KR102597559B1 - Compound for organic electronic element, organic electronic element comprising the same, and electronic device thereof - Google Patents

Abstract

An organic electric device including a compound represented by Formula 1, a first electrode, a second electrode, and an organic material layer between the first electrode and the second electrode, and an electronic device including the same are disclosed, and the compound represented by Formula 1 in the organic material layer By including, the driving voltage of the organic electric device can be lowered and the luminous efficiency and lifespan can be improved.

Description

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

The present invention relates to compounds for organic electric devices, organic electric devices using the same, and electronic devices thereof.

In general, organic luminescence refers to a phenomenon that converts electrical energy into light energy using organic materials. Organic electric devices that utilize this organic light emission phenomenon usually include an anode, a cathode, and an organic material layer formed between them. The organic material layer is often composed of a multi-layer structure made of different materials to increase the efficiency and stability of organic electric devices, and may be composed 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 as organic layers in organic electric devices can 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 the case of polycyclic ring compounds containing heteroatoms, the differences in properties depending on the material structure are very large, so they are applied to various layers as materials for organic electric devices. In particular, in polycyclic compounds, the band gap (HOMO, LUMO), electrical properties, chemical properties, physical properties, etc. are different depending on the number of rings, fused position, and type and arrangement of heteroatoms, so polycyclic compounds are used in organic electric devices. Research has been conducted to apply it to the organic layer.

For example, U.S. Patent Application Publication No. 2008-0145708 discloses an example in which a polycyclic ring compound is applied to a hole transport layer or phosphorescent host of an organic electric device, and Republic of Korea Patent Application Publication No. 10-2007-0012218. discloses an example in which a polycyclic ring compound is applied to the electron transport layer of an organic electric device.

In this way, the development of materials for organic electric devices based on the type, number, and location of heteroatoms of polycyclic ring compounds continues, and in particular, the development of host materials for the light-emitting layer using polycyclic ring compounds is increasingly required.

1. U.S. Publication No. 2008-0145708 2. Korean Publication No. 10-2007-0012218

The purpose of the present invention is to provide a polycyclic ring compound that can lower the driving voltage of the device and improve the luminous efficiency, color purity, and lifespan of the device, an organic electric device using the same, and an electronic device thereof.

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

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

By using the compound according to the embodiment of the present invention, not only can the driving voltage of the organic electric device be lowered, but also the luminous efficiency, color purity, and lifespan of the device can be greatly improved.

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

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

When adding reference numerals to components in each drawing, it should be noted that identical components are given the same reference numerals as much as possible even if they are shown in different drawings. Additionally, in describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description will be omitted.

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 used to distinguish the component from other components, and the nature, sequence, 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 or connected to that other component, but there is another component between each component. It will be understood that elements may be “connected,” “combined,” or “connected.”

Additionally, when a component, such as a layer, membrane, region, plate, etc., is said to be "on" or "on" another component, it means not only that it is "directly above" the other component, but also that there is another component in between. It should be understood that it can also include cases. Conversely, when an element is said to be "right on top" of another part, it should be understood to mean that there is no other part in between.

As used in this specification and the appended claims, unless otherwise noted, the following terms have the following meanings.

As used herein, the term “halo” or “halogen” refers to fluorine (F), bromine (Br), chlorine (Cl), or iodine (I), unless otherwise specified.

As used in the present invention, the term "alkyl" or "alkyl group", unless otherwise specified, has a single bond of 1 to 60 carbon atoms, and includes straight chain alkyl group, branched chain alkyl group, cycloalkyl (cycloaliphatic) group, and alkyl-substituted cyclo. It refers to radicals of saturated aliphatic functional groups, including alkyl groups and cycloalkyl-substituted alkyl groups.

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

As used in the present invention, the term "alkenyl group" or "alkynyl group", unless otherwise specified, has a double or triple bond of 2 to 60 carbon atoms each, and includes straight or branched chain groups, and is limited thereto. That is not the case.

The term “cycloalkyl” used in the present invention refers to alkyl forming a ring having 3 to 60 carbon atoms, unless otherwise specified, but is not limited thereto.

As used in the present invention, the term "alkoxyl group", "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, and is limited thereto, unless otherwise specified. That is not the case.

The term “aryloxyl group” or “aryloxy group” used in the present invention refers to an aryl group to which an oxygen radical is attached, and has 6 to 60 carbon atoms unless otherwise specified, but is not limited thereto.

As used in the present invention, the term "fluorenyl group" or "fluorenylene group" refers to a monovalent or divalent functional group in which R, R' and R" are all hydrogen in the following structure, respectively, unless otherwise specified. 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 and the carbon to which they are bonded This includes cases where they form a spiro compound together.

The terms “aryl group” and “arylene group” used in the present invention each have 6 to 60 carbon atoms unless otherwise specified, and are not limited thereto. In the present invention, an aryl group or arylene group includes a single ring type, a ring aggregate, a fused multiple ring system, a spiro compound, etc.

The term "heterocyclic group" used in the present invention includes not only aromatic rings such as "heteroaryl group" or "heteroarylene group" but also non-aromatic rings, and unless otherwise specified, each carbon number containing one or more heteroatoms. It refers to a ring numbered from 2 to 60, but is not limited thereto. As used herein, the term "heteroatom" refers to N, O, S, P or Si, unless otherwise specified, and the heterocyclic group refers to a single ring containing heteroatoms, a ring aggregate, a fused multiple ring system, or a ring group. refers to compounds, etc.

Additionally, the “heterocyclic group” may also include a ring containing SO ₂ instead of carbon forming the ring. For example, “heterocyclic group” includes the following compounds:

The term “ring” used in the present invention includes single rings and polycyclic rings, includes hydrocarbon rings as well as heterocycles containing at least one heteroatom, and includes aromatic and non-aromatic rings.

The term "polycyclic" used in the present invention includes ring assemblies such as biphenyl, terphenyl, etc., fused multiple ring systems, and spiro compounds, and includes not only aromatics but also non-aromatics, and hydrocarbons. Rings of course include heterocycles containing at least one heteroatom.

The term “ring assemblies” used in the present invention refers to two or more ring systems (single rings or fused ring systems) directly connected to each other through single or double bonds, and the direct connection between such rings. This means that the number of connections is one less than the total number of ring systems in this compound. In ring aggregates, the same or different ring systems may be directly connected to each other through single or double bonds.

The term “multiple fused ring system” used in the present invention refers to a fused ring form sharing at least two atoms, and includes a fused ring system of two or more hydrocarbons and at least one heteroatom. This includes forms in which at least one heterocyclic ring is fused. This fused multiple ring system may be an aromatic ring, a heteroaromatic ring, an aliphatic ring, or a combination of these rings.

The term "spiro compound" used in the present invention has a 'spiro union', and the spiro union refers to a connection made by two rings sharing only one atom. At this time, the atom shared between the two rings is called a 'spiro atom', and depending on the number of spiro atoms in one compound, they are 'monospiro-', 'dispiro-', and 'trispiro-' respectively. 'It is called a compound.

Additionally, when prefixes are named consecutively, it means that the substituents are listed in the order they are listed first. For example, an arylalkoxy group refers to an alkoxy group substituted with an aryl group, an alkoxycarbonyl group refers to a carbonyl group substituted with an alkoxy group, and an arylcarbonylalkenyl group refers to an alkenyl group substituted with an arylcarbonyl group. Arylcarbonyl group is a carbonyl group substituted with an aryl group.

Also, unless explicitly stated otherwise, in the term "substituted or unsubstituted" used in the present invention, "substituted" means 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 group, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₂₀ aryl group, C ₆ -C ₂₀ aryl group substituted with deuterium, C ₈ -C ₂₀ arylalkenyl group, silane group, boron means substituted with one or more substituents 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. and is not limited to these substituents.

In this specification, the 'group name' corresponding to the aryl group, arylene group, heterocyclic group, etc., as examples of each symbol and its substituent, may be written as the 'name of the group reflecting the valence', but is written as the 'parent compound name'. You may. For example, in the case of 'phenanthrene', a type of aryl group, the name of the group may be written by distinguishing the valence, such as the monovalent 'group' is 'phenanthryl' and the divalent group is 'phenanthrylene', but the valence and Regardless, it can also be written as the parent compound name, ‘phenanthrene’. Similarly, in the case of pyrimidine, it can be written as 'pyrimidine' regardless of the valence, or it can be written as the 'name of the group' of the valence, such as pyrimidineyl group in the case of monovalent group, pyrimidineylene in the case of divalent group, etc. there is.

