KR102469742B1 - Compound for organic electric element, organic electric element comprising the same and electronic device thereof - Google Patents

Abstract

The present invention provides a compound capable of improving high luminous efficiency, low driving voltage and lifetime of a device, an organic electric device using the same, and an electronic device thereof.

Description

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

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

In general, the organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material.

An organic electric device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer is often composed of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may include, 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 may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, according to their functions.

In the case of polycyclic cyclic compounds containing heteroatoms, the difference in properties depending on the material structure is very large, and they are applied to various layers as materials for organic electric devices. In particular, it is characterized by having different band gaps (HOMO, LUMO), electrical properties, chemical properties, physical properties, etc. depending on the number of rings, fused position, and type and arrangement of heteroatoms. this has been going on

For example, US Patent Application Publication No. US2008/0145708A1 (2008.06.19) discloses an embodiment in which a polycyclic compound is applied to a hole transport layer or a phosphorescent host of an organic electric device, and Korean Patent Publication No. 10-2007-0012218 (2007.01.25) discloses an example in which a polycyclic compound is applied to an electron transport layer of an organic electric device. Even now, development of materials for organic electric devices regarding the type, number, and location of heteroatoms of polycyclic cyclic compounds is actively progressing.

An object of the present invention is to provide a compound capable of improving the luminous efficiency and lifetime of a device while lowering the driving voltage of the device by using the characteristics of a polycyclic compound, 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 below. Any one of R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ in Formula 1 may form a condensed ring represented by Formula 1a below.

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 of the present invention, not only the driving voltage of the device can be lowered, but also the luminous efficiency and lifetime of the device can be greatly improved.

1 is a cross-sectional view of an organic light emitting device according to an embodiment of the present invention.

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

In adding reference numerals to components of each drawing, it should be noted that the same components have the same numerals as much as possible even if they are displayed on different drawings. In addition, 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.

Also, terms such as first, second, A, B, (a), and (b) may be used in describing the components of the present invention. These terms are only used to distinguish the component from other components, and the nature, order, or order of the corresponding component is not limited by the term. When an element is described as being “connected,” “coupled to,” or “connected” to another element, that element is directly connected or connectable to the other element, but there is another element between the elements. It will be understood that elements may be “connected”, “coupled” or “connected”.

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

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

As used herein, unless otherwise specified, the term "alkyl" or "alkyl group" has a single bond of 1 to 60 carbon atoms, and includes a straight-chain alkyl group, a branched-chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cycloalkyl group, and the like. A radical of a saturated aliphatic functional group, including an alkyl group, a cycloalkyl-substituted alkyl group.

As used herein, the term "haloalkyl group" or "halogenalkyl group" refers to an alkyl group substituted with a halogen unless otherwise specified.

As used herein, the term "heteroalkyl group" means that at least one of the carbon atoms constituting the alkyl group is replaced with a heteroatom.

As used herein, the term "alkenyl group" or "alkynyl group" has a double bond or triple bond of 2 to 60 carbon atoms, respectively, and includes straight or branched chain groups, unless otherwise specified, and is limited thereto. It is not.

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

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

As used herein, the term "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" refers to an alkenyl group to which an oxygen radical is attached, and unless otherwise specified, 2 to 60 It has a carbon number of, but is not limited thereto.

As used herein, the term "aryloxyl group" or "aryloxy group" 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.

The terms "aryl group" and "arylene group" used herein have 6 to 60 carbon atoms, respectively, unless otherwise specified, but are not limited thereto. In the present invention, an aryl group or an arylene group refers to a single-ring or multi-ring aromatic ring, and includes an aromatic ring formed by bonding or reacting with adjacent substituents. For example, the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, anthracenyl group, a fluorene group, a spirofluorene group, or a spirobifluorene group.

The prefix “aryl” or “ar” refers to a radical substituted with an aryl group. For example, an arylalkyl group is an alkyl group substituted with an aryl group, an arylalkenyl group is an alkenyl group substituted with an aryl group, and a radical substituted with an aryl group has carbon atoms described herein.

Also, when the prefixes are named consecutively, it means that the substituents are listed in the order listed first. For example, an arylalkoxy group means an alkoxy group substituted with an aryl group, an alkoxylcarbonyl group means a carbonyl group substituted with an alkoxyl group, and an arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group. Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

The term "heteroalkyl" as used herein, unless otherwise specified, means an alkyl containing one or more heteroatoms. As used herein, the term "heteroaryl group" or "heteroarylene group" refers to an aryl group or arylene group having 2 to 60 carbon atoms each containing at least one heteroatom, unless otherwise specified, and is limited thereto It does not, and includes at least one of a single ring and a multi-ring, and may be formed by combining adjacent functional groups.

As used herein, the term "heterocyclic group" includes at least one heteroatom, has 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, and includes a heteroaliphatic ring and a heterocyclic group, unless otherwise specified. Contains an aromatic ring. It may also be formed by combining adjacent functional groups.

As used herein, the term "heteroatom" refers to N, O, S, P or Si unless otherwise specified.

In addition, 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.

Unless otherwise specified, the term "aliphatic" as used herein means an aliphatic hydrocarbon ring having 1 to 60 carbon atoms, and "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

Unless otherwise specified, the term "ring" used herein refers to a fused ring composed of an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a heterocyclic ring having 2 to 60 carbon atoms, or a combination thereof, Contains saturated or unsaturated rings.

Other hetero compounds or heteroradicals other than the aforementioned hetero compounds include, but are not limited to, one or more heteroatoms.

Unless otherwise specified, the term "carbonyl" as used herein is represented by -COR', where R' is hydrogen, an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 30 carbon atoms, or a carbon atom of 3 to 30 carbon atoms. A cycloalkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

Unless otherwise specified, the term "ether" as used herein is represented by -R-O-R', wherein R or R' are each independently hydrogen, an alkyl group of 1 to 20 carbon atoms, or a carbon atom of 6 to 30 carbon atoms. It is an aryl group, a C3-C30 cycloalkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, or a combination thereof.

In addition, unless explicitly stated otherwise, “substituted” in the term “substituted or unsubstituted” as used herein means deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxyl 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, deuterium-substituted C ₆ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ arylalkenyl group, silane group, boron group, germanium group, and C ₂ ~ C ₂₀ means substituted with one or more substituents selected from the group consisting of heterocyclic groups, but is not limited to these substituents.

In addition, unless explicitly stated otherwise, the chemical formula used in the present invention applies the same as the substituent definition by the exponent definition of the following formula.

Here, when a is an integer of 0, substituent R ¹ does not exist, and when a is an integer of 1, one substituent R ¹ is bonded to any one of the carbon atoms forming the benzene ring, and when a is an integer of 2 or 3 Each is combined as follows, wherein R ¹ may be the same or different from each other, and when a is an integer of 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while indicating the hydrogen bonded to the carbon forming the benzene ring. is omitted.

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 element 100 according to the present invention includes a first electrode 120, a second electrode 180, and a first electrode 110 and a second electrode 180 formed on a substrate 110. ) is provided with an organic material layer containing the compound according to the present invention. In this case, the first electrode 120 may be an anode (anode), and the second electrode 180 may be a cathode (negative electrode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may 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, other layers except for the light emitting layer 150 may not be formed. A hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, a buffer layer 141, and the like may be further included, and an electron transport layer 160 may serve as a hole blocking layer.

In addition, although not shown, the organic electric element according to the present invention may further include a protective layer or a capping layer formed on a surface opposite to the organic material layer among at least one surface of the first electrode and the second electrode.

The compound according to the present invention applied to the organic layer is a host or dopant of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, the electron injection layer 170, and the light emitting layer 150 or the light efficiency improvement layer. material can be used. Preferably, the compound of the present invention may be used as the light emitting layer 150 .

On the other hand, even in the same core, since the band gap, electrical properties, interface properties, etc. may vary depending on which substituent is attached to which position, the selection of the core and the combination of sub-substituents bonded thereto are also very important. It is important, and in particular, long life and high efficiency can be achieved at the same time when the optimal combination of the energy level and T1 value between each organic material layer and the intrinsic properties of the material (mobility, interfacial property, etc.) is achieved.

Therefore, in the present invention, by forming a light emitting layer using the compound represented by Formula 1, the energy level and T1 value between each organic material layer, and the intrinsic properties (mobility, interface properties, etc.) of the material are optimized to optimize the lifetime of the organic electric device. and efficiency can be improved at the same time.

An organic light emitting device according to an embodiment of the present invention may be manufactured using a physical vapor deposition (PVD) method. For example, the anode 120 is formed by depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate, and the hole injection layer 130, the hole transport layer 140, the light emitting layer 150, and 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.

In addition, the organic material layer is formed by a solution process or a solvent process other than a deposition method using various polymer materials, such as a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, a roll-to-roll process, and a doctor blading process. It can be manufactured with a smaller number of layers by a method such as a printing process, a screen printing process, or a thermal transfer method. Since the organic layer according to the present invention can be formed in various ways, the scope of the present invention is not limited by the forming method.

