WO2018159961A1 - Compound for organic electric element, organic electric element using same, and electronic device - Google Patents

Abstract

Disclosed are: a compound represented by chemical formula 1; an organic electric element comprising a first electrode, a second electrode, and an organic material layer between the first and second electrodes; and an electronic device comprising the same, wherein the compound represented by chemical formula 1 is contained in the organic material layer, so that the driving voltage of the organic electric element can be lowered and the light emission efficiency and service life of the organic electric element can be improved.

Description

Compound for organic electric element, organic electric element using same and electronic device thereof

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

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material.

An organic electric element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. In this case, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

The material used as the organic material layer in the organic electric element may be classified into a light emitting material and a charge transport material such as a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function.

Polycyclic cyclic compounds containing heteroatoms are applied to various layers as materials of organic electric devices due to the large difference in characteristics depending on the material structure. In particular, the band gaps (HOMO, LUMO), electrical properties, chemical properties, and physical properties are different depending on the number of rings (rings), fused positions (bonding positions), heteroatoms, and arrangements. Applications and developments in layers of electrical devices have been in progress.

In addition, until now, the development of materials for organic electric devices for the type, number, and position of hetero atoms in a 5-ring cyclic compound has been actively progressed, and examples thereof include US 5843607, KR 1523124, KR 2008-7016107, KR 1346467, and the like. Can be mentioned. The prior patent discloses an embodiment in which a 5-ring cyclic compound is applied to a hole transport layer or a light emitting layer (host) of an organic electric device.

Since the invention of the US Pat. No. 5843607 and KR 2008-7016107, the heteroatomic species in the 5-membered cyclic compound consists only of nitrogen (N), has been a benzobisbenzofuran core consisting of only oxygen (O). A KR 1523124 patent has been disclosed, and an indenofluorene core composed only of carbon (C) atoms in the 5-membered ring compound has been disclosed in the KR 1346467 patent.

After the development of the 5-membered cyclic compound of the isotype atomic type as described above, the development of the 5-membered ring compound for the heteroatomic type was made. And attempts to overcome low oxidative stability.

In general, when molecules are stacked, there is a strong electrical interaction with more adjacent π-electrons, which is closely related to charge carrier mobility.

In other words, NN type homocyclic cyclic compounds have an edge-to-face arrangement when molecules are stacked, whereas heterocyclic cyclic compounds having heteroatoms with different heteroatoms have a packing structure of molecules. The antiparallelcofacial π-stacking structure faces in the opposite direction, resulting in a face-to-face arrangement of molecules. Asymmetrically arranged heteroatoms N which are responsible for this lamination structure The steric effect of the substituents being substituted results in relatively high carrier mobility and high oxidative stability ( Org . Lett . 2008, 10, 1199).

Despite these advantages described above, the development of a stable and efficient organic material layer for an organic electric device has not been made yet. Therefore, the development of new materials is continuously required, and in particular, the development of the host material and the hole transport layer material of the light emitting layer is urgently required.

The present invention has been proposed to solve the conventional problems as described above, and the present inventors have continued to study to increase the packing density in the polycyclic compound, the core (hexacyclic heterocyclic ring containing phenanthrene structure) hetero An object of the present invention is to provide a compound capable of improving the efficiency and lifespan of a device by changing the type and substitution positions of atoms, an organic electric device using the same, and an electronic device thereof.

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

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

According to the present invention, by introducing a core (six-membered heterocyclic ring containing a phenanthrene structure) to increase the packing density, and using a specific compound that limits the type and number of heteroatoms, etc. as a material of the organic electric element, high thermal It shows stability, high carrier mobility and high oxidative stability, and has a T1 value and an energy band gap which is easy to balance charge in the light emitting layer, thereby improving luminous efficiency, heat resistance, lifespan, etc. Can be.

1 is an exemplary view of an organic electroluminescent device according to the present invention.

[Description of the code]

100: organic electric element 110: substrate

120: first electrode 130: hole injection layer

140: hole transport layer 141: buffer layer

150: light emitting layer 151: light emitting auxiliary layer

160: electron transport layer 170: electron injection layer

180: second electrode

Hereinafter, exemplary 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 reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In addition, in describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

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

In addition, 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 "on top of" but also another component in between. It is to be understood that this may also include cases. On the contrary, when a component is said to be "directly above" another part, it should be understood to mean that there is no other part in the middle.

As used in this specification and the appended claims, unless otherwise indicated, the meanings of the following terms are as follows.

The term "halo" or "halogen" as used herein is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I) unless otherwise indicated.

As used herein, the term "alkyl" or "alkyl group" has a single bond of 1 to 60 carbon atoms, unless otherwise indicated, and is a straight chain alkyl group, branched chain alkyl group, cycloalkyl (alicyclic) group, alkyl-substituted cyclo Radicals of saturated aliphatic functional groups, including alkyl 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 term "alkenyl group" or "alkynyl group", unless stated otherwise, has a double or triple bond of 2 to 60 carbon atoms, and includes a straight or branched chain group, and is not limited thereto. It is not.

The term "cycloalkyl" as used herein, unless otherwise stated, refers to alkyl forming a ring having 3 to 60 carbon atoms, without being limited thereto.

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

As used herein, the term "aryloxyl group" or "aryloxy group" means an aryl group to which an oxygen radical is attached, and unless otherwise specified, has a carbon number of 6 to 60, but is not limited thereto.

As used herein, the term "fluorenyl group" or "fluorenylene group" means a monovalent or divalent functional group in which R, R 'and R "are all hydrogen in the following structures, unless otherwise stated, and" Substituted fluorenyl group "or" substituted fluorenylene group "means that at least one of the substituents R, R ', and R" is a substituent other than hydrogen, and R and R' are bonded to each other to form a carbon It includes the case of forming a compound by spying together.

As used herein, the terms "aryl group" and "arylene group" have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto. In the present invention, the aryl group or arylene group includes monocyclic, ring aggregate, conjugated ring system, spiro compound and the like.

As used herein, the term "heterocyclic group" includes not only aromatic rings, such as "heteroaryl groups" or "heteroarylene groups," but also non-aromatic rings, and each carbon number includes one or more heteroatoms unless otherwise specified. It means a ring of 2 to 60, but is not limited thereto. As used herein, the term “heteroatom” refers to N, O, S, P or Si unless otherwise indicated, and heterocyclic groups are monocyclic, ring aggregates, conjugated multiple ring systems, spies, including heteroatoms. Means a compound or the like.

"Heterocyclic groups" may also include rings comprising SO ₂ in place of the carbon forming the ring. For example, a "heterocyclic group" includes the following compounds.

As used herein, the term “ring” includes monocyclic and polycyclic rings, includes hydrocarbon rings as well as heterocycles including at least one heteroatom, and includes aromatic and nonaromatic rings.

As used herein, the term "polycyclic" includes ring assemblies, fused multiple ring systems and spiro compounds, such as biphenyl, terphenyl, and the like, including aromatics as well as nonaromatics, hydrocarbons The ring as well includes heterocycles comprising at least one heteroatom.

As used herein, the term "ring assemblies" means that two or more ring systems (single or conjugated ring systems) are directly connected to each other through a single bond or a double bond and directly between such rings. It 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 directly connected to each other via a single bond or a double bond.

As used herein, the term "conjugated multiple ring systems" refers to a covalently fused ring form of at least two atoms, including a ring system in which two or more hydrocarbons are fused together and at least one heteroatom. And heterocyclic systems having at least one conjugated form. These conjugated several ring systems can be aromatic rings, heteroaromatic rings, aliphatic rings or combinations of these rings.

As used herein, the term "spiro compound" has a "spiro union", and a spiro linkage means a linkage formed by two rings sharing one atom only. In this case, the atoms shared by the two rings are called spiro atoms, and according to the number of spiro atoms in a compound, they are respectively referred to as 'monospyro-', 'diespyro-' and 'trispyro-' It is called a compound.

Also, when prefixes are named consecutively, it means that the substituents are listed in the order described first. For example, an arylalkoxy group means an alkoxy group substituted with an aryl group, an alkoxycarbonyl group means a carbonyl group substituted with an alkoxy group, and in the case of an arylcarbonylalkenyl group, an alkenyl group substituted with an arylcarbonyl group is used herein. The arylcarbonyl group is a carbonyl group substituted with an aryl group.

