WO2014088285A1 - Compound for organic electronic element, organic electronic element using same, and electronic device therewith - Google Patents

Abstract

Provided are a novel compound allowing the luminous efficiency, stability, and service life of an element to be improved, an organic electronic element using the compound, and an electronic device comprising the organic electronic element.

Description

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

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

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

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

The biggest problem for organic electroluminescent devices is life and efficiency. As the display becomes larger, such efficiency and life problems must be solved.

Efficiency, lifespan, and driving voltage are related to each other, and as efficiency increases, the driving voltage decreases relatively, and as the driving voltage decreases, crystallization of organic materials due to Joule heating generated during driving decreases. It shows a tendency to increase the life.

However, simply improving the organic material layer does not maximize the efficiency. This is because a long life and high efficiency can be achieved at the same time when an optimal combination of energy level, T1 value, and intrinsic properties (mobility, interfacial properties, etc.) of each organic material layer is achieved.

In addition, in order to solve the problem of light emission in the hole transport layer in the organic electroluminescent device, a light emitting auxiliary layer must exist between the hole transport layer and the light emitting layer, and different light emission auxiliary according to each light emitting layer (R, G, B) is required. It is time to develop the floor.

In general, electrons are transferred from the electron transport layer to the light emitting layer, and holes are transferred from the hole transport layer to the light emitting layer to generate excitons by recombination.

However, the material used in the hole transport layer has a low TMO value because it has to have a low HOMO value, which causes the exciton generated in the light emitting layer to pass to the hole transport layer, resulting in charge unbalance in the light emitting layer. This causes light emission in the hole transport layer or at the hole transport layer interface, resulting in a decrease in color purity, efficiency and lifespan of the organic electronic device.

In addition, the driving voltage can be reduced by using a material having a high hole mobility, but the hole mobility is faster than the electron mobility, resulting in charge unbalance in the light emitting layer. The color purity and efficiency of the electric device is lowered and the lifespan is shortened.

Therefore, the development of a light emitting auxiliary layer having a high T1 value and a HOMO level between the hole transport layer HOMO energy level and the light emitting layer HOMO energy level is urgently required.

On the other hand, while delaying the penetration of metal oxide into the organic layer from the anode electrode (ITO), which is one of the causes of shortening the life of the organic electronic device, stable properties, that is, high glass transition even for Joule heating generated during driving of the device. There is a need for development of a hole injection layer material having a temperature. The low glass transition temperature of the hole transport layer material has the property of lowering the uniformity of the surface of the thin film when the device is driven, which has been reported to have a great influence on the device life. In addition, the OLED device is mainly formed by a deposition method, which requires development of a material that can withstand a long time during deposition, that is, a material having strong heat resistance.

That is, in order to fully exhibit the excellent characteristics of the organic electric device, the materials constituting the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, a light emitting auxiliary layer material, etc. Supported by the material should be preceded, but development of a stable and efficient organic material layer for an organic electric device has not been made yet. Therefore, the development of new materials continues to be required, and in particular, the development of materials for the light emitting auxiliary layer and the hole transport layer is urgently required.

The present invention uses a non-linear linking group (a structure broken upon bonding with an amine group) to a carbazole core, which is widely used as an OLED hole transport material, and is also a bulky substituent to nitrogen (N) of carbazole. Compounds that have high T1 value, wide band gap and excellent charge balance to improve device's high luminous efficiency, low driving voltage, high heat resistance, color purity and lifetime An object of the present invention is to provide an organic electric device using the same and an electronic device thereof.

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

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

By using the compound according to the present invention, high luminous efficiency, low driving voltage, and high heat resistance of the device can be achieved, and color purity and life of the device can be greatly improved.

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

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

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

In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It is to be understood that the elements may be "connected", "coupled" or "connected".

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

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

As used herein, the term "alkyl" or "alkyl group" has a single bond of 1 to 60 carbon atoms, unless otherwise indicated, and is a straight chain alkyl group, branched chain alkyl group, cycloalkyl (alicyclic) group, alkyl-substituted cyclo Radicals of saturated aliphatic functional groups, including alkyl groups, cycloalkyl-substituted alkyl groups.

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

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

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

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

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

As used herein, the term "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" means an alkenyl group to which an oxygen radical is attached, and unless otherwise stated, it is 2 to 60 It has carbon number of, It is not limited to this.

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

As used herein, the terms "aryl group" and "arylene group" have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto. In the present invention, an aryl group or an arylene group means an aromatic of a single ring or multiple rings, and includes an aromatic ring formed by neighboring substituents participating in a bond or a reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, a spirofluorene group.

The prefix "aryl" or "ar" means 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 the radical substituted with an aryl group has the carbon number described herein.

Also, when prefixes are named consecutively, it means that the substituents are listed in the order described first. For example, an arylalkoxy group means an alkoxy group substituted with an aryl group, an 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.

As used herein, the term “heteroalkyl” means an alkyl including one or more heteroatoms unless otherwise indicated. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or arylene group having 2 to 60 carbon atoms, each containing one or more heteroatoms, unless otherwise specified. It may include at least one of a single ring and multiple rings, and may be formed by combining adjacent functional groups.

As used herein, the term “heterocyclic group” includes one or more heteroatoms, unless otherwise indicated, and has from 2 to 60 carbon atoms, and includes at least one of single and multiple rings, heteroaliphatic rings and hetero Aromatic rings. Adjacent functional groups may be formed in combination.

The term "heteroatom" as used herein refers to N, O, S, P or Si unless otherwise stated.

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

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

Unless otherwise stated, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a hetero ring having 2 to 60 carbon atoms or a combination thereof. Saturated or unsaturated rings.

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

Unless otherwise stated, the term "carbonyl" used in the present invention is represented by -COR ', wherein R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 3 to 30 carbon atoms. 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 -RO-R ', wherein R or R' are each independently of each other hydrogen, an alkyl group having 1 to 20 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.

Also, unless stated otherwise, the term "substituted" in the term "substituted or unsubstituted" as used in the present invention is 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, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ C ₂₀ aryl alkenyl group, a silane group, a boron Group, germanium group, and C ₂ ~ C _{20 It} is meant to be substituted with one or more substituents selected from the group consisting of, but not limited to these substituents.

Also, unless otherwise stated, the formulas used in the present invention apply equally to the definitions of substituents based on the exponential definition of the following formulas.

Herein, when a is an integer of 0, the substituent R ¹ is absent, when a is an integer of 1, one substituent R ¹ is bonded to any one of carbons forming the benzene ring, and a is an integer of 2 or 3 Are each bonded as follows, where R ¹ may be the same or different from each other, and when a is an integer from 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the indication of 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, the organic electric device 100 according to the present invention includes a first electrode 120, a second electrode 180, a first electrode 110, and a second electrode 180 formed on a substrate 110. ) Is provided with an organic material layer containing a compound according to the present invention. In this case, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

The organic layer may include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, and an electron injection layer 170 on the first electrode 120 in sequence. At this time, the remaining layers except for the light emitting layer 150 may not be formed. The hole blocking layer, the electron blocking layer, the light emitting auxiliary layer 151, the buffer layer 141 may be further included, and the electron transport layer 160 may serve as the hole blocking layer.

In addition, although not shown, the organic electric device according to the present invention may further include a protective layer or a light efficiency improving layer (Capping layer) formed on one surface of the at least one surface of the first electrode and the second electrode opposite to the organic material layer.

The compound according to the present invention applied to the organic material layer of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, the electron injection layer 170, the host of the dopant or light efficiency improvement layer of the light emitting layer 150 It may be used as a material. Preferably, the compound of the present invention may be used as the light emitting layer 150, hole transport layer 140 and / or light emitting auxiliary layer 151.

Meanwhile, even in the same core, band gaps, electrical characteristics, and interface characteristics may vary depending on which substituents are bonded at which positions. Therefore, the selection of cores and the combination of sub-substituents bound thereto are also very significant. Importantly, long life and high efficiency can be achieved at the same time when an optimal combination of energy level and T1 value and intrinsic properties (mobility, interfacial properties, etc.) of each organic material layer is achieved.

As described above, in order to solve the light emission problem in the hole transport layer in the organic electroluminescent device, it is preferable to form a light emitting auxiliary layer between the hole transport layer and the light emitting layer, and according to each of the light emitting layers R, G, and B, It is time to develop different emission auxiliary layers. Meanwhile, in the case of the light emitting auxiliary layer, it is difficult to infer the characteristics of the organic material layer used even if a similar core is used, since the correlation between the hole transport layer and the light emitting layer (host) must be understood.

Therefore, in the present invention, by forming a light emitting layer or an auxiliary light emitting layer using a compound represented by the formula (1) by optimizing the energy level (level) and T1 value between each organic material layer, the intrinsic properties (mobility, interface characteristics, etc.) of the organic material The life and efficiency of the electric device can be improved at the same time.

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a PVD method. For example, the anode 120 is formed by depositing a metal or a conductive metal oxide 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 are formed thereon. After forming the organic material layer including the 160 and the electron injection layer 170, it can be prepared by depositing a material that can be used as the cathode 180 thereon.

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

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

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

In addition, the organic electroluminescent device according to the present invention may be one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a monochromatic or white illumination device.

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

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

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

<Formula 1>

In Formula 1, m is an integer of 1 to 4, n is an integer of 1 to 3,

R^One And R²Are independently of each other hydrogen; heavy hydrogen; Tritium; halogen; C₆~ C₆₀Aryl group; Fluorenyl groups; Containing at least one hetero atom of O, N, S, Si, and P C₂~ C₆₀Heterocyclic group of; C_One~ C₅₀An alkyl group; C₂~ C₂₀Alkenyl group; -L²-N (Ar²) (Ar³); C_One~ C₃₀An alkoxyl group; And C₆~ C₃₀It is selected from the group consisting of; aryloxyl group. For example, R^One And R²May independently from each other be hydrogen, phenyl, naphthyl and the like.

In Formula 1, Ar ¹ is a fluorenyl group; C ₆ ~ C ₆₀ Aryl group; C ₂ ~ C ₂₀ Alkenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₁ ~ C ₅₀ Alkyl group; -L ² -N (Ar ² ) (Ar ³ ); And a C ₆ ~ C ₆₀ aromatic ring and C ₃ ~ C ₆₀ Alicyclic ring fused ring group; it is selected from the group consisting of. By way of example, Ar ¹ is ethyl, propene, phenyl, biphenyl, terphenyl, naphthyl, 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorene, 9,9- Spiro-bifluorene, pyridine, isoquinoline, dibenzothiophene, dibenzofuran and the like.

In Formula 1, L ¹ and L ² are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; A C ₂ to C _{60 divalent} heterocyclic group including at least one hetero atom of O, N, S, Si, and P; Divalent fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And divalent aliphatic hydrocarbon group; It is selected from the group consisting of. By way of example, L ¹ and L ² are independently of each other a single bond, phenyl, biphenyl, naphthyl, 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorene, dibenzoti Offen, dibenzofuran and the like.

In Formula 1, Ar²                  And Ar³Are independent of each other, C₆~ C₆₀Aryl group; Fluorenyl groups; C containing at least one hetero atom of O, N, S, Si, and P₂~ C₆₀Heterocyclic group of; C_One~ C₅₀An alkyl group; C₆~ C₆₀Of aromatic rings and C₃~ C₆₀Fused ring of aliphatic ring of; And C₂~ C₂₀Alkenyl group; is selected from the group consisting of. By way of example, Ar²                  And Ar³Are independently of each other phenyl, biphenyl, terphenyl, naphthyl, phenanthrene, methylphenyl, fluorophenyl, deuterated phenyl, propenyl-phenyl, 9,9-dimethyl-9H-fluorene, 9,9- Diphenyl-9H-fluorene, 9,9-spiro-bifluorene, thiophene, benzothiophene, dibenzothiophene, dibenzofuran, indole, pyridine, quinoline, isoquinoline, benzoquinoline and the like.

