KR101503766B1 - Pyrene derivatives and organic light-emitting diode including the same - Google Patents

Abstract

The present invention relates to a pyrene-based derivative and an organic electroluminescent device comprising the same as a light emitting material, and more particularly to a pyrene-based derivative represented by the following formula (A) and an organic electroluminescent device comprising the same.
(A)

Description

FIELD OF THE INVENTION The present invention relates to a pyrene derivative compound and an organic electroluminescent device including the same,

The present invention relates to a pyrene derivative compound and an organic electroluminescent device comprising the same as a light emitting material. More particularly, the present invention relates to a pyrene derivative compound having a longer life characteristic and excellent in light emission characteristics such as driving voltage and current efficiency, And an electroluminescent 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. On the other hand, an organic light emitting diode (OLED), which is a new flat display device, is a display using a self-luminous phenomenon and has a wide viewing angle and can be made thinner and thinner than a liquid crystal display, And 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 electroluminescent device using an organic light emitting phenomenon usually has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to enhance the efficiency and stability of the organic electroluminescent device, the organic material layer may have a multi-layer 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 the organic electroluminescent device, holes are injected into the anode, electrons are injected into the organic layer, and excitons are formed when injected holes and electrons meet. When it falls back to the ground state, the light comes out. Such an organic electroluminescent device is known to have properties 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 electroluminescent 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 light-emitting efficiency through the light-emitting layer.

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, the excitons generated in the light emitting layer are transported to the dopant to emit light with high efficiency. 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.

In order for the organic electroluminescent device to sufficiently exhibit the above-described excellent characteristics, materials constituting the organic material layer in the device, such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material are supported by a stable and efficient material Should be preceded.

On the other hand, studies have been made to introduce a deuterium-substituted compound as the organic material in order to improve the efficiency and stability of the organic light emitting device.

Compounds substituted with deuterium are known to exhibit differences in thermodynamic behavior compared to compounds bonded with hydrogen because the atomic mass of deuterium is two times greater than hydrogen resulting in lower zero energy and lower vibration energy levels Because. In addition, physicochemical properties such as chemical bond lengths related to deuterium appear to be different from hydrogen, and in particular, the CD bond elongation amplitude is smaller than that of CH bonds, so that the van der Waals radius of deuterium is smaller than hydrogen, Indicating that the bond is shorter and stronger than the CH bond.

In addition, when substituted with deuterium, the energy of the bottom state is lowered. As the bond length of deuterium and carbon becomes shorter, the molecular hardcore volume is reduced, and thus, the electro polar polarizability can be reduced, It is known that the thin film volume can be increased by weakening the intermolecular interaction. These properties can make the crystallinity of the thin film lower, that is, amorphous state, and can generally be effective for increasing OLED lifetime and driving characteristics, and the heat resistance can be further improved.

As a related art related to the organic light emitting compound containing deuterium, Japanese Patent Laid-Open Publication No. 10-1111406 discloses a method in which an amine compound containing carbazole is replaced with deuterium, or a compound containing deuterium substituted compound is mixed, And Patent Document 10-1068224 discloses a technique using a host as an anthracene derivative containing a phenyl group in which hydrogen in the phenyl group is substituted with deuterium.

However, there is a continuing need for development of an organic material layer for an organic electroluminescence device which is stable, efficient, and has a long life span, despite efforts to manufacture the long-life device.

Patent Registration No. 10-1111406 (Apr. 12, 2012)

Korean Patent Registration No. 10-1068224 (September 28, 2011)

Accordingly, a first technical object of the present invention is to provide a pyrene derivative compound for an organic electroluminescent device having a long life, low driving voltage and excellent luminous efficiency.

A second object of the present invention is to provide an organic electroluminescent device comprising the pyrene derivative compound.

In order to achieve the first technical object, the present invention provides a pyrene-based derivative represented by the following formula (A).

 (A)

In the above formula (A)

R ₁ to R ₁₀ are the same or different from each other and each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, An 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, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, A silyl group having a substituent selected from an aryl group having 6 to 10 carbon atoms and may form a condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero with an adjacent group,

One of R ₁ to R ₁₀ is a substituent represented by the following formula 1 and at least one of R ₁ to R ₁₀ is deuterium. In this case, the degree of deuteration of the deuterium bonded to the pyrene of the pyrene derivative Which is the percentage of all deuterium directly bonded to the pyrene relative to the sum of all the hydrogen directly bonded to the pyrene and all the deuterium directly bonded to the pyrene) is at least 40%.

 [Structural formula 1]

In the above structural formula 1,

X ₁ to X ₁₀ are the same as or different from each other and each independently represent a substituent group as defined in R ₁ to R ₁₀ , wherein the substituent X ₉ is a substituent represented by the following structural formula 2.

[Structural formula 2]

In the above structural formula 2,

L ₁ represents a single bond, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms,

* Is a bonding site between pyrene and anthracene in the above-mentioned formula (A).

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, The present invention provides an organic light emitting device comprising at least one pyrene derivative compound represented by the formula (A).

According to the present invention, the pyrene derivative compound represented by the formula (A) has improved heat resistance as compared with the existing material, has a long life, has stable and excellent luminescence characteristics, and therefore, It is possible to drive at low voltage and improve the luminous efficiency.

1 is a schematic view of an organic electroluminescent device according to one embodiment of the present invention.
Figure 2 is a graph illustrating the life evaluation of a device in accordance with one embodiment of the present invention.
3 is a graph illustrating the life evaluation of a device according to another embodiment of the present invention.
4 is a graph showing the life evaluation of a device according to another embodiment of the present invention.

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

The present invention is a pyrene derivative compound contained in a light emitting layer of an organic electroluminescent device, and is characterized by being a compound represented by the following formula (A), and the substituent of the pyrene derivative is described in more detail below.

 (A)

In the above formula (A)

R ₁ to R ₁₀ are the same or different from each other and each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, An 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, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, A silyl group having a substituent selected from an aryl group having 6 to 10 carbon atoms and may form a condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero with an adjacent group,

One of R ₁ to R ₁₀ is a substituent represented by the following formula 1 and at least one of R ₁ to R ₁₀ is deuterium. In this case, the degree of deuteration of the deuterium bonded to the pyrene of the pyrene derivative Which is the percentage of all deuterium directly bonded to the pyrene relative to the sum of all the hydrogen directly bonded to the pyrene and all the deuterium directly bonded to the pyrene) is at least 40%.