Also, unless expressly stated, the term "substituted" in the term "substituted or unsubstituted" refers to deuterium, halogen, amino groups, nitrile groups, nitro groups, C ₁ -C ₂₀ alkyl groups, 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 Substituted by at least one substituent selected from the group consisting of a group, a germanium group, and a C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P It is not limited to these substituents.

The group name corresponding to the aryl group, arylene group, heterocyclic group, etc. exemplified in each symbol and examples of the substituents in this specification may describe 'the name of the group reflecting the singer', but is described as 'the parent compound name'. You may. For example, in the case of phenanthrene, which is a kind of aryl group, the monovalent group is phenanthryl and the divalent group may be grouped with a singer, such as phenanthryl, to describe the group name. Regardless, it may be described as the parent compound name 'phenanthrene'. Similarly, in the case of pyrimidine, it may be described as 'pyrimidine' irrespective of the valence, or as the 'name of the group' of the singer, such as pyrimidinyl group in the case of monovalent and pyrimidinylene in the case of divalent. have.

In addition, unless otherwise stated, the formulas used in the present invention apply equally to the substituent definitions based on the exponential definitions of the following formulas.

Herein, when a is an integer of 0, the substituent R ¹ is absent, that is, when a is 0, it means that all of the carbons forming the benzene ring are bonded to hydrogen. Omitted formulas and compounds may be omitted. In addition, when a is an integer of 1, one substituent R ¹ is bonded to any one of carbons forming a benzene ring, and when a is an integer of 2 or 3, for example, a is 4 to 6 In the case of an integer of, it is bonded to the carbon of the benzene ring in a similar manner, and when a is an integer of 2 or more, R ¹ may be the same as or different from each other.

1 is an exemplary view of an organic electric device according to an embodiment of the present invention.

Referring to FIG. 1, an organic electric device 100 according to an embodiment of the present invention may include a first electrode 120, a second electrode 180, and a first electrode 120 formed on a substrate 110. An organic material layer including the compound according to the present invention is provided between the two electrodes 180. 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 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 on the first electrode 120 in sequence. In this case, at least one of these layers may be omitted, or may further include a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, an electron transport auxiliary layer (not shown), a buffer layer 141, or the like. 160) may serve as a hole blocking layer.

In addition, although not shown, the organic electronic device according to an embodiment of the present invention further includes a protective layer or a light efficiency improving layer formed on one surface of the at least one surface of the first electrode and the second electrode opposite to the organic material layer. can do.

Compound according to an embodiment of the present invention applied to the organic layer is a hole injection layer 130, a hole transport layer 140, a light emitting auxiliary layer 151, an electron transport auxiliary layer, an electron transport layer 160, an electron injection layer ( 170, a host or dopant material of the light emitting layer 150, or a material of the light efficiency improving layer. For example, the compound of the present invention may be used as the light emitting layer 150, the hole transport layer 140 and / or the light emitting auxiliary layer 151 material, preferably as a host material of the light emitting layer 150.

Meanwhile, even in the same core, band gaps, electrical characteristics, and interface characteristics may vary depending on which substituents are bonded at which positions. Therefore, the selection of the cores and the combination of sub-substituents bonded thereto may be performed. In particular, long life and high efficiency can be simultaneously achieved when an optimal combination of energy level and T ₁ value and intrinsic properties (mobility, interfacial properties, etc.) between organic layers is achieved.

Therefore, in the present invention, by forming the light emitting layer 150 using the compound represented by the formula (1) by optimizing the energy level and T ₁ value between each organic material layer, the intrinsic properties (mobility, interfacial characteristics, etc.) of the organic organic device Can improve the service life and efficiency at the same time.

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using various deposition methods. It may be manufactured using a deposition method such as PVD or CVD. For example, the anode 120 is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate, and the hole injection layer 130 thereon. , By forming an organic material layer including a hole transport layer 140, a light emitting layer 150, an electron transport layer 160 and an electron injection layer 170, and then depositing a material that can be used as the cathode 180 thereon have. In addition, the light emitting auxiliary layer 151 may be further formed between the hole transport layer 140 and the light emitting layer 150, and an electron transport auxiliary layer may be further formed between the light emitting layer 150 and the electron transport layer 160.

In addition, the organic material layer is a solution or 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 in fewer layers by methods such as ding process, screen printing process, or thermal transfer method. Since the organic material layer according to the present invention may be formed in various ways, the scope of the present invention is not limited by the forming method.

The organic electric element according to an embodiment of the present invention may be a top emission type, a bottom emission type or a double-sided emission type according to the material used.

WOLED (White Organic Light Emitting Device) has the advantage that can be manufactured using the color filter technology of the existing LCD while being easy to realize high resolution and excellent processability. Various structures for white organic light emitting devices mainly used as backlight devices have been proposed and patented. Representatively, a side-by-side method in which R (Red), G (Green), and B (Blue) light emitting parts are mutually planarized, and a stacking method in which R, G, and B light emitting layers are stacked up and down. And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light therefrom. May also be applied to these WOLEDs.

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

Another embodiment of the present invention may include a display device including the organic electric element of the present invention described above, and an electronic device including a control unit for controlling the display device. In this case, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.

Hereinafter, the compound which concerns on one aspect of this invention is demonstrated.

Compound according to an aspect of the present invention is represented by the following formula (1).

<Formula 1>

In Formula 1, each symbol is defined as follows.

A ring is an aromatic ring of C ₆ . For example, the A ring may be a benzene ring.

X is selected from the group consisting of S, O and C (R ') (R ").

Ar ¹ is an aryl group of C ₆ -C ₆₀ ; Fluorenyl group; C ₂ -C ₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ -C ₆₀ and an aromatic ring of C ₆ -C ₆₀ ; An alkyl group of C ₁ -C ₅₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; -L ^a -N (R ^a ) (R ^b ); An alkoxyl group of C ₁ -C ₃₀ ; And it may be selected from the group consisting of C ₆ -C ₃₀ aryloxy group.

When Ar ¹ is an aryl group, it is preferably a C ₆ -C ₃₀ aryl group, more preferably a C ₆ -C ₁₈ aryl group, specifically phenyl, biphenyl, naphthyl, fluoranthene, phenanthrene, Triphenylene, pyrene and the like. When Ar ¹ is a heterocyclic group, preferably a heterocyclic group of C ₂ -C ₃₀ , more preferably a heterocyclic group of C ₂ -C ₁₈ , specifically imidazole, pyridine, pyrimidine, triazine, quina Sleepy, benzoquinazoline, dibenzoquinazoline, quinoxaline, isoquinoline, pyridopyrimidine, pyridoindole, carbazole, indolocarbazole, dibenzofuran, benzothienopyridine, benzothienopyrimidine , Benzofuropyrimidine, dimethylbenzoindenopyrimidine, phenanthropuropyrimidine, naphthopuropyrimidine, naphthothiopyrimidine, dibenzothiophene, thianthrene and the like. When Ar ¹ is a fluorenyl group, it may be 9,9-dimethyl-9H-fluorene, 9,9'-spirobifluorene, or the like. If the Ar ¹ is an alkenyl group, this preferably is the case of the number of days, such as C ₂ -C ₁₀ alkene group, more preferably a C ₂ -C ₅ alkenyl, in particular ethenyl, and, Ar ¹ is a halogen, such as F Can be.

R ¹ to R ³ are each independently of deuterium; Tritium; halogen; Cyano group; Nitro group; C ₆ -C ₆₀ aryl group; Fluorenyl group; C ₂ -C ₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ -C ₆₀ and an aromatic ring of C ₆ -C ₆₀ ; An alkyl group of C ₁ -C ₅₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; -L ^a -N (R ^a ) (R ^b ); An alkoxyl group of C ₁ -C ₃₀ ; And C ₆ -C ₃₀ It may be selected from the group consisting of an aryloxy group, adjacent groups may be bonded to each other to form a ring.

