KR20200092515A - Compound for organic electric element, organic electric element comprising the same and electronic device thereof - Google Patents

Abstract

The present invention relates to a compound for an organic electric element, an organic electric element using the same, and an electronic device thereof. According to the present invention, high luminous efficiency, low driving voltage, and high heat resistance of the element can be achieved, and color purity and lifetime of the element can be improved.

Description

Compounds for organic electrical devices, organic electrical devices using the same, and electronic devices thereof {COMPOUND FOR ORGANIC ELECTRIC ELEMENT, ORGANIC ELECTRIC ELEMENT COMPRISING THE SAME AND ELECTRONIC DEVICE THEREOF}

The present invention relates to a compound for an organic electric element, an organic electric element using the same, and an electronic device thereof.

In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material. An organic electric device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic material layer is often composed of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may be formed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

Materials used for the organic material layer in the organic electrical device may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, depending on their function.

In addition, the light emitting material may be classified into a high molecular weight type and a low molecular weight type according to the molecular weight, and a fluorescent material derived from the singlet excited state of the electron and a phosphorescent material derived from the triplet excited state of the electron according to the light emission mechanism. Can. In addition, the luminescent material may be divided into blue, green, and red luminescent materials and yellow and orange luminescent materials necessary for realizing a better natural color according to the luminous color.

On the other hand, when only one material is used as the light emitting material, the problem of the maximum light emission wavelength shifting to a long wavelength due to intermolecular interaction and a decrease in color purity or efficiency of the device due to the light emission attenuation effect occurs, so that the increase in color purity and energy transfer In order to increase the luminous efficiency through, a host/dopant system may be used as a luminescent material. The principle is that when a small amount of the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with the light emitting layer, exciton generated in the light emitting layer is transported as a dopant to produce light with high efficiency. At this time, since the wavelength of the host moves to the wavelength of the dopant, light of a desired wavelength can be obtained according to the type of the dopant used.

Currently, the portable display market is increasing in size with a large-area display. Since the portable display has a battery that is a limited power supply, more efficient power consumption is required than the power consumption required in the existing portable display. In addition, in addition to efficient power consumption, luminous efficiency and lifetime issues must also be solved.

Efficiency, life, and driving voltage are related to each other. As the efficiency increases, the driving voltage decreases relatively, and as the driving voltage decreases, crystallization of organic materials due to Joule heating generated during driving decreases, resulting in less It shows a tendency to increase life. However, simply improving the organic layer does not maximize efficiency. This is because long life and high efficiency can be achieved at the same time when the energy level and T1 value between each organic material layer and the intrinsic properties of materials (mobility, interfacial properties, etc.) are optimally combined. Therefore, there is a need to develop a light emitting material that has high thermal stability and can efficiently achieve charge balance in the light emitting layer.

That is, in order to sufficiently exhibit the excellent characteristics of the organic electric device, materials constituting an organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, a light emitting auxiliary layer material, are stable and efficient It should be preceded by the material, but the development of a stable and efficient organic material layer material for an organic electric device has not been sufficiently achieved.

An object of the present invention is to provide a compound capable of improving the device's high luminous efficiency, low driving voltage, high heat resistance, color purity and lifetime, and an organic electric device using the same and its electronic device.

In one aspect, the present invention provides a compound represented by the formula below.

In another aspect, the present invention provides an organic electric device using the compound represented by the formula and an electronic device thereof.

By using the compound according to the present invention, it is possible to achieve high luminous efficiency, low driving voltage, and high heat resistance of the device, and improve the color purity and lifetime of the device.

1 to 3 are views schematically showing an organic electric device according to embodiments of the present invention.
4 is a schematic diagram of an electronic device according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

In adding reference numerals to the components of each drawing, it should be noted that the same components are given the same reference numerals as possible even though they are displayed on different drawings. In addition, in describing the present invention, when it is determined that detailed descriptions of related well-known structures or functions may obscure the subject matter of the present invention, detailed descriptions thereof will be omitted.

In addition, in describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are only for distinguishing the component from other components, and the nature, order, or order of the component is not limited by the term. When a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to the other component, but another component between each component It will be understood that elements may be "connected", "coupled" or "connected".

Also, if a component such as a layer, film, region, plate, etc. is said to be "on" or "on" another component, it is not only when the other component is "directly above", but also with another component in the middle. It should be understood that the case may be included. Conversely, it should be understood that when a component is said to be “just above” another part, it means that there is no other part in between.

Terms used in this specification and in the appended claims are as follows, unless stated otherwise.

The terms “halo” or “halogen” as used herein include fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), unless otherwise noted.

The term "alkyl" or "alkyl group" as used herein has 1 to 60 carbons connected by a single bond, unless otherwise specified, and is a straight chain alkyl group, branched chain alkyl group, cycloalkyl (alicyclic) group, alkyl-substituted By radicals of saturated aliphatic functional groups, including cycloalkyl groups, cycloalkyl-substituted alkyl groups.

As used herein, the term “haloalkyl group” or “halogenalkyl group” means an alkyl group substituted with halogen, unless otherwise specified.

As used herein, the terms "alkenyl" or "alkynyl" have a double bond or a triple bond, respectively, and include a straight or branched chain group, and have 2 to 60 carbon atoms, unless otherwise specified. It is not limited.

As used herein, the term "cycloalkyl" means an alkyl forming a ring having 3 to 60 carbon atoms, unless otherwise specified, and is not limited thereto.

As used herein, the term "alkoxy group" or "alkyloxy group" refers to an alkyl group to which an oxygen radical is attached, and has a carbon number of 1 to 60 unless otherwise specified, but is not limited thereto.

As used herein, the terms "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" means an alkenyl group to which an oxygen radical is attached, 2 to 60 unless otherwise specified. Has carbon number, but is not limited thereto.

As used herein, the terms "aryl group" and "arylene group" have 6 to 60 carbon atoms, respectively, unless otherwise specified, but are not limited thereto. In this specification, an aryl group or an arylene group includes monocyclic, ring aggregates, conjugated several ring systems, compounds, and the like. For example, the aryl group may refer to a phenyl group, a monovalent functional group of biphenyl, a monovalent functional group of naphthalene, a fluorenyl group, or a substituted fluorenyl group.

As used herein, the terms "fluorenyl group" or "fluorenylene group" means a monovalent or divalent functional group of fluorene, respectively, unless otherwise specified, and "substituted fluorenyl group" or "substituted flu. Orenylene group" means a monovalent or divalent functional group of substituted fluorene, and "substituted fluorene" means at least one of the following substituents R, R', R", R'" is a functional group other than hydrogen Means that R and R'are bonded to each other to form a compound as a spy together with the carbon to which they are bonded.

In addition, R, R', R" and R"' are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, 3 It may be a heterocyclic group having a carbon number of 30 to 30, for example, the aryl group may be phenyl, biphenyl, naphthalene, anthracene or phenanthrene, the heterocyclic group pyrrole, furan, thiophene, pyrazole, imidazole , Triazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, indole, benzofuran, quinazoline or quinoxaline, for example, the substituted fluorenyl and fluorenylene groups are 9,9, respectively. It may be a monovalent or divalent functional group of -dimethylfluorene, 9,9-diphenylfluorene and 9,9'-spyrobi[9H-fluorene].

The term "ring assemblies" as used herein refers to two or more ring systems (single or fused ring systems) directly connected to each other through a single bond or a double bond, and directly between such rings. This means that the number of linkages is one less than the total number of ring systems in this compound. Ring aggregates may have the same or different ring systems connected directly to each other through single or double bonds.

Since the aryl group includes a ring aggregate in the present specification, the aryl group includes biphenyl and terphenyl in which a benzene ring, which is a single aromatic ring, is connected by a single bond. In addition, since the aryl group also includes a compound in which the aromatic ring system bonded to the aromatic single ring is connected by a single bond, for example, a compound in which the aromatic ring system fluorene bonded to the aromatic single ring is connected by a single bond is also included. do.

