KR102391274B1 - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

The present invention relates to a compound for an organic electric device, an organic electric element using the same, and an electronic device including the organic electric element. According to the present invention, an organic electric element having high luminous efficiency and high heat resistance can be provided, It is possible to improve the lifespan of the electric device.

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 usually has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic 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, such as a hole injection material, a hole transport material, an electron transport material, an electron injection material, according to their function. In addition, the light emitting material can be classified into a high molecular type and a low molecular type according to the molecular weight, and can be classified into a fluorescent material derived from a singlet excited state of an electron and a phosphorescent material derived from a triplet excited state of an electron according to the light emission mechanism. there is. In addition, the light emitting material may be divided into blue, green, and red light emitting materials and yellow and orange light emitting materials necessary for realizing a better natural color according to the emission color.

On the other hand, when only one material is used as a light emitting material, the maximum emission wavelength shifts to a longer wavelength due to intermolecular interaction, and there is a problem in that the color purity is lowered or the efficiency of the device is decreased due to the emission attenuation effect. A host/dopant system may be used as a light emitting material in order to increase the luminous efficiency through the The principle is that when a small amount of a dopant having a smaller energy band gap than that of the host forming the emission layer is mixed in the emission layer, excitons generated in the emission layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength band of the dopant, light having a desired wavelength can be obtained according to the type of dopant used.

Currently, the portable display market is a large-area display, and the size thereof is increasing, so that power consumption greater 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 by simply 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 organic electroluminescent devices, 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 T1 value because they must 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 interface It causes light emission 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, and it is urgently needed to develop a light emitting auxiliary layer having a high T1 value and hole mobility within an appropriate driving voltage range. is required

However, this cannot be achieved simply with the structural characteristics of the core of the material present in the organic material layer, and the characteristics of the core and sub-substituent of each material, and an appropriate combination between the light-emitting auxiliary layer and the hole transporting layer, and the light-emitting auxiliary layer and the light-emitting layer. When this happens, high-efficiency and long-life devices can be realized.

Meanwhile, development of materials for the light emitting layer and the light emitting auxiliary layer having stable characteristics against Joule heating generated during device driving, that is, a high glass transition temperature, is also required. The low glass transition temperature of the light emitting layer and the light emitting auxiliary layer material lowers the uniformity of the thin film surface during device driving, and the material may be deformed due to heat generated during device driving, which is reported to have a significant impact on device lifespan.

Therefore, it is necessary to develop a material that can withstand a long time during deposition, that is, a material with strong heat resistance, and a light emitting material that can efficiently achieve charge balance in the light emitting layer is required. In order to fully exhibit the excellent characteristics of an organic electric device, materials constituting the organic layer in the device, for example, hole injection material, hole transport material, light emitting material, electron transport material, electron injection material, light emitting auxiliary layer material, etc. are stable and efficient materials. It should be supported by the above, in particular, the development of the light emitting auxiliary layer and the host material of the light emitting layer is urgently required.

An object of the present invention is to provide a compound having high heat resistance and improving luminous efficiency and lifespan of a device, an organic electric device using the same, and an electronic device including the organic electric device.

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

<Formula 1>

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

By using the compound according to the present invention, it is possible to achieve high luminous efficiency and high heat resistance of the device, and there is an effect that can improve the lifespan.

1 to 3 schematically show an organic electric device according to embodiments of the present invention.
4 shows a chemical formula according to an aspect of the present invention.

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

In order to describe the present embodiments, it should be noted that, in adding reference numerals to components of each drawing, the same components are given the same reference numerals as much as possible even though they are indicated in 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 the drawings referenced below, no scale ratio applies.

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 elements from other elements, and the essence, order, or order of the elements 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 also be “connected,” “coupled,” or “connected.”

Further, 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” another component, but also when another component is in between. It should be understood that cases may be included. Conversely, when it is said that an element is "on top of" another part, it should be understood to mean that there is no other part in the middle.

Terms used in this specification and the appended claims are as follows, unless otherwise stated, without departing from the spirit of the present invention.

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

The term "alkyl" or "alkyl group" as used in this application, unless otherwise specified, has 1 to 60 carbons linked by a single bond, straight chain alkyl group, branched chain alkyl group, cycloalkyl (alicyclic) group, alkyl-substituted means a radical of saturated aliphatic functional groups including cycloalkyl groups and 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" or "alkynyl" as used in this application, unless otherwise specified, has a double bond or a triple bond, respectively, includes a straight or branched chain group, and has 2 to 60 carbon atoms, but is limited thereto it is not going to be

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

As used herein, the term “alkoxy group” or “alkyloxy group” refers to an alkyl group to which an oxygen radical is bonded, and has 1 to 60 carbon atoms unless otherwise specified, but is not limited thereto.

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

The terms "aryl group" and "arylene group" used in the present application have 6 to 60 carbon atoms, respectively, unless otherwise specified, but are not limited thereto. In the present application, the aryl group or the arylene group includes a single ring type, a ring aggregate, a fused multiple ring-based compound, and the like. For example, the aryl group may include a phenyl group, a monovalent functional group of biphenyl, a monovalent functional group of naphthalene, a fluorenyl group, and a substituted fluorenyl group, and the arylene group may include a fluorenylene group, a substituted fluorenylene group. may include a group.

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 between such rings It means that the number of direct links is one less than the total number of ring systems in the compound. In a ring aggregate, the same or different ring systems may be directly linked to each other through single or double bonds.

Since the aryl group in the present application includes a ring aggregate, the aryl group includes biphenyl and terphenyl in which a single aromatic benzene ring is connected by a single bond. In addition, since the aryl group includes compounds in which an aromatic single ring and a fused aromatic ring system are connected by a single bond, for example, a compound in which a benzene ring, which is an aromatic single ring, and a fluorene, a fused aromatic ring system, are connected by a single bond are also included. do.

As used herein, the term "fused multiple ring system" refers to a fused ring type that shares 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. The fused multiple ring system may be an aromatic ring, a heteroaromatic ring, an aliphatic ring, or a combination of these rings. For example, in the case of an aryl group, it may be a naphthalenyl group, a phenanthrenyl group, a fluorenyl group, etc., but is not limited thereto.

The term "spiro compound" as used in the present application 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.

As used herein, the terms "fluorenyl group", "fluorenylene group", and "fluorentriyl group" are, unless otherwise specified, in the following structures, R, R', R" and R'" are all hydrogen. It refers to a monovalent, divalent or trivalent functional group, and “substituted fluorenyl group”, “substituted fluorenylene group” or “substituted fluorentriyl group” is a substituent R, R', R", R' "means that at least one of " is a substituent other than hydrogen, and includes cases in which R and R' are bonded to each other to form a spiro compound together with the carbon to which they are bonded. In the present specification, the fluorenyl group, the fluorenylene group, and the fluorentriyl group may all be referred to as fluorene groups regardless of valences such as monovalent, divalent, trivalent, and the like.

In addition, the R, R', R" and R'" are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, 3 to It may be a heterocyclic group having 30 carbon atoms, for example, the aryl group may be phenyl, biphenyl, naphthalene, anthracene or phenanthrene, and the heterocyclic group may be pyrrole, furan, thiophene, pyrazole, imidazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, indole, benzofuran, quinazoline or quinoxaline. For example, the substituted fluorenyl group and the fluorenylene group are monovalent to 9,9-dimethylfluorene, 9,9-diphenylfluorene and 9,9'-spirobi[9H-fluorene], respectively. It may be a functional group or a divalent functional group.

The term "heterocyclic group" used in this application includes not only aromatic rings such as "heteroaryl group" or "heteroarylene group" but also non-aromatic rings, and unless otherwise specified, each carbon number including 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.

For example, the “heterocyclic group” may include a compound including a heteroatom group such as SO ₂ , P=O, etc., such as the following compounds instead of carbon forming a ring.

As used herein, the term "ring" includes monocyclic and polycyclic rings, and includes hydrocarbon rings as well as heterocycles including 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.

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

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" used in this application, "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 group, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₂₀ aryl group, C ₆ -C ₂₀ aryl group substituted with deuterium, C ₈ -C ₂₀ arylalkenyl group, silane group, boron group, germanium group, and O, N, S, Si and P containing at least one heteroatom selected from the group consisting of C ₂ -C ₂₀ heterocyclic group means substituted with one or more substituents selected from the group consisting of and is not limited to these substituents.

In the present application, the 'functional 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 functional group reflecting the valence', but it is described as 'the name of the parent compound' You may. For example, in the case of 'phenanthrene', which is a type of aryl group, the monovalent 'group' is 'phenanthryl (group)', and the divalent group is 'phenanthrylene (group)', etc. It can be described, but it can also be described as 'phenanthrene', which is the name of the parent compound, regardless of the valence.

Similarly, in the case of pyrimidine, regardless of the valence, it is described as 'pyrimidine', or if it is monovalent, it is pyrimidinyl (group), and if it is divalent, the 'group of the valence, such as pyrimidinylene (group), etc. It can also be written in the name of '. Therefore, in the present application, when the type of the substituent is described as the name of the parent compound, it may mean an n-valent 'group' formed by the detachment of a hydrogen atom bonding to a carbon atom and/or a hetero atom of the parent compound.

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

In addition, unless there is an explicit explanation, the formula used in the present application is the same as the definition of the substituent by the exponent 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 display of hydrogen bonded to carbon 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 carbon 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.

Unless otherwise stated in the present application, forming a ring means that adjacent groups combine with each other to form a single ring or fused multiple rings, and the single ring and the formed fused multiple rings are at least one hydrocarbon ring as well as a hydrocarbon ring. It includes heterocycles containing heteroatoms, and may include aromatic and non-aromatic rings.

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

Meanwhile, the term "bridged bicyclic compound" as used in the present application refers to a compound in which two rings share three or more atoms to form a ring, unless otherwise specified. In this case, the shared atom may include carbon or a hetero atom.

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

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

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

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

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

For example, a capping layer 180 may be formed on the second electrode 170 . In the case of a top emission organic light emitting device, the capping layer 180 is formed on the second electrode 170 . It is possible to reduce optical energy loss due to surface plasmon polaritons (SPPs) of SPPs, and in the case of a bottom emission organic light emitting device, the capping layer 180 may serve as a buffer for the second electrode 170 . .

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

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

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

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

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

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

The first stack ST1 is an organic material layer formed on the first electrode 110, which is a first hole injection layer 320, a first hole transport layer 330, a first emission layer 340, and a first electron transport layer ( 350) may be included.

The second stack ST2 may include a second hole injection layer 420 , a second hole transport layer 430 , a second emission layer 440 , and a second electron transport layer 450 .

As described above, the first stack and the second stack may be organic material layers having the same stacked structure or organic material layers having different stacked structures.

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

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

In this case, the second hole transport layer 430 includes the second stack ST2 in which the energy level is set higher than the triplet excited state energy level of the second light emitting layer 440 .