 [Structural formula 1]

In the above structural formula 1,

X ₁ to X ₁₀ are the same as or different from each other and each independently represent a substituent group as defined in R ₁ to R ₁₀ , wherein the substituent X ₉ is a substituent represented by the following structural formula 2.

[Structural formula 2]

In the above structural formula 2,

L ₁ represents a single bond, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms,

* Is a bonding site between pyrene in [Formula A] and anthracene in [Formula 1].

In the present invention, in the term "substituted or unsubstituted", "substituted" means a group selected from the group consisting of deuterium, a cyano group, a halogen group, an alkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, Quot; means a group substituted with at least one substituent selected from the group consisting of

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, isoamyloxy, 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 in the silyl group may be substituted with the same substituent as the aryl group.

More specifically, in the present invention, X ₁ to X ₁₀ (substituent bonded to an anthracene group) in the above-mentioned structural formula 1 are independently selected from the group consisting of hydrogen, deuterium, a halogen atom, a hydroxyl group, a cyano 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 alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted phenyl group, Substituted or unsubstituted indenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted azulenyl, substituted or unsubstituted heptalenyl (substituted or unsubstituted naphthyl, substituted or unsubstituted naphthyl, heptalenyl, substituted or unsubstituted indacenyl, substituted or unsubstituted acenaphthyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted phenalenyl, Substituted or unsubstituted Substituted or unsubstituted phenanthrenyl, substituted or unsubstituted anthryl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted Substituted or unsubstituted pyrene, pyrenyl, substituted or unsubstituted chrysenyl, substituted or unsubstituted naphthacenyl, substituted or unsubstituted picenyl, substituted or unsubstituted perylene Substituted or unsubstituted pyrazolyl groups such as perylenyl, substituted or unsubstituted pentaphenyl, substituted or unsubstituted hexacenyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted pyrazolyl ), A substituted or unsubstituted imidazolyl, a substituted or unsubstituted imidazolinyl, a substituted or unsubstituted imidazopyridinyl, a substituted or unsubstituted imidazolopyrimidine Imidazopyrimidinyl, substituted < RTI ID = 0.0 > A substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted pyrazinyl group, Substituted or unsubstituted quinolinyl, substituted or unsubstituted phthalazinyl, substituted or unsubstituted indolizinyl, substituted or unsubstituted naphthyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted quinolinyl, Naphthyridinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted cinnolinyl, substituted or unsubstituted indazolyl, substituted or unsubstituted carbazole di carbazolyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted phenanthridinyl, substituted or unsubstituted pyranyl, substituted or unsubstituted chromenyl group ( chromenyl), a substituted or unsubstituted furanyl group, A substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted isothiazolyl group, a substituted or unsubstituted benzothiophenyl group, A substituted or unsubstituted benzoimidazolyl group, a substituted or unsubstituted isoxazolyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted dibenzopuranyl group, a substituted or unsubstituted dibenzopyranyl group, Or an unsubstituted triazinyl group, or a substituted or unsubstituted oxadiazolyl group.

More specifically, X ₁ to X ₁₀ (meaning a substituent bonded to an anthracene group) in the above-mentioned [structural formula 1] are independently selected from the group consisting of hydrogen, deuterium, halogen atoms, hydroxyl group, cyano group, nitro group, Substituted or unsubstituted alkyl group-substituted or unsubstituted C1-C20 alkenyl group-substituted or unsubstituted C2-C20 alkynyl group.

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

Z ₁ to Z ₇ independently represent hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amino, amido, hydrazine hydrazone carboxyl group or its salt, phosphoric acid or its salt, alkyl group having 1 to 10 carbon atoms, An alkoxy group of 1 to 10 carbon atoms, 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 a salt thereof, 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, a naphthyl group, a fluorenyl group, a phenanthrenyl group, an anthryl group, a pyrenyl group, a chrysenyl group, A halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, A phenyl group substituted with at least one of a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkylthio group having 1 to 10 carbon atoms, a naphthyl group, , A phenanthrenyl group, an anthryl group, a pyrenyl group and a klycenyl group indolyl group benzoimidazolyl group carbazole yl group imidazolyl group imidazolinyl group imidazopyrimidinyl group pyridinyl group pyrimidinyl group triazinyl 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 a salt thereof, a phosphoric acid or a salt thereof, An alkyl group, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms and an naphthyl group, an indolyl group substituted with at least one of a naphthyl group, a benzoimidazolyl group, An imidazolidinyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, a pyridinyl group, a pyrimidinyl group, a triazinyl group, and a quinolinyl group (alkyl of 1 to 10 carbon atoms) amino group and an imidazolyl group, (Aryl having 1 to 10 carbon atoms) amino groups, and the aryl group having 6 to 10 carbon atoms is selected from a phenyl group, a naphthyl group, a fluorenyl group, a phenanthrenyl group, an anthryl group, a pyrenyl group and a klycenyl group Which one is chosen.

)로 표시되는 치환기일 수 있다. In the present invention, the substituent X ₉ Lt; 2 >

). ≪ / RTI >

)로 표시되는 치환기인 경우, 상기 구조식 2의 L₁ 은 단일 결합일 수 있다.In the present invention, the substituent X ₉ Is represented by the formula 2 (

), L < ₁ > in the above formula (2) May be a single bond.

In the present invention, at least 7 substituents in the substituents other than the anthracene group of the structural formula 1 among the substituents bonded to the pyrene group are hydrogen or deuterium.

In this case, the degree of deuteration of deuterium bonded to the pyrene of the pyrene-based derivative may be preferably 50% or more, more preferably 60% or more, still more preferably 70% or more, Can be more than 80%. In the present invention, the [structural formula 1] of the pyrene derivative may be represented by [substituent 1] to [substituent 9], [substituent 17] to [substituent 26], [substituent 28], [ [Substituent group 33], [Substituent group 40] to [Substituent group 49], [Substituent group 52], [Substituent group 53], [Substituent group 56] May be any one selected from the group consisting of a substituent group [69], [substituent group 71], [substituent group 73] to [substituent group 83], [substituent group 88] to [substituent group 92], [substituent group 94]

Here, the following substituents [1] to [9], [Substituent group 17] to [Substituent group 26], [Substituent group 28], [Substituent group 29], [Substituent group 31] [Substituent group 69], [Substituent group 56], [Substituent group 57], [Substituent group 59] to [Substituent group 65] 83], [Substituent group 88] to [Substituent group 92], [Substituent group 94], and [Substituent group 95] means a site bonded to the pyrenyl group.