In addition, unless explicitly stated otherwise, the chemical formula used in the present invention is applied identically to the substituent definition according to the exponent definition of the following chemical formula.

Here, when a is an integer of 0, it means that the substituent R ¹ is absent. That is, when a is 0, it means that hydrogen is bonded to all the carbons forming the benzene ring. In this case, the hydrogen bonded to the carbon is indicated as You can omit it and write the chemical formula or compound. In addition, when a is an integer of 1, one substituent R ¹ is bonded to any one of the carbons forming the benzene ring, and when a is an integer of 2 or 3, it can be bonded as follows, for example, and a is 4 to 6 Even when it is an integer, it is bonded to the carbon of the benzene ring in a similar way, and when a is an integer of 2 or more, R ¹ may be the same or different.

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

Referring 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 110. An organic layer containing a compound according to the present invention is provided between the two electrodes 180. At this time, the first electrode 120 may be an anode and the second electrode 180 may be a cathode. In the case of the inverted type, the first electrode may be the cathode and the second electrode may be the anode.

The organic material layer may sequentially 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. At this time, at least one of these layers may be omitted, or a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, an electron transport auxiliary layer, a buffer layer 141, etc. may be further included, and an electron transport layer 160, etc. It may also act as a hole blocking layer.

In addition, although not shown, the organic electric device according to an embodiment of the present invention further includes a protective layer or a light efficiency improvement layer (capping layer) formed on at least one side of the first electrode and the second electrode opposite to the organic layer. can do.

The 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), etc., may be used as a host or dopant material for the light emitting layer 150, or as a material for a light efficiency improvement layer. For example, the compound of the present invention can be used as a material for the light-emitting layer 150, and preferably as a host material for the light-emitting layer 150.

On the other hand, even if it is the same core, the band gap, electrical properties, and interface properties may vary depending on which substituent is attached to which position, so the selection of the core and the combination of sub-substituents attached to it are important. Research is needed, and in particular, long lifespan and high efficiency can be achieved at the same time when the energy level and T ₁ value between each organic layer and the intrinsic properties of the material (mobility, interface properties, etc.) are optimally combined.

Therefore, in the present invention, the light emitting layer 150 is formed using a compound represented by Formula 1, thereby optimizing the energy level and T ₁ value between each organic material layer and the intrinsic properties of the material (mobility, interface properties, etc.) to form an organic electric device. Lifespan and efficiency can be improved simultaneously.

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

In addition, the organic material layer uses a variety of polymer materials, such as a solution process or solvent process rather than a deposition method, such as spin coating process, nozzle printing process, inkjet printing process, slot coating process, dip coating process, roll-to-roll process, and doctor bleed process. It can be manufactured with fewer layers by methods such as a printing process, screen printing process, or thermal transfer method. Since the organic material layer according to the present invention can be formed by various methods, 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-emitting type, a rear-emitting type, or a double-sided emitting type depending on the material used.

WOLED (White Organic Light Emitting Device) has the advantage of being easy to achieve high resolution and having excellent fairness, while being manufactured using the color filter technology of existing LCDs. Various structures for white organic light emitting devices, mainly used as backlight devices, are being proposed and patented. Representatively, a side-by-side method in which R (Red), G (Green), and B (Blue) light emitting parts are arranged in parallel with each other in a plane, and a stacking method in which R, G, and B light emitting layers are stacked top and bottom. There is a color conversion material (CCM) method that uses electroluminescence by a blue (B) organic light-emitting layer and photo-luminescence of an inorganic phosphor using light therefrom, and the present invention. can be applied to these WOLEDs as well.

Additionally, the organic electric device according to an embodiment of the present invention may be one of an organic electroluminescence device, an organic solar cell, an organic photoreceptor, an organic transistor, and a device for monochromatic or white lighting.

Another embodiment of the present invention may include a display device including the organic electric device of the present invention described above, and an electronic device including a control unit that controls the display device. At this time, the electronic device may be a current or future wired or 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 consoles, various TVs, and various computers.

Hereinafter, a compound according to one aspect of the present invention will be described.

The compound according to one aspect of the present invention is represented by the following formula (1).

<Formula 1>

In Formula 1, each symbol is defined as follows.

Ring A is one of the following formulas 1-1 to 1-3.

<Formula 1-1> <Formula 1-2> <Formula 1-3>

R ¹ to R ¹⁷ are independently hydrogen; heavy hydrogen; halogen; Cyano group; nitro group; C ₆ -C ₆₀ aryl group; fluorenyl group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Se, Si and P; A fused ring group of an aromatic ring of C ₆ -C ₆₀ and an aliphatic ring of C ₃ -C ₆₀ ; C ₁ -C ₅₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkyne group; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; -L ¹ -Ar ¹ ; -L'-N(R ^a )(R ^b ); and combinations thereof, and adjacent groups may be bonded to each other to form a ring.

In addition, R ¹ to R ¹⁷ can form a ring by combining adjacent groups, and the ring formed at this time is an aromatic ring of C ₆ -C ₆₀ ; fluorene; C ₂ -C ₆₀ heterocycle containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; Or it may be a fused ring group of a C ₆ -C ₆₀ aromatic ring and a C ₃ -C ₆₀ aliphatic ring.

When R ¹ to R ¹⁷ are aryl, preferably a C ₆ to C ₃₀ aryl group, more preferably a C ₆ to C ₁₈ aryl group, examples include phenyl, biphenyl, terphenyl, naphthyl, It may be phenanthrene, pyrene, etc. When R ¹ to R ¹⁷ are heterocyclic groups, preferably C ₂ to C ₃₀ heterocyclic groups, more preferably C ₂ to C ₁₂ heterocyclic groups, examples include pyrimidine, triazine, and quinazoline. , carbazole, benzocarbazole, benzothienopyrimidine, dibenzofuran, dibenzothiophene, etc. When R ¹ to R ¹⁷ are a fluorenyl group, they may be 9,9-dimethyl-9H-fluorene.

X is N(-L ¹ -Ar ¹ ), O, S or C(R')(R").

Ar ¹ is an aryl group of C ₆ -C ₆₀ ; fluorenyl group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Se, Si and P; A fused ring group of an aromatic ring of C ₆ -C ₆₀ and an aliphatic ring of C ₃ -C ₆₀ ; -L'-N(R ^a )(R ^b ); and combinations thereof.

When Ar ¹ is an aryl group, preferably a C ₆ to C ₃₀ aryl group, more preferably a C ₆ to C ₁₈ aryl group, examples include phenyl, biphenyl, terphenyl, naphthyl, phenanthrene, pi It may be lene, triphenylene, fluoranthene, etc. When Ar ¹ is a heterocyclic group, preferably a C ₂ to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₁₆ heterocyclic group, examples include triazole, pyridine, pyrimidine, triazine, Quinazoline, benzoquinazoline, dibenzoquinazoline, carbazole, dibenzothiophene, dibenzofuran, benzothienopyrimidine, dibenzofuropyrimidine, benzofuropyrimidine, pyridopyridazine, benzoline It may be naphthofuran, phenanthroline, benzofuropyrimidine, naphthothyenopyrimidine, dimethylbenzoindenopyrimidine, etc. When Ar ¹ is a fluorenyl group, it may be 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorene, 9,9'-spirobifluorene, etc.

wherein L ¹ and L' are independently a single bond; C ₆ -C ₆₀ arylene group; fluorenylene group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Se, Si and P; A fused ring group of an aromatic ring of C ₆ -C ₆₀ and an aliphatic ring of C ₃ -C ₆₀ ; and combinations thereof.

When L ¹ and L' are an aryl group, they are preferably an arylene group of C ₆ to C ₃₀ , more preferably an arylene group of C ₆ to C ₁₂ , and examples thereof may be phenyl, biphenyl, naphthalene, etc. When L ¹ and L' are heterocyclic groups, preferably C ₂ to C ₃₀ heterocyclic groups, more preferably C ₂ to C ₁₆ heterocyclic groups, examples include pyridine, pyrimidine, triazine, It may be quinazoline, benzoquinazoline, dibenzoquinazoline, carbazole, benzocarbazole, benzothienopyrimidine, dibenzofuran, benzofuropyrimidine, pyridopyridazine, etc.