As used herein, the term "conjugated multiple ring system" means a fused ring form sharing at least two atoms, and a ring system of two or more hydrocarbons is a conjugated form and at least one heteroatom is included. And a heterocyclic system in which at least one is conjugated. These conjugated multiple ring systems may be aromatic rings, heteroaromatic rings, aliphatic rings or combinations of these rings.

The term "spiro compound" as used herein has a'spiro union', and a spiro linkage refers to a link made by two rings sharing only one atom. At this time, the atoms shared by the two rings are called'spyro atoms', and these are'monospyro-','dispiro-', and'trispyro' depending on the number of spy atoms in a compound. It is called a compound.

As used herein, the term "heterocyclic group" includes aromatic rings such as "heteroaryl group" or "heteroarylene group" as well as non-aromatic rings, and each carbon atom containing one or more heteroatoms unless otherwise specified. It means a ring of 2 to 60, but is not limited thereto. The term "heteroatom" as used herein refers to N, O, S, P or Si unless otherwise specified, and the heterocyclic group is a monocyclic, ring aggregate containing heteroatoms, multiple conjugated ring systems, spies Means a compound and the like.

In addition, "heterocyclic group" may include a ring containing SO ₂ instead of carbon forming a ring. For example, "heterocyclic group" includes the following compounds.

The term "ring" as used herein includes monocyclic and polycyclic, includes hydrocarbon rings as well as heterocycles containing at least one heteroatom, and includes aromatic and non-aromatic rings.

The term "polycyclic" as used herein includes ring assemblies, fused multiple ring systems and spiro compounds, such as biphenyls, terphenyls, aromatics as well as non-aromatics, and hydrocarbons. Rings include, of course, heterocycles comprising at least one heteroatom.

In addition, when the prefix is named consecutively, it means that the substituents are listed in the order described first. For example, in the case of an arylalkoxy group, it means an alkoxy group substituted with an aryl group, in the case of an alkoxycarbonyl group, it means a carbonyl group substituted with an alkoxy group, and in the case of an arylcarbonyl alkenyl group, it means an alkenyl group substituted with an arylcarbonyl group, wherein An arylcarbonyl group is a carbonyl group substituted with an aryl group.

Also, unless expressly stated, the term "substituted" in the term "substituted or unsubstituted" as used herein is deuterium, halogen, amino group, nitrile group, nitro group, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₁ -C ₂₀ alkylamine group, C ₁ -C ₂₀ alkylthiophene group, C ₆ -C ₂₀ arylthiophene group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₂₀ aryl group, of a C ₆ -C ₂₀ aryl group substituted with a heavy hydrogen, C ₈ -C ₂₀ aryl alkenyl group, a silane group, a boron Means a group, a germanium group, and one or more substituents selected from the group consisting of C ₂ -C ₂₀ heterocyclic groups including at least one heteroatom selected from the group consisting of O, N, S, Si and P. And is not limited to these substituents.

In the present specification, the'functional group name' corresponding to an aryl group, arylene group, heterocyclic group, etc. exemplified as an example of each symbol and its substituent may describe'the name of a functional group reflecting a singer', but is described as a'parent compound name' You may. For example, in the case of'phenanthrene', which is a kind of aryl group, the monovalent'group' is'phenanthryl (group)' and the divalent group is'phenanthrylene (group)', and the singer is classified to describe the group's name. It can be done, but it can be described as the parent compound name'phenanthrene' regardless of the singer. Similarly, in the case of pyrimidine, regardless of the valence, it is described as'pyrimidine', or in the case of monovalent, pyrimidinyl (group), in the case of divalent, pyrimidineylene (group), etc. It may be written as'name'. Accordingly, in the present specification, when the type of a substituent is described as a parent compound name, it may mean an n-valent'group' formed by detaching a hydrogen atom bonded to a carbon atom and/or a heteroatom of the parent compound.

In addition, unless expressly stated, the formula used in the present specification is applied in the same manner as the substituent definition by the exponent definition of the following formula.

Here, when a is 0, the substituent R ¹ is absent, when a is 1, one substituent R ¹ is bound to any one of carbons forming a benzene ring, and when a is 2 or 3, respectively In this case, R ¹ may be the same or different from each other, and when a is an integer of 4 to 6, it binds to the carbon of the benzene ring in a similar manner, while the indication of hydrogen bound to the carbon forming the benzene ring is omitted .

In this specification, the substituents are bonded to each other to form a ring, a plurality of substituents bonded to each other is a carbon atom; It means to form a saturated or unsaturated ring by sharing at least one atom of the heteroatoms O, N, S, Si and P. For example, in the case of naphthalene, an adjacent methyl group and a butadienyl group substituted in any one benzene ring share one carbon to form an unsaturated ring, or a vinyl group and a propylene group share one carbon to be unsaturated. It can be regarded as forming a ring. In addition, in the case of fluorene, it can be regarded as an aryl group having 13 carbon atoms by itself, but it can also be seen that two methyl groups substituted with a biphenyl group are combined with each other to share one carbon to form a ring.

Organic Electrical Devices FIGS. 1 to 3 are exemplary views of organic electrical devices according to embodiments of the present invention.

Referring first to FIG. 1, the organic electric device 100 according to an embodiment of the present invention includes a first electrode 120, a second electrode 180, and a first electrode 120 formed on a substrate (not shown). Between the second electrode 180 and the organic material layer including the compound according to the present invention.

In this case, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160 and an electron injection layer 170. Specifically, the hole injection layer 130, the hole transport layer 140, the light emitting layer 150, the electron transport layer 160 and the electron injection layer 170 may be sequentially disposed on the first electrode 120.

In addition, referring to FIG. 2, the organic electric device 200 according to another embodiment of the present invention includes a hole injection layer 230, a hole transport layer 240, and a buffer layer sequentially disposed on the first electrode 220. 243), a light emitting auxiliary layer 253, a light emitting layer 250, an electron transport layer 260, an electron injection layer 270 and a second electrode 280 may be included.

Meanwhile, although not illustrated in FIG. 2, an electron transport auxiliary layer may be further disposed between the light emitting layer 250 and the electron transport layer 260.

In addition, referring to FIG. 3, the organic electric device 300 according to another embodiment of the present invention includes a first stack disposed between the first electrode 320 and the second electrode 380 disposed opposite each other ( ST1), a second stack ST2, and a charge generation layer (CGL). Here, the charge generation layer CGL may be disposed at the boundary between the first stack ST1 and the second stack ST2. The charge generation layer CGL may include a first charge generation layer 390 and a second charge generation layer 391. The charge generation layer CGL may increase a current efficiency generated in each light emitting layer between the first and second light emitting layers 351 and 352 and may serve to distribute charges smoothly.

In addition, the first stack ST1 includes a first hole injection layer 331 sequentially disposed on the first electrode 120, a first hole transport layer 341, a first light emitting layer 351, and a first electron transport layer ( 361).

The second stack ST2 may include a second hole transport layer 342, a second emission layer 352, a second electron transport layer 362 and an electron injection layer 170. The second hole transport layer 342, the second emission layer 352, the second electron transport layer 362, and the electron injection layer 370 may be sequentially disposed on the second charge generation layer 391.

The first light emitting layer 351 may include a light emitting material including a blue fluorescent dopant in the blue host, and the second light emitting layer 352 may include a green host doped with a greenish yellow dopant and a red dopant. However, the materials included in each of the first and second light emitting layers 351 and 352 according to the exemplary embodiment of the present invention are not limited thereto.

Here, the second hole transport layer 342 includes a second stack ST2 in which the energy level is set higher than the triplet excitation state energy level of the second emission layer 352.

At this time, since the energy level of the second hole transport layer 342 is higher than that of the second light emitting layer 352, the triplet exciton of the second light emitting layer 352 is transferred to the second hole transport layer 342 and the light emission efficiency It can prevent falling. That is, the second hole transport layer 342 may function as an exciton blocking layer that functions to transport holes from the unique second light emitting layer 352 and prevents triplet excitons from falling over. .