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In the present invention, it is preferable that the above-mentioned [formula 1] of the pyrene derivative is the [substituent 1] to [substituent 9], [substituent 17] to [substituent 26], [substituent 28], [substituent 29] [Substituent group 33], [Substituent group 40] to [Substituent group 49], [Substituent group 52], [Substituent group 53] Is any one selected from the group consisting of [substituent], [substituent 71], [substituent 73] to [substituent 83], [substituent 88] to [substituent 92], [substituent 94] Among R1 to R10 which are substituents of the pyrene-based derivative, substituents other than hydrogen may be 1 to 6, preferably 1 or 2.

In this case, the substituents other than hydrogen in R1 to R10 in the pyrene group are each independently a cycloalkyl group having 3 to 12 carbon atoms and an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, oxygen, or a sulfur atom May be selected from a silyl group having a substituent selected from an alkyl group having 1 to 2 carbon atoms, 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.

In the present invention, when only one substituent which is not a hydrogen is present among R1 to R10 which are substituents bonded to the pyrene group, the one substituent may be a methyl group, an ethyl group, a propyl group, a butyl group, a cyclopentyl group, a cyclohexyl group, Or the like.

In the present invention, when the [structural formula 1] of the pyrene-based derivative compound is any one selected from the group consisting of the [substituent groups 1] to [substituent group 100], the deuteration of the pyrene- Can be 50% or more.

The structure 1 of the present invention is an anthracene ring having a substituent, and the substituent can be fused with neighboring substituents to form a ring.

On the other hand, the anthracenyl group of the structural formula 1 may be bonded to the pyrene group with the linking group L ₁ of the structural formula 1 interposed therebetween. In this case, the emission wavelength can be controlled by adjusting the energy bandgap of the pyrene derivative by the above-mentioned L1.

In driving an organic light emitting device in which such a pyrene derivative compound is employed between a pair of electrodes (an anode and a cathode), the pyrene derivative is used in an organic layer between a pair of electrodes, between organic layers, The organic EL device employing the pyrene based derivative compound can have excellent driving voltage, efficiency, brightness, and long life time characteristics.

Hereinafter, a method of producing the pyrene-based derivative of the present invention will be briefly described.

The compound of formula (A) of the present invention can be prepared through the following Reaction Schemes 1 to 3.

[Reaction Scheme 1]

(Here, '-D / H' means that the substituent directly bonded to the pyrene is hydrogen or deuterium.)

[Reaction Scheme 2]

(Wherein X is any one of Br, Cl, and I)

[Reaction Scheme 3]

The reaction scheme 1 is a step for preparing pyrene in which some hydrogen in pyrene is deuterium-substituted. In the above step, '-D / H' means that the substituent directly bonded to the pyrene is hydrogen or deuterium.

The deuterium substitution reaction of Scheme 1 can be carried out by reacting pyrene and a material containing a deuterium source together at 150 to 350 degrees Celsius in a high pressure reactor under a transition metal catalyst, and maintaining the reaction time for about 1 hour to 5 days.

Further, in the present invention, in order to improve the degree of deuteration by the deuterium substitution reaction, the reaction in the high-pressure reactor may be repeated two to five times, depending on how much the deuterium conversion degree of the user is adjusted.

Examples of the deuterium source used in Reaction Scheme 1 include heavy water (D2O), d-6 acetone. d-6 Benzene. CD ₃ OD (deuterium substituted methanol), and the like, but are not limited thereto.

As the transition metal catalyst, transition metals such as Ni, Pd, Pt, and Co may be used.

The dehydrogenation catalyst may be supported on a support, and examples of the support include silica, alumina, aluminosilicate, activated carbon, and the like, but not limited to Ni on Si / Al (silica / A catalyst in which nickel is supported on alumina), Pd / C (a catalyst in which palladium is supported on activated carbon), and the like can be used.

Further, in the above deuteration step, when hydrogen is heated in a solvent containing a deuterium source under an acid catalyst or stirring is carried out under an acid catalyst, a hydrogen group (proton) bonded to the pyrene can be exchanged with deuterium to introduce a deuterium group into the pyrene.

The deuterium source corresponding to the solvent used here is water (D2O), d-6 acetone. d-6 Benzene. CD ₃ OD (deuterium substituted methanol), and the like, but are not limited thereto.

The reaction under the above-mentioned acid catalyst can be carried out at a temperature of 40 to 200 ° C., and the reaction time is preferably 30 minutes to 3 days.

Examples of the acid catalyst used in Reaction Scheme 1 include, but are not limited to, inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as acetic acid and paratoluenesulfonic acid, and Lewis acids such as AlCl 3 and EtAlCl 2.

In the present invention, the reaction scheme 2 is a step of introducing a halogen group into a deutero-substituted pyrene. The halogen group-containing pyrene (X = Br, Cl, I) can be produced by monohalizing or dihalogenating hydrogen of pyrene by a halogenation reaction.

When a substituent other than hydrogen and deuterium is introduced into the pyrene, it is possible to introduce a substituent by replacing one of the bromine with the substituent by dibromination.

More specifically, when the halogen-substituted pyrene has a substituent other than a halogen group such as aryl or alkyl, the pyrene obtained by the deuterium substitution reaction is subjected to a dihalogenation reaction, and the halogen of the halogen is reacted with boronic acid Such as isobutyl, isobutyl, isobutyl, isobutyl, isobutyl, isobutyl, isobutyl, isobutyl, and the like.

In Scheme 3, pyrene derivative compounds represented by Formula A of the present invention are prepared by reacting an anthracene derivative having deuterium-substituted and halogen-containing pyrene obtained from Reaction Scheme 2 with an anthracene derivative having a boronic acid group.

The anthracene derivative used in Reaction Scheme 3 may be a compound in which the boronic acid group is bonded as a substituent in the compound of Formula 1 defined in Formula A of the present invention.

In some cases, the pyrene derivative of formula (A) may be prepared by designing the anthracene derivative to include a halogen group and the deuterated substituted pyrene to include a boronic acid group.

As a result, the compound of the above formula (A) obtained by the reaction formula (3) can substitute the anthracenyl group of the above formula (1) at various positions of the pyrene, depending on the position of the pyrene in which the halogen as the substituent in the pyrene is bonded.

Further, the compound of formula (A) of the present invention can be prepared through the following reaction formula (4) and (5).

