KR20210125639A - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

The present invention provides: a compound represented by chemical formula 1; an organic electric element comprising a first electrode, a second electrode, and an organic material layer between the first electrode and the second electrode; and an electronic device including the organic electric element. By including the compound represented by chemical formula 1 in the organic material layer, a driving voltage of the organic electric element can be lowered, and luminous efficiency and lifespan can be improved.

Description

A compound for an organic electric device, an organic electric device using the same, and an electronic device thereof

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

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. An organic electric device using an organic light emitting phenomenon generally has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic layer is often formed of a multilayer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

Lifespan and efficiency are the most problematic in organic electroluminescent devices, and as displays become larger, these problems of efficiency and lifespan must be solved.

Efficiency, lifespan, and driving voltage are related to each other, and when the efficiency is increased, the driving voltage is relatively decreased. It shows a tendency to increase the lifespan.

However, the efficiency cannot be maximized simply by improving the organic material layer. This is because, when the energy level and T1 value between each organic material layer, and the intrinsic properties (mobility, interfacial properties, etc.) of materials are optimally combined, long lifespan and high efficiency can be achieved at the same time.

In addition, in order to solve the light emitting problem in the hole transport layer in recent organic electroluminescent devices, a light emitting auxiliary layer should exist between the hole transport layer and the light emitting layer, and different light emitting auxiliary layers according to each light emitting layer (R, G, B). development is needed.

An object of the present invention is to provide a compound capable of lowering the driving voltage of a device and improving the luminous efficiency 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 following 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, the driving voltage of the device can be lowered, and the luminous efficiency and lifespan of the device can be greatly improved.

1 to 3 are exemplary views of an organic electroluminescent device according to the present invention.
4 shows a chemical formula according to an aspect of the present invention.

The terms "aryl group" and "arylene group" used in the present invention have 6 to 60 carbon atoms, respectively, unless otherwise specified, but are not limited thereto. In the present invention, the aryl group or the arylene group may include a monocyclic type, a ring aggregate, a fused multiple ring system, a spiro compound, and the like. In addition, unless otherwise specified in the present specification, the aryl group may include a fluorenyl group and the arylene group may include a fluorenylene group.

As used herein, the term "fluorenyl group" refers to a substituted or unsubstituted fluorenyl group, "fluorenylene group" refers to a substituted or unsubstituted fluorenyl group, and as used in the present invention, the fluorenyl group or The fluorenylene group includes a case in which R and R' are bonded to each other in the following structure to form a spiro compound together with the carbon to which they are bonded.

"Substituted fluorenyl group", "substituted fluorenylene group" means that at least one of R, R', R" in the following structure is a substituent other than hydrogen, and in the present specification, regardless of the valence, a fluorenyl group , a fluorenylene group, a fluorentriyl group, etc. may all be called a fluorene group.

As used herein, the term "spiro compound" has a 'spiro linkage', and the spiro linkage means a linkage formed by sharing only one atom between two rings. At this time, the atoms shared by the two rings are called 'spiro atoms', and they are respectively 'monospiro-', 'dispiro-', 'trispiro-', depending on the number of spiro atoms in a compound. ' It's called a compound.

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, the number of carbon atoms each containing at least one heteroatom It means a ring of 2 to 60, but is not limited thereto. As used herein, the term "heteroatom" refers to N, O, S, P or Si, unless otherwise specified, and the heterocyclic group is a monocyclic group including a heteroatom, a ring aggregate, a fused multiple ring system, a spy means a compound or the like. _{In addition, a compound including a heteroatom group such as SO 2} , P=O, etc. may be included in the heterocyclic group, such as the following compounds instead of carbon forming a ring.

The term "aliphatic ring group" used in the present invention means a cyclic hydrocarbon other than an aromatic hydrocarbon, and includes a monocyclic ring, a ring aggregate, a fused multiple ring system, a spiro compound, etc., and unless otherwise specified, the number of carbon atoms It means a ring of 3 to 60, but is not limited thereto. For example, even when benzene, which is an aromatic ring, and cyclohexane, which is a non-aromatic ring, are fused, it corresponds to an aliphatic ring.

In the present specification, the 'group name' corresponding to the aryl group, arylene group, heterocyclic group, etc. exemplified as examples of each symbol and its substituents may be described as 'the name of the group reflecting the valence', but is described as 'name of the parent compound' You may. For example, in the case of 'phenanthrene', which is a type of aryl group, the monovalent 'group' is 'phenanthryl' and the divalent group is 'phenanthrylene'. Regardless, it can also be described as the name of the parent compound, 'phenanthrene'. Similarly, in the case of pyrimidine, regardless of the valence, it can be described as 'pyrimidine', or in the case of monovalent, as a pyrimidinyl group, in the case of divalent, as the 'name of the group' of the corresponding valence, such as pyrimidinylene. have.

In addition, in the present specification, in describing the compound name or the substituent name, numbers or alphabets indicating positions may be omitted. For example, pyrido[4,3-d]pyrimidine to pyridopyrimidine, benzofuro[2,3-d]pyrimidine to benzofuropyrimidine, 9,9-dimethyl-9H-flu Orene can be described as dimethylfluorene and the like. Therefore, both benzo[g]quinoxaline and benzo[f]quinoxaline can be described as benzoquinoxaline.

In addition, unless there is an explicit explanation, the formula used in the present invention is the same as the definition of the substituent by the exponential definition of the following formula.

Here, when a is an integer of 0, the substituent R ¹ means that it does not exist, that is, when a is 0, it means that all hydrogens are bonded to the carbons forming the benzene ring, and in this case, the indication of hydrogen bonded to carbon is shown. It can be omitted and the chemical formula or compound can be described. 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 may be bonded as follows, for example, a is 4 to 6 Even if it is an integer of , it is bonded to the carbon of the benzene ring in a similar manner, and when a is an integer of 2 or more, R ¹ may be the same as or different from each other.

In addition, unless otherwise described in the present specification, when representing a condensed ring, the number in 'number-condensed ring' indicates the number of rings to be condensed. For example, a form in which three rings are condensed with each other, such as anthracene, phenanthrene, benzoquinazoline, etc., may be expressed as a 3-condensed ring.

In addition, unless otherwise specified in the present specification, when a ring is expressed in the form of a 'numeric atom' such as a 5-membered ring, a 6-membered ring, etc., the number in 'number-atom' indicates the number of elements forming the ring. For example, thiophene or furan may correspond to a 5-membered ring, and benzene or pyridine may correspond to a 6-membered ring.

In addition, unless otherwise stated in the present specification, the ring formed by bonding adjacent groups to each other is a C ₆ ~ C ₆₀ aromatic ring group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; And C ₃ ~ C ₆₀ An aliphatic ring group; may be selected from the group consisting of. For example, when adjacent groups are bonded to each other to form an aromatic ring, the aromatic ring may be benzene, naphthalene, phenanthrene, or the like.

At this time, unless otherwise specified in the present specification, 'neighboring groups' refers to each other when describing the following chemical formula as an example, R ₁ and R _{2 each other} , R ₂ and R _{3 each other} , R ₃ and R _{4 each other} , Not only R ₅ and R _{6 but also R 7} and R ₈ sharing one carbon are included, and not immediately adjacent, such as _{R 1} and R ₇ , R ₁ and R _{8 ,} or R ₄ and R _{5 , etc.} Substituents bonded to ring constituents (such as carbon or nitrogen) may also be included. That is, if there is a substituent on a ring constituent element such as carbon or nitrogen immediately adjacent to it, they may be a neighboring group, but if no substituent is bonded to a ring constituent element at the immediately adjacent position, it is bonded to the next ring constituent element It can be a group adjacent to the substituent group, and also the substituents bonded to the same ring constituent carbon can be said to be adjacent groups.

_{When substituents bonded to the same carbon as R 7} and R ₈ in the following formula combine with each other to form a ring, a compound including a spiro moiety may be formed.

,

,

In addition, in the present specification, the expression 'adjacent groups may combine with each other to form a ring' is used in the same meaning as 'adjacent groups combine with each other to selectively form a ring', and at least one pair of It means a case where adjacent groups are bonded to each other to form a ring.