In addition, for the function of the exciton blocking layer, the first hole transport layer 341 may also be set to an energy level higher than the triplet excitation energy level of the first light emitting layer 351. Further, the first electron transport layer 361 is also set to an energy level higher than the energy level of the triplet excited state of the first light emitting layer 351, and the second electron transport layer 362 is also tripled excited of the second light emitting layer 352 It is desirable to set the energy level higher than the energy level of the state.

Meanwhile, the organic electric device 300 of FIG. 3 may be an organic electric device 300 that emits white light by a mixing effect of light emitted from the first light emitting layer 351 and the second light emitting layer 352, but the present invention The embodiment of the present invention is not limited thereto.

The compound according to the present invention is a hole injection layer (130, 230), hole transport layer (140, 240), buffer layer 243, light emitting auxiliary layer 253, electron transport layer (160, 260), electrons of Figure 1 or 2 It may be used as a material such as the injection layers 170 and 270 or a host or dopant material of the light emitting layers 150 and 250. For example, the compound of the present invention may be used as a material for the light-emitting auxiliary layer 253 of FIG. 2.

In addition, the compound according to the present invention is the first hole injection layer 331 of Figure 3, the first hole transport layer 341, the first light emitting layer 351, the first electron transport layer 361, the first charge generating layer 390 ), the second charge transport layer 391, the second hole transport layer 342, the second emission layer 352, the second electron transport layer 362 and the electron injection layer 370 may be used as materials. For example, the compound of the present invention may be used as a material for the first hole transport layer 341, and in some cases, may also be used as the second charge generating layer 391.

On the other hand, even in the same core, since a band gap, an electrical characteristic, an interface characteristic, etc. can be changed depending on which substituent is attached to which position, the selection of the core and the combination of sub-substituents coupled thereto Research is necessary, and long life and high efficiency can be achieved at the same time when energy levels and T1 values between each organic material layer and the intrinsic properties of materials (mobility, interfacial properties, etc.) are optimally combined.

The organic electroluminescent device according to embodiments of the present invention may be manufactured using various deposition methods. It may be manufactured using a deposition method such as Physical Vapor Deposition (PVD) or Chemical Vapor Deposition (CVD), for example, by depositing a metal or conductive metal oxide or an alloy thereof on a substrate, the anodes 120, 220, 320), a hole injection layer (130, 230, 330), a hole transport layer (140, 240, 340), a light emitting layer (150, 250, 351, 352), an electron transport layer (160, 260, 361, 362) ) And an electron injection layer (170, 270, 370) after forming an organic layer, and then depositing a material that can be used as the cathode (180, 280, 380).

In addition, the organic material layer is a solution process or a solvent process (e.g., spin coating process), nozzle printing process, inkjet printing process, slot coating process, dip coating process, roll-to-roll process, doctor blading using various polymer materials It can be produced with fewer layers by methods such as a process, a screen printing process, or a thermal transfer method. Since the organic material layer according to the present invention can be formed in various ways, the scope of the present invention is not limited by the formation method.

The organic electric device according to an embodiment of the present invention may be a front emission type, a back emission type, or a double-sided emission type, depending on the material used.

WOLED (White Organic Light Emitting Device) has the advantage of being easy to realize high resolution and excellent processability, and can be manufactured using the color filter technology of the existing LCD. Various structures for white organic electric devices mainly used as backlight devices have been proposed and patented. Typically, the R (Red), G (Green), and B (Blue) light emitting units are arranged in a mutually planar side-by-side manner, and a stacking method in which the R, G, and B light emitting layers are stacked up and down. There is, there is a color conversion material (CCM) method using electroluminescence of the blue (B) organic light emitting layer and photo-luminescence of the inorganic phosphor using light therefrom, the present invention May be applied to such WOLED.

In addition, the organic electric device according to an embodiment of the present invention may be one of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, a monochromatic or white lighting device.

Another embodiment of the present invention may include an electronic device including a display device including the above-described organic electric element of the present invention and a control unit for controlling the display device. At this time, the electronic device may be a current or future wired or wireless communication terminal, and may include all electronic devices such as mobile communication terminals such as mobile phones, PDAs, electronic dictionaries, PMPs, remote controls, navigation, game machines, various TVs, and various computers. .

4 is an exemplary diagram of an electronic device according to another embodiment of the present invention.

The electronic device 400 may include an electronic device including a display device 410 including the organic electric element 430 of the present invention and a control unit 420 controlling the display device. At this time, the electronic device may be a current or future wired/wireless communication terminal, and includes all electronic devices such as mobile communication terminals such as mobile phones, PDAs, electronic dictionaries, PMPs, remote controls, navigation, game machines, various TVs, and various computers.

The control unit 420 applies a driving voltage and/or signal to the organic electric device, for example, a plurality of gate lines, a gate driving circuit driving the gate lines, a plurality of data lines, and the data lines It may include a data driving circuit for driving the controller and for controlling the gate driving circuit and the data driving circuit.

The controller supplies various control signals to the data driving circuit and the gate driving circuit to control the data driving circuit and the gate driving circuit.

Hereinafter, a compound according to an aspect of the present invention will be described. The compound according to an aspect of the present invention is represented by Formula 1 below.

<Formula 1>

Hereinafter, X, A ring to D ring, Ar ¹ to Ar ⁴ , L ¹ and L ² described in Chemical Formula 1 will be described.

The A to D rings are each independently a C ₆ to C ₆₀ aryl group or a C ₂ to C ₆₀ heterocyclic group, and at least one of the A to D rings is a C ₁₀ to C ₆₀ aryl group or C _It may be a heterocyclic group of ₁₀ ~ C ₆₀ . The A ring to the D ring may be the same as each other, or may be different from each other.

When the A ring to D ring is an aryl group, for example, the A ring to D ring may be each independently a C ₆ to C ₅₀ aryl group, a C ₆ to C ₃₀ aryl group, or a C ₆ to C ₁₀ aryl group. have.

When A to D rings are heterocyclic groups, for example, A to D rings are each independently C ₂ to C ₅₀ heterocyclic groups, C ₂ to C ₃₀ heterocyclic groups, or C ₂ to C ₁₀ of It may be a heterocyclic group.

The A ring may be substituted with R ¹ , the B ring may be substituted with R ² , the C ring may be substituted with R ³ , and the D ring may be substituted with R ⁴ .

R ¹ to R ⁴ are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Nitro group; C ₆ ~ C ₆₀ Aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; And aryloxy groups of C ₆ to C ₃₀ .

When R ¹ to R ⁴ are alkyl groups, R ¹ to R ⁴ may be C ₁ to C ₃₀ alkyl groups, C ₁ to C ₂₀ alkyl groups, or C ₁ to C ₁₀ alkyl groups, for example, The alkyl group may be a C ₁ to C ₁₀ straight chain alkyl group, a branched chain alkyl group, a cycloalkyl group, an alkyl-substituted cycloalkyl group, or a cycloalkyl-substituted alkyl group.

When R ¹ to R ⁴ are aryl groups, R ¹ to R ⁴ may be C ₆ to C ₄₀ aryl groups, C ₆ to C ₃₀ aryl groups, or C ₆ to C ₂₀ aryl groups, for example. , R ¹ to R ⁴ may be selected from benzene, naphthalene, anthracene, phenanthrene, tetracene, benzoanthracene, triphenylene, biphenyl, terphenyl and substituted or unsubstituted fluorene, respectively.

The X may be O, S, NR', CR'R'' or SiR'R''.

R'and R'' are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; And aryloxy groups of C ₆ to C ₃₀ .

L ¹ and L ² are each independently a single bond; C ₆ ~ C ₆₀ Aryl group; C ₃ ~ C ₆₀ aliphatic ring group; And C ₂ to C ₆₀ heterocyclic groups including at least one hetero atom among O, N, S, Si, and P.

When L ¹ and L ² are aryl groups, L ¹ and L ² may be each independently an aryl group of C ₆ to C _40, an aryl group of C ₆ to C ₃₀ , or an aryl group of C ₆ to C ₂₀ , For example, L ¹ to L ³ may each independently be selected from benzene, naphthalene, anthracene, phenanthrene, tetracene, benzoanthracene, triphenylene, biphenyl, terphenyl and substituted or unsubstituted fluorene.

