KR102328297B1 - Compound for organic electronic element, organic electronic element comprising the same, and electronic device thereof - Google Patents

Abstract

Disclosed are an organic electric device comprising a compound represented by Formula 1, a first electrode, a second electrode, and an organic material layer between the first electrode and the second electrode, and an electronic device including the same, wherein the organic layer is a compound represented by Formula 1 By including, it is possible to lower the driving voltage of the organic electric device, it is possible to improve the luminous efficiency and lifespan.

Description

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

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

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

A material used as an organic layer in an organic electric device may be classified into a light emitting material and a charge transport material, for example, a hole injection material, a hole transport material, an electron transport material, an electron injection material, etc. according to their function.

Currently, the portable display market is a large-area display, and its size is increasing, and thus, a higher power consumption than the power consumption required by the existing portable display is required. Therefore, power consumption has become an important factor for a portable display having a limited power supply such as a battery, and efficiency and lifespan problems are also important factors that must be solved.

Efficiency, lifespan, and driving voltage are related to each other, and when the efficiency is increased, the driving voltage is relatively decreased. It shows a tendency to increase the lifespan. However, the efficiency cannot be maximized simply by improving the organic material layer. This is because, when the energy level and T1 value between each organic material layer, and the intrinsic properties (mobility, interfacial properties, etc.) of materials are optimally combined, long lifespan and high efficiency can be achieved at the same time.

In addition, recently, in order to solve the problem of light emission in the hole transport layer in the organic electroluminescent device, a method of using a light emitting auxiliary layer between the hole transport layer and the light emitting layer is being studied. Since the material properties are different, it is necessary to develop a light-emitting auxiliary layer according to each light-emitting layer.

In general, electrons are transferred from the electron transport layer to the emission layer, and holes are transferred from the hole transport layer to the emission layer, and excitons are generated by recombination.

However, most of the materials used for the hole transport layer have a low T ₁ value because they should have a low HOMO value. As a result, excitons generated in the light emitting layer are passed to the hole transport layer interface or the hole transport layer. As a result, the hole transport layer It causes light emission at the interface or charge unbalance in the light emitting layer to emit light at the hole transport layer interface.

When light is emitted at the hole transport layer interface, the color purity and efficiency of the organic electric device are lowered and the lifespan is shortened. Therefore, it should be a material having a HOMO level between the HOMO energy level of the hole transport layer and the HOMO energy level of the light emitting layer, have a high T1 value, and within a suitable driving voltage range (within the blue device driving voltage range of a full device) hole mobility (hole The development of a light emitting auxiliary layer having mobility) is urgently required.

However, this cannot simply be achieved with the structural characteristics of the core of the light-emitting auxiliary layer material, and the characteristics of the core and sub-substituents of the light-emitting auxiliary layer material, and an appropriate combination between the light-emitting auxiliary layer and the hole transport layer, and the light-emitting auxiliary layer and the light-emitting layer. When this happens, a device with high efficiency and long life can be realized.

On the other hand, it is also necessary to develop materials for the hole injection/transport layer and the light emitting auxiliary layer having stable characteristics against Joule heating generated during device driving, that is, a high glass transition temperature.

The low glass transition temperature of the material of the hole transport layer and the light emitting auxiliary layer decreases the uniformity of the thin film surface when driving the device, and the material may be deformed due to heat generated during device driving, which is reported to have a great effect on the device life. .

In addition, OLED devices are mainly formed by a deposition method, and there is a need to develop a material that can withstand a long time during deposition, that is, a material with strong heat resistance.

That is, in order to sufficiently exhibit the excellent characteristics of an organic electric device, the material constituting the organic layer in the device, for example, 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. is stable and efficient. It should be supported by materials, but the development of stable and efficient organic layer materials for organic electric devices has not yet been sufficiently made. Therefore, the development of new materials is continuously required, and in particular, the development of materials used for the hole transport layer, the light emitting auxiliary layer, the light emitting layer, etc. is urgently required.

The present invention has been proposed to solve the conventional problems as described above, and at the same time provides a compound having an efficient electron blocking ability and hole transport ability, and at the same time, high luminous efficiency, low driving voltage, and high heat resistance of a device using such a compound An object of the present invention is to provide a compound capable of improving color purity and lifespan, an organic electric device using the same, and an electronic device thereof.

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

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

According to the present invention, the hole transfer ability and thermal stability are improved by introducing an amine into the four-ring heterocyclic core or using a specific compound with a limited number of the four-ring heterocyclic core as a material for the organic electric device. It has a HOMO energy level, a high T1 value, and a high refractive index, which is easy to achieve charge balance in the light emitting layer, so that the luminous efficiency, heat resistance, lifespan, etc. of the organic electric device can be improved, and the driving voltage can be lowered.

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

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

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

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

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

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

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

The term "alkyl" or "alkyl group" as used herein, unless otherwise specified, has a single bond having 1 to 60 carbon atoms, a straight chain alkyl group, a branched chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cyclo means a radical of saturated aliphatic functional groups including alkyl groups, cycloalkyl-substituted alkyl groups.

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

The term "alkenyl group" or "alkynyl group" used in the present invention, unless otherwise specified, has a double or triple bond of 2 to 60 carbon atoms, respectively, and includes a straight or branched chain group, and is limited thereto it is not

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

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

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

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

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

The term "heterocyclic group" used in the present invention includes not only aromatic rings such as "heteroaryl group" or "heteroarylene group" but also non-aromatic rings, and unless otherwise specified, the number of carbon atoms each containing at least one heteroatom It means a ring of 2 to 60, but is not limited thereto. As used herein, the term "heteroatom" refers to N, O, S, P or Si, unless otherwise specified, and the heterocyclic group is a monocyclic group including a heteroatom, a ring aggregate, a fused multiple ring system, a spy means a compound or the like.

In addition, the "heterocyclic group" may include a ring including _{SO 2 instead of carbon forming the ring.} For example, "heterocyclic group" includes the following compounds.

As used herein, the term "ring" includes monocyclic and polycyclic rings, and includes hydrocarbon rings as well as heterocycles containing at least one heteroatom, and includes aromatic and non-aromatic rings.

As used herein, the term "polycyclic" includes ring assemblies such as biphenyl, terphenyl, etc., fused multiple ring systems and spiro compounds, and includes aromatic as well as non-aromatic, hydrocarbon Rings include, of course, heterocycles containing at least one heteroatom.

As used herein, the term "ring assemblies" refers to two or more ring systems (single or fused ring systems) directly connected to each other through a single bond or a double bond, and a direct connection between such rings It means that the number of linkages is one less than the total number of ring systems in this compound. In a ring aggregate, the same or different ring systems may be directly connected to each other through single or double bonds.

As used herein, the term "fused multiple ring system" means a fused ring form shared by at least two atoms, and includes a fused ring system of two or more hydrocarbons and at least one heteroatom. and a form in which at least one heterocyclic system is fused. These fused multiple ring systems may be an aromatic ring, a heteroaromatic ring, an aliphatic ring, or a combination of these rings.

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

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

In addition, unless otherwise explicitly stated, in the term "substituted or unsubstituted" as used herein, "substitution" means deuterium, halogen, amino group, nitrile group, nitro group, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ Alkoxy group, C ₁ -C ₂₀ Alkylamine group, C ₁ -C ₂₀ Alkylthiophene group, C ₆ -C ₂₀ Arylthiophene group, C ₂ -C ₂₀ Alkenyl group, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₂₀ aryl group, of a C ₆ -C ₂₀ aryl group substituted with a heavy hydrogen, C ₈ -C ₂₀ aryl alkenyl group, a silane group, a boron One or more substituents selected from the group consisting of a _{group, a germanium group, a fluorenyl group, and a C 2} -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P It means substituted with, but is not limited to these substituents.

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

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

Here, when a is an integer of 0, the substituent R ¹ means that it does not exist, that is, when a is 0, it means that all hydrogens are bonded to the carbons forming the benzene ring, and in this case, the indication of hydrogen bonded to carbon is shown. It can be omitted and the chemical formula or compound can be described. In addition, when a is an integer of 1, one substituent R ¹ is bonded to any one of the carbons forming the benzene ring, and when a is an integer of 2 or 3, it may be bonded as follows, for example, a is 4 to 6 Even if it is an integer of , it is bonded to the carbon of the benzene ring in a similar manner, and when a is an integer of 2 or more, R ¹ may be the same as or different from each other.

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

Referring to FIG. 1 , an organic electric device 100 according to an embodiment of the present invention includes a first electrode 120 , a second electrode 180 , and a first electrode 120 formed on a substrate 110 , and the second electrode 120 . An organic material layer including the compound according to the present invention is provided between the two electrodes 180 . In this case, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may sequentially include a hole injection layer 130 , a hole transport layer 140 , a light emitting layer 150 , an electron transport layer 160 , and an electron injection layer 170 on the first electrode 120 . At this time, at least one of these layers may be omitted, or may further include a hole blocking layer, an electron blocking layer, a light emission auxiliary layer 151, an electron transport auxiliary layer, a buffer layer 141, etc., and the electron transport layer 160, etc. It may also serve as a hole blocking layer.

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

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

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

As already described, in general, 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 in each light emitting layer (R, G, B) It is time to develop different light emitting auxiliary layers. On the other hand, in the case of the light emitting auxiliary layer, since the correlation between the hole transport layer and the light emitting layer (host) must be understood, it will be very difficult to infer the characteristics of the organic material layer used even if a similar core is used.

Therefore, in the present invention, the energy level and T ₁ value between each organic material layer, the intrinsic properties of the material (mobility, interfacial properties, etc.), etc. It is possible to simultaneously improve the lifespan and efficiency of the organic electric device by optimizing it.

Preferably, the compound represented by Formula 1 according to the present invention may be used as a material for the light emitting auxiliary layer according to each light emitting layer (R, G, B).

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

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

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

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

In addition, the organic electric device according to an embodiment of the present invention may be one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, and a device for single color or white lighting.

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

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

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

<Formula 1>

In Formula 1, each symbol may be defined as follows.

X and Y are independently of each other N-(L ² -Ar ¹ ), S, O or C(R')(R"), provided that when X and Y are both C(R')(R") Exclude.

n is an integer of 1 or 2, and when n is 2, a plurality of X and Y may be the same as or different from each other.

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

When R′ and R″ are an alkyl group, it may be preferably a C ₁ -C ₃₀ alkyl group, more preferably a C ₁ -C ₁₀ alkyl group, specifically a methyl group.