When R ¹ to R ³ are aryl groups, preferably C ₆ -C ₃₀ aryl groups, more preferably C ₆ -C ₁₈ aryl groups, specifically phenyl, biphenyl, naphthyl, benzophenanthrene and the like This can be When R ¹ to R ³ are heterocyclic groups, preferably C ₂ -C ₃₀ heterocyclic group, more preferably C ₂ -C ₁₆ heterocyclic group, specifically imidazole, pyridine, pyrimidine, tri Azine, quinazoline, benzoquinazolin, dibenzoquinazolin, quinoxaline, isoquinoline, pyridopyrimidine, pyridoindole, carbazole and the like.

a is an integer of 0-4, b is an integer of 0 or 1, and c is an integer of 0-5. When a and c are each an integer of 2 or more, a plurality of R ¹ may be the same or different from each other, a plurality of R ² may be the same or different from each other, and adjacent R ¹ and / or neighboring R ^{3 may be} mutually different. Can be joined to form a ring. The ring formed by combining adjacent groups with each other may be an aromatic ring or a hetero ring, preferably an aromatic ring of C ₆ -C ₃₀ or a hetero ring of C ₂ -C ₃₀ , for example, a benzene ring, naphthalene, or the like. This can be

L ¹ and L ^a are each independently a single bond; C ₆ -C ₆₀ arylene group; Fluorenylene groups; C ₂ -C ₆₀ heterocyclic group including at least one hetero atom selected from the group consisting of O, N, S, Si and P; And a fused ring group of C ₃ -C ₆₀ aliphatic ring and C ₆ -C ₆₀ aromatic ring.

When L ¹ and L ^a are an arylene group, preferably an arylene group of C ₆ -C ₃₀ , more preferably an arylene group of C ₆ -C ₁₂ , and specifically, may be phenyl, biphenyl, naphthyl, or the like. have. When L ¹ and L ^a are heterocyclic groups, preferably C ₂ -C ₃₀ heterocyclic group, more preferably C ₂ -C ₁₆ heterocyclic group, specifically imidazole, pyrimidine, triazine, Quinazolin, benzoquinazolin, dibenzoquinazolin, quinoxaline, isoquinoline, carbazole, pyridoindole, dibenzofuran, pyridopyrimidine, benzothienopyridine, benzothienopyrimidine, naphthocydine Enopyrimidine, benzofuropyrimidine, naphthopurypyrimidine, phenanthropuropyrimidine, dimethylbenzoindenopyrimidine and the like.

R ', R ", R ^a and R ^b independently of each other C ₆ -C ₆₀ aryl group; Fluorenyl group; O, N, S, Si and P containing at least one heteroatom selected from the group consisting of A heterocyclic group of C ₂ -C ₆₀ , a fused ring group of an aliphatic ring of C ₃ -C ₆₀ and an aromatic ring of C ₆ -C ₆₀ , an alkyl group of C ₁ -C ₅₀ , an alkenyl group of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; an alkoxyl group of C ₁ -C ₃₀ ; and an aryloxy group of C ₆ -C _30. R ′ and R ″ may be bonded to each other to form a ring. When R 'and R "combine with each other to form a ring, a spiro compound is formed.

A ring, a ring formed by bonding of adjacent groups of R ¹ to R ^{3 with} each other, R ′ and R ″ ring formed by bonding with each other, Ar ¹ , R ¹ to R ³ , L ¹ , L ^a , R ', R ", R ^a and R ^b are each deuterium; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C ₁ -C _20; An alkoxyl group of C ₁ -C ₂₀ ; An alkyl group of C ₁ -C ₂₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; Aryl group of C ₆ -C ₂₀ ; C ₆ -C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A cycloalkyl group of C ₃ -C ₂₀ ; C ₇ -C ₂₀ arylalkyl group; Arylalkenyl group of C ₈ -C ₂₀ ; And one or more substituents selected from the group consisting of a combination thereof.

Preferably, Formula 1 may be represented by one of the following Formula 2 to Formula 13.

   <Formula 2> <Formula 3> <Formula 4> <Formula 5>

   <Formula 6> <Formula 7> <Formula 8> <Formula 9>

   <Formula 10> <Formula 11> <Formula 12> <Formula 13>

In Formulas 2 to 13, symbols such as Ar ¹ , L ¹ , R ¹ to R ³ , R ′, R ″, a, b, and c may be defined as defined in Formula 1.

Preferably, in Formula 1 to Formula 13, Ar ¹ may be represented by the following Formula A-1 or A-2.

<Formula A-1> <Formula A-2>

In Formula A-1, the Z ring is C ₆ -C ₆₀ monocyclic or polycyclic aromatic ring; Or a C ₂ -C ₆₀ heterocyclic group including at least one hetero atom selected from the group consisting of O, N, S, Si, and P.

In Chemical Formula A-1, Q ¹ to Q ⁴ may be N, C (R ^c ) or C independently of each other, provided that they are C when combined with L ¹ .

In Formula A-2, Q ⁵ to Q ⁹ are each independently N or C (R ^c ).

R ^c is hydrogen; heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C ₁ -C _20; An alkoxyl group of C ₁ -C ₂₀ ; An alkyl group of C ₁ -C ₂₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; Aryl group of C ₆ -C ₂₀ ; C ₆ -C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A cycloalkyl group of C ₃ -C ₂₀ ; C ₇ -C ₂₀ arylalkyl group; Arylalkenyl group of C ₈ -C ₂₀ ; And selected from the group consisting of a combination thereof, adjacent R ^c may be bonded to each other to form a ring. The ring formed by bonding of adjacent R ^{c to} each other may be an aromatic ring or a hetero ring, and preferably an aromatic ring of C ₆ -C ₂₀ or a hetero ring of C ₂ -C ₂₀ .

Preferably, in Formula A-1, the Z ring may be represented by one of the following Formulas Z-1 to Z-15.

<Formula Z-1> <Formula Z-2> <Formula Z-3> <Formula Z-4> <Formula Z-5>

<Formula Z-6> <Formula Z-7> <Formula Z-8> <Formula Z-9> <Formula Z-10>

<Formula Z-11> <Formula Z-12> <Formula Z-13> <Formula Z-14> <Formula Z-15>

In Chemical Formulas Z-1 to Z-15, the mark (*) represents a site which binds to a ring including Q ¹ to Q ⁴ , and W ¹ and W ² independently of each other are a single bond, NL ² -Ar ² , S, O or C (R ^d ) (R ^e ), and V are independently of each other N or C (R ^f ).

L ² is a single bond; C ₆ -C ₂₀ arylene group; C ₆ -C ₂₀ arylene group substituted with deuterium; Fluorenylene groups; C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; And it may be selected from the group consisting of C ₃ -C ₂₀ cycloalkyl group.

Ar ² , R ^d , R ^e and R ^f are each independently hydrogen, deuterium; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C ₁ -C _20; An alkoxyl group of C ₁ -C ₂₀ ; An alkyl group of C ₁ -C ₂₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; Aryl group of C ₆ -C ₂₀ ; C ₆ -C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A cycloalkyl group of C ₃ -C ₂₀ ; C ₇ -C ₂₀ arylalkyl group; Arylalkenyl group of C ₈ -C ₂₀ ; And a combination thereof, R ^d and R ^e may be bonded to each other to form a ring, and neighboring R ^{f may} also be bonded to each other to form a ring.

In Formula A-1, at least one of Q ¹ to Q ⁴ is preferably N, and at least one structure containing N (nitrogen) may be represented by one of Formulas Z-16 to Z-50. .

<Formula Z-16> <Formula Z-17> <Formula Z-18> <Formula Z-19> <Formula Z-20>

<Formula Z-21> <Formula Z-22> <Formula Z-23> <Formula Z-24> <Formula Z-25>

<Formula Z-26> <Formula Z-27> <Formula Z-28> <Formula Z-29> <Formula Z-30>

<Formula Z-31> <Formula Z-32> <Formula Z-33> <Formula Z-34> <Formula Z-35>

<Formula Z-36> <Formula Z-37> <Formula Z-38> <Formula Z-39> <Formula Z-40>

<Formula Z-41> <Formula Z-42> <Formula Z-43> <Formula Z-44> <Formula Z-45>

<Formula Z-46> <Formula Z-47> <Formula Z-48> <Formula Z-49> <Formula Z-50>

In Formulas Z-16 to Z-50, W ¹ and W ² are the same as defined above, and R ^o is hydrogen, deuterium; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C ₁ -C _20; An alkoxyl group of C ₁ -C ₂₀ ; An alkyl group of C ₁ -C ₂₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; Aryl group of C ₆ -C ₂₀ ; C ₆ -C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A cycloalkyl group of C ₃ -C ₂₀ ; C ₇ -C ₂₀ arylalkyl group; Arylalkenyl group of C ₈ -C ₂₀ ; And combinations thereof, and adjacent R ^o may combine with each other to form a ring. At this time, the ring is C ₆ -C ₂₀ aromatic ring; C ₂ -C ₂₀ heterocycle comprising at least one heteroatom selected from the group consisting of O, N, S, Si and P; And combinations thereof may be selected from the group.