Ar ¹ to Ar ⁴ are each independently C ₆ to C ₆₀ aryl groups; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; And aryloxy groups of C ₆ to C ₃₀ .

When Ar ¹ to Ar ⁴ are aryl groups, Ar ¹ to Ar ⁴ may be C ₆ to C ₄₀ aryl groups, C ₆ to C ₃₀ aryl groups, or C ₆ to C ₂₀ aryl groups, for example, Ar ¹ to Ar ⁴ may be selected from benzene, naphthalene, anthracene, phenanthrene, tetracene, benzoanthracene, triphenylene, biphenyl, terphenyl and substituted or unsubstituted fluorene, respectively.

When Ar ¹ to Ar ⁴ are heterocyclic groups, for example, Ar ¹ to Ar ⁴ are each independently C ₂ to C ₅₀ heterocyclic groups, C ₂ to C ₃₀ heterocyclic groups, or C ₂ to C _It may be a heterocyclic group of ₁₀ .

In R ¹ to R ⁴ , L ¹ , L ² and Ar ¹ to Ar ⁴ , the aryl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group and aryloxy group are each deuterium; Nitro group; Nitrile group; Halogen group; Amino group; A silane group unsubstituted or substituted with an alkyl group of C ₁ to C ₂₀ or an aryl group of C ₆ to C ₂₀ ; Siloxane groups; C ₁ ~ C ₂₀ alkylthio; C ₁ ~ C ₂₀ Alkoxy group; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₆ ~ C ₂₀ aryl group; C ₆ ~ C ₂₀ aryl group substituted with deuterium; C ₂ ~ C ₂₀ heterocyclic group; C ₃ ~ C ₂₀ cycloalkyl group; One or more substituents selected from the group consisting of C ₇ to C ₂₀ arylalkyl groups and C ₈ to C ₂₀ arylalkenyl groups may be substituted, and these substituents may combine with each other to form a ring.

When the compound of Formula 1 is used in the organic material layer of the organic electronic device, an organic electrical device having excellent luminous efficiency and lifetime can be manufactured.

In Chemical Formula 1, at least one of the A ring and the B ring may be independently selected from the following Chemical Formulas a-1 to a-7.

Formula a-1 Formula a-2

Formula a-3 Formula a-4

Formula a-5 Formula a-6

Formula a-7

In the above formulas a-1 to a-7, * may indicate a position where each of the formulas a-1 to a-7 is condensed. That is, the * portion of Formulas a-1 to a-7 may mean a position where the A to B rings are condensed with a ring containing X in Formula 1.

Z ¹ to Z ⁴⁸ may each independently be CR ^a or N.

Z ¹ to Z ^48, when any one of the N, and the other Z ¹ to Z ⁴⁸ that is directly bonded to the N of Z ¹ to Z ⁴⁸ may be ^a CR. That is, Z ¹ to Z ⁴⁸ are not selected so that N is bonded to each other.

The R ^a is the same as R ¹ defined in Chemical Formula 1.

In the compound of Formula 1, when one or more of the A ring and the B ring are each independently selected from Formulas a-1 to a-7, the compound of Formula 1 provides an organic electric device having excellent luminous efficiency and lifetime. Can.

In Chemical Formula 1, at least one of the C ring and the D ring may be independently selected from the following Chemical Formulas b-1 to b-7.

Formula b-1 Formula b-2 Formula b-3

Formula b-4 Formula b-5 Formula b-6 Formula b-7

In the formulas b-1 to b-7, one of *2 and *3 may be bonded to the carbon which is bonded to the A ring and the B ring, and the other to the L ¹ or L ² .

Carbon bonded to the A ring and the B ring may refer to carbon represented by *4 below in Chemical Formula 1.

That is, one of *2 and *3 may mean a portion connected by a single bond with the carbon indicated above.

Z ⁴⁹ to Z ⁸⁴ may be CR ^b or N.

Z ⁴⁹ to Z ^84, when any one of the N, the other Z ⁴⁹ to Z ⁸⁴ that is directly bonded to the N of Z ⁴⁹ to Z ⁸⁴ may be a CR ^b. That is, Z ⁴⁹ to Z ⁸⁴ are not selected so that N is bonded to each other.

The R ^b is the same as the R ¹ defined in claim ¹ .

In the compound of Formula 1, when one or more of the C ring and the D ring are each independently selected from Formulas b-1 to b-7, the compound of Formula 1 provides an organic electroluminescent device having excellent luminous efficiency and lifetime. Can.

In the compound of Formula 1, when one or more of the A ring and the B ring are each independently selected from Formulas a-1 to a-7, the compound of Formula 1 provides an organic electric device having excellent luminous efficiency and lifetime. Can.

The compound represented by Chemical Formula 1 may be represented by the following Chemical Formula 2 or Chemical Formula 3.

[Formula 2] [Formula 3]

In Formula 2 or Formula 3, A to D rings, Ar ¹ to Ar ⁴ , L ¹ and L ² are the same as defined in Formula 1.

In the compound represented by Chemical Formula 1, the compound represented by Chemical Formula 2 or Chemical Formula 3 may provide an organic electric device having excellent luminous efficiency and lifetime.

The compound represented by Chemical Formula 1 may be represented by the following Chemical Formula 4 or Chemical Formula 5.

[Formula 4] [Formula 5]

In Formula 4 or Formula 5, n, m, o and p are integers of 0 to 4, and X, A ring, C ring, and Ar ¹ to Ar ⁴ , R ¹ to R ⁴ are the same as defined in Formula 1 Do.

In the compound represented by Chemical Formula 1, the compound represented by Chemical Formula 4 or Chemical Formula 5 may provide an organic electric device having excellent luminous efficiency and lifetime.

The compound represented by Chemical Formula 1 may be represented by any one of the following Chemical Formulas 6 to 13.

[Formula 6] [Formula 7]

[Formula 8] [Formula 9]

[Formula 10] [Formula 11]

[Formula 12] [Formula 13]

In Formulas 6 to 13, X, Ar ¹ to Ar ⁴ , R ¹ to R ⁴ , L ¹ and L ² are the same as defined in Formula 1.

The q, u, w and y are integers from 0 to 6, and the r, s, t and v are integers from 0 to 4,

In the compound represented by Chemical Formula 1, the compound represented by any one of Chemical Formulas 6 to 13 may provide an organic electric device having excellent luminous efficiency and lifetime.

The compound represented by Formula 1 may be one of the following compounds, but is not limited thereto.

As another embodiment, the present invention provides an organic electric device containing the compound represented by the formula (1).

The organic electric element includes a first electrode; A second electrode; And an organic material layer positioned between the first electrode and the second electrode. The organic material layer may include a compound represented by Chemical Formula 1, and the compound represented by Chemical Formula 1 may be a hole injection layer or a hole in the organic material layer. It may be contained in at least one of the transport layer, the light emitting auxiliary layer, the light emitting layer, the electron transport layer and the electron injection layer. In particular, the compound represented by Chemical Formula 1 may be included in the light-emitting auxiliary layer.

Specifically, to provide an organic electrical device comprising one of the compounds represented by the formula (1) in the organic layer, more specifically, the organic layer includes a compound represented by the individual formula (1-1 to 2-52) It provides an organic electrical device.

In another embodiment, the at least one layer of the hole injection layer, the hole transport layer, the light emitting auxiliary layer, the light emitting layer, the electron transport layer and the electron injection layer of the organic layer, the compound is contained alone, or the It provides an organic electrical device characterized in that the compound is contained in a combination of two or more different from each other, or the compound is contained in a combination of two or more different compounds.

In another embodiment, a layer in which the compound is contained alone, the compound is contained in two or more different combinations, or the compound is contained in a combination of two or more different compounds may be a light-emitting auxiliary layer.

