoms. A pyrene derivative, characterized in that any one selected from the group consisting of a heteroaryl group having 3 to 18 carbon atoms, an alkylsilyl group having 1 to 12 carbon atoms, an arylsilyl group having 6 to 18 carbon atoms. The method according to any one of claims 1 to 5,
The pyrene derivative is a pyrene derivative, characterized in that two amine groups are the same. The method according to any one of claims 1 to 5,
The pyrene derivative is a pyrene derivative, characterized in that the two amine groups are asymmetric with each other. The method of claim 1,
Any one of pyrene derivatives selected from the following [Compound 1] to [Compound 117].
[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 37] [Compound 39]

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

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

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

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

[Compound 52] [Compound 53] [Compound 54]

[Compound 55] [Compound 56] [Compound 57]

[Compound 58] [Compound 59] [Compound 60]

[Compound 61] [Compound 62] [Compound 63]

[Compound 64] [Compound 65] [Compound 66]

[Compound 67] [Compound 68] [Compound 69]

[Compound 70] [Compound 71] [Compound 72]

[Compound 73] [Compound 74] [Compound 75]

[Compound 76] [Compound 77] [Compound 78]

[Compound 79] [Compound 80] [Compound 81]

[Compound 82] [Compound 83] [Compound 84]

[Compound 85] [Compound 86] [Compound 87]

[Compound 88] [Compound 89] [Compound 90]

[Compound 91] [Compound 92] [Compound 93]

[Compound 94] [Compound 95] [Compound 96]

[Compound 97] [Compound 98] [Compound 99]

[Compound 100] [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]

A first electrode;
A second electrode opposed to the first electrode; And
And an organic layer interposed between the first electrode and the second electrode, wherein the organic layer comprises at least one organic light emitting compound of any one of claims 1 to 5 and 11. device. The method of claim 12,
And the organic layer comprises at least one of a hole injection layer, a hole transport layer, a hole injection function, and a hole injection function and at least one of a functional layer, a light emitting layer, an electron transport layer, and an electron injection layer. The method of claim 12,
The organic layer interposed between the first electrode and the second electrode includes a light emitting layer,
The light emitting layer comprises a host and a dopant, wherein the organic light emitting compound is used as a dopant. The method of claim 13,
At least one layer selected from each of the layers may be formed by a deposition process or a solution process. The method of claim 12,
The organic light emitting device is a flat panel display device; Flexible display devices; Monochrome or white flat lighting devices; And a monochromatic or white flexible lighting device. The organic light emitting device of claim 1, wherein the organic light emitting device is used.

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