Since the energy level of the second hole transport layer 430 is higher than that of the second light emitting layer 440 , triplet excitons of the second light emitting layer 440 pass to the second hole transport layer 430 and the luminous efficiency is lowered. it can be prevented That is, the second hole transport layer 430 functions as an exciton blocking layer for preventing triplet excitons from crossing while performing a function of transporting holes from the inherent second light emitting layer 440. .

In addition, for the function of the exciton blocking layer, the first hole transport layer 330 may also be set to an energy level higher than the triplet excitation energy level of the first light emitting layer 340 . In addition, the first electron transport layer 350 is also set to an energy level higher than the energy level of the triplet excited state of the first light emitting layer 340 , and the second electron transport layer 450 is also triplet excited by the second light emitting layer 440 . It is preferably set to an energy level higher than the energy level of the state.

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

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

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

The organic electric device according to FIGS. 1 to 3 may further include a protective layer (not shown) and an encapsulation layer (not shown). The protective layer may be disposed on the capping layer, and the encapsulation layer is disposed on the capping layer, and a side portion of at least one of the first electrode, the second electrode, and the organic material layer to protect the first electrode, the second electrode, and the organic material layer may be formed to cover the

The protective layer may provide a planarized surface so that the encapsulation layer is uniformly formed, and may serve to protect the first electrode, the second electrode, and the organic material layer during the manufacturing process of the encapsulation layer.

The encapsulation layer may serve to prevent the penetration of external oxygen and moisture into the organic electric device.

On the other hand, even with the same and similar 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 the sub-substituents coupled thereto In particular, when the energy level and T1 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.

Therefore, in the present invention, by using the compound represented by Chemical Formula 1 as a material of the light-emitting auxiliary layer 220, the light-emitting layer 140, 340, 440, and/or the capping layer 180, the energy level and T1 value between each organic material layer, By optimizing the intrinsic properties (mobility, interfacial properties, etc.) of the material, the lifetime and efficiency of the organic electric device could be improved at the same time.

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 110, and the hole injection layer 120, 320, 420), the hole transport layers 130, 330, 430, the light emitting layers 140, 340, 440, the electron transport layers 150, 350, 450 and the electron injection layer 160 after forming the organic material layer including the It may be manufactured by depositing a material that can be used as the cathode 170 thereon. In addition, a light-emitting auxiliary layer 220 between the hole transport layers 130 , 330 , 430 and the light emitting layers 140 , 340 , 440 , and an electron transport auxiliary layer between the light emitting layer 140 and the electron transport layer 150 (not shown) may be further formed or may be formed in a stack structure as described above.

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 a material used.

The organic electric device according to an embodiment of the present invention may include an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, a device for monochromatic lighting, a device for a quantum dot display, and the like.

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,

1) Ring A or Ring B is each independently selected from R ² Or unsubstituted, C ₆ ~ C ₆₀ Arylene group; fluorenylene group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; or a combination thereof,

2) X is NR', O, S or CR'R'';

3) L ¹ is a single bond; NR', O, S or CR'R''

4) R ¹ , R ² , R′ and R” are independently of each other hydrogen; heavy hydrogen; halogen; cyano group; nitro group; C ₆ ~ C ₆₀ Aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ 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 An alkoxyl group; C ₆ ~ C ₃₀ Aryloxy group; -L ² -NR ³ R ⁴ ; Or adjacent groups may combine with each other to form a ring,

5) R ¹ , R ² , R′ and R” is at least one selected from a C ₆ ~ C ₆₀ aryl group, a fluorenyl group, a C ₂ ~ C ₆₀ heterocyclic group, or -L ² -NR ³ R ⁴ and ,

6) L ² is a single bond; C ₆ ~ C ₆₀ Arylene group; fluorenylene group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; or a combination thereof,

7) R ³ and R ⁴ are each independently hydrogen; heavy hydrogen; halogen; cyano group; nitro group; C ₆ ~ C ₆₀ Aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ 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 An alkoxyl group; C ₆ ~ C ₃₀ It is an aryloxy group,

8) n is an integer from 0 to 4,

9) The R ^{1 to 4} , R′, R″, L ² , A ring, B ring, and a ring formed by bonding adjacent groups to each other are deuterium; halogen; C ₁ -C ₂₀ alkyl group or C ₆ - A silane group unsubstituted or substituted with a C ₂₀ aryl group; a siloxane group; a boron group; a germanium group; a cyano group; an amino group; a nitro group; a C ₁ -C ₂₀ alkylthio group; a C ₁ -C ₂₀ alkoxy group; C ₆ -C ₂₀ Arylalkoxy 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; Deuterium substituted C ₆ -C ₂₀ Aryl group; Fluorenyl group; C ₂ -C ₂₀ Heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; C ₃ -C ₂₀ Aliphatic group It may be further substituted with one or more substituents selected from the group consisting of a ring group; a C ₇ -C ₂₀ arylalkyl group; a C ₈ -C ₂₀ arylalkenyl group; and combinations thereof.

In the above, when R ^1-4 , R' and R" are an aryl group, preferably a C ₆ -C ₃₀ aryl group, more preferably a C ₆ -C ₁₈ aryl group, such as phenyl, biphenyl, naph tyl, terphenyl, and the like.

When the R ^1-4 , R', R", L ² , A ring and B ring are a heterocyclic group, Preferably, a C ₂ ~ C ₃₀ heterocyclic group, more preferably a C ₂ ~ C ₁₈ heterocyclic group, such as dibenzofuran, dibenzothiophene, naphthobenzothiophene, naphthobenzofuran, etc. may be .

When R ^{1 to 4} , R', R", L ² , Ring A and Ring B are fluorenyl groups, preferably 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H- It may be a fluorenyl group, 9,9'-spirobifluorene, or the like.

When the L ² , ring A and ring B are arylene groups, preferably a C ₆ ~ C ₃₀ arylene group, more preferably a C ₆ ~ C ₁₈ arylene group, such as phenyl, biphenyl, naphthyl, terphenyl etc.

When R ^{1 to 4} , R' and R" are an alkyl group, it may be preferably a C ₁ to C ₁₀ alkyl group, for example, methyl, t-butyl, or the like.

When R ^{1 to 4} , R' and R" are alkoxyl groups, preferably a C ₁ to C ₂₀ alkoxyl group, more preferably a C ₁ to C ₁₀ alkoxyl group, such as methoxy, t-butoxy etc.

The R ^1-4 , R', R", L ² , the ring formed by bonding adjacent groups of the A ring and the B ring to each other is a C ₆ to C ₆₀ aromatic ring group; a fluorenyl group; O, N, S, A C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of Si and P; or a C ₃ ~ C ₆₀ aliphatic ring group, for example, when adjacent groups are bonded to each other to form an aromatic ring , preferably a C ₆ ~ C ₂₀ aromatic ring, more preferably a C ₆ ~ C ₁₄ aromatic ring, such as benzene, naphthalene, phenanthrene, and the like.

Preferably, Chemical Formula 1 may be represented by one of Chemical Formulas 2 to 5, but is not limited thereto.

<Formula 2> <Formula 3> <Formula 4> <Formula 5>

In Formulas 2 to 5, R ^{1 to 4} , R′, R″, L ¹ , L ² , A ring, B ring, and n are the same as defined in Formula 1 above.

Also preferably, Ring A of Formula 1 may be represented by one of Formulas A-1 to A-3 below, but is not limited thereto.

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

In Formulas A-1 to A-3,

1) wherein R ² is the same as defined in Formula 1,

2) X ¹ is NR', O, S or CR'R'',

3) * represents a portion bonding to N and a portion bonding to L ¹ in Formula 1,

4) R' and R'' are as defined in Formula 1 above,

5) m, o and p are each independently an integer of 0-4; q and r are each independently an integer of 0-3.

Also preferably, B in Formula 1 may be represented by one of Formulas B-1 to B-8, but is not limited thereto.

<Formula B-1> <Formula B-2> <Formula B-3> <Formula B-4>

<Formula B-5> <Formula B-6> <Formula B-7> <Formula B-8>

In Formulas B-1 to B-8,

1) R ² is as defined in Formula 1 above,

2) *2 represents the portion bonded to the carbon of the pentagonal ring including X,

3) *3 represents a portion that binds to L ¹ ,

4) X ² is NR', O, S or CR'R",

5) R' and R'' are as defined in Formula 1 above,

6) s is an integer from 0 to 3; t is an integer from 0 to 5; u is an integer from 0 to 4.

Meanwhile, the compound represented by Formula 1 may be one of the following P-1 to P-120, but is not limited thereto.

In another embodiment of the present invention, the present invention provides a first electrode; a second electrode; and an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer includes the compound represented by Formula 1 alone or in combination.

As another embodiment of the present invention, the present invention provides a first electrode; a second electrode; an organic material layer formed between the first electrode and the second electrode; and a capping layer, wherein the capping layer is formed on one side of both surfaces of the first electrode and the second electrode that is not in contact with the organic material layer, and the organic material layer or the capping layer is represented by Formula 1 The compounds used alone or in combination are included.

The organic material layer includes at least one of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer. That is, at least one layer of the hole injection layer, the hole transport layer, the light emitting auxiliary layer, the light emitting layer, the electron transport auxiliary layer, the electron transport layer and the electron injection layer included in the organic material layer contains the compound represented by Formula 1 alone or by mixing can

Preferably, the organic material layer includes at least one of the hole transport layer, the light emitting auxiliary layer, and the light emitting layer. That is, the compound may be included in at least one of the hole transport layer, the light emitting auxiliary layer, and the light emitting layer alone or in combination.

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

Preferably, the organic material layer further includes a charge generating layer formed between the two or more stacks.

Another aspect of the present invention is to provide an electronic device including a display device including an organic electric device including the compound represented by Chemical Formula 1 and a controller for driving the display device.

In an embodiment of the present invention, the compound of Formula 1 may be included alone, the compound may be included in a combination of two or more different types, or the compound may be included in a combination of two or more other compounds.

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

< Synthesis example >

The final product represented by Chemical Formula 1 according to the present invention may be synthesized as shown in Scheme 1 below, but is not limited thereto.

<Scheme 1>

In Scheme 1, m is n-1.

The compound represented by SUB I according to the present invention may be prepared as in Scheme 2 below, but is not limited thereto.

<Scheme 2>

1. SUB I-1 Synthesis example

1) In an argon atmosphere, 2-bromoaniline (73.6 g, 427.7 mmol) was dissolved in toluene (800 ml) in a round bottom flask, and then 1-bromo-9-chloro-3H-benzo[e]indole (80 g, 285.2) mmol), Pd(OAc) ₂ (3.20 g, 14.3 mmol), BINAP(2,2′-bis(diphenylphosphino)-1,1′-binaphthyl) (13.3 g, 21.4 mmol) and NaOt-Bu (38.4 g, 399.2 mmol) and stirred at 100 °C. After completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was subjected to silica gel column and recrystallization to obtain 44.5 g of SUB I-1-4 (yield: 42%). .