The organic electric element according to the present invention may be a top emission type, a bottom emission type or a double side emission type depending on the material used.

WOLED (White Organic Light Emitting Device) has the advantage of being easy to realize high resolution and excellent processability, and can be manufactured using the color filter technology of the existing LCD. Various structures for a white organic light emitting device mainly used as a backlight device have been proposed and patented. Representatively, a side-by-side method in which R (Red), G (Green), and B (Blue) light emitting units are arranged in parallel on a mutually flat surface, and a stacking method in which R, G, and B light emitting layers are stacked up and down There is, and there is a color conversion material (CCM) method using electroluminescence by a blue (B) organic light emitting layer and photo-luminescence of an inorganic phosphor using light from the electroluminescent layer. may also be applied to these WOLEDs.

In addition, the organic electric device according to the present invention may be one of an organic light emitting device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a device for monochromatic or white lighting.

Another embodiment of the present invention may include an electronic device including a display device including the above-described organic electric element of the present invention and a control unit controlling the display device. At this time, the electronic device may be a current or future wired/wireless communication terminal, and includes all electronic devices such as 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, a compound according to an aspect of the present invention will be described. A compound according to one aspect of the present invention is represented by Formula 1 below.

In Formula 1,

R ¹ to R ¹⁴ are each independently hydrogen; heavy hydrogen; tritium; 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 O, N, S, Si, and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; C ₁ -C ₅₀ Alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; -L ^a -N(R ^a )(R ^b ); C ₁ -C ₃₀ alkoxyl group; And C ₆ -C ₃₀ It is selected from the group consisting of an aryloxy group or adjacent groups may be bonded to each other to form a ring, and R ¹ to R ¹⁴ that do not form a ring are the same as those defined above,

However, any one of R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ forms a condensed ring represented by Formula 1a,

When R ⁵ and R ⁶ form a condensed ring represented by Formula 1a, R ⁵ represents a bond connected to ** and R ⁶ represents a bond connected to *,

When R ⁶ and R ⁷ form a condensed ring represented by Formula 1a, R ⁶ represents a bond connected to ** and R ⁷ represents a bond connected to *,

When R ⁸ and R ⁹ form a condensed ring represented by Formula 1a, R ⁸ represents a bond connected to ** and R ⁹ represents a bond connected to *,

When R ⁹ and R ¹⁰ form a condensed ring represented by Formula 1a, R ⁹ represents a bond connected to ** and R ¹⁰ represents a bond connected to *,

X is one of S, O and C(Ar ² )(Ar ³ );

Ar ¹ is each independently a C ₆ -C ₆₀ aryl group; fluorenyl group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; C ₁ -C ₅₀ Alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; -L ^a -N(R ^a )(R ^b ); C ₁ -C ₃₀ alkoxyl group; And C ₆ -C ₃₀ It is selected from the group consisting of an aryloxy group,

Ar ² and Ar ³ are i) each independently a C ₆ -C ₆₀ aryl group; fluorenyl group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; C ₁ -C ₅₀ Alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₁ -C ₃₀ alkoxyl group; And C ₆ -C ₃₀ It is selected from the group consisting of an aryloxy group, or ii) Ar ² and Ar ³ are bonded to each other to form a spiro compound together with C to which they are bonded,

R ^a and R ^b are each independently a C ₆ -C ₆₀ aryl group; fluorenyl group; a C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; C ₁ -C ₅₀ Alkyl group; A fused ring group of a C ₆ -C ₆₀ aromatic ring and a C ₃ -C ₆₀ aliphatic ring; And C ₂ -C ₂₀ alkenyl group; is selected from the group consisting of,

L ¹ and L ^a are each independently a single bond; C ₆ -C ₆₀ arylene group; Fluorenylene group; a C ₂ -C ₆₀ divalent heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; A divalent fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; And it is selected from the group consisting of a divalent aliphatic hydrocarbon group, L ¹ and L ^a (except for a single bond) are each deuterium; halogen; 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; A deuterium-substituted C ₆ -C ₂₀ aryl group; fluorenyl group; C ₂ -C ₂₀ heterocyclic group; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ arylalkyl group; -N(R ^c )(R ^d ); And a C ₈ -C ₂₀ arylalkenyl group; may be substituted with one or more substituents selected from the group consisting of,

Wherein R ^c and R ^d are each independently a C ₆ -C ₆₀ aryl group; fluorenyl group; It may be selected from the group consisting of a C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P.

Here, each of the aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group, and aryloxy group is 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 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; A deuterium-substituted C ₆ -C ₂₀ aryl group; fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ arylalkyl group; And it may be further substituted with one or more substituents selected from the group consisting of a C ₈ -C ₂₀ arylalkenyl group.

Here, the aryl group may have 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, and in the case of the heterocyclic group, carbon atoms 2 to 60, preferably 2 carbon atoms ~ 30, more preferably, it may be a heterocyclic ring having 2 to 20 carbon atoms, and in the case of the alkyl group, the number of carbon atoms is 1 to 50, preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 20 carbon atoms It may be an alkyl group of 1 to 10.

In the case of the above-mentioned aryl group or arylene group, specifically, the aryl group or arylene group is each independently a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group, or a phenylene group, a biphenylene group, a terphenylene group, or a naphthyl group. It may be a rene group or a phenanthrylene group.

More specifically, the compound represented by Formula 1 may be any one of the following compounds, but is not limited to the following compounds.

Formula 1 may be represented by one of Formulas 2 to 5 below.

The R ¹ to R ¹⁴ , X, Ar ¹ and L ¹ are the same as those defined in Chemical Formula 1.

Ar ¹ of Formula 1 may be represented by one of Formulas A-1 to A-3 below.

In Formula A-1, Q ¹ to Q ⁴ are each independently N, CR ^e , and carbon (C) bonded to L ¹ , and one of Q ¹ to Q ⁴ is carbon (C) bonded to L ¹ . ego,

In Formula A-2, Q ¹ to Q ⁴ are each independently N or CR ^e ,

In Formula A-3, Q ⁵ to Q ⁹ are each independently N or CR ^e ,

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

In the above formulas A-1 to A-3,

R ^e 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 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; A deuterium-substituted C ₆ -C ₂₀ aryl group; fluorenyl group; a C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ arylalkyl group; and a C ₈ -C ₂₀ arylalkenyl group.

Ring Z of Chemical Formula A-1 and Chemical Formula A-2 may be each independently represented by one of the following Chemical Formulas.

In the above formulas Z-1 to Z-15, the mark * denotes a bonding moiety bonded to a ring containing Q ¹ to Q ⁴ to form a fused ring,

W ¹ and W ² are each independently one of a single bond, NL ² -Ar ⁴ , S, O, C(Ar ⁵ )(Ar ⁶ ),

V is N, CR ^e independently of each other,

L ² is a single bond; C ₆ -C ₆₀ arylene group; Fluorenylene group; a C ₂ -C ₆₀ divalent heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; A divalent fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; And it is selected from the group consisting of a divalent aliphatic hydrocarbon group,

Ar ⁴ to Ar ⁶ are C ₆ -C ₂₀ aryl groups; fluorenyl group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; C ₁ -C ₅₀ Alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₁ -C ₃₀ alkoxyl group; And C ₆ -C ₃₀ It is selected from the group consisting of an aryloxy group,

Ar ⁵ and Ar ⁶ may combine with each other to form a spiro compound together with carbon (C) to which they are bonded,

R ^e is the same as the definition of R ^e in Formulas A-1 to A-3.

At least one of Q ¹ to Q ⁴ may be N.

In Chemical Formulas A-1 and A-2, at least one of Q ¹ to Q ⁴ includes N may be one of the following Chemical Formulas Z-16 to Z-50.

W ¹ and W ² are each independently one of a single bond, NL ² -Ar ⁴ , S, O, C(Ar ⁵ )(Ar ⁶ ), and R ^e 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 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; A deuterium-substituted C ₆ -C ₂₀ aryl group; fluorenyl group; a C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ arylalkyl group; and a C ₈ -C ₂₀ arylalkenyl group.

In this case, although R ^e is shown identically in Chemical Formulas Z-16 to Z-50, it may be independently the same or different from each other at each position in each Chemical Formula. For example, 5 R ^e in Formula Z-16 are each independently 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 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; A deuterium-substituted C ₆ -C ₂₀ aryl group; fluorenyl group; a C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ arylalkyl group; and a C ₈ -C ₂₀ arylalkenyl group.

More specifically, the compound represented by Formula 1 may be any one of the following compounds, but is not limited to the following compounds.

As another embodiment, the present invention provides a compound for an organic electric device represented by Formula 1 above.

In another embodiment, the present invention provides an organic electric device containing the compound represented by Formula 1 above.

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

That is, the compound represented by Formula 1 may be used as a material for a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport layer, or an electron injection layer. In particular, the compound represented by Formula 1 may be used as a material for the light emitting layer. Specifically, an organic electric device including one of the compounds represented by Formula 1 is provided in the organic layer, and more specifically, the An organic electric device including the compounds represented by the individual chemical formulas (1-1 to 4-38) in the organic material layer is provided.

