KR102166850B1 - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

In the present invention, a novel compound containing an amino group at both ends of a molecule and an organic light emitting device including the same are provided.

Description

Novel compound and organic light emitting device comprising the same

The present invention relates to a novel compound and an organic light emitting device comprising the same.

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic light-emitting device using the organic light-emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.

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

Development of new materials for organic materials used in organic light emitting devices as described above is continuously required.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to a novel compound including a condensed ring structure in which four or more rings are fused as a central structure, and an amino group on both sides of the condensed ring structure, and an organic light emitting device including the same.

The present invention provides compounds of formula 1:

[Formula 1]

In Formula 1,

Ar ₁ to Ar ₄ are each independently a substituted or unsubstituted C _6-60 aryl group; Or N, O and S containing one or more heteroatoms selected from the group consisting of, and is a substituted or unsubstituted C _2-60 heteroaryl,

R ₁ and R ₂ are hydrogen, or R ₁ and R ₂ together form a structure of the following formula 2a or the following formula 2b,

R ₃ and R ₄ are hydrogen, or R ₃ and R ₄ together form a structure of the following formula 2a or the following formula 2b,

However, all of R ₁ to R ₄ are not hydrogen,

[Formula 2a]

[Formula 2b]

A and B together form a structure of the following formula 3a or the following formula 3b,

[Formula 3a]

[Formula 3b]

In Formulas 3a and 3b,

R ₅ to R ₈ are each independently hydrogen, deuterium, halogen, cyano, nitro, amino, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _1-60 haloalkyl, substituted or unsubstituted Substituted C _1-60 alkoxy, substituted or unsubstituted C _1-60 haloalkoxy, substituted or unsubstituted C _3-60 cycloalkyl, substituted or unsubstituted C _2-60 alkenyl, substituted or unsubstituted C _{6 -60} aryl, substituted or unsubstituted C _6-60 aryloxy, or at least one heteroatom selected from the group consisting of N, O and S, and is substituted or unsubstituted C _2-60 heteroaryl ; Or R ₅ and R ₆ , and R ₇ and R ₈ are linked to each other to include a C _6-12 aromatic cyclic group, or a heteroatom selected from the group consisting of N, O and S C _2-12 To form a heterocyclic group.

In addition, the present invention is a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound of Formula 1 above.

The compound of Formula 1 described above may be used as a material for light emission, electron transport, or electron injection in the organic material layer of the organic light emitting device, and is particularly useful as a blue fluorescent dopant in the light emitting layer. In addition, when the compound of Formula 1 is applied to an organic light-emitting device, the efficiency of the organic light-emitting device, low driving voltage, and lifetime characteristics may be improved.

1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
FIG. 2 shows an example of an organic light-emitting device composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 7, an electron transport layer 8, and a cathode 4 I did it.

Hereinafter, it will be described in more detail to aid the understanding of the present invention.

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

Means a bond connected to another substituent.

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or it means a substituted or unsubstituted substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O and S atoms, or linked with two or more substituents among the above-exemplified substituents . For example, "a substituent to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.

In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but it is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the ester group may be substituted with an oxygen of the ester group with a straight chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.

In the present specification, the boron group specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, and a phenyl boron group, but is not limited thereto.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cycloheptylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present specification, the alkenyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but is preferably 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

Etc. However, it is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group including at least one of O, N, Si and S as a heterogeneous element, and the number of carbons is not particularly limited, but it is preferably 2 to 60 carbon atoms. Examples of heterocyclic groups include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, Acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group , Indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, Isoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, but are not limited thereto.

In the present specification, the aryl group among the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group and the alkylamine group is the same as the example of the aforementioned alkyl group. In the present specification, for heteroaryl among heteroarylamines, the description of the aforementioned heterocyclic group may be applied. In the present specification, the alkenyl group of the aralkenyl group is the same as the example of the alkenyl group described above. In the present specification, the description of the aryl group described above may be applied except that the arylene is a divalent group. In the present specification, the description of the aforementioned heterocyclic group may be applied except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aryl group or the cycloalkyl group described above may be applied except that the hydrocarbon ring is formed by bonding of two substituents. In the present specification, the heterocycle is not a monovalent group, and the description of the above-described heterocyclic group may be applied, except that two substituents are bonded to each other.

On the other hand, the present invention provides a compound of formula (1):

[Formula 1]

In Formula 1,

Ar ₁ to Ar ₄ are each independently a substituted or unsubstituted C _6-60 aryl group; Or substituted or unsubstituted C _2-60 heteroaryl containing at least one heteroatom selected from the group consisting of N, O and S,

R ₁ and R ₂ are hydrogen, or R ₁ and R ₂ together form a structure of the following formula 2a or the following formula 2b,

R ₃ and R ₄ are hydrogen, or R ₃ and R ₄ together form a structure of the following formula 2a or the following formula 2b,

However, all of R ₁ to R ₄ are not hydrogen,

[Formula 2a]

[Formula 2b]

A and B together form a structure of the following formula 3a or the following formula 3b,

[Formula 3a]

[Formula 3b]

In Formulas 3a and 3b,

R ₅ to R ₈ are each independently hydrogen, deuterium, halogen, cyano, nitro, amino, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _1-60 haloalkyl, substituted or unsubstituted Substituted C _1-60 alkoxy, substituted or unsubstituted C _1-60 haloalkoxy, substituted or unsubstituted C _3-60 cycloalkyl, substituted or unsubstituted C _2-60 alkenyl, substituted or unsubstituted C _{6 -60} aryl, substituted or unsubstituted C _6-60 aryloxy, or substituted or unsubstituted C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S, or Or R ₅ and R ₆ , and R ₇ and R ₈ are linked to each other to include a C _6-12 aromatic cyclic group, or a heteroatom selected from the group consisting of N, O and S C _2-12 To form a heterocyclic group.

Specifically, in Formula 1, the A and B together may form any one of the following Formulas 4a to 4d, and in this case, A and B form a hexagonal ring, thereby bonding to both phenyl rings It is possible to increase the stability of the molecule by reducing the steric hindrance due to the structure of formula 2a and 2b. In addition, it is easy to control the electron density between the amines bonded to both sides of the central ring structure, so that when this is employed in an organic light emitting device, it can exhibit long life and high efficiency.