R ¹ and R ² are each independently deuterium; tritium; halogen; cyano group; nitro; C ₆ -C ₆₀ Aryl group; fluorenyl group; _{C 2} -C ₆₀ A heterocyclic group comprising at least one heteroatom selected from the group consisting of O, N, S, Si and P; C ₃ -C ₆₀ A fused ring group of an aliphatic ring and a C ₆ -C _{60 aromatic ring;} C ₁ -C ₅₀ Alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₁ -C ₃₀ alkoxyl group; and C ₆ -C ₃₀ may be selected from the group consisting of an aryloxy group, and when a plurality of R ¹ are present, neighboring R ¹ may be bonded to each other to form a ring, and a plurality of R ² may be present. Even in this case, adjacent R ² may be bonded to each other to form a ring. a is an integer of 0 to 3, b is an integer of 0 to 2, and when a and b are integers of 2 or 3, a plurality of R ¹ may be the same as or different from each other, and a plurality of R ² may be the same as or may be different.

When R ¹ and R ² are aryl groups, they may be preferably _{C 6} -C _{30 aryl groups, more preferably C 6} -C ₁₀ aryl groups, and may be illustratively phenyl, naphthyl, etc., and R ¹ And when R ² is a heterocyclic group, preferably a C ₂ -C ₃₀ heterocyclic group, more preferably a C ₂ -C ₁₅ heterocyclic group, for example, pyridine, dibenzothiophene, carbazole, 5 , 5-dimethyl -5 H - may be a fluoro Reno thiophene. In addition, when adjacent R ¹ and/or R ² are bonded to each other to form a ring, the formed ring may be a C ₆ -C ₃₀ aryl group or a C ₂ -C ₃₀ heterocyclic group, for example, benzene It can be a ring.

The Ar ¹ is a C ₆ -C ₆₀ aryl group; _{C 2} -C ₆₀ A heterocyclic group comprising at least one heteroatom selected from the group consisting of O, N, S, Si and P; fluorenyl group; C ₆ -C ₆₀ A fused ring group of an aromatic ring and a C ₃ -C _{60 aliphatic ring;} C ₁ -C ₅₀ Alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; It is selected from the group consisting _{of a C 1} -C ₃₀ alkoxyl group and a C ₆ -C _{30 aryloxy group.}

When Ar ¹ is an aryl group, it may be preferably a C ₆ -C ₃₀ aryl group, more preferably a C ₆ -C ₁₈ aryl group, for example, phenyl, naphthyl, biphenyl, anthracene, terphenyl, triphenyl. It may be ren, phenanthryl, etc., and when Ar ¹ is a heterocyclic group, it may be a C ₂ -C ₃₀ heterocyclic group, more preferably a C ₂ -C ₁₆ heterocyclic group, and is illustratively pyridine; Pyrimidine, triazine, quinoline, quinoxaline, quinazoline, benzoquinazoline, dibenzoquinazoline, phenanthridine, dibenzothiophene, carbazole, dibenzofuran, naphthobenzofuran, benzoxanthene, benzothi enoic pyrimidine, and the like can be a benzo Pew pyrimidine, Ar ¹ is a fluorene group if illustratively 9,9-dimethyl -9 H - fluorene as fluorene, 9,9'-fluorene-by espionage etc. this can be

The L ² is a single bond; C ₆ -C ₆₀ Arylene group; fluorenylene group; _{C 2} -C ₆₀ A heterocyclic group containing at least one hetero atom of O, N, S, Si and P; and a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring fused ring group.

When L ² is an arylene group, it may be preferably a C ₆ -C ₃₀ arylene group, more preferably a C ₆ -C ₁₈ arylene group, and may be illustratively phenyl, naphthyl, anthracene, biphenyl, etc. and L ² is a heterocyclic group, preferably a C ₂ -C ₃₀ heterocyclic group, more preferably a C ₂ -C ₁₆ heterocyclic group, and exemplarily pyridine, pyrimidine, triazine, carbazole , dibenzothiophene, quinazoline, benzoquinazoline, dibenzoquinazoline, benzothienopyrimidine, benzofuropyrimidine, and the like.

L ¹ is a single bond; C ₆ -C ₆₀ Arylene group; fluorenylene group; _{C 2} -C ₆₀ A heterocyclic group containing at least one hetero atom of O, N, S, Si and P; C ₃ -C ₆₀ A fused ring group of an aliphatic ring and a C ₆ -C _{60 aromatic ring;} And it is selected from the group consisting of Formula 1a, provided that only when n is an integer of 1, L ¹ is Formula 1a below. That is, L ¹ is determined according to n, and when n is an integer of 1, it is represented by the following formula (1a), and when n is an integer of 2, a single bond; C ₆ -C ₆₀ Arylene group; fluorenylene group; _{C 2} -C ₆₀ A heterocyclic group containing at least one hetero atom of O, N, S, Si and P; and a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring fused ring group; is selected from the group consisting of.

When L ¹ is an arylene group, it may be preferably a C ₆ -C ₃₀ arylene group, more preferably a C ₆ -C ₁₈ arylene group, and may be illustratively phenyl, biphenyl, triphenylene, etc. When , L ¹ is a heterocyclic group, it may be preferably a C ₂ -C ₃₀ heterocyclic group, more preferably a C ₂ -C ₁₂ heterocyclic group, and may be exemplarily dibenzothiophene, carbazole, etc. have.

<Formula 1a>

In Formula 1a, each symbol may be defined as follows.

Ar ² and Ar ³ are each independently a C ₆ -C ₆₀ aryl group; _{C 2} -C ₆₀ A heterocyclic group comprising at least one heteroatom selected from the group consisting of O, N, S, Si and P; fluorenyl group; It may be selected from the group consisting of a fused ring group of a C ₆ -C ₆₀ aromatic ring and a C ₃ -C _{60 aliphatic ring, and a C 1} -C _{50 alkyl group.} m is an integer of 1 or 2, and when m is an integer of 2, a plurality of Ar ² may be the same as or different from each other, and a plurality of Ar ^{3 may} also be the same or different from each other.

When Ar ² and Ar ³ are aryl groups, they may be preferably a _{C 6} -C _{30 aryl group, more preferably a C 6} -C ₁₈ aryl group, for example, phenyl, biphenyl, naphthyl, triphenylene, It may be terphenyl, phenanthryl, etc., and when Ar ² and Ar ³ are a heterocyclic group, preferably a C ₂ -C ₃₀ heterocyclic group, more preferably a C ₂ -C ₁₈ heterocyclic group. For example, pyridine, dibenzofuran, dibenzothiophene, benzonaphthofuran, carbazole, thienocarbazole, benzothienocarbazole, etc. may be used, and when Ar ² and Ar ³ are fluorenyl groups illustratively, 9,9-dimethyl -9 H - fluorene, 9,9-diphenyl -9 H - fluorenyl, 9,9'-by espionage as fluorene, 7,7-dimethyl -7 H - It may be benzofluorene, spirobenzofluorene-11,9'fluorene, or the like.

L ³ is a single bond; C ₆ -C ₆₀ Arylene group; fluorenylene group; _{C 2} -C ₆₀ A heterocyclic group containing at least one hetero atom of O, N, S, Si and P; and a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring fused ring group.

When L ³ is an arylene group, it may be preferably a C ₆ -C ₃₀ arylene group, more preferably a C ₆ -C ₁₂ arylene group, and may be exemplarily benzene, naphthalene, biphenyl, or the like, L ^{In the case of a trivalent} heterocyclic group, it is preferably a C ₂ -C ₃₀ heterocyclic group, more preferably a C ₂ -C ₁₂ heterocyclic group, and may be exemplarily dibenzothiophene, dibenzofuran, etc. When , L ³ is fluorene, it may be exemplarily 9,9-dimethyl-9 H -fluorene.

In Formulas 1 and 1a, when each symbol is an aryl group, an arylene group, a fluorenyl group, a fluorenylene group, a heterocyclic group, a fused ring group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryloxy group, respectively silver deuterium; halogen; a silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C _{20 aryl group;} Phosphine oxide unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C _{20 aryl group;} siloxane group; boron group; germanium group; cyano group; nitro group; C ₁ -C ₂₀ Alkylthio group; C ₁ -C ₂₀ An alkoxyl group; C ₁ -C ₂₀ Alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₆ -C ₂₀ Aryl group; _{a C 6} -C ₂₀ aryl group substituted with deuterium; fluorenyl group; _{C 2} -C ₂₀ A heterocyclic group comprising at least one heteroatom selected from the group consisting of O, N, S, Si and P; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ Arylalkyl group; -N(R ^a )(R ^b ); and a C ₈ -C ₂₀ arylalkenyl group; may be substituted with one or more substituents selected from the group consisting of, and when each of these substituents is adjacent, they may combine with each other to form a ring.

wherein R ^a and R ^b are each independently selected from a C ₆ -C ₆₀ aryl group; fluorenyl group; It may be selected from the group consisting of; _{C 2} -C ₆₀ heterocyclic group containing at least one hetero atom of O, N, S, Si and P.

In Formula 1, when n is 1, Formula 1 may be represented by Formula 2 or Formula 3 below.

<Formula 2> <Formula 3>

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

In Formula 1, when n is 2, Formula 1 may be represented by Formula 4 below.

<Formula 4>

In Formula 4, X, Y, R ¹ , R ² , L ¹ , a and b are the same as defined in Formula 1 above.

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

.

.

In another embodiment, the present invention provides an organic electric device including a first electrode, a second electrode, and an organic material layer formed with the first electrode and the second electrode, wherein the organic material layer contains the compound represented by the formula (1) .

The organic layer includes at least one of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer, and the organic layer is a single compound represented by Formula 1 Or it may contain a mixture of two or more compounds. In addition, a light efficiency improving layer may be further formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer, and the organic material layer is a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip It may be formed by a coating process or a roll-to-roll process.

Hereinafter, the synthesis example of the compound represented by Formula 1 used in the organic material layer of the present invention and the preparation example of the organic electric device will be described in detail with reference to Examples, but the scope of the present invention is limited to the following examples it is not

Synthesis example

The compound represented by Formula 1 according to the present invention (final products) is synthesized by the reaction route of the following Schemes 1 to 3, but is not limited thereto. In the following scheme, X, Y, R ¹ , R ² , L ¹ to L ³ , Ar ¹ to Ar ³ , a, b and m are the same as defined in Formula 1 above, and Hal ³ is Br or Cl.