Hereinafter, the laminated structure of the organic electric device containing the compound of the present invention will be described with reference to FIGS. 1 to 3 .

In adding reference numerals to the components of each drawing, it should be noted that the same components are given the same reference numerals as much as possible even though they are indicated 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 thereof will be omitted.

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

Also, when a component, such as a layer, membrane, region, plate, etc., is said to be “on” or “on” another component, this means not only when it is “directly above” the other component, but also when there is another component in between. It should be understood that cases may be included. Conversely, it should be understood that when an element is said to be "on top of" another part, it means that there is no other part in the middle.

1 to 3 are exemplary views of an organic electric device according to an embodiment of the present invention.

Referring to FIG. 1 , an organic electric device 100 according to an embodiment of the present invention includes a first electrode 110 , a second electrode 170 , and a first electrode 110 formed on a substrate (not shown). ) and an organic material layer formed between the second electrode 170 .

The first electrode 110 may be an anode (anode), the second electrode 170 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may include a hole injection layer 120 , a hole transport layer 130 , a light emitting layer 140 , an electron transport layer 150 , and an electron injection layer 160 . Specifically, the hole injection layer 120 , the hole transport layer 130 , the light emitting layer 140 , the electron transport layer 150 , and the electron injection layer 160 may be sequentially formed on the first electrode 110 .

Preferably, the light efficiency improving layer 180 may be formed on one side of both surfaces of the first electrode 110 or the second electrode 170 not in contact with the organic material layer, and when the light efficiency improving layer 180 is formed The light efficiency of the organic electric device may be improved.

For example, the light efficiency improving layer 180 may be formed on the second electrode 170 . In the case of a top emission organic light emitting device, the light efficiency improving layer 180 is formed to form the second electrode 170 . ) can reduce optical energy loss due to surface plasmon polaritons (SPPs), and in the case of a bottom emission organic light emitting device, the light efficiency improvement layer 180 serves as a buffer for the second electrode 170 . can do.

A buffer layer 210 or a light emitting auxiliary layer 220 may be further formed between the hole transport layer 130 and the light emitting layer 140 , which will be described with reference to FIG. 2 .

Referring to FIG. 2 , the organic electric device 200 according to another embodiment of the present invention includes a hole injection layer 120 , a hole transport layer 130 , a buffer layer 210 sequentially formed on the first electrode 110 , It may include a light emitting auxiliary layer 220 , a light emitting layer 140 , an electron transport layer 150 , an electron injection layer 160 , and a second electrode 170 , and a light efficiency improving layer 180 is formed on the second electrode. can be

Although not shown in FIG. 2 , an electron transport auxiliary layer may be further formed between the light emitting layer 140 and the electron transport layer 150 .

In addition, according to another embodiment of the present invention, the organic material layer may have a form in which a plurality of stacks including a hole transport layer, a light emitting layer, and an electron transport layer are formed. This will be described with reference to FIG. 3 .

Referring to FIG. 3 , an organic electric device 300 according to another embodiment of the present invention includes two stacks ST1 and ST2 of an organic material layer formed of a multilayer between the first electrode 110 and the second electrode 170 . More than one set may be formed, and a charge generating layer (CGL) may be formed between stacks of organic material layers.

Specifically, the organic electric device according to an embodiment of the present invention includes a first electrode 110 , a first stack ST1 , a charge generation layer (CGL), a second stack ST2, and a second electrode. 170 and the light efficiency improving layer 180 may be included.

The first stack ST1 is an organic material layer formed on the first electrode 110 , which is a first hole injection layer 320 , a first hole transport layer 330 , a first emission layer 340 , and a first electron transport layer 350 . ), and the second stack ST2 may include a second hole injection layer 420 , a second hole transport layer 430 , a second emission layer 440 , and a second electron transport layer 450 . . As such, the first stack and the second stack may be organic material layers having the same stacked structure or organic material layers having different stacked structures.

A charge generation layer CGL may be formed between the first stack ST1 and the second stack ST2 . The charge generation layer CGL may include a first charge generation layer 360 and a second charge generation layer 361 . The charge generating layer CGL is formed between the first light emitting layer 340 and the second light emitting layer 440 to increase the efficiency of current generated in each light emitting layer and smoothly distribute charges.

The first light-emitting layer 340 may include a light-emitting material including a blue fluorescent dopant in a blue host, and the second light-emitting layer 440 includes a material in which a green host is doped with a greenish yellow dopant and a red dopant. may be included, but the material of the first light emitting layer 340 and the second light emitting layer 440 according to an embodiment of the present invention is not limited thereto.

In FIG. 3 , n may be an integer of 1 to 5. When n is 2, the charge generation layer CGL and the third stack may be additionally stacked on the second stack ST2 .

When a plurality of light emitting layers are formed by the multilayer stack structure method as shown in FIG. 3 , an organic electroluminescent device that emits white light by the mixing effect of light emitted from each light emitting layer can be manufactured as well as light of various colors. It is also possible to manufacture an organic electroluminescent device that emits light.

The compound represented by Chemical Formula 1 of the present invention is a hole injection layer (120, 320, 420), a hole transport layer (130, 330, 430), a buffer layer 210, a light emitting auxiliary layer 220, an electron transport layer (150, 350) , 450), the electron injection layer 160, the light emitting layers 140, 340, 440 or the light efficiency improvement layer 180 may be used as a material, preferably, the light emission auxiliary layer 220 and / or the light efficiency improvement layer 180 ) can be used as a material for

A study on the selection of a core and a combination of sub-substituents bonded thereto because the band gap, electrical properties, and interfacial properties, etc. may vary depending on which position and which substituent is bonded even for the same and similar core In particular, when the energy level and T ₁ value between each organic material layer, and the intrinsic properties of the material (mobility, interfacial properties, etc.) are optimally combined, long lifespan and high efficiency can be achieved at the same time.

Therefore, in the present invention, by using the compound represented by Chemical Formula 1 as a material for the light emission auxiliary layer 220 and/or the light efficiency improving layer 180 , the energy level and T ₁ value between each organic material layer, and the intrinsic properties of the material (mobility) , interface characteristics, etc.) can be optimized to simultaneously improve the lifetime and efficiency of the organic electric device.

The 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, by depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate to form the anode 110, and the hole injection layer 120 thereon , after forming an organic material layer including the hole transport layer 130, the light emitting layer 140, the electron transport layer 150 and the electron injection layer 160, it can be manufactured by depositing a material that can be used as the cathode 170 thereon. have. In addition, an auxiliary light emitting layer 220 may be formed between the hole transport layer 130 and the light emitting layer 140 , and an electron transport auxiliary layer (not shown) may be further formed between the light emitting layer 140 and the electron transport layer 150 . It can also be formed in a stack structure as shown.

In addition, the organic layer is a solution process or a solvent process rather 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, Dr. Blay 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 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 top emission type, a back emission type, or a double-sided emission type depending on the material used.

In addition, the organic electric device according to an embodiment of the present invention may be selected from the group consisting of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, a device for monochromatic lighting, and a device for a quantum dot display.

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 for controlling the display device. In this case, 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 control, a navigation system, a game machine, various TVs, and various computers.

Hereinafter, the 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 may be defined as follows.

Ring A is represented by the following formula 1-1, and Q is represented by the following formula 1-2.

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

,

,

In Formula 1-1, * represents a condensation (bonding) site.

X ¹ X ² , and X ³ are each independently O, S, C(R′)(R″) or N(R).

R ¹ to R ⁶ are each independently hydrogen; heavy hydrogen; halogen; cyano group; nitro group; C ₆ ~ C ₆₀ Aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ aliphatic group; C ₁ ~ C ₃₀ Alkyl group; C ₂ ~ C ₃₀ Alkenyl group; C ₂ ~ C ₃₀ Alkynyl group; C ₁ ~ C ₃₀ An alkoxyl group; C ₆ ~ C ₃₀ Aryloxy group; and -L′-N(R _a )(R _b ), adjacent groups may be bonded to each other to form a ring, and one of ^{R 3} to R ⁶ is bonded to ^{L 2 .} That is, one of R ³ to R ⁶ binds and L ^2, and is combined with N If the L ² is a single bond.

a is an integer from 0 to 3, b, c, d, e and f are each an integer from 0 to 4, and when each of these is an integer of 2 or greater, each of R ^{1 ,} each of R ^{2 ,} each of R ^{3 ,} each of R ⁴ , ^{each of R 5 and} each of R ⁶ are the same as or different from each other.