In another embodiment, in at least one layer of the hole injection layer, the hole transport layer, the light emitting auxiliary layer, the light emitting layer, the electron transport layer and the electron injection layer of the organic material layer, the compound is contained alone, or the It provides an organic electric device characterized in that the compound is contained in a combination of two or more different types, or the compound is contained in a combination of two or more types with other compounds. In other words, each layer may contain a compound corresponding to Formula 1 alone, or may include a mixture of two or more types of compounds represented by Formula 1, and the compounds of claims 1 to 6 and compounds not applicable to the present invention. Mixtures with may be included. Here, the compound that does not correspond to the present invention may be a single compound or may be two or more compounds. In this case, when the above compounds are contained in a combination of two or more kinds of other compounds, the other compounds may be known compounds of each organic material layer or may be compounds to be developed in the future. In this case, the compound contained in the organic material layer may be composed of only the same type of compound, but may also be a mixture of two or more different types of compounds represented by Formula 1.

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

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

[ synthesis example ]

The compound represented by Chemical Formula 1 according to the present invention (final products) is synthesized by reacting Sub 2 with one of Sub 1A to Sub 1D as shown in Schemes 1 to 4 below, but is not limited thereto. In this case, R ¹ to R ¹⁴ , X, Ar ¹ and L ¹ are the same as those defined in Formula 1, and Hal ¹ is Br or Cl.

I. Sub 1A to Sub Synthesis of 1D

Sub 1A to Sub 1D in Reaction Schemes 1 to 4 may be synthesized by the reaction pathways of Reaction Schemes 5 and 6 below, but are not limited thereto.

은 R⁵, R⁶, R⁸, R⁹ 중 하나가 Br인 것을 의미한다.

means that one of R ⁵ , R ⁶ , R ⁸ , and R ⁹ is Br.

Synthesis examples of specific compounds belonging to Sub 1 are as follows.

1. Sub 1A-1 synthesis example

(1) Synthesis of Sub 1A-I-1

After dissolving the starting material phenylboronic acid (41.33 g, 338.96 mmol) in THF (1180ml) in a round bottom flask, 3,8-dibromo-1-nitronaphthalene (123.40 g, 372.86 mmol), Pd(PPh ₃ ) ₄ (15.67 g, 13.56 mmol), NaOH (40.68 g, 1016.89 mmol) and water (590ml) were added and stirred at 80°C. After the reaction was completed, extraction was performed with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 71.19 g (yield: 64%) of the product.

(2) Synthesis of Sub 1A-II-1

After dissolving Sub 1A-I-1 (71.19 g, 216.94 mmol) obtained in the above synthesis in o -dichlorobenzene (1900ml) in a round bottom flask, triphenylphosphine (142.25 g, 542.34 mmol) 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. After drying the organic layer with MgSO ₄ and concentrating, the resulting compound was recrystallized using a silicagel column to obtain 44.97 g (yield: 70%) of the product.

(3) Synthesis of Sub 1A-III-1

After dissolving Sub 1A-II-1 (19.75 g, 66.69 mmol) obtained in the above synthesis in THF (220ml) in a round bottom flask, (2-(methylsulfinyl)phenyl)boronic acid (12.27 g, 66.69 mmol), Pd ( PPh ₃ ) ₄ (3.08 g, 2.67 mmol), NaOH (8.00 g, 200.06 mmol) and water (110 ml) were added and stirred at 80°C. After the reaction was completed, extraction was performed with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 17.07 g (yield: 72%) of the product.

(4) Synthesis of Sub 1A-1

Sub 1A-III-1 (17.07 g, 48.02 mmol) obtained in the above synthesis was put together with triflic acid (63.7ml, 720.35 mmol) in a round bottom flask, stirred at room temperature for 24 hours, and then an aqueous solution of pyridine (840ml, pyridine: H ₂ O = 1 : 5) was slowly added dropwise and stirred at reflux for 30 minutes. After the reaction was completed, extraction was performed with CH ₂ Cl ₂ and water, and the organic layer was dried with MgSO ₄ , concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 7.61 g (yield: 49%) of the product.

2. Sub 1A-2 synthesis example

(1) Synthesis of Sub 1A-III'-2

(2-hydroxyphenyl)boronic acid (11.62 g, 84.21 mmol), Pd(PPh ₃ ) ₄ (3.89 g, 3.37 mmol), NaOH (10.11 g, 252.63 mmol), THF (280ml) and water (140ml) were added, and 21.62 g (yield: 83%) of the product was obtained using the Sub 1A-III-1 synthesis method.

(2) Synthesis of Sub 1A-2

Sub 1A-III'-2 (21.62 g, 69.89 mmol) obtained in the above synthesis was added together with Pd(OAc) ₂ (1.57 g, 6.99 mmol) and 3-nitropyridine (0.87 g, 6.99 mmol) in a round bottom flask and C After dissolving with ₆ F ₆ (105ml) and DMI (70ml), tert -butyl peroxybenzoate (27.15 g, 139.77 mmol) was added and stirred at 90°C. After the reaction was completed, extraction was performed with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 8.81 g (yield: 41%) of the product.

3. Sub 1A-6 synthesis example

(1) Synthesis of Sub 1A-I-6

3,8-dibromo-1-nitronaphthalene (50.24 g, 151.79 mmol), Pd ( PPh ₃ ) ₄ (6.38 g, 5.52 mmol), NaOH (16.56 g, 413.96 mmol), THF (480 ml), water (240 ml) were added and the product was obtained by using the Sub 1A-I-1 synthesis method above to obtain 47.15 g (yield: 60%) was obtained.

(2) Synthesis of Sub 1A-II-6

Triphenylphosphine (54.29 g, 207.00 mmol) and o -dichlorobenzene (725ml) were added to Sub 1A-I-6 (47.15 g, 82.80 mmol) obtained in the above synthesis, and 29.82 g of product was obtained using the above Sub 1A-II-1 synthesis method. (Yield: 67%) was obtained.

(3) Synthesis of Sub 1A-III-6

(2-(methylsulfinyl)phenyl)boronic acid (10.21 g, 55.48 mmol), Pd(PPh ₃ ) ₄ (2.56 g, 2.22 mmol), After adding NaOH (6.66 g, 166.45 mmol), THF (180ml) and water (90ml), 24.83 g (yield: 75%) of the product was obtained using the Sub 1A-III-1 synthesis method.

(4) Synthesis of Sub 1A-6

Triflic acid (55.2ml, 624.14 mmol) and pyridine aqueous solution (730ml, pyridine : H ₂ O = 1 : 5) were added to Sub 1A-III-6 (24.83 g, 41.61 mmol) obtained in the above synthesis, and the Sub 1A- 1 synthesis method was used to obtain 10.81 g of product (yield: 46%).

4.Sub 1A-19 synthesis example

(1) Synthesis of Sub 1A-I-19

Starting material (3'-(dibenzo[b,d]thiophen-3-yl(9-phenyl-9H-carbazol-3-yl)amino)-[1,1'-biphenyl]-4-yl)boronic acid (91.41 g, 143.60 mmol), 3,8-dibromo-1-nitronaphthalene (52.28 g, 157.96 mmol), Pd(PPh ₃ ) ₄ (6.64 g, 5.74 mmol), NaOH (17.23 g, 430.79 mmol), THF ( 500ml) and water (250ml) were added, and 70.19 g (yield: 58%) of the product was obtained using the Sub 1A-I-1 synthesis method.

(2) Synthesis of Sub 1A-II-19

Triphenylphosphine (54.61 g, 208.20 mmol) and o -dichlorobenzene (730ml) were added to Sub 1A-I-19 (70.19 g, 83.28 mmol) obtained in the above synthesis, and 42.54 g of product was obtained using the above Sub 1A-II-1 synthesis method. (Yield: 63%) was obtained.

(3) Synthesis of Sub 1A-III-19

(2-(methylsulfinyl)phenyl)boronic acid (9.65 g, 52.47 mmol), Pd(PPh ₃ ) ₄ (2.43 g, 2.10 mmol), After adding NaOH (6.30 g, 157.40 mmol), THF (170ml) and water (85ml), 27.39 g (yield: 60%) of the product was obtained using the Sub 1A-III-1 synthesis method.

(4) Synthesis of Sub 1A-19

Triflic acid (41.8ml, 472.19 mmol) and pyridine aqueous solution (550ml, pyridine : H ₂ O = 1 : 5) were added to Sub 1A-III-19 (27.39 g, 31.48 mmol) obtained in the above synthesis, and the Sub 1A- 1 synthesis method was used to obtain 11.34 g of product (yield: 43%).

5. Sub 1B-1 synthesis example

(1) Synthesis of Sub 1B-I-1

1,5-dibromo-4-nitronaphthalene (188.34 g, 569.08 mmol), Pd(PPh ₃ ) ₄ (23.91 g, 20.69 mmol), NaOH (62.08 g, 1552.04 mmol), THF (1800ml), and water (900ml) were added, and 117.14 g (yield: 69%) of the product was obtained using the Sub 1A-I-1 synthesis method.