R ^a and R ^b are each independently an aryl group of C ₆ -C ₆₀ ; fluorenyl group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Se, Si and P; A fused ring group of an aromatic ring of C ₆ -C ₆₀ and an aliphatic ring of C ₃ -C ₆₀ ; and combinations thereof, and R ^a and R ^b may be combined with each other to form a ring. R ^a and R ^b may be phenyl, biphenyl, naphthalene, 9,9-dimethyl-9H-fluorene, etc.

R' and R" are a C ₁ -C ₅₀ alkyl group; a C ₆ -C ₆₀ aryl group; a fluorenyl group; and at least one heteroatom selected from the group consisting of O, N, S, Se, Si and P. a heterocyclic group containing C ₂ -C ₆₀ ; and a fused ring group of an aromatic ring of C ₆ -C ₆₀ and an aliphatic ring of C ₃ -C ₆₀ , and R' and R" are combined with each other to form a ring. can be formed. R' and R" may be phenyl, methyl, etc.

R ¹ to R ¹⁷ , R', R", R ^a , R ^b , Ar ¹ , L' and L are an aryl group, an arylene group, a fluorenyl group, a fluorenylene group, a hetero ring group, a fused ring group, When it is an alkyl group, alkenyl group, alkynyl group, alkoxy group, or aryloxy group, or when adjacent groups are combined with each other to form a ring, each of them is deuterium; halogen; C ₁ -C ₂₀ alkyl group or C ₆ -C ₂₀ Silane group substituted or unsubstituted with an aryl group; siloxane group; boron group; germanium group; cyano group; nitro group; C ₁ -C ₂₀ alkylthio group; C ₁ -C ₂₀ alkoxyl 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; fluorenyl group; O, N, C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of S, Si and P; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ arylalkyl group; C ₈ -C It may be further substituted with one or more substituents selected from the group consisting of an arylalkenyl group of ₂₀ ; and combinations thereof.

Formula 1 may be represented by any one of Formulas 2 to 7 below.

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

<Formula 5> <Formula 6> <Formula 7>

In Formulas 2 to 7, the definitions of R ¹ to R ¹⁷ and X are the same as those defined in Formula 1.

Preferably, Formula 1 may be represented by any one of the following Formulas 8-1 to 11-6. In the following formulas ^8-1 to 8-6, in formula ¹ , In formulas 11-1 to 10-6, X is S, and in formulas 11-1 to 11-6, X is O.

<Formula 8-1> <Formula 8-2> <Formula 8-3>

<Formula 8-4> <Formula 8-5> <Formula 8-6>

<Formula 9-1> <Formula 9-2> <Formula 9-3>

<Formula 9-4> <Formula 9-5> <Formula 9-6>

<Formula 10-1> <Formula 10-2> <Formula 10-3>

<Formula 10-4> <Formula 10-5> <Formula 10-6>

<Formula 11-1> <Formula 11-2> <Formula 11-3>

<Formula 11-4> <Formula 11-5> <Formula 11-6>

In Formulas 8-1 to 11-6, R ¹ to R ¹⁷ are as defined in Formula 1.

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

.

.

In another embodiment, the present invention includes a first electrode; second electrode; and an organic material layer located between the first electrode and the second electrode and containing the compound represented by Formula 1 or formed by Formula 1. At this time, the compound represented by Formula 1 may be included in at least one layer among 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 of the organic material layer, and may be a single compound or It may be contained as a component of a mixture of two or more types. That is, the compound represented by Formula 1 can be used as a material for a hole injection layer, a hole transport layer, an auxiliary light emitting layer, a light emitting layer, an auxiliary electron transport layer, an electron transport layer, or an electron injection layer. Preferably, the compound represented by Formula 1 can be used as a phosphorescent host material of the light-emitting layer, more preferably a red phosphorescent host material.

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

Hereinafter, the synthesis example of the compound represented by Formula 1 and the manufacturing example of the organic electric device according to the present invention will be described in detail through examples, but the present invention is not limited to the following examples.

Synthesis example

Illustratively, compounds (final products) according to the present invention may be synthesized according to Schemes 1 and 2 below, but are not limited thereto. In the following reaction formula, each symbol is the same as defined in Chemical Formula 1.

<Scheme 1> When X is N(-L'-Ar ¹ ) and X=Br, I or Cl

<Scheme 2> When X=S, O, C(R')(R") and X ¹ = I, Br or Cl

, a는 1~4의 정수, b는 0~4의 정수이며, a+b=4이고, R"'은 화학식 1에서 R¹⁰~R¹³에 해당하고, X'= S, O 또는 C(R')(R")에 해당하며, L²는 L¹과 같다.In the A ring and A" ring of Scheme 2, Z=

, a is an integer from 1 to 4, b is an integer from 0 to 4, a+b=4, R"' corresponds to R ¹⁰ to R ¹³ in Formula 1, and X'=S, O or C ( Corresponds to R')(R"), and L ² is the same as L ¹ .

I. Synthesis of Core

1. Core 1-1 Synthesis example

(1) Core A-1 synthesis

Add 1,5-dibromonaphthalene (70g, 244.78mmol) to a round bottom flask and dissolve in THF (1077ml), then (2-nitrophenyl)boronic acid (40.86g, 244.78mmol), Pd(PPh ₃ ) ₄ (4.24g, 3.67mmol), K ₂ CO ₃ (50.75g, 367.17mmol), and water (539ml) were added and stirred at 90°C. When the reaction was completed, extraction was performed with CH ₂ Cl ₂ and water, the organic layer was dried with MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silicagel column to obtain 28.12 g of product (yield: 35%).

(2) Core A-2 synthesis

Core A-1 (45g, 137.12mmol) was placed in a round bottom flask and dissolved in o -dichlorobenzene (686ml), then triphenylphosphine (89.92g, 342.81mmol) was added and stirred at 200°C. When the reaction was completed, o -dichlorobenzene was removed through distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried with MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silicagel column to obtain 29.65 g of product (yield: 73%).

(3) Core A-3 synthesis

Core A-2 (29g, 97.91mmol), 1-chloro-2-iodobenzene (35.02g, 146.88mmol), Cu powder (0.21g, 3.26mmol), K ₂ CO ₃ (13.53g, 97.92mmol), 18- Add Crown-6 (1.73g, 6.53mmol) and nitrobenzene (343ml) and reflux for 12 hours. When the reaction is completed, the temperature of the reactant is cooled to room temperature and nitrobenzene is removed. Extracted with MC and washed with water. The organic layer was dried with MgSO ₄ and concentrated, and the resulting organic material was separated using a silicagel column to obtain 26.28 g of product (yield: 66%).

(4) Core A-4 synthesis

Core A-3 (31.88g, 78.39mmol) was placed in a round bottom flask and dissolved in toluene (823mL), then 2-chloroaniline (10g, 78.39mmol), Pd ₂ (dba) ₃ (0.72g, 0.78mmol), P( t -Bu) ₃ (0.32g, 1.57mmol) and NaO t -Bu (7.53g, 78.39mmol) were added and stirred at 100°C. When the reaction was completed, extraction was performed with CH ₂ Cl ₂ and water, the organic layer was dried with MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silicagel column to obtain 20.61 g of product (yield: 58%).

(5) Core 1-1 synthesis

Core A-4 (20.61g, 45.46mmol), Pd(OAc) ₂ (1.02g, 4.55mmol), P(t-Bu) ₃ (1.84g, 9.09mmol), K ₂ CO ₃ (37.70g, 272.76mmol) ), DMA (341ml) was added and refluxed at 170°C for 12 hours. When the reaction is completed, the temperature of the reactant is cooled to room temperature, extracted with MC, and washed with water. The organic layer was dried with MgSO4 and concentrated, and the resulting organic material was separated using a silicagel column to obtain 7.96g of product (yield: 46%).