[Formula 4a]

[Formula 4b]

[Formula 4c]

[Formula 4d]

In Formulas 4a to 4d,

D ₁ and D ₂ are each independently selected from the group consisting of O, S, and CR, but D ₁ and D ₂ are not CR at the same time,

R is hydrogen; heavy hydrogen; C _1-20 alkyl; C _3-20 cycloalkyl; C _4-20 alkylcycloalkyl; C _6-20 aryl; C _7-20 arylalkyl; And C _7-20 is selected from the group consisting of alkylaryl.

In addition, Chemical Formula 4d may have more specifically, any one of the following structures.

More specifically, the compound of Formula 1 may be any one of the compounds of Formulas 5a to 5x:

[Formula 5a]

[Formula 5b]

[Formula 5c]

[Formula 5d]

[Formula 5e]

[Formula 5f]

[Chemical Formula 5g]

[Formula 5h]

[Formula 5i]

[Formula 5j]

[Formula 5k]

[Chemical Formula 5l]

[Chemical Formula 5m]

[Formula 5n]

[Formula 5o]

[Chemical Formula 5p]

[Formula 5q]

[Formula 5r]

[Formula 5s]

[Formula 5t]

[Chemical Formula 5u]

[Formula 5v]

[Chemical Formula 5w]

[Formula 5x]

In Formulas 5a to 5x, Ar ₁ to Ar ₄ , D ₁ , and D ₂ are as defined above.

In addition, in Formula 1, Ar ₁ to Ar ₄ may each independently be any one selected from the group consisting of the following.

Above,

X is O, S, or CY ₁ Y ₂ ,

Y ₁ and Y ₂ are each independently hydrogen; heavy hydrogen; C _1-20 alkyl; C _3-20 cycloalkyl; C _4-20 alkylcycloalkyl; C _6-20 aryl; C _7-20 arylalkyl; Or C _7-20 alkylaryl, or are linked to each other to form a C _4-20 aliphatic ring or a C _6-20 aromatic ring group,

Z ₁ to Z ₃ are each independently deuterium; halogen; Cyano; Nitro; Amino; C _1-20 alkyl; C _1-20 haloalkyl; C _6-20 aryl; Silyl (SiH ₃ ); C _1-20 alkylsilyl; And O or S is selected from the group consisting of C _2-20 heteroaryl containing one or more heteroatoms,

n1 to n13 are each independently an integer of 0 to 3.

More specifically, in Formula 1, Ar ₁ to Ar ₄ may each independently be any one selected from the group consisting of the following functional groups.

Among them, when considering the excellent effect of improving the lifespan characteristics of the organic light-emitting device according to the structure of the functional group bonded to the amino group and electron density control, the Ar ₁ to Ar ₄ may each independently be selected from the group consisting of the following functional groups. .

In addition, in Chemical Formula 1, Ar ₁ and Ar ₄ , and Ar ₂ and Ar ₃ have the same structure as each other; Alternatively, Ar ₁ to Ar ₄ may all have the same structure. Among them, when considering the effect of reducing the steric hindrance according to the structural control of the functional groups Ar ₁ to Ar ₄ bonded to the amino group in the condensed ring structure in Chemical Formula 1 and improving the long life characteristics of the organic light emitting device accordingly, the Ar ₁ And Ar ₄ , and Ar ₂ and Ar ₃ may have the same structure.

More specifically, representative examples of the compound represented by Formula 1 are as follows:

Formula 1, which has the structure as described above, includes a condensed ring structure in which four or more ring structures are fused as a central structure, and by including amino groups on both sides of the condensed ring structure, it can act as a blue fluorescent dopant. have. In particular, in the condensed ring structure, Formula 2a or 2b controls the electron density between the amine groups on both sides to control the wavelength of the dopant to emit blue light. In addition, when A and B form a pentagonal ring structure, the steric hindrance between the structures formed by Formula 2a or 2b increases, and between these structures and the substituents Ar ₁ to Ar ₄ bonded to the amino groups on both sides As the steric hindrance increases, the stability of the molecule can be greatly reduced. However, in the present invention, by forming a hexagonal ring structure between A and B according to Formula 3a or 3b, the angle increases and the intramolecular steric hindrance decreases as compared to the case of forming a pentagonal ring structure, resulting in better molecular stability. Can be indicated. As a result, the organic light emitting device employing the same can exhibit a longer life.

On the other hand, the compound (I) of Formula 1, for example, after the Suzuki reaction through the coupling between the halide (II) and the organoboron compound (III) as shown in the following Reaction Formula 1, the resultant, including a condensation central structure It can be prepared by an aryl amination reaction between the aryl compound (IV) and the amine compound (V). The manufacturing method may be more specific in the manufacturing examples to be described later.

[Scheme 1]

In Reaction Scheme 1, R ₁ to R ₄ are as defined above,

X ₁₁ , X ₁₂ , X ₂₁ , and X ₂₂ are each independently a halogen group such as I, Br, Cl, or -Otf (triflates),

D forms the structure of the following formula 3a or the following formula 3b,

[Formula 3a]

[Formula 3b]

In Formulas 3a and 3b, R ₅ to R ₈ are as defined above,

P ₁ and P ₂ are each independently a boron (B)-containing organic group such as a boronic acid group, a boronic acid ester group, or a boronic acid pinacol ester group,

Ar and Ar' are functional groups corresponding to Ar ₁ and Ar ₂ , or Ar ₃ and Ar ₄ , respectively, in Formula 1, and Ar ₁ to Ar ₄ are as defined in, and specifically, each independently substituted or unsubstituted A C _6-60 aryl group; Or N, O and S containing one or more heteroatoms selected from the group consisting of, and is a substituted or unsubstituted C _2-60 heteroaryl.

Specifically, in the first step for preparing compound (I) of Formula 1, the organoboron compound (III) is subjected to a Suzuki coupling reaction in the presence of the halide (II) and a base and a catalyst to form a condensation center structure. This is a step of preparing an aryl compound (IV) containing.