A ring formed by bonding adjacent groups to each other is a C ₆ ~ C ₆₀ aromatic ring, O, N, S, Si and P including at least one heteroatom of at least one C ₂ ~ C ₆₀ heterocyclic ring, or C ₃ ~ It may be a _{C 60 aliphatic ring.} For example, when adjacent groups are bonded to each other to form an aromatic ring, preferably a C ₆ ~ C ₂₀ aromatic ring, more preferably a C ₆ ~ C ₁₄ aromatic ring, such as benzene, naphthalene, phenanthrene, etc. can be formed.

Ar ¹ is a C ₆ ~ C ₆₀ aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; And C ₃ ~ C _{60 It} is selected from the group consisting of an aliphatic cyclic group.

L ^{1 To} L ^{3 Are} each independently a single bond; C ₆ ~ C ₆₀ Arylene group; fluorenylene group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; And C ₃ ~ C _{60 It} is selected from the group consisting of an aliphatic cyclic group.

Wherein R' and R" are each independently hydrogen; deuterium; halogen; cyano group; nitro group; C ₆ ~ C ₆₀ aryl group; fluorenyl group; O, N, S, at least one heteroatom of S, Si and P Containing C ₂ ~ C ₆₀ Heterocyclic group; C ₃ ~ C ₆₀ Aliphatic ring group; C ₁ ~ C ₃₀ Alkyl group; C ₂ ~ C ₃₀ Alkenyl group; C ₂ ~ C ₃₀ Alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; C ₆ ~ C ₃₀ Aryloxy group; And -L'-N (R _a ) (R _b ) is selected from the group consisting of, R' and R" are bonded to each other to form a ring can be formed When R' and R" combine with each other to form a ring, a spiro compound is formed.

The L' is a single bond; C ₆ ~ C ₆₀ Arylene group; fluorenylene group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; And C ₃ ~ C _{60 It} is selected from the group consisting of an aliphatic cyclic group.

The R, R _a and R _b are each independently a C ₆ ~ C ₆₀ aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; And C ₃ ~ C _{60 It} is selected from the group consisting of an aliphatic cyclic group.

When ^{at least one of R 1} to R ⁶ , Ar ¹ , R, R _a , and R _b is an aryl group, the aryl group is, for example, C ₆ to C ₃₀ , C ₆ to C ₂₉ , C ₆ to C ₂₈ , C ₆ ~C ₂₇ , C ₆ ~C ₂₆ , C ₆ ~C ₂₅ , C ₆ ~C ₂₄ , C ₆ ~C ₂₃ , C ₆ ~C ₂₂ , C ₆ ~C ₂₁ , C ₆ ~C ₂₀ , C ₆ ~C ₁₉ , C ₆ ~C ₁₈ , C ₆ ~C ₁₇ , C ₆ ~C ₁₆ , C ₆ ~C ₁₅ , C ₆ ~C ₁₄ , C ₆ ~C ₁₃ , C ₆ ~C ₁₂ , C ₆ ~C ₁₁ , C ₆ ~ C ₁₀ , C ₆ , C ₁₀ , C ₁₂ , C ₁₃ , C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ , _{may be an aryl group such as C 18} , and specifically, phenyl, biphenyl, naphthyl, terphenyl, phenanthrene, fluoranthene, and the like.

When ^{at least one of L 1} to L ³ and L' is an arylene group, the arylene group is, for example, C ₆ ~ C ₃₀ , C ₆ ~ C ₂₉ , C ₆ ~ C ₂₈ , C ₆ ~ C ₂₇ , C ₆ ~C ₂₆ , C ₆ ~C ₂₅ , C ₆ ~C ₂₄ , C ₆ ~C ₂₃ , C ₆ ~C ₂₂ , C ₆ ~C ₂₁ , C ₆ ~C ₂₀ , C ₆ ~C ₁₉ , C ₆ ~C ₁₈ , C ₆ ~C ₁₇ , C ₆ ~C ₁₆ , C ₆ ~C ₁₅ , C ₆ ~C ₁₄ , C ₆ ~C ₁₃ , C ₆ ~C ₁₂ , C ₆ ~C ₁₁ , C ₆ ~C ₁₀ , It _{may be an arylene group such as C 6} , C ₁₀ , C ₁₂ , C ₁₃ , C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ , C ₁₈ , and specifically, phenylene, biphenyl, naphthylene, terphenyl, phenane. Tren, or the like.

When ^{at least one of R 1} to R ⁶ , Ar ¹ , R, R _a , R _b , L ¹ to L ³ , and L' is a heterocyclic group, the heterocyclic group is, for example, C ₂ to C ₃₀ , C ₂ to C ₂₉ , C ₂ ~C ₂₈ , C ₂ ~C ₂₇ , C ₂ ~C ₂₆ , C ₂ ~C ₂₅ , C ₂ ~C ₂₄ , C ₂ ~C ₂₃ , C ₂ ~C ₂₂ , C ₂ ~C ₂₁ , C ₂ ~C ₂₀ , C ₂ ~C ₁₉ , C ₂ ~C ₁₈ , C ₂ ~C ₁₇ , C ₂ ~C ₁₆ , C ₂ ~C ₁₅ , C ₂ ~C ₁₄ , C ₂ ~C ₁₃ , C ₂ ~C ₁₂ , C ₂ ~C ₁₁ , C ₂ ~C ₁₀ , C ₂ ~C ₉ , C ₂ ~C ₈ , C ₂ ~C ₇ , C ₂ ~C ₆ , C ₂ ~C ₅ , C ₂ ~ C ₄ , C ₂ ~C ₃ , C ₂ , C ₃ , C ₄ , C ₅ , C ₆ , C ₇ , C ₈ , C ₉ , C ₁₀ , C ₁₁ , C ₁₂ , C ₁₃ , C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ , C ₁₈ , C ₁₉ , C ₂₀ , C ₂₁ , C ₂₂ , C ₂₃ , C ₂₄ , C ₂₅ , C ₂₆ , C ₂₇ , C ₂₈ , C _{29 It} may be a heterocyclic group such as, Specifically, pyridine, pyrimidine, pyrazine, pyridazine, triazine, furan, pyrrole, silol, indene, indole, phenyl-indole, benzoindole, phenyl-benzoindole, pyrazinoindole, quinoline, isoquinoline, benzoquinoline, Pyridoquinoline, quinazoline, benzoquinazoline, dibenzoquinazoline, phenanthroquinazoline, quinoxaline, benzoquinoxaline, dibenzoquinoxaline, benzofuran, naphthobenzofuran, dibenzofuran, phenanthrobenzofuran, Dynaphthofuran, thiophene, benzothiophene, dibenzothiophene, naphthobenzothiophene, phenanthrobenzothiophene, dinaphthothiophene, carbazole, phenyl-carbazole, benzocarbazole, phenyl-benzocarbazole , naphthyl-benzocarbazole, dibenzocarbazole, indolocarbazole, benzofuropyridine, benzothienopyridine, benzofuropyridine, benzothienopyrimidine, benzofuro Pyrimidine, benzothienopyrazine, benzofuropyrazine, benzoimidazole, benzothiazole, benzoxazole, benzosilol, phenanthroline, dihydro-phenylphenazine, 10-phenyl-10H-phenoxazine, phenoxy Photography, phenothiazine, dibenzodioxin, benzodibenzodioxin, cyanthrene, 9,9-dimethyl-9H-xanthrene, 9,9-dimethyl-9H-thioxanthrene, dihydrodimethylphenyl acrylic acid Dean, spiro [fluorene-9,9'-xanthene], and the like.

When ^{at least one of R 1} to R ⁶ , Ar ¹ , R, R _a , and R _b is a fluorenyl group, or at least one of L ¹ to L ³ , L′ is a fluorenylene group, the fluorenyl group or The fluorenylene group is 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorene, 9,9'-spirobifluorene, spiro[benzo[ b ]fluorene-11 , 9'- fluorene], benzo [b] fluorene, diphenyl-11,11- -11 H - benzo [b] fluorene, 9- (naphthalen-2-yl) -9 H 9-phenyl - fluoren etc.