2. Core 1-9 Synthesis example

(1) Core A-5 synthesis

1,6-dibromonaphthalene (100g, 349.69mmol), THF (1539ml), (2-nitrophenyl)boronic acid (58.37g, 349.69mmol), Pd(PPh ₃ ) ₄ (6.06g, 5.25mmol), K ₂ CO ₃ (72.50g, 524.53mmol), and water (769ml) were used to obtain 47.05g of product (yield: 41%) using the synthesis method of Core A-1.

(2) Core A-6 synthesis

Core A-5 (47.05g, 143.37mmol), o -dichlorobenzene (717ml), and triphenylphosphine (94.01g, 358.43mmol) were used to obtain 30.57g of product (yield: 72%) using the Core A-2 synthesis method.

(3) Core A-7 synthesis

Core A-6 (30.57g, 103.22mmol), 1-chloro-2-iodobenzene (51.08g, 154.83mmol), Cu powder (0.33g, 5.16mmol), K ₂ CO ₃ (21.40g, 154.83mmol), 18 -Crown-6 (2.73g, 10.32mmol) and nitrobenzene (361ml) were used to obtain 39.08g of product (yield: 76%) using the synthesis method of Core A-3.

(4) Core A-8 synthesis

Core A-7 (39.08g, 96.09mmol), Pd(OAc) ₂ (1.08g, 4.80mmol), P(t-Bu) ₃ (1.94g, 9.61mmol), K ₂ CO ₃ (39.84g, 288.26mmol) ), DMA (721ml) was used to obtain 15.30g of product (yield: 43%) using the synthesis method of Core 1-1.

(5) Core A-9 synthesis

Core-8 (50g, 135.04mmol), bis(pinacolato)diboron (37.72g, 148.55mmol), PdCl ₂ (dppf) ₂ (2.96g, 4.05mmol), KOAc (39.76g, 405.13mmol), DMF (851ml) Add and reflux at 120°C for 6 hours. When the reaction is completed, the temperature of the reactant is cooled to room temperature, extracted with MC, and washed with water. The organic layer was dried with MgSO ₄ and concentrated, and the resulting organic material was separated using a silicagel column to obtain 46.21 g of product (yield: 82%).

(6) Core A-10 synthesis

Core A-9 (46.21g, 110.73mmol), THF (487ml), methyl 5-bromo-2-iodobenzoate (37.75g, 110.73mmol), Pd(PPh ₃ ) ₄ (1.92g, 1.66mmol), K ₂ CO ₃ (22.96g, 166.10mmol), and water (244ml) were used to obtain 39.65g of product (yield: 71%) using the synthesis method of Core A-1.

(7) Core A-11 synthesis

After dissolving Core A-10 (39.65g, 78.61mmol) in THF (393ml) in a round bottom flask, methylmagnesium bromide (37.49g, 314.45mmol) was slowly added dropwise and stirred at room temperature. When the reaction was completed, extraction was performed with diethyl ether and water, and the organic layer was dried with MgSO ₄ and concentrated to obtain an intermediate product. This intermediate product was dissolved in acetic acid solution (314ml), HCl (6ml) was added, and refluxed. When the reaction was completed, water was added and stirred, and the resulting solid was filtered under reduced pressure and washed with water and methanol to obtain 14.91 g of the product as a white powder (yield: 39% over two steps).

(8) Core 1-9 synthesis

Core A-11 (14.91g, 30.65mmol), bis(pinacolato)diboron (8.56g, 33.72mmol), PdCl ₂ (dppf) ₂ (0.67g, 0.92mmol), KOAc (9.02g, 91.96mmol), DMF ( 193.11ml) was used to obtain 13.90g of product (yield: 85%) using the synthesis method of Core A-9.

3. Core 1-10 Synthesis example

(1) Core A-12 synthesis

1,7-dibromonaphthalene (70g, 244.78mmol), THF (1077ml), (2-nitrophenyl)boronic acid (40.86g, 244.78mmol), Pd(PPh ₃ ) ₄ (4.24g, 3.67mmol), K ₂ CO ₃ (50.75g, 367.17mmol), and water (539ml) were used to obtain 36.95g of product (yield: 46%) using the synthesis method of Core A-1.

(2) Core A-13 synthesis

Core A-12 (45g, 137.12mmol), o -dichlorobenzene (686ml), and triphenylphosphine (89.92g, 342.81mmol) were used to obtain 28.02g of product (yield: 69%) using the Core A-2 synthesis method.

(3) Core A-14 synthesis

Core A-13 (28g, 94.54mmol), 1,2-diiodobenzene (45.78g, 141.81mmol), Cu powder (0.3g, 4.73mmol), K ₂ CO ₃ (19.60g, 141.81mmol), 18-Crown- 6 (2.50g, 9.45mmol) and nitrobenzene (330ml) were used to obtain 37.21g of product (yield: 79%) using the synthesis method of Core A-3.

(4) Core A-15 synthesis

Core A-14 (85g, 170.63mmol), Pd(OAc) ₂ (1.92g, 8.53mmol), P(t-Bu) ₃ (3.45g, 17.06mmol), K ₂ CO ₃ (70.75g, 511.88mmol) , DMA (1280ml) was used to obtain 25.90g of product (yield: 41%) using the synthesis method of Core 1-1.

(5) Core A-16 synthesis

Core A-15 (25.9g, 69.95mmol), bis(pinacolato)diboron (19.54g, 76.95mmol), PdCl ₂ (dppf) ₂ (1.54g, 2.10mmol), KOAc (20.60g, 209.86mmol), DMF ( 441ml) and refluxed at 120°C for 6 hours. When the reaction is completed, the temperature of the reactant is cooled to room temperature, extracted with MC, and washed with water. The organic layer was dried with MgSO ₄ and concentrated, and the resulting organic material was separated using a silicagel column to obtain 23.35 g of product (yield: 80%).

(6) Core A-17 synthesis

Core A-16 (23g, 55.11mmol), THF (242ml), 1-bromo-2-nitrobenzene (11.13g, 55.11mmol), Pd(PPh ₃ ) ₄ (1.91g, 1.65mmol), K ₂ CO ₃ (22.85g, 165.34mmol), and water (121ml) were used to obtain 19.09g of product (yield: 84%) using the synthesis method of Core A-1.

(7) Core 1-8 synthesis

Core A-17 (19g, 46.07mmol), o -dichlorobenzene (230ml), and triphenylphosphine (30.21g, 115.17mmol) were used to obtain 7.71g of product (yield: 44%) using the Core A-2 synthesis method.

4. Core 1-12 Synthesis example

(1) Core A-18 synthesis

Core A-16 (80g, 191.70mmol), THF (843ml), 4-bromo-2-iodo-1-nitrobenzene (62.86g, 191.70mmol), Pd(PPh ₃ ) ₄ (3.32g, 2.88mmol), K ₂ CO ₃ (39.74g, 287.55mmol), and water (422ml) were used to obtain 69.70g of product (yield: 74%) using the synthesis method of Core A-1.

(2) Core A-19 synthesis

Core A-18 (69.70g, 141.86mmol), o -dichlorobenzene (709ml), and triphenylphosphine (93.02g, 354.64mmol) were used to obtain 27.37g of product (yield: 42%) using the Core A-2 synthesis method.

(3) Core A-20 synthesis

Core A-19 (27.37g, 59.58mmol), bis(pinacolato)diboron (16.64g, 65.54mmol), PdCl ₂ (dppf) ₂ (1.31g, 1.79mmol), KOAc (17.54g, 178.75mmol), DMF ( 375ml) was used to obtain 26.25g of product (yield: 87%) using the synthesis method of Core A-9.

(4) Core 1-12 synthesis

Core A-20 (10g, 19.75mmol), THF (87ml), Sub 1-39 (8.66g, 19.75mmol), Pd(PPh ₃ ) ₄ (0.68g, 0.59mmol), K ₂ CO ₃ (8.19g, 59.24 mmol) and water (43 ml) were used to obtain 11.51 g of product (yield: 79%) using the synthesis method of Core A-1.

5. Core 1-16 Synthesis example

(1) Core A-21 synthesis

Core A-16 (50g, 119.81mmol), THF (527ml), 4-bromo-2-iodophenol (35.81g, 119.81mmol), Pd(PPh ₃ ) ₄ (2.08g, 1.8mmol), K ₂ CO ₃ (24.84g, 179.72mmol), and water (264ml) were used to obtain 40.99g of product (yield: 74%) using the synthesis method of Core A-1.