Wherein the aryl group, heterocyclic group, fluorenyl group, alkyl group, alkenyl group, fused ring group, alkoxyl group, aryloxyl group, arylene group, fluorenylene group, aliphatic hydrocarbon group are each deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; -L'-N (R ') (R "), wherein L' is a single bond; C ₆ ~ C ₆₀ arylene group; fluorenylene group; at least one hetero of O, N, S, Si and P C ₂ ~ C ₆₀ heterocyclic group containing an atom, C ₃ ~ C ₆₀ alicyclic ring and C ₆ ~ C ₆₀ Aromatic ring fused ring group; and divalent C ₁ ~ C ₆₀ aliphatic hydrocarbon group; It is selected from the group, wherein R 'and R "are independently of each other C ₆ ~ C ₆₀ An aryl group; Fluorenyl group; C ₂ ~ C containing at least one heteroatom of O, N, S, Si and P A heterocyclic group of ₆₀ , a C ₁ -C ₅₀ alkyl group and a C ₂ -C ₂₀ alkenyl group; C ₁ ~ C ₂₀ of the import alkylthio; C ₁ -C ₂₀ alkoxyl group; C ₁ ~ C ₂₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₆ -C ₂₀ aryl group; C ₆ ~ C ₂₀ aryl group substituted with deuterium; Fluorenyl groups; C ₂ ~ C ₂₀ heterocyclic group; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ arylalkyl group; And C ₈ ~ C ₂₀ It may be further substituted with one or more substituents selected from the group consisting of; arylalkenyl group.

In Formula 1, L ¹ is selected from the following group.

In Formula 1, Ar ² and Ar ³ are independently selected from the following group.

In the group, Q ¹ is C (R ^a ) or N, Q ² is C (R ^b ) (R ^c ), N (R ^d ), S or O, k is an integer from 1 to 4, and R ^a and R ^e are i), independently of each other, hydrogen; heavy hydrogen; C ₆ ~ C ₆₀ Aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₁ ~ C ₃₀ Alkoxy group; And fluorenyl group; or ii) a plurality of R ^e may combine with neighboring groups to form an aromatic ring together with carbon bonded thereto.

In addition, the R ^b to R ^d is i) independently of each other C ₆ ~ C ₆₀ An aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₁ ~ C ₃₀ Alkoxyl group; or ii) R ^b and R ^c may be bonded to each other to form a Spiro compound with fluorene to which they are bonded.

Specifically, Chemical Formula 1 may be represented by the following Chemical Formula 2 or Chemical Formula 3.

In Formulas 2 and 3, Ar ² , Ar ³ , R ¹ , R ² , m and n may be defined as defined in Formula 1.

In Formula 2, X is C (R ^f ) (R ^g ), S or O, wherein R ^f and R ^g is i) independently of each other C ₆ ~ C ₆₀ An aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; And C ₁ ~ C ₃₀ alkoxyl group; or ii) R ^f and R ^g may be bonded to each other to form a Spiro compound together with fluorene to which they are bonded.

In Formulas 2 and 3, o is an integer of 1 to 4, p is an integer of 1 to 3, and q and r are integers of 1 to 5 independently of each other.

In Formula 2 and Formula 3, R ³ to R ⁶ are i) hydrogen independently of each other; heavy hydrogen; Tritium; halogen; C ₆ ~ C ₆₀ Aryl group; C ₂ -C ₆₀ heterocyclic group containing at least one hetero atom of O, N, S, Si and P; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₁ -C ₃₀ alkoxyl group; And C ₆ ~ C ₃₀ An aryloxyl group; or ii) neighboring groups may combine with each other to form an aromatic ring with the carbon bonded to them.

Specifically, Chemical Formula 1 may be represented by the following Chemical Formula 4 or Chemical Formula 5.

In Formulas 4 and 5, Ar ¹ to Ar ³ , R ¹ , R ² , m and n may be defined as defined in Formula 1.

In Formula 5, Q ³ is C (R ^h ) (R ⁱ ), N (R ^j ), S or O, wherein R ^h to R ^j are i) independently of each other C ₆ ~ C ₆₀ aryl group ; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₁ ~ C ₃₀ Alkoxyl group; or ii) R ^h and R ⁱ may be bonded to each other to form a Spiro compound with fluorene to which they are bonded.

More specifically, Chemical Formulas 1 to 5 may be one of the following compounds.

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

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

In this case, the organic electric element includes a first electrode; Second electrode; And an organic material layer disposed between the first electrode and the second electrode. The organic material layer may include a compound represented by Chemical Formula 1, and Chemical Formula 1 may include a hole injection layer, a hole transport layer, and an emission auxiliary layer of the organic material layer. Or it may be contained in at least one layer of the light emitting layer. That is, the compound represented by Formula 1 may be used as a material of a hole injection layer, a hole transport layer, a light emitting auxiliary layer or a light emitting layer. Specifically, it provides an organic electroluminescent device comprising one of the compounds represented by Formula 2 to Formula 5 in the organic material layer, and more specifically, the present invention is an organic electroluminescent device comprising a compound represented by the respective formula in the organic material layer To provide.

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

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

Synthesis Example

Compound represented by Formula 1 according to the present invention (Final Product) is prepared by reacting Sub 1 and Sub 2 as shown in Scheme 1, but is not limited thereto.

<Scheme 1>

(Ar ¹ to Ar ³ , L ¹ , R ¹ , R ² , m and n are the same as defined in Formula 1 above, and when L ¹ is a single bond, Br is directly bonded to the phenyl group which is the linking group.)

I. Synthesis of Sub 1

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

<Scheme 2>

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

1.Synthesis of Sub 1-A1

<Scheme 3>

(1) Sub 1-I-A1 Synthesis

After starting material phenylboronic acid (412.96g, 3386.9mmol) was dissolved in THF in a round bottom flask, 4-bromo-2-iodo-1-nitrobenzene (1665.83g, 5080.3mmol), Pd (PPh ₃ ) ₄ (195.69g , 169.3 mmol), K ₂ CO ₃ (1404.29 g, 10160.6 mmol), water were added and stirred at 80 ° C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to give the product 659.32g (yield: 70%).

(2) Sub 1-II-A1 Synthesis

Sub 1-I-A1 (659.32g, 2370.8mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene in a round bottom flask, triphenylphosphine (1554.59g, 5927mmol) was added and stirred at 200 ° C. After the reaction was completed, o -dichlorobenzene was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was purified by silicagel column and recrystallized to give 431.76 g (yield: 74%) of product.

(3) Sub 1-III-A1 Synthesis

Sub 1-II-A1 (50.69g, 206mmol) obtained in the above synthesis was dissolved in nitrobenzene in a round bottom flask, iodobenzene (63.03g, 309mmol), Na ₂ SO ₄ (29.26g, 206mmol), K ₂ CO ₃ ( 28.47 g, 206 mmol), Cu (3.93 g, 61.8 mmol) were added and stirred at 200 ° C. After the reaction was completed, nitrobenzene was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was silicagel column and recrystallized to give the product 48.45g (73% yield).

(4) Sub 1-IV-A1 Synthesis

Sub 1-III-A1 (48.45g, 150.4mmol) obtained in the above synthesis was dissolved in DMF in a round bottom flask, and then Bis (pinacolato) diboron (42g, 165.4mmol), Pd (dppf) Cl₂(3.68g, 4.5mmol), KOAc (44.27 g, 451.1 mmol) was added and stirred at 90 ° C. When the reaction is complete, remove DMF by distillation₂Cl₂And extracted with water. MgSO organic layer₄After drying and concentration, the resulting compound was silicagel column and recrystallized to give 46.64g (yield: 84%) of the product.

(5) Sub 1-V-A1 (Sub 1-C1) synthesis

Sub 1-IV-A1 (46.64 g, 126.3 mmol) obtained in the above synthesis was dissolved in THF in a round bottom flask, followed by 1,3-dibromobenzene (44.69 g, 189.5 mmol), Pd (PPh ₃ ) ₄ (7.3 g, 6.3 mmol), K ₂ CO ₃ (52.37 g, 378.9 mmol), water were added and stirred at 80 ° C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was silicagel column and recrystallized to give the product 36.22g (yield: 72%).

(6) Sub 1-VI-A1 Synthesis

Sub 1-V-A1 (36.22g, 90.9mmol) obtained in the above synthesis was dissolved in DMF in a round bottom flask, Bis (pinacolato) diboron (25.4g, 100mmol), Pd (dppf) Cl₂(2.23g, 2.7mmol), KOAc (26.77 g, 272.8 mmol) was added and stirred at 90 ° C. When the reaction is complete, remove DMF by distillation₂Cl₂And extracted with water. MgSO organic layer₄The resulting compound was dried over and concentrated with silicagel column and recrystallized to give 33.21 g (yield: 82%) of the product.

(7) Sub 1-A1 Synthesis

Sub 1-VI-A1 (10.52 g, 23.6 mmol) obtained in the above synthesis was dissolved in THF in a round bottom flask, followed by 1-bromo-4-iodobenzene (10.02 g, 35.4 mmol) and Pd (PPh ₃ ) ₄ (1.36). g, 1.2 mmol), K ₂ CO ₃ (9.79 g, 70.9 mmol), water were added and stirred at 80 ° C. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain 9.08 g (yield: 81%) of the product.

2. Synthesis of Sub 1-A2

<Scheme 4>

(1) Sub 1-III-A2 Synthesis

Sub 1-II-A1 (23.94g, 97.3mmol) obtained in the above synthesis of 4-iodo-1,1'-biphenyl (40.87g, 145.9mmol), Na ₂ SO ₄ (13.82g, 97.3mmol), K ₂ CO ₃ (13.44 g, 97.3 mmol), Cu (1.85 g, 29.2 mmol) and nitrobenzene were obtained using the Sub 1-III-A1 synthesis method to obtain 27.51 g (yield: 71%) of the product.

(2) Sub 1-IV-A2 Synthesis

Sub 1-III-A2 (27.51g, 69.1mmol) obtained in the above synthesis to Bis (pinacolato) diboron (19.29g, 76mmol), Pd (dppf) Cl₂(1.69g, 2.1mmol), KOAc (20.34 g, 207.2 mmol) and DMF were obtained using 26.76 g (yield: 87%) of the product using the Sub 1-IV-A1 synthesis method.

(3) Sub 1-V-A2 (Sub 1-C2) synthesis

Sub 1-IV-A2 (26.76g, 60.1mmol) obtained in the above synthesis was obtained with 1,3-dibromobenzene (21.26g, 90.1mmol), Pd (PPh ₃ ) ₄ (3.47g, 3mmol), K ₂ CO ₃ (24.91 g, 180.3 mmol), THF, and water were used for the Sub 1-V-A1 synthesis to give 22.23 g (yield: 78%) of product.

(4) Sub 1-VI-A2 Synthesis

Sub 1-V-A2 (22.23g, 46.9mmol) obtained in the above synthesis to Bis (pinacolato) diboron (13.09g, 51.5mmol), Pd (dppf) Cl₂(1.15g, 1.4mmol), KOAc (13.8g, 140.6mmol) and DMF were obtained using the Sub 1-VI-A1 synthesis method to yield 20.53g (yield: 84%) of product.