<Scheme 1>

In Scheme 1, in the case of the amine (HN-Ar ² Ar ³ ) reactant, the synthesis method disclosed in Korean Patent Registration No. 10-1251451 (published on April 5, 2013) of the present applicant was used.

<Scheme 2>

<Scheme 3>

I. Synthesis of Sub 1 and Sub 2

Sub 1 and Sub 2 of Schemes 1 to 3 may be synthesized by the reaction routes of Schemes 4 and 5, but are not limited thereto. Hal ² , Hal ³ , and Hal ⁵ are I, Br or Cl.

In Scheme 4 below, when L ³ is a single bond, Sub 1-III is Sub 1, and the cyclization reaction is specifically synthesized using the following materials. That is, when X, Y = S, CF ₃ SO ₃ H/Pyridine/H ₂ O, and when X, Y = O, Pd(OAc) ₂ /BzOOt-Bu/3-nitropyridine/C ₆ F ₆ / DMI, PPh ₃ / o -DCB for X, Y = NL ² -Ar ¹ , i) R-Mg-Br (R = R for X, Y = C(R')(R")) ', R”)/THF, ii) HCl/Acetic acid is used for synthesis.

<Scheme 4>

<Scheme 5>

In Scheme 5, when L ³ is not a single bond, Sub 1 is synthesized through a Sub 1-III -> Sub 1-IV reaction and a Sub 1-IV -> Sub 1 reaction.

Synthesis examples of specific compounds belonging to Sub 1 and Sub 2 are as follows.

1. Sub 1-7, Sub 1-IV-7, Sub 1-21 Synthesis example

<Scheme 6>

(1) Sub 1-II-7 synthesis

After dissolving the starting material Sub 1-I-7 (CAS Registry Number: 190788-59-1) (50.68 g, 203.48 mmol) in THF (710ml) in a round-bottom flask, 1,4-dibromo-2-nitrobenzene ( CAS Registry Number: 3460-18-2) (62.87 g, 223.82 mmol), Pd(PPh ₃ ) ₄ (9.41 g, 8.14 mmol), NaOH (24.42 g, 610.43 mmol), water (355 ml) were added and 80° C. stirred in. After completion of the reaction, _{extraction with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 49.31 g (yield: 75%) of the product.

(2) Sub 1-M-7 synthesis

Sub 1-II-7 (49.31 g, 152.62 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene (2290 ml) in a round-bottom flask, triphenylphosphine (200.15 g, 763.08 mmol) was added and stirred at 200 °C. When the reaction was completed, o- dichlorobenzene was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized by silicagel column to obtain 24.52 g (yield: 62%) of the product.

(3) Sub 1-M'-7 synthesis

Sub 3-1 (CAS Registry Number: 591-50-4) (24.52 g, 120.19 mmol) obtained in the above synthesis was dissolved in toluene (1800ml) in a round-bottom flask, Sub 1-M-7 (62.28 g, 240.38) mmol), Pd ₂ (dba) ₃ (3.30 g, 3.61 mmol), 50% P( t- Bu) ₃ (3.5ml, 7.21 mmol), NaO t- Bu (34.65 g, 360.57 mmol) were added and 100° C. stirred in. After completion of the reaction, _{extraction with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 27.80 g (yield: 69%) of the product.

(4) Sub 1-7 synthesis

After dissolving Sub 1-M'-7 (20.11 g, 59.99 mmol) obtained in the above synthesis with toluene (600ml) in a round-bottom flask, Sub 3-10 (CAS Registry Number: 1591-31-7) (16.80 g, 59.99 mmol), Pd ₂ (dba) ₃ (1.65 g, 1.80 mmol), 50% P( t -Bu) ₃ (1.8ml, 3.60 mmol), NaO t -Bu (17.30 g, 179.98 mmol) were added and 100 stirred at °C. After completion of the reaction, _{extraction with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 19.01 g (yield: 65%) of the product.

(5) Synthesis of Sub 1-IV-7

Sub 1-7 (7.81 g, 16.02 mmol) obtained in the above synthesis was dissolved in DMF (80ml) in a round-bottom flask, and then Bis(pinacolato)diboron (4.48 g, 17.63 mmol), Pd(dppf)Cl ₂ (0.39 g) , 0.48 mmol), KOAc (4.72 g, 48.07 mmol) was added and stirred at 90°C. When the reaction was completed, DMF was removed through distillation, and 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 recrystallized using silicagel column to obtain 6.94 g (yield: 81%) of the product.

(6) Sub 1-21 synthesis

Sub 1-M'-7 (7.59 g, 22.64 mmol) obtained in the above synthesis was dissolved in toluene (225 ml) in a round-bottom flask, Sub 3-29 (CAS Registry Number: 502161-03-7) (8.36 g, 22.64 mmol), Pd ₂ (dba) ₃ (0.62 g, 0.68 mmol), 50% P( t -Bu) ₃ (0.7 ml, 1.36 mmol), NaO t -Bu (6.53 g, 67.93 mmol) were added and 100 stirred at °C. After completion of the reaction, _{extraction with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 7.83 g (yield: 60%) of the product.

2. Sub 1-34, Sub 1-107, Sub 1-117, Sub 2-10, Sub 2-12 Synthesis example

<Scheme 7>

(1) Synthesis of Sub 1-II-34

1,4-dibromo-2-nitrobenzene (CAS Registry Number: 3460-18-2) (306.77) to the starting material Sub 1-I-34 (CAS Registry Number: 1310563-21-3) (264.25 g, 992.82 mmol) g, 1092.11 mmol), Pd(PPh ₃ ) ₄ (45.89 g, 39.71 mmol), NaOH (119.14 g, 2978.47 mmol), THF (2780ml), and water (1390ml) were added and the synthesis method of Sub 1-II-7 was followed. 236.42 g (yield: 70%) of the product was obtained.

(2) Synthesis of Sub 1-II'-34

Sub 1-II-34 (236.42 g, 694.96 mmol) obtained in the above synthesis was put in a round-bottom flask with triflic acid (430.5ml, 4864.75 mmol) and stirred at room temperature for 24 hours, followed by an aqueous solution of pyridine (5680ml, pyridine: H ₂ O = 1: 5) was slowly added dropwise and stirred under reflux for 30 minutes. After completion of the reaction, _{extraction with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 141.34 g (yield: 66%) of the product.

(3) Synthesis of Sub 1-M-34

Triphenylphosphine (300.76 g, 1146.68 mmol) and o- dichlorobenzene (3200ml) were added to Sub 1-II'-34 (141.34 g, 458.67 mmol) obtained in the above synthesis, and the product 87.40 using the Sub 1-M-7 synthesis method. g (yield: 69%) was obtained.

(4) Sub 1-34 synthesis

To Sub 1-M-34 (68.76 g, 249.00 mmol) obtained in the above synthesis, Sub 3-1 (CAS Registry Number: 591-50-4) (50.80 g, 249.00 mmol), Pd ₂ (dba) ₃ (6.84 g) , 7.47 mmol) 50% P( t- Bu) ₃ (7.3ml, 14.94 mmol), NaO t- Bu (71.79 g, 746.99 mmol), and toluene (1660ml) were added, and the product was synthesized using the Sub 1-7 synthesis method. 64.03 g (yield: 73%) was obtained.

(5) Synthesis of Sub 1-IV-34

To Sub 1-34 (59.21 g, 168.09 mmol) obtained in the above synthesis, Bis(pinacolato)diboron (46.95 g, 184.90 mmol), Pd(dppf)Cl ₂ (4.12 g, 5.04 mmol), KOAc (49.49 g, 504.27 mmol) and DMF (840ml) were added, and 58.40 g (yield: 87%) of the product was obtained by using the Sub 1-IV-7 synthesis method.

(6) Sub 1-117 synthesis

After dissolving Sub 1-IV-34 (20.98 g, 52.54 mmol) obtained in the above synthesis in THF (220 ml) in a round-bottom flask, 1,3-dibromo-5-chlorobenzene (CAS Registry Number: 14862-52-3) (21.31 g, 78.81 mmol), Pd(PPh ₃ ) ₄ (2.43 g, 2.10 mmol), K ₂ CO ₃ (21.78 g, 157.62 mmol), water (110 ml) were added and stirred at 80 °C. When the reaction was completed, the reaction was _{extracted with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 14.59 g (yield: 60%) of the product.

(7) Sub 2-10 synthesis

After dissolving Sub 1-IV-34 (13.32 g, 33.36 mmol) obtained in the above synthesis in THF (110 ml) in a round-bottom flask, Sub 1-M-34 (9.21 g, 33.36 mmol), Pd(PPh ₃ ) ₄ (1.54 g, 1.33 mmol), NaOH (4.00 g, 100.07 mmol), water (55 ml) were added and stirred at 80°C. After completion of the reaction, _{extraction with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 13.91 g (yield: 89%) of the product.

(8) Sub 1-107 synthesis

After dissolving Sub 1-IV-34 (23.94 g, 59.95 mmol) obtained in the above synthesis in THF (210ml) in a round-bottom flask, 1,3-dibromobenzene (CAS Registry Number: 108-36-1) (15.56 g, 65.95 mmol), Pd(PPh ₃ ) ₄ (2.77 g, 2.40 mmol), K ₂ CO ₃ (24.86 g, 179.86 mmol), water (105 ml) were added and stirred at 80° C. After completion of the reaction, _{extraction with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 16.18 g (yield: 63%) of the product.

(9) Sub 1-V-107 synthesis

Sub 1-107 (9.78 g, 22.83 mmol) obtained in the above synthesis was dissolved in DMF (115ml) in a round-bottom flask, and then Bis(pinacolato)diboron (6.38 g, 25.11 mmol), Pd(dppf)Cl ₂ (0.56 g) , 0.68 mmol), KOAc (6.72 g, 68.50 mmol) was added and stirred at 90°C. When the reaction was completed, DMF was removed through distillation, and 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 recrystallized using silicagel column to obtain 8.68 g (yield: 80%) of the product.

(10) Sub 2-12 synthesis

After dissolving Sub 1-V-107 (8.68 g, 18.26 mmol) obtained in the above synthesis in THF (60 ml) in a round-bottom flask, Sub 1-M-34 (5.04 g, 18.26 mmol), Pd(PPh ₃ ) ₄ (0.84 g, 0.73 mmol), NaOH (2.19 g, 54.77 mmol), water (30 ml) were added and stirred at 80°C. After completion of the reaction, _{extraction with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 7.66 g (yield: 77%) of the product.