In other words, each layer may include a compound corresponding to Formula 1 alone, a mixture of two or more compounds of Formula 1, and a mixture of a compound represented by Formula 1 and a compound not corresponding to the present invention. This can be included. Here, the compound not corresponding to the present invention may be a single compound, or may be two or more compounds. At this time, when the compound is contained in a combination of two or more different compounds, the other compound may be a known compound of each organic layer, or a compound to be developed in the future. At this time, the compound contained in the organic material layer may be composed of only the same kind of compound, but may also be a mixture of two or more heterogeneous compounds represented by Chemical Formula 1.

For example, in the organic material layer, two compounds having different structures from each other may be mixed in a molar ratio of 99:1 to 1:99.

In another embodiment of the present invention, the present invention is a light efficiency improving layer formed on at least one side of the one side of the first electrode opposite to the organic layer or one side of the second electrode opposite to the organic layer. It provides an organic electrical device further comprising a.

Hereinafter, examples of the synthesis of the compound represented by Chemical Formula 1 according to the present invention and the manufacturing example of the organic electric device will be specifically described with reference to Examples, but the present invention is not limited to the following Examples.

[Synthesis example]

The compound represented by Chemical Formula 1 according to the present invention (final product 1) is synthesized as shown in Reaction Scheme 1 below, but is not limited thereto. X, A ring to D ring, Ar ¹ to Ar ⁴ , L ¹ and L ² are the same as defined in Formula 1, Hal ¹ and Hal ² are I or Br, and Sub1 and Sub2 may be the same or different from each other. have. Pd ₂ (dba) ₃ described in Synthesis Example is Tris(dibenzylideneacetone)dipalladium(0).

<Scheme 1>

I. Core Synthesis

The core of Reaction Scheme 1 is synthesized by the reaction route of Reaction Scheme 2 below, but is not limited thereto.

X, A ring to D ring, L ¹ and L ² are the same as defined in Formula 1, Hal ¹ and Hal ² are I or Br and Hal ³ is I, Br or Cl.

<Reaction Scheme 2>

1. Core1 Synthesis Example

(1) Inter1-1 Synthesis Example

2-Bromo-1-Phenoxynaphthalene (50.0 g, 167 mmol) was dissolved in THF (tetrahydrofuran) (370 mL) in a round bottom flask under a nitrogen atmosphere, and then cooled to -78 °C. Then n- BuLi (67 mL, 167 mmol) was slowly titrated and the mixture stirred for 30 min. Subsequently, (4-bromophenyl)(4-iodophenyl)methanone (64.7 g, 167mmol) was dissolved in THF (tetrahydrofuran) (186 mL) and then slowly titrated in a reaction round bottom flask. After further stirring at -78°C (1 Hr), the temperature is gradually raised to room temperature. After the reaction was completed, the mixture was extracted with ethyl acetate and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was silicagel column and recrystallized to obtain 82.2 g of product (yield: 81%).

(2) Core1 synthesis example

Inter1-1 (82.2 g, 135 mmol) and acetic acid (340 mL) and concentrated hydrochloric acid (54 mL) obtained in the above synthesis were placed in a round bottom flask and stirred at 80°C for 3H under a nitrogen atmosphere. After the reaction was completed, extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain 52.3 g of product (yield: 68%).

2. Core5 Synthesis Example

(1) Inter1-5 synthesis example

2-bromo-3-phenoxynaphthalene (50.0 g, 167 mmol), n-BuLi (67 mL, 167 mmol), (3-bromophenyl)(4-iodophenyl)methanone (64.7 g, 167 mmol) was synthesized by Inter1-1 Using was obtained 79.2 g of product (yield: 78%).

(2) Core5 synthesis example

Inter1-5 (79.2 g, 130 mmol) obtained in the synthesis, acetic acid (330 mL) and concentrated hydrochloric acid (52 mL) were obtained using the Core1 synthesis method to obtain 47.6 g of the product (yield: 62%).

3. Core11 Synthesis Example

(1) Inter1-11 synthesis example

1-bromo-2-phenoxybenzene (50.0 g, 201 mmol), n-BuLi (80 mL, 201 mmol), (4-bromonaphthalen-1-yl)(3-iodophenyl)methanone (87.7 g, 201 mmol) above 101-1 g of product (yield: 83%) was obtained using the Inter1-1 synthesis method.

(2) Core11 synthesis example

Inter1-11 (101.2 g, 167 mmol) and acetic acid (420 mL) and concentrated hydrochloric acid (67 mL) obtained in the synthesis were obtained using the Core1 synthesis method to obtain 56.0 g of product (yield: 57%).

4. Core14 Synthesis Example

(1) Inter1-14 synthesis example

1-bromo-2-phenoxybenzene (50.0 g, 201 mmol), n-BuLi (80 mL, 201 mmol), (4-bromonaphthalen-2-yl)(4-iodophenyl)methanone (87.7 g, 201 mmol) above 102.4 g of product (yield: 84%) was obtained using the Inter1-1 synthesis method.

(2) Core14 synthesis example

Inter1-14 (102.4 g, 169 mmol) and acetic acid (420 mL) and concentrated hydrochloric acid (67 mL) obtained in the synthesis were obtained using the Core1 synthesis method to obtain 64.6 g of product (yield: 65%).

5. Core17 Synthesis Example

(1) Inter1-17 synthesis example

2-bromo-1-(naphthalen-1-yloxy)naphthalene (50.0 g, 143 mmol), n-BuLi (57 mL, 143 mmol), (3-bromophenyl)(4-iodophenyl)methanone (55.4 g, 143 mmol ) Using the Inter1-1 synthesis method to obtain 77.2 g of product (yield: 82%).

(2) Core17 synthesis example

Inter1-17 (77.2 g, 117 mmol) obtained in the synthesis, acetic acid (290 mL) and concentrated hydrochloric acid (47 mL) were obtained using the Core1 synthesis method to obtain 47.3 g of the product (yield: 63%).

6. Core26 Synthesis Example

(1) Inter1-26 synthesis example

(2-bromonaphthalen-1-yl)(phenyl)sulfane (50.0 g, 159 mmol), n-BuLi (63 mL, 159 mmol), (3-bromophenyl)(4-iodophenyl)methanone (61.4 g, mmol) Using the Inter1-1 synthesis method, 83.1 g of a product (yield: 84%) was obtained.

(2) Core26 synthesis example

Inter1-26 (83.1 g, 133 mmol) obtained from the synthesis, acetic acid (330 mL) and concentrated hydrochloric acid (53 mL) were obtained using the Core1 synthesis method to obtain 54.0 g of product (yield: 67%).

7. Core31 Synthesis Example

(1) Inter1-31 synthesis example

(1-bromonaphthalen-2-yl)(phenyl)sulfane (50.0 g, 159 mmol), n-BuLi (63 mL, 159 mmol), (4-bromophenyl)(4-iodophenyl)methanone (61.4 g, 159 mmol) To obtain a product 71.2 g (yield: 72%) using the Inter1-1 synthesis method.

(2) Synthesis example of Core31

Inter1-31 (71.2 g, 114 mmol) and acetic acid (290 mL) and concentrated hydrochloric acid (46 mL) obtained in the synthesis were obtained using the Core1 synthesis method to obtain 38.7 g of product (yield: 56%).

8. Core35 Synthesis Example

(1) Inter1-35 synthesis example

(2-bromophenyl)(phenyl)sulfane (50.0 g, 189 mmol), n-BuLi (75 mL, 189 mmol), (4-bromonaphthalen-1-yl)(3-iodophenyl)methanone (82.4 g, 189 mmol) It was obtained the product 94.0 g (yield: 80%) using the Inter1-1 synthesis method.

(2) Core35 synthesis example

Inter1-35 (94.0 g, 151 mmol) and acetic acid (380 mL) and concentrated hydrochloric acid (60 mL) obtained in the above synthesis were used to obtain 55.7 g of the product (yield: 61%) using the Core1 synthesis method.

9. Core38 Synthesis Example

(1) Inter1-38 synthesis example

(2-bromophenyl)(phenyl)sulfane (50.0 g, 189 mmol), n-BuLi (75 mL, 189 mmol), (4-bromonaphthalen-2-yl)(4-iodophenyl)methanone (82.4 g, 189 mmol) To obtain a product 92.9 g (yield: 79%) using the Inter1-1 synthesis method.