At this time, as the base, sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide may be used, and as the catalyst, tetrakis-(triphenylphosphine)palladium (Pd(PPH ₃ ) ₄ ), palladium acetate, etc. A palladium catalyst can be used. In addition, the reaction is dichloromethane, ethyl acetate, diethyl ether, acetonitrile, isopropyl alcohol, acetone, tetrahydrofuran (THF), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), or toluene. It can be carried out in one or more organic solvents.

In addition, the Suzuki coupling reaction of Scheme 1 may be performed in the range of 80°C to 120°C.

Next, the second step for preparing the compound (I) of Formula 1 is a step of reacting the aryl compound (IV) and the amine compound (V) prepared in the first step for an arylation reaction in the presence of a base.

At this time, the base is an organic base such as pyridine or triethylamine; Or an inorganic base such as an alkali metal or alkaline earth metal hydroxide, carbonate, or sulfate, and any one or a mixture of two or more of them may be used.

During the aryl amination reaction, a catalyst for accelerating the reaction may be optionally further used. The catalyst is tris (dibenzylideneacetone) dipalladium (Tris (dibenzylideneacetone) dipalladium (0), Pd ₂ (dba) ₃ ), tetrakis (triphenylphosphine) palladium (tetrakis (triphenylphosphine) palladium (0)) Tris (Dibenzylideneacetone) A palladium-based catalyst such as dipalladium chloroform or a palladium salt may be used.

The aryl amination reaction may also be carried out in an organic solvent, wherein the organic solvent is as defined above.

Meanwhile, a halide (II), an organoboron compound (III), and an amine-based compound used as starting materials in the preparation of the compound of Formula 1 may be directly prepared or may be obtained commercially.

The compound of Formula 1 may be prepared by appropriately replacing the starting material according to the structure of the compound to be prepared by referring to Scheme 1 above.

On the other hand, the present invention provides an organic light emitting device including the compound of Formula 1. For example, the present invention provides a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes a compound represented by Formula 1 do.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like as an organic material layer. In addition, at least one of an electron blocking layer and a hole blocking layer may be further included between the hole transport layer and the emission layer, and between the emission layer and the electron transport layer, respectively. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

In addition, the organic material layer may include a hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes, and the hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 above. Including the indicated compound.

In addition, the organic material layer may include an emission layer, and the emission layer includes the compound represented by Chemical Formula 1.

In addition, the organic material layer may include an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes the compound represented by Formula 1 above.

In addition, the electron transport layer, the electron injection layer, or the layer that simultaneously injects and transports electrons includes the compound represented by Formula 1 above. In particular, the compound represented by Formula 1 according to the present invention has excellent thermal stability, a deep HOMO level of 6.0 eV or more, high triplet energy (ET), and hole stability. In addition, when the compound represented by Formula 1 is used in an organic material layer capable of simultaneously injecting electrons and transporting electrons, an n-type dopant used in the art may be mixed and used.

In addition, the organic material layer may include an emission layer and an electron transport layer, and the emission layer may include a compound represented by Formula 1 above.

In addition, the organic light emitting device according to the present invention may be an organic light emitting device having a structure (normal type) in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting device according to the present invention may be an inverted type organic light emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light-emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.

1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. In such a structure, the compound represented by Formula 1 may be included in the emission layer.

FIG. 2 shows an example of an organic light-emitting device composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 7, an electron transport layer 8, and a cathode 4 I did it. In such a structure, the compound represented by Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the light emitting layer, and the electron transport layer, and more specifically, may be included in the light emitting layer.

In addition, the organic light emitting device according to an embodiment of the present invention may be made of a substrate, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode. The compound represented by Formula 1 may be included in the emission layer.

The organic light-emitting device according to the present invention may be manufactured by materials and methods known in the art, except that at least one of the organic material layers includes the compound represented by Chemical Formula 1. In addition, when the organic light-emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate. And, after forming an organic material layer including at least one of a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, it can be prepared by depositing a material that can be used as a cathode thereon. In addition, when the organic material layer further includes an electron blocking layer and a hole blocking layer between the hole transport layer and the emission layer, and between the emission layer and the electron transport layer, respectively, the step of forming these layers may be further included. In addition to this method, an organic light-emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

In addition, the compound represented by Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

In addition to such a method, an organic light-emitting device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited thereto.

For example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode, and the second electrode is an anode.

As the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material layer. Specific examples of the cathode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of a metal and an oxide such as ZnO:Al or SNO ₂ :Sb; Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, but are not limited thereto.

It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

The hole injection material is a layer that injects holes from the electrode, and the hole injection material has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and is generated in the light emitting layer. A compound that prevents migration of the excitons to the electron injection layer or the electron injection material and has excellent thin film formation ability is preferable. It is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light emitting layer.As a hole transport material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer and having high mobility for holes This is suitable. Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer including a conjugated portion and a non-conjugated portion, but are not limited thereto.

The light-emitting material is a material capable of emitting light in a visible light region by transporting and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples of 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole, and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The emission layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group, and the styrylamine compound is substituted or unsubstituted As a compound in which at least one arylvinyl group is substituted on the arylamine, one or two or more substituents selected from the group consisting of an aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto. The dopant content may range from 1% to 99% relative to the amount of the host of the light emitting layer.

The electron transport material is a layer that receives electrons from the electron injection layer and transports electrons to the emission layer. This is suitable. Specific examples include Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials that have a low work function and are followed by an aluminum layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium, and samarium, and in each case an aluminum layer or a silver layer follows.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and their derivatives, metals Complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include lithium 8-hydroxyquinolinato, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is not limited to this.

In addition, when the organic light emitting device further includes at least one of an electron blocking layer and a hole blocking layer, respectively, between the hole transport layer and the emission layer, and between the emission layer and the electron transport layer, the electron blocking layer prevents electrons from reaching the anode. As a layer, it may be formed under the same conditions as the electron injection layer. The electron blocking layer is made of a material having a function of transporting holes and having a remarkably small ability to transport electrons. By blocking electrons while transporting holes, the probability that electrons and holes recombine can be improved.