When ^{at least one of R 1} to R ⁶ is an alkyl group, the alkyl group is, for example, C ₁ to C ₂₀ , C ₁ to C ₁₀ , C ₁ to C ₄ , C ₁ , C ₂ , C ₃ , C _{4 ,} etc. It may be an alkyl group, specifically methyl, ethyl, propyl, t-butyl, and the like.

When ^{at least one of R 1} to R ⁶ is an alkoxy group, the alkoxy group is, for example, C ₁ to C ₂₀ , C ₁ to C ₁₀ , C ₁ to C ₄ , C ₁ , C ₂ , C ₃ , C _{4 ,} etc. It may be an alkoxy group, specifically methoxy, ethoxy, t-butoxy, and the like.

When ^{at least one of R 1} to R ⁶ is an alkenyl group, the alkenyl group is, for example, C ₂ to C ₂₀ , C ₂ to C ₁₀ , C ₂ to C ₄ , C ₂ , C ₃ , C ₄ Alkenes such as It may be a diary, and specifically may be a vinyl group, a propenyl group, or the like.

The aryl group, an arylene group, a fluorenyl group, a fluorenylene group, a heterocyclic group, an aliphatic ring group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxyl group, an aryloxy group, a ring formed by bonding adjacent groups to each other, and A ring formed by combining R′ and R″ is deuterium; halogen; a silane group unsubstituted or substituted with a _{C 1} -C ₂₀ alkyl group or C ₆ -C _{20 aryl group; C 1} -C ₂₀ alkyl group or C ₆ -C ₂₀ Phosphine oxide unsubstituted or substituted with an aryl group; Siloxane group; Cyano group; Nitro group; C ₁ -C ₂₀ Alkylthio group; C ₁ -C _{20 Alkoxy group; C 6} -C ₂₀ Aryloxy group; C ₆ -C ₂₀ Arylthio 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; Flu _{Orenyl group; C 2} -C ₂₀ heterocyclic group comprising at least one heteroatom selected from the group consisting of O, N, S, Si and P; C ₃ -C ₂₀ aliphatic ring group; And -L'- and may be substituted with one or more substituents selected from the group consisting of N(R _a )(R _{b ), wherein L′, R a} and R _b are as defined above.

The aryl group, fluorenyl group, heterocyclic group, aliphatic ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, arylene group, fluorenylene group, and a ring formed by bonding adjacent groups to each other When substituted with this aryl group, each of these is preferably C ₆ -C ₂₀ , C ₆ -C ₁₉ , C ₆ -C ₁₈ , C ₆ -C ₁₇ , C ₆ -C ₁₆ , C ₆ -C ₁₅ , C ₆ ~C ₁₄ , C ₆ ~C ₁₃ , C ₆ ~C ₁₂ , C ₆ ~C ₁₁ , C ₆ ~C ₁₀ , C ₆ , C ₁₀ , C ₁₂ , C ₁₃ , C ₁₄ , C ₁₅ , C ₁₆ , It may be substituted with an aryl group such as C ₁₇ , C _{18 .}

The aryl group, fluorenyl group, heterocyclic group, aliphatic ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, arylene group, fluorenylene group, and a ring formed by bonding adjacent groups to each other When substituted with this heterocyclic group, each of these is C ₂ ~ C ₂₀ , C ₂ ~ C ₁₉ , C ₂ ~ C ₁₈ , C ₂ ~ C ₁₇ , C ₂ ~ C ₁₆ , C ₂ ~ C ₁₅ , C ₂ ~ C ₁₄ , C ₂ ~C ₁₃ , C ₂ ~C ₁₂ , C ₂ ~C ₁₁ , C ₂ ~C ₁₀ , C ₂ ~C ₉ , C ₂ ~C ₈ , C ₂ ~C ₇ , C ₂ ~C ₆ , C ₂ ~C ₅ , C ₂ ~C ₄ , C ₂ ~C ₃ , C ₂ , C ₃ , C ₄ , C ₅ , C ₆ , C ₇ , C ₈ , C ₉ , C ₁₀ , C ₁₁ , C ₁₂ , C ₁₃ , C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ , C ₁₈ , C ₁₉ , C ₂₀ may be substituted with a heterocyclic group.

The aryl group, fluorenyl group, heterocyclic group, aliphatic ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, arylene group, fluorenylene group, and a ring formed by bonding adjacent groups to each other When substituted with this alicyclic group, each of these is preferably C ₆ ~ C ₂₀ , C ₆ ~ C ₁₉ , C ₆ ~ C ₁₈ , C ₆ ~ C ₁₇ , C ₆ ~ C ₁₆ , C ₆ ~ C ₁₅ , C ₆ ~C ₁₄ , C ₆ ~C ₁₃ , C ₆ ~C ₁₂ , C ₆ ~C ₁₁ , C ₆ ~C ₁₀ , C ₆ , C ₁₀ , C ₁₂ , C ₁₃ , C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ , may be substituted with an aliphatic ring group such as _{C 18 .}

The aryl group, fluorenyl group, heterocyclic group, aliphatic ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, arylene group, fluorenylene group, and a ring formed by bonding adjacent groups to each other When substituted with this alkyl group, each of these may be substituted with an alkyl group such as C ₁ ~C ₂₀ , C ₁ ~C ₁₀ , C ₁ ~ C ₄ , C ₁ , C ₂ , C ₃ , C ₄ .

The aryl group, fluorenyl group, heterocyclic group, aliphatic ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, arylene group, fluorenylene group, and a ring formed by bonding adjacent groups to each other When substituted with this alkoxy group, each of these may be substituted with an alkoxy group such as C ₁ ~C ₂₀ , C ₁ ~C ₁₀ , C ₁ ~C ₄ , C ₁ , C ₂ , C ₃ , C ₄ .

Formula 1 may be represented by Formula 1-a or Formula 1-b.

<Formula 1-a> <Formula 1-b>

In Formulas 1-1 and 1-2, X ¹ , X ² , R ¹ , R ² , Ar ¹ , Q, L ¹ to L ³ , a, and b are the same as defined in Formula 1 above.

In addition, Chemical Formula 1 may be represented by one of the following Chemical Formulas 1-c to 1-f.

<Formula 1-c> <Formula 1-d>

<Formula 1-e> <Formula 1-f>

In Formula 1-c to Formula 1-f, X ¹ to X ³ , R ¹ to R ⁶ , L ¹ to L ³ , Ar ¹ , a to f are the same as defined in Formula 1, and R ^3' is the formula It is defined the same as ^{R 3 defined in 1, R 5' is defined the same as R 5} defined in Formula 1, and c' and e' are each an integer of 0-3.

Formula 1-2 may be represented by one of the following Formulas 1-2a to 1-2d.

<Formula 1-2a> <Formula 1-2b>

<Formula 1-2c> <Formula 1-2d>

In Formulas 1-2a to 1-2d, R ³ to R ⁶ , c to f, R′, R″, and R are as defined in Formula 1.

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

.

.

In another aspect of the present invention, the present invention provides an organic electric device including an anode, a cathode, and an organic material layer formed between the anode and the cathode, wherein the organic material layer includes the compound represented by Formula 1 above.

In another aspect of the present invention, the present invention provides an organic electric device comprising an anode, a cathode, an organic material layer formed between the anode and the cathode, and a light efficiency improving layer. In this case, the light efficiency improving layer is formed on one side of both surfaces of the anode or the cathode that is not in contact with the organic material layer, and the organic material layer or the light efficiency improving layer may include the compound represented by Formula 1 above.

The organic material layer includes at least one of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer, and preferably, the compound may be included in the light emission auxiliary layer.

The organic material layer may include two or more stacks including a hole transport layer, a light emitting layer, and an electron transport layer sequentially formed on the anode, and may further include a charge generating layer formed between the two or more stacks.

In another aspect of the present invention, there is provided an electronic device including a display device including the organic electric device represented by Formula 1, and a control unit for driving the display device.