(2) Synthesis of Sub 1B-II-1

Triphenylphosphine (234.07 g, 892.40 mmol) and o -dichlorobenzene (2500ml) were added to Sub 1B-I-1 (117.14 g, 356.96 mmol) obtained in the above synthesis, and 78.23 g of product was obtained using the above Sub 1A-II-1 synthesis method. (Yield: 74%) was obtained.

(3) Synthesis of Sub 1B-III-1

(2-(methylsulfinyl)phenyl)boronic acid (12.27 g, 66.69 mmol), Pd(PPh ₃ ) ₄ (3.08 g, 2.67 mmol), After adding NaOH (8.00 g, 200.06 mmol), THF (220ml) and water (110ml), 16.59 g (yield: 70%) of the product was obtained using the Sub 1A-III-1 synthesis method.

(4) Synthesis of Sub 1B-1

Triflic acid (62.0ml, 700.10 mmol) and pyridine aqueous solution (818ml, pyridine : H ₂ O = 1 : 5) were added to Sub 1B-III-1 (16.59 g, 46.67 mmol) obtained in the above synthesis, and the Sub 1A- 1 synthesis method was used to obtain 11.62 g of product (yield: 77%).

6. Sub 1B-2 synthesis example

(1) Synthesis of Sub 1B-III'-2

(2-hydroxyphenyl)boronic acid (8.05 g, 58.35 mmol), Pd(PPh ₃ ) ₄ (2.70 g, 2.33 mmol), NaOH (7.00 g, 175.04 mmol), THF (190ml), and water (95ml) were added, and 15.52 g (yield: 86%) of a product was obtained using the above Sub 1A-III-1 synthesis method.

(2) Synthesis of Sub 1B-2

Pd(OAc) ₂ (1.13 g, 5.02 mmol), 3-nitropyridine (0.62 g, 5.02 mmol), tert -butyl peroxybenzoate (19.49 g , 100.34 mmol), C ₆ F ₆ (75ml), and DMI (50ml) were added, and 8.48 g (yield: 55%) of the product was obtained using the Sub 1A-2 synthesis method.

7. Sub 1B-3 synthesis example

(1) Synthesis of Sub 1B-III”-3

(2-(methoxycarbonyl)phenyl)boronic acid (15.20 g, 84.45 mmol), Pd(PPh ₃ ) ₄ (3.90 g, 3.38 mmol), After adding NaOH (10.13 g, 253.34 mmol), THF (280ml) and water (140ml), 21.07 g (yield: 71%) of the product was obtained using the Sub 1A-III-1 synthesis method.

(2) Synthesis of Sub 1B-3

After dissolving Sub 1B-III”-3 (21.07 g, 59.96 mmol) obtained in the above synthesis in THF (300ml) in a round bottom flask, methylmagnesium bromide 1.0M in THF (239.8ml, 239.84 mmol) was slowly added dropwise thereto, It was stirred at room temperature. Upon completion of the reaction, the mixture was extracted with diethyl ether and water, and the organic layer was dried over MgSO ₄ and concentrated to obtain an intermediate product. This intermediate product was dissolved in acetic acid solution (250ml) and refluxed after adding HCl (5ml). When the reaction was completed, water was added, and the solid produced after stirring was filtered under reduced pressure and washed with water and methanol to obtain 14.59 g of the product as a white powder (yield: 73% over two steps).

8. Sub 1B-11 synthesis example

(1) Synthesis of Sub 1B-III'-11

(2-hydroxy-5-(phenanthren-2-yl(phenyl)amino)phenyl)boronic acid (20.62 g, 50.88 mmol), Pd( PPh ₃ ) ₄ (2.35 g, 2.04 mmol), NaOH (6.11 g, 152.65 mmol), THF (170 ml) and water (85 ml) were added and the product obtained by the Sub 1A-III-1 synthesis method above was 23.18 g (yield: 79%) was obtained.

(2) Synthesis of Sub 1B-11

Pd(OAc) ₂ (0.90 g, 4.02 mmol), 3-nitropyridine (0.50 g, 4.02 mmol), tert -butyl peroxybenzoate (15.61 g , 80.39 mmol), C ₆ F ₆ (60ml), and DMI (40ml) were added, and 9.93 g (yield: 43%) of a product was obtained using the Sub 1A-2 synthesis method.

9. Sub 1B-23 synthesis example

(1) Synthesis of Sub 1B-I-23

1,5-dibromo-4-nitronaphthalene (114.97 g, 347.37 mmol), Pd(PPh ₃ ) ₄ to the starting material (4-(bis(4-fluorophenyl)amino)phenyl)boronic acid (102.67 g, 315.79 mmol) (14.60 g, 12.63 mmol), NaOH (37.89 g, 947.37 mmol), THF (1100 ml) and water (550 ml) were added to obtain 88.93 g (yield: 53%) of the product using the Sub 1A-I-1 synthesis method. got it

(2) Synthesis of Sub 1B-II-23

Triphenylphosphine (109.75 g, 418.42 mmol) and o -dichlorobenzene (1465ml) were added to Sub 1B-I-23 (88.93 g, 167.37 mmol) obtained in the above synthesis, and 50.14 g of product was obtained using the above Sub 1A-II-1 synthesis method. (Yield: 60%) was obtained.

(3) Synthesis of Sub 1B-III”-23

(2-(methoxycarbonyl)phenyl)boronic acid (18.07 g, 100.41 mmol), Pd(PPh ₃ ) ₄ (4.64 g, 4.02 mmol), NaOH (12.05 g, 301.23 mmol), THF (330ml), and water (165ml) were added to obtain 32.85 g of product (yield: 59%) using the Sub 1A-III-1 synthesis method.

(4) Synthesis of Sub 1B-23

After obtaining an intermediate product by using methylmagnesium bromide 1.0M in THF (236.9ml, 236.94 mmol) and THF (295ml) to Sub 1B-III”-23 (32.85 g, 59.23 mmol) obtained in the above synthesis, acetic acid solution ( 250ml) and HCl (5ml) were added to obtain 19.71 g of product (yield: 62% over two steps) using the Sub 1B-3 synthesis method.

10. Sub 1C-1 synthesis example

(1) Synthesis of Sub 1C-I-1

1,3-dibromo-8-nitronaphthalene (114.68 g, 346.52 mmol), Pd(PPh ₃ ) ₄ (14.56 g, 12.60 mmol), NaOH (37.80 g, 945.05 mmol), THF (1100ml), and water (550ml) were added, and 77.53 g (yield: 75%) of a product was obtained using the Sub 1A-I-1 synthesis method.

(2) Synthesis of Sub 1C-II-1

Triphenylphosphine (154.92 g, 590.64 mmol) and o -dichlorobenzene (1655ml) were added to Sub 1C-I-1 (77.53 g, 236.26 mmol) obtained in the above synthesis, and 47.58 g of product was obtained using the above Sub 1A-II-1 synthesis method. (Yield: 68%) was obtained.

(3) Synthesis of Sub 1C-III-1

(2-(methylsulfinyl)phenyl)boronic acid (16.71 g, 90.80 mmol), Pd(PPh ₃ ) ₄ (4.20 g, 3.63 mmol), After adding NaOH (10.90 g, 272.39 mmol), THF (300ml), and water (150ml), 23.56 g (yield: 73%) of the product was obtained using the Sub 1A-III-1 synthesis method.

(4) Synthesis of Sub 1C-1

Triflic acid (88.0ml, 994.23 mmol) and pyridine aqueous solution (1160ml, pyridine : H ₂ O = 1 : 5) were added to Sub 1C-III-1 (23.56 g, 66.28 mmol) obtained in the above synthesis, and the Sub 1A- 1 synthesis method was used to obtain 10.08 g of product (yield: 47%).

11. Sub 1C-2 synthesis example

(1) Synthesis of Sub 1C-III'-2

(2-hydroxyphenyl)boronic acid (9.44 g, 68.48 mmol), Pd(PPh ₃ ) ₄ (3.17 g, 2.74 mmol), NaOH (8.22 g, 205.43 mmol), THF (230ml), and water (115ml) were added and 18.64 g (yield: 88%) of the product was obtained using the Sub 1A-III-1 synthesis method.

(2) Synthesis of Sub 1C-2

Pd(OAc) ₂ (1.35 g, 6.03 mmol), 3-nitropyridine (0.75 g, 6.03 mmol), tert -butyl peroxybenzoate (23.41 g , 120.51 mmol), C ₆ F ₆ (90ml), and DMI (60ml) were added, and 7.78 g (yield: 42%) of the product was obtained using the Sub 1A-2 synthesis method.