(2) Core A-22 synthesis

Add Core A-21 (40.99g, 88.66mmol) to a round bottom flask along with Pd(OAc) ₂ (1.99g, 8.87mmol) and 3-nitropyridine (1.10g, 8.87mmol), C ₆ F ₆ (133 ml), After dissolving in DMI (89ml), tert -butyl peroxybenzoate (34.44g, 177.31mmol) was added and stirred at 90°C. When the reaction was completed, extraction was performed with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silicagel column to obtain 16.73.g (yield: 41%) of the product.

(3) Core 1-16 synthesis

Core A-22 (16.73g, 36.34mmol), bis(pinacolato)diboron (10.15g, 39.98mmol), PdCl ₂ (dppf) ₂ (0.8g, 1.09mmol), KOAc (10.70g, 109.03mmol), DMF ( 229ml) was used to obtain 15.12g of product (yield: 82%) using the above synthesis method of Core A-9.

6. Core 1-21 Synthesis example

(1) Core A-23 synthesis

1-bromo-8-chloronaphthalene (138g, 414.45mmol), THF (1824ml), (2-nitrophenyl)boronic acid (69.18g, 414.45mmol), Pd(PPh ₃ ) ₄ (7.18g, 6.22mmol), K ₂ CO ₃ (85.92g, 621.68mmol), and water (912ml) were used to obtain 89.77g of product (yield: 66%) using the synthesis method of Core A-1.

(2) Core A-24 synthesis

Core A-23 (89.68g, 273.27mmol), o -dichlorobenzene (1366ml), and triphenylphosphine (179.19g, 683.18mmol) were used to obtain 62.32g of product (yield: 77%) using the Core A-2 synthesis method.

(3) Core A-25 synthesis

Core A-24 (62.32g, 210.42mmol), 1-chloro-2-iodobenzene (75.26g, 315.63mmol), Cu powder (0.67g, 10.52mmol), K ₂ CO ₃ (43.62g, 315.63mmol), 18 -Crown-6 (5.56g, 21.04mmol) and nitrobenzene (736ml) were used to obtain 63.33g of product (yield: 74%) using the synthesis method of Core A-3.

(4) Core A-26 synthesis

Core A-25 (63.33g, 155.71mmol), Pd(OAc) ₂ (1.75g, 7.79mmol), P(t-Bu) ₃ (3.15g, 15.57mmol), K ₂ CO ₃ (64.56g, 467.14mmol) ), DMA (1168ml) was used to obtain 23.64g of product (yield: 41%) using the synthesis method of Core 1-1.

(5) Core A-27 synthesis

Core A-26 (23.64g, 63.85mmol), bis(pinacolato)diboron (17.84g, 70.23mmol), PdCl ₂ (dppf) ₂ (1.4g, 1.92mmol), KOAc (18.80g, 191.55mmol), DMF ( 402ml) was used to obtain 21.32g of product (yield: 80%) using the synthesis method of Core A-9.

(6) Core A-28 synthesis

Core A-27 (21.32g, 51.09mmol), THF (225ml), 1-bromo-2-nitrobenzene (10.32g, 51.09mmol), Pd(PPh ₃ ) ₄ (1.77g, 1.53mmol), K ₂ CO ₃ (21.18g, 153.26mmol), and water (112ml) were used to obtain 15.17g of product (yield: 72%) using the synthesis method of Core A-1.

(7) Core 1-21 synthesis

Core A-28 (15.17g, 36.78mmol), o -dichlorobenzene (184ml), and triphenylphosphine (24.12g, 91.95mmol) were used to obtain 10.21g of product (yield: 73%) using the Core A-2 synthesis method.

7. Core 1-30 Synthesis example

(1) Core A-29 synthesis

1-bromo-5-iodonaphthalene (130g, 390.43mmol), THF (1718ml), (2-nitrophenyl)boronic acid (65.17g, 390.43mmol), Pd(PPh ₃ ) ₄ (6.77g, 5.86mmol), K ₂ CO ₃ (80.94g, 585.64mmol), and water (859ml) were used to obtain 92.25g of product (yield: 72%) using the synthesis method of Core A-1.

(2) Core A-30 synthesis

Core A-29 (92.25g, 281.10mmol), o -dichlorobenzene (1406ml), and triphenylphosphine (184.33g, 702.76mmol) were used to obtain 63.27g of product (yield: 76%) using the Core A-2 synthesis method.

(3) Core A-31 synthesis

Core A-30 (63.27g, 213.63mmol), 1-chloro-2-iodobenzene (76.41g, 320.44mmol), Cu powder (0.45g, 7.12mmol), K ₂ CO ₃ (29.53g, 213.63mmol), 18 -Crown-6 (3.76g, 14.24mmol) and nitrobenzene (748ml) were used to obtain 54.74g of product (yield: 63%) using the synthesis method of Core A-3.

(4) Core A-32 synthesis

Core A-31 (54.74g, 134.59mmol), Pd(OAc) ₂ (1.51g, 6.73mmol), P(t-Bu) ₃ (2.72g, 13.46mmol), K ₂ CO ₃ (55.81g, 403.78mmol) ), DMA (1009ml) was used to obtain 20.93g of product (yield: 42%) using the synthesis method of Core 1-1.

(5) Core A-33 synthesis

Core A-32 (20.93g, 56.53mmol), bis(pinacolato)diboron (15.79g, 62.18mmol), PdCl ₂ (dppf) ₂ (1.24g, 1.70mmol), KOAc (16.64g, 169.59mmol), DMF ( 356ml) was used to obtain 19.34g of product (yield: 82%) using the synthesis method of Core A-9.

(6) Core A-34 synthesis

Core A-33 (40g, 95.85mmol), THF (422ml), 1-bromo-2-nitrobenzene (19.36g, 95.85mmol), Pd(PPh ₃ ) ₄ (3.32g, 2.88mmol), K ₂ CO ₃ (39.74g, 287.55mmol), and water (211ml) were used to obtain 34.39g of product (yield: 87%) using the synthesis method of Core A-1.

(7) Core 1-30 synthesis

Core A-34 (34.39g, 83.38mmol), o -dichlorobenzene (417ml), and triphenylphosphine (54.67g, 208.45mmol) were used to obtain 22.21g of product (yield: 70%) using the Core A-2 synthesis method.

8. Core 1-32 Synthesis example

(1) Core A-35 synthesis

Core A-33 (35g, 83.87mmol), THF (369ml), N-(3-bromo-4-nitrophenyl)-9,9-dimethyl-N-phenyl-9H-fluoren-3-amine (40.71g, 83.87 mmol), Pd(PPh ₃ ) ₄ (2.91g, 2.52mmol), K ₂ CO ₃ (34.77g, 251.61mmol), and water (185ml) were used to obtain 43.18g of product (yield: 74%) using the synthesis method of Core A-1.

(2) Core 1-32 synthesis

Core A-35 (43.18g, 62.06mmol), o -dichlorobenzene (310ml), and triphenylphosphine (40.69g, 155.14mmol) were used to obtain 27.60g of product (yield: 67%) using the Core A-2 synthesis method.

9. Core 1-37 Synthesis example

(1) Core A-36 synthesis

Core A-9 (35g, 83.87mmol), THF (369ml), 1-bromo-2-nitrobenzene (16.94g, 83.87mmol), Pd(PPh ₃ ) ₄ (2.91g, 2.52mmol), K ₂ CO ₃ (34.77g, 251.61mmol), and water (185ml) were used to obtain 27.33g of product (yield: 79%) using the synthesis method of Core A-1.

(2) Core 1-37 synthesis

Core A-36 (27.33g, 66.26mmol), o -dichlorobenzene (331ml), and triphenylphosphine (43.45g, 165.66mmol) were used to obtain 9.58g of product (yield: 38%) using the Core A-2 synthesis method.

10. Core 1-45 Synthesis example

(1) Core A-37 synthesis

Core A-16 (50g, 119.81mmol), THF (527ml), 1-bromo-2-nitrobenzene (24.20g, 119.81mmol), Pd(PPh ₃ ) ₄ (4.15g, 3.59mmol), K ₂ CO ₃ (49.68g, 359.44mmol), and water (264ml) were used to obtain 19.77g of product (yield: 40%) using the synthesis method of Core A-1.