Hereinafter, examples of the synthesis of the compound represented by Formula 1 and the preparation of the 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 (Final Product) represented by Formula 1 according to the present invention may be prepared by reacting Sub 1 and Sub 2 as shown in Scheme 1 below, but is not limited thereto.

<Scheme 1> (Hal is I, Br or Cl)

Sub 1's Synthesis example

Sub 1 of Scheme 1 may be synthesized by Scheme 2 below, but is not limited thereto.

<Scheme 2>

1. Sub 1-18 Synthesis example

(1) Synthesis of Sub 1-18b

After dissolving Sub 1-18a (50 g, 280.9mmol) in THF (1404ml), Sub 1-18a' (70.1g, 280.9mmol), Pd(PPh ₃ ) ₄ (19.5g, 16.85mmol), NaOH (33.7 g, 842.6 mmol) and water (702 ml) are added and reacted at 80°C. Upon completion of the reaction _{, the mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 69.8 g of a product. (Yield: 82.1%)

(2) Synthesis of Sub 1-18c

Sub 1-18b (69.8 g, 230.5 mmol) was dissolved in THF (1153 ml), mehtylmagnesium bromide 1.0 M in THF (132.8 ml) was titrated and reacted at room temperature. Thereafter, acetic acid (1153 ml) and H ₂ SO ₄ (30.1 ml) were added, stirred at room temperature for 24 hours, water and pyridine (5:1) were added, and refluxed for 30 minutes. Upon completion of the reaction, _{extraction is performed with CH 2} Cl ₂ and water, and the organic layer is dried over _{MgSO 4 and concentrated.} Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 32.2 g of a product. (Yield: 49%)

(3) Synthesis of Sub 1-18

After dissolving Sub 1-18c (32.2 g, 113.1 mmol) in toluene (565 ml), Sub 1-18c' (10.5 g, 113.1 mmol), Pd ₂ (dba) ₃ (3.1 g, 3.4 mmol), P ( t-Bu) ₃ (1.4 g, 6.8 mmol) and NaOt-Bu (21.7 g, 226.1 mmol) are added and reacted at 80°C. When the reaction is completed, _{extraction is performed with CH 2} Cl ₂ and water, and the organic layer is dried over _{MgSO 4 and concentrated.} Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 28.0 g of a product. (Yield: 72.5%)

2. Sub 1-34 Synthesis example

(1) Synthesis of Sub 1-34b

After dissolving Sub 1-34a (50.0 g, 207.6 mmol) in THF (1038 ml), Sub 1-34a' (52.8 g, 207.6 mmol), Pd(PPh ₃ ) ₄ (14.4 g, 12.5 mmol), NaOH ( 86.1 g, 622.8 mmol) and water (519 ml) were added, and the same procedure was followed for the synthesis of Sub 1-18b to obtain 52.8 g of the product. (Yield: 78.6%)

(2) Synthesis of Sub 1-34c

Sub 1-34b (52.8 g, 163.2 mmol) was dissolved in 1,2-dichlorobenzene (909 ml), PPh ₃ (119.2 g, 454.3 mmol) was added, and refluxed for 5 hours. Upon completion of the reaction _{, the mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 38.1 g of a product. (Yield: 86.4%)

(3) Synthesis of Sub 1-34

After dissolving Sub 1-34c (38.1 g, 157.0 mmol) in toluene (785 ml), Sub 1-34c' (28.8 g, 157.0 mmol), Pd ₂ (dba) ₃ (4.3 g, 4.7 mmol), P ( t-Bu) ₃ (1.9 g, 9.4 mmol) and NaOt-Bu (30.2 g, 314.0 mmol) were added, and the same procedure was followed for the synthesis of Sub 1-18 to obtain 43.2 g of a product. (Yield: 70.7%)

3. Sub 1-49 Synthesis example

(1) Sub 1- 49b synthesis

After dissolving Sub 1-49a (50.0 g, 199.9 mmol) in THF (1000 ml), Sub 1-49a' (47.3 g, 199.9 mmol), Pd(PPh ₃ ) ₄ (13.9 g, 12.0 mmol), NaOH ( 24.0 g, 599.8 mmol) and water (500 ml) were added, and the same procedure was followed for the synthesis of Sub 1-18b to obtain 58.7 g of the product. (Yield: 81.1%)

(2) Synthesis of Sub 1-49c

After dissolving Sub 1-49b (58.7 g, 162.2 mmol) in 1,2-dichlorobenzene (811 ml), PPh ₃ (106.4 g, 405.6 mmol) was added, and proceeding as in the synthesis method of Sub 1-34c, the product 45.6 g were obtained. (Yield: 85.3%)

(3) Synthesis of Sub 1-49d

After dissolving Sub 1-49c (45.6 g, 138.3 mmol) in toluene (277 ml), Cu powder (10.5 g, 165.9 mmol), 18-Crown-6 (4.4 g, 16.6 mmol), K ₂ CO ₃ (114.6) g, 829.5 mmol) and iodobenzene (56.4 g, 276.5 mmol) were added and refluxed for 8 hours. Upon completion of the reaction _{, the mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Then, the concentrate was separated by a silica gel column and recrystallized to obtain 46.1 g of a product. (Yield: 82.2%)

(4) Synthesis of Sub 1-49

After dissolving Sub 1-49d (46.1 g, 113.6 mmol) in toluene (568 ml), Sub 1-49d' (10.6 g, 113.6 mmol), Pd ₂ (dba) ₃ (3.1 g, 3.4 mmol), P ( t-Bu) ₃ (1.4 g, 6.8 mmol) and NaOt-Bu (21.8 g, 227.1 mmol) were added, and the same procedure was followed for the synthesis of Sub 1-18 to obtain 40.7 g of a product. (Yield: 77.4%)

4. Sub 1-56 Synthesis example

(1) Synthesis of Sub 1-56b

After dissolving Sub 1-56a (50.0 g, 265.9 mmol) in THF (1330 ml), Sub 1-56a' (66.3 g, 265.9 mmol), Pd(PPh ₃ ) ₄ (18.4 g, 12.0 mmol), NaOH ( 31.9 g, 797.7 mmol) and water (665 ml) were added, and the same procedure was followed for the synthesis of Sub 1-18b to obtain 66.8 g of the product. (Yield: 80.3%)

(2) Synthesis of Sub 1-56c

Sub 1-56b (66.8 g, 213.6 mmol) was dissolved in THF (1068 ml), mehtylmagnesium bromide 1.0 M in THF (123.0 ml) acetic acid (1068 ml), H ₂ SO ₄ (27.9 ml) was added, 32.1 g of the product was obtained in the same manner as in the synthesis method of Sub 1-18c. (Yield: 51.0%)

(3) Synthesis of Sub 1-56

After dissolving Sub 1-56c (32.1 g, 108.9 mmol) in toluene (544 ml), Sub 1-56c' (28.2 g, 259.35 mmol), Pd ₂ (dba) ₃ (3.0 g, 3.3 mmol), P ( t-Bu) ₃ (1.3 g, 6.5 mmol) and NaOt-Bu (20.9 g, 217.8 mmol) were added, and the same procedure was followed for the synthesis of Sub 1-18 to obtain 41.0 g of a product. (Yield: 72.7%)

5. Sub 1-77 Synthesis example

(1) Synthesis of Sub 1-77b

After dissolving Sub 1-77a (50.0 g, 210.9 mmol) in THF (1055 ml), Sub 1-77a' (50.1 g, 210.9 mmol), Pd(PPh ₃ ) ₄ (14.6 g, 12.7 mmol), NaOH ( 25.3 g, 632.7 mmol) and water (527 ml) were added, and the same procedure was followed for the synthesis of Sub 1-18b to obtain 60.0 g of the product. (Yield: 81.3%)

(2) Synthesis of Sub 1-77c

Sub 1-77b (60.0 g, 171.5 mmol) was dissolved in acetic acid (686 ml), H ₂ O ₂ (17.2 ml) was added thereto, and the mixture was stirred for 8 hours. Upon completion of the reaction _{, the mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 56.5 g of a product. (Yield: 90.0%)

(3) Synthesis of Sub 1-77d

Sub 1-77c (55.6 g, 154.3 mmol) was dissolved in H ₂ SO ₄ (169.4 ml) and refluxed for 5 hours. When the reaction was completed, the resulting solid was neutralized to pH 10, filtered under reduced pressure, and washed with water. Then, the solid was recrystallized to obtain 46.5 g of the product. (Yield: 90.2%)

(4) Synthesis of Sub 1-77

After dissolving Sub 1-77d (46.5 g, 139.3 mmol) in toluene (696 ml), Sub 1-77d' (34.2 g, 139.3 mmol), Pd ₂ (dba) ₃ (3.8 g, 4.2 mmol), P ( t-Bu) ₃ (1.7 g, 8.4 mmol) and NaOt-Bu (26.8 g, 278.6 mmol) were added, followed by the same procedure as in Sub 1-18 above to obtain 54.1 g of a product. (Yield: 71.6%)

The compound belonging to Sub 1 may be a compound as follows, but is not limited thereto, and Table 1 shows FD-MS (Field Desorption-Mass Spectrometry) values of the following compounds.