In addition, the hole blocking layer is a layer capable of improving the life and efficiency of a device by preventing injected holes from entering the electron transport layer through the light emitting layer, and is a nitrogen-containing heterocyclic derivative such as an oxadiazole derivative or a triazole derivative. , Phenanthroline derivatives, BCP, or aluminum complexes, but are not limited thereto. Specifically, the hole blocking layer may include a nitrogen-containing heterocyclic derivative as known in Korean Patent Registration No. 10-1052973 and Korean Patent Registration No. 10-1317495.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type, or a double-sided emission type depending on the material used.

In addition, the compound represented by Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

Preparation of the compound represented by Formula 1 and an organic light emitting device including the same will be described in detail in the following examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

[Synthesis Example]

Synthesis Example 1: Synthesis of Compound 1

1) Synthesis of compound 1-1

1-boromodibenzo[b,d]furan-1-amine (40.0g, 152.6mmol) and Bi(NO ₃ ) ₃ 5H ₂ O (74.0g, 152.6mmol), CH ₂ Cl _{2 in a} 3-neck flask (763ml) and acetic anhydride (87ml, 915.6mmol) were added and stirred at room temperature for 5hr. When the reaction was completed, a saturated aqueous solution of NaHCO ₃ was added, transferred to a separatory funnel, and extracted with ethyl acetate. The extract was dried over MgSO ₄ and then purified by silica gel column chromatography to obtain 42.6 g of a solid compound 1-1 (yield 80%, MS[M+H] ⁺ = 349).

2) Synthesis of compound 1-2

Compound 1-1 (42.0g, 120.3mmol), 2M HCl (241ml, 481.2mmol), THF (480ml), and EtOH (240ml) were heated in a two necked flask under reflux conditions in an argon atmosphere for 8 hours. After the reaction was completed, the organic solvent was concentrated under reduced pressure after cooling to room temperature. After neutralizing the concentrate with 2M NaOH aqueous solution, it was transferred to a separatory funnel and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ and purified by silica gel column chromatography to obtain 28.4 g of a solid compound 1-2 (yield 77%, MS[M+H] ⁺ = 307).

3) Synthesis of compound 1-3

Compound 1-2 (28.0g, 91.2mmol), 182ml of 1M HCl, and 300ml of water were added to a three-necked flask, cooled to 0°C, and stirred for 1 hour. NaNO ₂ at the same temperature (12.6g, 182.4mmol) 300ml of aqueous solution was added dropwise to the reaction solution and stirred for 1 hour. Then, 400 ml of an aqueous solution of potassium iodide (68.5g, 273.5mmol) was slowly added dropwise, followed by stirring for 5 hours. After completion of the reaction, Na ₂ S ₂ O ₃ aqueous solution was added, transferred to a separatory funnel, and extracted with ethyl acetate. The extract was dried over MgSO ₄ and purified by silica gel column chromatography to obtain 32.4 g of a solid compound 1-3 (yield 85%, MS[M+H] ⁺ = 418).

4) Synthesis of compound 1-4

After dissolving compound 1-3 (32.0g, 76.6mmol) and 180ml of DMF in a three-necked flask, 24g of Cu powder was added and stirred under reflux conditions. After 3 hours, 24 g of Cu powder was added and stirred for 24 hours. After completion of the reaction, the mixture was cooled to room temperature, water (1000 ml) was added, and the solid was filtered, transferred to a separatory funnel, and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ and purified by silica gel column chromatography to obtain 16.3 g of a solid compound 1-4 (yield 73%, MS[M+H] ⁺ = 582).

5) Synthesis of compound 1-5

Compound 1-4 (16.0g, 27.5mmol), iron powder (7.7g, 137.4mmol), acetic acid (65ml) and EtOH (90mL) were added to a three-necked flask, and stirred for 10 hours under reflux conditions. After the reaction was completed, 200 ml of water was added to dilute it, neutralized with an aqueous potassium carbonate solution, transferred to a separatory funnel, and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ and purified by silica gel column chromatography to obtain 13.1 g of compound 1-5 (yield 91%, MS[M+H] ⁺ = 522).

6) Synthesis of compound 1-6

Compound 1-5 (13.0g, 24.9mmol), 100ml of 1M HCl, and 150ml of water were added to a three-necked flask, cooled to 0°C, and stirred for 1 hour. 150ml of NaNO ₂ (6.9g, 99.6mmol) aqueous solution was added dropwise to the reaction solution at the same temperature and stirred for 1 hour. Then, 200 ml of an aqueous solution of potassium iodide (37.4 g, 149.4 mmol) was slowly added dropwise and stirred for 5 hours. After completion of the reaction, Na ₂ S ₂ O ₃ aqueous solution was added, transferred to a separatory funnel, and extracted with ethyl acetate. The extract was dried over MgSO ₄ and purified by silica gel column chromatography to obtain 15.4 g of a solid compound 1-6 (yield 83%, MS[M+H] ⁺ = 744).

7) Synthesis of compound 1-7

Compound 1-6 (15.0g, 20.2mmol) and 1,2-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene (7.0g, 21.2) in a 3-neck flask mmol) in THF (200ml), and K ₂ CO ₃ (11.1g, 80.6mmol) was dissolved in 100ml of H ₂ O and added. Here Pd(PPh ₃ ) ₄ (0.2g, 0.2mmol) was added, and the mixture was stirred for 8 hours under reflux conditions in an argon atmosphere. When the reaction was completed, after cooling to room temperature, the reaction solution was transferred to a separatory funnel, water (300 mL) was added and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ , filtered and concentrated, and the sample was purified by silica gel column chromatography to obtain 9.1 g of solid compound 1-7 (yield 80%, MS[M+H] ⁺ = 566). .