[Reaction Scheme 4]

 [Reaction Scheme 5]

The pyrene (X = Br, Cl, I) having a halogen group in the above Reaction Scheme 4 may be commercially purchased or may be prepared by monobromination of the hydrogen of pyrene by a bromination reaction or by a method of dihalogenation.

The deuterium substitution reaction in Scheme 4 can be carried out according to the reaction conditions of Scheme 1 described above for pyrene (X = Br, Cl, I) having a halogen group.

'-D / H' in the structural formula showing a pyrene-substituted pyrene in part of the hydrogen in the above reaction formula 4 means having hydrogen or deuterium as a substituent.

On the other hand, when the halogen-substituted pyrene has a substituent other than hydrogen such as aryl or alkyl other than halogen, the hydrogen atom in the substituent such as aryl or alkyl may be substituted with deuterium by deuterium substitution reaction. In the case where the halogen-substituted pyrene is intended to have a substituent containing hydrogen such as aryl or alkyl, in order not to substitute the hydrogen atom contained in the substituent with deuterium, the deuterium-substituted pyrene is reacted with the deuterium May be achieved by introducing an unsubstituted substituent and then introducing halogen into the pyrene.

In Scheme 5, pyrene derivative compounds represented by Formula A of the present invention are prepared by reacting an anthracene derivative having deutero-substituted and halogen-containing groups obtained from Scheme 4 with an anthracene derivative having a boronic acid group.

The anthracene derivative used in Reaction Scheme 5 may be a boric acid compound in which a boronic acid group is bonded to the substituent of the structural formula 1 defined in Formula A of the present invention, And a pyrene-based derivative of the formula (A) can be prepared, wherein the pyrene-substituted derivative of the formula (A) comprises the boron-substituted pyrene group.

As a result, the compound of the above formula (A) obtained by the reaction formula (5) can substitute the anthracenyl group of the above formula (1) at various positions of the pyrene, depending on the position of the pyrene in which the halogen as the substituent in the pyrene is bonded.

The compound represented by the formula (A) of the present invention is preferably a compound represented by the general formula (1), wherein the substituent of the pyrene is hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, 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, and the like And can control the crystallinity or organic electroluminescent properties of the pyridene-based compound.

The anthracene derivative used in the present invention may also be substituted with hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms An alkyl 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 aryloxy group having 5 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, Or an unsubstituted aryl group having 5 to 50 carbon atoms, a heteroaryl group having 3 to 50 carbon atoms having a substituted or unsubstituted heteroatom, O, N, or S, and the like have.

In detail, with respect to the degree of deuteration used in the present specification,

In general, a "deuterated derivative" of compound X means having the same structure as compound X, but with at least one D replacing H.

The terms "% deuterated" and "% deuterated" refer to the ratio of deuterium to the sum of all hydrogen and deuterium bonded directly to compound X as a percentage.

Thus, if two of the six hydrogens of benzene are deuterated, the degree of deuteration of the compound C6H4D2 can be deemed 2 / (4 + 2) * 100 = 33% deuteration.

The degree of deuteration of deuterium substituted with pyrene derivative compounds in the present invention can be expressed as a percentage of all deuterium directly bonded to the pyrene with respect to the sum of all hydrogen directly bonded to the pyrene and all deuterium bonded directly to the pyrene.

More specifically, the degree of deuteration of the deuterium-substituted pyrene can be represented by indicating the number of deuterium-substituted hydrogen atoms in a total of 10 hydrogen-substituted positions when the pyrene has no substituent other than hydrogen or deuterium. In this case, since the number of deuterium-substituted units may differ for each individual molecule, the degree of deuteration should be indicated by calculating the degree of substitution on average.

On the other hand, in the case of one substituent, that is, in the case of pyrene having one substituent such as the halogen, the degree of deuteration can be obtained by finding the average value of the number of deuterium substituted at the remaining nine hydrogen substitution sites.

Therefore, when an average of 3.5 deuterium atoms is substituted, the deuteration degree of the pyrene having one halogen substituent can be represented by 3.5 * 100/9 = 38.9%.

If an average of 4.5 deuterium atoms is substituted for hydrogen at the hydrogen position of the pyrene by pyrogenation reaction of the pyrene having the bromine group at the 1-position and the phenyl group at the 5-position, the degree of deuteration is 4.5 * 100/8 = 56.25%.

The organic electroluminescent device of the present invention comprises a first electrode, a second electrode facing the first electrode, and an organic layer interposed between the first electrode and the second electrode, Or more.

In the present invention, the phrase "(organic layer) contains one or more pyrene derivative compounds" means that one kind of pyrene derivative compounds belonging to the category of the present invention (organic layer) Quot; may include two or more other condensed ring compounds. "

 Preferably, the organic layer containing the compound of the present invention is a light emitting layer interposed between the first electrode and the second electrode, and the organic layer may include a hole injection layer, a hole transport layer, a hole injection function, At least one of a functional layer, a light emitting layer, an electron transporting layer, and an electron injecting layer which are simultaneously present.

In the present invention, the organic layer includes at least one of a hole injecting layer, a hole transporting layer, a functional layer having a hole injecting function and a hole transporting function (hereinafter referred to as "H-functional layer") Functional derivative (hereinafter referred to as "H-functional layer") having both the hole injection layer, the hole transport layer, the hole injection function and the hole transport function .

In addition, the present invention provides an organic light emitting device wherein the light emitting layer further comprises a dopant when the organic layer is a light emitting layer, and the pyrene derivative contained in the light emitting layer functions as a host.

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 electroluminescent 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) may be additionally stacked, and an electron transport layer (ETL) may be further stacked between the cathode and the organic emission layer. The hole transport layer is laminated in order to facilitate the 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 diamine, triamine or tetra Amine 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) triphenylamine) can be used.

In addition, the electron transport layer used in the organic electroluminescent device according to the present invention can transport electrons supplied from the cathode smoothly to the organic luminescent layer and inhibit the movement of holes which are not bonded in the organic luminescent layer, .

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

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.

The organic electroluminescent device according to the present invention can be used for a display device, a display device, an element for a single color or a white light, and the like.

1 is a cross-sectional view showing the structure of an organic electroluminescent device of the present invention. The organic electroluminescent device according to the present invention includes an anode 20, a hole transport layer 40, an organic emission layer 50, an electron transport layer 60 and a cathode 80, The electron injecting 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.

The organic electroluminescent device of the present invention and its manufacturing method will be described with reference to FIG. 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.

The light emitting layer may further include a dopant, and the compound of the present invention contained in the light emitting layer may serve as a host.