[Table 1]

Sub 2's Synthesis example

Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 3 below, but is not limited thereto.

<Scheme 3> (Hal is I, Br or Cl, X' is X ³ , and ^{one of R 3} to R ⁶ is Hal-L ² )

1. Sub 2-5 Synthesis example

(1) Sub 2- Synthesis of 5b

2-iodobenzoic acid (30.0 g, 121.0 mmol), phenol (22.8 g, 241.9 mmol), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (54.3 g, 362.7 mmol), pyridine (1.9 mL), copper powder (1.0 g, 15.72 mmol), CuI (1.0 g, 5.44 mmol) in a round flask, DMF (968 mL) was added, and refluxed for 3 hours. When the reaction is complete, after cooling to room temperature, 3M HCl is added until the precipitation is complete. Then, when the precipitation was completed, the precipitate was washed with water and dried to obtain 22.5 g of the product. (yield 87%)

(2) Synthesis of Sub 2-5c

Sub 2-5b (22.5 g, 105 mmol), a starting material, was placed in a round-bottom flask, and H ₂ SO ₄ (750 mL) was added thereto, followed by refluxing until all of the starting material was dissolved. When all the starting materials are dissolved, cool to room temperature, and then add ice water to precipitate. After that, the precipitate was washed with water and then dried and dissolved with _{CH 2} Cl _{2 .} Thereafter, it was separated by a silica gel column and recrystallized to obtain 14.0 g of a product. (Yield 68%)

(3) Sub 2-5d synthesis

After dissolving 2-bromo-1,1'-biphenyl (19.1 g, 71.4 mmol) in THF (130 mL) under a nitrogen atmosphere, it was cooled to -78°C. Then, n- BuLi (29 mL) is slowly titrated, and the mixture is stirred for 30 minutes. After dissolving Sub 2-5c (14.0 g, 71.4 mmol) in THF (120 mL), the mixture was slowly titrated, and stirred at -78°C for 1 hour to slowly raise the temperature of the reactant to room temperature. When the reaction was completed, the mixture was extracted with ethyl acetate and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 23.1 g of a product. (Yield 84%)

(4) Synthesis of Sub 2-5

Sub 2-5d (23.1 g, 59.9 mmol), acetic acid (150 mL) and HCl (24 mL) are added to a round-bottom flask and stirred at 60-80°C under nitrogen atmosphere for 3 hours. Upon completion of the reaction _{, the mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 19.8 g (yield 90%) of the product.

2. Sub 2-15 Synthesis example

(1) Sub 2- Synthesis of 15b

In a round-bottom flask, add 2-iodobenzoic acid (30.0 g, 121 mmol), 4-chlorobenzenethiol (17.5 g, 121 mmol), KOH (33.9 g, 605 mmol) and Copper powder (0.77 g, 12.2 mmol) and water (800 mL) and refluxed for 12 hours. When the reaction is complete, after cooling to room temperature, 3M HCl is added until the precipitation is complete. When the precipitation was completed, the precipitate was washed with water and dried to obtain 28.5 g of a product. (yield 89%)

(2) Synthesis of Sub 2-15c

Sub 2-15b (28.5 g, 107.7 mmol) was placed in a round-bottom flask, and H ₂ SO ₄ (770 mL) was added thereto, followed by the same procedure as in the synthesis example of Sub 2-5c to obtain 19.4 g of a product. (Yield 68%)

(3) Sub 2-15d synthesis

2-bromo-1,1'-biphenyl (17.1 g, 73.28 mmol), THF (130 mL), n- BuLi (29 mL), Sub 2-15c (19.4 g, 73.28 mmol) and THF (120 mL) 24.4 g of the product was obtained in the same manner as in the synthesis method of Sub 2-5d. (Yield 83%)

(4) Synthesis of Sub 2-15

Sub 2-15d (24.4 g, 60.83 mmol), acetic acid (152 mL) and HCl (24 mL) were used in the same manner as in the synthesis method of Sub 2-5 to obtain 20.7 g (yield 89%) of the product.

3. Sub 2-41 Synthesis example

(1) Synthesis of Sub 2-41b

2-(2-bromo-5-chlorophenyl)propan-2-ol (50.0 g, 200.4 mmol), benzylboronic acid (27.2 g, 200.4 mmol), K ₂ CO ₃ (83.1 g, 601.1 mmol), Pd (PPh _{3 )} ) ₄ (13.89 g, 12.02 mmol), THF (1002 ml) and water (501 ml) were used in the same manner as in the synthesis of Sub 1-18b above to obtain 44.9 g (yield: 86%) of the product.

(2) Sub 2-41b' synthesis

_{H 2} SO ₄ (270 mL) was added to Sub 2-41b (44.9 g, 172.3 mmol), followed by stirring at room temperature for 2 hours. When the reaction was completed, purified water was slowly added, and then an aqueous NaOH solution was slowly added to adjust the pH to 7. Then, after extraction with ethyl acetate and distilled water, the organic layer was MgSO ₄ dried and concentrated. Then, the concentrate _{was crystallized with CH 2} Cl ₂ and Hexane to obtain 35.1 g of the product. (Yield 84%)

(3) Synthesis of Sub 2-41c

Sub 2-41b' (35.1 g, 144.8 mmol) was added with acetic acid (1052 ml) and heated to 58 ° C. CrO ₃ (23.2 g, 231.6 mmol) was dissolved in acetic acid and then added dropwise to the heated mixture. Stirred for 4 hours. Upon completion of the reaction, the solvent was removed, water was added to form crystals, and the mixture was extracted with _{CH 2} Cl _{2 and water.} Then, the organic layer was dried over MgSO ₄ and filtered. Thereafter, the filtrate was distilled under reduced pressure to remove the solvent, and then recrystallized using ethanol and water (3:1) to obtain 30 g of a product. (Yield 81%)

(4) Synthesis of Sub 2-41d

Using Sub 2-41c (30 g, 116.9 mmol), 2-bromo-1,1'-biphenyl (27.2 g, 116.9 mmol), and n -BuLi (47 mL), proceed as in the synthesis method of Sub 2-5d. 41.3 g of the product was obtained. (yield 86%)

(5) Synthesis of Sub 2-41

Using Sub 2-41d (41.3 g, 100.5 mmol), acetic acid (251 mL) and HCl (40 mL), the same procedure was followed for the synthesis of Sub 2-5 to obtain 34.4 g of the product. (Yield 87%)

4. Sub 2-44 Synthesis example

(1) Sub 2- Synthesis of 44a

In a round-bottom flask, add 2-iodobenzoic acid (20.0 g, 80.6 mmol), 4-chloroaniline (20.6 g, 161 mmol), Cu(OAc) ₂ (1.0 g), sodium acetate (7.9 g, 96.8 mmol) and water ( 540 mL) and refluxed for 5 hours. When the reaction is complete, after cooling to room temperature, 3M HCl is added until the precipitation is complete. When the precipitation was completed, the precipitate was washed with water and dried to obtain 16.4 g of a product. (Yield 82%)

(2) Synthesis of Sub 2-44a'