8) Synthesis of compound 1

Compound 1-7 (9.0g, 15.9mmol), bis(4-(tert-butyl)phenyl)amine (9.8g, 35.0mmol), Pd ₂ (dba) ₃ (0.2g, 0.2mmol), in a 3-neck flask Tri-tert-butylphosphine (0.1g, 0.5mmol), sodium tert-butoxide (2.3g, 23.8mmol) and Toluene (300ml) were added, and the mixture was stirred for 10 hours under reflux conditions in an argon atmosphere. When the reaction was completed, after cooling to room temperature, 200 ml of H ₂ O was added, and the reaction solution was transferred to a separatory funnel and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ , filtered and concentrated, and the sample was purified by silica gel column chromatography, and then 7.2 g of compound 1 was obtained through sublimation purification (yield 47%, MS[M+H] ⁺ = 697).

Synthesis Example 2: Synthesis of Compound 2

1) Synthesis of compound 2-1

In the synthesis of 7) compound 1-7 of Synthesis Example 1, 1,2-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene was added to furan-3,4- Compound 2-1 was synthesized by performing the same method, except for changing to diyldiboronic acid to be used.

2) Synthesis of compound 2

In the synthesis of 8) compound 1 of Synthesis Example 1, instead of compound 1-7, compound 2-1, and bis(4-(tert-butyl)phenyl)amine, instead of 4-(tert-butyl)-N-phenylaniline. Compound 2 was synthesized by performing the same method, except that it was used.

Synthesis Example 3: Synthesis of Compound 3

1) Synthesis of compound 3-1

In the synthesis of 7) compound 1-7 of Synthesis Example 1, 1,2-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene was added to thiophene-2,3- Compound 3-1 was synthesized by performing the same method, except that it was changed to diyldiboronic acid and used.

2) Synthesis of compound 3

In the synthesis of 8) compound 1 of Synthesis Example 1, compound 3-1 instead of compound 1-7, and N-(4-(tert-butyl)phenyl)-2 instead of bis(4-(tert-butyl)phenyl)amine Compound 3 was synthesized by performing the same method, except for changing to -methylaniline.

Synthesis Example 4: Synthesis of Compound 4

1) Synthesis of compound 4-1

In a 3-neck flask, 4-bromonaphthalen-1-amine (35.0g, 157.6mmol) and Bi(NO ₃ ) ₃ 5H ₂ O (76.4g, 157.6mmol), CH ₂ Cl ₂ (800ml), acetic anhydride (89ml, 945.6mmol) and stirred at room temperature for 5hr. When the reaction was completed, a saturated aqueous solution of NaHCO ₃ was added, transferred to a separatory funnel, and extracted with ethyl acetate. The extract was dried over MgSO ₄ and then purified by silica gel column chromatography to obtain 38.0 g of a solid compound 4-1 (yield 78%, MS[M+H] ⁺ = 309).

2) Synthesis of compound 4-2

Compound 4-1 (38.0g, 122.9mmol), 2M HCl (246ml, 491.7mmol), THF (500ml), EtOH (250ml) in a two necked flask were heated for 8 hours under reflux conditions in an argon atmosphere. After the reaction was completed, the organic solvent was concentrated under reduced pressure after cooling to room temperature. The concentrate was neutralized with 2M NaOH aqueous solution, transferred to a separatory funnel, and extracted using CH ₂ Cl ₂ . The extract was dried over MgSO ₄ and purified by silica gel column chromatography to obtain 28.4 g of a solid compound 4-2 (yield 80%, MS[M+H] ⁺ = 267).

3) Synthesis of compound 4-3

Compound 4-2 (25.0g, 93.6mmol), 187ml of 1M HCl, and 300ml of water were added to a three-necked flask, cooled to 0°C, and stirred for 1 hour. At the same temperature, 300 ml of an aqueous solution of NaNO ₂ (12.9 g, 187.2 mmol) was added dropwise to the reaction solution, followed by stirring for 1 hour. Then, 400 ml of an aqueous solution of potassium iodide (70.3 g, 280.8 mmol) was slowly added dropwise and stirred for 5 hours. After completion of the reaction, Na ₂ S ₂ O ₃ aqueous solution was added, transferred to a separatory funnel, and extracted with ethyl acetate. The extract was dried over MgSO ₄ and purified by silica gel column chromatography to obtain 25.5 g of a solid compound 4-3 (yield 72%, MS[M+H] ⁺ = 378).

4) Synthesis of compound 4-4

After dissolving compound 4-3 (25.0g, 66.1mmol) and 140ml of DMF in a three-necked flask, 21g of Cu powder was added and stirred under reflux conditions. After 3 hours, 21g of Cu powder was added and stirred for 24 hours. After the reaction was completed, water (800ml) was added after cooling to room temperature, and the solid was filtered, transferred to a separatory funnel, and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ and purified by silica gel column chromatography to obtain 14.1 g of a solid compound 4-4 (yield 85%, MS[M+H] ⁺ = 502).

5) Synthesis of compound 4-5

Compound 4-4 (14.0g, 27.9mmol), iron powder (7.8g, 139.4mmol), acetic acid (63ml) and EtOH (90mL) were added to a three-necked flask and stirred for 10hr under reflux conditions. After the reaction was completed, 200 ml of water was added to dilute it, neutralized with an aqueous potassium carbonate solution, transferred to a separatory funnel, and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ and then purified by silica gel column chromatography to obtain 11.7 g of compound 4-5 (yield 95%, MS[M+H] ⁺ = 442).

6) Synthesis of compound 4-6

Compound 4-5 (11.0g, 24.9mmol), 100ml of 1M HCl, and 150ml of water were added to a three-necked flask, cooled to 0°C, and stirred for 1 hour. At the same temperature, 150 ml of an aqueous NaNO ₂ (6.9 g, 99.6 mmol) solution was added dropwise to the reaction solution, followed by stirring for 1 hour. Then, 200 ml of an aqueous solution of potassium iodide (37.4 g, 149.4 mmol) was slowly added dropwise and stirred for 6 hours. After completion of the reaction, Na ₂ S ₂ O ₃ aqueous solution was added, transferred to a separatory funnel, and extracted with ethyl acetate. The extract was dried over MgSO ₄ and then purified by silica gel column chromatography to give 12.7 g of a solid of compound 4-6 (yield 77%, MS[M+H] ⁺ = 664).