(5) Sub 1-A2 Synthesis

Sub 1-VI-A2 (8.69 g, 16.7 mmol) obtained in the above synthesis was prepared with 1-bromo-4-iodobenzene (7.07 g, 25 mmol), Pd (PPh ₃ ) ₄ (0.96 g, 0.8 mmol), and K ₂ CO ₃ (6.91 g, 50 mmol), THF, and water were obtained using the Sub 1-A1 synthesis method to obtain 7.61 g (yield: 83%) of the product.

3. Synthesis of Sub 1-A21

Scheme 5

Sub 1-VI-A1 (12.36g, 27.8mmol) obtained in the above synthesis of 2-bromo-7-iodo-9,9-dimethyl-9 H -fluorene (16.61g, 41.6mmol), Pd (PPh ₃ ) ₄ (1.6 g, 1.4 mmol), K ₂ CO ₃ (11.51 g, 83.3 mmol), THF, and water were obtained using the Sub 1-A1 synthesis method to obtain 12.95 g (yield: 79%) of the product.

4.Synthesis of Sub 1-A26

<Scheme 6>

(1) Synthesis of Sub 1-III-A26

Sub 1-II-A1 (48.04g, 195.2mmol) obtained in the above synthesis to 5'-bromo-1,1 ': 3', 1 ''-terphenyl (90.54g, 292.8mmol), Na ₂ SO ₄ (27.73 g, 195.2 mmol), K ₂ CO ₃ (26.98 g, 195.2 mmol), Cu (3.72 g, 58.6 mmol) and nitrobenzene were obtained using 62.97 g (yield: 68%) of the product using the Sub 1-III-A1 synthesis method. Got it.

(2) Sub 1-IV-A26 Synthesis

Sub 1-III-A26 (62.97g, 132.7mmol) obtained in the above synthesis to Bis (pinacolato) diboron (37.08g, 146mmol), Pd (dppf) Cl₂(3.25g, 4mmol), KOAc (39.08 g, 398.2 mmol) and DMF were obtained using the Sub 1-IV-A1 synthesis method to yield 56.07 g (yield: 81%) of the product.

(3) Sub 1-V-A26 Synthesis

Sub 1-IV-A26 (56.07 g, 107.5 mmol) obtained in the above synthesis was obtained with 1,3-dibromobenzene (38.05 g, 161.3 mmol), Pd (PPh ₃ ) ₄ (6.21 g, 5.4 mmol), and K ₂ CO ₃ ( 44.58 g, 322.6 mmol), THF, and water were used to obtain the product 41.43 g (yield: 70%) using the Sub 1-V-A1 synthesis method.

(4) Sub 1-VI-A26 Synthesis

Sub 1-V-A26 (41.43g, 75.3mmol) obtained in the above synthesis to Bis (pinacolato) diboron (21.02g, 82.8mmol), Pd (dppf) Cl₂(1.84g, 2.3mmol), KOAc (22.16 g, 225.8 mmol) and DMF were used to obtain the product 35.08 g (yield: 78%) using the Sub 1-VI-A1 synthesis method.

(5) Sub 1-A26 Synthesis

Sub 1-VI-A26 (10.69 g, 17.9 mmol) obtained in the above synthesis was prepared using 1-bromo-4-iodobenzene (7.59 g, 26.8 mmol), Pd (PPh ₃ ) ₄ (1.03 g, 0.9 mmol), and K ₂ CO. ₃ (7.42 g, 53.7 mmol), THF, and water were used to obtain the product 8.52 g (yield: 76%) using the Sub 1-A1 synthesis method.

5. Synthesis of Sub 1-A29

Scheme 7

(1) Sub 1-III-A29 Synthesis

Sub 1-II-A1 (41.09 g, 167 mmol) obtained in the above synthesis of 3-bromo-9,9-dimethyl-9 H- fluorene (68.41 g, 250.4 mmol), Na ₂ SO ₄ (23.72 g, 167 mmol), 51.23 g (yield: 70%) of K ₂ CO ₃ (23.08 g, 167 mmol), Cu (3.18 g, 50.1 mmol) and nitrobenzene were obtained using the Sub 1-III-A1 synthesis method.

(2) Sub 1-IV-A29 synthesis

Sub 1-III-A29 (51.23 g, 116.9 mmol) obtained in the above synthesis to Bis (pinacolato) diboron (32.65 g, 128.6 mmol), Pd (dppf) Cl₂(2.86g, 3.5mmol), KOAc (34.41 g, 350.6 mmol) and DMF were obtained using the Sub 1-IV-A1 synthesis method to give 48.22 g (yield: 85%) of product.

(3) Sub 1-V-A29 (Sub 1-C8) synthesis

Sub 1-IV-A29 (48.22g, 99.3mmol) obtained in the above synthesis was obtained with 1,3-dibromobenzene (35.15g, 149mmol), Pd (PPh ₃ ) ₄ (5.74g, 5mmol), K ₂ CO ₃ (41.19g , 298 mmol), THF, and water were used for the Sub 1-V-A1 synthesis to obtain 38.84 g (yield: 76%) of product.

(4) Sub 1-VI-A29 Synthesis

Sub 1-V-A29 (38.84g, 75.5mmol) obtained in the above synthesis to Bis (pinacolato) diboron (21.09g, 83mmol), Pd (dppf) Cl₂(1.85g, 2.3mmol), KOAc (22.23 g, 226.5 mmol) and DMF were used to obtain the product 33.91 g (yield: 80%) using the Sub 1-VI-A1 synthesis method.

(5) Sub 1-A29 Synthesis

Sub 1-VI-A29 (9.61 g, 17.1 mmol) obtained in the above synthesis was subjected to 1-bromo-4-iodobenzene (7.26 g, 25.7 mmol), Pd (PPh ₃ ) ₄ (0.99 g, 0.9 mmol), K ₂ CO ₃ (7.1 g, 51.3 mmol), THF, and water were used to obtain 8.09 g (yield: 80%) of the product using the Sub 1-A1 synthesis method.

6.Synthesis of Sub 1-A35

Scheme 8

(1) Sub 1-III-A35 Synthesis

Obtained in the above Synthesis Sub 1-II-A1 (63.72g , 258.9mmol) in 2-bromo-9,9-diphenyl- 9 H -fluorene (154.31g, 388.4mmol), Na 2 SO 4 (36.78g, 258.9mmol ), K ₂ CO ₃ (35.79 g, 258.9 mmol), Cu (4.94 g, 77.7 mmol) and nitrobenzene were obtained using the Sub 1-III-A1 synthesis method to obtain 88.84 g (yield: 61%) of the product.

(2) Sub 1-IV-A35 Synthesis

Sub 1-III-A35 (88.84g, 157.9mmol) obtained in the above synthesis to Bis (pinacolato) diboron (44.12g, 173.7mmol), Pd (dppf) Cl₂(3.87g, 4.7mmol), KOAc (46.5 g, 473.8 mmol) and DMF were obtained using the Sub 1-IV-A1 synthesis method to yield 74.13 g (yield: 77%) of the product.

(3) Synthesis of Sub 1-V-A35 (Sub 1-C12)

Sub 1-IV-A35 (74.13 g, 121.6 mmol) obtained in the above synthesis was prepared with 1,3-dibromobenzene (43.03 g, 182.4 mmol), Pd (PPh ₃ ) ₄ (7.03 g, 6.1 mmol), and K ₂ CO ₃ ( 50.42 g, 364.8 mmol), THF, and water were used to give the product 54.36 g (yield: 70%) using the Sub 1-V-A1 synthesis method.

(4) Sub 1-VI-A35 Synthesis

Sub 1-V-A35 (54.36g, 85.1mmol) obtained in the above synthesis to Bis (pinacolato) diboron (23.78g, 93.6mmol), Pd (dppf) Cl₂(2.09g, 2.6mmol), KOAc (25.06 g, 255.4 mmol) and DMF were obtained using the Sub 1-VI-A1 synthesis method to obtain 43.19 g (yield: 74%) of the product.

(5) Sub 1-A35 Synthesis

Sub 1-VI-A35 (12.29 g, 17.9 mmol) obtained in the above synthesis was prepared using 1-bromo-4-iodobenzene (7.61 g, 26.9 mmol), Pd (PPh ₃ ) ₄ (1.04 g, 0.9 mmol), and K ₂ CO. ₃ (7.43 g, 53.8 mmol), THF, and water were used to obtain 9.61 g (yield: 75%) of the product using the Sub 1-A1 synthesis method.

7.Synthesis of Sub 1-A36

Scheme 9

(1) Sub 1-III-A36 Synthesis

Sub-1 II-A1 obtained in the above Synthesis (59.25g, 240.8mmol) in 3-bromo-9,9-diphenyl- 9 H -fluorene (143.48g, 361.1mmol), Na 2 SO 4 (34.2g, 240.8mmol ), K ₂ CO ₃ (33.27 g, 240.8 mmol), Cu (4.59 g, 72.2 mmol) and nitrobenzene were obtained using the Sub 1-III-A1 synthesis method to obtain 85.32 g (yield: 63%) of the product.

(2) Sub 1-IV-A36 Synthesis

Sub 1-III-A36 (85.32g, 151.7mmol) obtained in the above synthesis to Bis (pinacolato) diboron (42.37g, 166.8mmol), Pd (dppf) Cl₂(3.72g, 4.6mmol), KOAc (44.66 g, 455 mmol) and DMF were obtained using the Sub 1-IV-A1 synthesis method to yield 73.04 g (yield: 79%) of the product.

(3) Synthesis of Sub 1-V-A36 (Sub 1-C13)

Sub 1-IV-A36 (73.04 g, 119.8 mmol) obtained in the above synthesis was converted into 1,3-dibromobenzene (42.4 g, 179.7 mmol), Pd (PPh ₃ ) ₄ (6.92 g, 6 mmol), and K ₂ CO ₃ (49.68 g, 359.5 mmol), THF, and water were used to obtain the product 55.86 g (yield: 73%) using the Sub 1-V-A1 synthesis method.

(4) Sub 1-VI-A36 Synthesis

Sub 1-V-A36 (55.86g, 87.5mmol) obtained in the above synthesis to Bis (pinacolato) diboron (24.43g, 96.2mmol), Pd (dppf) Cl₂(2.14g, 2.6mmol), KOAc (25.75 g, 262.4 mmol) and DMF were used to give 42.58 g (yield: 71%) of the product using the Sub 1-VI-A1 synthesis method.

(5) Sub 1-A36 Synthesis

Sub 1-VI-A36 (11.85g, 17.3mmol) obtained in the above synthesis was subjected to 1-bromo-4-iodobenzene (7.33g, 25.9mmol), Pd (PPh ₃ ) ₄ (1g, 0.9mmol), K ₂ CO ₃ (7.17 g, 51.8 mmol), THF, and water were used to obtain 9.39 g (yield: 76%) of the product using the Sub 1-A1 synthesis method.

8. Synthesis of Sub 1-A43

Scheme 10

(1) Sub 1-III-A43 Synthesis

Sub 1-II-A1 (52.13g, 211.8mmol) obtained in the above synthesis of 2-bromodibenzo [ b , d ] thiophene (83.61g, 317.7mmol), Na ₂ SO ₄ (30.09g, 211.8mmol), K ₂ CO ₃ (29.28 g, 211.8 mmol), Cu (4.04 g, 63.5 mmol) and nitrobenzene were obtained using 62.61 g (yield: 69%) of the product using the Sub 1-III-A1 synthesis method.

(2) Sub 1-IV-A43 synthesis

Sub 1-III-A43 (62.61g, 146.2mmol) obtained in the above synthesis to Bis (pinacolato) diboron (40.83g, 160.8mmol), Pd (dppf) Cl₂(3.58g, 4.4mmol), KOAc (43.04 g, 438.5 mmol) and DMF were obtained using 58.37 g (yield: 84%) of the product using the Sub 1-IV-A1 synthesis method.