(2) Core38 synthesis example

Inter1-38 (92.9 g, 149 mmol) and acetic acid (370 mL) and concentrated hydrochloric acid (60 mL) obtained in the above synthesis were used to obtain 51.4 g of product (yield: 57%) using the Core1 synthesis method.

10. Core42 Synthesis Example

(1) Inter1-42 synthesis example

(2-bromonaphthalen-1-yl)(naphthalen-1-yl)sulfane (50.0 g, 137 mmol), n-BuLi (55 mL, 137 mmol), (3-bromophenyl)(3-iodophenyl)methanone (53.0 g , 137 mmol) using the Inter1-1 synthesis method to obtain 75.6 g (yield: 82%) of the product.

(2) Core42 synthesis example

Inter1-42 (75.6 g, 112 mmol) and acetic acid (280 mL) and concentrated hydrochloric acid (45 mL) obtained in the synthesis were obtained using the Core1 synthesis method to obtain 46.3 g of the product (yield: 63%).

Compounds belonging to the core may be the following compounds, but are not limited thereto, and Table 1 shows the field desorption-mass spectrometry (FD-MS) values of some compounds belonging to the core.

II. Synthesis of Sub 1

Sub 1 of Reaction Scheme 3 may be synthesized by the reaction route of Reaction Scheme 3 (disclosed in Korean Registered Patent No. 10-1251451 of the applicant (published on April 5, 2013)), but is not limited thereto.

Z ¹ is Ar ¹ or Ar ³ , Z ² is Ar ² or Ar ⁴ , and Ar ¹ to Ar ⁴ are the same as defined in Formula 1.

<Scheme 3>

The compounds belonging to Sub 1 may be the following compounds, but are not limited thereto, and Table 2 shows the field desorption-mass spectrometry (FD-MS) values of some compounds belonging to Sub 1.

III. Final product synthesis example

1. 1-1 Synthesis Example

After dissolving Core1 (26.2 g, 44.5 mmol) obtained in the above synthesis in toluene (220 mL) in a round bottom flask, Sub1-1 (15.8 g, 93.4 mmol), Pd ₂ (dba) ₃ (1.22 g, 1.33 mmol) , P( t -Bu) ₃ (0.54 g, 2.67 mmol), NaO t -Bu (8.5 g, 88.9 mmol) was added and stirred at 110°C. After the reaction was completed, the organic layer was extracted with CH ₂ Cl ₂ and water, dried over MgSO ₄ and concentrated, and the resulting compound was silicagel column and recrystallized to obtain 18.5 g of product (yield: 79%).

2. Synthesis Example 1-10

(1) Inter2-10 synthesis example

After dissolving Core5 (23.8 g, 40.4 mmol) obtained in the above synthesis in toluene (200 mL) in a round bottom flask, Sub1-1 (6.8 g, 40.4 mmol), Pd ₂ (dba) ₃ (1.11 g, 1.21 mmol) , P( t -Bu) ₃ (0.49 g, 2.42 mmol), NaO t -Bu (7.8 g, 80.8 mmol) was added and stirred at 50°C. After the reaction was completed, the organic layer was extracted with CH ₂ Cl ₂ and water, dried over MgSO ₄ and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain 18.8 g of product (yield: 74%).

(2) 1-10 Synthesis Example

After dissolving Inter2-10 (18.8 g, 29.9 mmol) obtained in the above synthesis in toluene (150 mL) in a round bottom flask, Sub1-9 (9.6 g, 29.9 mmol), Pd ₂ (dba) ₃ (0.82 g, 0.90) mmol), P( t -Bu) ₃ (0.36 g, 1.79 mmol), NaO t -Bu (5.7 g, 59.8 mmol) was added and stirred at 110 °C. After the reaction was completed, extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain 20.3 g of product (yield: 78%).

3. 1-22 synthesis example

(1) Inter2-22 synthesis example

Core11 (28.0 g, 47.5 mmol), Sub1-7 (15.3 g, 47.5 mmol), Pd ₂ (dba) ₃ (1.31 g, 1.43 mmol), P( t -Bu) ₃ (0.58 g, 2.85 mmol), NaO t- Bu (9.1 g, 95.0 mmol) was obtained using the synthesis method of Inter2-10 above to obtain 27.2 g of product (yield: 73%).

(2) 1-22 synthesis example

Inter2-22 (27.2 g, 34.7 mmol), Sub1-1 (5.9 g, 34.7 mmol), Pd ₂ (dba) ₃ (0.95 g, 1.04 mmol), P( t -Bu) ₃ (0.42 g, 2.08 mmol) , NaO t -Bu (6.7 g, 69.4 mmol) was obtained using the synthesis method of 1-10 above to give 24.5 g of product (yield: 81%).

4. 1-28 synthesis example

(1) Inter2-28 synthesis example

Core14 (32.3 g, 54.8 mmol), Sub1-6 (13.4 g, 54.8 mmol), Pd ₂ (dba) ₃ (1.51 g, 1.64 mmol), P( t -Bu) ₃ (0.67 g, 3.29 mmol), NaO t- Bu (10.5 g, 109.6 mmol) was obtained using the synthesis method of Inter2-10 above to obtain 29.1 g of the product (yield: 75%).

(2) 1-28 synthetic example

Inter2-28 (29.1 g, 41.1 mmol), Sub1-1 (7.0 g, 41.1 mmol), Pd ₂ (dba) ₃ (1.13 g, 1.23 mmol), P( t -Bu) ₃ (0.50 g, 2.47 mmol) , NaO t -Bu (7.9 g, 82.2 mmol) was obtained 23.5 g (yield: 72%) of the product using the synthesis method of 1-10 above.

5. 1-34 Synthesis Example

(1) Inter2-34 synthesis example

Core17 (23.7 g, 37.1 mmol), Sub1-1 (6.2 g, 37.1 mmol), Pd ₂ (dba) ₃ (1.02 g, 1.11 mmol), P( t -Bu) ₃ (0.45 g, 2.22 mmol), NaO t- Bu (7.1 g, 74.1 mmol) was obtained using the synthesis method of Inter2-10, 19.4 g (yield: 77%) of the product.

(2) 1-34 Synthesis Example

Inter2-34 (19.4 g, 28.5 mmol), Sub1-12 (7.7 g, 28.5 mmol), Pd ₂ (dba) ₃ (0.78 g, 0.86 mmol), P( t -Bu) ₃ (0.35 g, 1.71 mmol) , NaO t -Bu (5.5 g, 57.1 mmol) was obtained 18.1 g (yield: 73%) of the product using the synthesis method of 1-10 above.

6. 2-4 Synthesis Example

(1) Inter2-52 synthesis example

Core26 (27.0 g, 44.6 mmol), Sub1-33 (12.7 g, 44.6 mmol), Pd ₂ (dba) ₃ (1.23 g, 1.34 mmol), P( t -Bu) ₃ (0.54 g, 2.68 mmol), NaO t- Bu (8.6 g, 89.2 mmol) was obtained using the synthesis method of Inter2-10 above to obtain 26.9 g of product (yield: 79%).

(2) 2-4 Synthesis Example

Inter2-52 (26.9 g, 35.2 mmol), Sub1-1 (6.0 g, 35.2 mmol), Pd ₂ (dba) ₃ (0.97 g, 1.06 mmol), P( t -Bu) ₃ (0.43 g, 2.11 mmol) , NaO t -Bu (6.8 g, 70.5 mmol) was obtained using the synthesis method of 1-10 above to obtain 22.5 g of product (yield: 75%).

7. 2-14 Synthesis Example

(1) Inter2-62 synthesis example

Core31 (19.4 g, 32.0 mmol), Sub1-10 (7.0 g, 32.0 mmol), Pd ₂ (dba) ₃ (0.88 g, 0.96 mmol), P( t -Bu) ₃ (0.39 g, 1.92 mmol), NaO t- Bu (6.2 g, 64.1 mmol) was obtained using the synthesis method of Inter2-10, 17.0 g (yield: 76%) of the product.