2) To a round bottom flask was added SUB I-1-4 (44.5 g, 215.3 mmol), Pd(OAc) ₂ (4.83 g, 21.5 mmol) and Na ₂ CO ₃ (31.94 g, 301.4 mmol), and DMF ( 500ml), followed by stirring at 160°C. After completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using silica gel column to obtain 25.7 g of SUB I-1-3 (yield: 74%). .

3) SUB I-1-3 (25.7 g, 88.4 mmol), (2-hydroxyphenyl)boronic acid (13.41 g, 97.2 mmol), Pd ₂ (dba) ₃ (2.4 g, 2.7 mmol), 50 in a round bottom flask % P(t-Bu) ₃ (2.2 ml, 5.3 mmol) and K ₂ CO ₃ (24.4 g, 176.8 mmol) were added, dissolved in 200 ml of THF and 70 ml of H ₂ O, and stirred at 65° C. Upon completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using silica gel column to obtain 24.6 g of SUB I-1-2 (yield: 80%). .

4) SUB I-1-2 (24.6 g, 70.6 mmol) was dissolved in CH ₂ Cl ₂ (500 mL) under an argon atmosphere, and trietylamine (14.8 ml, 105.9 mmol) was added thereto, followed by cooling to 0°C. Triflic anhydride (14.3 ml, 84.7 mmol) was added dropwise while maintaining at 0° C., and the mixture was stirred at room temperature for 12 hours. Upon completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using silica gel column to obtain 27.5 g of SUB I-1-1 (yield 81%).

5) Under argon atmosphere, SUB I-1-1 (27.5 g, 57.2 mmol), Pd ₂ (dba) ₃ (3.14 g, 3.4 mol), X-Phos (2-Dicyclohexylphosphino-2′,4′,6′) -triisopropylbiphenyl) (3.3 g, 6.9 mmol) and K ₃ PO ₄ (36.4 g, 171.6 mmol) were dissolved in xylene (600 mL) and refluxed for 6 hours. After the reaction, the precipitated solid was removed by filtration. This was subjected to silica gel column and recrystallization to obtain 12.8 g of SUB I-1 (yield 68%).

2. SUB I-11 Synthesis example

1) In an argon atmosphere, 2-bromoaniline (86.71 g, 504.0 mmol) was dissolved in toluene (700 ml) in a round-bottom flask, and then 1-bromo-9-chloronaphtho[2,1-b]thiophene (10.0 g, 336.0) mmol), Pd(OAc) ₂ (3.77 g, 16.8 mmol), BINAP (15.7 g, 25.2 mmol) and NaOt-Bu (48.4 g, 504.0 mmol) were added and stirred at 100°C. Upon completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using silica gel column to obtain 62.7 g of SUB I-11-4 (yield: 48%). .

2) To a round bottom flask was added SUB I-11-4 (62.7 g, 161.3 mmol), Pd(OAc) ₂ (3.6 g, 16.1 mmol) and Na ₂ CO ₃ (25.6 g, 241.9 mmol), and DMF ( 300ml), followed by stirring at 160°C. Upon completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was subjected to silica gel column and recrystallization to obtain 33.3 g of SUB I-11-3 (yield: 67%). .

3) SUB I-11-3 (33 g, 108.1 mmol), (2-hydroxyphenyl)boronic acid (3.3 g, 118.9 mmol), Pd ₂ (dba) ₃ (2.9 g, 3.2 mmol), 50 in a round bottom flask % P(t-Bu) ₃ (2.6 ml, 6.5 mmol) and K ₂ CO ₃ (29.9 g, 216.1 mmol) were added, dissolved in THF 200 ml and H ₂ O 70 ml, and stirred at 65° C. After completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using silica gel column to obtain 28.8 g of SUB I-11-2 (yield: 73%). .

4) SUB I-11-2 (28.0 g, 76.7 mmol) was dissolved in CH ₂ Cl ₂ (200 mL) under an argon atmosphere, Trietylamine (16.0 ml, 115.1 mmol) was added, and the mixture was cooled to 0°C. Triflic anhydride (15.5 ml, 25.98 mmol) was added dropwise while maintaining the temperature at 0°C, and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was subjected to silica gel column and recrystallization to obtain SUB I-11-1 (27.1 g, yield 71%). .

5) under argon atmosphere, SUB I-11-1 (27 g, 54.5 mmol), Pd ₂ (dba) ₃ (2.5 g, 2.7 mol), X-Phos (2.6 g, 5.4 mmol) and K ₃ PO ₄ ( 34.7 g, 163.4 mmol) was dissolved in xylene (110 mL) and refluxed for 6 hours. After the reaction, the precipitated solid was removed by filtration. This was subjected to silica gel column and recrystallization to obtain SUB I-11 (11.9 g, yield 63%).

3. SUB I-14 Synthesis example

1) In an argon atmosphere, after dissolving 2-bromo-4-chloroaniline (88.46 g, 428.4 mmol) in toluene (800 ml) in a round-bottom flask, 1-bromo-9-chloronaphtho[2,1-b]thiophene ( 85.0 g, 285.6 mmol), Pd(OAc) ₂ (3.2 g, 14.3 mmol), BINAP (13.3 g, 21.4 mmol) and NaOt-Bu (41.2 g, 428.4 mmol) were added and stirred at 100°C. After completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was subjected to silica gel column and recrystallization to obtain 39.9 g of SUB I-14-4 (yield: 33%). .

2) In a round bottom flask, SUB I-14-4 (35 g, 82.7 mmol), Pd(OAc) ₂ (1.86 g, 8.3 mmol) and Na ₂ CO ₃ (12.3 g, 115.8 mmol) were added and DMF (500ml) ), and then stirred at 160 °C. After completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using silica gel column to obtain 19.8 g of SUB I-14-3 (yield: 70%). .

3) SUB I-14-3 (19 g, 55.5 mmol), (2-hydroxyphenyl)boronic acid (8.4 g, 61.1 mmol), Pd ₂ (dba) ₃ (1.5 g, 1.7 mmol), 50 in a round bottom flask % P(t-Bu) ₃ (1.4 ml, 3.3 mmol) and K ₂ CO ₃ (23.0 g, 166.5 mmol) were added, dissolved in 150 ml of THF and 50 ml of H 2 O, and stirred at 65° C. After completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using silica gel column to obtain 18.6 g of SUB I-14-2 (yield: 84%). .

4) SUB I-14-2 (18.6 g, 46.5 mmol) was dissolved in CH ₂ Cl ₂ (500 mL) under an argon atmosphere, Trietylamine (9.7 ml, 69.8 mmol) was added, and the mixture was cooled to 0°C. Triflic anhydride (9.4 ml, 55.8 mmol) was added dropwise while maintaining the temperature at 0°C, and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was subjected to silica gel column and recrystallization to obtain SUB I-14-1 (19.5 g, yield 79%). .

5) under argon atmosphere, SUB I-14-1 (19 g, 35.7 mmol), Pd ₂ (dba) ₃ (2.0 g, 2.1 mol), X-Phos (2.0 g, 4.3 mmol) and K ₃ PO ₄ ( 22.7 g, 107.2 mmol) was dissolved in xylene (200 mL) and refluxed for 6 hours. After the reaction, the precipitated solid was filtered off. This was subjected to silica gel column and recrystallization to obtain SUB I-14 (8.3 g, yield 61%).

4. SUB I-25 Synthesis example

1) In an argon atmosphere, 2-bromoaniline (85.2 g, 495.5 mmol) was dissolved in toluene (800 ml) in a round-bottom flask, and then 1-bromo-9-chloronaphtho[2,1-b]furan (93.0 g, 330.3) mmol), Pd(OAc) ₂ (3.7 g, 16.5 mmol), BINAP (15.4 g, 24.8 mmol) and NaOt-Bu (47.6 g, 495.5 mmol) were added and stirred at 100°C. After completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using silica gel column to obtain 33.2 g of SUB I-25-4 (yield: 27%). .

2) To a round bottom flask was added SUB I-25-4 (33 g, 88.6 mmol), Pd(OAc) ₂ (2.0 g, 8.9 mmol) and Na ₂ CO ₃ (14.1 g, 132.8 mmol), and DMF ( 500ml) and stirred at 160°C. After completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was subjected to silica gel column and recrystallization to obtain 17.6 g of SUB I-25-3 (yield: 68%). .

3) In a round bottom flask, SUB I-25-3 (17.6 g, 60.3mmol), (5-chloro-2-hydroxyphenyl)boronic acid (11.5 g, 66.4 mmol), Pd ₂ (dba) ₃ (1.8 g, 1.7 mmol), 50% P(t-Bu) ₃ (1.5 ml, 3.6 mmol) and K ₂ CO ₃ (25.0 g, 181.0 mmol) were added, dissolved in 150 ml of THF and 50 ml of H ₂ O, and stirred at 65° C. After completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using silica gel column to obtain 16.4 g of SUB I-25-2 (yield: 71%). .

4) SUB I-25-2 (16 g, 41.7 mmol) was dissolved in CH ₂ Cl ₂ (500 mL) under an argon atmosphere, Trietylamine (8.7 ml, 62.5 mmol) was added, and the mixture was cooled to 0°C. Triflic anhydride (8.4 ml, 50 mmol) was added dropwise while maintaining at 0°C, and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was subjected to silica gel column and recrystallization to obtain SUB I-25-1 (15.9 g, yield 74%). .

5) under argon atmosphere, SUB I-25-1 (15.5 g, 30 mmol), Pd ₂ (dba) ₃ (1.4 g, 1.5 mol), X-Phos (1.7 g, 3.6 mmol) and K ₃ PO ₄ ( 19.1 g, 90.1 mmol) was dissolved in xylene (100 mL) and refluxed for 6 hours. After the reaction, the precipitated solid was removed by filtration. This was subjected to silica gel column and recrystallization to obtain SUB I-14 (10.9 g, yield 64%).

5. SUB I-38 Synthesis example

1) In an argon atmosphere, 2-bromoaniline (104.3 g, 606.0 mmol) was dissolved in toluene (800 ml) in a round-bottom flask, and then 1-bromo-9-chloronaphtho[2,1-b]thiophene (100.0 g, 404) mmol), Pd(OAc) ₂ (4.5 g, 20.2 mmol), BINAP (18.9 g, 30.3 mmol) and NaOt-Bu (58.2 g, 606.0 mmol) were added and stirred at 100°C. After completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was subjected to silica gel column and recrystallization to obtain 50.6 g of SUB I-38-4 (yield: 37%). .