(3) Sub 1-V-A43 synthesis

Sub 1-IV-A43 (58.37g, 122.8mmol) obtained in the above synthesis was obtained with 1,3-dibromobenzene (43.45g, 184.2mmol), Pd (PPh ₃ ) ₄ (7.09g, 6.1mmol), K ₂ CO ₃ ( 50.91 g, 368.3 mmol), THF, and water were used to obtain 46.45 g (yield: 75%) of the product using the Sub 1-V-A1 synthesis method.

(4) Sub 1-VI-A43 Synthesis

Sub 1-V-A43 (46.45g, 92.1mmol) obtained in the above synthesis to Bis (pinacolato) diboron (25.72g, 101.3mmol), Pd (dppf) Cl₂(2.26g, 2.8mmol), KOAc (27.11 g, 276.2 mmol) and DMF were used to obtain the product 40.63 g (yield: 80%) using the Sub 1-VI-A1 synthesis method.

(5) Sub 1-A43 Synthesis

Sub 1-VI-A43 (9.78 g, 17.7 mmol) obtained in the above synthesis was prepared using 1-bromo-4-iodobenzene (7.53 g, 26.6 mmol), Pd (PPh ₃ ) ₄ (1.02 g, 0.9 mmol), and K ₂ CO. ₃ (7.35 g, 53.2 mmol), THF, and water were used to obtain 8.13 g (yield: 79%) of the product using the Sub 1-A1 synthesis method.

9. Sub 1-A46 Synthesis Example

Scheme 11

(1) Sub 1-III-A46 Synthesis

Sub 1-II-A1 (57.92g, 235.4mmol) obtained in the above synthesis 3-bromodibenzo [ b , d ] furan (87.23g, 353mmol), Na ₂ SO ₄ (33.43g, 235.4mmol), K ₂ CO ₃ (32.53g, 235.4mmol), Cu (4.49g, 70.6mmol) and nitrobenzene were obtained using the Sub 1-III-A1 synthesis method to give 63.07g (yield: 65%) of the product.

(2) Sub 1-IV-A46 Synthesis

Bis (pinacolato) diboron (42.73g, 168.3mmol), Pd (dppf) Cl in Sub 1-III-A46 (63.07g, 153mmol) obtained in the above synthesis₂(3.75g, 4.6mmol), KOAc (45.04g, 458.9mmol) and DMF were obtained using 55.51g (yield: 79%) of the product using the Sub 1-IV-A1 synthesis method.

(3) Sub 1-V-A46 (Sub 1-C19) Synthesis

Sub 1-IV-A46 (55.51g, 120.8mmol) obtained in the above synthesis was obtained with 1,3-dibromobenzene (42.76g, 181.3mmol), Pd (PPh ₃ ) ₄ (6.98g, 6mmol), K ₂ CO ₃ (50.11 g, 362.5 mmol), THF, and water were used to obtain 44.26 g (yield: 75%) of the product using the Sub 1-V-A1 synthesis method.

(4) Sub 1-VI-A46 Synthesis

Sub 1-V-A46 (44.26g, 90.6mmol) obtained from the above synthesis to Bis (pinacolato) diboron (25.32g, 99.7mmol), Pd (dppf) Cl₂(2.22g, 2.7mmol), KOAc (26.68 g, 271.9 mmol) and DMF were obtained using the Sub 1-VI-A1 synthesis method to obtain 37.36 g (yield: 77%) of product.

(5) Sub 1-A46 Synthesis

Sub 1-VI-A46 (10.65 g, 19.9 mmol) obtained in the above synthesis was prepared with 1-bromo-4-iodobenzene (8.44 g, 29.8 mmol), Pd (PPh ₃ ) ₄ (1.15 g, 1 mmol), K ₂ CO ₃ (8.25 g, 59.7 mmol), THF, and water were used to obtain 8.98 g (yield: 80%) of the product using the Sub 1-A1 synthesis method.

10. Synthesis of Sub 1-A51

Scheme 12

Sub 1-VI-A2 (10.16 g, 19.5 mmol) obtained in the above synthesis was prepared with 1-bromo-3-iodobenzene (8.27 g, 29.2 mmol), Pd (PPh ₃ ) ₄ (1.13 g, 1 mmol), K ₂ CO ₃ (8.08 g, 58.5 mmol), THF, and water were obtained using the Sub 1-A1 synthesis method to obtain 7.94 g (yield: 74%) of the product.

11.Synthesis of Sub 1-A59

Scheme 13

Sub 1-VI-A26 (10.81g, 18.1mmol) obtained in the above synthesis was subjected to 1-bromo-3-iodobenzene (7.68g, 27.1mmol), Pd (PPh ₃ ) ₄ (1.05g, 0.9mmol), K ₂ CO ₃ (7.5 g, 54.3 mmol), THF, and water were used to obtain 8.05 g (yield: 71%) of the product using the Sub 1-A1 synthesis method.

12.Synthesis of Sub 1-A64

Scheme 14

Sub 1-VI-A29 (10.29g, 18.3mmol) obtained in the above synthesis was subjected to 1-bromo-3-iodobenzene (7.78g, 27.5mmol), Pd (PPh ₃ ) ₄ (1.06g, 0.9mmol), K ₂ CO ₃ (7.6 g, 55 mmol), THF, and water were obtained using the Sub 1-A1 synthesis method to yield 8.33 g (yield: 77%) of the product.

13.Synthesis of Sub 1-A67

Scheme 15

Sub 1-VI-A35 (13.62g, 19.9mmol) obtained in the above synthesis was subjected to 1-bromo-3-iodobenzene (8.43g, 29.8mmol), Pd (PPh ₃ ) ₄ (1.15g, 1mmol), K ₂ CO ₃ (8.24 g, 59.6 mmol), THF, and water were used to obtain 9.94 g (yield: 70%) of the product using the Sub 1-A1 synthesis method.

14. Synthesis of Sub 1-A68

Scheme 16

Sub 1-VI-A36 (12.87g, 18.8mmol) obtained in the above synthesis was subjected to 1-bromo-3-iodobenzene (7.97g, 28.2mmol), Pd (PPh ₃ ) ₄ (1.08g, 0.9mmol), K ₂ CO ₃ (7.78 g, 56.3 mmol), THF, and water were used to obtain 9.66 g (yield: 72%) of the product using the Sub 1-A1 synthesis method.

15. Synthesis of Sub 1-A75

Scheme 17

Sub 1-VI-A43 (12.29g, 22.3mmol) obtained in the synthesis described above, 1-bromo-3-iodobenzene (9.46g, 33.4mmol), Pd (PPh ₃ ) ₄ (1.29g, 1.1mmol), K ₂ CO ₃ (9.24 g, 66.9 mmol), THF, and water were used to obtain the product 10.09 g (yield: 78%) using the Sub 1-A1 synthesis method.

16. Synthesis of Sub 1-A79

Scheme 18

Sub 1-VI-A46 (11.93 g, 22.3 mmol) obtained in the above synthesis was prepared using 1-bromo-3-iodobenzene (9.45 g, 33.4 mmol), Pd (PPh ₃ ) ₄ (1.29 g, 1.1 mmol), and K ₂ CO. ₃ (9.24 g, 66.8 mmol), THF, and water were used to obtain 9.43 g (yield: 75%) of the product using the Sub 1-A1 synthesis method.

17. Synthesis of Sub 1-A83

Scheme 19

Sub 1-VI-A1 (9.38g, 21.1mmol) obtained in the above synthesis of 1-bromo-2-iodobenzene (8.94g, 31.6mmol), Pd (PPh ₃ ) ₄ (1.22g, 1.1mmol), K ₂ CO ₃ (8.73 g, 63.2 mmol), THF, and water were obtained using the Sub 1-A1 synthesis method to obtain 6.99 g (yield: 70%) of the product.

18.Synthesis of Sub 1-A89

Scheme 20

Sub 1-VI-A26 (11.57g, 19.4mmol) obtained in the above synthesis was prepared with 1-bromo-2-iodobenzene (8.22g, 29mmol), Pd (PPh ₃ ) ₄ (1.12g, 1mmol), K ₂ CO ₃ ( 8.03 g, 58.1 mmol), THF, and water were used to obtain 7.76 g (yield: 64%) of the product using the Sub 1-A1 synthesis method.

19. Synthesis of Sub 1-A92

Scheme 21

Sub 1-VI-A29 (12.08g, 21.5mmol) obtained in the above synthesis of 1-bromo-2-iodobenzene (9.13g, 32.3mmol), Pd (PPh ₃ ) ₄ (1.24g, 1.1mmol), K ₂ CO ₃ (8.92 g, 64.5 mmol), THF, and water were used to obtain 8.64 g (yield: 68%) of the product using the Sub 1-A1 synthesis method.

20. Synthesis of Sub 1-A95

Scheme 22

Sub 1-VI-A35 (16.56 g, 24.2 mmol) obtained in the above synthesis was prepared with 1-bromo-2-iodobenzene (10.25 g, 36.2 mmol), Pd (PPh ₃ ) ₄ (1.4 g, 1.2 mmol), and K ₂ CO. ₃ (10.01 g, 72.5 mmol), THF, and water were obtained using the Sub 1-A1 synthesis method to obtain 10.18 g (yield: 59%) of the product.

21.Synthesis of Sub 1-A96

Scheme 23

Sub 1-VI-A36 (15.69 g, 22.9 mmol) obtained in the above synthesis was prepared with 1-bromo-2-iodobenzene (9.71 g, 34.3 mmol), Pd (PPh ₃ ) ₄ (1.32 g, 1.1 mmol), K ₂ CO ₃ (9.49 g, 68.6 mmol), THF, and water were used to obtain 9.81 g (yield: 60%) of the product using the Sub 1-A1 synthesis method.

22. Synthesis of Sub 1-A101

Scheme 24

(1) Synthesis of Sub 1-III-A101

Sub 1-II-A1 (33.01g, 134.1mmol) obtained in the above synthesis of 2-bromo-9,9'-spirobi [fluorene] (79.53g, 201.2mmol), Na ₂ SO ₄ (19.05g, 134.1mmol) , K ₂ CO ₃ (18.54 g, 134.1 mmol), Cu (2.56 g, 40.2 mmol) and nitrobenzene were obtained using the Sub 1-III-A1 synthesis method to obtain 39.84 g (yield: 53%) of the product.

(2) Sub 1-IV-A101 Synthesis

Sub 1-III-A101 (39.84g, 71.1mmol) obtained in the above synthesis to Bis (pinacolato) diboron (19.86g, 78.2mmol), Pd (dppf) Cl₂(1.74g, 2.1mmol), KOAc (20.93 g, 213.2 mmol) and DMF were used to obtain the product 32.82 g (yield: 76%) using the Sub 1-IV-A1 synthesis method.

(3) Sub 1-V-A101 Synthesis

Sub 1-IV-A101 (32.82 g, 54 mmol) obtained in the above synthesis was converted into 1,3-dibromobenzene (19.12 g, 81 mmol), Pd (PPh ₃ ) ₄ (3.12 g, 2.7 mmol), and K ₂ CO ₃ (22.4 g). , 162.1 mmol), THF, and water were obtained using the Sub 1-V-A1 synthesis method to obtain 24.42 g (yield: 71%) of product.