3. Sub 1-60, Sub 2-18 Synthesis example

<Scheme 8>

(1) Sub 1-II-60 synthesis

1,4-dibromo-2-nitrobenzene (CAS Registry Number: 3460-18-2) (63.54) to the starting material Sub 1-I-60 (CAS Registry Number: 269409-97-4) (45.26 g, 205.65 mmol) g, 226.22 mmol), Pd(PPh ₃ ) ₄ (9.51 g, 8.23 mmol), NaOH (24.68 g, 616.96 mmol), THF (720ml), and water (360ml) were added and the above synthesis method of Sub 1-II-7 was followed. was used to obtain 47.18 g (yield: 78%) of the product.

(2) Sub 1-II'-60 synthesis

Sub 1-II-60 (47.18 g, 160.42 mmol) obtained in the above synthesis was placed in a round-bottom flask with Pd(OAc) ₂ (3.60 g, 16.04 mmol), 3-nitropyridine (1.99 g, 16.04 mmol) and C ₆ After dissolving in F ₆ (240ml) and DMI (160ml), tert- butyl peroxybenzoate (62.32 g, 320.84 mmol) was added and the mixture was stirred at 90°C. After completion of the reaction, _{extraction with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 19.68 g (yield: 42%) of the product.

(3) Sub 1-M-60 synthesis

Triphenylphosphine (44.18 g, 168.44 mmol) and o- dichlorobenzene (590ml) were added to Sub 1-II'-60 (19.68 g, 67.38 mmol) obtained in the above synthesis, and the product 11.57 using the Sub 1-M-7 synthesis method. g (yield: 66%) was obtained.

(4) Sub 1-60 synthesis

Sub 1-M-60 (11.57 g, 44.48 mmol) obtained in the above synthesis was added to Sub 3-7 (CAS Registry Number: 90-14-2) (11.30 g, 44.48 mmol), Pd ₂ (dba) ₃ (1.22 g) , 1.33 mmol) 50% P( t -Bu) ₃ (1.3ml, 2.67 mmol), NaO t -Bu (12.83 g, 133.45 mmol), and toluene (445ml) were added and the product was synthesized using the Sub 1-7 synthesis method. 12.20 g (yield: 71%) was obtained.

(5) Sub 1-IV-60 synthesis

Bis(pinacolato)diboron (4.96 g, 19.54 mmol), Pd(dppf)Cl _{2 to Sub 1-60 (6.86 g, 17.76 mmol) obtained in the above synthesis} (0.44 g, 0.53 mmol), KOAc (5.23 g, 53.28 mmol) and DMF (90ml) were added, and the product 6.54 g (yield: 85%) was obtained using the Sub 1-IV-7 synthesis method.

(6) Sub 2-18 synthesis

To Sub 1-IV-60 (6.54 g, 15.09 mmol) obtained in the above synthesis, Sub 1-M-34 (4.17 g, 15.09 mmol), Pd(PPh ₃ ) ₄ (0.70 g, 0.60 mmol), NaOH (1.81 g) , 45.28 mmol), THF (50ml), and water (25ml) were added, and 6.37 g (yield: 84%) of the product was obtained using the Sub 2-10 synthesis method.

4. Sub 1-75 Synthesis example

<Scheme 9>

(1) Synthesis of Sub 1-II-75

2,6-dibromophenol (CAS Registry Number: 608-33-3) (39.74 g, 157.75 mmol) in the starting material Sub 1-I-34 (CAS Registry Number: 1310563-21-3) (38.17 g, 143.41 mmol) ), Pd(PPh ₃ ) ₄ (6.63 g, 5.74 mmol), NaOH (17.21 g, 430.23 mmol), THF (500 ml), and water (250 ml) were added, and the product 32.13 was synthesized using the above Sub 1-II-7 synthesis method. g (yield: 72%) was obtained.

(2) Synthesis of Sub 1-II'-75

_{Triflic acid (137ml, 1548.73 mmol) and pyridine aqueous solution (1810ml, pyridine: H 2} O = 1: 5) were added to Sub 1-II-75 (32.13 g, 103.25 mmol) obtained in the above synthesis, and the Sub 1-II Using the '-34 synthesis method, 16.72 g of the product (yield: 58%) was obtained.

(3) Sub 1-75 synthesis

To Sub 1-II'-75 (16.72 g, 59.90 mmol) obtained in the above synthesis, Pd(OAc) ₂ (1.34 g, 5.99 mmol), 3-nitropyridine (0.74 g, 5.99 mmol), tert- butyl peroxybenzoate (23.27 g) , 119.79 mmol), C ₆ F ₆ (90 ml), and DMI (60 ml) were added, and 6.64 g (yield: 40%) of the product was obtained by using the Sub 1-II′-60 synthesis method.

5. Sub 1-81 Synthesis example

<Scheme 10>

(1) Synthesis of Sub 1-I-81

After dissolving the starting material 3-bromonaphthalen-2-ol (CAS Registry Number: 30478-88-7) (28.61 g, 128.26 mmol) in DMF (640ml) in a round-bottom flask, Bis(pinacolato)diboron (35.83 g, 141.08 mmol), Pd(dppf)Cl ₂ (3.14 g, 3.85 mmol), KOAc (37.76 g, 384.77 mmol) was added and stirred at 90°C. When the reaction was completed, DMF was removed through distillation, and 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 recrystallized using silicagel column to obtain 27.02 g (yield: 78%) of the product.

(2) Synthesis of Sub 1-II-81

5-bromo-2-iodophenol (CAS Registry Number: 858855-11-5) (32.89 g, 110.02 mmol), Pd(PPh ₃ ) ₄ ( 4.62 g, 4.00 mmol), NaOH (12.00 g, 300.07 mmol), THF (350ml), and water (175ml) were added, and 25.22 g (yield: 80%) of the product was obtained using the Sub 1-II-7 synthesis method. .

(3) Sub 1-81 synthesis

To Sub 1-II-81 (25.22 g, 80.02 mmol) obtained in the above synthesis, Pd(OAc) ₂ (1.80 g, 8.00 mmol), 3-nitropyridine (0.99 g, 8.00 mmol), tert- butyl peroxybenzoate (31.08 g, 160.04 mmol), C ₆ F ₆ (120 ml), and DMI (80 ml) were added, and 9.46 g (yield: 38%) of the product was obtained using the Sub 1-II′-60 synthesis method.

6. Sub 1-134 Synthesis example

<Scheme 11>

(1) 4- bromo -One- iodo -2-( methylsulfinyl ) benzene synthesis

The starting materials (5-bromo-2-iodophenyl)(methyl)sulfane (CAS Registry Number: 1824602-11-0) (26.95 g, 81.92 mmol) and vanadium(V) oxide (1.49 g, 8.19 mmol) were mixed in a round bottom. After dissolving in acetonitrile (330ml) in a flask, the temperature was lowered to 0°C using an ice bath, 35% H ₂ O ₂ (11.2ml, 122.88 mmol) was added thereto, and the mixture was stirred at 10°C. When the reaction was completed, water was added to the reaction product, the temperature was slowly raised to room temperature, extracted with ethyl acetate and water, and the organic layer _{was dried over MgSO 4} and concentrated to obtain 21.20 g (yield: 75%) of the product.

(2) Sub 1-II-134 synthesis

To the starting material Sub 1-I-34 (CAS Registry Number: 1310563-21-3) (21.20 g, 79.65 mmol), 4-bromo-1-iodo-2-(methylsulfinyl)benzene (30.23 g, 87.62 mmol), Pd(PPh ₃ ) ₄ (3.68 g, 3.19 mmol), NaOH (9.56 g, 238.95 mmol), THF (280 ml), and water (140 ml) were added and 22.20 g of the product was added using the above Sub 1-II-7 synthesis method ( Yield: 78%) was obtained.

(3) Synthesis of Sub 1-III-134

_{Triflic acid (82.5ml, 932.04 mmol) and pyridine aqueous solution (1090ml, pyridine: H 2} O = 1: 5) were added to Sub 1-II-134 (22.20 g, 62.14 mmol) obtained in the above synthesis, and the Sub 1- 11.11 g (yield: 61%) of the product was obtained by using II'-34 synthesis method.

(4) Synthesis of Sub 1-IV-134

To Sub 1-III-134 (11.11 g, 37.89 mmol) obtained in the above synthesis, Bis(pinacolato)diboron (10.58 g, 41.68 mmol), Pd(dppf)Cl ₂ (0.93 g, 1.14 mmol), KOAc (11.16 g, 113.68 mmol) and DMF (190ml) were added, and 10.57 g (yield: 82%) of the product was obtained using the Sub 1-IV-7 synthesis method.

(5) Sub 1-134 synthesis

1,3-dibromo-5-chlorobenzene (CAS Registry Number: 14862-52-3) (12.60 g, 46.60 mmol), Pd (PPh ₃ ) to the starting material Sub 1-IV-134 (10.57 g, 31.06 mmol) ₄ (1.44 g, 1.24 mmol), K ₂ CO ₃ (12.88 g, 93.19 mmol), THF (130ml), and water (65ml) were added and the product 7.15 g (yield: 57%) using the above Sub 1-117 synthesis method. ) was obtained.

7. Sub 1-139 Synthesis Example

<Scheme 12>

(1) Synthesis of Sub 1-II-139

4,4,5,5-tetramethyl-2-(2-(methylthio)phenyl)-1,3,2-dioxaborolane (CAS Registry Number: 1072945-09-5) (58.38 g, 233.37 mmol) as a starting material methyl 5-bromo-2-iodobenzoate (CAS Registry Number: 181765-86-6) (87.52 g, 256.71 mmol), Pd(PPh ₃ ) ₄ (10.79 g, 9.33 mmol), NaOH (28.00 g, 700.11 mmol), THF (820ml) and water (410ml) were added, and 62.96 g (yield: 80%) of the product was obtained by using the Sub 1-II-7 synthesis method.

(2) Synthesis of Sub 1-II'-139

Sub 1-II-139 (62.96 g, 186.70 mmol) obtained in the above synthesis was dissolved in THF (930 ml) in a round-bottom flask, methylmagnesium bromide 1.0M in THF (746.8 ml, 746.79 mmol) was slowly added dropwise, and then at room temperature. stirred in. When the reaction was completed, diethyl ether and water were extracted, and the organic layer _{was dried over MgSO 4} and concentrated to obtain an intermediate product. This intermediate product was dissolved in acetic acid solution (750ml), and HCl (15ml) was added thereto, followed by reflux. When the reaction was completed, water was added and the resulting solid was filtered under reduced pressure after stirring and washed with water and methanol to obtain 25.03 g of a product (yield: 42% over two steps).