Preferably, Chemical Formula 1 may be represented by the following Chemical Formula 14.

<Formula 14>

In Formula 14, A ring, X, R ¹ to R ³ , L ¹ , Ar ¹ , L ^a , a, b and c are the same as defined in Formula 1, L ^b and L ^c is the same as L ^a R ⁱ , R ^j , R ^k , R ^l , R ^m , R ⁿ may be defined the same as R ^a , R ^b defined in Formula 1, and l is an integer of 0 to 4 , m is an integer of 0 or 1, n is an integer of 0-5. However, a + l ≦ 4, c + n ≦ 5 and b + m ≦ 1.

when a is 2 or more integer, a plurality of R ¹ may be the same as or different from each other, may be the same as or different from each other R ^3, if c is a plurality of two or more integer, l is an integer of 2 or more when the plurality of -L ^a - N (R ⁱ ) (R ^j ) may be the same as or different from each other, and when n is an integer of 2 or more, a plurality of -L ^c -N (R ^m ) (R ⁿ ) may be the same or different from each other.

Specifically, Formula 1 may be one of the following compounds.

In another aspect of the present invention, the present invention provides an organic electric device comprising a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode. At this time, the organic layer contains a compound represented by the formula (1).

The organic 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 represented by the formula (1) is a single compound or two The above mixture is included in at least one layer of the hole injection layer, the hole transport layer, the light emitting auxiliary layer and the light emitting layer.

Another aspect of the present invention provides an electronic device including a display device including the organic electric element and a control unit for driving the display device.

Hereinafter, the synthesis examples of the compound represented by the formula (1) and the production examples of the organic electric device according to the present invention will be described in detail by way of examples, but the present invention is not limited to the following examples.

Synthesis Example

Illustratively, the compound according to the present invention (Final Products) is prepared by reacting Sub 1 and Sub 2 as in Scheme 1, but is not limited thereto.

Scheme 1 X = S, O, C (R ') (R' ')

(In Formula 1, Ring A, X, R ¹ to R ³ , L ¹ , Ar ¹ , a, b and c are the same as defined in Formula 1, Hal ¹ is Br or Cl.)

I. Synthesis of Sub 1

Sub 1 of Scheme 1 may be synthesized by the reaction route of the following scheme, but is not limited thereto.

Sub 1-1 Synthesis Example

(1) Sub S-1 synthesis

Put 2-bromophenanthrene (8.2g, 32 mmol) and Hexane 160ml in a round bottom flask and add TMEDA (24ml, 0.16mol) and n-BuLi (1.6M, 100ml, 0.16mol) using dropping funnel. After the reactor was stirred under nitrogen for 3 hours, S ₂ Cl ₂ (6.4 ml, 0.08 mol) was slowly added thereto and reacted at room temperature for 24 hours. When the reaction was completed, the resulting compound was silicagel column and recrystallized to give the product 5.7g (59% yield).

(2) Sub S-2 synthesis

Sub S-1 (5.7g, 20mmol) was added to the round bottom flask, followed by Nitrophenyl boronic acid (3.7g, 22mmol), Pd (PPh ₃ ) ₄ (0.03 ~ 0.05 equiv), K ₂ CO ₃ (3 equiv), THF (10 mL) and water (5 mL) were added, followed by heating to reflux at 80 ° C to 90 ° C. After the reaction was completed, distilled water was added to the round bottom flask at room temperature, the reaction product was diluted, and extracted with methylene chloride and water. The extracted organic layer was dried over MgSO ₄ and concentrated. The concentrated product was silicagel column and recrystallized to give the product (3.2g yield: 50%).

(3) Sub 1-1 synthesis

Add Sub S-2 (3.2g, 10mmol) to the round bottom flask and add Triphenylphoshine (7.8g, 30mmol) and o-DCB (10 mL). It is heated to reflux at 180 ° C to 190 ° C under nitrogen. After the reaction was completed, the organic layer was filtered and dried over Silic and celite, concentrated, and the resulting compound was silicagel column and recrystallized to give the product 1.0g (yield: 33%).

2.Sub 1-21 Synthesis Example

(1) Sub S-3 synthesis

MC 300ml was added to a round bottom flask containing phenanthro [4,5-bcd] furan (5.0g, 26 mmol) and bromine (4.1g, 26 mmol) and stirred at room temperature for 1 hour. The reaction was recrystallized to give 1.4 g (30% yield) of product Sub S-3.

(2) Sub S-4 Synthesis

Sub S-3 (14 g, 78 mmol) obtained in the above synthesis was placed in a round bottom flask, followed by 2-chloroaniline (9.9 g, 78 mmol), Pd (OAc) ₂ (0.5 g, 2.3 mmol), P (t-Bu ) ₃ (1 g, 4.6 mmol), NaOt-Bu (22 g, 234 mmol) and toluene (250 ml) were added, heated to reflux at 120 ° C. and stirred. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, and the extracted organic layer was dried over MgSO ₄ and concentrated. The concentrated product was then silicagel column and recrystallized to give 13.6 g (yield: 55%) of the product Sub S-4.

(3) Sub 1-21 synthesis

Sub S-4 (13.6 g, 43 mmol) obtained in the above synthesis was added to a round bottom flask with Pd (OAc) ₂ (0.3 g, 1.2 mmol), [(t-Bu) ₃ PH] BF ₄ (1.2 g, 4.3 mmol). ), K ₂ CO ₃ (17.8g, 129 mmol) and DMA (200ml) were added thereto, and the mixture was kept at 150 ° C and stirred under reflux. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to give the product 4.8 g (yield: 40%).

3.Sub 1-25 Synthesis Example

(1) Sub S-5 synthesis

2,7-dibromophenanthrene (10.5 g, 32 mmol) is added under 200 ml of Hexane. TMEDA (24ml, 0.16mol) and n-BuLi (1.6M, 100ml, 0.16mol) are added through dropping funnel. After stirring for 3 hours under nitrogen, S ₂ Cl ₂ (6.4ml, 0.08mol) was slowly added and reacted at room temperature for 24 hours. After the reaction mixture was cooled, the layers were separated under water: methylene chloride (MC) and purified by column (n-Hexane: methylene chloride) to obtain 7.1 g (yield 60%) of the product.

(2) Sub S-6 synthesis

Sub S-5 (7.1g, 19.2mmol) was added to a round bottom flask and (2-nitrophenyl) boronic acid (3.7g, 22mmol), Pd (PPh ₃ ) ₄ (0.03 ~ 0.05 equiv), K ₂ CO ₃ (3 Equivalent), THF (10 mL), and water (5 mL). Heat reflux at 80 ° C to 90 ° C. When the reaction is complete, distilled water is diluted at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was purified by silicagel column and recrystallized to give the product (4.1g yield: 53%).

(3) Sub S-7 synthesis

Add Sub S-6 (4.1 g, 10 mmol) to a round bottom flask and add Triphenylphoshine (7.8 g, 30 mmol) and o-DCB (10 mL). It is heated to reflux at 180 ° C to 190 ° C under nitrogen. After the reaction was completed, the organic layer was dried by filtration with Silica and celite, concentrated and the resulting compound was purified by silicagel column and recrystallization to give the product 1.1g (yield: 30%).

(4) Sub 1-25 Synthesis

Sub S-7 (11 g, 30 mmol), Iodobenzene (6.1 g, 30 mmol), Pd ₂ (dba) ₃ (1 g, 0.1 mmol), (t-Bu) ₃ P (0.4 g, 0.002 mmol), NaOt-Bu (8.61 g, 90 mmol) was dissolved in anhydrous Toluene and refluxed. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated. The resulting product was purified by silicagel column and recrystallized to obtain 10.8 g of the product. (Yield 80%)

4.Sub 1-45 Synthesis Example

(1) Sub S-8 synthesis

In a round bottom flask, 2-bromo-4,4-dimethyl-4H-cyclopenta [def] phenanthrene (8.9g, 30mmol) was added (2-nitrophenyl) boronic acid (6.1g, 36mmol), Pd (PPh ₃ ) ₄ ( Add 0.03 to 0.05 equivalent), K ₂ CO ₃ (3 equiv), THF (100 mL), and water (50 mL). Heat reflux at 80 ° C to 90 ° C. When the reaction is complete, distilled water is diluted at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was purified by silicagel column and recrystallized to give the product (6.7g yield: 65%).