(2) 2-14 Synthesis Example

Inter2-62 (17.0 g, 24.4 mmol), Sub1-11 (5.3 g, 24.4 mmol), Pd ₂ (dba) ₃ (0.67 g, 0.73 mmol), P( t -Bu) ₃ (0.30 g, 1.46 mmol) , NaO t -Bu (4.7 g, 48.7 mmol) was obtained 15.9 g (yield: 78%) of the product using the synthesis method of 1-10 above.

8. 2-22 Synthesis Example

(1) Inter2-70 synthesis example

Core35 (27.9 g, 46.1 mmol), Sub1-7 (14.8 g, 46.1 mmol), Pd ₂ (dba) ₃ (1.27 g, 1.38 mmol), P( t -Bu) ₃ (0.56 g, 2.77 mmol), NaO t- Bu (8.9 g, 92.2 mmol) was obtained using the synthesis method of Inter2-10 above to obtain 26.5 g of product (yield: 72%).

(2) 2-22 synthetic example

Inter2-70 (26.5 g, 33.2 mmol), Sub1-1 (5.6 g, 33.2 mmol), Pd ₂ (dba) ₃ (0.91 g, 1.00 mmol), P( t -Bu) ₃ (0.40 g, 1.99 mmol) , NaO t -Bu (6.4 g, 66.4 mmol) was obtained using the synthesis method of 1-10 above to obtain 22.7 g of product (yield: 77%).

9. 2-27 Synthesis Example

(1) Inter2-75 synthesis example

Core38 (25.7 g, 42.5 mmol), Sub1-1 (7.2 g, 42.5 mmol), Pd ₂ (dba) ₃ (1.17 g, 1.27 mmol), P( t -Bu) ₃ (0.52 g, 2.55 mmol), NaO t- Bu (8.2 g, 84.9 mmol) was obtained using the synthesis method of Inter2-10 above to give 22.8 g of product (yield: 83%).

(2) 2-27 synthetic example

Inter2-75 (22.8 g, 35.2 mmol), Sub1-4 (8.6 g, 35.2 mmol), Pd ₂ (dba) ₃ (0.97 g, 1.06 mmol), P( t -Bu) ₃ (0.43 g, 2.11 mmol) , NaO t -Bu (6.8 g, 70.5 mmol) was obtained 20.3 g (yield: 71%) of the product using the synthesis method of 1-10 above.

10. 2-35 Synthesis Example

(1) Inter2-83 synthesis example

Core42 (23.2 g, 35.4 mmol), Sub1-10 (7.8 g, 35.4 mmol), Pd ₂ (dba) ₃ (0.97 g, 1.06 mmol), P( t -Bu) ₃ (0.43 g, 2.12 mmol), NaO t- Bu (6.8 g, 70.8 mmol) was obtained using the synthesis method of Inter2-10 above to obtain 18.8 g (yield: 71%) of the product.

(2) 2-35 synthetic example

Inter2-83 (18.8 g, 25.1 mmol), Sub1-11 (5.5 g, 25.1 mmol), Pd ₂ (dba) ₃ (0.69 g, 0.75 mmol), P( t -Bu) ₃ (0.31 g, 1.51 mmol) , NaO t -Bu (4.8 g, 50.3 mmol) was obtained using the synthesis method of 1-10 above to obtain 16.0 g of product (yield: 72%).

Meanwhile, FD-MS values of the compounds 1-1 to 1-52 and the compounds 2-1 to 2-52 of the present invention prepared according to the above synthesis examples are shown in Table 3 below.

The synthesis example is for some exemplary compounds of the compounds represented by Formula 1, the reaction is BuchwaldHartwig cross coupling reaction, Suzuki cross-coupling reaction, Miyaura borylation reaction, Suzuki cross-coupling reaction, Intramolecular acid-induced cyclization reaction (J. mater. Chem. 1999, 9, 2095.), Pd(II)-catalyzed oxidative cyclization reaction (Org. Lett. 2011, 13, 5504) and PPh3-mediated reductive cyclization reaction (J. Org. Chem. 2005 , 70, 5014.), Lithium-halogen exchange reaction, Grignard reaction and Cyclic Dehydration reaction. Those skilled in the art will readily understand that the reaction proceeds even if other substituents defined in Chemical Formula 1 are combined in addition to the substituents specified in the specific synthetic examples.

Manufacturing evaluation of organic electric devices

[Example 1] Red organic electric device (light emitting auxiliary layer)

An organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention as a light-emitting auxiliary layer material. First, N1-(naphthalen-2-yl)-N4,N4-bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N1 as a hole injection layer first on an ITO layer (anode) formed on a glass substrate -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) film was vacuum deposited to form a thickness of 60 nm. Subsequently, 4,4-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (hereinafter abbreviated as -NPD) as a hole transport compound on this film was vacuum-deposited to a thickness of 60 nm to form a hole transport layer. Formed. Subsequently, the light-emitting auxiliary layer was formed by vacuum-depositing the compound 1-1 of the invention to a thickness of 20 nm as the light-emitting auxiliary layer material. After forming the light-emitting auxiliary layer, CBP[4,4'-N,N'-dicarbazole-biphenyl] as the host and (piq)2Ir(acac) [bis-(1-phenyl isoquinolyl) as the dopant on the top of the light-emitting auxiliary layer )iridium(III)acetylacetonate] was deposited at a weight of 95:5 to deposit a 30 nm thick light emitting layer on the light emitting auxiliary layer. As the hole blocking layer, (1,1'-bisphenyl)-4-oleito)bis(2-methyl-8-quinolineoleito)aluminum (hereinafter abbreviated as BAlq) is vacuum deposited to a thickness of 10 nm, and the electron transport layer Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was deposited to a thickness of 40 nm. Thereafter, an organic electroluminescent device was manufactured by depositing LiF, a halogenated alkali metal, as an electron injection layer to a thickness of 0.2 nm, and then depositing Al to a thickness of 150 nm to use as a cathode.

[Example 2] to [Example 20]

The same method as in Example 1, except that Compounds 1-3 to 1-48, 2-2 to 2-48 of the present invention described in Table 4 below were used instead of Compound 1-1 of the present invention as a light-emitting auxiliary layer material. An organic electroluminescent device was produced.

[Comparative Example 1]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the auxiliary light emitting layer was not used.

[Comparative Example 2] to [Comparative Example 4]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compounds A to D were used as the light-emitting auxiliary layer material.

[Comparative Compound A] [Comparative Compound B] [Comparative Compound C] [Comparative Compound D]

The electroluminescence (EL) characteristics were measured by the PR-650 of photoresearch by applying a direct bias DC voltage to the organic electroluminescent elements of the examples and comparative examples prepared as described above, and the measurement result showed the luminance at the standard of 2500 cd/m2. T95 life was measured by a life measurement equipment manufactured by Max Science. Table 4 below shows the results of device fabrication and evaluation.

As can be seen from the results of Table 4, when a red organic electroluminescent device was produced using the material for an organic electroluminescent device of the present invention as a light-emitting auxiliary layer material, a light-emitting auxiliary layer was not used or Comparative Compounds A to Comparative Compounds It is possible to significantly improve the luminous efficiency and lifetime of the organic electroluminescent device than the comparative example using D.

In other words, the results of Comparative Examples 2 to 5 using Comparative Compounds A to D were superior to Comparative Example 1 without using the light-emitting auxiliary layer, similar to Comparative Compound A, but the benzene ring in the xanthene linker Examples 1 to 20 of the compound of the present invention to be fused showed remarkably excellent results in efficiency and life.

This is because the HOMO or LUMO energy level of the compound of the present invention has an appropriate value between the hole transport layer and the light emitting layer, and thus the holes and electrons form a charge balance, and light emission occurs inside the light emitting layer rather than the hole transport layer interface. It is judged that efficiency and lifetime are maximized.