(3) Sub 1-II”-139 synthesis

Sub 1-II'-139 (25.03 g, 78.40 mmol) and vanadium(V) oxide (1.43 g, 7.84 mmol) obtained in the above synthesis were dissolved in acetonitrile (315ml) in a round bottom flask, and then 0 using an ice bath. The temperature was lowered to °C and 35% H ₂ O ₂ (10.7ml, 117.60 mmol) was added and stirred at 10 °C. When the reaction was completed, water was added to the reaction product, the temperature was slowly raised to room temperature, extracted with ethyl acetate and water, and the organic layer _{was dried over MgSO 4} and concentrated to obtain 19.45 g (yield: 74%) of the product.

(4) Sub 1-139 synthesis

_{Triflic acid (35.9ml, 406.10 mmol) and pyridine aqueous solution (475ml, pyridine: H 2} O = 1: 5) were added to Sub 1-II-139 (19.45 g, 58.01 mmol) obtained in the above synthesis, and the Sub 1- 11.79 g (yield: 67%) of the product was obtained by using the II'-34 synthesis method.

8. Sub 1-143 Synthesis example

<Scheme 13>

(1) Synthesis of Sub 1-II-143

2,6-dibromophenol (CAS Registry Number: 608-33-3) (79.60 g, 315.97 mmol) in the starting material Sub 1-I-143 (CAS Registry Number: 653589-95-8) (75.29 g, 287.25 mmol) ), Pd(PPh ₃ ) ₄ (13.28 g, 11.49 mmol), NaOH (34.47 g, 861.74 mmol), THF (1000ml), and water (500ml) were added and the product 67.05 was synthesized using the above Sub 1-II-7 synthesis method. g (yield: 76%) was obtained.

(2) Sub 1-II'-143 synthesis

To Sub 1-II-143 (67.05 g, 218.30 mmol) obtained in the above synthesis, Pd(OAc) ₂ (4.90 g, 21.83 mmol), 3-nitropyridine (84.80 g, 436.61 mmol), tert- butyl peroxybenzoate (2.71 g, 21.83 mmol), C ₆ F ₆ (330 ml), and DMI (220 ml) were added, and 28.64 g (yield: 43%) of the product was obtained using the Sub 1-II′-60 synthesis method.

(3) Sub 1-143 synthesis

Sub 1-II'-143 (28.64 g, 93.86 mmol) obtained in the above synthesis was dissolved in THF (470 ml) in a round-bottom flask, methylmagnesium bromide 1.0M in THF (375.4 ml, 375.45 mmol) was slowly added dropwise, Stirred at room temperature. Upon completion of the reaction, the mixture was extracted with diethyl ether and water, and the organic layer _{was dried over MgSO 4} and concentrated to obtain an intermediate product. This intermediate product was dissolved in acetic acid solution (375ml), HCl (7.5ml) was added, and 12.94 g (yield: 48% over two steps) of the product was obtained using the Sub 1-II'-139 synthesis method.

9. Sub 1-155 Synthesis example

<Scheme 14>

(1) Synthesis of Sub 1-II-155

2,4-dibromo-1-nitrobenzene (CAS Registry Number: 51686-78-3) (60.25) to the starting material Sub 1-I-143 (CAS Registry Number: 653589-95-8) (51.11 g, 194.99 mmol) g, 214.49 mmol), Pd(PPh ₃ ) ₄ (9.01 g, 7.80 mmol), NaOH (23.40 g, 584.98 mmol), THF (680ml), and water (340ml) were added and the above synthesis method of Sub 1-II-7 was followed. was used to obtain 46.54 g (yield: 71%) of the product.

(2) Synthesis of Sub 1-II'-155

Triphenylphosphine (90.79 g, 346.14 mmol) and o- dichlorobenzene (970ml) were added to Sub 1-II-155 (46.54 g, 138.45 mmol) obtained in the above synthesis, and 28.21 g of the product using the Sub 1-M-7 synthesis method (Yield: 67%) was obtained.

(3) Synthesis of Sub 1-M-155

Sub 1-II'-155 (28.21 g, 92.75 mmol) obtained in the above synthesis was dissolved in THF (465 ml) in a round-bottom flask, methylmagnesium bromide 1.0M in THF (371 ml, 371.01 mmol) was slowly added dropwise, and then at room temperature. stirred in. When the reaction was completed, diethyl ether and water were extracted, and the organic layer _{was dried over MgSO 4} and concentrated to obtain an intermediate product. This intermediate product was dissolved in acetic acid solution (375ml), HCl (7.5ml) was added, and 11.41 g of the product (yield: 43% over two steps) was obtained using the Sub 1-II'-139 synthesis method.

(4) Sub 1-155 synthesis

To Sub 1-M-155 (11.41 g, 39.87 mmol) obtained in the above synthesis, Sub 3-7 (CAS Registry Number: 90-14-2) (10.13 g, 39.87 mmol), Pd ₂ (dba) ₃ (1.10 g) , 1.20 mmol) 50% P( t- Bu) ₃ (1.2ml, 2.39 mmol), NaO t- Bu (11.50 g, 119.61 mmol), and toluene (400ml) were added and the product was synthesized using the Sub 1-7 synthesis method. 12.33 g (yield: 75%) was obtained.

Compounds belonging to Sub 1 and Sub 2 may be the following compounds, but are not limited thereto, and Table 1 shows Field Desorption-Mass Spectrometry (FD-MS) values of some compounds belonging to Sub 1 and Sub 2.

[Table 1]

II. Synthesis of Sub 3

Sub 3 of Scheme 3 may be synthesized by the reaction route of Scheme 12, but is not limited thereto. Hal ³ is Br or Cl and Hal ⁴ is I or Br.

<Scheme 15>

Synthesis examples of specific compounds belonging to Sub 3 are as follows.

1. Sub 3-44 Synthesis example

<Scheme 16>

(1) Synthesis of Sub 3-I-44

The starting material, 1-amino-2-naphthoic acid (CAS Registry Number: 4919-43-1) (75.11 g, 401.25 mmol) was placed in a round-bottom flask with urea (CAS Registry Number: 57-13-6) (168.69 g, 2808.75 mmol) and stirred at 160 °C. After confirming the reaction by TLC, it was cooled to 100° C., water (200 ml) was added, and the mixture was stirred for 1 hour. Upon completion of the reaction, the resulting solid was filtered under reduced pressure, washed with water, and dried to obtain 63.86 g (yield: 75%) of the product.

(2) Synthesis of Sub 3-II-44

Sub 3-I-44 (63.86 g, 300.94 mmol) obtained in the above synthesis was dissolved in POCl ₃ (200ml) at room temperature in a round-bottom flask, and then N , N- Diisopropylethylamine (97.23 g, 752.36 mmol) was slowly added dropwise. , and stirred at 90 °C. When the reaction was completed, after concentration, ice water (500ml) was added, and the mixture was stirred at room temperature for 1 hour. The resulting solid was filtered under reduced pressure and dried to obtain 67.47 g of a product (yield: 90%).

(3) Sub 3-44 synthesis

Sub 3-II-44 (67.47 g, 270.86 mmol) obtained in the above synthesis was dissolved in THF (950 ml) in a round-bottom flask, and then 4,4,5,5-tetramethyl-2-phenyl-1,3,2- dioxaborolane (CAS Registry Number: 24388-23-6) (60.80 g, 297.94 mmol), Pd(PPh ₃ ) ₄ (12.52 g, 10.83 mmol), K ₂ CO ₃ (112.30 g, 812.57 mmol), water (475 ml) were added and stirred at 90°C. When the reaction was completed, the reaction was _{extracted with CH 2} Cl ₂ and water, and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized by silicagel column to obtain 44.89 g (yield: 57%) of the product.

2. Sub 3-49 Synthesis example

<Scheme 17>

To the starting material 2,4-dichlorobenzo[4,5]thieno[3,2- d ]pyrimidine (CAS Registry Number: 160199-05-3) (35.15 g, 137.78 mmol), 2-(dibenzo[b,d] furan-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (CAS Registry Number: 947770-80-1) (44.58 g, 151.56 mmol), Pd(PPh ₃ ) ₄ (6.37 g, 5.51 mmol), K ₂ CO ₃ (57.13 g, 413.33 mmol), THF (480ml), and water (240ml) were added and 22.92 g of the product (Yield: 43%) using the Sub 3-44 synthesis method. got

The compound belonging to Sub 3 may be the following compounds, but is not limited thereto, and Table 2 shows FD-MS (Field Desorption-Mass Spectrometry) values of some compounds belonging to Sub 3 .

[Table 2]

III. Product synthesis

1. P 1-9 Synthesis example

<Scheme 18>

Sub 1-21 (7.21 g, 12.51 mmol) obtained in the above synthesis was dissolved in toluene (125ml) in a round-bottom flask, and then di([1,1'-biphenyl]-4-yl)amine (4.02 g, 12.51 mmol) ), Pd ₂ (dba) ₃ (0.34 g, 0.38 mmol), 50% P( t- Bu) ₃ (0.4ml, 0.75 mmol), NaO t- Bu (3.61 g, 37.52 mmol) were added and at 100° C. stirred. After completion of the reaction, _{extraction with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 8.07 g (yield: 79%) of the product.

2. P 1-18 Synthesis example

<Scheme 19>

N -([1,1'-biphenyl]-4-yl)-9,9-diphenyl-9 H -fluoren-2-amine (4.86 g) in Sub 1-7 (4.88 g, 10.01 mmol) obtained in the above synthesis , 10.01 mmol), Pd ₂ (dba) ₃ (0.28 g, 0.30 mmol), 50% P( t- Bu) ₃ (0.3ml, 0.60 mmol), NaO t- Bu (2.89 g, 30.04 mmol), toluene ( 100 ml) was added and the product 7.59 g (yield: 85%) was obtained by using the above P 1-9 synthesis method.

3. P 1-49 Synthesis example

<Scheme 20>

In Sub 1-34 (4.56 g, 12.95 mmol) obtained in the above synthesis, N -(naphthalen-1-yl)-9,9-diphenyl-9 H- fluoren-2-amine (5.95 g, 12.95 mmol), Pd ₂ (dba) ₃ (0.36 g, 0.39 mmol), 50% P( t- Bu) ₃ (0.4ml, 0.78 mmol), NaO t- Bu (3.73 g, 38.84 mmol), toluene (130ml) were added and the P Using the 1-9 synthesis method, 7.85 g (yield: 83%) of the product was obtained.