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 further include various dopant materials.

In this case, the dopant may be a compound represented by Formula 1 or Formula 2 below.

≪ Formula 1 >

In the above formula (1)

A is an aryl group having 5 to 50 carbon atoms, a heteroaryl group having 3 to 50 carbon atoms having 0, N or S as the hetero atom, an arylene group having 6 to 60 carbon atoms, a hetero atom having 3 to 50 carbon atoms having 0, A heteroarylene group, and a heteroarylene group,

X1 and X2 are each independently an arylene group having 6 to 30 carbon atoms or a single bond, X1 and X2 may be bonded to each other,

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

Y1 to Y2 each independently represent an aryl 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, a heteroalkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, A halogen atom, an aryloxy group having 6 to 24 carbon atoms, an alkylsilyl group having 1 to 40 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, germanium, phosphorus, boron, deuterium and hydrogen And Y1 to Y2 may be the same or different from each other and may form a condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero with an adjacent group.

More specifically, in the above formula (1), X 1 to X 2 are each independently a phenylene group, a pentalanylene group, an indenylene group, a naphthylene group, an azulenylene group, a heptarenylene group, an indacenylene group, an acenaphthylene group, a fluorenyl A phenanthrenylene group, a phenanthrenylene group, an anthrylene group, a fluoranthenylene group, a triphenylenylene group, a pyrenylene group, a chrysenylene group, a naphthacenylene group, a picenylene group, a perylenylene group, An imidazolidinyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, a pyridinyl group, a pyrazinyl group, a pyrimidinyl group, a pyrazolyl group, A naphthyridinylene group, a quinazolinylene group, a cinnolinylene group, an indazolylene group, a carbazolylene group, a phenazylene group, a phenanthrene group, a phenanthrene group, an imidazolylene group, Phenanthridinylene group, paranylene group, chromenylene A benzoimidazolyl group, an isoxazolyl group, a benzoimidazolyl group, a benzoimidazolyl group, a benzofuranyl group, a benzofuranyl group, a thiophenylene group, a benzothiophenylene group, an isothiazolylene group, Lt; / RTI > or oxadiazolene group.

(2)

In the above formula (2)

A is an aryl group having 5 to 50 carbon atoms, a heteroaryl group having 3 to 50 carbon atoms having 0, N or S as the hetero atom, an arylene group having 6 to 60 carbon atoms, a hetero atom having 3 to 50 carbon atoms having 0, A heteroarylene group, and a heteroarylene group,

C _y is 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 fused. The substituted hydrogen may be substituted with deuterium or alkyl, and may be the same or different from each other.

B (R ₅ ) (R ₆ )] _p -, and p is an integer of 1 to 3, and when p is 2 or more, R ₅ and R ₆ are the same or different from each other

R ₁ , R ₂ , R _3, R ₅ and R ₆ are each independently selected from the group consisting of hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, A salt of phosphoric acid or its salt, an alkyl group of 1 to 60 carbon atoms, an alkenyl group of 2 to 60 carbon atoms, an alkynyl group of 2 to 60 carbon atoms, an alkoxy group of 1 to 60 carbon atoms, an alkylthio group of 1 to 60 carbon atoms Alkylthio, a cycloalkyl group having 3 to 60 carbon atoms, an aryl group having 6 to 60 carbon atoms, an aryloxy group having 5 to 60 carbon atoms, an arylthio group having 5 to 60 carbon atoms, a heteroaryl group having 2 to 60 carbon atoms, (Aryl having 6 to 60 carbon atoms) amino group, di (alkyl having 1 to 60 carbon atoms) amino group, or (aryl having 6 to 60 carbon atoms) amino group, Lt; / RTI > to 30;

n is an integer from 1 to 4;

a is an integer of 1 to 4, and when a is 2 or more, two or more R _{3 s} are the same as or different from each other, and R ₃ In the case of plural, each R < ₃ > may be in fused form.

More specifically, R ₁ , R ₂ and R ₃ in the above formula (2) independently represent hydrogen, deuterium, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, , A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a phenyl group, a pentaranyl group (such as a methyl group or an ethyl group), a sulfonic acid group or a salt thereof, pentalenyl, indenyl, naphthyl, azulenyl, heptalenyl, indacenyl, acenaphthyl, fluorenyl, phenalene, Phenanthrenyl, phenanthrenyl, anthryl, fluoranthenyl, triphenylenyl, pyrenyl, chrysenyl, naphtha, phenanthrenyl, phenanthrenyl, Naphthacenyl, picenyl, perylenyl, pentenyl, The compounds of formula (I) are preferably selected from the group consisting of pentaphenyl, hexacenyl, pyrrolyl, pyrazolyl, imidazolyl, imidazolinyl, imidazopyridinyl, A pyridinyl group, an imidazopyrimidinyl group, a pyridinyl group, a pyrazinyl group, a pyrimidinyl group, an indolyl group, a purinyl group, a quinolinyl group, a quinolinyl group, And examples thereof include a phthalazinyl group, an indolizinyl group, a naphthyridinyl group, a quinazolinyl group, a cinnolinyl group, an indazolyl group, a carbazolyl group, A phenanthridinyl group, a pyranyl group, a chromenyl group, a furanyl group, a benzofuranyl group, a thiophenyl group, a benzothiophenyl group, a phenanthridinyl group, ), Isothiazolyl, benzoimidazolyl, isoxazolyl, It may be selected from the group (isoxazolyl), dibenzo-thiophenyl group (dibenzothiophenyl), dibenzo-furanyl group (dibenzopuranyl), triazinyl group (triazinyl), or oxadiazolyl group consisting of sol weather (oxadiazolyl).

More specifically, R ₁ , R ₂ and R ₃ in the above-mentioned structural formula 1 may independently be a pyrene-based derivative represented by one of the following formulas (4A) to (4H).