12. Sub 1C-29 synthesis example

(1) Synthesis of Sub 1C-III-30

(4'-(di([1,1'-biphenyl]-4-yl)amino)-3-(methylsulfinyl)-[1, 1'-biphenyl] -4-yl) boronic acid (43.56 g, 75.16 mmol), Pd(PPh ₃ ) ₄ (3.47 g, 3.01 mmol), NaOH (9.02 g, 225.49 mmol), THF (250ml), water ( 125 ml) was added and 32.17 g (yield: 57%) of the product was obtained using the Sub 1A-III-1 synthesis method.

(2) Synthesis of Sub 1C-30

Triflic acid (56.9ml, 642.59 mmol) and pyridine aqueous solution (750ml, pyridine : H ₂ O = 1 : 5) were added to Sub 1C-III-30 (32.17 g, 42.84 mmol) obtained in the above synthesis, and the Sub 1A- 1 synthesis method was used to obtain 12.32 g of product (yield: 40%).

13. Sub 1D-1 synthesis example

(1) Synthesis of Sub 1D-I-1

1,2-dibromo-8-nitronaphthalene (110.59 g, 334.16 mmol), Pd(PPh ₃ ) ₄ (14.04 g, 12.15 mmol), NaOH (36.45 g, 911.34 mmol), THF (1000ml), and water (500ml) were added, and 52.84 g (yield: 53%) of a product was obtained using the Sub 1A-I-1 synthesis method.

(2) Synthesis of Sub 1D-II-1

Triphenylphosphine (105.58 g, 402.55 mmol) and o -dichlorobenzene (1100ml) were added to Sub 1D-I-1 (52.84 g, 161.02 mmol) obtained in the above synthesis, and 32.43 g of product was obtained using the above Sub 1A-II-1 synthesis method. (Yield: 68%) was obtained.

(3) Synthesis of Sub 1D-III-1

(2-(methylsulfinyl)phenyl)boronic acid (10.38 g, 56.42 mmol), Pd(PPh ₃ ) ₄ (2.61 g, 2.26 mmol), NaOH (6.77 g, 169.27 mmol), THF (180ml), and water (90ml) were added to obtain 15.04 g of product (yield: 75%) using the above Sub 1A-III-1 synthesis method.

(4) Synthesis of Sub 1D-1

Triflic acid (56.2ml, 634.69 mmol) and pyridine aqueous solution (740ml, pyridine : H ₂ O = 1 : 5) were added to Sub 1D-III-1 (15.04 g, 42.31 mmol) obtained in the above synthesis, and the Sub 1A- 8.76 g (yield: 64%) of the product was obtained using the synthesis method 1.

14. Sub 1D-7 synthesis example

(1) Synthesis of Sub 1D-I-7

1,2-dibromo-10-nitrophenanthrene (98.52 g, 258.56 mmol), Pd(PPh ₃ ) ₄ (10.86 g, 9.40 mmol), NaOH (28.21 g, 705.16 mmol), THF (820ml), and water (410ml) were added, and 41.78 g (yield: 47%) of the product was obtained using the Sub 1A-I-1 synthesis method.

(2) Synthesis of Sub 1D-II-7

Triphenylphosphine (72.43 g, 276.16 mmol) and o -dichlorobenzene (770ml) were added to Sub 1D-I-7 (41.78 g, 110.46 mmol) obtained in the above synthesis, and 22.95 g of product was obtained using the above Sub 1A-II-1 synthesis method. (Yield: 60%) was obtained.

(3) Synthesis of Sub 1D-III'-7

(2-hydroxyphenyl)boronic acid (9.14 g, 66.29 mmol), Pd(PPh ₃ ) ₄ (3.06 g, 2.65 mmol), NaOH (7.95 g, 198.86 mmol), THF (220ml) and water (110ml) were added, and 19.54 g (yield: 82%) of the product was obtained using the Sub 1A-III-1 synthesis method.

(4) Synthesis of Sub 1D-7

Pd(OAc) ₂ (1.22 g, 5.44 mmol), 3-nitropyridine (0.67 g, 5.44 mmol), tert -butyl peroxybenzoate (21.12 g , 108.73 mmol), C ₆ F ₆ (82ml), and DMI (54ml) were added, and 10.49 g (yield: 54%) of the product was obtained using the Sub 1A-2 synthesis method.

15. Sub 1D-12 synthesis example

(1) Synthesis of Sub 1D-III-12

(3'-([1,1'-biphenyl]-3-yl(phenyl)amino)-3-(methylsulfinyl)-[1, 1'-biphenyl] -4-yl) boronic acid (25.53 g, 50.72 mmol), Pd(PPh ₃ ) ₄ (2.34 g, 2.03 mmol), NaOH (6.09 g, 152.15 mmol), THF (170ml), water ( 85 ml) was added and 18.48 g (yield: 54%) of the product was obtained using the Sub 1A-III-1 synthesis method.

(2) Synthesis of Sub 1D-12

Triflic acid (36.3ml, 410.76 mmol) and pyridine aqueous solution (480ml, pyridine : H ₂ O = 1 : 5) were added to Sub 1D-III-12 (18.48 g, 27.38 mmol) obtained in the above synthesis, and the Sub 1A- 1 synthesis method was used to obtain 11.09 g of product (yield: 63%).

Compounds belonging to Sub 1A to Sub 1D may be the following compounds, but are not limited thereto, and Table 1 shows Field Desorption-Mass Spectrometry (FD-MS) values of some compounds belonging to Sub 1A to Sub 1D.

II . Sub Composite of 2

Sub 2 of Reaction Scheme 1 may be synthesized by the reaction pathway of Reaction Scheme 22, but is not limited thereto. At this time, Hal ¹ and Hal ² are Br or Cl.

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

1. Sub 2-22 synthesis example

After dissolving 1,3-dibromobenzene (20.17 g, 85.50 mmol) as a starting material in THF (300ml) in a round bottom flask, 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 added and Stir. After the reaction was completed, extraction was performed with CH ₂ Cl ₂ and water, and the organic layer was dried with MgSO ₄ , concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 20.65 g (yield: 63%) of the product.

2. Sub 2-28 synthesis example

2-(dibenzo[b,d]thiophen-4-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 (280 ml), water (140 ml) were added and the product was 19.32 g (yield: 71%) using Sub 2-22 synthesis above. got

3. Sub 2-31 synthesis example

4,4,5,5-tetramethyl-2-(naphthalen-1-yl-d7)-1,3,2-dioxaborolane (29.54 g, 113.11 mmol), Pd(PPh ₃ ) ₄ (4.75 g, 4.11 mmol), K ₂ CO ₃ (42.63 g, 308.47 mmol), THF (360 ml), water (180 ml) were added and the product was 18.03 g (yield: 60%) using Sub 2-22 synthesis above. got

4. Sub 2-50 synthesis example

(1) Synthesis of Sub 2-I-50

The starting material, 1-amino-2-naphthoic acid (75.11 g, 401.25 mmol) was added to a round bottom flask together with urea (168.69 g, 2808.75 mmol) and stirred at 160°C. After confirming the reaction by TLC, the mixture was cooled to 100°C, water (200ml) was added, and the mixture was stirred for 1 hour. Upon completion of the reaction, the resulting solid was filtered under reduced pressure, washed with water and dried to obtain 63.86 g of the product (yield: 75%).

(2) Synthesis of Sub 2-II-50

Sub 2-I-50 (63.86 g, 300.94 mmol) obtained in the above synthesis was dissolved in POCl ₃ (200ml) at room temperature in a round bottom flask, N , N -Diisopropylethylamine (97.23 g, 752.36 mmol) was slowly added dropwise thereto. , and stirred at 90 °C. Upon completion of the reaction, after concentrating, ice water (500ml) was added and stirred at room temperature for 1 hour. The resulting solid was filtered under reduced pressure and dried to obtain 67.47 g of product (yield: 90%).

(3) Synthesis of Sub 2-50

4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane (60.80 g, 297.94 mmol) and Pd (PPh) were added to Sub 2-II-50 (67.47 g, 270.86 mmol) obtained in the above synthesis. 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 was 44.89 g (yield: 57%) using the Sub 2-22 synthesis method above. got

5. Sub 2-70 synthesis example

4,4,5,5 -tetramethyl-2-(naphthalen-2-yl)- 1,3,2-dioxaborolane (35.07 g, 138.02 mmol), Pd(PPh ₃ ) ₄ (5.80 g, 5.02 mmol), K ₂ CO ₃ (52.02 g, 376.41 mmol), THF (440 ml), water (220 ml) were added and the product was 19.58 g (yield: 45%) using Sub 2-22 synthesis above. got

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.

III . Product synthesis

After dissolving one of Sub 1A to Sub 1D (1 equivalent) in toluene in a round bottom flask, Sub 2 (1 equivalent), Pd ₂ (dba) ₃ (0.03 equiv.), (t-Bu)3P (0.06 equiv.), 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, and the organic layer was dried with MgSO ₄ , concentrated, and the resulting compound was recrystallized using a silica gel column to obtain a final product.