After dissolving Sub 2-44a (16.4 g, 66.2 mmol) in toluene (330 mL), bromonaphthalene (10.4 g, 66.2 mmol), Pd ₂ (dba) ₃ (1.82 g, 1.99 mmol), P( t- Bu) ₃ (0.80 g, 3.97 mmol), NaO t -Bu (12.7 g, 132 mmol) was added and stirred at 60°C. Upon completion of the reaction _{, the mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 11.7 g of a product. (Yield 74%)

(3) Sub 2- 44c synthesis

Sub 2-44a' (11.7 g, 49.0 mmol) and H ₂ SO ₄ (350 mL) were used in the same manner as in the synthesis method of Sub 2-5c to obtain 6.9 g of the product. (Yield 68%)

(4) Sub 2- 44d synthesis

2-bromo-2'-chloro-1,1'-biphenyl (7.7 g, 33.2 mmol), n -BuLi (13 mL), Sub 2-44c (6.9 g, 33.2 mmol) using the above Sub 2-5c Proceeded as in the synthesis example of to obtain 10.3 g of the product. (Yield 82%)

(5) Synthesis of Sub 2-44

Sub 2-44d (10.3 g, 27.2 mmol), acetic acid (68 mL) and HCl (11 mL) were used in the same manner as in the synthesis example of Sub 2-5 to obtain 10.2 g of the product. (yield 92%)

The compound belonging to Sub 2 may be a compound as follows, but is not limited thereto, and Table 2 below shows FD-MS values of the following compounds.

[Table 2]

of the final compound Synthesis example

1. P-18 Synthesis example

After dissolving Sub 1-18 (10.0 g, 29.3 mmol) in toluene (146 ml), Sub 2-15 (11.2 g, 29.3 mmol), Pd ₂ (dba) ₃ (0.8 g, 0.9 mmol), P(t) -Bu) ₃ (0.4 g, 1.8 mmol) and NaOt-Bu (5.6 g, 58.6 mmol) were added. Upon completion of the reaction, _{extraction was performed with CH 2} Cl ₂ and water, and the organic layer _{was dried over MgSO 4} and concentrated. Thereafter, the concentrate was separated by a silica gel column and recrystallized to obtain 14.3 g of a product. (Yield: 70.9%)

2. P-34 Synthesis example

After dissolving Sub 1-34 (10.0 g, 25.7 mmol) in toluene (128 ml), Sub 2-5 (9.4 g, 25.7 mmol), Pd ₂ (dba) ₃ (0.7 g, 0.8 mmol), P(t) -Bu) ₃ (0.3 g, 1.5 mmol) and NaOt-Bu (4.9 g, 51.4 mmol) were added, and the same procedure was followed in the same manner as in the synthesis example of Sub 1-18 to obtain 14.1 g of a product. (Yield: 76.4%)

3. P-59 Synthesis example

After dissolving Sub 1-49 (10.0 g, 21.6 mmol) in toluene (108 ml), Sub 2-36 (8.3 g, 21.6 mmol), Pd ₂ (dba) ₃ (0.6 g, 0.7 mmol), P(t) -Bu) ₃ (0.3 g, 1.3 mmol) and NaOt-Bu (4.2 g, 43.2 mmol) were added, and the same procedure was followed in the synthesis example of Sub 1-18 to obtain 13.2 g of a product. (Yield: 75.4%)

4. P-57 Synthesis example

After dissolving Sub 1-56 (10.0 g, 19.3 mmol) in toluene (97 ml), Sub 2-41 (7.6 g, 19.3 mmol), Pd ₂ (dba) ₃ (0.5 g, 0.6 mmol), P(t -Bu) ₃ (0.2 g, 1.2 mmol) and NaOt-Bu (3.7 g, 38.6 mmol) were added, and the same procedure was followed in the synthesis example of Sub 1-18 to obtain 11.7 g of a product. (Yield: 69.5%)

5. P-80 Synthesis example

After dissolving Sub 1-78 (10.0 g, 19.0 mmol) in toluene (95 ml), Sub 2-16 (7.0 g, 19.0 mmol), Pd ₂ (dba) ₃ (0.5 g, 0.6 mmol), P(t -Bu) ₃ (0.2 g, 1.1 mmol) and NaOt-Bu (3.6 g, 38.0 mmol) were added, and the same procedure as in the synthesis example of Sub 1-18 above was followed to obtain 11.9 g of a product. (Yield: 73.1%)

FD-MS values of compounds P-1 to P-100 of the present invention prepared according to the above synthesis examples are shown in Table 3 below.

[Table 3]

Manufacturing evaluation of organic electric devices

[ Example One] Red organic electroluminescent device ( light emitting layer )

N1-(naphthalen-2-yl)-N4,N4-bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N1-phenylbenzene-1,4 on the ITO layer (anode) formed on the glass substrate After vacuum deposition of a -diamine (hereinafter abbreviated as '2-TNATA') film to form a hole injection layer with a thickness of 60 nm, N,N'-bis(1-naphthalenyl)-N,N'-bis-phenyl- A (1,1'-biphenyl)-4,4'-diamine (hereinafter abbreviated as 'NPB') film was vacuum-deposited to a thickness of 60 nm to form a hole transport layer.

Then, on the hole transport layer, the compound P-18 of the present invention is vacuum-deposited to a thickness of 20 nm to form a light emitting auxiliary layer, and [4,4'-N,N'-dicarbazole as a host on the light emission auxiliary layer. -biphenyl] (hereinafter abbreviated as 'CBP') and bis-(1-phenyl isoquinolyl)iridium(III)acetylacetonate (hereinafter _{abbreviated as '(piq) 2} Ir(acac)') as the dopant, but these A light emitting layer having a thickness of 30 nm was deposited by doping with a dopant so that the weight ratio was 95:5.

Then, on the hole transport layer, the compound P-18 of the present invention is vacuum-deposited to a thickness of 20 nm to form a light-emitting auxiliary layer, and 4,4'-N,N'-dicarbazole- as a host on the light-emitting auxiliary layer biphenyl (hereinafter abbreviated as 'CBP') and bis-(1-phenyl isoquinolyl)iridium(III)acetylacetonate (hereinafter _{abbreviated as '(piq) 2} Ir(acac)') as the dopant, but these weight ratios are 95 A light emitting layer having a thickness of 30 nm was deposited by doping with a dopant to be :5.

Next, (1,1'-biphenyl-4-olato)bis(2-methyl-8-quinolinolato)aluminum (hereinafter abbreviated as 'BAlq') was vacuum-deposited to a thickness of 10 nm on the light emitting layer to form a hole blocking layer was formed, and tris(8-quinolinol)aluminum (hereinafter _{abbreviated as Alq 3} ) was deposited on the hole blocking layer to a thickness of 40 nm to form an electron transport layer.

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

[ Example 2] to [ Example 15]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compound of the present invention described in Table 4 was used instead of the compound P-18 of the present invention as a material for the light emitting auxiliary layer.

[ comparative example One]

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

[ comparative example 2] to [ comparative example 4]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that one of the following Comparative Compounds A to C was used as the light emitting auxiliary layer material.

<Comparative compound A> <Comparative compound B> <Comparative compound C>

By applying a forward bias DC voltage to the organic electroluminescent devices manufactured by Examples 1 to 15 and Comparative Examples 1 to 4 of the present invention, the electroluminescence (EL) characteristics were obtained with PR-650 of Photoresearch. It was measured, and the T95 lifespan was measured through the life measuring equipment of McScience at ^{2500cd/m 2 standard luminance.} The measurement results are shown in Table 4 below.

[Table 4]

From the results of Table 4, when the compound of the present invention is used as a material for the light-emitting auxiliary layer, the driving voltage of the device can be lowered compared to when the light-emitting auxiliary layer is not formed (Comparative Example 1) or when the comparative compound is used (Comparative Examples 2 to 4) It can be seen that the luminous efficiency and lifespan are significantly improved.

Comparative Compounds A to C are similar to the compounds of the present invention in that they contain a 4-condensed ring moiety, but the compounds of the present invention differ in that at least one of the substituents of the amino group is a spirocyclic compound. Due to these differences, the LUMO levels of the comparative compound and the compound of the present invention are different. Table 5 below shows the LUMO values of the compound of the present invention and the comparative compounds A to C having similar compound structures. The LUMO values in Table 5 below are data measured using the DFT method (B3LYP/6-31g(D)) of the Gaussian program.