(2) Sub S-9 synthesis

Triphenylphoshine (15.6 g, 60 mmol) o-DCB (10 ml) was added to Sub S-8 (6.7 g, 20 mmol), and the mixture was stirred at 180-190 ° C under nitrogen. The organic layer was dried by filtration through silica and celite, concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain the product 1.2g (20% yield).

(3) Sub S-10 synthesis

Sub S-9 (12 g, 40 mmol) obtained in the synthesis was dissolved in MC (200 ml) and bromine (6.3 g 40 mmol) was dissolved in MC (50 ml) and dropwise. When the reaction was completed, the extracted organic layer was concentrated to dryness in MC / H ₂ O to silica column and recrystallized to give the product (4.3 g, 30%).

(4) Sub 1-45 Synthesis

Sub S-10 (4.3g, 12mmol) was added to the round bottom flask and 3-iodo-9-phenyl-9H-carbazole (5.5g, 15mmol), Pd (PPh ₃ ) ₄ (0.03 ~ 0.05 equiv), K ₂ CO _{Add 3} (3 equiv), THF (50 mL) and water (25 mL). Heat reflux at 80 ° C to 90 ° C. When the reaction is complete, distilled water is diluted at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was purified by silicagel column and recrystallized to give the product (43.3g yield: 44%).

5.Sub 1-52 Synthesis Example

(1) Sub S-11 Synthesis

3-bromotriphenyleno [1,12-bcd] thiophene (16.8g, 50mmol, CAS 1345989-54-9) was added to a round bottom flask and (2-nitrophenyl) boronic acid (9.3g, 55mmol), Pd (PPh ₃ ) ₄ (0.03-0.05 equiv), K ₂ CO ₃ (3 equiv), THF (200 mL), and water (100 mL) are added. Heat reflux at 80 ° C to 90 ° C. When the reaction is complete, distilled water is diluted at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was purified by silicagel column and recrystallized to give the product (10.4g yield: 55%).

(2) Sub 1-52 Synthesis

Triphenylphoshine (21.32 g, 82 mmol) o-DCB (10 ml) was added to Sub S-11 (10.4 g, 27.5 mmol) obtained in the above synthesis, and stirred at 180 to 190 ° C under nitrogen. The organic layer was dried by filtration with silica and celite, and concentrated to give 5.7 g (yield 60%) of the product by silicagel column and recrystallization.

6.Sub 1-67 Synthesis Example

(1) Sub S-12 Synthesis

Add 2-bromo-4,4-diphenyl-4H-cyclopenta [def] phenanthrene (21g, 50mmol, cas 1016652-68-8) to the round bottom flask and add (3-nitronaphthalen-2-yl) boronic acid (11g, 55mmol). ), Pd (PPh ₃ ) ₄ (0.03-0.05 equiv), K ₂ CO ₃ (3 equiv), THF (200 mL), and water (100 mL). Heat reflux at 80 ° C to 90 ° C. When the reaction is complete, distilled water is diluted at room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was purified by silicagel column and recrystallized to give the product (11.7g yield: 49%).

(2) Sub 1-67 Synthesis

Triphenylphoshine (19 g, 72 mmol) o-DCB (10 ml) was added to Sub S-12 (12.5 g, 24 mmol) obtained in the above synthesis, and stirred at 180 to 190 ° C under nitrogen. The organic layer was dried by filtration with silica and celite, concentrated, and then the resulting compound was purified by silicagel column and recrystallized to give the product 6.0g (60% yield).

The compound belonging to Sub 1 may be, but is not limited to, the following compounds. Table 1 shows FD-MS values of compounds belonging to Sub 1.

TABLE 1

II. Synthesis of Sub 2

The compound belonging to Sub 2 of Scheme 1 may be synthesized by the following Scheme 2, but is not limited thereto. Hal ¹ and Hal ² are Br or Cl.

<Scheme 2>

Synthesis examples of specific compounds belonging to Sub 2 are as follows.

Sub 2-15 Synthesis Example

In starting 1,4-dibromobenzene (18.92 g, 80.20 mmol), 2- (dibenzo [b, d] thiophen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane ( 27.37 g, 88.22 mmol), Pd (PPh ₃ ) ₄ (3.71 g, 3.21 mmol), K ₂ CO ₃ (33.25 g, 240.61 mmol), THF (280ml), water (140ml) were added and stirred at 90 ° C. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain 19.22 g (yield: 70%) of the product.

2.Sub 2-16 Synthesis Example

Starting materials 1,3-dibromobenzene (20.10 g, 85.45 mmol), THF (300 ml), 4,4,5,5-tetramethyl-2- (triphenylen-2-yl) -1,3,2-dioxaborolane (33.32 g, 94.05 mmol), Pd (PPh ₃ ) ₄ (3.95 g, 3.42 mmol), K ₂ CO ₃ (35.45 g, 256.51 mmol), water (150 ml) were obtained using 19 g of the product using the Sub 2-15 synthesis. Yield: 60%).

3.Sub 2-36 Synthesis Example

4,4,5,5-tetramethyl-2- (naphthalen-1-yl-d7) -1,3,2-dioxaborolane (29.54 g, 113.11) in starting material 2,4-dibromopyrimidine (25 g, 103 mmol) mmol), Pd (PPh ₃ ) ₄ (5 g, 4.33 mmol), K ₂ CO ₃ (43.21 g, 307.47 mmol), THF (360 ml), water (180 ml) were added and the product 20 g (Yield: 70%) using the Sub 2-15 synthesis Got.

4.Sub 2-52 Synthesis Example

The starting material 2,4-dichlorobenzo [4,5] thieno [3,2- d ] pyrimidine (32 g, 125.6 mmol) was added to 4,4,5,5-tetramethyl-2- (naphthalen-2-yl)- 1,3,2-dioxaborolane (35 g, 138 mmol), Pd (PPh ₃ ) ₄ (5.80 g, 5.02 mmol), K ₂ CO ₃ (52 g, 376.41 mmol), THF (440 ml), water (220 ml) were added and the product 19.58 g (yield: 45%) was obtained using the Sub 2-15 synthesis. Got.

5.Sub 2-77 Synthesis Example

(1) Sub 2-I-77 Synthesis

2-amino-1-naphthoic acid (75 g, 401 mmol), a starting material, was added together with urea (168.7 g, 2808.75 mmol) in a round bottom flask and stirred at 160 ° C. After confirming the reaction by TLC, it was cooled to 100 ℃ and water (200ml) was added and stirred for 1 hour. When the reaction was completed, the resulting solid was filtered under reduced pressure, washed with water and dried to obtain 64 g (yield: 76%) of the product.

(2) Sub 2-II-77 Synthesis

Sub 2-I-77 (63.86 g, 300.94 mmol) obtained in the above synthesis was put into a round bottom flask and dissolved in POCl ₃ (200 ml) at room temperature, and N , N- Diisopropylethylamine (97.23 g, 752.36 mmol) was slowly added dropwise. Then, it stirred at 90 degreeC. After the reaction was completed, concentrated, iced water (500ml) was added and stirred at room temperature for 1 hour. The resulting solid was filtered under reduced pressure and dried to give 68 g (yield: 90%) of the product.

(2) Sub 2-77 Synthesis

To Sub 2-II-77 (67.47 g, 270.86 mmol) obtained in the above synthesis, 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane (60.80 g, 297.94 mmol), Pd (PPh ₃ ) ₄ (12.52 g, 10.83 mmol), K ₂ CO ₃ (112.30 g, 812.57 mmol), THF (950 ml), water (475 ml) were added and the product 45 g (yield: 58%) using the Sub 2-15 synthesis Got.

6.Sub 2-87 Synthesis Example

After starting bromobenzene (40.68 g, 259.09 mmol) was dissolved in toluene (1360 ml) in a round bottom flask, aniline (26.54 g, 285.00 mmol), Pd ₂ (dba) ₃ (7.12 g, 7.77 mmol), 50% P ( t -Bu) ₃ (10.1 ml, 20.73 mmol), NaO t -Bu (74.70 g, 777.28 mmol) was added and stirred at 80 ° C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to give the product 32.88 g (yield: 75%).