7) Synthesis of compound 4-7

In a three-necked flask, compound 4-6 (12.0g, 18.1mmol) and furan-2,3-diyldiboronic acid (3.0g, 19.0mmol) were dissolved in THF (180ml) and K ₂ CO ₃ (10.0g, 72.3mmol) was added. Dissolve in 90 ml of H ₂ O. Pd(PPh ₃ ) ₄ (0.2g, 0.2mmol) was added thereto, and the mixture was stirred for 8 hours under reflux conditions under an argon atmosphere. When the reaction was completed, after cooling to room temperature, the reaction solution was transferred to a separatory funnel, water (250 mL) was added and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography to give 7.6 g of compound 4-7 in a solid state (yield 88%, MS[M+H] ⁺ = 476).

8) Synthesis of compound 4

In a three-necked flask, compound 4-7 (7.5g, 15.9mmol), N-(4-(tert-butyl)phenyl)-3-methylaniline (8.3g, 34.7mmol), Pd ₂ (dba) ₃ (0.2g, 0.2mmol), tri-tert-butylphosphine (0.1g, 0.5mmol), sodium tert-butoxide (2.3g, 23.6mmol), and Toluene (300ml) were added and stirred for 10 hours under reflux conditions under an argon atmosphere. When the reaction was completed, after cooling to room temperature, 200 ml of H ₂ O was added, and the reaction solution was transferred to a separatory funnel and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography, and then 5.6 g of compound 4 was obtained through sublimation purification (yield 45%, MS[M+H ] ⁺ = 793).

Synthesis Example 5: Synthesis of Compound 5

1) Synthesis of compound 5-1

Compound 5-1 was carried out in the same manner, except that furan-2,3-diyldiboronic acid was changed to thiophene-3,4-diyldiboronic acid in the synthesis of 7) compound 4-7 of Synthesis Example 4 Was synthesized.

2) Synthesis of compound 5

In the synthesis of 8) compound 4 of Synthesis Example 4, compound 5-1 instead of compound 4-7, and N-phenyl-4-(trimethylsilyl) instead of N-(4-(tert-butyl)phenyl)-3-methylaniline Compound 5 was synthesized using the same method, except that it was changed to aniline and used.

Synthesis Example 6: Synthesis of Compound 6

1) Synthesis of compound 6-1

2-nitroaniline (40.0g, 289.6mmol), N-bromosuccinimide (51.5g, 292.5mmol) and acetic acid (434ml) were added to a three-necked flask and stirred for 1 hr under reflux conditions. After the reaction was completed, Na ₂ S ₂ O ₃ aqueous solution was added, CH ₂ Cl ₂ was added, and the mixture was transferred to a separatory funnel and extracted with CH ₂ Cl ₂ . After drying the extract with MgSO ₄ , the organic solvent was distilled under reduced pressure to obtain 59.7 g of a solid compound 6-1 (yield 95%, MS[M+H] ⁺ = 212).

2) Synthesis of compound 6-2

Compound 6-1 (30.0g, 138.2mmol) was dissolved in THF (450ml) in a three-necked flask, and boron trifluoride diethyl etherate (72ml, 580.6mmol) was slowly added dropwise at 30°C over 20 minutes. After stirring for 10 minutes, a mixture of tert-butyl nitrite (66ml, 90%, 497.6mmol) and THF 350ml was slowly added dropwise at the same temperature. After the temperature was set to -10 ℃, diethyl ether 700ml was slowly added dropwise, and stirred for 1 hour. When the reaction is complete, the solid is filtered and washed with diethyl ether, and the obtained solid, KI (27.7g, 110.6mmol), iodine (14.0g, 55.3mmol), and 550ml of acetonitrile are added to a new two-necked flask and stirred at room temperature for 2 hours. I did. After the reaction was completed, it was heated for 8 hours under reflux conditions in an argon atmosphere. Na ₂ S ₂ O ₃ aqueous solution was added, CH ₂ Cl ₂ was added, and then transferred to a separatory funnel and extracted with CH ₂ Cl ₂ . After drying the extract with MgSO ₄ , the organic solvent was distilled under reduced pressure to obtain 38.5 g of a solid compound 6-2 (yield 85%, MS[M+H] ⁺ = 328).

3) Synthesis of compound 6-3

Compound 6-2 (35.0g, 106.7mmol) and dry THF (160ml) were added to a three-necked flask, and phenyl-magnesium chloride (2M in THF, 59ml, 117.4mmol) was added dropwise at -60°C under an argon atmosphere. After stirring for 5 minutes, trimethyl borate (14ml, 128.1mmol) was added dropwise to the reaction solution, followed by stirring for 30 minutes. After completion of the reaction, 2M HCl aqueous solution (107ml) was added at room temperature, and the reaction solution was transferred to a separatory funnel, followed by extraction with diethyl ether. The extract was dried over MgSO ₄ and recrystallized with ethyl acetate to give 20.4 g of a solid compound 6-3 (yield 75%, MS[M+H] ⁺ = 255).

4) Synthesis of compound 6-4

In a three-necked flask, compound 1-3 (30.0g, 71.8mmol), compound 6-3 (20.1g, 79mmol), 2M Na ₂ CO ₃ aqueous solution (144mL, 287.1mmol), DME (144mL), toluene (144mL), Pd(PPh ₃ ) ₄ (8.3g, 7.2mmol) was added and stirred for 8 hours under reflux conditions under an argon atmosphere. When the reaction was completed, after cooling to room temperature, the reaction solution was transferred to a separatory funnel, water (300 mL) was added and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ , filtered and concentrated, and the sample was purified by silica gel column chromatography to obtain 20.6 g of a solid compound 6-4 (yield 67%, MS[M+H] ⁺ = 429). .

5) Synthesis of compound 6-5

Compound 6-4 (20.0g, 46.6mmol), iron powder (13.0g, 233.1mmol), acetic acid (105ml) and EtOH (150mL) were added to a three-necked flask and stirred for 10 hours under reflux conditions. After the reaction was completed, 300ml of water was added to dilute, neutralized with aqueous potassium carbonate solution, transferred to a separatory funnel, and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ and then purified by silica gel column chromatography to obtain 16.5 g of compound 6-5 (yield 95%, MS[M+H] ⁺ = 442).