(4) Sub 1-VI-A101 Synthesis

Sub 1-V-A101 (24.42g, 38.4mmol) obtained in the above synthesis to Bis (pinacolato) diboron (10.72g, 42.2mmol), Pd (dppf) Cl₂(0.94g, 1.2mmol), KOAc (11.29 g, 115.1 mmol) and DMF were used to obtain the product 18.88 g (yield: 72%) using the Sub 1-VI-A1 synthesis method.

(5) Sub 1-A101 Synthesis

Sub 1-VI-A101 (17.74g, 25.9mmol) obtained in the above synthesis was subjected to 1-bromo-2-iodobenzene (11.01g, 38.9mmol), Pd (PPh ₃ ) ₄ (1.5g, 1.3mmol), K ₂ CO ₃ (10.76 g, 77.8 mmol), THF, and water were obtained using the Sub 1-A1 synthesis method to obtain 10.36 g (yield: 56%) of the product.

23. Synthesis of Sub 1-A104

Scheme 25

Sub 1-VI-A43 (16.13 g, 29.2 mmol) obtained in the above synthesis was prepared with 1-bromo-2-iodobenzene (12.41 g, 43.9 mmol), Pd (PPh ₃ ) ₄ (1.69 g, 1.5 mmol), and K ₂ CO. ₃ (12.13 g, 87.7 mmol), THF, and water were used to obtain the product 10.7 g (yield: 63%) using the Sub 1-A1 synthesis method.

24. Synthesis of Sub 1-A107

Scheme 26

Sub 1-VI-A46 (12.94g, 24.2mmol) obtained in the above synthesis was subjected to 1-bromo-2-iodobenzene (10.26g, 36.3mmol), Pd (PPh ₃ ) ₄ (1.4g, 1.2mmol), K ₂ CO ₃ (10.02 g, 72.5 mmol), THF, and water were used to obtain 8.87 g (yield: 65%) of the product using the Sub 1-A1 synthesis method.

Meanwhile, examples of Sub 1 are as follows, but are not limited thereto, and their FD-MSs are shown in Table 1 below.

TABLE 1

II. Synthesis of Sub 2

Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 27 below. It is not limited to this.

Scheme 27

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

1.Synthesis of Sub 2-6

Scheme 28

After starting material 2-bromo-9,9-diphenyl-9 H -fluorene (41.72g, 105mmol) was dissolved in toluene in a round bottom flask, aniline (19.56g, 210mmol), Pd ₂ (dba) ₃ (2.88g , 3.2 mmol), 50% P ( t -Bu) ₃ (4.1 ml, 8.4 mmol), NaO t -Bu (30.28 g, 315 mmol) was added and stirred at 40 ° C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was silicagel column and recrystallized to give the product 32.25g (yield: 75%).

2. Synthesis of Sub 2-7

Scheme 29

[1,1'-biphenyl] -4-amine (13.31g, 78.7mmol), Pd ₂ (dba) in 2-bromo-9,9-diphenyl-9 H -fluorene (15.63g, 39.3mmol) as starting materials ₃ (1.08g, 1.2mmol), 50% P ( t -Bu) ₃ (1.5ml, 3.1mmol), NaO t -Bu (11.34g, 118mmol), toluene were obtained using the above Sub 2-6 synthesis. g (yield 76%) was obtained.

3. Synthesis of Sub 2-13

Scheme 30

Aniline (14.02g, 150.6mmol), Pd ₂ (dba) ₃ (2.07g, 2.3mmol), 50% P ( t -Bu) ₃ (2.9ml, 6mmol) in bromobenzene (11.82g, 75.3mmol) , NaO t -Bu (21.71 g, 225.8 mmol) and toluene were obtained using the Sub 2-6 synthesis method to obtain 10.19 g (yield: 80%) of the product.

4. Synthesis of Sub 2-16

Scheme 31

Starting material bromobenzene (14.93g, 95.1mmol) in [1,1'-biphenyl] -4-amine (32.18g, 190.2mmol), Pd ₂ (dba) ₃ (2.61g, 2.9mmol), 50% P ( t- Bu) ₃ (3.7 ml, 7.6 mmol), NaO t -Bu (27.42 g, 285.3 mmol) and toluene were obtained using the Sub 2-6 synthesis method to obtain 19.36 g (yield: 83%) of the product.

5.Synthesis of Sub 2-17

Scheme 32

[1,1'-biphenyl] -4-amine (37.15g, 219.6mmol), Pd ₂ (dba) ₃ (3.02g) in the starting material 4-bromo-1,1'-biphenyl (25.59g, 109.8mmol) , 3.3 mmol), 50% P ( t -Bu) ₃ (4.3 ml, 8.8 mmol), NaO t -Bu (31.65 g, 329.3 mmol), toluene were obtained using 27.87 g (yield) of the product using the above Sub 2-6 synthesis. : 79%).

6.Synthesis of Sub 2-20

Scheme 33

Starting material 1-bromonaphthalene (12.85g, 62.1mmol) to aniline (11.56g, 124.1mmol), Pd ₂ (dba) ₃ (1.7g, 1.9mmol), 50% P ( t -Bu) ₃ (2.4ml, 5 mmol), NaO t -Bu (17.89 g, 186.2 mmol) and toluene were obtained using the Sub 2-6 synthesis method to obtain 10.07 g (yield: 74%) of the product.

7.Synthesis of Sub 2-40

Scheme 34

Aniline (11.43g, 122.7mmol), Pd ₂ (dba) ₃ (1.69g, 1.8mmol), 50% P ( t -Bu) _{3 as} starting material 2-bromo-5-phenylthiophene (14.67g, 61.3mmol) (2.4 ml, 4.9 mmol), NaO t -Bu (17.69 g, 184 mmol) and toluene were obtained using the Sub 2-6 synthesis method to obtain 10.95 g (yield: 71%) of the product.

8. Synthesis of Sub 2-70

Scheme 35

Aniline (10.73g, 115.2mmol), Pd ₂ (dba) ₃ (1.58g, 1.7mmol), 50% in starting material 3-bromo-9,9-dimethyl-9 H -fluorene (15.74g, 57.6mmol) _{P (t -Bu) 3 (2.2ml} , 4.6mmol), NaO t -Bu (16.61g, 172.9mmol), using the Sub 2-6 synthesis of toluene 13.81g (yield 84%) of product was obtained.

9.Synthesis of Sub 2-71

Scheme 36

[1,1'-biphenyl] -4-amine (11.73g, 69.3mmol), Pd ₂ (dba) in 3-bromo-9,9-dimethyl-9 H- fluorene (9.47g, 34.7mmol) as starting materials ₃ (0.95 g, 1 mmol), 50% P ( t -Bu) ₃ (1.4 ml, 2.8 mmol), NaO t -Bu (10 g, 104 mmol), toluene were obtained using 10.28 g ( Yield: 82%).

10. Synthesis of Sub 2-74

Scheme 37

Naphthalen-2-amine (12.24g, 85.5mmol), Pd ₂ (dba) ₃ (1.17g, 1.3mmol) as starting material 3-bromo-9,9-dimethyl-9 H -fluorene (11.68g, 42.8mmol) ), 50% P ( t -Bu) ₃ (1.7 ml, 3.4 mmol), NaO t -Bu (12.33 g, 128.3 mmol) and toluene were obtained using the above Sub 2-6 synthesis. 11.04 g (yield: 77% )

11.Synthesis of Sub 2-76

Scheme 38

Aniline (6.86g, 73.2mmol), Pd ₂ (dba) ₃ (1.01g, 1.1mmol), 50% in starting material 3-bromo-9,9-diphenyl-9 H -fluorene (14.54g, 36.6mmol) P ( t -Bu) ₃ (1.4ml, 2.9mmol), NaO t -Bu (10.55g, 109.8mmol) and toluene were obtained using the Sub 2-6 synthesis method to give 11.24g (yield: 75%) of the product.

12.Synthesis of Sub 2-81

Scheme 39

In the starting material 3-bromopyridine (13.81g, 87.4mmol), aniline (16.28g, 174.8mmol), Pd ₂ (dba) ₃ (2.4g, 2.6mmol), 50% P ( t -Bu) ₃ (3.4ml, 7 mmol), NaO t -Bu (25.2 g, 262.2 mmol) and toluene were obtained using the Sub 2-6 synthesis method to obtain 9.97 g (yield: 67%) of the product.

13.Synthesis of Sub 2-82

Scheme 40

Aniline (18.02g, 193.5mmol), Pd ₂ (dba) ₃ (2.66g, 2.9mmol), 50% P ( t -Bu) in starting material 3- (4-bromophenyl) pyridine (22.65g, 96.8mmol) ₃ (3.8 ml, 7.7 mmol), NaO t -Bu (27.9 g, 290.3 mmol) and toluene were obtained using the Sub 2-6 synthesis method to obtain 16.44 g (yield: 69%) of the product.

Meanwhile, examples of Sub 2 are as follows, but are not limited thereto, and their FD-MSs are shown in Table 2 below.

TABLE 2

III. Synthesis of Final Product

Sub 2 (1 equiv) was dissolved in toluene in a round bottom flask, then Sub 1 (1.2 equiv), Pd ₂ (dba) ₃ (0.03 equiv), P ( t -Bu) ₃ (0.08 equiv), NaO t -Bu (3 equiv) was added and stirred at 100 ° C. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain a final product.

1.Synthesis of Product A17

Scheme 41

Sub 2-6 (4.46 g, 10.9 mmol) obtained in the above synthesis was dissolved in toluene in a round bottom flask, and then Sub 1-A2 (7.19 g, 13.1 mmol), Pd ₂ (dba) ₃ (0.3 g, 0.3 mmol) , 50% P ( t- Bu) ₃ (0.4 ml, 0.9 mmol), NaO t -Bu (3.14 g, 32.7 mmol) was added and stirred at 100 ° C. After completion of the reaction, 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 purified by silicagel column and recrystallized to obtain a product (6.8g (71%)).

2. Synthesis of Product A21

Scheme 42

Sub 2-7 (7.58 g, 15.6 mmol) obtained in the above synthesis in Sub 1-A1 (8.89 g, 18.7 mmol), Pd ₂ (dba) ₃ (0.43 g, 0.5 mmol), 50% P ( t -Bu) ₃ (0.6 ml, 1.2 mmol), NaO t -Bu (4.5 g, 46.8 mmol) and toluene were obtained using the Product A17 synthesis method to obtain 10.02 g (yield: 73%) of the product.

3. Synthesis of Product A162

Scheme 43

Sub 2-17 (5.68g, 17.7mmol) obtained in the above synthesis Sub 1-A21 (12.52g, 21.2mmol), Pd ₂ (dba) ₃ (0.49g, 0.5mmol), 50% P ( t -Bu) ₃ (0.7 ml, 1.4 mmol), NaO t -Bu (5.1 g, 53 mmol) and toluene were obtained using the Product A17 synthesis method to obtain 10.28 g (yield: 70%) of the product.

4.Synthesis of Product A183

Scheme 44

Sub 2-71 (3.89 g, 10.8 mmol) obtained in the above synthesis in Sub 1-A26 (8.09 g, 12.9 mmol), Pd ₂ (dba) ₃ (0.3 g, 0.3 mmol), 50% P ( t -Bu) ₃ (0.4 ml, 0.9 mmol), NaO t -Bu (3.1 g, 32.3 mmol) and toluene were obtained using the Product A17 synthesis method to obtain 7.13 g (yield: 73%) of the product.

5.Synthesis of Product A191

Scheme 45

Sub 2-17 (3.58 g, 11.1 mmol) obtained in the above synthesis in Sub 1-A29 (7.89 g, 13.4 mmol), Pd ₂ (dba) ₃ (0.31 g, 0.3 mmol), 50% P ( t -Bu) ₃ (0.4 ml, 0.9 mmol), NaO t -Bu (3.21 g, 33.4 mmol) and toluene were obtained using the Product A17 synthesis method to obtain 7.04 g (yield: 76%) of the product.