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

Z ₁ to Z ₇ independently represent hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amino, amido, hydrazine hydrazone carboxyl group or its salt, phosphoric acid or its salt, alkyl group having 1 to 10 carbon atoms, An alkoxy group of 1 to 10 carbon atoms, 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 a salt thereof, 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, a naphthyl group, a fluorenyl group, a phenanthrenyl group, an anthryl group, a pyrenyl group, a chrysenyl group, A halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, A phenyl group substituted with at least one of a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkylthio group having 1 to 10 carbon atoms, a naphthyl group, , A phenanthrenyl group, an anthryl group, a pyrenyl group and a klycenyl group indolyl group benzoimidazolyl group carbazole yl group imidazolyl group imidazolinyl group imidazopyrimidinyl group pyridinyl group pyrimidinyl group triazinyl 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 a salt thereof, a phosphoric acid or a salt thereof, An alkyl group, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms and an naphthyl group, an indolyl group substituted with at least one of a naphthyl group, a benzoimidazolyl group, An imidazolidinyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, a pyridinyl group, a pyrimidinyl group, a triazinyl group, and a quinolinyl group (alkyl of 1 to 10 carbon atoms) amino group and an imidazolyl group, (Aryl having 1 to 10 carbon atoms) amino groups, and the aryl group having 6 to 10 carbon atoms is selected from a phenyl group, a naphthyl group, a fluorenyl group, a phenanthrenyl group, an anthryl group, a pyrenyl group and a klycenyl group Which one is chosen.

In the present invention, B in Formula 2 may be a single bond.

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. Synthesis of Compound H1

1-1. Deuterium substituted Pyrene  Synthesis of derivatives

A mixture of 50 g (0.247 mol) of pyrene, 44.7 mL (2.472 mol) of D ₂ O and 1.5 g (0.025 mol) of Nickel on silica / alumina to 65 wt% loading powder was placed in a sealed high pressure reactor under a nitrogen atmosphere, / RTI &gt; After cooling to room temperature, the resulting solid was filtered, and recrystallized with toluene to obtain 37 g of pyrene (71% yield) of deutero-substituted.

The 1 H NMR spectrum was found to be almost identical to the 6.8 of the 10 pyrene aromatic protons being replaced by deuterium.

Synthesis Example 1-1-b) Synthesis of deutero-substituted 1-bromopyrene

21 g (100 mmol) of deutero-substituted pyrene prepared in Synthesis Example 1-1-a and 12.4 ml (110 mmol) of a 48% aqueous solution of bromic acid were dissolved in 200 ml of a 1: 1 methanol-ether mixed solution, and 3.4 g ) Is added dropwise at 10? 15 占 폚 for 15 minutes. After stirring at room temperature for 12 hours, the reaction was completed. The solvent was concentrated under reduced pressure. The resulting crystals were dissolved in ethyl acetate, washed with water and brine, and dried over anhydrous sodium sulfate. And recrystallized from monochlorobenzene to obtain 26 g (yield: 90%) of 1-bromoprene substituted with deuterium which was a light brown solid.

1-2. Synthesis of Anthracene Derivative Having Structure 1

Synthesis Example 1-2-a) Synthesis of 9-Phenylanthracene

To a 500 ml three-neck round bottom flask was added 9.7 g (79 mmol) of phenyl boronic acid, 17 g (66 mmol) of 9-bromoanthracene, 18.3 g (132 mmol) of potassium carbonate, 1.5 g (1 mmol) of water, 35 ml of water, 90 ml of toluene and 90 ml of tetrahydrofuran were placed and subjected to a reflux reaction.

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.

Synthesis Example 1-2-b) Synthesis of 9-phenyl-10-bromoanthracene

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. (0.063 mol) was diluted in 50 ml of dichloromethane and reacted slowly. After completion of the reaction, the layers were separated to remove the aqueous layer, and the organic layer was concentrated under reduced pressure, and crystals were precipitated with MeOH and then recrystallized to obtain 13.4 g of yellow 9-phenyl-10-bromoanthracene crystals (yield: 75.5%)

Synthesis Example 1-2-c) Synthesis of 9-phenyl-10-anthracene boronic acid

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%).

1-3. Synthesis of pyrene derivative H1 containing an anthracene derivative of the present invention

10.2 g (34 mmol) of the 9-phenyl-10-anthracene boronic acid prepared in Synthesis Example 1-2-c, the dehydrogenated 1-bromopyrylene 8.9 g (31 mmol), potassium carbonate (8.6 g, 62 mmol), Pd (PPh 3) 4 (0.7 g, 1 mmol) was allowed ml of toluene 50 mL, 50 mL tetrahydrofuran, 20 mL water reflux.

After completion of the reaction, the resulting crystals were filtered and recrystallized several times with toluene to synthesize Compound H1 (3.6 g, yield 25%).

MS (MALDI-TOF): m / z 458-464 [M] ⁺

Synthesis Example 2. Synthesis of Compound H2

Using the same method as in the synthesis of compound H1 except that 3-tolylboronic acid was used instead of phenylboronic acid in Synthesis Example 1-2-a), 3.6 g of pale yellow solid compound H2 with a yield of 25% .

MS (MALDI-TOF): m / z 472-477 [M] ^&lt; ^{+ &}

Synthesis Example 3. Synthesis of Compound H3

Using the same method as in the synthesis of Compound H1 except that 1-naphthylboronic acid was used instead of phenylboronic acid in Synthesis Example 1-2-a), 4.5 g of pale yellow solid compound with a yield of 28% H3.

MS (MALDI-TOF): m / z 508-513 [M] ^&lt; ^{+ &}

Synthesis Example 4. Synthesis of Compound H4

Using the same method as in the synthesis of Compound H1 except that pentaduteriophenylboronic acid was used instead of phenylboronic acid in Synthesis Example 1-2-a), 3.8 g of pale yellow solid with a yield of 26% Compound H4 was obtained.

MS (MALDI-TOF): m / z 463-468 [M] ^&lt; ^{+ &}

Synthesis Example 5. Synthesis of Compound H5

5-1. Synthesis of Deuterated Substituted Pyrene Derivatives

Synthesis Example 5-1-b) Synthesis of deutero-substituted 1,6-dibromopyrrene

21 g (100 mmol) of deutero-substituted pyrene prepared in Synthesis Example 1-1-a and 320 mL of dichloromethane were charged into a reactor, and a solution prepared by mixing 10 mL (195 mmol) of bromine and 60 mL of dichloromethane was added dropwise over 10 hours, Stir overnight. The reaction is terminated and the resulting solid is filtered off and washed several times with methanol and dichloromethane. After recrystallization with monochlorobenzene several times and drying, 12 g of light gray solid deuterated substituted 1,6-dibromopyrene was synthesized. (Yield: 33%)

Synthesis Example 5-1-b) Synthesis of intermediate 5-1-b

Synthesis was carried out in the same manner except that deuterium-substituted 1,6-dibromopyrene, which was the intermediate prepared in Synthesis Example 5-1-a, was used instead of 9-bromoanthracene used in Synthesis Example 1-2-a, 20 g (yield 69%) of intermediate 5-1-b was obtained.