7.Sub 2-90 Synthesis Example

In the starting material 4-bromo-1,1'-biphenyl (24.5 g, 102.38 mmol), aniline (11 g, 112 mmol), Pd ₂ (dba) ₃ (2.79 g, 3.00 mmol), 50% P ( t- Bu) ₃ (4.1 ml, 8.15 mmol), NaO t -Bu (29.25 g, 304.38 mmol), toluene (710 ml) were added to give 21.55 g (yield: 85%) of the product using the above Sub 2-87 synthesis. .

8.Sub 2-92 Synthesis Example

To starting material 2-bromodibenzo [b, d] thiophene (40 g, 146.31 mmol) aniline (16 g, 165.10 mmol), Pd ₂ (dba) ₃ (4.03 g, 4.34 mmol), 50% P ( t -Bu ) ₃ (5.6 ml, 11.59 mmol), NaO t -Bu (41.76 g, 434.47 mmol), toluene (760 ml) were added and 35 g (yield: 85%) of the product was obtained using the Sub 2-87 synthesis.

Compounds belonging to Sub 2 may be the following compounds, but are not limited thereto, and Table 2 shows Field Desorption-Mass Spectrometry (FD-MS) values of some compounds belonging to Sub 2.

TABLE 2

III. Product Synthesis

The compound belonging to Sub 1 (1 equivalent) was dissolved in toluene in a round bottom flask, and then the compound belonging to Sub 2 (1 equivalent), Pd ₂ (dba) ₃ (0.03 equiv), (t-Bu) ₃ P (0.06 equiv) and NaOt-Bu (3 equiv) were stirred at 100 ° C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was silicagel column and recrystallized to obtain a final product (final product).

1.P 1-1 Synthesis Example

Sub 1-1 (10 g, 33.62 mmol), Sub 2-1 (5.27 g, 33.62 mmol), Pd ₂ (dba) ₃ (1 g, 0.1 mmol), (t-Bu) ₃ P (0.4 g, 0.002 mmol) and NaOt-Bu (9.61 g, 100 mmol) were dissolved in anhydrous Toluene and refluxed for 3 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated. The resulting product was purified by silicagel column and recrystallized to obtain 10 g (yield: 80%) of the product.

2.P 1-6 Synthesis Example

Sub 1-1 (10 g, 33.62 mmol), Sub 2-75 (9 g, 33.62 mmol), Pd ₂ (dba) ₃ (1 g, 0.1 mmol), (t-Bu) ₃ P (0.4 g, 0.002 mmol) and NaOt-Bu (9.61 g, 100 mmol) were prepared using the same method as the synthesis method for P 1-1. 17 g (yield: 95%) was obtained.

3.P 1-15 Synthesis Example

Sub 1-1 (10 g, 33.62 mmol), Sub 2-70 (12.7 g, 33.62 mmol), Pd ₂ (dba) ₃ (1 g, 0.1 mmol), (t-Bu) ₃ P (0.4 g, 0.002 mmol) and NaOt-Bu (9.61 g, 100 mmol) were prepared in the same manner as in the above P 1-1 synthesis. Yield: 92%).

4.P 1-58 Synthesis Example

Sub 1-8 (10 g, 35.53 mmol), Sub 2-52 (12.3 g, 35.53 mmol), Pd ₂ (dba) ₃ (1 g, 0.1 mmol), (t-Bu) ₃ P (0.4 g, 0.002 mmol) and NaOt-Bu (11.2 g, 106 mmol) were prepared in the same manner as in the above P 1-1 synthesis. Yield: 95%).

5.P 1-60 Synthesis Example

Sub 1-9 (15 g, 48.79 mmol), Sub 2-51 (20.6 g, 48.79 mmol), Pd ₂ (dba) ₃ (1.3 g, 0.1 mmol), (t-Bu) ₃ P (0.5 g, 0.003 mmol), NaOt-Bu (14 g, 146 mmol) was added to 22 g ( Yield: 65%).

6.P 1-108 Synthesis Example

Sub 1-17 (6 g, 12.46 mmol), Sub 2-79 (3.62 g, 12.46 mmol), Pd ₂ (dba) ₃ 6.58 g of (0.34 g, 0.37 mmol), (t-Bu) ₃ P (0.15 g, 0.75 mmol) and NaOt-Bu (3.59 g, 37.38 mmol) were obtained in the same manner as the synthesis method of P 1-1. . (Yield 72%)

7.P 1-104 Synthesis Example

Sub 1-54 (5 g, 15.0 mmol), Sub 2-1 (5.5 g, 15.0 mmol), Pd ₂ (dba) ₃ (0.6 g, 0.05 mmol), (t-Bu) ₃ P (0.25 g, 0.0015 mmol) and NaOt-Bu (5 g, 47 mmol) were prepared in the same manner as in the above P 1-1 synthesis. Yield: 70%).

8.P 2-7 Synthesis Example

Sub 1-25 (11 g, 24.32 mmol), Sub 2-88 (10 g, 24.32 mmol), Pd ₂ (dba) ₃ (0.9 g, 0.09 mmol), (t-Bu) ₃ P (0.3 g, 0.002 mmol), NaOt-Bu (7 g, 72.96 mmol) were prepared in the same manner as in the P 1-1 synthesis. Yield: 88%).

9.P 2-19 Synthesis Example

Sub 1-36 (10 g, 18.92 mmol), Sub 2-90 (4.64 g, 18.92 mmol), Pd ₂ (dba) ₃ (0.6 g, 0.06 mmol), (t-Bu) ₃ P (0.1 g, 0.001 mmol), NaOt-Bu (5.4 g, 56.76 mmol) were prepared in the same manner as in the above P 1-1 synthesis. Yield: 90%).

10.P 2-20 Synthesis Example

Sub 1-37 (9 g, 18.42 mmol), Sub 2-96 (3.6 g, 18.42 mmol), Pd ₂ (dba) ₃ (0.5 g, 0.05 mmol), (t-Bu) ₃ P (0.1 g, 0.001 mmol), NaOt-Bu (4.8 g, 55.26 mmol) were prepared in the same manner as in the P 1-1 synthesis. Yield: 88%).

11.P 2-17 Synthesis Example

Sub 1-34 (10.1 g, 20.00 mmol), Sub 2-95 (3.6 g, 20.00 mmol), Pd ₂ (dba) ₃ (0.5 g, 0.05 mmol), (t-Bu) ₃ P (0.1 g, 0.001 mmol) and NaOt-Bu (4.8 g, 55.26 mmol) were prepared in the same manner as in the above P 1-1 synthesis. Yield: 80%).

The FD-MS values of the compounds P 1-1 to P 1-109 and P 2-1 to P 2-46 of the present invention prepared according to the synthesis examples described above are shown in Table 3 below.

TABLE 3

In the above, an exemplary synthesis example of the present invention represented by Chemical Formula 1 has been described, but these are all Buchwald-Hartwig cross coupling 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), Grignard reaction, Cyclic Dehydration reaction and PPh ₃ -mediated reductive cyclization reaction ( J. Org . Chem . 2005, 70, 5014.) and other substituents defined in Formula 1 (substituting A ring, X, R ¹ to R ³ , L ¹ , Ar ^1, etc.) in addition to the substituents specified in the specific synthesis examples, the reaction proceeds. Those skilled in the art will readily understand.

Manufacturing Evaluation of Organic Electrical Device

[ Example  One] Red organic electroluminescent device Phosphorescent Host

4,4 ', 4' '-Tris [2-naphthyl (phenyl) amino] triphenylamine (hereinafter referred to as "2-TNATA") is vacuum-deposited on an ITO layer (anode) formed on a glass substrate. A layer was formed.

Thereafter, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (hereinafter referred to as "NPD") is vacuum deposited to a thickness of 60 nm on the hole injection layer to form a hole transport layer. The compound P 1-9 of the present invention is used as the host material and bis- (1-phenylisoquinoline) iridium (III) acetylacetonate (hereinafter referred to as "(piq) ₂ Ir (acac)") as a dopant material on the hole transport layer. The light emitting layer having a thickness of 95: 5 was deposited to form a light emitting layer having a thickness of 30 nm.