6) Synthesis of compound 6-6

Compound 6-5 (16.0g, 37.0mmol), 150ml of 1M HCl, and 200ml of water were added to a three-necked flask, cooled to 0°C, and stirred for 1 hour. At the same temperature, 200 ml of an aqueous solution of NaNO ₂ (10.2 g, 148.1 mmol) was added dropwise to the reaction solution, followed by stirring for 1 hour. Then, 300 ml of an aqueous solution of potassium iodide (55.7 g, 222.2 mmol) was slowly added dropwise and stirred for 6 hours. After completion of the reaction, Na ₂ S ₂ O ₃ aqueous solution was added, transferred to a separatory funnel, and extracted with ethyl acetate. The extract was dried over MgSO ₄ and purified by silica gel column chromatography to obtain 16.5 g of a solid compound 6-6 (yield 68%, MS[M+H] ⁺ = 654).

7) Synthesis of compound 6-7

Compound 6-6 (15.0g, 22.9mmol) and 1,2-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene (7.9g, 24.1) in a 3-neck flask mmol) in THF (230ml), K ₂ CO ₃ (12.7g, 91.8mmol) was dissolved in 115ml of H ₂ O and added. Pd(PPh ₃ ) ₄ (0.3g, 0.2mmol) was added thereto, and the mixture was stirred for 8 hours under reflux conditions under an argon atmosphere. When the reaction was completed, after cooling to room temperature, the reaction solution was transferred to a separatory funnel, water (300 mL) was added and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography to give 8.5 g of a solid compound 6-7 (yield 78%, MS[M+H] ⁺ = 476).

8) Synthesis of compound 6

Compound 6-7 (8.0g, 16.8mmol), N-(m-tolyl)dibenzo[b,d]furan-4-amine (10.1g, 37.0mmol), Pd(P(t-Bu) in a 3-neck flask ₃ ) ₂ ) (0.2g, 0.3mmol), sodium tert-butoxide (2.4g, 25.2mmol), and Toluene (330ml) were added and stirred for 8 hours under reflux conditions under an argon atmosphere. When the reaction was completed, the mixture was cooled to room temperature, 220 ml of H ₂ O was added, and the reaction solution was transferred to a separatory funnel and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography, and 5.8 g of compound 6 was obtained through sublimation purification (yield 40%, MS[M+H ] ⁺ = 861).

Synthesis example 7: Synthesis of compound 7

1) Synthesis of compound 7-1

In a three necked flask, compound 4-3 (377.96g, 66.1mmol), compound 6-3 (18.5g, 72.8mmol), 2M Na ₂ CO ₃ aqueous solution (132mL, 264.6mmol), DME (132mL), toluene (132mL) , Pd(PPh ₃ ) ₄ (7.6g, 6.6mmol) was added, and the mixture was stirred for 8 hours under reflux conditions under an argon atmosphere. When the reaction was completed, after cooling to room temperature, the reaction solution was transferred to a separatory funnel, water (300 mL) was added and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography to obtain 20.6 g of a solid compound 7-1 (yield 69%, MS[M+H] ⁺ = 452).

2) Synthesis of compound 7-2

Compound 7-1 (20.0g, 44.2mmol), iron powder (12.4g, 221.2mmol), acetic acid (100ml) and EtOH (150mL) were added to a three-necked flask and stirred for 10 hours under reflux conditions. After the reaction was completed, 300 ml of water was added to dilute it, neutralized with an aqueous potassium carbonate solution, transferred to a separatory funnel, and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO _4, and then purified by silica gel column chromatography to obtain 13.9 g of compound 7-2 (yield 80%, MS[M+H] ⁺ = 392).

3) Synthesis of compound 7-3

Compound 7-2 (13.0g, 33.2mmol), 130ml of 1M HCl, and 180ml of water were added to a three-necked flask, cooled to 0°C, and stirred for 1 hour. At the same temperature, 180 ml of an aqueous solution of NaNO ₂ (9.2 g, 132.6 mmol) was added dropwise to the reaction solution, followed by stirring for 1 hour. Then, 250 ml of an aqueous solution of potassium iodide (49.8 g, 198.92 mmol) was slowly added dropwise and stirred for 6 hours. After completion of the reaction, Na ₂ S ₂ O ₃ aqueous solution was added, transferred to a separatory funnel, and extracted with ethyl acetate. The extract was dried over MgSO ₄ and purified by silica gel column chromatography to obtain 13.4 g of a solid compound 7-3 (yield 66%, MS[M+H] ⁺ = 614).

4) Synthesis of compound 7-4

In the synthesis of 7) compound 6-7 of Synthesis Example 6, compound 7-3 was used instead of compound 6-6, and 1,2-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan- Compound 7-4 was synthesized by performing the same method, except that furan-3,4-diyldiboronic acid was used instead of 2-yl)benzene.

5) Synthesis of compound 7

In the synthesis of 8) compound 6 of Synthesis Example 6, compound 7-4 instead of compound 6-7, and N-(4-(tert) instead of N-(m-tolyl)dibenzo[b,d]furan-4-amine Compound 7 was synthesized in the same manner, except for changing to -butyl)phenyl)dibenzo[b,d]furan-4-amine.

[Device Manufacturing Example]

Example 1

A glass substrate coated with a thin film of 1,400Å of ITO (Indium Tin Oxide) was put in distilled water dissolved in a detergent and washed with ultrasonic waves. At this time, a Decon™ CON705 product from Fischer Co. was used as a detergent, and distilled water secondarily filtered with a 0.22 μm sterilizing filter manufactured by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water was finished, ultrasonic cleaning was performed for 10 minutes with a solvent of isopropyl alcohol, acetone, and methanol, and dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

On the prepared ITO transparent electrode, the following [HI-A] and hexaazatriphenylene (HAT) were sequentially thermally vacuum deposited to a thickness of 650 Å and 50 Å, respectively, to form a hole injection layer.