1. P1-10 synthesis example

After dissolving Sub 1A-1 (5.74 g, 17.75 mmol) obtained in the above synthesis with toluene (180ml) in a round bottom flask, Sub 2-50 (5.16 g, 17.75 mmol), Pd ₂ (dba) ₃ (0.49 g, 0.53 mmol), 50% P( t -Bu) ₃ (0.5ml, 1.06 mmol), NaO t -Bu (5.12 g, 53.25 mmol) were added and stirred at 100°C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 7.18 g (yield: 70%) of the product.

2. pages 1-19 synthesis example

Sub 2-1 (2.19 g, 13.97 mmol), Pd ₂ (dba) ₃ (0.38 g, 0.42 mmol) 50% P( t -Bu) ₃ to Sub 1A-6 (7.89 g, 13.97 mmol) obtained in the synthesis above (0.4ml, 0.84 mmol), NaO t -Bu (4.03 g, 41.92 mmol), and toluene (140ml) were added, and 7.52 g (yield: 84%) of a product was obtained using the P 1-10 synthesis method.

3. P1-22 synthesis example

Sub 2-19 (5.73 g, 20.37 mmol), Pd ₂ (dba) ₃ (0.56 g, 0.61 mmol) 50% P( t -Bu) ₃ to Sub 1A-2 (6.26 g, 20.37 mmol) obtained in the above synthesis (0.6ml, 1.22 mmol), NaO t -Bu (5.87 g, 61.10 mmol), and toluene (205ml) were added, and 7.34 g of product (yield: 71%) was obtained using the P 1-10 synthesis method.

4. P1-47 synthesis example

Sub 2-8 (2.59 g, 11.11 mmol), Pd ₂ (dba) ₃ (0.31 g, 0.33 mmol) 50% P( t -Bu) ₃ to Sub 1A-19 (9.31 g, 11.11 mmol) obtained in the above synthesis (0.3ml, 0.67 mmol), NaO t -Bu (3.20 g, 33.33 mmol), and toluene (110ml) were added, and 7.04 g (yield: 64%) of a product was obtained using the P 1-10 synthesis method.

5.P2-4 synthesis example

Sub 2-31 (5.55 g, 18.99 mmol), Pd ₂ (dba) ₃ (0.52 g, 0.57 mmol) 50% P( t -Bu) ₃ to Sub 1B-1 (6.14 g, 18.99 mmol) obtained in the synthesis above (0.6ml, 1.14 mmol), NaO t -Bu (5.47 g, 56.96 mmol), and toluene (190ml) were added, and 7.82 g of product (yield: 77%) was obtained using the P 1-10 synthesis method.

6.P2-30 synthesis example

Sub 2-70 (6.94 g, 20.01 mmol), Pd ₂ (dba) ₃ (0.55 g, 0.60 mmol) 50% P( t -Bu) ₃ to Sub 1B-2 (6.15 g, 20.01 mmol) obtained in the synthesis above (0.6ml, 1.20 mmol), NaO t -Bu (5.77 g, 60.03 mmol), and toluene (200ml) were added, and 7.66 g (yield: 62%) of a product was obtained using the P 1-10 synthesis method.

7.P2-34 synthesis example

Sub 2-50 (5.87 g, 20.18 mmol), Pd ₂ (dba) ₃ (0.55 g, 0.61 mmol) 50% P( t -Bu) ₃ to Sub 1B-3 (6.73 g, 20.18 mmol) obtained in the synthesis above (0.6ml, 1.21 mmol), NaO t -Bu (5.82 g, 60.55 mmol), and toluene (200ml) were added, and 7.12 g (yield: 60%) of a product was obtained using the P 1-10 synthesis method.

8. P2-39 synthesis example

Sub 2-25 (3.88 g, 12.04 mmol), Pd ₂ (dba) ₃ (0.33 g, 0.36 mmol) 50% P( t -Bu) ₃ to Sub 1B-11 (6.92 g, 12.04 mmol) obtained in the above synthesis (0.4ml, 0.72 mmol), NaO t -Bu (3.47 g, 36.13 mmol), and toluene (120ml) were added, and 7.17 g of product (yield: 73%) was obtained using the P 1-10 synthesis method.

9.P2-50 synthesis example

Sub 2-21 (5.01 g, 16.31 mmol), Pd ₂ (dba) ₃ (0.45 g, 0.49 mmol) 50% P( t -Bu) ₃ to Sub 1B-23 (8.75 g, 16.31 mmol) obtained in the above synthesis (0.5ml, 0.98 mmol), NaO t -Bu (4.70 g, 48.92 mmol), and toluene (160ml) were added, and 7.09 g (yield: 57%) of a product was obtained using the P 1-10 synthesis method.

10.P3-1 synthesis example

Sub 2-1 (3.75 g, 23.90 mmol), Pd ₂ (dba) ₃ (0.66 g, 0.72 mmol) 50% P( t -Bu) ₃ to Sub 1C-1 (7.73 g, 23.90 mmol) obtained in the above synthesis (0.7ml, 1.43 mmol), NaO t -Bu (6.89 g, 71.70 mmol), and toluene (240ml) were added, and 7.54 g of product (yield: 79%) was obtained using the P 1-10 synthesis method.

11.P 3-14 synthesis example

Sub 2-50 (5.76 g, 19.82 mmol), Pd ₂ (dba) ₃ (0.54 g, 0.59 mmol) 50% P( t -Bu) ₃ to Sub 1C-2 (6.09 g, 19.82 mmol) obtained in the synthesis above (0.6ml, 1.19 mmol), NaO t -Bu (5.71 g, 59.45 mmol), and toluene (200ml) were added to obtain 7.79 g of product (yield: 70%) using the P 1-10 synthesis method.

12. P3-36 synthesis example

Sub 2-1 (2.19 g, 13.92 mmol), Pd ₂ (dba) ₃ (0.38 g, 0.42 mmol) 50% P( t -Bu) ₃ to Sub 1C-30 (10.01 g, 13.92 mmol) obtained in the above synthesis (0.4ml, 0.84 mmol), NaO t -Bu (4.01 g, 41.77 mmol), and toluene (140ml) were added, and 7.53 g (yield: 68%) of a product was obtained using the P 1-10 synthesis method.

13.P4-3 synthesis example

Sub 2-28 (5.55 g, 16.36 mmol), Pd ₂ (dba) ₃ (0.45 g, 0.49 mmol) 50% P( t -Bu) ₃ to Sub 1D-1 (5.29 g, 16.36 mmol) obtained in the above synthesis (0.5ml, 0.98 mmol), NaO t -Bu (4.72 g, 49.07 mmol), and toluene (165ml) were added, and 7.14 g of product (yield: 75%) was obtained using the P 1-10 synthesis method.

14.P4-8 synthesis example

Sub 2-50 (5.43 g, 18.68 mmol), Pd ₂ (dba) ₃ (0.51 g, 0.56 mmol) 50% P( t -Bu) ₃ to Sub 1D-1 (6.04 g, 18.68 mmol) obtained in the synthesis above (0.5ml, 1.12 mmol), NaO t -Bu (5.38 g, 56.03 mmol), and toluene (190ml) were added, and 7.23 g (yield: 67%) of a product was obtained using the P 1-10 synthesis method.

15.P4-19 synthesis example

Sub 2-22 (7.91 g, 20.65 mmol), Pd ₂ (dba) ₃ (0.57 g, 0.62 mmol) 50% P( t -Bu) ₃ to Sub 1D-7 (7.38 g, 20.65 mmol) obtained in the synthesis above (0.6ml, 1.24 mmol), NaO t -Bu (5.95 g, 61.95 mmol), and toluene (205ml) were added, and 7.49 g (yield: 55%) of a product was obtained using the P 1-10 synthesis method.

16.P4-35 synthesis example

Sub 2-14 (4.25 g, 13.75 mmol), Pd ₂ (dba) ₃ (0.38 g, 0.41 mmol) 50% P( t -Bu) ₃ to Sub 1D-12 (8.84 g, 13.75 mmol) obtained in the above synthesis (0.4ml, 0.83 mmol), NaO t -Bu (3.97 g, 41.26 mmol), and toluene (140ml) were added, and 7.07 g (yield: 59%) of a product was obtained using the P 1-10 synthesis method.

The FD-MS values of some compounds of the present invention prepared according to the synthesis example as described above are shown in Table 3 below.

Meanwhile, although exemplary synthesis examples of the present invention represented by Formula 1 have been described above, they are all Buchwald-Hartwig cross-coupling reactions, Suzuki cross-coupling reactions, and PPh ₃ -mediated reductive cyclization reactions ( J. Org . Chem . 2005 , 70 , 5014.), Intramolecular acid-induced cyclization reaction ( J. mater. Chem . 1999, 9 , 2095.), Pd(II)-catalyzed oxidative cyclization reaction ( Org . Lett . 2011, 13 , 5504), Grignard It is based on reaction and cyclic dehydration reaction, etc., and other substituents defined in Formula 1 in addition to the substituents specified in the specific synthesis examples (R ¹ to R ¹⁴ , X, Ar ¹ , and substituents such as L ¹ ) are bonded to those skilled in the art that the above reaction proceeds If so, you will easily understand.