2) To a round bottom flask was added SUB I-38-4 (50 g, 147.6 mmol), Pd(OAc) ₂ (3.3 g, 14.8 mmol) and Na ₂ CO ₃ (23.5 g, 221.5 mmol), and DMF ( 700ml) and stirred at 160°C. After completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was subjected to silica gel column and recrystallization to obtain 24.7 g of SUB I-38-3 (yield: 65%). .

3) SUB I-38-3 (24.5 g, 95.1 mmol), (2-hydroxyphenyl)boronic acid (14.4 g, 104.6 mmol), Pd ₂ (dba) ₃ (2.6 g, 2.9 mmol), 50 in a round bottom flask % P(t-Bu) ₃ (2.3 ml, 5.7 mmol) and K ₂ CO ₃ (39.4 g, 142.6 mmol) were added, dissolved in THF 300 ml and H ₂ O 100 ml, and stirred at 65° C. After completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was subjected to silica gel column and recrystallization to obtain 29.4 g of SUB I-38-2 (yield: 79%). .

4) SUB I-38-2 (29 g, 74.1 mmol) was dissolved in CH ₂ Cl ₂ (500 mL) under an argon atmosphere, Trietylamine (15.5 ml, 111.1 mmol) was added, and the mixture was cooled to 0°C. Triflic anhydride (15 ml, 88.9 mmol) was added dropwise while maintaining at 0° C., followed by stirring at room temperature for 12 hours. After completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was subjected to silica gel column and recrystallization to obtain SUB I-38-1 (23.6 g, yield 79%). .

5) under argon atmosphere, SUB I-38-1 (23.6 g, 57.3 mmol), Pd ₂ (dba) ₃ (1.6 g, 1.7 mmol), X-Phos (3.3 g, 6.9 mmol) and K ₃ PO ₄ ( 36.5 g, 171.9 mmol) was dissolved in xylene (150 mL) and refluxed for 6 hours. After the reaction, the precipitated solid was filtered off. This was subjected to silica gel column and recrystallization to obtain SUB I-38 (13.8 g, yield 59%).

6. SUB I-51 Synthesis example

1) In an argon atmosphere, 2-bromoaniline (134.3 g, 780.9 mmol) was dissolved in toluene (900 ml) in a round bottom flask, and then 3-bromo-4-chloro-1H-indole (120.0 g, 520.6 mmol), Pd (OAc) ₂ (5.8 g, 26.0 mmol), BINAP (24.3 g, 39.0 mmol) and NaOt-Bu (75.1 g, 780.9 mmol) were added and stirred at 100°C. After completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was subjected to silica gel column and recrystallization to obtain SUB I-51-4 g 78.7 (yield: 47%). .

2) To a round bottom flask was added SUB I-51-4 (78.7 g, 244.7 mmol), Pd(OAc) ₂ (5.5 g, 24.5 mmol) and Na ₂ CO ₃ (38.9 g, 367.0 mmol), and DMF ( 700ml), followed by stirring at 160°C. After completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using silica gel column to obtain 35.9 g of SUB I-51-3 (yield: 61%). .

3) SUB I-51-3 (35.9 g, 149.3 mmol), 2-(phenylamino)phenol (41.5 g, 223.9 mmol), Pd ₂ (dba) ₃ (4.1 g, 4.5 mmol), 50% in a round bottom flask P(t-Bu) ₃ (3.6 ml, 9.0 mmol) and NaOt-Bu (28.7 g, 298.5 mmol) were added, dissolved in 300 ml of toluene, and stirred at 110°C. After completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using silica gel column to obtain 22.1 g of SUB I-51-2 (yield: 38%). .

4) SUB I-51-2 (22 g, 56.7 mmol) was dissolved in CH ₂ Cl ₂ (500 mL) under an argon atmosphere, Trietylamine (12 ml, 85.1 mmol) was added, and the mixture was cooled to 0°C. While maintaining at 0°C, Triflic anhydride (11.5 ml, 68.1 mmol) was added dropwise, followed by stirring at room temperature for 12 hours. After completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized by silica gel column to obtain SUB I-51-1 (19.8 g, yield 67%). .

5) under argon atmosphere, SUB I-51-1 (19.8 g, 38.0 mmol), Pd ₂ (dba) ₃ (1.7 g, 1.9 mmol), X-Phos (1.8 g, 3.8 mmol) and K ₃ PO ₄ ( 24.2 g, 114.0 mmol) was dissolved in xylene (100 mL) and refluxed for 6 hours. After the reaction, the precipitated solid was filtered off. This was subjected to silica gel column and recrystallization to obtain SUB I-51 (6.8 g, yield 48%).

On the other hand, the compound belonging to Sub I may be a compound as follows, but is not limited thereto.

Table 1 below shows FD-MS values of compounds belonging to Sub I.

compound FD-MS compound FD-MS SUB I-1 m/z=330.12 (C ₂₄ H ₁₄ N ₂ =330.39) SUB I-2 m/z=408.03 (C ₂₄ H ₁₃ BrN ₂ =409.29) SUB I-3 m/z=408.03 (C ₂₄ H ₁₃ BrN ₂ =409.29) SUB I-4 m/z=364.08 (C ₂₄ H ₁₃ ClN ₂ =364.83) SUB I-5 m/z=380.13 (C ₂₈ H ₁₆ N ₂ =380.45) SUB I-6 m/z=380.13 (C ₂₈ H ₁₆ N ₂ =380.45) SUB I-7 m/z=380.13 (C ₂₈ H ₁₆ N ₂ =380.45) SUB I-8 m/z=380.13 (C ₂₈ H ₁₆ N ₂ =380.45) SUB I-9 m/z=364.08 (C ₂₄ H ₁₃ ClN ₂ =364.83) SUB I-10 m/z=380.13 (C ₂₈ H ₁₆ N ₂ =380.45) SUB I-11 m/z=347.08 (C ₂₄ H ₁₃ NS=347.44) SUB I-12 m/z=424.99 (C ₂₄ H ₁₂ BrNS=426.33) SUB I-13 m/z=424.99 (C ₂₄ H ₁₂ BrNS=426.33) SUB I-14 m/z=381.04 (C ₂₄ H ₁₂ ClNS=381.88) SUB I-15 m/z=381.04 (C ₂₄ H ₁₂ ClNS=381.88) SUB I-16 m/z=397.09 (C ₂₈ H ₁₅ NS=397.5) SUB I-17 m/z=397.09 (C ₂₈ H ₁₅ NS=397.5) SUB I-18 m/z=397.09 (C ₂₈ H ₁₅ NS=397.5) SUB I-19 m/z=397.09 (C ₂₈ H ₁₅ NS=397.5) SUB I-20 m/z=437.09 (C ₃₀ H ₁₅ NOS=437.52) SUB I-21 m/z=331.10 (C ₂₄ H ₁₃ NO=331.37) SUB I-22 m/z=409.01 (C ₂₄ H ₁₂ BrNO=410.27) SUB I-23 m/z=409.01 (C ₂₄ H ₁₂ BrNO=410.27) SUB I-24 m/z=365.06 (C ₂₄ H ₁₂ ClNO=365.82) SUB I-25 m/z=365.06 (C ₂₄ H ₁₂ ClNO=365.82) SUB I-26 m/z=381.12 (C ₂₈ H ₁₅ NO=381.43) SUB I-27 m/z=381.12 (C ₂₈ H ₁₅ NO=381.43) SUB I-28 m/z=381.12 (C ₂₈ H ₁₅ NO=381.43) SUB I-29 m/z=431.13 (C ₃₂ H ₁₇ NO=431.49) SUB I-30 m/z=437.09 (C ₃₀ H ₁₅ NOS=437.52) SUB I-31 m/z=356.13 (C ₂₆ H ₁₆ N ₂ =356.43) SUB I-32 m/z=434.04 (C ₂₆ H ₁₅ BrN ₂ =435.32) SUB I-33 m/z=390.09 (C ₂₆ H ₁₅ ClN ₂ =390.87) SUB I-34 m/z=406.15 (C ₃₀ H ₁₈ N ₂ =406.49) SUB I-35 m/z=406.15 (C ₃₀ H ₁₈ N ₂ =406.49) SUB I-36 m/z=373.09 (C ₂₆ H ₁₅ NS=373.47) SUB I-37 m/z=451.00 (C ₂₆ H ₁₄ BrNS=452.37) SUB I-38 m/z=407.05 (C ₂₆ H ₁₄ ClNS=407.92) SUB I-39 m/z=501.02 (C ₃₀ H ₁₆ BrNS=502.43) SUB I-40 m/z=501.02 (C ₃₀ H ₁₆ BrNS=502.43) SUB I-41 m/z=357.12 (C ₂₆ H ₁₅ NO=357.41) SUB I-42 m/z=435.03 (C ₂₆ H ₁₄ BrNO=436.31) SUB I-43 m/z=391.08 (C ₂₆ H ₁₄ ClNO=391.85) SUB I-44 m/z=485.04 (C ₃₀ H ₁₆ BrNO=486.37) SUB I-45 m/z=485.04 (C ₃₀ H ₁₆ BrNO=486.37) SUB I-46 m/z=370.11 (C ₂₆ H ₁₄ N ₂ O=370.41) SUB I-47 m/z=386.09 (C ₂₆ H ₁₄ N ₂ S=386.47) SUB I-48 m/z=371.09 (C ₂₆ H ₁₃ NO ₂ =371.40) SUB I-49 m/z=387.07 (C ₂₆ H ₁₃ NOS=387.46) SUB I-50 m/z=387.07 (C ₂₆ H ₁₃ NOS=387.46) SUB I-51 m/z=371.14 (C ₂₆ H ₁₇ N ₃ =371.44) SUB I-52 m/z=312.07 (C ₂₀ H ₁₂ N ₂ S=312.39) SUB I-53 m/z=296.09 (C ₂₀ H ₁₂ N ₂ O=296.33) SUB I-54 m/z=372.13 (C ₂₆ H ₁₆ N ₂ O=372.43) SUB I-55 m/z=388.10 (C ₂₆ H ₁₆ N ₂ S=388.49) SUB I-56 m/z=472.10 (C ₃₃ H ₁₆ N ₂ S=472.57) SUB I-57 m/z=360.13 (C ₂₅ H ₁₆ N ₂ O=360.42) SUB I-58 m/z=499.08 (C ₃₂ H ₁₅ ClFNO ₂ =499.93) SUB I-59 m/z=365.07 (C ₂₄ H ₁₂ FNS=365.43) SUB I-60 m/z=344.13 (C ₂₅ H ₁₆ N ₂ =344.42)

On the other hand, the compound belonging to Sub II may be a compound as follows, but is not limited thereto.