4. P 1-66 Synthesis example

<Scheme 21>

N - - (triphenylen-2- yl) -9 H -carbazol-3-amine (6.67 g, 12.48 mmol obtained in the above Synthesis Sub 1-60 (4.82 g, 12.48 mmol ) 9- (naphthalen-1-yl) in ), Pd ₂ (dba) ₃ (0.34 g, 0.37 mmol), 50% P( t- Bu) ₃ (0.4ml, 0.75 mmol), NaO t- Bu (3.60 g, 37.44 mmol), toluene (125ml) was added to obtain 7.97 g (yield: 76%) of the product using the above P 1-9 synthesis method.

5. P 1-78 Synthesis example

<Scheme 22>

Di(naphthalen-2-yl)amine (5.33 g, 19.80 mmol), Pd ₂ (dba) ₃ (0.54 g, 0.59 mmol), 50% P in Sub 1-81 (6.16 g, 19.80 mmol) obtained in the above synthesis ( t -Bu) ₃ (0.6ml, 1.19 mmol), NaO t -Bu (5.71 g, 59.40 mmol) and toluene (200ml) were added, and the product was 7.42 g (yield: 75%) using the above P 1-9 synthesis method. ) was obtained.

6. P 1-79 Synthesis example

<Scheme 23>

N -(9,9'-spirobi[fluoren]-4-yl)dibenzo[ b , d ]furan-4-amine (8.19 g, 16.45 mmol) in Sub 1-75 (4.56 g, 16.45 mmol) obtained in the above synthesis ), Pd ₂ (dba) ₃ (0.45 g, 0.49 mmol), 50% P( t- Bu) ₃ (0.5ml, 0.99 mmol), NaO t- Bu (4.74 g, 49.36 mmol), toluene (165ml) was added, and 8.22 g (yield: 72%) of the product was obtained using the above P 1-9 synthesis method.

7. P 1-107 Synthesis example

<Scheme 24>

N -([1,1'-biphenyl]-4-yl)dibenzo[ b , d ]thiophen-2-amine (4.93 g, 14.03 mmol) in Sub 1-107 (6.01 g, 14.03 mmol) obtained in the above synthesis , Pd ₂ (dba) ₃ (0.39 g, 0.42 mmol), 50% P( t- Bu) ₃ (0.4ml, 0.84 mmol), NaO t- Bu (4.05 g, 42.09 mmol), toluene (140ml) were added. and 8.73 g (yield: 89%) of the product was obtained by using the P 1-9 synthesis method.

8. P 1-137 Synthesis example

<Scheme 25>

(1) Sub 1'-117 synthesis

After dissolving N- phenyl-[1,1'-biphenyl]-4-amine (5.06 g, 20.63 mmol) in toluene (260ml) in a round bottom flask, Sub 1-117 (14.32 g, 30.94 mmol), Pd ₂ (dba) ₃ (0.57 g, 0.62 mmol), 50% P( t- Bu) ₃ (0.6ml, 1.24 mmol), NaO t- Bu (5.95 g, 61.88 mmol) was added and stirred at 80°C. After completion of the reaction, _{extraction with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 8.15 g (yield: 63%) of the product.

(2) P 1-137 synthesis

In Sub 1'-117 (8.15 g, 12.99 mmol) obtained in the above synthesis, N ,9-diphenyl-9 H -carbazol-2-amine (4.35 g, 12.99 mmol), Pd ₂ (dba) ₃ (0.36 g, 0.39) mmol), 50% P( t- Bu) ₃ (0.4ml, 0.78 mmol), NaO t- Bu (3.75 g, 38.98 mmol), and toluene (130ml) were added, and the product 9.74 was added using the above P 1-9 synthesis method. g (yield: 81%) was obtained.

9. P 1-140 Synthesis example

<Scheme 26>

N- phenyldibenzo[ b , d ]thiophen-2-amine (6.93 g, 25.16 mmol), Pd ₂ (dba) ₃ (0.35 g, 0.38 mmol) in Sub 1-134 (5.08 g, 12.58 mmol) obtained in the above synthesis , 50% P( t -Bu) ₃ (0.4ml, 0.75 mmol), NaO t -Bu (4.84 g, 50.33 mmol), and toluene (190ml) were added and 8.64 g of the product using the above P 1-9 synthesis method ( Yield: 82%) was obtained.

10. P 2-2 Synthesis example

<Scheme 27>

After dissolving Sub 1-7 (5.83 g, 11.96 mmol) obtained in the above synthesis in THF (80ml) in a round-bottom flask, Sub 1-IV-7 (6.39 g, 11.96 mmol), Pd(PPh ₃ ) ₄ (0.55) g, 0.48 mmol), NaOH (1.44 g, 35.88 mmol), water (40 ml) were added and stirred at 80°C. After completion of the reaction, _{extraction with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 8.77 g (yield: 90%) of the product.

11. P 2-13 Synthesis example

<Scheme 28>

After dissolving Sub 2-10 (6.74 g, 14.38 mmol) obtained in the above synthesis with toluene (145 ml) in a round-bottom flask, Sub 3-37 (CAS Registry Number: 80984-79-8) (4.49 g, 14.38 mmol) , Pd ₂ (dba) ₃ (0.40 g, 0.43 mmol) 50% P( t- Bu) ₃ (0.4ml, 0.86 mmol), NaO t- Bu (4.15 g, 43.15 mmol) were added and stirred at 100°C. . After completion of the reaction, _{extraction with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 8.36 g (yield: 83%) of the product.

12. P 2-17 Synthesis example

<Scheme 29>

Sub 2-10 (6.31 g, 13.47 mmol) obtained in the above synthesis to Sub 3-44 (3.92 g, 13.47 mmol), Pd ₂ (dba) ₃ (0.37 g, 0.40 mmol) 50% P( t- Bu) ₃ (0.4ml, 0.81 mmol), NaO t- Bu (3.88 g, 40.40 mmol), and toluene (135ml) were added, and the product 8.18 g (yield: 84%) was obtained using the above P 2-13 synthesis method.

13. P 2-29 Synthesis example

<Scheme 30>

Sub 2-18 (5.80 g, 11.54 mmol) obtained in the above synthesis, Sub 3-49 (4.46 g, 11.54 mmol), Pd ₂ (dba) ₃ (0.32 g, 0.35 mmol) 50% P( t- Bu) ₃ (0.3ml, 0.69 mmol), NaO t -Bu (3.33 g, 34.62 mmol), was added to toluene (115ml) and the product was 7.87 using the P 2-13 synthesis g (yield: 80%) was obtained.

14. P 2-38 Synthesis example

<Scheme 31>

To Sub 2-12 (7.58 g, 13.92 mmol) obtained in the above synthesis, Sub 3-44 (4.05 g, 13.92 mmol), Pd ₂ (dba) ₃ (0.38 g, 0.42 mmol) 50% P( t- Bu) ₃ (0.4ml, 0.83 mmol), NaO t- Bu (4.01 g, 41.75 mmol), and toluene (140ml) were added, and the product was 8.56 g (yield: 77%) by using the above P 2-13 synthesis method.

15. P 3-2 Synthesis example

<Scheme 32>

To Sub 1-139 (5.64 g, 18.60 mmol) obtained in the above synthesis, di([1,1'-biphenyl]-4-yl)amine (5.98 g, 18.60 mmol), Pd ₂ (dba) ₃ (0.51 g, 0.56 mmol) 50% P( t -Bu) ₃ (0.5ml, 1.12 mmol), NaO t -Bu (5.36 g, 55.80 mmol) and toluene (185ml) were added and the product 8.50 using the above P 1-9 synthesis method. g (yield: 84%) was obtained.

16. P 3-16 Synthesis example

<Scheme 33>

N -([1,1'-biphenyl]-4-yl)dibenzo[ b , d ]thiophen-2-amine (6.25 g, 17.78 mmol) in Sub 1-139 (5.39 g, 17.78 mmol) obtained in the above synthesis , Pd ₂ (dba) ₃ (0.49 g, 0.53 mmol) 50% P( t- Bu) ₃ (0.5ml, 1.07 mmol), NaO t- Bu (5.13 g, 53.33 mmol), toluene (180ml) were added and 8.26 g (yield: 81%) of the product was obtained by using the above P 1-9 synthesis method.

17. P 3-32 Synthesis example

<Scheme 34>

N- phenyl-9,9'-spirobi[fluoren]-4-amine (6.77 g, 16.61 mmol), Pd ₂ (dba) ₃ (0.46 g) in Sub 1-143 (4.77 g, 16.61 mmol) obtained in the above synthesis , 0.50 mmol) 50% P( t -Bu) ₃ (0.5ml, 1.00 mmol), NaO t -Bu (4.79 g, 49.83 mmol), and toluene (165ml) were added and the product was synthesized using the above P 1-9 synthesis method. 7.95 g (yield: 78%) was obtained.

18. P 3-44 Synthesis example

<Scheme 35>

N -(4-(naphthalen-1-yl)phenyl)dibenzo[ b , d ]furan-2-amine (6.10 g, 15.84 mmol), Pd in Sub 1-155 (6.53 g, 15.84 mmol) obtained in the above synthesis ₂ (dba) ₃ (0.44 g, 0.48 mmol) 50% P( t -Bu) ₃ (0.5 ml, 0.95 mmol), NaO t -Bu (4.57 g, 47.51 mmol), toluene (160 ml) were added and the P Using 1-9 synthesis method, 9.08 g (yield: 80%) of the product was obtained.