For example, in Schemes 1 to 4, one of Sub 1A to Sub 1D and Sub 2 -> Final Product reaction are based on the Buchwald-Hartwig cross coupling reaction, and in Scheme 5, Sub 1-II -> Sub 1-III reaction, Sub 1-II -> Sub 1-III' reaction, Sub 1-II -> Sub 1-III” reaction, starting material -> Sub 1-I reaction in Scheme 6, starting material -> Sub 2 reaction in Scheme 22 are all It is based on the Suzuki cross-coupling reaction. registration notice) was used.) In Scheme 5, the Sub 1-III -> Sub 1 reaction is based on the intramolecular acid-induced cyclization reaction ( J. mater. Chem . 1999, 9 , 2095.). Subsequently, Sub 1-III'-> Sub 1 reaction in Scheme 5 is based on the Pd(II)-catalyzed oxidative cyclization reaction ( Org . Lett . 2011, 13 , 5504), and in Scheme 5 Sub 1-III” -> The Sub 1 reaction is based on the Grignard reaction and the Cyclic Dehydration reaction, and in Scheme 6, the Sub 1-I -> Sub 1-II reaction is a PPh ₃ -mediated reductive cyclization reaction ( J. Org . Chem . 2005, 70 , 5014.) is based on Even if a substituent not specifically specified is attached, the above reactions will proceed.

Manufacturing evaluation of organic electric devices

[ Example 1] Green organic light emitting device (phosphorescent host)

An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention as a light emitting host material for the light emitting layer. First, a 4,4',4''-Tris[2-naphthyl(phenyl)amino]triphenylamine (abbreviated as 2-TNATA) film was vacuum-deposited on an ITO layer (anode) formed on a glass substrate to form a hole having a thickness of 60 nm. After forming the injection layer, a hole transport layer was formed by vacuum depositing an NPD film to a thickness of 60 nm as a hole transport compound on the hole injection layer. The compound P 1-1 of the present invention was used as a host on the hole transport layer, and tris(2-phenylpyridine)-iridium (hereinafter abbreviated as “Ir(ppy) ₃ ”) was used as a dopant material at a weight ratio of 95:5. A light emitting layer was deposited with a thickness of 30 nm by doping. Subsequently, (1,1'-bisphenyl)-4-oleato)bis(2-methyl-8-quinolinolato)aluminum (hereinafter abbreviated as BAlq) was vacuum deposited to a thickness of 10 nm as a hole-blocking layer. As a transport layer, tris(8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) was formed to a thickness of 40 nm. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then Al was deposited to a thickness of 150 nm and used as a cathode, thereby manufacturing an organic light emitting device.

[ Example 2] to [ Example 25] Green organic light emitting device

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the compound of the present invention shown in Table 4 was used instead of the compound P 1-1 according to Example 1 of the present invention as the green host material of the light emitting layer. .

[ comparative example 1] to [ comparative example 3]

Organic light emitting in the same manner as in Example 1, except that one of Comparative Compounds 1 to 3 listed in Table 4 was used instead of Compound P 1-1 according to Example 1 of the present invention as a host material of the light emitting layer. device was manufactured.

By applying a forward bias DC voltage to the organic light emitting devices manufactured by Examples 1 to 25 and Comparative Examples 1 to 3 of the present invention, electroluminescence (EL) characteristics were measured with Photoresearch's PR-650. It was measured, and as a result of the measurement, the T95 life was measured through a life measurement equipment manufactured by McScience at a standard luminance of 5000 cd / m ² , and the measurement results are shown in Table 4 below.

As can be seen from the measurement results of Table 4, it was confirmed that the device using the compound according to an embodiment of the present invention as a phosphorescent green host material of the light emitting layer had significantly improved luminous efficiency and lifetime than Comparative Compounds 1 to 4. .

Comparing the six-ringed heterocyclic compounds, compared to Comparative Compounds 2 to 4, which contain N as the core element in the hexagonal and pentagonal rings, the core element is N in the hexagonal ring and the core in the pentagonal ring. It can be seen that the compound of the present invention, in which the element is a heteroatom type including one of S, O, and CR'R”, exhibits higher efficiency and higher lifetime.

In general, when molecules are stacked, as the number of adjacent π-electrons increases, they have strong electrical interactions, which are closely related to charge carrier mobility.

Comparative compounds 2 to 4, which are N-N type six-ringed heterocyclic compounds, have an edge-to-face arrangement order between molecules because they are heterocyclic cores of the N-N type when the molecules are stacked, which is It is believed to result in charge carrier mobility and low oxidative stability.

In the case of the compound of the present invention, since the heteroatoms in the cyclic compound have heterocyclic cores different from each other, the packing structure of the molecule has an antiparallelcofacial π-stacking structure. This makes the arrangement sequence between molecules face-to-face, and it is judged to have high efficiency by causing remarkably high carrier mobility due to the steric effect of Ar ¹ of the asymmetrically arranged heteroatom N, which is the cause of this layered structure. , it is judged that the lifetime is remarkably increased because it has high oxidation stability.

In addition, the compound of the present invention containing N in the hexagonal ring has a form more suitable for stably accepting both holes and electrons than Comparative Compound 3 in which N is included in the pentagonal ring, resulting in better charge balance in the light emitting layer. It is judged that the luminous efficiency and lifespan are increased by making it good.

[ Example 26] Red organic light emitting device (phosphorescent host)

An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention as a light emitting host material for the light emitting layer. First, a 2-TNATA film was vacuum-deposited on an ITO layer (anode) formed on a glass substrate to form a 60 nm-thick hole injection layer, and then a 60-nm-thick NPD film was vacuum-deposited as a hole transport compound on the hole injection layer to form a hole injection layer. A transport layer was formed. Compound P 1-9 of the present invention was used as a host on the hole transport layer, and a light emitting layer having a thickness of 30 nm was deposited by doping (piq) ₂ Ir(acac) in a weight ratio of 95:5 as a dopant material. Subsequently, BAlq was vacuum deposited to a thickness of 10 nm as a hole blocking layer, and Alq ₃ was deposited to a thickness of 40 nm as an electron transport layer. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then Al was deposited to a thickness of 150 nm and used as a cathode to manufacture an organic light emitting device.

[ Example 27] to [ Example 50] Red organic light emitting device

An organic light emitting device was manufactured in the same manner as in Example 26, except that the compounds of the present invention shown in Table 5 were used instead of Compound P 1-9 according to Example 26 of the present invention as the red host material of the light emitting layer. .

[ comparative example 4] to [ comparative example 6]

Same as Example 26 except that one of Comparative Compound 1, Comparative Compound 4, and Comparative Compound 5 described in Table 5 was used instead of Compound P 1-9 according to Example 26 as the host material of the light emitting layer. An organic light emitting device was manufactured using the method.

By applying a forward bias DC voltage to the organic light emitting devices manufactured by Examples 26 to 50 and Comparative Examples 4 to 6 of the present invention, electroluminescence (EL) characteristics were measured with Photoresearch's PR-650. It was measured, and as a result of the measurement, the T95 life was measured through a life measurement equipment manufactured by McScience at a standard luminance of 2500 cd / m ² , and the measurement results are shown in Table 5 below.

As can be seen from the measurement results of Table 5, the device using the compound according to an embodiment of the present invention as a phosphorescent red host material of the light emitting layer significantly improved the luminous efficiency and lifetime compared to Comparative Compound 1 and Comparative Compounds 5 to 9. confirmed that it has been This is because the heteroatom in the cyclic compound has a heterocyclic core with different heteroatoms and the structure in which N is included in the hexagonal ring is not only in the light emitting layer of the green organic light emitting device (used as a host) but also in the light emitting layer of the red organic light emitting device (used as a host). It can be confirmed that it acts as a major factor in improving the performance of the device.

The compound of the present invention used as a host material in the light emitting layer has high oxidation stability and high charge carrier mobility to achieve more effective charge balance. In particular, among the compounds of the present invention, benzoquinazoline, benzothienopyrimidine, When a specific substituent such as benzofuropyrimidine is introduced, it shows a structure suitable for accepting both holes and electrons and at the same time has an appropriate T1 value to facilitate charge transfer from the host to the dopant, resulting in It can be seen that the best device results are obtained in terms of luminous efficiency and lifetime.

In addition, in the case of a phosphorescent host, it is necessary to understand the relationship between the hole transport layer and the dopant. Even if a similar core is used, it will be very difficult to infer the excellent electrical properties of the phosphorescent host of the compound of the present invention.