Subsequently, (1,1'-biphenyl-4-olato) bis (2-methyl-8-quinolinolato) aluminu (hereinafter referred to as "BAlq") is vacuum deposited to a thickness of 10 nm on the light emitting layer to form a hole blocking layer. Then, tris- (8-hydroxyquinoline) aluminum (hereinafter referred to as “Alq ₃ ”) was deposited to a thickness of 40 nm on the hole blocking layer to form an electron transport layer.

Next, LiF was deposited to a thickness of 0.2 nm on the electron transport layer to form an electron injection layer, and then Al was deposited to a thickness of 150 nm on the electron injection layer to form a cathode.

[ Example  2] to [ Example  19] Red organic electroluminescent device

An organic electroluminescent device was manufactured according to the same method as Example 1 except for using the compound of the present invention shown in Table 4 instead of the compound P-9 of the present invention as a host material of the emission layer.

[ Comparative example  1] to [ Comparative example  4]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that one of Comparative Compounds 1 to 4 shown in Table 4 was used instead of the compound P-9 of the present invention as a host material of the emission layer.

<Comparative Compound 1> <Comparative Compound 2> <Comparative Compound 3> <Comparative Compound 4>

Electroluminescence (EL) characteristics by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared by Examples 1 to 19 and Comparative Examples 1 to 4 of the present invention The T95 lifetime was measured using a lifespan measuring instrument manufactured by McScience Inc. at 2500 cd / m ² reference luminance, and the measurement results are shown in Table 4 below.

TABLE 4

As can be seen from Table 4, it can be seen that the device using the compound according to an embodiment of the present invention as a phosphorescent red host material of the light emitting layer is significantly improved luminous efficiency and lifetime than Comparative Compound 1 to Comparative Compound 3.

Comparing heteroatoms in a six-membered cyclic compound, N in one pentagonal ring and S, O or C (R ^a ) (R ^b ) in another pentagonal ring than Comparative Compound 2, in which the pentagonal ring contains the same heteroatom N It can be seen that when the compound of the present invention, which is a heteroatom type containing one, is used as a host material, the efficiency and lifespan of the organic light emitting device is further improved.

In general, when molecules are stacked, there is a strong electrical interaction with more adjacent π-electrons, which is closely related to charge carrier mobility. Comparative compound 2, a NN-type six-membered heterocyclic compound, is a NN-type heterocyclic core when the molecules are stacked, so that the sequence between the molecules has an edge-to-face configuration, which results in low charge carrier mobility. And low oxidative stability.

On the other hand, the compound of the present invention has an antiparallelcofacial π-stacking structure in which the packing structure of the molecule faces oppositely since the heteroatoms in the cyclic compound have different heterocyclic cores. This makes the arrangement order between molecules into a face-to-face form, and due to the steric effect of the substituent (Ar ^{1 in} Formula ¹ ) attached to the asymmetrically arranged heteroatom N, which is the cause of the lamination structure, it has a significantly high carrier mobility. It is considered that the organic light emitting device has high efficiency as a result. In addition, since the structure has a high oxidation stability, the life of the organic light emitting device is considered to be significantly increased.

In addition, when the ring condensed to the pentagonal ring containing S like Comparative Compound 3 is a hexagonal ring containing Sp ³ carbon, it has a lower packing density and lower thermal stability than the compound of the present invention. Will be displayed. Therefore, when Comparative Compound 3 is used as a host material of the organic light emitting device, it is resistant to Joule's heat generated in the organic layer, between each layer of the organic layer, and between the organic layer and the metal electrode during electroluminescence under high temperature and high temperature environment. It was confirmed that the resistance was reduced.

On the other hand, when the compound of the present invention condensed with pentagonal ring is used as a host material of the organic light emitting device, the driving voltage can be lowered with high packing density, and Joule's heat generated when driving the device is reduced. Since it is possible to improve the thermal stability, it can be seen that the life is significantly increased than the comparative compound 3.

In particular, in the case of the compound of the present invention in which a specific substituent such as benzothienopyrimidine, benzofuropyrimidine, benzoquinazoline, etc. is introduced, it is suitable to accommodate both holes and electrons. In addition to the structure, it has an appropriate T1 value to facilitate charge transfer from the host to the dopant. Therefore, when using the compound as a host material, it was confirmed that the luminous efficiency and lifespan of the organic light emitting device can be improved.

[ Example  20] Green Organic Light Emitting Diode  Phosphorescent Host

A 2-TNATA film was vacuum-deposited on the ITO layer (anode) formed on the glass substrate to form a hole injection layer having a thickness of 60 nm, and then a NPD was vacuum deposited on the hole injection layer to a thickness of 60 nm to form a hole transport layer.

Subsequently, the compound P 1-63 of the present invention is used as a host material and tris (2-phenylpyridine) -iridium (hereinafter, abbreviated as “Ir (ppy) ₃ ”) as a dopant material on the hole transport layer. The light emitting layer was deposited to a thickness of 95: 5 to form a light emitting layer with a thickness of 30 nm.

Next, BAlq was vacuum deposited to a thickness of 10 nm on the light emitting layer to form a hole blocking layer, and Alq ₃ was formed to a thickness of 40 nm on the hole blocking layer to form an electron transport layer.

Thereafter, LiF was deposited to a thickness of 0.2 nm on the electron transport layer to form an electron injection layer, and then Al was deposited to a thickness of 150 nm on the electron injection layer to form a cathode.

[ Example  21] to [ Example  36] Green Organic Light Emitting Diode

An organic electroluminescent device was manufactured according to the same method as Example 20 except for using the compound of the present invention shown in Table 5 instead of the compound P 1-63 as a host material of the emission layer.

[ Comparative example  5] to [ Comparative example  8]

An organic electroluminescent device was manufactured according to the same method as Example 20 except for using one of Comparative Compounds 1 and 5 to 7 as shown in Table 5 instead of Compound P 1-63 as a host material of the emission layer. It was.

<Comparative Compound 5> <Comparative Compound 6> <Comparative Compound 7>

Electroluminescence (EL) characteristics by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared by Examples 20 to 36 and Comparative Examples 5 to 8 of the present invention The T95 lifetime was measured using a lifespan measuring instrument manufactured by McScience Inc. at 5000 cd / m ² reference luminance, and the measurement results are shown in Table 5 below.

TABLE 5

From the measurement results of Table 5, it was confirmed that the device using the compound according to the embodiment of the present invention as a phosphorescent green host material of the light emitting layer significantly improved luminous efficiency and lifetime than Comparative Compound 1, Comparative Compound 5 and Comparative Compound 6 Can be. This is because the heterocyclic atoms in the cyclic compound have heterocyclic heterocyclic cores, and the structure having high thermal stability is used not only in the light emitting layer of the red organic electroluminescent device (used as a host) but also in the light emitting layer of the green organic electroluminescent device (used as a host). This is because it is a major factor in improving the performance of the device.

Comparing Comparative Compound 7 to Compounds of the Invention (particularly Compounds P 1-63), the compounds of the present invention are represented by X (which is S, O or C (R ′) (R ″) at the benzocarbazole position of It can be seen that the ring containing, and the indole is located at the benzothiophene position of Comparative Compound 7. Thus, the compound of the present invention having a similar core but different substitution positions of heteroatoms compared to Comparative Compound 7. When using as a phosphorescent green host material it can be seen that the efficiency of the organic electric device is much improved compared to the case of using the comparative compound 7.

In the case of Comparative Compound 7, a substituent having an ET characteristic (electron transfer) such as triazine is bound to "N of benzocarbazole", and a substituent having an ET characteristic in "N of indole" in the case of the compound of the present invention. Because is combined. Since benzocarbazole is a core with stronger hole characteristics than indole, substituents with ET properties are more affected by cores, resulting in weaker ET properties of substituents, while indole has weaker hole properties than benzocarbazole. As a result, substituents with ET properties are less affected by the core. Therefore, when a substituent having a strong ET property is substituted, the compound of the present invention may exhibit stronger ET property than Comparative Compound 7, and thus electrons may be transferred from the electron transport layer to the light emitting layer more quickly, thereby improving charge balance in the light emitting layer. Therefore, the efficiency of the organic electric element is improved.

On the other hand, the phosphorescent host material of the device should be appropriately selected in consideration of the interaction between the hole transport layer and the dopant, it is very difficult to infer the excellent electrical properties of the compound of the present invention in the phosphorescent host even if a similar core is used. will be.