6.Synthesis of Product A203

Scheme 46

Sub 2-16 (2.67 g, 10.9 mmol) obtained in the above synthesis in Sub 1-A35 (9.33 g, 13.1 mmol), Pd ₂ (dba) ₃ (0.3 g, 0.3 mmol), 50% P ( t -Bu) ₃ (0.4 ml, 0.9 mmol), NaO t -Bu (3.14 g, 32.7 mmol) and toluene were obtained using the Product A17 synthesis method to obtain 6.79 g (yield: 71%) of the product.

7.Synthesis of Product A210

Scheme 47

Sub 2-70 (3.04g, 10.7mmol) obtained in the above synthesis Sub 1-A36 (9.14g, 12.8mmol), Pd ₂ (dba) ₃ (0.29g, 0.3mmol), 50% P ( t -Bu) ₃ (0.4 ml, 0.9 mmol), NaO t -Bu (3.07 g, 32 mmol) and toluene were obtained using the Product A17 synthesis method to obtain 7.25 g (yield: 74%) of the product.

8.Synthesis of Product A216

Scheme 48

Sub 2-6 (4.45 g, 10.9 mmol) obtained in the above synthesis in Sub 1-A43 (7.57 g, 13 mmol), Pd ₂ (dba) ₃ (0.3 g, 0.3 mmol), 50% P ( t -Bu) ₃ (0.4 ml, 0.9 mmol), NaO t -Bu (3.13 g, 32.6 mmol) and toluene were obtained using the Product A17 synthesis method to obtain 6.82 g (yield: 69%) of the product.

9.Synthesis of Product A219

Scheme 49

Sub 2-16 (3.17 g, 12.9 mmol) obtained in the above synthesis to Sub 1-A46 (8.75 g, 15.5 mmol), Pd ₂ (dba) ₃ (0.35 g, 0.4 mmol), 50% P ( t -Bu) ₃ (0.5 ml, 1 mmol), NaO t -Bu (3.73 g, 38.8 mmol) and toluene were obtained using the Product A17 synthesis method to give 6.97 g (yield: 74%) of the product.

10.Synthesis of Product A230

Scheme 50

Sub 2-6 (4.63 g, 11.3 mmol) obtained in the above synthesis in Sub 1-A51 (7.47 g, 13.6 mmol), Pd ₂ (dba) ₃ (0.31 g, 0.3 mmol), 50% P ( t- Bu) ₃ (0.4 ml, 0.9 mmol), NaO t -Bu (3.26 g, 33.9 mmol) and toluene were obtained using the Product A17 synthesis method to obtain 7.16 g (yield: 72%) of the product.

11.Synthesis of Product A270

Scheme 51

Sub 2-76 (4.27 g, 10.4 mmol) obtained in the above synthesis in Sub 1-A59 (7.84 g, 12.5 mmol), Pd ₂ (dba) ₃ (0.29 g, 0.3 mmol), 50% P ( t -Bu) ₃ (0.4 ml, 0.8 mmol), NaO t -Bu (3.01 g, 31.3 mmol) and toluene were obtained using the Product A17 synthesis method to obtain 6.47 g (yield: 65%) of the product.

12.Synthesis of Product A277

Scheme 52

Sub 2-17 (3.71 g, 11.5 mmol) obtained in the above synthesis to Sub 1-A64 (8.18 g, 13.9 mmol), Pd ₂ (dba) ₃ (0.32 g, 0.3 mmol), 50% P ( t -Bu) ₃ (0.5 ml, 0.9 mmol), NaO t -Bu (3.33 g, 34.6 mmol) and toluene were obtained using the Product A17 synthesis method to obtain 7.39 g (yield: 77%) of the product.

13.Synthesis of Product A285

Scheme 53

Sub 2-20 (2.46 g, 11.2 mmol) obtained in the above synthesis in Sub 1-A67 (9.62 g, 13.5 mmol), Pd ₂ (dba) ₃ (0.31 g, 0.3 mmol), 50% P ( t -Bu) ₃ (0.4 ml, 0.9 mmol), NaO t -Bu (3.23 g, 33.7 mmol) and toluene were obtained using the Product A17 synthesis method to obtain 6.99 g (yield: 73%) of product.

14.Synthesis of Product A292

Scheme 54

Sub 2-40 (2.72g, 10.8mmol) obtained in the above synthesis Sub 1-A68 (9.28g, 13mmol), Pd ₂ (dba) ₃ (0.3g, 0.3mmol), 50% P ( t -Bu) ₃ (0.4 ml, 0.9 mmol), NaO t -Bu (3.12 g, 32..5 mmol) and toluene were obtained using the Product A17 synthesis method to yield 6.42 g (yield: 67%) of the product.

15.Synthesis of Product A297

Scheme 55

Sub 2-13 (2.39 g, 14.1 mmol) obtained in the above synthesis in Sub 1-A75 (9.84 g, 16.9 mmol), Pd ₂ (dba) ₃ (0.39 g, 0.4 mmol), 50% P ( t- Bu) ₃ (0.6ml, 1.1mmol), NaO t -Bu (4.07g, 42.4mmol) and toluene were obtained using the Product A17 synthesis method to give 6.61 g (yield: 70%) of product.

16.Synthesis of Product A303

Scheme 56

Sub 2-82 (3.36g, 13.6mmol) obtained in the above synthesis Sub 1-A79 (9.24g, 16.4mmol), Pd ₂ (dba) ₃ (0.37g, 0.4mmol), 50% P ( t -Bu) ₃ (0.5 ml, 1.1 mmol), NaO t -Bu (3.93 g, 40.9 mmol) and toluene were obtained using the Product A17 synthesis method to obtain 6.07 g (yield: 61%) of the product.

17.Synthesis of Product A311

Scheme 57

Sub 2-6 (4.89 g, 11.9 mmol) obtained in the above synthesis in Sub 1-A83 (6.8 g, 14.3 mmol), Pd ₂ (dba) ₃ (0.33 g, 0.4 mmol), 50% P ( t- Bu) ₃ (0.5 ml, 1 mmol), NaO t -Bu (3.44 g, 35.8 mmol) and toluene were obtained using the Product A17 synthesis method to give 6.42 g (yield: 67%) of the product.

18.Synthesis of Product A330

Scheme 58

Sub 2-6 (4.12 g, 10.1 mmol) obtained in the above synthesis in Sub 1-A89 (7.56 g, 12.1 mmol), Pd ₂ (dba) ₃ (0.28 g, 0.3 mmol), 50% P ( t -Bu) ₃ (0.4 ml, 0.8 mmol), NaO t -Bu (2.9 g, 30.2 mmol) and toluene were obtained using the Product A17 synthesis method to yield 6.15 g (yield: 64%) of the product.

19.Synthesis of Product A339

Scheme 59

Sub 2-70 (3.42 g, 12 mmol) obtained in the above synthesis in Sub 1-A92 (8.49 g, 14.4 mmol), Pd ₂ (dba) ₃ (0.33 g, 0.4 mmol), 50% P ( t- Bu) ₃ (0.5 ml, 1 mmol), NaO t -Bu (3.46 g, 36 mmol) and toluene were obtained using the Product A17 synthesis method to obtain 6.57 g (yield: 69%) of the product.

20.Synthesis of Product A348

Scheme 60

Sub 2-82 (2.83g, 11.5mmol) obtained in the above synthesis Sub 1-A95 (9.85g, 13.8mmol), Pd ₂ (dba) ₃ (0.32g, 0.3mmol), 50% P ( t -Bu) ₃ (0.4 ml, 0.9 mmol), NaO t -Bu (3.31 g, 34.5 mmol) and toluene were obtained using the Product A17 synthesis method to obtain 5.76 g (yield: 57%) of the product.

21.Synthesis of Product A350

Scheme 61

Sub 2-16 (2.74 g, 11.2 mmol) obtained in the above synthesis in Sub 1-A96 (9.58 g, 13.4 mmol), Pd ₂ (dba) ₃ (0.31 g, 0.3 mmol), 50% P ( t -Bu) ₃ (0.4 ml, 0.9 mmol), NaO t -Bu (3.22 g, 33.5 mmol) and toluene were obtained using the Product A17 synthesis method to obtain 6.38 g (yield: 65%) of the product.

22.Synthesis of Product A353

Scheme 62

Sub 2-13 (1.95 g, 11.5 mmol) obtained in the above synthesis to Sub 1-A101 (9.85 g, 13.8 mmol), Pd ₂ (dba) ₃ (0.32 g, 0.3 mmol), 50% P ( t -Bu) ₃ (0.4 ml, 0.9 mmol), NaO t -Bu (3.32 g, 34.6 mmol) and toluene were obtained using 6.37 g (yield: 69%) of the product using the Product A17 synthesis method.

23. Synthesis of Product A359

Scheme 63

Sub 2-81 (2.49g, 14.6mmol) obtained in the above synthesis in Sub 1-A104 (10.19g, 17.6mmol), Pd ₂ (dba) ₃ (0.4g, 0.4mmol), 50% P ( t- Bu) ₃ (0.6 ml, 1.2 mmol), NaO t -Bu (4.22 g, 43.9 mmol) and toluene were obtained using the Product A17 synthesis method to obtain 6.17 g (yield: 63%) of the product.

24.Synthesis of Product A363

Scheme 64

Sub 2-74 (4.18 g, 12.5 mmol) obtained in the above synthesis in Sub 1-A107 (8.44 g, 15 mmol), Pd ₂ (dba) ₃ (0.34 g, 0.4 mmol), 50% P ( t- Bu) ₃ (0.5 ml, 1 mmol), NaO t -Bu (3.59 g, 37.4 mmol) and toluene were obtained using 6.74 g (yield: 66%) of the product using the Product A17 synthesis method.

25. Synthesis of Product C2

Scheme 65

Sub 2-3 (6g, 16.6mmol) obtained in the above synthesis Sub 1-C1 (7.93g, 19.9mmol), Pd ₂ (dba) ₃ (1.21g, 1.3mmol), 50% P ( t -Bu) ₃ (0.7 ml, 1.66 mmol), NaO t -Bu (73.03 g, 49.8 mmol) and toluene were obtained using the Product A17 synthesis method to give 8.11 g (yield: 72%) of product.

26.Synthesis of Product C8

Scheme 66

Sub 2-7 (5.18g, 10.7mmol) obtained in the above synthesis to Sub 1-C1 (5.1g, 12.8mmol), Pd ₂ (dba) ₃ (0.29g, 0.3mmol), 50% P ( t -Bu) ₃ (0.4 ml, 0.9 mmol), NaO t -Bu (3.08 g, 32 mmol) and toluene were obtained using the Product A17 synthesis method to obtain 6.53 g (yield: 76%) of the product.

27.Synthesis of Product C21

Scheme 67

Sub 2-17 (3.59 g, 11.2 mmol) obtained in the above synthesis in Sub 1-C7 (6.9 g, 13.4 mmol), Pd ₂ (dba) ₃ (0.31 g, 0.3 mmol), 50% P ( t- Bu) ₃ (0.4 ml, 0.9 mmol), NaO t -Bu (3.22 g, 33.5 mmol) and toluene were obtained using the Product A17 synthesis method to obtain 6.3 g (yield: 74%) of the product.