Table 2 below shows FD-MS values of compounds belonging to Sub II.

compound FD-MS compound FD-MS SUB II-1 m/z=112.01 (C ₆ H ₅ Cl=112.56) SUB II-2 m/z=188.04 (C ₁₂ H ₉ Cl=188.65) SUB II-3 m/z=113.00 (C ₅ H ₄ ClN=113.54) SUB II-4 m/z=189.03 (C ₁₁ H ₈ ClN=189.64) SUB II-5 m/z=163.02 (C ₉ H ₆ ClN=163.6) SUB II-6 m/z=114.00 (C ₄ H ₃ ClN ₂ =114.53) SUB II-7 m/z=266.06 (C ₁₆ H ₁₁ ClN ₂ =266.73) SUB II-8 m/z=392.11 (C ₂₆ H ₁₇ ClN ₂ =392.89) SUB II-9 m/z=267.06 (C ₁₅ H ₁₀ ClN ₃ =267.72) SUB II-10 m/z=317.07 (C ₁₉ H ₁₂ ClN ₃ =317.78) SUB II-11 m/z=353.14 (C ₂₁ H ₁₄ BN ₃ O ₂ =353.19) SUB II-12 m/z=393.1 (C ₂₅ H ₁₆ ClN ₃ =393.87) SUB II-13 m/z=228.05 (C ₁₃ H ₉ ClN ₂ =228.68) SUB II-14 m/z=240.05 (C ₁₄ H ₉ ClN ₂ =240.69) SUB II-15 m/z=346.03 (C ₂₀ H ₁₁ ClN ₂ S=346.83) SUB II-16 m/z=240.05 (C ₁₄ H ₉ ClN ₂ =240.69) SUB II-17 m/z=240.05 (C ₁₄ H ₉ ClN ₂ =240.69) SUB II-18 m/z=316.08 (C ₂₀ H ₁₃ ClN ₂ =316.79) SUB II-19 m/z=290.06 (C ₁₈ H ₁₁ ClN ₂ =290.75) SUB II-20 m/z=308.05 (C ₁₈ H ₁₀ ClFN ₂ =308.74) SUB II-21 m/z=290.06 (C ₁₈ H ₁₁ ClN ₂ =290.75) SUB II-22 m/z=290.06 (C ₁₈ H ₁₁ ClN ₂ =290.75) SUB II-23 m/z=290.06 (C ₁₈ H ₁₁ ClN ₂ =290.75) SUB II-24 m/z=238.03 (C ₁₄ H ₇ ClN ₂ =238.67) SUB II-25 m/z=296.02 (C ₁₆ H ₉ ClN ₂ S=296.77) SUB II-26 m/z=310.03 (C ₁₇ H ₁₁ ClN ₂ S=310.8) SUB II-27 m/z=296.02 (C ₁₆ H ₉ ClN ₂ S=296.77) SUB II-28 m/z=280.04 (C ₁₆ H ₉ ClN ₂ O=280.71) SUB II-29 m/z=218.99 (C ₁₁ H ₆ ClNS=219.69) SUB II-30 m/z=216.02 (C ₁₀ H ₅ ClN ₄ =216.63) SUB II-31 m/z=261.95 (C ₁₂ H ₇ BrS=263.15) SUB II-32 m/z=322.00 (C ₁₈ H ₁₁ BrO=323.19) SUB II-33 m/z=311.96 (C ₁₆ H ₉ BrS=313.21) SUB II-34 m/z=295.98 (C ₁₆ H ₉ BrO=297.15) SUB II-35 m/z=278.05 (C ₁₈ H ₁₁ ClO=278.74) SUB II-36 m/z=353.10 (C ₂₄ H ₁₆ ClN=353.85) SUB II-37 m/z=241.04 (C ₁₃ H ₈ ClN ₃ =241.68) SUB II-38 m/z=241.04 (C ₁₃ H ₈ ClN ₃ =241.68) SUB II-39 m/z=242.04 (C ₁₂ H ₇ ClN ₄ =242.67) SUB II-40 m/z=316.08 (C ₂₀ H ₁₃ ClN ₂ =316.79) SUB II-41 m/z=219.99 (C ₁₀ H ₅ ClN ₂ S=220.67) SUB II-42 m/z=296.98 (C ₁₅ H ₈ BrNO=298.14) SUB II-43 m/z=275.08 (C ₁₈ H ₁₃ NS=275.37) SUB II-44 m/z=351.11 (C ₂₄ H ₁₇ NS=351.47) SUB II-45 m/z=375.11 (C ₂₆ H ₁₇ NS=375.49) SUB II-46 m/z=427.14 (C ₃₀ H ₂₁ NS=427.57) SUB II-47 m/z=401.12 (C ₂₈ H ₁₉ NS=401.53) SUB II-48 m/z=352.10 (C ₂₃ H ₁₆ N ₂ S=352.46) SUB II-49 m/z=381.06 (C ₂₄ H ₁₅ NS ₂ =381.51) SUB II-50 m/z=457.10 (C ₃₀ H ₁₉ NS ₂ =457.61) SUB II-51 m/z=351.11 (C ₂₄ H ₁₇ NS=351.47) SUB II-52 m/z=275.08 (C ₁₈ H ₁₃ NS=275.37) SUB II-53 m/z=351.11 (C ₂₄ H ₁₇ NS=351.47) SUB II-54 m/z=325.09 (C ₂₂ H ₁₅ NS=325.43) SUB II-55 m/z=293.07 (C ₁₈ H ₁₂ FNS=293.36) SUB II-56 m/z=401.12 (C ₂₈ H ₁₉ NS=401.53) SUB II-57 m/z=402.12 (C ₂₇ H ₁₈ N ₂ S=402.52) SUB II-58 m/z=351.11 (C ₂₄ H ₁₇ NS=351.47) SUB II-59 m/z=275.08 (C ₁₈ H ₁₃ NS=275.37) SUB II-60 m/z=289.09 (C ₁₉ H ₁₅ NS=289.40) SUB II-61 m/z=325.09 (C ₂₂ H ₁₅ NS=325.43) SUB II-62 m/z=351.11 (C ₂₄ H ₁₇ NS=351.47) SUB II-63 m/z=325.09 (C ₂₂ H ₁₅ NS=325.43) SUB II-64 m/z=351.11 (C ₂₄ H ₁₇ NS=351.47) SUB II-65 m/z=325.09 (C ₂₂ H ₁₅ NS=325.43) SUB II-66 m/z=275.08 (C ₁₈ H ₁₃ NS=275.37) SUB II-67 m/z=259.10 (C ₁₈ H ₁₃ NO=259.31) SUB II-68 m/z=259.10 (C ₁₈ H ₁₃ NO=259.31) SUB II-69 m/z=425.14 (C ₃₀ H ₁₉ NO ₂ =425.49) SUB II-70 m/z=359.13 (C ₂₆ H ₁₇ NO=359.43) SUB II-71 m/z=335.13 (C ₂₄ H ₁₇ NO=335.41) SUB II-72 m/z=385.15 (C ₂₈ H ₁₉ N ₂ O=385.47) SUB II-73 m/z=169.09 (C ₃₁₂ H ₁₁ N=169.23) SUB II-74 m/z=245.12 (C ₁₈ H ₁₅ N=245.33) SUB II-75 m/z=219.10 (C ₁₆ H ₁₃ N=219.29) SUB II-76 m/z=245.12 (C ₁₈ H ₁₅ N=245.33) SUB II-77 m/z=246.12 (C ₁₇ H14N ₂ =246.31) SUB II-78 m/z=321.15 (C ₂₄ H ₁₉ N=321.42) SUB II-79 m/z=269.12 (C ₂₀ H ₁₅ N ₃ =269.35) SUB II-80 m/z=183.10 (C ₁₃ H ₁₃ N=183.25) SUB II-81 m/z=245.12 (C ₁₈ H ₁₅ N=245.33) SUB II-82 m/z=269.12 (C ₂₀ H ₁₅ N ₂ S=269.35) SUB II-83 m/z=336.16 (C ₂₄ H ₂₀ N ₂ =336.44) SUB II-84 m/z=336.16 (C ₂₄ H ₂₀ N ₂ =336.44) SUB II-85 m/z=412.19 (C ₃₀ H ₂₄ N ₂ =412.54 ) SUB II-86 m/z=289.09 (C ₁₉ H ₁₅ NS=289.40) SUB II-87 m/z=174.12 (C ₁₂ H ₆ D ₅ N=174.26 ) SUB II-88 m/z=195.10 (C ₁₄ H ₁₃ N=195.27 ) SUB II-89 m/z=407.17 (C ₃₁ H ₂₁ N=407.52) SUB II-90 m/z=285.15 (C ₂₁ H ₁₉ N=285.39) SUB II-91 m/z=409.18 (C ₃₁ H ₂₃ N=409.53) SUB II-92 m/z=386.18 (C ₂₈ H ₂₂ N ₂ =386.50) SUB II-93 m/z=346.03 (C ₂₀ H ₁₁ ClN ₂ S=346.83) SUB II-94 m/z=310.03 (C ₁₇ H ₁₁ ClN ₂ S=310.80) SUB II-95 m/z=308.05 (C ₁₈ H ₁₀ ClFN ₂ =308.74) SUB II-96 m/z=240.05 (C ₁₄ H ₉ ClN ₂ =240.69) SUB II-97 m/z=164.01 (C ₈ H ₅ ClN ₂ =164.59) SUB II-98 m/z=208.02 (C ₁₀ H ₆ ClFN ₂ =208.62) SUB II-99 m/z=128.10 (C ₆ H ₁₃ BO ₂ =127.98) SUB II-100 m/z=199.08 (C ₁₁ H ₁₀ BNO ₂ =199.02) SUB II-101 m/z=190.03 (C ₁₀ H ₇ ClN ₂ =190.63) SUB II-102 m/z=248.10 (C ₁₆ H ₁₃ BO ₂ =248.09)

III. Final compound synthesis

1. P-7 Synthesis example

After dissolving SUB I-1 (5.0 g, 15.1 mmol) in toluene (30 ml) in a round bottom flask, SUB II-9 (4.5 g, 16.6 mmol), Pd ₂ (dba) ₃ (0.42 g, 0.5 mmol) , 50% P(t-Bu) ₃ (0.4 ml, 0.9 mmol) and NaOt-Bu (2.2 g, 22.7 mmol) were added and stirred at 110°C. Upon completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was subjected to silica gel column and recrystallization to obtain 5.6 g of product P-7 (yield: 68%).

2. P-37 Synthesis example

1) SUB I-11 (10 g, 28.8 mmol) was completely dissolved in 300 ml of THF in a round-bottom flask, and N-bromoSuccinimide (5.12 g, 28.8 mmol) was added dropwise, followed by stirring at room temperature for 16 hours. Upon completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized to obtain 13.4 g of a product SUB I-12 (yield: 91%).

2) After dissolving SUB I-12 (7.0 g, 16.4 mmol) in toluene (30 ml) in a round bottom flask, SUB II-11 (6.4 g, 18.1 mmol), Pd ₂ (dba) ₃ (0.45 g, 0.5) mmol), 50% P(t-Bu) ₃ (0.4 ml, 1.0 mmol), K ₂ CO ₃ (4.5 g, 32.8 mmol) and 10 ml water were added and stirred at 110° C. Upon completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was subjected to silica gel column and recrystallization to obtain 7.6 g of product P-37 (yield: 71%).