(2) Core 1-45 synthesis

Core A-37 (19.77g, 47.93mmol), o -dichlorobenzene (240ml), and triphenylphosphine (31.43g, 119.83mmol) were used to obtain 6.57g of product (yield: 36%) using the Core A-2 synthesis method.

11. Core 1-48 Synthesis example

(1) Core A-38 synthesis

7-bromo-1-iodonaphthalene (50g, 150.16mmol), THF (661ml), (2-nitro-5-(9-(4-phenylbenzo[h]quinazolin-2-yl)-9H-carbazol-3-yl )phenyl)boronic acid (88.06g, 150.16mmol), Pd(PPh3)4 (2.6g, 2.25mmol), K2CO3 (31.13g, 225.25mmol), and water (330ml) using the synthesis method of Core A-1 above. 66.24g of product (yield: 59%) was obtained.

(2) Core A-39 synthesis

Core A-38 (100g, 133.75mmol), o -dichlorobenzene (669ml), and triphenylphosphine (87.70g, 334.38mmol) were used to obtain 29.67g of product (yield: 31%) using the Core A-2 synthesis method.

(3) Core A-40 synthesis

Core A-39 (100g, 139.73mmol), 1-chloro-2-iodobenzene (49.98g, 209.60mmol), Cu powder (0.30g, 4.66mmol), K ₂ CO ₃ (19.31g, 139.73mmol), 18- Crown-6 (2.46g, 9.32mmol) and nitrobenzene (489ml) were used to obtain 70.17g of product (yield: 61%) using the synthesis method of Core A-3.

(4) Core A-41 synthesis

Core A-40 (100g, 121.04mmol) with Pd(OAc) ₂ (1.36g, 6.05mmol), P(t-Bu) ₃ (2.45g, 12.10mmol), K ₂ CO ₃ (50.19g, 363.11mmol) , DMA (908ml) was used to obtain 38.24g of product (yield: 40%) using the synthesis method of Core 1-1.

(5) Core A-42 synthesis

Core A-41 (55.4g, 70.15mmol), bis(pinacolato)diboron (19.60g, 77.16mmol), PdCl ₂ (dppf) ₂ (1.54g, 2.10mmol), KOAc (20.65g, 210.45mmol), DMF ( 442ml) was used to obtain 44.03g of product (yield: 75%) using the synthesis method of Core A-9.

(6) Core A-43 synthesis

Core 4-42 (44g, 52.58mmol), THF (231ml), (2-bromophenyl)(methyl)sulfane (10.68g, 52.58mmol), Pd(PPh ₃ ) ₄ (1.82g, 1.58mmol), K ₂ CO ₃ (21.80g, 157.74mmol), and water (116ml) were used to obtain 32.41g of product (yield: 74%) using the synthesis method of Core A-1.

(7) Core A-44 synthesis

Core A-43 (32.40g, 38.89mmol), H ₂ O ₂ (3.31g, 97.24mmol) and acetic acid (194ml) were added to a round bottom flask and stirred at room temperature. When the reaction was completed, acetic acid was removed and water was added to obtain a solid. The solid was dissolved in CH ₂ Cl ₂ and concentrated on a silicagel column to obtain 28.07 g of product. (yield: 85%)

(8) Core 1-48 synthesis

Core A-44 (28g, 32.98mmol) was dissolved in an excess of H ₂ SO ₄ (66ml) in a round bottom flask, and then stirred at 40°C. When the reaction was completed, it was neutralized to pH 8-9 with 0.2 N NaOH aqueous solution. Water was removed through a reduced-pressure filter, extracted with CH ₂ Cl ₂ , concentrated, and recrystallized using a silicagel column to obtain 7.01 g of product. (yield: 26%)

Core compound example

II. Synthesis of Sub 1

1. Synthesis of Sub 1-35

Phenylboronic acid pinacol ester (22.3 g, 109 mmol), THF (240 ml), 2,4,6-trichloropyrimidine (10 g, 54.5 mmol), Pd(PPh ₃ ) ₄ (3.8 g, 3.27 mmol), K ₂ CO ₃ (45.2 g, 327 mmol), and water (120 ml) were added and stirred at 90°C. When the reaction was completed, extraction was performed with CH ₂ Cl ₂ and water, the organic layer was dried with MgSO ₄ and concentrated, and the resulting organic material was recrystallized using a silicagel column to obtain 9.5 g of product. (Yield: 65%)

2. Sub 1-47 synthesis

(1) Sub 1-I-2 synthesis

The starting material, 2-aminobenzoic acid (15.22 g, 111 mmol), was added to a round bottom flask along with urea (46.66 g, 776.9 mmol) and stirred at 160°C. After confirming the reaction by TLC, the mixture was cooled to 100°C, water (55ml) 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 14.58 g of product (yield: 81%).

(2) Sub 1-II-2 synthesis

Sub 1-I-2 (14.58 g, 89.9 mmol) obtained in the above synthesis was dissolved in POCl ₃ (60ml) in a round bottom flask at room temperature, and then N,N-Diisopropylethylamine (29.05 g, 224.8 mmol) was slowly added dropwise. , and stirred at 90°C. When the reaction was completed, it was concentrated, then ice water (120ml) was added and stirred at room temperature for 1 hour. The resulting solid was filtered under reduced pressure and dried to obtain 15.39 g of product (yield: 86%).

(3) Sub 1-47 synthesis

Phenylboronic acid pinacol ester (19.2 g, 75.4 mmol), THF (332 ml), 2,4-dichloroquinazoline (15 g, 75.4 mmol), Pd(PPh ₃ ) ₄ (2.6 g, 2.26 mmol), K ₂ CO ₃ (31.2 g, 226 mmol), and water (166 ml) were used to obtain 9.64 g of product using the Sub 1-35 synthesis method. (Yield: 49%)

3. Sub 1-3 synthesis

(1) Sub 1-I-3 synthesis

The starting material, 10-aminophenanthrene-9-carboxylic acid (60.22 g, 253.8 mmol), urea (106.71 g, 1776.8 mmol), and water (130ml) were mixed using the Sub 1-I-47 synthesis method to obtain 41.94 g of product (yield: 63%) was obtained.

(2) Sub 1-II-3 synthesis

POCl ₃ (110ml), N , N -Diisopropylethylamine (51.67 g, 399.8 mmol) were added to Sub 1-I-3 (41.94 g, 159.9 mmol) obtained in the above synthesis using the Sub 1-II-47 synthesis method to produce product 40.19. g (yield: 84%) was obtained.

(3) Sub 1-56 synthesis

Sub 1-II-3 (40.19 g, 134.3 mmol) obtained from the above synthesis was mixed with 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane (30.16 g, 147.8 mmol), Pd(PPh) ₃ ) ₄ (6.21 g, 5.4 mmol), K ₂ CO ₃ (55.7 g, 403 mmol), THF, and water were used to obtain 23.81 g of product (yield: 52%) using the Sub 1-35 synthesis method.

4. Sub 1-62 synthesis

Phenylboronic acid pinacol ester (14.4 g, 70.6 mmol), THF (310 ml), 2,4-dichlorobenzo[4,5]thieno[3,2-d]pyrimidine (18 g, 70.6 mmol), Pd(PPh ₃ ) ₄ (2.4 g, 2.1 mmol), K ₂ CO ₃ (29.3 g, 212 mmol), and water (155 ml) were used to obtain 9.21 g of product using the Sub 1-35 synthesis method. (Yield: 44%)

Exemplary Compounds of Sub 1

III. Final product synthesis

Product 1 Synthesis

1.P1-1 Synthesis example

Add Core 1-1 (9.5g, 24.97mmol) to a round bottom flask, dissolve in toluene (262mL), and then add Sub 1-1 (3.92g, 24.97mmol), Pd ₂ (dba) ₃ (0.69g, 0.75mmol) ), P( t -Bu) ₃ (0.30g, 1.50mmol), NaO t -Bu (7.20g, 74.91mmol) were added and stirred at 100°C. When the reaction was completed, extraction was performed with CH ₂ Cl ₂ and water, the organic layer was dried with MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silicagel column to obtain 10.15 g of product (yield: 89%).