5-2. Synthesis of pyrene derivative H5 containing an anthracene derivative of the present invention

Was synthesized in the same manner as Intermediate 5-1-b except for using the synthesized intermediate 5-1-b instead of the deuterium-substituted 1-bromopyrrene used in Synthesis Example 1-3 to obtain 3.4 g (yield 30%) of the compound H5.

MS (MALDI-TOF): m / z 534-539 [M] ^&lt; ^{+ &}

Synthesis Example 6. Synthesis of Compound H6

6-1. Synthesis of Anthracene Derivative Having Structure 1

Synthesis Example 6-1-a) Synthesis of intermediate 6-1-a

Phenyl-10-anthraceneboronic acid (8.5 g, 29 mmol), 4-bromo-1-iodonaphthalene (10.0 g, 30 mmol) prepared in Synthesis Example 1-2-c, potassium carbonate (8.3 g, 60mmol), Pd (PPh 3) 4 (0.7 g, 1 mmol) was allowed to reflux ml of toluene 50 mL, 50 mL tetrahydrofuran and water 20 mL.

After completion of the reaction, the resulting crystals were filtered and recrystallized from hexane to obtain Intermediate 6-1-a (10 g, yield 73%).

Synthesis Example 6-1-b) Synthesis of intermediate 6-1-b

The above-prepared intermediate 6-1-a (10 g, 22 mmol) was dissolved in 80 mL of THF in a round bottom flask. After cooling to -78 ° C, n-BuLi in n-hexane (1.6M) (16 mL) was added slowly. After the addition, trimethylborate (3.2 g, 31 mmol) was added at -78 ° C for 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 toluene to obtain 7 g (yield: 76%) of intermediate 6-1-b.

6-2. The pyrene derivative H6 synthesis including the anthracene derivative of the present invention

Except that the intermediate 6-1-b prepared above was used in place of the 9-phenyl-10-anthraceneboronic acid used in Synthesis Example 1-3, 2.8 g (yield: 32%) of a pale yellow solid compound H6 %) Was synthesized.

MS (MALDI-TOF): m / z 584-589 [M] ^&lt; ^{+ &}

Synthesis Example 7: Synthesis of Compound H 7

7-1. Synthesis of Deuterated Substituted Pyrene Derivatives

Synthesis Example 7-1-a) Synthesis of intermediate 7-1-a

21 g (100 mmol) of the deutero-substituted pyrene prepared in Synthesis Example 1-1-a and 320 mL of chloroform were added to the reactor, and 19.7 g of N-bromosuccinimide was dissolved in 80 mL of chloroform and slowly added dropwise. Lt; / RTI &gt; After the reaction was completed, the mixture was washed with water and extracted. The organic layer was concentrated under reduced pressure and recrystallized from monochlorobenzene to obtain 20 g (yield 69%) of intermediate 7-1-a.

7-2. The pyrene derivative H7 synthesis including the anthracene derivative of the present invention

Except that the intermediate 7-1-a synthesized in the above Synthesis Example 1-3 was used instead of the deuterated substituted 1-bromopyrane used in the above Synthesis Example 1-3, 3.7 g (Yield: 31%) of Compound H7 was obtained.

MS (MALDI-TOF): m / z 458-464 [M] ⁺

Synthesis Example 8. Synthesis of Compound H 8

Using the same method as that for compound H1 except that 3-pyridinylboronic acid was used instead of phenylboronic acid in Synthesis Example 1-2-a), 3.5 g of pale yellow solid compound with a yield of 31% H8.

MS (MALDI-TOF): m / z 459-464 [M] ^&lt; ^{+ &}

Device fabrication and evaluation: Examples 1 to 24

The ITO glass was patterned so as to have a light emitting area of 2 mm * 2 mm and then cleaned. After the ITO glass was mounted in a vacuum chamber, the base pressure was adjusted to 1 * 10 ^-7 torr, and CuPc (800 Å) and α-NPD (300 Å) were sequentially deposited on the ITO. a film forming (250 Å) and then by film-forming in the order of _{Alq 3 (350Å), LiF (} 5 Å), Al (500 Å) was prepared in an organic electroluminescent device. On the other hand, one of the following compounds [4] to [6] was used as a dopant substance.

Comparative Examples 1 to 3

The light emitting layer further comprises an anthracene compound represented by the following formula (3) as a host compound, and the dopant material is one of compounds represented by the following formulas (4) to (6) Respectively.

Here, Formula 6 is a mixed substance (6a: 6b = 30: 70, molar ratio) having a structure represented by the following Formulas 6a and 6b.

 [Chemical Formula 3]

[Chemical Formula 6]

[Formula 6a] [Formula 6b]

Evaluation example

The voltage, the current density, the luminance, the luminescent color, and the lifetime were measured for the organic electroluminescent devices manufactured according to Examples 1 to 24 and Comparative Examples 1 to 3. The results are shown in Table 1 below, Are graphically shown in [Figure 2] to [Figure 4]. T97 means the time required for the luminance to be reduced to 97% of the initial luminance.

As shown in Table 1, since the organic electroluminescent device comprising the organic electroluminescent compound according to the present invention can have a relatively high molecular weight by the organic electroluminescent material including deuterium, The glass transition temperature or melting point can be increased, thereby improving heat resistance and longevity, so that it can be utilized in various display devices.

The evaluation results of the lifetime of the organic light emitting device manufactured by the present invention are shown in FIGS. 2 to 4. FIG. FIG. 2 is a graph showing life evaluation in Examples 1 to 8 and Comparative Example 1, FIG. 3 is a graph showing life evaluation in Examples 9 to 16 and Comparative Example 2, and FIG. 4 The lifetime evaluation in Examples 17 to 24 is a graph. The T97 values of the samples shown in the graphs of FIGS. 2 to 4 are larger than the T97 values of the respective comparative examples.

Therefore, it can be seen that the lifetime characteristics of the light emitting materials according to the embodiments of the present invention implement the longer life characteristics than the devices manufactured by the method of the comparative example.