3. P-44 Synthesis example

After dissolving SUB I-14 (8.0 g, 20.9 mmol) in toluene (40 ml) in a round bottom flask, SUB II-76 (5.6 g, 23.0 mmol), Pd ₂ (dba) ₃ (0.6 g, 0.6 mmol) , 50% P(t-Bu) ₃ (0.5 ml, 1.3 mmol) and NaOt-Bu (3.0 g, 31.4 mmol) were added and stirred at 110°C. Upon completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was subjected to silica gel column and recrystallization to obtain 8.7 g of product P-44 (yield: 70%).

4. P-46 Synthesis example

1) SUB I-25 (10.0 g, 27.3 mmol) was dissolved in aqueous toluene (60 ml) in a round bottom flask, and then Bis(Pinacolato)diboron (13.9 g, 54.7 mmol), Pd ₂ (dba) ₃ (0.5 g) , 0.5 mmol), X-Phos (0.5 g, 1.1 mmol) and KOAc (8.05 g, 82.0 mmol) were added and stirred at 110°C. Upon completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was subjected to silica gel column and recrystallization to obtain 9.7 g of the product SUB I-25-B (yield: 78%). got it

2) After dissolving SUB I-25-B (9.7 g, 21.2 mmol) in toluene (40 ml) in a round bottom flask, SUB II-10 (7.4 g, 23.3 mmol), Pd ₂ (dba) ₃ (0.58 g) , 0.6 mmol), 50% P(t-Bu) ₃ (0.5 ml, 1.3 mmol), K ₂ CO ₃ (3.4 g, 31.8 mmol) and 15 ml of water were added and stirred at 110°C. Upon completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized using silica gel column to obtain 8.3 g of product P-46 (yield: 64%).

5. P-114 Synthesis example

1) SUB I-38 (20.0 g, 49.0 mmol) was dissolved in toluene (150 ml) in a round bottom flask, (2-nitrophenyl)boronic acid (12.3 g, 73.5 mmol), Pd ₂ (dba) ₃ (1.35) g, 4.5 mmol), 50% P(t-Bu) ₃ (1.2 ml, 2.9 mmol), K ₂ CO ₃ (13.6 g, 98.1 mmol) and 50 ml water were added and stirred at 110° C. Upon completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was subjected to silica gel column and recrystallization to obtain 15.3 g of product P-114-2 (yield: 62%). .

2) P-114-2 (15.0 g, 30.3 mmol) was dissolved in xylene (100 ml) in a round bottom flask, and triphenylphosphine (23.9 g, 91 mmol) was added thereto, followed by stirring at 160°C. After completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was subjected to silica gel column and recrystallization to obtain 10.1 g of product P-114-1 (yield: 72%). .

3) After dissolving P-114-1 (10.0 g, 21.6 mmol) in toluene (40 ml) in a round bottom flask, bromobenzene (4.07 g, 25.9 mmol), Pd ₂ (dba) ₃ (0.59 g, 0.6 mmol) , 50% P(t-Bu) ₃ (0.5 ml, 1.3 mmol) and NaOt-Bu (3.1 g, 32.4 mmol) were added and stirred at 110°C. Upon completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was subjected to silica gel column and recrystallization to obtain 6.4 g of product P-114 (yield: 64%).

6. P-116 Synthesis example

After dissolving SUB I-51 (6.0 g, 16.2 mmol) in toluene (30 ml) in a round bottom flask, SUB II-25 (5.3 g, 17.8 mmol), Pd ₂ (dba) ₃ (0.4 g, 0.5 mmol) , 50% P(t-Bu) ₃ (0.4 ml, 1.0 mmol) and NaOt-Bu (2.3 g, 24.2 mmol) were added and stirred at 110°C. Upon completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was subjected to silica gel column and recrystallization to obtain 5.8 g of product P-116 (yield: 57%).

7. P-117 Synthesis example

After dissolving SUB I-38 (6.0 g, 14.7 mmol) in THF (100 ml) in a round bottom flask, (1-phenylnaphthalen-2-yl)boronic acid (4.0 g, 16.2 mmol), Pd(PPh ₃ ) ₄ (0.5 g, 0.4 mmol), NaOH (1.7 g, 44.1 mmol) and 30 ml of water were added and stirred at 65°C. Upon completion of the reaction, after extraction with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was subjected to silica gel column and recrystallization to obtain 5.5 g of a product P-117 (yield: 59%).

Meanwhile, the FD-MS values of the compounds P-1 to P-120 of the present invention prepared according to the above synthesis examples are shown in Table 3 below.

compound FD-MS compound FD-MS P-1 m/z=406.15 (C ₃₀ H ₁₈ N ₂ =406.49) P-2 m/z=406.15 (C ₃₀ H ₁₈ N ₂ =406.49) P-3 m/z=407.14 (C ₂₉ H ₁₇ N ₃ =407.48) P-4 m/z=483.17 (C ₃₅ H ₂₁ N ₃ =483.57) P-5 m/z=408.14 (C ₂₈ H ₁₆ N ₄ =408.46) P-6 m/z=560.20 (C ₄₀ H ₂₄ N ₄ =560.66) P-7 m/z=561.20 (C ₃₉ H ₂₃ N ₅ =561.65) P-8 m/z=611.21 (C ₄₃ H ₂₅ N ₅ =611.71) P-9 m/z=637.23 (C ₄₅ H ₂₇ N ₅ =637.75) P-10 m/z=687.24 (C ₄₉ H ₂₉ N ₅ =687.81) P-11 m/z=522.18 (C ₃₇ H ₂₂ N ₄ =522.61) P-12 m/z=534.18 (C ₃₈ H ₂₂ N ₄ =534.62) P-13 m/z=534.18 (C ₃₈ H ₂₂ N ₄ =534.62) P-14 m/z=534.18 (C ₃₈ H ₂₂ N ₄ =534.62) P-15 m/z=610.22 (C ₄₄ H ₂₆ N ₄ =610.72) P-16 m/z=584.20 (C ₄₂ H ₂₄ N ₄ =584.68) P-17 m/z=584.20 (C ₄₂ H ₂₄ N ₄ =584.68) P-18 m/z=584.20 (C ₄₂ H ₂₄ N ₄ =584.68) P-19 m/z=584.20 (C ₄₂ H ₂₄ N ₄ =584.68) P-20 m/z=532.17 (C ₃₈ H ₂₀ N ₄ =532.61) P-21 m/z=590.16 (C ₄₀ H ₂₂ N ₄ S=590.70) P-22 m/z=590.16 (C ₄₀ H ₂₂ N ₄ S=590.7) P-23 m/z=574.18 (C ₄₀ H ₂₂ N ₄ O=574.64) P-24 m/z=513.13 (C ₃₅ H ₁₉ N ₃ S=513.62) P-25 m/z=510.16 (C ₃₄ H ₁₈ N ₆ =510.56) P-26 m/z=562.15 (C ₄₀ H ₂₂ N ₂ S=562.69) P-27 m/z=572.19 (C ₄₂ H ₂₄ N ₂ O=572.67) P-28 m/z=573.22 (C ₄₂ H ₂₇ N ₃ =573.7) P-29 m/z=689.28 (C ₅₁ H ₃₅ N ₃ =689.86) P-30 m/z=647.24 (C ₄₈ H ₂₉ N ₃ =647.78) P-31 m/z=628.17 (C ₄₃ H ₂₄ N ₄ S=628.75) P-32 m/z=654.19 (C ₄₅ H ₂₆ N ₄ S=654.79) P-33 m/z=551.15 (C ₃₈ H ₂₁ N ₃ S=551.67) P-34 m/z=590.18 (C ₄₂ H ₂₆ N ₂ S=590.74) P-35 m/z=590.18 (C ₄₂ H ₂₆ N ₂ S=590.74) P-36 m/z=628.17 (C ₄₃ H ₂₄ N ₄ S=628.75) P-37 m/z=654.19 (C ₄₅ H ₂₆ N ₄ S=654.79) P-38 m/z=551.15 (C ₃₈ H ₂₁ N ₃ S=551.67) P-39 m/z=590.18 (C ₄₂ H ₂₆ N ₂ S=590.74) P-40 m/z=590.18 (C ₄₂ H ₂₆ N ₂ S=590.74) P-41 m/z=628.17 (C ₄₃ H ₂₄ N ₄ S=628.75) P-42 m/z=654.19 (C ₄₅ H ₂₆ N ₄ S=654.79) P-43 m/z=551.15 (C ₃₈ H ₂₁ N ₃ S=551.67) P-44 m/z=590.18 (C ₄₂ H ₂₆ N ₂ S=590.74) P-45 m/z=590.18 (C ₄₂ H ₂₆ N ₂ S=590.74) P-46 m/z=612.20 (C ₄₃ H ₂₄ N ₄ O=612.69) P-47 m/z=638.21 (C ₄₅ H ₂₆ N ₄ O=638.73) P-48 m/z=535.17 (C ₃₈ H ₂₁ N ₃ O=535.61) P-49 m/z=574.20 (C ₄₂ H ₂₆ N ₂ O=574.68) P-50 m/z=574.20 (C ₄₂ H ₂₆ N ₂ O=574.68) P-51 m/z=612.20 (C ₄₃ H ₂₄ N ₄ O=612.69) P-52 m/z=638.21 (C ₄₅ H ₂₆ N ₄ O=638.73) P-53 m/z=535.17 (C ₃₈ H ₂₁ N ₃ O=535.61) P-54 m/z=574.20 (C ₄₂ H ₂₆ N ₂ O=574.68) P-55 m/z=574.20 (C ₄₂ H ₂₆ N ₂ O=574.68) P-56 m/z=612.20 (C ₄₃ H ₂₄ N ₄ O=612.69) P-57 m/z=638.21 (C ₄₅ H ₂₆ N ₄ O=638.73) P-58 m/z=535.17 (C ₃₈ H ₂₁ N ₃ O=535.61) P-59 m/z=574.20 (C ₄₂ H ₂₆ N ₂ O=574.68) P-60 m/z=574.20 (C ₄₂ H ₂₆ N ₂ O=574.68) P-61 m/z=432.16 (C ₃₂ H ₂₀ N ₂ =432.53) P-62 m/z=509.19 (C ₃₇ H ₂₃ N ₃ =509.61) P-63 m/z=482.18 (C ₃₆ H ₂₂ N ₂ =482.59) P-64 m/z=586.22 (C ₄₂ H ₂₆ N ₄ =586.7) P-65 m/z=587.21 (C ₄₁ H ₂₅ N ₅ =587.69) P-66 m/z=637.23 (C ₄₅ H ₂ 7N ₅ =637.75) P-67 m/z=713.26 (C ₅₁ H ₃₁ N ₅ =713.84) P-68 m/z=548.20 (C ₃₉ H ₂₄ N ₄ =548.65) P-69 m/z=560.20 (C ₄₀ H ₂₄ N ₄ =560.66) P-70 m/z=666.19 (C ₄₆ H ₂₆ N ₄ S=666.8) P-71 m/z=560.20 (C ₄₀ H ₂₄ N ₄ =560.66) P-72 m/z=636.23 (C ₄₆ H ₂₈ N ₄ =636.76) P-73 m/z=610.22 (C ₄₄ H ₂₆ N ₄ =610.72) P-74 m/z=630.19 (C ₄₃ H ₂₆ N ₄ S=630.77) P-75 m/z=616.17 (C ₄₂ H ₂₄ N ₄ S=616.74) P-76 m/z=600.20 (C ₄₂ H ₂₄ N ₄ O=600.68) P-77 m/z=538.15 (C ₃₈ H ₂₂ N ₂ S=538.67) P-78 m/z=598.20 (C ₄₄ H ₂₆ N ₂ O=598.71) P-79 m/z=588.17 (C ₄₂ H ₂₄ N ₂ S=588.73) P-80 m/z=572.19 (C ₄₂ H ₂₄ N ₂ O=572.67) P-81 m/z=637.23 (C ₄₅ H ₂₇ N ₅ =637.75) P-82 m/z=558.21 (C ₄₂ H ₂₆ N ₂ =558.68) P-83 m/z=705.22 (C ₅₀ H ₃₁ N ₃ S=705.88) P-84 m/z=610.22 (C ₄₄ H ₂₆ N ₄ =610.72) P-85 m/z=678.22 (C ₄₈ H ₂₇ FN ₄ =678.77) P-86 m/z=423.11 (C ₃₀ H ₁₇ NS=423.53) P-87 m/z=500.13 (C ₃₅ H ₂₀ N ₂ S=500.62) P-88 m/z=577.16 (C ₄₀ H ₂₃ N ₃ S=577.71) P-89 m/z=604.17 (C ₄₁ H ₂₄ N ₄ S=604.73) P-90 m/z=656.23 (C ₄₇ H ₃₂ N ₂ S=656.85) P-91 m/z=617.16 (C ₄₂ H ₂₃ N ₃ OS=617.73) P-92 m/z=577.16 (C ₄₀ H ₂₃ N ₃ S=577.71) P-93 m/z=566.18 (C ₄₀ H ₂₆ N ₂ S=566.72) P-94 m/z=407.13 (C ₃₀ H ₁₇ NO=407.47) P-95 m/z=463.10 (C ₃₂ H ₁₇ NOS=463.55) P-96 m/z=559.19 (C ₄₂ H ₂₅ NO=559.67) P-97 m/z=510.17 (C ₃₇ H ₂₂ N ₂ O=510.60) P-98 m/z=741.28 (C ₅₄ H ₃₅ N ₃ O=741.89) P-99 m/z=485.15 (C ₃₄ H ₁₉ N ₃ O=485.55) P-100 m/z=588.20 (C ₄₁ H ₂₄ N ₄ O=588.67) P-101 m/z=600.20 (C ₄₂ H ₂₄ N ₄ O=600.68) P-102 m/z=538.15 (C ₃₈ H ₂₂ N ₂ S=538.67) P-103 m/z=448.12 (C ₃₁ H ₁₆ N ₂ O ₂ =448.48) P-104 m/z=570.09 (C ₃₇ H ₁₈ N ₂ OS ₂ =570.68) P-105 m/z=559.18 (C ₃₈ H ₁₇ D ₅ N ₂ OS=559.7) P-106 m/z=664.24 (C ₄₅ H29FN4=644.75) P-107 m/z=479.17 (C ₃₄ H ₂₅ NS=479.64) P-108 m/z=574.20 (C ₄₂ H ₂₆ N ₂ O=574.68) P-109 m/z=472.10 (C ₃₃ H ₁₆ N ₂ S=472.57) P-110 m/z=484.12 (C ₃₀ H ₁₇ FN ₄ S=484.55) P-111 m/z=512.19 (C ₃₇ H ₂₄ N ₂ O=512.61) P-112 m/z=618.17 (C ₄₃ H ₂₃ FN ₂ O ₂ =618.67) P-113 m/z=674.25 (C ₄₉ H ₃₀ N ₄ =674.81) P-114 m/z=538.15 (C ₃₈ H ₂₂ N ₂ S=538.67) P-115 m/z=612.17 (C ₄₄ H ₂₄ N ₂ S=612.75) P-116 m/z=631.18 (C ₄₂ H ₂₅ N ₅ S=631.76) P-117 m/z=575.17 (C ₄₂ H ₂₅ NS=575.73) P-118 m/z=562.15 (C ₄₀ H ₂₂ N ₂ S=562.69) P-119 m/z=627.18 (C ₄₄ H ₂₅ N ₃ S=627.77) P-120 m/z=582.21 (C ₄₄ H ₂₆ N ₂ =582.71)