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

CROSS-REFERENCE TO RELATED APPLICATION

This patent application is filed with the Korean Patent Application No. 10-2017-0026034 filed on February 28, 2017 in the United States Patent Act, sections 119 to 121, 365 (35 USC §19 to §121, §365 ), The contents of which are hereby incorporated by reference in their entirety. In addition, if this patent application claims priority for the same reason for countries other than the United States, all its contents are incorporated into this patent application by reference.

Claims (12)

Compound represented by the following formula (1): <Formula 1>

In Chemical Formula 1, A ring is an aromatic ring of C ₆ , X is selected from the group consisting of S, O and C (R ') (R "), Ar ¹ is an aryl group of C ₆ -C ₆₀ ; Fluorenyl group; C ₂ -C ₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ -C ₆₀ and an aromatic ring of C ₆ -C ₆₀ ; An alkyl group of C ₁ -C ₅₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; -L ^a -N (R ^a ) (R ^b ); An alkoxyl group of C ₁ -C ₃₀ ; And it is selected from the group consisting of C ₆ -C ₃₀ aryloxy group, R ¹ to R ³ are each independently of deuterium; Tritium; halogen; Cyano group; Nitro group; C ₆ -C ₆₀ aryl group; Fluorenyl group; C ₂ -C ₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ -C ₆₀ and an aromatic ring of C ₆ -C ₆₀ ; An alkyl group of C ₁ -C ₅₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; -L ^a -N (R ^a ) (R ^b ); An alkoxyl group of C ₁ -C ₃₀ ; And C ₆ -C _{30 It} is selected from the group consisting of an aryloxy group, adjacent groups may be bonded to each other to form a ring, a is an integer of 0 to 4, b is an integer of 0 or 1, c is Is an integer from 0 to 5, L ¹ and L ^a are each independently a single bond; C ₆ -C ₆₀ arylene group; Fluorenylene groups; C ₂ -C ₆₀ heterocyclic group including at least one hetero atom selected from the group consisting of O, N, S, Si and P; And a fused ring group of an aliphatic ring of C ₃ -C ₆₀ and an aromatic ring of C ₆ -C ₆₀ . R ', R ", R ^a and R ^b are each independently a C ₆ -C ₆₀ aryl group; fluorenyl group; at least one heteroatom selected from the group consisting of O, N, S, Si and P C ₂ -C ₆₀ heterocyclic group; C ₃ -C ₆₀ alicyclic ring and C ₆ -C ₆₀ aromatic ring group; C ₁ -C ₅₀ Alkyl group; C ₂ -C ₂₀ Alkenyl group; C An alkynyl group of ₂ -C ₂₀ ; an alkoxyl group of C ₁ -C ₃₀ ; and an aryloxy group of C ₆ -C ₃₀ , and R ′ and R ″ may combine with each other to form a ring, A ring, a ring formed by bonding of adjacent groups of R ¹ to R ^{3 with} each other, R ′ and R ″ ring formed by bonding with each other, Ar ¹ , R ¹ to R ³ , L ¹ , L ^a , R ', R ", R ^a and R ^b are each deuterium; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C ₁ -C _20; An alkoxyl group of C ₁ -C ₂₀ ; An alkyl group of C ₁ -C ₂₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; Aryl group of C ₆ -C ₂₀ ; C ₆ -C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A cycloalkyl group of C ₃ -C ₂₀ ; C ₇ -C ₂₀ arylalkyl group; Arylalkenyl group of C ₈ -C ₂₀ ; And one or more substituents selected from the group consisting of a combination thereof. The method of claim 1, Formula 1 is a compound characterized in that represented by one of the following formula 2 to formula 13:    <Formula 2> <Formula 3> <Formula 4> <Formula 5>

   <Formula 6> <Formula 7> <Formula 8> <Formula 9>

   <Formula 10> <Formula 11> <Formula 12> <Formula 13>

In Chemical Formulas 2 to 13, Ar ¹ , L ¹ , R ¹ to R ³ , R ′, R ″, a, b, and c are the same as defined in claim 1. The method of claim 1, Ar ¹ is a compound characterized in that represented by the formula A-1 or A-2: <Formula A-1> <Formula A-2>

In Formula A-1, Q ¹ to Q ⁴ are independently of each other N, C (R ^c ) or C, and when combined with L ¹ , is C, In Formula A-2, Q ⁵ to Q ⁹ are each independently N or C (R ^c ), R ^c is hydrogen; heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C ₁ -C _20; An alkoxyl group of C ₁ -C ₂₀ ; An alkyl group of C ₁ -C ₂₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; Aryl group of C ₆ -C ₂₀ ; C ₆ -C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A cycloalkyl group of C ₃ -C ₂₀ ; C ₇ -C ₂₀ arylalkyl group; Arylalkenyl group of C ₈ -C ₂₀ ; And selected from the group consisting of a combination thereof, adjacent R ^c may combine with each other to form a ring, In Formula A-1, the Z ring is one of the following Formulas Z-1 to Z-15, <Formula Z-1> <Formula Z-2> <Formula Z-3> <Formula Z-4> <Formula Z-5>

<Formula Z-6> <Formula Z-7> <Formula Z-8> <Formula Z-9> <Formula Z-10>

<Formula Z-11> <Formula Z-12> <Formula Z-13> <Formula Z-14> <Formula Z-15>

In Chemical Formulas Z-1 to Z-15, the mark (*) represents a moiety bonded to a ring including Q ¹ to Q ⁴ , W ¹ and W ² are each independently a single bond, NL ² -Ar ² , S, O or C (R ^d ) (R ^e ), V is independently of each other N or C (R ^f ), L ² is a single bond; C ₆ -C ₂₀ arylene group; C ₆ -C ₂₀ arylene group substituted with deuterium; Fluorenylene groups; C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; And it is selected from the group consisting of C ₃ -C ₂₀ cycloalkyl group, Ar ² , R ^d , R ^e and R ^f are each independently hydrogen, deuterium; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C ₁ -C _20; An alkoxyl group of C ₁ -C ₂₀ ; An alkyl group of C ₁ -C ₂₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; Aryl group of C ₆ -C ₂₀ ; C ₆ -C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A cycloalkyl group of C ₃ -C ₂₀ ; C ₇ -C ₂₀ arylalkyl group; Arylalkenyl group of C ₈ -C ₂₀ ; And a combination thereof, R ^d and R ^e may be bonded to each other to form a ring, and neighboring R ^{f may} also be bonded to each other to form a ring. The method of claim 3, wherein At least one of Q ¹ to Q ⁴ is N; The method of claim 1, Formula 1 is a compound characterized in that represented by the following formula (14): <Formula 14>

In Chemical Formula 14, Ring A, X, R ¹ to R ³ , L ¹ , Ar ¹ , L ^a , a, b and c are the same as defined in claim 1, L ^b and L ^c are the same as L ^{a in} claim 1 R ⁱ , R ^j , R ^k , R ^l , R ^m , R ⁿ are defined the same as R ^a , R ^{b of} claim 1, l is an integer from 0 to 4, m is an integer from 0 or 1, n is an integer from 0 to 5, provided that a + l ≦ 4, c + n ≦ 5, b + m ≦ 1, and a is 2 In case of an integer greater than or equal to the plurality of R ¹ may be the same as or different from each other, when c is an integer of 2 or more, a plurality of R ³ may be equal to or different from each other, when l is an integer of 2 or more, a plurality of -L ^a -N ⁱ ) (R ^j ) may be the same as or different from each other, and when n is an integer of 2 or more, a plurality of -L ^c -N (R ^m ) (R ⁿ ) may be the same or different from each other. The method of claim 1, Compounds characterized in that one of the following compounds:

. A first electrode; Second electrode; And an organic material layer formed between the first electrode and the second electrode and containing the compound of any one of claims 1 to 6. The method of claim 7, wherein The organic 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, And at least one of the hole injection layer, the hole transport layer, the light emitting auxiliary layer, and the light emitting layer comprises the compound as a single compound or two or more compounds. The method of claim 8, The compound of claim 1, wherein the compound is included in the light emitting layer. The method of claim 7, wherein The organic material layer is formed by 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 electronic device of claim 7; And And a controller for driving the display device. The method of claim 11, The organic electronic device is an electronic device, characterized in that selected from the group consisting of an organic electroluminescent device, an organic solar cell, an organic photoconductor, an organic transistor, and a monochromatic or white illumination element.

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