[ Example 51] green organic light emitting device ( hole transport layer )

An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention as a hole transport layer material. First, a 2-TNATA film was vacuum deposited on an ITO layer (anode) formed on a glass substrate to form a 60 nm thick hole injection layer, and then the compound P-40 of the present invention was applied to the hole injection layer to a thickness of 60 nm. A hole transport layer was formed by vacuum deposition. 4,4'-N,N'-dicarbazole-biphenyl (hereinafter abbreviated as “CBP”) was used as a host on the hole transport layer, and Ir(ppy) ₃ was doped at a weight ratio of 90:10 as a dopant material. A light emitting layer was deposited with a thickness of 30 nm. Subsequently, BAlq was vacuum deposited to a thickness of 10 nm as a hole blocking layer, and Alq ₃ was deposited to a thickness of 40 nm as an electron transport layer. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then Al was deposited to a thickness of 150 nm and used as a cathode, thereby manufacturing an organic light emitting device.

[ Example 52] to [ Example 71] green organic light emitting device

An organic light emitting device was manufactured in the same manner as in Example 51, except that the compound of the present invention shown in Table 6 was used instead of Compound P 1-40 according to Example 51 as the hole transport layer material.

[ comparative example 7]

An organic light emitting diode was manufactured in the same manner as in Example 51, except that Comparative Compound 6 shown in Table 6 was used instead of Compound P 1-00 according to Example 51 as the hole transport layer material.

A forward bias DC voltage was applied to the organic light emitting devices manufactured by Examples 51 to 71 and Comparative Example 7 of the present invention, and electroluminescence (EL) characteristics were measured with PR-650 of Photoresearch, which Measurement result 5000cd / m ² At the standard luminance, T95 life was measured through life measurement equipment manufactured by McScience, and the measurement results are shown in Table 6 below.

As can be seen from the measurement results of Table 6, it was confirmed that the device using the compound according to one embodiment of the present invention as a hole transport layer material had significantly improved luminous efficiency and lifetime compared to Comparative Compound 6.

As a result, since it has a deep HOMO energy level and a high T1 value, which are inherent characteristics of the compound of the present invention, the ability to block electrons is improved and holes are smoothly transported to the light emitting layer, resulting in excitons passing through the light emitting layer. It is judged that the efficiency is improved as it is more easily generated within the In addition, it can be confirmed that the lifespan is increased due to high thermal stability.

Combining the characteristics described above, such as deep HOMO energy level, high T1 value, and high thermal stability, it is possible to combine an amine group (-L ^a -N(R ^a )(R ^b )) into a 6-ring heterocycle like the compound of the present invention. It can be seen that the band gap, electrical properties, interface properties, etc. can be greatly changed according to the introduction, and it can be confirmed that this acts as a major factor in improving the performance of the device. In addition, in the case of the hole transport layer, it is necessary to understand the mutual relationship with the light emitting layer (host). Even if a similar core is used, it will be very difficult even for a person skilled in the art to infer the characteristics of the hole transport layer in which the compound of the present invention is used.

In addition, in the evaluation results of the above-described device fabrication, the device characteristics of the compound of the present invention applied to the light emitting layer as a host material and the hole transport layer as a hole transport material were described, but the compound of the present invention was used as a hole injection layer, a light emitting auxiliary layer, an electron transport layer, It may be applied to all other layers such as an electron injection layer and a light emitting auxiliary layer.

The above description is merely illustrative 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. Therefore, the embodiments disclosed in this specification are intended to explain, not limit, 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 construed according to the claims, and all techniques within the scope equivalent thereto should be construed as being included in the scope of the present invention.

Claims (12)

A compound represented by one of Formulas 2 to 5 below.

In Formulas 2 to 5,
The R ¹ to R ¹⁴ are each independently hydrogen; heavy hydrogen; tritium; 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 O, N, S, Si, and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; C ₁ -C ₅₀ Alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; -L ^a -N(R ^a )(R ^b ); C ₁ -C ₃₀ alkoxyl group; And C ₆ -C ₃₀ It is selected from the group consisting of an aryloxy group or adjacent groups may be bonded to each other to form a ring, and R ¹ to R ¹⁴ that do not form a ring are the same as those defined above,
X is one of S, O and C(Ar ² )(Ar ³ ),
Ar ¹ is each independently a C ₆ -C ₆₀ aryl group; fluorenyl group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; C ₁ -C ₅₀ Alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; -L ^a -N(R ^a )(R ^b ); C ₁ -C ₃₀ alkoxyl group; And C ₆ -C ₃₀ It is selected from the group consisting of an aryloxy group,
Ar ² and Ar ³ are i) each independently a C ₆ -C ₆₀ aryl group; fluorenyl group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; C ₁ -C ₅₀ Alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₁ -C ₃₀ alkoxyl group; And C ₆ -C ₃₀ It is selected from the group consisting of an aryloxy group, or ii) Ar ² and Ar ³ are bonded to each other to form a spiro compound together with C to which they are bonded,
R ^a and R ^b are each independently a C ₆ -C ₆₀ aryl group; fluorenyl group; a C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; C ₁ -C ₅₀ Alkyl group; A fused ring group of a C ₆ -C ₆₀ aromatic ring and a C ₃ -C ₆₀ aliphatic ring; And C ₂ -C ₂₀ alkenyl group; is selected from the group consisting of,
Wherein L ¹ and L ^a are each independently a single bond; C ₆ -C ₆₀ arylene group; Fluorenylene group; a C ₂ -C ₆₀ divalent heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; A divalent fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; And it is selected from the group consisting of a divalent aliphatic hydrocarbon group, wherein each of L ¹ and L ^a (except for a single bond) is deuterium; halogen; 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; A deuterium-substituted C ₆ -C ₂₀ aryl group; fluorenyl group; C ₂ -C ₂₀ heterocyclic group; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ arylalkyl group; -N(R ^c )(R ^d ); And a C ₈ -C ₂₀ arylalkenyl group; may be substituted with one or more substituents selected from the group consisting of,
Wherein R ^c and R ^d are each independently a C ₆ -C ₆₀ aryl group; fluorenyl group; It is selected from the group consisting of a C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P;
Each of the aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group, and aryloxy group is 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 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; A deuterium-substituted C ₆ -C ₂₀ aryl group; fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ arylalkyl group; And it may be further substituted with one or more substituents selected from the group consisting of a C ₈ -C ₂₀ arylalkenyl group. delete According to claim 1,
A compound characterized in that Ar ¹ of Formulas 2 to 5 is represented by one of the following Formulas A-1 to Formulas A-3.

In Formula A-1, Q ¹ to Q ⁴ are each independently N, CR ^e , and carbon (C) bonded to L ¹ , and one of Q ¹ to Q ⁴ is carbon (C) bonded to L ¹ . ego,
In Formula A-2, Q ¹ to Q ⁴ are each independently N or CR ^e ,
In Formula A-3, Q ⁵ to Q ⁹ are each independently N or CR ^e ,
In Formulas A-1 and A-2, Z is a C ₆ -C ₆₀ monocyclic or polycyclic aromatic ring; Or selected from the group consisting of a C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P;
In the above formulas A-1 to A-3,
R ^e 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 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; A deuterium-substituted C ₆ -C ₂₀ aryl group; fluorenyl group; a C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ arylalkyl group; and a C ₈ -C ₂₀ arylalkenyl group. According to claim 3,
A compound characterized in that the Z ring of Formula A-1 and Formula A-2 is each independently one of the following formulas.

In the above formulas Z-1 to Z-15, the mark * denotes a bonding moiety bonded to a ring containing Q ¹ to Q ⁴ to form a fused ring,
W ¹ and W ² are each independently one of a single bond, NL ² -Ar ⁴ , S, O, C(Ar ⁵ )(Ar ⁶ ),
V is N, CR ^e independently of each other,
L ² is a single bond; C ₆ -C ₆₀ arylene group; Fluorenylene group; a C ₂ -C ₆₀ divalent heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; A divalent fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; And it is selected from the group consisting of a divalent aliphatic hydrocarbon group,
Ar ⁴ to Ar ⁶ are aryl groups; fluorenyl group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; C ₁ -C ₅₀ Alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₁ -C ₃₀ alkoxyl group; And C ₆ -C ₃₀ It is selected from the group consisting of an aryloxy group,
Ar ⁵ and Ar ⁶ may combine with each other to form a spiro compound together with carbon (C) to which they are bonded,
R ^e is the same as the R ^e defined in claim 3. According to claim 3,
A compound, characterized in that at least one of the Q ¹ to Q ⁴ is N. According to claim 1,
A compound characterized in that it is one of the following compounds.

a first electrode; a second electrode; and an organic material layer disposed between the first electrode and the second electrode, wherein the organic material layer contains the compound of any one of claims 1, 3 to 6. organic electric element. According to claim 7,
The compound is contained in at least one of the hole injection layer, the hole transport layer, the light emitting auxiliary layer, and the light emitting layer of the organic layer, and the compound includes one single compound or two or more compounds as components of a mixture. organic electric element. According to claim 7,
The organic electric device, characterized in that the compound is used as a phosphorescent host material in the light emitting layer of the organic material layer. According to claim 7,
The organic 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 electric element of claim 7; and a control unit driving the display device. According to claim 11,
The electronic device according to claim 1 , wherein the organic electric element is one of an organic light emitting element, an organic solar cell, an organic photoreceptor, an organic transistor, and an element for monochromatic or white light.

Images