Manufacturing evaluation of organic electric devices

( Example 1) 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, on an ITO layer (anode) formed on a glass substrate, N ¹ -(naphthalen-2-yl)-N ⁴ ,N ⁴ -bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N ¹ -Phenylbenzene-1,4-diamine (hereinafter, 2-TNATA) was vacuum-deposited to a thickness of 60 nm to form a hole injection layer.

4,4-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (hereinafter abbreviated as NPB) as a hole transport compound was vacuum deposited on the hole injection layer to a thickness of 60 nm to form a hole transport layer did

After vacuum deposition of the compound P-1 of the present invention to a thickness of 20 nm on the hole transport layer to form a light-emitting auxiliary layer, 4,4'-N,N'-dicarbazole-biphenyl (hereinafter, CBP) on the light-emitting auxiliary layer ) as a host material, and bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate (hereinafter, (piq) ₂ Ir(acac)) as a dopant material, doped at a 95:5 weight ratio, and vacuum to a thickness of 30 nm A light emitting layer was formed by vapor deposition.

Then, (1,1'-bisphenyl)-4-oleato)bis(2-methyl-8-quinolineoleato)aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm on the light emitting layer to form holes A blocking layer was formed, and tris(8-quinolinol)aluminum (hereinafter abbreviated as Alq3) was vacuum-deposited to a thickness of 40 nm on the hole blocking layer to form an electron transport layer.

Then, an organic electroluminescent device was manufactured by depositing an alkali metal halide LiF to a thickness of 0.2 nm to form an electron injection layer, and then depositing Al to a thickness of 150 nm to form a cathode.

( Example 2) to ( Example 17)

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

( comparative example One)

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

( comparative example 2)

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the following comparative compound A was used instead of the compound P-1 of the present invention as the light emitting auxiliary layer material of Example 1.

<Comparative compound A>

A forward bias DC voltage was applied to the organic electroluminescent devices manufactured according to Examples 1 to 17 and Comparative Examples 1 to 2, and electroluminescence (EL) characteristics were measured with a PR-650 manufactured by photoresearch, 2500cd/ The T95 lifetime was measured using a lifetime measuring device manufactured by McScience at m ² standard luminance, and the measurement results are shown in Table 4 below.

compound drive voltage electric current
(mA/cm ² ) luminance
(cd/m ² ) efficiency
(cd/A) T(95) CIE x y Comparative Example (1) - 6.7 34.2 2500 7.3 75.6 0.61 0.31 Comparative Example (2) Comparative compound A 5.6 16.6 2500 15.1 90.5 0.60 0.34 Example (1) Compound (P-1) 5.0 14.2 2500 17.6 113.8 0.62 0.33 Example (2) Compound (P-26) 5.2 13.5 2500 18.5 109.5 0.62 0.33 Example (3) Compound (P-28) 5.0 14.1 2500 17.7 113.7 0.63 0.33 Example (4) Compound (P-29) 5.0 13.7 2500 18.2 113.6 0.63 0.31 Example (5) Compound (P-39) 5.1 13.6 2500 18.4 108.1 0.61 0.33 Example (6) Compound (P-44) 5.1 13.4 2500 18.6 109.2 0.61 0.35 Example (7) Compound (P-54) 5.2 13.0 2500 19.3 102.9 0.64 0.34 Example (8) Compound (P-59) 5.3 12.8 2500 19.5 104.0 0.64 0.32 Example (9) Compound (P-61) 5.3 14.0 2500 17.8 105.1 0.61 0.35 Example (10) Compound (P-78) 5.2 13.7 2500 18.3 109.3 0.60 0.32 Example (11) Compound (P-80) 5.2 13.5 2500 18.5 107.2 0.61 0.34 Example (12) Compound (P-83) 5.0 14.0 2500 17.9 114.2 0.65 0.34 Example (13) Compound (P-90) 5.2 13.2 2500 19.0 108.0 0.62 0.32 Example (14) Compound (P-98) 5.3 12.8 2500 19.6 101.3 0.63 0.31 Example (15) Compound (P-105) 5.1 13.7 2500 18.3 109.2 0.65 0.32 Example (16) Compound (P-115) 5.4 13.4 2500 18.7 106.2 0.63 0.33 Example (17) Compound (P-120) 5.1 14.0 2500 17.8 112.6 0.63 0.31

As can be seen from the results of Table 4, when a red organic light emitting device was manufactured using the material for an organic light emitting device of the present invention as a light emitting auxiliary layer material, the light emitting auxiliary layer was not used or the comparative compound A was used. It is possible to improve the efficiency and lifespan of the organic light emitting diode than before.

In other words, the results of Comparative Example 2 using Comparative Compound A were superior to those of Comparative Example 1 using no light emitting auxiliary layer, and Examples 1 to 17 of the present compound showed remarkably excellent results in efficiency and lifespan. .

Comparing the comparative compound A and the compound of the present invention, the comparative compound A has a core composed of a five-ring ring, and the compound of the present invention has a structure in which a four- or five-ring ring and a phenyl bonded to N are connected. .

Comparing the core of Comparative Compound A and the core of Compound P-83 of the present invention, it can be shown in Table 5 below.

Core of Comparative Compound A The core of the compound P-83 of the present invention

Dihedral
Angle 27.4 ^o 8.8 ^o

As shown in Table 5, looking at the dihedral angle of the core of the comparative compound A, it can be seen that the phenyl bonded to N and the naphthalene of the 5-ring structure show a structure twisted to 27.4 ^o due to steric hindrance, the compound P of the present invention Looking at the dihedral angle of the core of -83, it can be confirmed that the phenyl bonded to N and the naphthalene of the 5-ring structure are connected to 8.8 ^o . That is, it can be confirmed that the compound of the present invention has improved planarity of the structure of the core compared to Comparative Compound A.