2.P2-7 Synthesis example

Core 1-10 (5.5g, 14.46mmol), toluene (152mL), Sub 1-45 (3.86g, 14.46mmol), Pd ₂ (dba) ₃ (0.40g, 0.43mmol), P( t -Bu) ₃ (0.18g, 0.87mmol) and NaO t -Bu (4.17g, 43.37mmol) were used to obtain 7.33g of product (yield: 83%) using the above synthesis method.

3.P3-10 Synthesis example

Core 1-21 (5.8g, 15.25mmol), toluene (160mL), Sub 1-46 (3.67g, 15.25mmol), Pd ₂ (dba) ₃ (0.42g, 0.46mmol), P( t -Bu) ₃ (0.19g, 0.91mmol) and NaO t -Bu (4.40g, 45.74mmol) were used to obtain 7.22g of product (yield: 81%) using the synthesis method of P1-1.

4.P4-9 Synthesis example

Core 1-30 (4.7g, 12.35mmol), toluene (130mL), Sub 1-70 (6.13g, 12.35mmol), Pd ₂ (dba) ₃ (0.34g, 0.37mmol), P( t -Bu) ₃ (0.15g, 0.74mmol) and NaO t -Bu (3.56g, 37.06mmol) were used to obtain 7.28g of product (yield: 74%) using the synthesis method of P1-1.

5.P5-7 Synthesis example

Core 1-37 (4.5g, 11.83mmol), toluene (124mL), Sub 1-31 (6.67g, 11.83mmol), Pd ₂ (dba) ₃ (0.32g, 0.35mmol), P( t -Bu) ₃ (0.14g, 0.71mmol) and NaO t -Bu (3.41g, 35.48mmol) were used to obtain 7.25g of product (yield: 71%) using the synthesis method of P1-1.

6.P5-7 Synthesis example

Core 1-45 (5.6g, 14.72mmol), toluene (155mL), Sub 1-17 (5.85g, 14.72mmol), Pd ₂ (dba) ₃ (0.4g, 0.44mmol), P( t -Bu) ₃ (0.18g, 0.88mmol) and NaO t -Bu (4.24g, 44.16mmol) were used to obtain 7.08g of product (yield: 69%) using the synthesis method of P1-1.

Product 2 Synthesis

1.P1-20 Synthesis example

After dissolving Core 1-3 (6.9g, 13.18mmol) in THF (58ml) in a round bottom flask, Sub 1-92 (5.94g, 13.18mmol), Pd(PPh ₃ ) ₄ (0.46g, 0.40mmol), K ₂ CO ₃ (5.47g, 39.54mmol), and water (29ml) were added and stirred at 90°C. When the reaction was completed, extraction was performed with CH ₂ Cl ₂ and water, the organic layer was dried with MgSO ₄ and concentrated, and the resulting compound was recrystallized using a silicagel column to obtain 7.19 g of product (yield: 73%).

2.P2-15 Synthesis example

Core 1-13 (6.9g, 13.18mmol), THF (58ml), Sub 1-11 (5.05g, 13.18mmol), Pd(PPh ₃ ) ₄ (0.46g, 0.40mmol), K ₂ CO ₃ (5.47g , 39.54 mmol) and water (29 ml) were used to obtain 7.10 g of product (yield: 77%) using the synthesis method of P1-20.

3.P2-21 Synthesis example

Core 1-15 (8.2g, 16.16mmol), THF (71ml), Sub 1-58 (7.46g, 16.16mmol), Pd(PPh ₃ ) ₄ (0.56g, 0.48mmol), K ₂ CO ₃ (6.7g , 48.48mmol) and water (36ml) were used to obtain 7.14g of product (yield: 58%) using the synthesis method of P1-20.

4.P3-21 Synthesis example

Core 1-27 (8g, 15.77mmol), THF (69ml), Sub 1-50 (5.78g, 15.77mmol), Pd(PPh ₃ ) ₄ (0.55g, 0.47mmol), K ₂ CO ₃ (6.54g, 47.3 mmol) and water (35 ml) were used to obtain 7.07 g of product (yield: 63%) using the synthesis method of P1-20.

5.P3-22 Synthesis example

Core 1-28 (10.50g, 19.68mmol), THF (87ml), Sub 1-63 (5.84g, 19.68mmol), Pd(PPh ₃ ) ₄ (0.68g, 0.59mmol), K ₂ CO ₃ (8.16g , 59.05 mmol) and water (43 ml) were used to obtain 7.10 g of product (yield: 54%) using the synthesis method of P1-20.

6.P4-13 Synthesis example

Core 1-33 (6.2g, 11.84mmol), THF (52ml), Sub 1-98 (6.52g, 11.84mmol), Pd(PPh ₃ ) ₄ (0.41g, 0.36mmol), K ₂ CO ₃ (4.91g , 35.53 mmol) and water (26 ml) were used to obtain 7.19 g of product (yield: 70%) using the synthesis method of P1-20.

7.P4-16 Synthesis example

Core 1-35 (7g, 13.8mmol), THF (61ml), Sub 1-79 (5.16g, 13.80mmol), Pd(PPh ₃ ) ₄ (0.48g, 0.41mmol), K ₂ CO ₃ (5.72g, 41.39 mmol) and water (30 ml) were used to obtain 7.26 g of product (yield: 78%) using the synthesis method of P1-20.

8.P5-21 Synthesis example

Core 1-44 (6.8g, 10.34mmol), THF (45ml), Sub 1-44 (5.31g, 10.34mmol), Pd(PPh ₃ ) ₄ (0.36g, 0.31mmol), K ₂ CO ₃ (4.29g , 31.02 mmol) and water (23 ml) were used to obtain 7.18 g of product (yield: 72%) using the synthesis method of P1-20.

9.P6-18 Synthesis example

Core 1-51 (6g, 11.82mmol), THF (52ml), Sub 1-104 (5.99g, 11.82mmol), Pd(PPh ₃ ) ₄ (0.41g, 0.35mmol), K ₂ CO ₃ (4.90g, 35.47mmol) and water (26ml) were used to obtain 7.25g of product (yield: 76%) using the synthesis method of P1-20.

The FD-MS values of compounds P1-1 to P6-20 of the present invention prepared according to the above synthesis examples are shown in Table 1 below.

[Table 1]

Meanwhile, the above has described exemplary synthesis examples of the present invention represented by Formula 1, but these are all Buchwald-Hartwig cross coupling reaction, Suzuki cross-coupling reaction, and 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.), etc., and it is known to those skilled in the art that the above reaction proceeds even if other substituents defined in Formula 1 (substituents such as A, It will be easy to understand.

Manufacturing evaluation of organic electric devices

[ Example One] Red Organic electroluminescent device (phosphorescent host)

60 nm thick holes were created by vacuum depositing 4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine (hereinafter abbreviated as "2-TNATA") on the ITO layer (anode) formed on the glass substrate. After forming the injection layer, 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (hereinafter abbreviated as "NPD") was vacuum deposited to a thickness of 60 nm to form a hole transport layer. Next, on the hole transport layer, the present invention compound P1-8 was used as a host material, and bis-(1-phenylisoquinolyl)iridium(Ⅲ)acetylacetonate (hereinafter abbreviated as (piq) ₂ Ir(acac)) was used as a dopant material. A 30 nm thick light-emitting layer was formed by doping at a weight ratio of 95:5, and on the light-emitting layer, (1,1'-bisphenyl)-4-oleato)bis(2-methyl-8-quinolineoleato)aluminum ( (hereinafter abbreviated as BAlq) was vacuum deposited to a thickness of 10 nm to form a hole-blocking layer, and tris(8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) was deposited to a thickness of 40 nm on the hole-blocking layer. An electron transport layer was formed. Then, LiF was deposited on the electron transport layer to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device. .

[ Example 2] to [ Example 29] Red Organic electroluminescent device

An organic electroluminescent device was manufactured in the same manner as Example 1, except that the compounds of the present invention shown in Table 2 below were used as the red host material of the light emitting layer instead of the compound P1-8 of the present invention.

[ Comparative example 1] to [ Comparative example 5]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that one of Comparative Compounds 1 to 5 below was used instead of Compound P1-8 of the present invention as the red host material of the light emitting layer.