[Table 5]

Comparing the compound P-18 of the present invention and the comparative compound A, it is the same in that benzoindenothiophene and phenyl, which are 4-condensed rings, are bonded to the nitrogen of the amine group, but the other substituent is the case of Comparative Compound A is dibenzothiophene, but the compound P-18 of the present invention is different in that it is spiro [fluorene-9,9'-thioxanthene].

As shown in Table 5 above, this difference also affects the molecular energy level, and it can be seen that the LUMO energy level of the compound P-18 of the present invention is higher than that of the comparative compound A. Therefore, in the case of compound P-18 of the present invention, electrons passing from the light emitting layer to the hole transport layer or the light emission auxiliary layer can be more effectively blocked compared to the comparative compound A, and as a result, damage to the hole transport layer or light emission auxiliary layer is reduced. It can be minimized and the characteristics of the device are also judged to have improved results.

This tendency is equally applied to the case of the compound P-19 of the present invention and the comparative compound B, and also the case of the compound P-22 and the comparative compound C of the present invention, which have similar structures.

According to these results, even if the basic skeleton of the compound is similar, properties such as energy level (HOMO, LUMO), hole injection/transfer characteristics, and charge balance between holes and electrons may vary depending on the type of substituent, and as a result, the characteristics of the device also suggests that it may be different.

The above description is merely illustrative of the present invention, and those of ordinary skill in the art to which the present invention pertains 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 intended to illustrate, not to limit the present invention, and the scope of the present invention is not limited by these embodiments. The protection scope of the present invention should be construed by the following claims, and all descriptions within the scope equivalent thereto should be construed as being included in the scope of the present invention.

100, 200, 300: organic electric device 110: first electrode
120: hole injection layer 130: hole transport layer
140: light emitting layer 150: electron transport layer
160: electron injection layer 170: second electrode
180: light efficiency improvement layer 210: buffer layer
220: light emitting auxiliary layer 320: first hole injection layer
330: first hole transport layer 340: first light emitting layer
350: first electron transport layer 360: first charge generation layer
361: second charge generation layer 420: second hole injection layer
430: second hole transport layer 440: second light emitting layer
450: second electron transport layer CGL: charge generation layer
ST1: first stack ST2: second stack

Claims (13)

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

In Formula 1,
Ring A is represented by the following formula 1-1, Q is represented by the following formula 1-2,
<Formula 1-1><Formula1-2>

,

In Formula 1-1, * represents a binding site,
X ¹ X ² , and X ³ are each independently O, S, C(R′)(R″) or N(R),
R ¹ to R ⁶ , R′ and R″ are each independently hydrogen; deuterium; halogen; cyano group; nitro group; C ₆ to C ₆₀ aryl group; fluorenyl group; O, N, S, Si and P _{C 2} ~ C ₆₀ heterocyclic group containing at least one heteroatom; C ₃ ~ C ₆₀ aliphatic ring group; C ₁ ~ C ₃₀ alkyl group; C ₂ ~ C ₃₀ alkenyl group; C ₂ ~ C ₃₀ of alkynyl group; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; and -L'-N(R _a )(R _b ) selected from the group consisting of, adjacent groups are bonded to form a ring, R' and R" may combine with each other to form a ring, and one of ^{R 3} to R ⁶ is bonded to ^{L 2 ,}
a is an integer from 0 to 3, b, c, d, e and f are each an integer from 0 to 4, and when each of these is an integer of 2 or greater, each of R ^{1 ,} each of R ^{2 ,} each of R ^{3 ,} each of R ⁴ , ^{each of R 5 ,} each of R ⁶ are the same as or different from each other,
Ar ¹ is a C ₆ ~ C ₆₀ aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; And C ₃ ~ C _{60 It} is selected from the group consisting of an aliphatic cyclic group,
L ^{1 To} L ^{3 Are} each independently a single bond; C ₆ ~ C ₆₀ Arylene group; fluorenylene group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; And C ₃ ~ C _{60 It} is selected from the group consisting of an aliphatic cyclic group,
The L' is a single bond; C ₆ ~ C ₆₀ Arylene group; fluorenylene group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; And C ₃ ~ C _{60 It} is selected from the group consisting of an aliphatic cyclic group,
The R, R _a and R _b are each independently a C ₆ ~ C ₆₀ aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; And C ₃ ~ C _{60 It} is selected from the group consisting of an aliphatic cyclic group,
The aryl group, an arylene group, a fluorenyl group, a fluorenylene group, a heterocyclic group, an aliphatic ring group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxyl group, an aryloxy group, a ring formed by bonding adjacent groups to each other, and A ring formed by combining R′ and R″ is deuterium; halogen; a silane group unsubstituted or substituted with a _{C 1} -C ₂₀ alkyl group or C ₆ -C _{20 aryl group; C 1} -C ₂₀ alkyl group or C ₆ -C ₂₀ Phosphine oxide unsubstituted or substituted with an aryl group; Siloxane group; Cyano group; Nitro group; C ₁ -C ₂₀ Alkylthio group; C ₁ -C _{20 Alkoxy group; C 6} -C ₂₀ Aryloxy group; C ₆ -C ₂₀ Arylthio 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; Flu _{Orenyl group; C 2} -C ₂₀ heterocyclic group comprising at least one heteroatom selected from the group consisting of O, N, S, Si and P; C ₃ -C ₂₀ aliphatic ring group; And -L'- It may be substituted with one or more substituents selected from the group consisting of N(R _a )(R _{b ).} The method of claim 1,
Formula 1 is a compound, characterized in that represented by Formula 1-a or Formula 1-b:
<Formula 1-a><Formula1-b>

In Formulas 1-1 and 1-2, X ¹ , X ² , R ¹ , R ² , Ar ¹ , Q, L ¹ to L ³ , a, and b are the same as defined in claim 1 . The method of claim 1,
Formula 1 is a compound characterized in that it is represented by one of the following Formulas 1-c to 1-f:
<Formula 1-c><Formula1-d>

<Formula 1-e><Formula1-f>

In Formula 1-c to Formula 1-f, X ¹ to X ³ , R ¹ to R ⁶ , L ¹ to L ³ , Ar ¹ , a to f are the same as defined in claim 1 , and R ^3′ is in the same claim, and the R ³ defined in one of the preceding claims, and, R ^{5 'is} the same as that of R ⁵ as defined in claim 1, c' and e 'is an integer from 0 to 3, respectively. The method of claim 1,
A compound characterized in that Formula 1-2 is represented by one of the following Formulas 1-2a to 1-2d:
<Formula 1-2a><Formula1-2b>

<Formula 1-2c><Formula1-2d>

In Formulas 1-2a to 1-2d, R ³ to R ⁶ , c to f, R′, R″, and R are as defined in claim 1. The method of claim 1,
The compound represented by Formula 1 is a compound, characterized in that one of the following compounds:

. An organic electric device comprising a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode,
The organic material layer is an organic electric device comprising a compound represented by the formula (1) of claim 1. An organic electric device comprising a first electrode, a second electrode, and an organic material layer and a light efficiency improving layer formed between the first electrode and the second electrode,
The light efficiency improving layer is formed on one surface of both surfaces of the first electrode and the second electrode that is not in contact with the organic material layer,
The organic material layer or the light efficiency improving layer is an organic electric device, characterized in that it comprises a compound represented by the formula (1) of claim 1. 8. The method of claim 6 or 7,
The organic material layer is an organic electric device comprising at least one of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer and an electron injection layer. 9. The method of claim 8,
The compound is an organic electric device, characterized in that included in the light emitting auxiliary layer. 8. The method of claim 6 or 7,
The organic material layer comprises two or more stacks including a hole transport layer, a light emitting layer, and an electron transport layer sequentially formed on the first electrode. 11. The method of claim 10,
The organic material layer is an organic electric device, characterized in that it further comprises a charge generation layer formed between the two or more stacks. A display device comprising the organic electric device of claim 6 or 7; and
An electronic device comprising a; a control unit for driving the display device. 13. The method of claim 12,
The organic electric device is an electronic device, characterized in that selected from the group consisting of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, a device for monochromatic lighting, and a device for a quantum dot display.

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