28.Synthesis of Product C23

Scheme 68

Sub 2-70 (3.56 g, 12.5 mmol) obtained in the above synthesis in Sub 1-C8 (7.7 g, 15 mmol), Pd ₂ (dba) ₃ (0.34 g, 0.4 mmol), 50% P ( t -Bu) ₃ (0.5 ml, 1 mmol), NaO t -Bu (3.6 g, 37.4 mmol) and toluene were obtained using 6.92 g (yield: 77%) of the product using the Product A17 synthesis method.

On the other hand, FD-MS values of the compounds A1 ~ A392, C1 ~ C40 of the present invention prepared according to the synthesis examples as described above are shown in Table 3.

TABLE 3

On the other hand, in the above described an exemplary synthesis example of the present invention represented by the formula (1), these are all based on the Suzuki cross-coupling reaction, Ullmann reaction, Miyaura boration reaction and Buchwald-Hartwig cross coupling reaction and the substituents specified in the specific synthesis example In addition, it will be readily understood by those skilled in the art that the reaction proceeds even if other substituents defined in Chemical Formula 1 (substituents such as R ¹ , R ² , L ¹ , Ar ¹ , Ar ² , Ar ^3, etc.) are combined.

For example, reactions from the starting materials-> Sub 1-I, Sub 1-IV-> Sub 1-V, Sub 1-VI-> Sub 1, etc. in Scheme 2 are all based on the Suzuki cross-coupling reaction. The Sub 1-II-> Sub 1-III reaction is based on the Ullmann reaction, and in Scheme 2, Sub 1-III-> Sub 1-IV, Sub 1-V-> Sub 1-VI, etc. are based on the Miyaura boration reaction. The starting material in Scheme 27-> Sub 2, Product Synthesis Schemes (Scheme 41 to Scheme 68) is based on the Buchwald-Hartwig cross coupling reaction, and the reactions will proceed even if the substituents are not specified.

Manufacturing Evaluation of Organic Electrical Device

Example I-1 Green Organic Light Emitting Diode (Hole Transport Layer)

An organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention as a hole transport layer material. First, 4,4 ', 4 "-Tris [2-naphthyl (phenyl) amino] triphenylamine (hereinafter abbreviated as" 2-TNATA ") was vacuum-deposited on an ITO layer (anode) formed on an organic substrate. After the hole injection layer was formed, Compound A1 of the present invention was vacuum deposited on the hole injection layer to a thickness of 60 nm to form a hole transport layer, followed by 4,4'-N, N'-dicarbazole on the hole transport layer. dopant at a ratio of 90:10 by weight to 30 nm thick with -biphenyl (abbreviated as "CBP") as a host and tris (2-phenylpyridine) -iridium (abbreviated as "Ir (ppy) ₃ ") as a dopant. Vacuum evaporation to form a light emitting layer, followed by abbreviation as (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolineoleito) aluminum (hereinafter referred to as "BAlq"). ) Is vacuum deposited to a thickness of 10nm to form a hole blocking layer, and tris (8-quinolinol) aluminum (hereinafter abbreviated as "Alq ₃ ") is vacuum deposited to a thickness of 40nm on the hole blocking layer. The electron transport layer was formed, and then an organic electroluminescent device was manufactured by depositing an alkali metal halide of LiF in a thickness of 0.2 nm to form an electron injection layer, and then depositing Al in a thickness of 150 nm to form a cathode. .

[Examples I-2] to [Examples I-308] Green Organic Electroluminescent Device (Hole Transport Layer)

An organic electroluminescent device was manufactured in the same manner as in Example I-1, except that Compound A2 to C40 of the present invention shown in Table 4 were used instead of the compound A1 of the present invention as a hole transport layer material.

Comparative Example 1

An organic electroluminescent device was manufactured in the same manner as in Example I-1, except that Comparative Compound 1 was used instead of Compound A1 of the present invention as a hole transport layer material.

<Comparative Compound 1>

Comparative Example 2

An organic electroluminescent device was manufactured in the same manner as in Example I-1, except that Comparative Compound 2 was used instead of Compound A1 of the present invention as a hole transport layer material.

Comparative Compound 2

Comparative Example 3

An organic electroluminescent device was manufactured in the same manner as in Example I-1, except that Comparative Compound 3 was used instead of Compound A1 of the present invention as a hole transport layer material.

Comparative Compound 3

[Comparative Example 4]

An organic electroluminescent device was manufactured in the same manner as in Example I-1, except that Comparative Compound 4 was used instead of Compound A1 of the present invention as a hole transport layer material.

Comparative Compound 4

Electroluminescence with photo-search PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices prepared by Examples I-1 to I-308 and Comparative Examples 1 to 4 of the present invention (EL) characteristics were measured, and the T95 life was measured using a life-time measuring instrument manufactured by McScience Inc. at a luminance of 5000 cd / m 2, and the measurement results are shown in Table 4 below.

TABLE 4

As can be seen from the results of Table 4, the organic electroluminescent device using the compound of the present invention as the material of the hole transport layer has a relatively higher driving voltage than the organic electroluminescent device using the comparative compounds 1 to 4 as the material of the hole transport layer. It is low, and not only the luminous efficiency was improved, but also the lifespan was remarkably improved.

Such a result is particularly obtained by comparing a compound of the present invention (a non-linear type of linker type) with Comparative Compound 2 and Comparative Compound 4 (a linear type of linker type). Results show different results depending on the non-linear shape).

Deep HOMO energy levels and higher levels are found when the position of the linker connecting carbazole and amine (-NAr ² Ar ³ ) is in the meta (non-linear type) position than in the para (linear type) position. It showed T1 value and high thermal stability, which showed that the compound of the present invention was improved in driving voltage, efficiency, and lifetime compared to Comparative Compound 2 and Comparative Compound 4.

Meta-clamped (non-linear) connectors have shorter conjugation lengths than para (linear) connectors, resulting in wider band gaps. , The higher T1 value is.

Therefore, the meta-typed (non-linear type) connector improves the ability to block electrons at high T1 values, and at the same time, holes are smoothly transported to the light emitting layer due to the deep HOMO energy level, resulting in excitons emitting layer. It is believed that the efficiency is improved while being more easily generated within. In addition, it has a high thermal stability it can be seen that this extends the life.

Combining the above characteristics (deep HOMO energy level, high T1 value, high thermal stability), the band gap, electrical characteristics, and interface characteristics are different depending on the bonding position of the linking group between carbazole and amine (-NAr ² Ar ³ ). It can be seen that it can be changed greatly, which is a major factor in improving the performance of the device.

In addition, in the case of the hole transport layer, it is necessary to grasp the interrelationship with the light emitting layer (host), and even if a similar core is used, it will be very difficult for a person skilled in the art to infer the characteristics indicated in the hole transport layer in which the compound according to the present invention is used. .

Example II-1 Blue organic electroluminescent device (light emitting auxiliary layer)

An organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. First, a hole injection layer is formed by vacuum depositing 2-TNATA with a thickness of 60 nm on an ITO layer (anode) formed on an organic substrate, and then N, N'-Bis (1-naphthalenyl) -N on the hole injection layer. , N'-bis-phenyl- (1,1'-biphenyl) -4,4'-diamine (hereinafter abbreviated as "NPB") was vacuum deposited to a thickness of 60 nm to form a hole transport layer. Subsequently, the compound A1 of the present invention was vacuum-deposited to a thickness of 20 nm on the hole transport layer to form a light emitting auxiliary layer, and then 9,10-Di (2-naphthyl) anthracene (hereinafter referred to as “ADN”) on the light emitting auxiliary layer. Abbreviated) as a host, BD-052X (manufactured by Idemitsu kosan) as a dopant, and doped at a 93: 7 weight ratio to form a light emitting layer by vacuum deposition at a thickness of 30 nm. Subsequently, a hole blocking layer was formed by vacuum depositing BAlq to a thickness of 10 nm on the light emitting layer, and an electron transport layer was formed by vacuum depositing Alq ₃ to a thickness of 40 nm on the hole blocking layer. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then an Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

[Example II-2] to [Example II-80] Blue Organic Electroluminescent Device (Emission Auxiliary Layer)

An organic electroluminescent device was manufactured according to the same method as Example II-1 except for using Compound A2 to A378 of the present invention shown in Table 5 below instead of Compound A1 of the present invention.

[Comparative Example 5]

An organic electroluminescent device was manufactured in the same manner as in Example II-1, except that Comparative Compound 2 was used instead of Compound A1 of the present invention as a light-emitting auxiliary layer material.

Comparative Example 6

An organic electroluminescent device was manufactured in the same manner as in Example II-1, except that Comparative Compound 4 was used instead of Compound A1 of the present invention as a light-emitting auxiliary layer material.

Comparative Example 7

An organic electroluminescent device was manufactured in the same manner as in Example II-1, except that Comparative Compound 5 was used instead of Compound A1 of the present invention as a light-emitting auxiliary layer material.

Comparative Compound 5

Comparative Example 8

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

Electroluminescence with photo-search PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices prepared in Examples II-1 to II-80 and Comparative Examples 5 to 8 of the present invention (EL) characteristics were measured, and the T95 life was measured using the life-time measurement equipment manufactured by McScience Inc. at a luminance of 500 cd / m 2, and the measurement results are shown in Table 5 below.

TABLE 5

Example III-1 Green Organic Light Emitting Diode (light emitting auxiliary layer)

An organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. First, a hole injection layer was formed by vacuum depositing 2-TNATA with a thickness of 60 nm on an ITO layer (anode) formed on an organic substrate, and then a hole transport layer was formed by vacuum depositing NPB with a thickness of 60 nm on the hole injection layer. . Subsequently, the compound A1 of the present invention was vacuum-deposited to a thickness of 20 nm on the hole transport layer to form a light emitting auxiliary layer, and then 90:10 with CBP as a host and Ir (ppy) ₃ as a dopant on the light emitting auxiliary layer. Doped at a weight ratio to form a light emitting layer by vacuum deposition to a thickness of 30nm. Subsequently, a hole blocking layer was formed by vacuum depositing BAlq to a thickness of 10 nm on the light emitting layer, and an electron transport layer was formed by vacuum depositing Alq ₃ to a thickness of 40 nm on the hole blocking layer. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then an Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

[Example III-2] to [Example III-151] Green Organic Electroluminescent Element (Emission Sublayer)

An organic electroluminescent device was manufactured according to the same method as Example III-1 except for using the compounds A2 to C16 of the present invention shown in Table 6 instead of the compound A1 of the present invention as a light-emitting auxiliary layer material.

Comparative Example 9

An organic electroluminescent device was manufactured in the same manner as in Example III-1, except that Comparative Compound 2 was used instead of Compound A1 of the present invention as a light-emitting auxiliary layer material.

Comparative Example 10

An organic electroluminescent device was manufactured in the same manner as in Example III-1, except that Comparative Compound 3 was used instead of Compound A1 of the present invention as a light-emitting auxiliary layer material.

Comparative Example 11

An organic electroluminescent device was manufactured in the same manner as in Example III-1, except that Comparative Compound 4 was used instead of Compound A1 of the present invention as a light-emitting auxiliary layer material.

Comparative Example 12

An organic electroluminescent device was manufactured in the same manner as in Example III-1, except that Comparative Compound 5 was used instead of Compound A1 of the present invention as a light-emitting auxiliary layer material.

Comparative Example 13

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

Electroluminescence is performed by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared in Examples III-1 to III-151 and Comparative Examples 9 to 13 of the present invention. (EL) characteristics were measured, and the T95 life was measured using a life-time measuring instrument manufactured by McScience Inc. at a luminance of 5000 cd / m 2, and the measurement results are shown in Table 6 below.