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

[Table 3]

Meanwhile, although exemplary synthesis examples of the present invention represented by Chemical Formula 1 have been described above, these are all Buchwald-Hartwig cross coupling reaction, Suzuki cross-coupling reaction, Miyaura boration reaction, Suzuki cross-coupling reaction, and intramolecular acid-induced cyclization. reaction ( J. mater. Chem . 1999, 9 , 2095.), Pd(II)-catalyzed oxidative cyclization reaction ( Org . Lett . 2011, 13 , 5504) and PPh _3- mediated reductive cyclization reaction ( J. Org . Chem 2005, 70 ^{, 5014.), other substituents defined in Formula 1 (X, Y, R 1} , R ² , L ¹ , L ³ , Ar in addition to the substituents specified in specific synthesis examples based on Grignard reaction and Cyclic Dehydration reaction) ² , Ar ³ , a substituent such as a, b and m) will be easily understood by those skilled in the art that the reaction proceeds even if it is combined. For example, Sub 1 -> Final Product reaction in Scheme 1, Sub 2 -> Final Product reaction in Scheme 3, Sub 1-M -> Sub 1 reaction in Scheme 4 is based on the Buchwald-Hartwig cross coupling reaction, and in Scheme 2 Sub 1 -> Final Product reaction, Sub 1-I -> Sub 1-II reaction in Scheme 4, Sub IV -> Sub 1 reaction in Scheme 5, Sub IV -> Sub 2 reaction, Sub V -> Sub 2 reaction, Starting material -> Sub 3 reaction in Scheme 15 is based on Suzuki cross-coupling reaction, starting material -> Sub 1-I reaction in Scheme 4, Sub 1-III -> Sub 1-IV reaction in Scheme 5, Sub 1 -> Sub 1-V reaction is based on Miyaura boration reaction. Subsequently, in Scheme 3, the Sub 1-II -> Sub 1-III (Sub 1) reaction and the Sub 1-II -> Sub 1-M reaction are intramolecular acid-induced cyclization reactions when X and Y are S ( J. mater. Chem . 1999, 9 , 2095.), based on a Pd(II)-catalyzed oxidative cyclization reaction when X and Y are O ( Org . Lett . 2011, 13 , 5504), where X and Y is based on a _{PPh 3} -mediated reductive cyclization response ( J. Org. Chem . 2005, 70 ^{, 5014.) when NL 2} -Ar ¹ , and when X and Y are C(R')(R"), Grignard It is based on the reaction and cyclic dehydration reaction.

Manufacturing evaluation of organic electric devices

[ Example One] Green organic electroluminescent device ( 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 vacuumed to a thickness of 60 nm on an ITO layer (anode) formed on an organic substrate. After deposition to form a hole injection layer, the compound P 1-1 of the present invention was vacuum-deposited to a thickness of 60 nm on the hole injection layer to form a hole transport layer. Then, on the hole transport layer, 4,4'-N,N'-dicarbazole-biphenyl (hereinafter, abbreviated as “CBP”) as a host material, tris(2-phenylpyridine)-iridium (hereinafter, “Ir(ppy)” ) ₃ ”) was used as a dopant material, doped at a 95:5 weight ratio, and vacuum-deposited to a thickness of 30 nm to form a light emitting layer. Then, (1,1'-bisphenyl)-4-oleato)bis(2-methyl-8-quinolinoleato)aluminum (hereinafter abbreviated as “BAlq”) was vacuum-deposited on the light emitting layer to a thickness of 10 nm. A hole blocking layer was formed, and tris(8-quinolinol)aluminum (hereinafter _{abbreviated as “Alq 3} ”) was vacuum-deposited to a thickness of 40 nm on the hole blocking layer to form an electron transport layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

[ Example 2] to [ Example 44] Green organic electroluminescent device ( hole transport layer )

Carried out except for using the compounds P 1-2 to P 1-134 and P 3-2 to P 3-54 of the present invention described in Table 4 below instead of the compound P 1-1 of the present invention as the hole transport layer material, respectively An organic electroluminescent device was manufactured in the same manner as in Example 1.

[ comparative example 1] and [ comparative example 2] Green organic electroluminescent device ( hole transport layer )

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 1 and Comparative Compound 2 described in Table 4 were used instead of Compound P 1-1 of the present invention as a hole transport layer material.

<Comparative compound 1> <Comparative compound 2>

Electroluminescence (EL) characteristics by applying a forward bias DC voltage to the organic electroluminescent devices manufactured by Examples 1 to 44 and Comparative Examples 1 and 2 of the present invention and PR-650 from Photoresearch was measured, and as a result of the measurement, the T95 lifetime was measured using a lifetime measuring device manufactured by McScience at 5000 ^{cd/m 2 standard luminance, 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 a hole transport layer material has a relatively low driving voltage compared to the organic electroluminescent device using Comparative Compound 1 and Comparative Compound 2 as a hole transport layer material, and light emission It can be seen that not only the efficiency is improved, but also the lifespan is improved.

Comparison of the compound of the present invention and Comparative Compound 2 shows different results depending on the type of atoms (S, C, N, O) introduced into the core even if the structure has the same skeleton. In particular, as in Comparative Compound 2, when the core is ^{made of only Sp 3} carbon, even if the core is introduced on the same skeleton, it exhibits lower thermal stability than the compound of the present invention. It can be seen that heat resistance to Joule's heat and resistance under high-temperature environments are reduced.

In addition, different results by changing the type of heterocycle on the same skeleton can be confirmed through comparison of the compounds of the present invention, compounds of the present invention P 1-42, P 1-61, P 1-71, P 1-80, P 3-2, and P 3-26 have a significantly deeper HOMO energy level than the compound P 1-2 of the present invention, and accordingly, light emission when at least one of the heteroatoms introduced into the core has S or O It can be confirmed that the auxiliary layer material is more suitable.

In the case of the hole transport layer, it is necessary to understand the correlation 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 of the hole transport layer in which the compound according to the present invention is used.

[ Example 45] Red organic electroluminescent device ( light emitting 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 deposition of 2-TNATA to a thickness of 60 nm on an ITO layer (anode) formed on a glass substrate, and then NPB was vacuum deposited on the hole injection layer to a thickness of 60 nm to form a hole transport layer. did. Then, on the hole transport layer, the compound P 1-41 of the present invention was vacuum-deposited to a thickness of 20 nm to form a light-emitting auxiliary layer, and then CBP as a host material, bis-(1-phenylisoquinolyl) on the light-emitting auxiliary layer ) iridium(III)acetylacetonate (hereinafter _{abbreviated as “(piq) 2} Ir(acac)”) was used as a dopant material, doped in a 95:5 weight ratio, and vacuum-deposited to a thickness of 30 nm to form a light emitting layer. Subsequently, BAlq was vacuum-deposited to a thickness of 10 nm on the light emitting layer to form a hole blocking layer, and Alq ₃ was vacuum deposited to a thickness of 40 nm on the hole blocking layer to form an electron transport layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

[ Example 46] to [ Example 126] Red organic electroluminescent device ( light emitting layer )

Implemented except that compounds P 1-42 to P 1-142, P 3-2 to P 3-54 of the present invention described in Table 5 were used instead of compound P 1-41 of the present invention as a light emitting auxiliary layer material An organic electroluminescent device was manufactured in the same manner as in Example 45.

[ comparative example 3] Red organic electroluminescent device ( light emitting layer )

An organic electroluminescent device was manufactured in the same manner as in Example 45, except that the light-emitting auxiliary layer was not formed.

[ comparative example 4] and [ comparative example 5] Red organic electroluminescent device ( light emitting layer )

An organic electroluminescent device was manufactured in the same manner as in Example 45, except that Comparative Compound 2 and Comparative Compound 3 described in Table 5 were used instead of Compound P 1-41 of the present invention as a light emitting auxiliary layer material. .

<Comparative compound 3>

By applying a forward bias DC voltage to the organic electroluminescent devices manufactured by Examples 45 to 126 and Comparative Examples 3 to 5 of the present invention, electroluminescence (EL) with a PR-650 manufactured by photoresearch. The characteristics were measured, and as a result of the measurement ^{, the T95 lifespan was measured using a lifespan measuring device manufactured by McScience at 2500cd/m 2} standard luminance, and the measurement results are shown in Table 5 below.

[Table 5]

As can be seen from the results in Table 5, the organic electroluminescent device using the compound of the present invention as a light emitting auxiliary layer material has improved luminous efficiency and significantly improved lifespan compared to the organic electroluminescent device of Comparative Examples 3 to 5. .

It can be seen that the device using Comparative Compound 2, Comparative Compound 3, and the present invention compound as a light emitting auxiliary layer has improved luminous efficiency and lifetime compared to the device without the light emitting auxiliary layer. It can be seen that the results are significantly higher.

This is because the type of atoms introduced into the core (S, C, N, O) acts as a major factor in improving the performance of the device not only in the hole transport layer but also in the light emission auxiliary layer (red phosphorescence), resulting in high thermal stability and hole transport in the hole transport layer. It is thought that this is because it makes it easy to achieve charge balance in the light emitting layer with a deep HOMO energy level that can be efficiently transported.

In particular, among the compounds of the present invention, when the hetero valence type introduced into the 4-ring heterocyclic core has at least one S or O, the HOMO energy level and high refractive index are deeper than those of Comparative Compound 3 in which only N is introduced into the 3-ring heterocyclic core. As a result, it can be seen that the luminous efficiency and lifespan are significantly improved.

Combining the properties described above (high refractive index, high thermal stability, and deep HOMO energy level), the band gap, electrical It shows that the characteristics and interface characteristics can be significantly changed, and it can be confirmed that this acts as a major factor in improving the performance of the device.

In addition, in the evaluation results of the above-described device fabrication, the device characteristics in which the compound of the present invention is applied to only one of the hole transport layer and the light emission auxiliary layer have been described, but the compound of the present invention may be used by applying both the hole transport layer and the light emission auxiliary layer.

[ Example 127] Green organic electroluminescent device (phosphor host)

An organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention as a light emitting host material of the light emitting layer. First, a 2-TNATA film is vacuum-deposited on the ITO layer (anode) formed on a glass substrate to form a hole injection layer with a thickness of 60 nm, and then an NPD film as a hole transport compound on the hole injection layer is vacuum-deposited to a thickness of 60 nm. A transport layer was formed. The compound P 2-5 of the present invention was used as a host on the hole transport layer, and Ir(ppy) ₃ as a dopant material was doped at a weight ratio of 95:5 to deposit a light emitting layer to a thickness of 30 nm. Subsequently, BAlq was vacuum-deposited to a thickness of 10 nm as a hole blocking layer, and Alq ₃ was formed as a film to a thickness of 40 nm as an electron transport layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then Al was deposited to a thickness of 150 nm and used as a cathode to prepare an organic electroluminescent device.

[ Example 128] to [ Example 135] Green organic electroluminescent device (phosphor host)

Organic electrophoresis in the same manner as in Example 127, except that compounds P 2-13 to P 2-33 of the present invention described in Table 6 below were used as the light emitting host material of the light emitting layer instead of compound P 2-5 of the present invention. A light emitting device was manufactured.

[ comparative example 6] to [ comparative example 8] Green organic electroluminescent device (phosphor host)

An organic electroluminescent device was manufactured in the same manner as in Example 127, except that Comparative Compounds 4 to 6 described in Table 6 were used instead of Compound P 2-5 of the present invention as the light emitting host material of the light emitting layer. did.