Table 5 below shows the HOMO, LUMO and Eg values of Comparative Compounds A and B and Compound 1-2 of the present invention.

Referring to Table 5, Comparative Compound A has one more amine substituted compared to Comparative Compound B, and as such, the substitution of one more amine reduces HOMO and increases LUMO. In addition, Compound 1-2 of the present invention has one more ring formed on the core compared to Comparative Compound A, and as a result, one more ring is formed, and thus LUMO is lowered and the band gap tends to decrease.

That is, if this change in the parent nucleus plays a decisive role in the difference in physical properties of the compound, this suggests that a result that can not be inferred by a person skilled in the art can be derived.

Furthermore, In the case of the light-emitting auxiliary layer, the relationship between the hole transport layer and the light-emitting layer (host) needs to be understood. It will be very difficult.

In addition, in the evaluation results of the above-described device fabrication, the device characteristics in which the compound of the present invention is applied only to the light-emitting auxiliary layer were described, but the compound of the present invention can be applied to the hole transport layer or both the hole transport layer and the light-emitting auxiliary layer.

The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains will be capable of various modifications without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed herein are not intended to limit the present invention, but to explain the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The scope of protection of the present invention should be interpreted by the claims below, and all technologies within the scope equivalent thereto should be interpreted as being included in the scope of the present invention. The scope of protection of the present invention should be interpreted by the claims below, and all technologies within the scope equivalent thereto should be interpreted as being included in the scope of the present invention.

100, 200, 300: organic electric device
110, 120, 320: first electrode
130, 230, 330: hole injection layer
331: 1st hole injection layer
140, 240, 340: hole transport layer
341: first hole transport layer
342: second hole transport layer
243: buffer layer
150, 250: light emitting layer
351: first light emitting layer
352: second light emitting layer
253: auxiliary light emitting layer
160: electron transport layer
361: first electron transport layer
362: second electron transport layer
170, 370: electron injection layer
180, 280, 380: second electrode
390: first charge generating layer
391: second charge generating layer
ST1: First stack ST2: Second stack
CGL: charge generating layer
400: electronic device
410: display device
420: control unit
430: organic electric device

Claims (12)

Compound represented by the formula (1):
[Formula 1]

1) Rings A to D are each independently a C ₆ to C ₆₀ aryl group or C ₂ to C ₆₀ heterocyclic group, and at least one of A to D rings is a C ₁₀ to C ₆₀ aryl group, or Heterocyclic group of C ₁₀ ~ C ₆₀ ,
2) The A ring may be substituted by R ¹ , the B ring may be substituted by R ² , the C ring may be substituted by R ³ , and the D ring may be substituted by R ⁴ ,
3) R ¹ to R ⁴ are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Nitro group; C ₆ ~ C ₆₀ Aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; And C ₆ ~ C _{30 It} is selected from an aryloxy group,
4) X is O, S, NR', CR'R'' or SiR'R'',
5) R'and R'' are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; And C ₆ ~ C _{30 It} is selected from an aryloxy group,
6) L ¹ and L ² are each independently a single bond; C ₆ ~ C ₆₀ Aryl group; C ₃ ~ C ₆₀ aliphatic ring group; And C ₂ ~ C ₆₀ Heterocyclic group containing at least one heteroatom of O, N, S, Si and P,
7) Ar ¹ to Ar ⁴ are each independently C ₆ to C ₆₀ aryl groups; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; And C ₆ ~ C _{30 It} is selected from an aryloxy group,
8) In the R ¹ to R ⁴ , L ¹ , L ² and Ar ¹ to Ar ⁴ , the aryl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group and aryloxy group, respectively heavy hydrogen; Nitro group; Nitrile group; Halogen group; Amino group; A silane group unsubstituted or substituted with an alkyl group of C ₁ to C ₂₀ or an aryl group of C ₆ to C ₂₀ ; Siloxane groups; C ₁ ~ C ₂₀ alkylthio; C ₁ ~ C ₂₀ Alkoxy group; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₆ ~ C ₂₀ aryl group; C ₆ ~ C ₂₀ aryl group substituted with deuterium; C ₂ ~ C ₂₀ heterocyclic group; C ₃ ~ C ₂₀ cycloalkyl group; One or more substituents selected from the group consisting of C ₇ to C ₂₀ arylalkyl groups and C ₈ to C ₂₀ arylalkenyl groups may be substituted, and these substituents may combine with each other to form a ring. According to claim 1,
Compounds characterized in that at least one of the A ring and the B ring in Formula 1 is independently selected from the following Formulas a-1 to a-7:
Formula a-1 Formula a-2

Formula a-3 Formula a-4

Formula a-5 Formula a-6

Formula a-7

In Chemical Formulas a-1 to a-7,
* Represents the position where each of the formulas a-1 to a-7 is condensed,
Z ¹ to Z ⁴⁸ are, each independently, CR is ^a or N, Z ¹ to Z ⁴⁸ when any one of the N of the N of Z ¹ to Z ¹ to Z ⁴⁸ that is a direct bond and Z ⁴⁸ is CR ^a ego,
The R ^a is the same as the R ¹ defined in claim ¹ . According to claim 1,
Compounds characterized in that at least one of the C ring and D ring in the formula (1) is independently selected from the following formulas b-1 to b-7:
Formula b-1 Formula b-2 Formula b-3

Formula b-4 Formula b-5 Formula b-6 Formula b-7

In Formulas b-1 to b-7,
One of *2 and *3 is bonded to the carbon bonded to the A ring and the B ring, the other to the L ¹ or L ² ,
Z ⁴⁹ to Z ⁸⁴ are CR ^b or N, and when any one of Z ⁴⁹ to Z ⁸⁴ is N, Z ⁴⁹ to Z ⁸⁴ directly bonding to the N Z ⁴⁹ to Z ⁸⁴ is CR ^b ,
The R ^b is the same as the R ¹ defined in claim ¹ . The compound of claim 1, wherein the compound represented by Formula 1 is represented by Formula 2 or Formula 3 below:
[Formula 2] [Formula 3]

In Formula 2 and Formula 3,
Rings A to D, Ar ¹ to Ar ⁴ , L ¹ and L ² are the same as defined in claim 1. The compound of claim 1, wherein the compound represented by Formula 1 is represented by Formula 4 or Formula 5 below:
[Formula 4] [Formula 5]

In Chemical Formulas 4 and 5,
n, m, o and p are integers from 0 to 4,
X, A ring, C ring and Ar ¹ to Ar ⁴ , R ¹ to R ⁴ are the same as defined in claim 1. The compound of claim 1, wherein the compound represented by Formula 1 is represented by any one of the following Formulas 6 to 13:
[Formula 6] [Formula 7]

[Formula 8] [Formula 9]

[Formula 10] [Formula 11]

[Formula 12] [Formula 13]

In Chemical Formulas 6 to 13,
X, Ar ¹ to Ar ⁴ , R ¹ to R ⁴ , L ¹ and L ² are the same as defined in claim 1,
q, u, w and y are integers from 0 to 6,
r, s, t and v are integers from 0 to 4. According to claim 1,
The compound represented by Chemical Formula 1 is one of the following compounds.

A first electrode; A second electrode; And an organic material layer positioned between the first electrode and the second electrode, wherein the organic electric device comprises:
The organic material layer is an organic electrical device containing the compound of any one of claims 1 to 7. The method of claim 8,
The organic material layer includes at least one layer of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer,
The compound is a single compound of any one of claims 1 to 6 in at least one of the hole injection layer, hole transport layer, light-emitting auxiliary layer, light-emitting layer, electron transport auxiliary layer, electron transport layer and electron injection layer Or an organic electric device characterized in that it is included as a mixture of two or more compounds. The method of claim 8,
The organic layer is formed by at least one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process. A display device comprising the organic electroluminescent element of claim 8; And
An electronic device comprising a control unit for controlling the display device. The method of claim 8,
The organic electric element is an electronic device that is one of an organic electroluminescent element, an organic solar cell, an organic photoreceptor, an organic transistor and an element for monochromatic or white lighting.

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