TABLE 6

Example IV-1 Red Organic Light Emitting Diode (light emitting auxiliary layer)

An organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. First, a hole injection layer was formed by vacuum depositing 2-TNATA with a thickness of 60 nm on an ITO layer (anode) formed on an organic substrate, and then a hole transport layer was formed by vacuum depositing NPB with a thickness of 60 nm on the hole injection layer. . Subsequently, Compound A1 of the present invention was vacuum-deposited to a thickness of 20 nm on the hole transport layer to form a light emitting auxiliary layer, and then, CBP as a host on the light emitting auxiliary layer, bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate (Hereinafter abbreviated as " (piq) ₂ Ir (acac) &quot;) as a dopant, and then doped at a weight ratio of 95: 5 to form a light emitting layer by vacuum deposition to a thickness of 30 nm. Subsequently, a hole blocking layer was formed by vacuum depositing BAlq to a thickness of 10 nm on the light emitting layer, and an electron transport layer was formed by vacuum depositing Alq ₃ to a thickness of 40 nm on the hole blocking layer. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then an Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

[Examples IV-2] to [Examples IV-99] Red Organic Electroluminescent Device (Emitting Auxiliary Layer)

An organic electroluminescent device was manufactured according to the same method as Example IV-1 except for using the compounds A2 to A392 of the present invention shown in Table 7 instead of the compound A1 of the present invention.

Comparative Example 14

An organic electroluminescent device was manufactured in the same manner as in Example IV-1, except that Comparative Compound 2 was used instead of Compound A1 of the present invention as a light-emitting auxiliary layer material.

Comparative Example 15

An organic electroluminescent device was manufactured in the same manner as in Example IV-1, except that Comparative Compound 3 was used instead of Compound A1 of the present invention as a light-emitting auxiliary layer material.

[Comparative Example 16]

An organic electroluminescent device was manufactured in the same manner as in Example IV-1, except that Comparative Compound 4 was used instead of Compound A1 of the present invention as a light-emitting auxiliary layer material.

[Comparative Example 17]

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

Electroluminescence with photo-search PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices prepared in Examples IV-1 to IV-99 and Comparative Examples 14 to 17 of the present invention (EL) characteristics were measured, and the T95 life was measured using a life-time measuring instrument manufactured by McScience Inc. at a luminance of 2500 cd / m 2, and the measurement results are shown in Table 7 below.

TABLE 7

As can be seen from the results of Tables 5 to 7, the organic electroluminescent device using the compound of the present invention as a material for the light emitting auxiliary layer has improved luminous efficiency and lifespan compared to the organic electroluminescent devices of Comparative Examples 5 to 17. This has been significantly improved.

These results are similar to those of Table 4 above, even when Comparative Compound 2 to Comparative Compound 4, in which the linking group is a linear form, are used as the light emitting auxiliary layer, and the compounds of the present invention in a non-linear form. It can be seen that the compound of the present invention (L ¹ is a single bond) in which the amine group is directly bonded to the meta position shows a lower efficiency and a lower life than when the light emitting auxiliary layer is used. In the case of Comparative Compound 5, in which the main substituent is a heterocyclic group instead of the amine group (-NAr ² Ar ³ ), the linking group has the same non-linear structure as the compound of the present invention, but shows low efficiency and low lifetime. .

This is because when the heterocyclic group is introduced instead of the amine group (-NAr ² Ar ³ ), the T1 value is low. Therefore, the light emission is performed at the interface between the light emitting layer and the light emitting auxiliary layer instead of emitting light inside the light emitting layer. Judging.

As described above, the introduction of the linking group bent to the meta position acts as a major factor in improving the performance of the device in the light emitting auxiliary layer (blue fluorescence, green phosphorescence, red phosphorescence) as well as the hole transport layer, and shows similar tendency.

Another characteristic of the compounds of the present invention is that the smaller the bonding angle between the linking group L ¹ and the amine (-NAr ² Ar ³ ), the wider the bandgap and the higher the T1 value. It can be seen that the compound bound to the ortho position shows a higher luminous efficiency than the compound. In addition, since the compound bonded at the ortho position has a relatively low deposition temperature, not only can the luminous efficiency be improved, but the process time can be shortened and thermal damage can be reduced to improve the life.

Finally, the compound of the present invention used as the light emitting auxiliary layer forms a structurally twisted structure when introducing a bulky substituent to the nitrogen (N) of the carbazole, while packing density between materials in the light emitting auxiliary layer ( By lowering the packing density and adjusting the hole mobility, it is easy to achieve a charge balance in the light emitting layer, and as a result, it can be seen that the light emission efficiency is high.

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

[Description of the code]

100: organic electric element 110: substrate

120: first electrode 130: hole injection layer

140: hole transport layer 141: buffer layer

150: light emitting layer 151: light emitting auxiliary layer

160: electron transport layer 170: electron injection layer

180: second electrode

CROSS-REFERENCE TO RELATED APPLICATION

This patent application is related to US patent law No. 119 for Korean Patent Application No. 10-2012-0141364 filed in Korea on December 06, 2012 and Patent Application No. 10-2013-0132013 filed in Korea on November 01, 2013. Priority is claimed under section (a) (35 USC § 119 (a)), all of which is incorporated by reference in this patent application. In addition, if this patent application claims priority for the same reason for countries other than the United States, all its contents are incorporated into this patent application by reference.

Claims (13)

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

[In Formula 1, m is an integer from 1 to 4, n is an integer of 1 to 3, R^One And R²Are independently of each other hydrogen; heavy hydrogen; Tritium; halogen; C₆~ C₆₀Aryl group; Fluorenyl groups; Containing at least one hetero atom of O, N, S, Si, and P C₂~ C₆₀Heterocyclic group of; C_One~ C₅₀An alkyl group; C₂~ C₂₀Alkenyl group; -L²-N (Ar²) (Ar³); C_One~ C₃₀An alkoxyl group; And C₆~ C₃₀An aryloxyl group; selected from the group consisting of Ar ¹ is a fluorenyl group; C ₆ ~ C ₆₀ Aryl group; C ₂ ~ C ₂₀ Alkenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₁ ~ C ₅₀ Alkyl group; -L ² -N (Ar ² ) (Ar ³ ); And it is selected from the group consisting of a fused ring group of C ₆ ~ C ₆₀ aromatic ring and C ₃ ~ C ₆₀ Aliphatic ring, L ¹ and L ² are independently of each other a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; A C ₂ to C _{60 divalent} heterocyclic group including at least one hetero atom of O, N, S, Si, and P; Divalent fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And divalent aliphatic hydrocarbon group; selected from the group consisting of, Ar²                  And Ar³Are independent of each other, C₆~ C₆₀Aryl group; Fluorenyl groups; C containing at least one hetero atom of O, N, S, Si, and P₂~ C₆₀Heterocyclic group of; C_One~ C₅₀An alkyl group; C₆~ C₆₀Of aromatic rings and C₃~ C₆₀Fused ring of aliphatic ring of; And C₂~ C₂₀Alkenyl group; is selected from the group consisting of. Where the aryl group, heterocyclic group, fluorenyl group, alkyl group, alkenyl group, fused ring group, alkoxyl group, aryloxyl group, arylene group, fluorenylene group, aliphatic hydrocarbon group is further substituted with one or more substituents, respectively heavy hydrogen; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; -L'-N (R ') (R "), wherein L' is a single bond; C ₆ ~ C ₆₀ arylene group; fluorenylene group; at least one hetero of O, N, S, Si and P C ₂ ~ C ₆₀ heterocyclic group containing an atom, C ₃ ~ C ₆₀ alicyclic ring and C ₆ ~ C ₆₀ Aromatic ring fused ring group; and divalent C ₁ ~ C ₆₀ aliphatic hydrocarbon group; It is selected from the group, wherein R 'and R "are independently of each other C ₆ ~ C ₆₀ An aryl group; Fluorenyl group; C ₂ ~ C containing at least one heteroatom of O, N, S, Si and P A heterocyclic group of ₆₀ , a C ₁ -C ₅₀ alkyl group and a C ₂ -C ₂₀ alkenyl group; C ₁ ~ C ₂₀ of the import alkylthio; C ₁ -C ₂₀ alkoxyl group; C ₁ ~ C ₂₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₆ -C ₂₀ aryl group; C ₆ ~ C ₂₀ aryl group substituted with deuterium; Fluorenyl groups; C ₂ ~ C ₂₀ heterocyclic group; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ arylalkyl group; And C ₈ ~ C ₂₀ An aryl alkenyl group; It is further substituted with one or more substituents selected from the group consisting of. The method of claim 1, L ¹ is a compound, characterized in that selected from the group.

The method of claim 1, Wherein Ar ² and Ar ³ are independently selected from the following groups.

[In the above formula, Q ¹ is C (R ^a ) or N, Q ² is C (R ^b ) (R ^c ), N (R ^d ), S or O, k is an integer from 1 to 4, R ^a and R ^e are i) independently of each other, hydrogen; heavy hydrogen; C ₆ ~ C ₆₀ Aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₁ ~ C ₃₀ Alkoxy group; And fluorenyl group; or ii) a plurality of R ^e are each adjacent group is bonded to each other to form an aromatic ring with the carbon bonded to them, R ^b to R ^d are each independently i) a C ₆ ~ C ₆₀ aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₁ ~ C ₃₀ Alkoxyl group; or ii) R ^b and R ^c is bonded to each other to form a Spiro compound with the fluorene to which they are bonded.] The method of claim 1, Compound represented by the following formula (2) or formula (3).

[In Formula 2 and Formula 3, Ar ² , Ar ³ , R ¹ , R ² , m and n are the same as defined in claim 1, X is C (R ^f ) (R ^g ), S or O, R ^f and R ^g are each independently i) a C ₆ ~ C ₆₀ aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; And C ₁ ~ C ₃₀ alkoxyl group; or ii) R ^f and R ^g are bonded to each other to form a Spiro compound with fluorene to which they are bonded, o is an integer from 1 to 4, p is an integer of 1 to 3, q and r are each independently an integer from 1 to 5, R ³ to R ⁶ are i) independently of each other hydrogen; heavy hydrogen; Tritium; halogen; C ₆ ~ C ₆₀ Aryl group; C ₂ -C ₆₀ heterocyclic group containing at least one hetero atom of O, N, S, Si and P; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₁ -C ₃₀ alkoxyl group; And an aryloxyl group of C ₆ to C ₃₀ ; or ii) neighboring groups combine with each other to form an aromatic ring with carbon bonded thereto.] The method of claim 1, A compound represented by the following formula (4) or (5).

[In Formulas 4 and 5, Ar ¹ to Ar ³ , R ¹ , R ² , m and n are the same as defined in claim 1, Q ³ is C (R ^h ) (R ⁱ ), N (R ^j ), S or O, R ^h to R ^j are i) independently of each other C ₆ ~ C ₆₀ An aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₁ ~ C ₃₀ alkoxyl group; or ii) R ^h and R ⁱ are bonded to each other to form a Spiro compound with the fluorene to which they are bonded.] The method of claim 1, Compound which is one of the following compounds.

An organic electric device comprising the compound of claim 1. The method of claim 7, wherein A first electrode; Second electrode; And an organic material layer positioned between the first electrode and the second electrode, wherein the compound is contained in the organic material layer. The method of claim 8, The compound is an organic electric device, characterized in that contained in at least one layer of a hole injection layer, a hole transport layer, a light emitting auxiliary layer or a light emitting layer of the organic material layer. The method of claim 8, And an optical efficiency improving layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer. The method of claim 8, The organic material layer is formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process. A display device comprising the organic electronic device of claim 7; And And a controller for driving the display device. The method of claim 12, The organic electroluminescent device is at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a device for monochrome or white illumination.

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