On the hole injection layer, the following [HT-A] was vacuum-deposited to a thickness of 600Å to form a hole transport layer, and the following [HT-B] was thermally vacuum-deposited to a thickness of 50Å to form an electron blocking layer thereon. I did.

Subsequently, a mixture obtained by mixing 96% by weight of the following host [BH1] and 4% by weight of Compound 1 on the electron blocking layer was vacuum deposited to a thickness of 200 Å to form a light emitting layer.

Then, the following [ET-A] and [Liq] were thermally vacuum deposited to a thickness of 360Å at a ratio of 1:1 to form an electron transport layer, and then [Liq] was vacuum deposited to a thickness of 5Å to inject electrons. A layer was formed.

An organic light-emitting device was manufactured by sequentially depositing magnesium and silver on the electron injection layer in a ratio of 10:1 to a thickness of 220 Å and aluminum to a thickness of 1000 Å, respectively, to form a cathode.

Examples 2 to 14, and Comparative Examples 1 to 6

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the compound shown in Table 1 was used instead of the host material and the dopant material in Example 1.

Host Dopant Example 1 BH1 Compound 1 Example 2 BH1 Compound 2 Example 3 BH1 Compound 3 Example 4 BH1 Compound 4 Example 5 BH1 Compound 5 Example 6 BH1 Compound 6 Example 7 BH1 Compound 7 Example 8 BH2 Compound 1 Example 9 BH2 Compound 3 Example 10 BH2 Compound 5 Example 11 BH2 Compound 7 Example 12 BH3 Compound 2 Example 13 BH3 Compound 4 Example 14 BH3 Compound 6 Comparative Example 1 BH1 BD1 Comparative Example 2 BH1 BD2 Comparative Example 3 BH2 BD2 Comparative Example 4 BH2 BD3 Comparative Example 5 BH3 BD1 Comparative Example 6 BH3 BD3

By applying a current to the organic light emitting devices prepared in Examples 1 to 14 and Comparative Examples 1 to 6, voltage, efficiency, color coordinates, and lifetime (T95) were measured, respectively, and the results are shown in Table 1 below.

At this time, voltage, efficiency, and color coordinates were measured by applying a current density of 10 mA/cm ² , and life (T95) refers to the time from the current density of 20 mA/cm ² until the initial luminance decreases to 95%.

@ 10mA / cm ² @ 20mA / cm ² V cd/A CIE-x CIE-y Life (hr) Example 1 3.51 5.23 0.138 0.130 150 Example 2 3.55 5.21 0.138 0.131 150 Example 3 3.51 5.28 0.138 0.130 140 Example 4 3.53 5.26 0.139 0.130 160 Example 5 3.52 5.21 0.138 0.129 140 Example 6 3.59 5.20 0.139 0.131 150 Example 7 3.55 5.24 0.137 0.130 150 Example 8 3.43 5.21 0.138 0.132 160 Example 9 3.42 5.23 0.138 0.130 150 Example 10 3.38 5.33 0.137 0.130 170 Example 11 3.40 5.30 0.138 0.131 160 Example 12 3.62 5.27 0.137 0.132 180 Example 13 3.64 5.17 0.136 0.133 180 Example 14 3.61 5.31 0.137 0.132 190 Comparative Example 1 3.91 4.83 0.138 0.131 90 Comparative Example 2 3.95 4.86 0.138 0.131 80 Comparative Example 3 3.81 4.85 0.140 0.132 100 Comparative Example 4 3.78 4.80 0.141 0.131 80 Comparative Example 5 4.15 4.89 0.139 0.130 120 Comparative Example 6 4.04 4.81 0.139 0.141 130

As shown in Table 2, the amine compound according to the present invention exhibits excellent luminous efficiency and particularly excellent device characteristics with a long lifespan than the case of using the compounds of [BD1] to [BD3] according to the prior art. In addition, these characteristics are effective for various host materials, indicating high applicability as an organic light-emitting device.

1: substrate 2: anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: light emitting layer 8: electron transport layer

Claims (10)

Compounds of Formula 1:
[Formula 1]

In Formula 1,
Ar ₁ to Ar ₄ are each independently any one selected from the group consisting of,

R ₁ and R ₂ together form the structure of formula 2b,
R ₃ and R ₄ are hydrogen, or R ₃ and R ₄ together form a structure of the following formula 2a or the following formula 2b,
[Formula 2a]

[Formula 2b]

A and B together form any one of the following formulas 4a to 4d,
[Formula 4a]

[Formula 4b]

[Formula 4c]

[Formula 4d]

In Formulas 4a to 4d,
D ₁ and D ₂ are each independently selected from the group consisting of O, S, and CR, but D ₁ and D ₂ are not CR at the same time,
R is hydrogen.
delete The method of claim 1,
A compound which is any one of the compounds of formulas 5a to 5l, and 5u to 5x:
[Formula 5a] [Formula 5b]

[Formula 5c] [Formula 5d]

[Formula 5e] [Formula 5f]

[Chemical Formula 5g] [Chemical Formula 5h]

[Formula 5i] [Formula 5j]

[Formula 5k] [Formula 5l]

[Formula 5u] [Formula 5v]

[Chemical Formula 5w] [Chemical Formula 5x]

In Formulas 5a to 5l, and 5u to 5x,
Ar ₁ to Ar ₄ are as defined in claim 1,
D ₁ and D ₂ are each independently selected from the group consisting of O, S, and CR, but D ₁ and D ₂ are not CR at the same time,
R is hydrogen.
delete delete The method of claim 1,
In Formula 1, Ar ₁ and Ar ₄ , and Ar ₂ and Ar ₃ have the same structure as each other; Or Ar ₁ to Ar ₄ all have the same structure.
The method of claim 1,
Any one selected from the group consisting of the following compounds, a compound.

A dopant comprising a compound according to any one of claims 1, 3, 6 and 7.
A first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode,
At least one of the organic material layers includes the compound according to any one of claims 1, 3, 6, and 7.
The method of claim 9,
The organic material layer including the compound is an emission layer, an organic light-emitting device.

Images