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 (19)

A pyrene-based derivative represented by the following formula [A]
(A)

In the above formula (A)
R ₁ to R ₁₀ are the same or different from each other and each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, An 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, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, A silyl group having a substituent selected from an aryl group having 6 to 10 carbon atoms, and may form a condensed ring of an adjacent group and a divalent, aromatic, aliphatic hetero or aromatic hetero,
One of R ₁ to R ₁₀ is a substituent represented by the following formula 1 and at least one of R ₁ to R ₁₀ is deuterium. In this case, the degree of deuteration of the deuterium bonded to the pyrene of the pyrene derivative Which is the percentage of all deuterium directly bonded to the pyrene relative to the sum of all the hydrogen directly bonded to the pyrene and all the deuterium directly bonded to the pyrene) is at least 40%.
[Structural formula 1]

In the above structural formula 1,
X ₁ to X ₁₀ are the same as or different from each other and each independently represent a substituent group as defined in R ₁ to R ₁₀ , wherein the substituent X ₉ is a substituent represented by the following structural formula 2.
[Structural formula 2]

In the above structural formula 2,
L ₁ represents a single bond, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms,
* Is a bonding site between pyrene and anthracene in the above [formula (A)]
The 'substituted' in the 'substituted or unsubstituted' refers to a group selected from the group consisting of deuterium, a cyano group, a halogen group, an alkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, and a heteroaryl group having 1 to 24 carbon atoms. Quot; means substituted with at least one substituent. delete delete delete The method according to claim 1,
Wherein L &lt; ₁ &gt; in the structural formula (2) is a single bond. The method according to claim 1,
Wherein at least 7 substituents in the substituents other than the anthracene group of the structural formula 1 among the substituents bonded to the pyrene group are hydrogen or deuterium. 6. The method of claim 5,
Wherein at least 7 substituents in the substituents other than the anthracene group of the structural formula 1 among the substituents bonded to the pyrene group are hydrogen or deuterium. The method according to claim 6,
Wherein the degree of deuteration of the deuterium bonded to the pyrene of the pyrene-based derivative is 50% or more. 8. The method of claim 7,
Wherein the degree of deuteration of the deuterium bonded to the pyrene of the pyrene-based derivative is 50% or more. 10. The method according to claim 8 or 9,
Wherein the degree of deuteration of the deuterium bonded to the pyrene of the pyrene-based derivative is 60% or more. The method according to claim 1,
In the above formula (A), the [formula 1]
[Substituent group 1] to [Substituent group 9], [Substituent group 17] to [Substituent group 26], [Substituent group 28], [Substituent group 29] , [Substituent group 52], [Substituent group 53], [Substituent group 56], [Substituent group 57], [Substituent group 59] to [Substituent group 65] , [Substituent group 88] to [Substituent group 92], [Substituent group 94], [Substituent group 95]

12. The method of claim 11,
R 1 to R 10, which are substituents of the above-mentioned formula (A), have 1 or 2 substituents which are not hydrogen,
In this case, the substituents other than hydrogen are each independently selected from the group consisting of alkyl groups having 1 to 5 carbon atoms, alkyl groups having 3 to 12 carbon atoms in the alkyl group, aryl groups having 6 to 10 carbon atoms in the alkyl group, heteroaryl having 1 to 2 oxygen atoms 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. 13. The method of claim 12,
R 1 to R 10, which are the substituents of the above-mentioned formula (A), have one substituent which is not a hydrogen,
In this case, the substituent which is not the hydrogen is one selected from a methyl group, an ethyl group, a propyl group, a butyl group, a cyclopentyl group, a cyclohexyl group and a phenyl group. 12. The method of claim 11,
Wherein the degree of deuteration of the deuterium bonded to the pyrene of the pyrene-based derivative is 50% or more. The first electrode
A second electrode facing the first electrode,
Wherein the organic layer comprises an organic layer interposed between the first electrode and the second electrode, wherein the organic layer is a pyrene-based derivative compound of any one of claims 1, 5 to 9, 11 to 14, And at least one organic light-emitting material. 16. The method of claim 15,
Wherein the organic layer interposed between the first electrode and the second electrode is a light emitting layer. 16. The method of claim 15,
Wherein the organic layer comprises at least one of a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a light emitting layer, an electron transporting layer, and an electron injecting layer. 17. The method of claim 16,
Wherein the light emitting layer further comprises a dopant, and the pyrene derivative acts as a host in the light emitting layer, 19. The method of claim 18,
Wherein the dopant is a compound represented by the following general formula (1) or (2)
[Chemical Formula 1] &lt; EMI ID =

Among the above-mentioned formulas (1) and (2)
A is an aryl group having 5 to 50 carbon atoms, a heteroaryl group having 3 to 50 carbon atoms having 0, N or S as the hetero atom, an arylene group having 6 to 60 carbon atoms, a carbon number having 3 to 50 Lt; RTI ID = 0.0 &gt; of: &lt; / RTI &gt;
In the above formula (1)
X1 and X2 are each independently an arylene group having 6 to 30 carbon atoms or a single bond, X1 and X2 may be bonded to each other;
Y1 to Y2 each independently represent an aryl 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, a heteroalkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, An aryl group having 1 to 24 carbon atoms, a cyano group, a halogen group, an aryloxy group having 6 to 24 carbon atoms, an alkylsilyl group having 1 to 40 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, germanium, phosphorus, boron, deuterium, Y1 to Y2 are the same or different from each other and may form a condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero with an adjacent group;
l and m are each an integer of 1 to 20, and n is an integer of 1 to 4;
In the above formula (2)
C _y is 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 fused form. Also, the hydrogen sites in the cycloalkane may be substituted with deuterium or alkyl of 1 to 20 carbon atoms, and are the same or different from each other;
B It is a single bond or _{- [C (R 5) (} R 6)] p] - , and wherein p is being from 1 to 3 integer, not less than p 2 2 or R ₅ and R ₆ are the same or different from each other;
R ₁ , R ₂ , R _3, R ₅ and R ₆ independently represent 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 sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, an alkyl group having 1 to 60 carbon atoms, an alkenyl group having 2 to 60 carbon atoms, an alkynyl group having 2 to 60 carbon atoms, an alkoxy group having 1 to 60 carbon atoms, Alkylthio, a cycloalkyl group having 3 to 60 carbon atoms, an aryl group having 6 to 60 carbon atoms, an aryloxy group having 5 to 60 carbon atoms, an arylthio group having 5 to 60 carbon atoms, a heteroaryl group having 2 to 60 carbon atoms, (Alkyl group having 1 to 60 carbon atoms), an amino group (having 6 to 60 carbon atoms), an amino group (having 6 to 60 carbon atoms), an amino group (having 6 to 60 carbon atoms), an alkylsilyl group having 1 to 40 carbon atoms Among the arylsilyl groups having a carbon number of 6 or 30, And,
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.

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