It is judged that as the planarity of the structure is improved, the hole characteristics are improved, and thus holes are moved to the host quickly, and the charge balance of the device is improved, thereby increasing the efficiency. In addition, as the planarity of the structure is improved, the stability of the structure is improved, and it is determined that this affects the lifespan of the device.

In conclusion, it is judged that the superior efficiency and lifespan of the compound of the present invention compared to Comparative Compound A is the result of improved planarity of the structure of the core.

In the case of the light-emitting auxiliary layer, it is necessary to understand the correlation between the hole transport layer and the light-emitting layer (host). It will be very difficult.

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 only to the light-emitting auxiliary layer has been described, but the compound of the present invention may be applied to the hole transport layer or both the hole transport layer and the light emission auxiliary layer may be applied.

( Example 18) red organic light emitting device (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, on an ITO layer (anode) formed on a glass substrate, N ¹ -(naphthalen-2-yl)-N ⁴ , N ⁴ -bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N ¹ -Phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) film was vacuum-deposited to form a hole injection layer with a thickness of 60 nm.

4,4-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (hereinafter abbreviated as NPB) as a hole transport compound on the hole injection layer was vacuum-deposited to a thickness of 60 nm to form a hole transport layer. .

Thereafter, the compound P-8 of the present invention is used as a host material on the hole transport layer, and bis-(1-phenylisoquinolyl) iridium(III)acetylacetonate (hereinafter, abbreviated as “(piq) ₂ Ir(acac)”) is used as a dopant material. was used and doped at a 95:5 weight ratio to deposit a light emitting layer to a thickness of 30 nm.

Next, on the emission layer, (1,1'-bisphenyl)-4-oleato)bis(2-methyl-8-quinolineoleato)aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm to form holes A blocking layer was formed, and tris(8-quinolinol)aluminum (hereinafter abbreviated as Alq3) was deposited as an electron transport layer on the hole blocking layer to a thickness of 40 nm.

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

( Example 19) to ( Example 33)

Example 18 An organic light emitting diode was manufactured in the same manner as in Example 18, except that the compound of the present invention described in Table 6 was used instead of the compound P-8 of the present invention as the host material.

( comparative example 3) and ( comparative example 4)

An organic electroluminescent device was manufactured in the same manner as in Example 18, except that Comparative Compound B and Comparative Compound C were used as host materials of Example 1.

<Comparative compound B> <Comparative compound C>

Electroluminescence (EL) characteristics by applying a forward bias DC voltage to the organic electroluminescent devices manufactured by Examples 18 to 33 and Comparative Examples 3 to 4 of the present invention and PR-650 manufactured by Photoresearch was measured, and the T95 lifespan was measured using a life measuring device of McScience at 2500cd/m ² standard luminance, and the measurement results are shown in Table 6 below.

compound drive voltage electric current
(mA/cm2) luminance
(cd/m2) efficiency
(cd/A) T(95) CIE x y Comparative Example (3) Comparative compound B 6.7 34.2 2500 7.3 75.6 0.64 0.34 Comparative Example (4) Comparative compound C 5.7 15.4 2500 16.2 89.1 0.60 0.31 Example (18) Compound (P-8) 5.2 12.2 2500 20.4 107.7 0.63 0.31 Example (19) Compound (P-12) 5.3 12.6 2500 19.8 108.8 0.60 0.34 Example (20) Compound (P-13) 5.3 12.1 2500 20.7 105.6 0.63 0.33 Example (21) Compound (P-21) 5.5 12.4 2500 20.2 104.6 0.63 0.33 Example (22) Compound (P-36) 5.3 12.8 2500 19.5 98.0 0.62 0.32 Example (23) Compound (P-43) 5.4 12.6 2500 19.8 96.0 0.65 0.33 Example (24) Compound (P-48) 5.6 12.5 2500 20.0 100.8 0.61 0.35 Example (25) Compound (P-51) 5.5 12.6 2500 19.9 102.8 0.60 0.33 Example (26) Compound (P-66) 5.3 12.3 2500 20.4 105.5 0.64 0.33 Example (27) Compound (P-69) 5.4 12.6 2500 19.8 106.6 0.64 0.34 Example (28) Compound (P-81) 5.4 12.1 2500 20.6 104.5 0.63 0.33 Example (29) Compound (P-89) 5.4 12.9 2500 19.4 95.9 0.63 0.32 Example (30) Compound (P-100) 5.6 12.5 2500 20.0 100.7 0.64 0.32 Example (31) Compound (P-106) 5.5 13.1 2500 19.1 103.5 0.64 0.34 Example (32) Compound (P-116) 5.3 13.0 2500 19.3 107.8 0.64 0.35 Example (33) Compound (P-119) 5.5 12.7 2500 19.7 97.0 0.61 0.35

As can be seen from the results of Table 6, when a red organic light emitting device is manufactured using the material for an organic light emitting device of the present invention as a host material, organic electroluminescence is higher than that of Comparative Examples using Comparative Compound B or Comparative Compound C It is possible to improve the efficiency and lifespan of the device.

In other words, the results of Comparative Example 4 using Comparative Compound C were superior to Comparative Example 3 using Comparative Compound B, and Examples 18 to 33 of the present compound showed remarkably excellent results in efficiency and lifespan.

Comparing the comparative compound C with the compound of the present invention, the comparative compound C has a core composed of a five-ring ring, and the compound of the present invention has a structure in which a four- or five-ring ring and a phenyl bonded to N are connected.

As shown in Table 5, it is determined that the planarity of the core structure is improved, thereby improving the hole characteristics, and the charge balance of the device is improved, thereby increasing the efficiency. In addition, as the planarity of the structure is improved, the stability of the structure is improved, and it is determined that the lifetime of the device is affected.

That is, it is judged that the characteristics of the compound of the present invention having superior efficiency and lifespan compared to Comparative Compound C are the result of improved planarity of the structure of the core.

The above description is merely illustrative of the present invention, and those of ordinary skill in the art to which the present invention pertains may include other compounds within a range that does not depart from the essential characteristics of the present invention, such as a method for improving performance, etc. transformation will be possible.

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

Claims (12)

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

In Formula 1,
1) Ring A is substituted with R ² or unsubstituted, C ₆ ~ C ₃₀ Arylene group; fluorenylene group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₃₀ A heterocyclic group; or a combination thereof,
2) Ring B is R ² Or unsubstituted, C ₆ ~ C ₃₀ Arylene group; or a combination thereof,
3) X is NR', O or S;
4) L ¹ is a single bond; or NR', O, S or CR'R'';
5) R ¹ and R ² are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₃₀ Aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₃₀ A heterocyclic group; C ₁ ~ C ₂₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₁ ~ C ₂₀ An alkoxyl group; -L ² -NR ³ R ⁴ ; or a combination thereof; Or adjacent groups may combine with each other to form a ring,
6) R' is a C ₆ ~ C ₃₀ aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₃₀ A heterocyclic group; C ₁ ~ C ₂₀ Alkyl group; -L ² -NR ³ R ⁴ ; or a combination thereof; Or adjacent groups may combine with each other to form a ring,
7) R” is a C ₆ ~ C ₃₀ aryl group; C ₁ ~ C ₂₀ Alkyl group; Or adjacent groups may combine with each other to form a ring,
8) R ¹ , R ² , and R′ and R” is at least one of a C ₆ ~ C ₃₀ aryl group, a fluorenyl group, a C ₂ ~ C ₃₀ heterocyclic group, -L ² -NR ³ R ⁴ is selected from
9) L ² is a single bond; Or C ₆ ~ C ₃₀ Arylene group,
10) R ³ and R ⁴ are each independently a C ₆ ~ C ₃₀ aryl group; fluorenyl group; Or O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₃₀ A heterocyclic group,
11) n is an integer from 0 to 4,
12) The R ^1-4 , R', R", L ² , the A ring, the B ring, and the ring formed by bonding adjacent groups to each other are deuterium; halogen; cyano group; amino group; C ₁ -C ₂₀ Alkoxy group; C ₁ -C ₂₀ Alkyl group; C ₂ -C ₂₀ Alkenyl group; C ₆ -C ₂₀ Aryl group; C ₆ -C ₂₀ Aryl group substituted with deuterium; Fluorenyl group; O, N, C ₂ -C ₂₀ heterocyclic group comprising at least one heteroatom selected from the group consisting of S, Si and P; C ₃ -C ₂₀ aliphatic ring group; and one or more substituents selected from the group consisting of combinations thereof can be further substituted with The compound according to claim 1, wherein Ring A of Formula 1 is represented by one of the following Formulas A-1 to A-3:
<Formula A-1><FormulaA-2><FormulaA-3>

In Formulas A-1 to A-3,
1) wherein R ² is the same as defined in claim 1,
2) X ¹ is NR', O, S or CR'R'',
3) * represents a portion bonding to N and a portion bonding to L ¹ in Formula 1 of claim 1,
4) R' and R'' are as defined in claim 1 above,
5) m, o and p are each independently an integer of 0-4; q and r are each independently an integer of 0-3. The compound according to claim 1, wherein B in Formula 1 is represented by one of the following Formulas B-1 to B-4:
<Formula B-1><FormulaB-2><FormulaB-3><FormulaB-4>

In Formulas B-1 to B-4,
1) R ² is as defined in claim 1 above,
2) *2 represents the portion bonded to the carbon of the pentagonal ring including X,
3) *3 represents a portion that binds to L ¹ ,
4) s is an integer from 0 to 3; t is an integer from 0 to 5; The compound according to claim 1, wherein the compound represented by Formula 1 is one of the following P-1 to P-84:

a first electrode; a second electrode; and an organic material layer formed between the first electrode and the second electrode,
The organic material layer is an organic electric device comprising the compound represented by the formula (1) of claim 1 alone or in combination. a first electrode; a second electrode; an organic material layer formed between the first electrode and the second electrode; And in the organic electric device comprising a capping layer,
The capping layer is formed on one side of both surfaces of the first electrode and the second electrode that is not in contact with the organic material layer,
The organic material layer or the capping layer is an organic electric device comprising the compound represented by Formula 1 of claim 1 alone or in combination. 7. The method according to claim 5 or 6,
The organic material layer is an organic electric device comprising at least one of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer and an electron injection layer. 8. The method of claim 7,
The organic material layer comprises at least one of the hole transport layer, the light emitting auxiliary layer and the light emitting layer. 7. The method according to claim 5 or 6,
The organic material layer is an organic electric device comprising two or more stacks including a hole transport layer, a light emitting layer and an electron transport layer sequentially formed on the anode. 10. The method of claim 9,
The organic material layer is an organic electric device, characterized in that it further comprises a charge generation layer formed between the two or more stacks. A display device comprising the organic electric device of claim 5 or claim 6; and a controller for driving the display device. 12. The method of claim 11,
The organic electric device is an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, an electronic device, characterized in that selected from the group consisting of a single color lighting device and a quantum dot display device.

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