<Comparative compound 4> <Comparative compound 5> <Comparative compound 6>

By applying a forward bias DC voltage to the organic electroluminescent devices manufactured by Examples 127 to 135 and Comparative Examples 6 to 8 of the present invention, electroluminescence (EL) with a PR-650 manufactured by photoresearch. The characteristics were measured, and as a result of the measurement, the T95 lifespan was measured using a lifespan measuring device manufactured by McScience at 5000cd ^{/m 2 standard luminance, and the measurement results are shown in Table 6 below.}

[Table 6]

[ Example 136] Red organic electroluminescent device (phosphor host)

An organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention as a light emitting host material of the light emitting layer. First, a 2-TNATA film is vacuum-deposited on the ITO layer (anode) formed on a glass substrate to form a hole injection layer with a thickness of 60 nm, and then an NPD film as a hole transport compound on the hole injection layer is vacuum-deposited to a thickness of 60 nm. A transport layer was formed. The compound P 2-6 of the present invention was used as a host on the hole transport layer, and (piq) ₂ Ir(acac) was doped as a dopant material in a weight ratio of 95:5 to deposit a light emitting layer to a thickness of 30 nm. Subsequently, BAlq was vacuum-deposited to a thickness of 10 nm as a hole blocking layer, and Alq ₃ was formed as a film to a thickness of 40 nm as an electron transport layer. Thereafter, LiF, which is an alkali metal halide, was deposited as an electron injection layer to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm and used as a cathode to prepare an organic electroluminescent device.

[ Example 137] to [ Example 144] Red organic electroluminescent device (phosphor host)

In the same manner as in Example 136, except that the compounds P 2-17 to P 2-38 of the present invention described in Table 7 below were used as the light emitting host material of the light emitting layer, respectively, instead of the compound P 2-6 of the present invention. A light emitting device was manufactured.

[ comparative example 9] and [ comparative example 10] Red organic electroluminescent device (phosphor host)

An organic electroluminescent device was manufactured in the same manner as in Example 136, except that Comparative Compound 4 and Comparative Compound 7 described in Table 7 were used instead of Compound P 2-6 of the present invention as the light emitting host material of the light emitting layer. did.

<Comparative compound 7>

Electroluminescence (EL) by applying a forward bias DC voltage to the organic electroluminescent devices manufactured by Examples 136 to 144 and Comparative Examples 9 and 10 of the present invention and PR-650 of Photoresearch Company The characteristics were measured, and as a result of the measurement ^{, the T95 lifespan was measured using a lifespan measuring device manufactured by McScience at 2500cd/m 2} standard luminance, and the measurement results are shown in Table 7 below.

[Table 7]

As can be seen from the measurement results in Tables 6 and 7, the device using the compound according to an embodiment of the present invention as a phosphorescent green and red host material of the light emitting layer has higher luminous efficiency and lifetime than Comparative Compounds 4 to 7 It was confirmed that remarkably improved.

In particular, the bis-type compound of the present invention in which two 4-ring heterocycles are connected is more smoothly charged from the host to the dopant than Comparative Compounds 5 to 7, which are single 4-ring heterocycles, As a result, it can be confirmed that the charge balance in the light emitting layer becomes easier, and the light emitting efficiency and lifespan are increased.

In other words, the compound of the present invention used as a host material in the light emitting layer has the most appropriate T1 value and energy bandgap to facilitate charge transfer from the host to the dopant, and accordingly, significantly high luminous efficiency and high lifespan during device measurement. It can be seen that indicates

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

The above description is merely illustrative of the present invention, and various modifications will be possible without departing from the essential characteristics of the present invention by those of ordinary skill in the art to which the present invention pertains. Accordingly, the embodiments disclosed in the present specification are not intended to limit the present invention, but to explain, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be construed by the claims, and all technologies within the scope equivalent thereto should be construed as being included in the scope of the present invention.

100: organic electric device 110: substrate
120: first electrode 130: hole injection layer
140: hole transport layer 141: buffer layer
150: light emitting layer 151: light emitting auxiliary layer
160: electron transport layer 170: electron injection layer
180: second electrode

Claims (10)

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

In Formula 1,
X and Y are independently of each other N-(L ² -Ar ¹ ), S, O or C(R')(R"), provided that when X and Y are both C(R')(R") except,
n is an integer of 1 or 2, and when n is 2, a plurality of X and Y are the same as or different from each other,
Wherein R' and R" are each independently a C ₆ -C ₆₀ aryl group; O, N, S, Si and P C ₂ -C ₆₀ heterocyclic ring containing at least one heteroatom selected from the group consisting of group; fluorenyl group; C ₃ -C ₆₀ aliphatic ring and C ₆ -C ₆₀ fused ring group of aromatic ring; C ₁ -C ₅₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ an alkynyl group; a C ₁ -C ₃₀ alkoxyl group; and a C ₆ -C ₃₀ aryloxy group selected from the group consisting of, R′ and R″ may be bonded to each other to form a ring,
R ¹ and R ² are each independently deuterium; tritium; halogen; cyano group; nitro; C ₆ -C ₆₀ Aryl group; fluorenyl group; _{C 2} -C ₆₀ A heterocyclic group comprising at least one heteroatom selected from the group consisting of O, N, S, Si and P; C ₃ -C ₆₀ A fused ring group of an aliphatic ring and a C ₆ -C _{60 aromatic ring;} C ₁ -C ₅₀ Alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₁ -C ₃₀ alkoxyl group; and C ₆ -C ₃₀ selected from the group consisting of an aryloxy group, adjacent R ¹ may combine with each other to form a benzene ring, and adjacent R ² may combine with each other to form a ring, and a is 0 to an integer of 3, b is an integer from 0 to 2,
The Ar ¹ is a C ₆ -C ₆₀ aryl group; _{C 2} -C ₆₀ A heterocyclic group comprising at least one heteroatom selected from the group consisting of O, N, S, Si and P; fluorenyl group; C ₆ -C ₆₀ A fused ring group of an aromatic ring and a C ₃ -C _{60 aliphatic ring;} C ₁ -C ₅₀ Alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₁ -C ₃₀ alkoxyl group; And C ₆ -C _{30 It} is selected from the group consisting of an aryloxy group,
The L ² is a single bond; C ₆ -C ₆₀ Arylene group; fluorenylene group; _{C 2} -C ₆₀ A heterocyclic group containing at least one hetero atom of O, N, S, Si and P; and a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring fused ring group is selected from the group consisting of,
L ¹ is a single bond; C ₆ -C ₆₀ Arylene group; fluorenylene group; _{C 2} -C ₆₀ A heterocyclic group containing at least one hetero atom of O, N, S, Si and P; C ₃ -C ₆₀ A fused ring group of an aliphatic ring and a C ₆ -C _{60 aromatic ring;} And it is selected from the group consisting of Formula 1a, provided that only when n is an integer of 1, L ¹ is Formula 1a,
<Formula 1a>

In Formula 1a,
Ar ² and Ar ³ are each independently a C ₆ -C ₆₀ aryl group; _{C 2} -C ₆₀ A heterocyclic group comprising at least one heteroatom selected from the group consisting of O, N, S, Si and P; fluorenyl group; It is selected from the group consisting of a fused ring group of a _{C 6} -C ₆₀ aromatic ring and a C ₃ -C _{60 aliphatic ring and a C 1} -C _{50 alkyl group,}
m is an integer of 1 or 2, and when m is an integer of 2, a plurality of Ar ² are the same as or different from each other, and a plurality of Ar ³ are also the same or different from each other,
L ³ is a single bond; C ₆ -C ₆₀ Arylene group; fluorenylene group; _{C 2} -C ₆₀ A heterocyclic group containing at least one hetero atom of O, N, S, Si and P; and a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring fused ring group is selected from the group consisting of,
Each of the aryl group, arylene group, fluorenyl group, fluorenylene group, heterocyclic group, fused-ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group and aryloxy group is deuterium; halogen; a silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C _{20 aryl group;} Phosphine oxide unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C _{20 aryl group;} siloxane group; boron group; germanium group; cyano group; nitro group; C ₁ -C ₂₀ Alkylthio group; C ₁ -C ₂₀ An alkoxyl group; C ₁ -C ₂₀ Alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₆ -C ₂₀ Aryl group; _{a C 6} -C ₂₀ aryl group substituted with deuterium; fluorenyl group; _{C 2} -C ₂₀ A heterocyclic group comprising at least one heteroatom selected from the group consisting of O, N, S, Si and P; C ₃ -C ₂₀ cycloalkyl group; C ₇ -C ₂₀ Arylalkyl group; -N(R ^a )(R ^b ); and C ₈ -C ₂₀ arylalkenyl group; may be substituted with one or more substituents selected from the group consisting of, and when each of these substituents is adjacent, they may be bonded to each other to form a ring,
wherein R ^a and R ^b are each independently selected from a C ₆ -C ₆₀ aryl group; fluorenyl group; It is selected from the group consisting of; _{C 2} -C ₆₀ heterocyclic group containing at least one hetero atom of O, N, S, Si and P. The method of claim 1,
Formula 1 is a compound, characterized in that represented by Formula 2 or Formula 3:
<Formula 2><Formula3>

In Formulas 2 and 3, X, Y, R ¹ , R ² , L ³ , Ar ² , Ar ³ , a and b are the same as defined in claim 1 . The method of claim 1,
Formula 1 is a compound characterized in that represented by the following Formula 4:
<Formula 4>

In Formula 4, X, Y, R ¹ , R ² , L ¹ , a and b are the same as defined in claim 1. The method of claim 1,
In Formula 1, X is N-(L ² -Ar ¹ ), and Y is S or O. The method of claim 1,
The compound represented by Formula 1 is a compound, characterized in that one of the following compounds:

. a first electrode; a second electrode; and at least one organic material layer formed between the first electrode and the second electrode,
The organic layer is an organic electric device, characterized in that it contains the compound of any one of claims 1 to 5. 7. The method of claim 6,
The organic material layer includes at least one layer of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer and an electron injection layer containing the compound,
The compound contained in the organic material layer is an organic electric device, characterized in that a single compound or a mixture of two or more compounds. 7. The method of claim 6,
The organic material layer is an organic electric device, characterized in that formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process. A display device comprising the organic electric device of claim 6; and a controller for driving the display device. 10. The method of claim 9,
The organic electroluminescent device is an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, and an electronic device, characterized in that one of a single color or white lighting device.

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