<Comparative compound 1> <Comparative compound 2> <Comparative compound 3>

<Comparative compound 4> <Comparative compound 5>

Electroluminescence (EL) characteristics were measured using PR-650 from Photoresearch by applying a forward bias direct current voltage to the organic electroluminescent devices manufactured in Examples 1 to 33 and Comparative Examples 1 to 5 of the present invention. was measured, and as a result of the measurement, the T95 lifespan was measured using a lifespan measurement equipment manufactured by McScience at a standard luminance of 2500 cd/m ² , and the measurement results are shown in Tables 2 and 3 below.

Table 2 below shows the measurements of an organic electroluminescent device using a compound with X=N-L1-Ar1 in Formula 1, and Table 3 shows a compound with It is a result.

[Table 2]

[Table 3]

As can be seen from the results of Table 2 and Table 3, the organic electroluminescent device using the material for organic electroluminescent device of the present invention as a phosphorescent host has significantly improved luminous efficiency and lifespan compared to the case using the comparative compound, and has low driving force. Voltage is shown.

In more detail, the device characteristics were superior when Comparative Compounds 2 to 5, which have indolocarbazole as the main skeleton, were used as host materials rather than CBP (Comparative Compound 1), which is generally used as a host material. , when the compound of the present invention was used as a host material, it showed better results in terms of driving voltage, efficiency, and lifespan than Comparative Compound 2 to Comparative Compound 5.

Comparing Comparative Examples 2 to 5 using Comparative Compounds 2 to 5, Comparative Compound 2 or Comparative Compound 3 in which indole is fused to the indolocarbazole skeleton is benzothiophene. It can be seen that the device characteristics are superior to Comparative Compound 4 or Comparative Compound 5 in which benzothiophen or benzofuran is fused, and the indolocarbazole skeleton is better than Comparative Compound 2 or Comparative Compound 3. The compound of the present invention in which carbazole, dibenzothiophen, dibenzofuran, or fluorene is fused maintains or slightly reduces the driving voltage and increases luminous efficiency. It was found that the effect of improvement and longevity was maximized.

In addition, it can be confirmed that among the compounds of the present invention, compounds fused with carbazole exhibit better device characteristics than compounds fused with dibenzothiophene, dibenzofuran, or fluorene. This is because, as can be seen in Table 4 below, the physical properties of the compound change significantly as one more phenyl is fused to the core. Comparing the physical properties of Comparative Compound 2 and Compound P1-8 of the present invention, differences can be seen in the energy levels of the compounds, especially the HOMO level and T1 level, and therefore, the difference in the physical properties of these compounds can be seen in the device during device deposition. It acts as a major factor in improving performance (for example, energy balance), resulting in different device results.

[Table 4]

The above description is merely an illustrative description of the present invention, and those skilled in the art will be able to make various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in this specification are for illustrative purposes rather than limiting 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 in accordance with the claims below, and all technologies within the equivalent scope should be interpreted as being included in the scope of rights of the present invention.

100: organic electric device 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

Claims (11)

Compound represented by Formula 1:
<Formula 1>

In Formula 1,
Ring A is one of the following formulas 1-1 to 1-3,
<Formula 1-1><Formula1-2><Formula1-3>

R ¹ to R ¹⁷ are independently hydrogen; heavy hydrogen; halogen; Cyano group; nitrogyne; C ₆ -C ₆₀ aryl group; fluorenyl group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Se, Si and P; A fused ring group of an aromatic ring of C ₆ -C ₆₀ and an aliphatic ring of C ₃ -C ₆₀ ; C ₁ -C ₅₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkyne group; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; -L ¹ -Ar ¹ ; -L'-N(R ^a )(R ^b ); And it is selected from the group consisting of combinations thereof, and adjacent groups can be combined with each other to form a ring,
X is N(-L ¹ -Ar ¹ ), O, S or C(R')(R"),
Ar ¹ is an aryl group of C ₆ -C ₆₀ ; fluorenyl group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Se, Si and P; A fused ring group of an aromatic ring of C ₆ -C ₆₀ and an aliphatic ring of C ₃ -C ₆₀ ; -L'-N(R ^a )(R ^b ); and is selected from the group consisting of combinations thereof,
wherein L ¹ and L' are independently a single bond; C ₆ -C ₆₀ arylene group; fluorenylene group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Se, Si and P; A fused ring group of an aromatic ring of C ₆ -C ₆₀ and an aliphatic ring of C ₃ -C ₆₀ ; and is selected from the group consisting of combinations thereof,
R ^a and R ^b are each independently an aryl group of C ₆ -C ₆₀ ; fluorenyl group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Se, Si and P; A fused ring group of an aromatic ring of C ₆ -C ₆₀ and an aliphatic ring of C ₃ -C ₆₀ ; and combinations thereof, and R ^a and R ^b may be combined with each other to form a ring,
R' and R" are a C ₁ -C ₅₀ alkyl group; a C ₆ -C ₆₀ aryl group; a fluorenyl group; and at least one heteroatom selected from the group consisting of O, N, S, Se, Si and P. a heterocyclic group containing C ₂ -C ₆₀ ; and a fused ring group of an aromatic ring of C ₆ -C ₆₀ and an aliphatic ring of C ₃ -C ₆₀ , and R' and R" are combined with each other to form a ring. can form,
R ¹ to R ¹⁷ , R', R", R ^a , R ^b , Ar ¹ , L' and L are an aryl group, an arylene group, a fluorenyl group, a fluorenylene group, a hetero ring group, a fused ring group, An alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryloxy group, or a ring formed by combining adjacent groups is substituted with deuterium; halogen; C ₁ -C ₂₀ alkyl group or C ₆ -C ₂₀ aryl group, respectively. Unsubstituted silane group; siloxane group; boron group; germanium group; cyano group; nitro group; C ₁ -C ₂₀ alkylthio group; C ₁ -C ₂₀ alkoxyl 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; fluorenyl group; O, N, S, Si and C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of P; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ arylalkyl group; C ₈ -C ₂₀ arylalkene It may be further substituted with one or more substituents selected from the group consisting of; and combinations thereof. According to clause 1,
The above Chemical Formula 1 is a compound characterized in that it is represented by one of the following Chemical Formulas 2 to 7:
<Formula 2><Formula3><Formula4>

<Formula 5><Formula6><Formula7>

In Formulas 2 to 7, the definitions of R ¹ to R ¹⁷ and X are the same as those defined in claim 1. According to clause 1,
The above Chemical Formula 1 is a compound characterized in that it is represented by one of the following Chemical Formulas 8-1 to 11-6:
<Formula 8-1><Formula8-2><Formula8-3>

<Formula 8-4><Formula8-5><Formula8-6>

<Formula 9-1><Formula9-2><Formula9-3>

<Formula 9-4><Formula9-5><Formula9-6>

<Formula 10-1><Formula10-2><Formula10-3>

<Formula 10-4><Formula10-5><Formula10-6>

<Formula 11-1><Formula11-2><Formula11-3>

<Formula 11-4><Formula11-5><Formula11-6>

In Formulas 8-1 to 11-6, R ¹ to R ¹⁷ are as defined in claim 1. According to clause 1,
Formula 1 is a compound characterized in that it is one of the following compounds:

. first electrode; second electrode; and an organic material layer formed between the first electrode and the second electrode.
The organic material layer is an organic electric device characterized in that it contains the compound of any one of claims 1 to 4. According to clause 5,
The compound is included in at least one layer 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 of the organic material layer, and the compound is one type of single compound or two or more types. An organic electric device characterized in that it is used as a mixture. According to clause 6,
An organic electric device, characterized in that the compound is included in the light-emitting layer. According to clause 5,
The organic material layer is an organic electric device characterized in that it is formed by a spin coating process, nozzle printing process, inkjet printing process, slot coating process, dip coating process, or roll-to-roll process. According to clause 5,
An organic electric device further comprising a light efficiency improvement layer formed on at least one side of the first electrode and the second electrode opposite to the organic material layer. A display device including the organic electric element of claim 5; and
An electronic device comprising a control unit that drives the display device. According to clause 10,
An electronic device, wherein the organic electric device is one of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, and a monochromatic lighting device.

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