KR20210030522A - 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 element, the organic electric element using the same, and an electronic device including the organic electric element. According to the present invention, it is possible to provide the organic electric element having high luminous efficiency, low driving voltage, and high heat resistance, and it is possible to improve color purity and lifespan of the organic electric element.

Description

Compound for organic electric device, organic electric device using the same, and electronic device thereof {COMPOUND FOR ORGANIC ELECTRONIC ELEMENT 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 emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy by using an organic material. An organic electric device using the organic light emission phenomenon has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer is often made of a multilayer structure composed of different materials in order to increase the efficiency and stability of the organic electronic device, and may be formed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like.

Materials used as an organic material layer in an organic electric device can be classified into light-emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, according to their functions. And the light-emitting material can be classified into a high molecular type and a low molecular type according to the molecular weight, and according to the light emitting mechanism, it can be classified into a fluorescent material derived from the singlet excited state of the electron and a phosphorescent material derived from the triplet excited state of the electron. have. In addition, the light-emitting material may be classified into blue, green, and red light-emitting materials and yellow and orange light-emitting materials necessary to realize a better natural color according to the light-emitting color.

On the other hand, when only one material is used as a light-emitting material, the maximum light-emitting wavelength shifts to a long wavelength due to the interaction between molecules, and the color purity decreases or the efficiency of the device decreases due to the light-emitting attenuation effect. A host/dopant system may be used as a light-emitting material in order to increase the luminous efficiency through. The principle is that when a small amount of a dopant having an energy band gap smaller than that of the host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting 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 of the dopant, light having a desired wavelength can be obtained according to the type of dopant used.

Currently, the portable display market is increasing in size as a large-area display, and for this reason, power consumption that is greater than the power consumption required by the existing portable display is required. Therefore, power consumption has become an important factor for portable displays that have a limited power supply source, such as a battery, and efficiency and life issues are also important factors that must be solved.

Efficiency, lifespan, and driving voltage are related to each other. As the efficiency increases, the driving voltage decreases relatively, and as the driving voltage decreases, crystallization of organic materials by Joule heating generated during driving decreases. It shows a tendency to increase the lifespan. However, the efficiency cannot be maximized simply by improving the organic material layer. This is because the long life and high efficiency can be achieved at the same time when the optimum combination of the energy level and T1 value between each organic material layer and the intrinsic properties of the material (mobility, interfacial properties, etc.) is achieved.

In addition, in order to solve the problem of light emission in the hole transport layer in recent 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 material properties are different, it is time to develop a light-emitting auxiliary layer for each light-emitting layer.

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

However, in the case of the material used for the hole transport layer, since it must have a low HOMO value, most have a low T1 value, and as a result, excitons generated in the light-emitting layer pass to the hole transport layer interface or the hole transport layer, and as a result, the hole transport layer interface. Light emission in the light emitting layer or charge unbalance in the light emitting layer is caused 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 deteriorated, and the lifespan is shortened. Therefore, it must 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, has a high T1 value, and has a suitable driving voltage range (within the range of the driving voltage of the blue device of the full device). Mobility) is urgently required to develop a light emitting auxiliary layer.

However, this cannot be achieved simply with the structural characteristics of the core of the light-emitting auxiliary layer material, and the characteristics of the core and sub-substituents of the light-emitting auxiliary layer material, and a suitable combination between the light-emitting auxiliary layer and the hole transport layer, and the light-emitting auxiliary layer and the light-emitting layer are made When it is lost, a high-efficiency and high-life device can be implemented.

Meanwhile, development of materials for a light-emitting layer and a light-emitting auxiliary layer having stable properties, that is, a high glass transition temperature, against Joule heating generated when the device is driven is also required. The low glass transition temperature of the light-emitting layer and the light-emitting auxiliary layer material decreases the uniformity of the thin film surface when the device is driven, and the material may be deformed due to heat generated when the device is driven, which is reported to have a great effect on the life of the device.

Therefore, it is necessary to develop a material that can withstand a long time during evaporation, that is, a material with strong heat resistance, and materials that form the organic material layer in the device, such as hole injection materials, hole transport materials, and light emission, are required to fully exhibit the excellent characteristics of organic electronic devices. A material, an electron transport material, an electron injection material, and a light-emitting auxiliary layer material should be supported by a stable and efficient material. In particular, development of materials used for the light-emitting auxiliary layer and the light-emitting layer is urgently required.

An object of the present invention is to provide a compound having high heat resistance, lowering the driving voltage of the device, and improving the luminous efficiency, color purity, and lifetime of the device, an organic electric device using the same, and an electronic device including the organic electric device It is done.

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

<Formula 1>

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

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, high luminous efficiency, low driving voltage, and high heat resistance of the device can be achieved, and color purity and lifespan of the device can be improved.

1 to 3 schematically illustrate organic electric devices 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, in adding reference numerals to elements in each drawing, it should be noted that the same elements are assigned the same numerals as possible, even if they are indicated on different drawings. In addition, in describing the present invention, when it is determined that a detailed description of a related known configuration or function may obscure the subject matter of the present invention, a detailed description thereof will be omitted. In the drawings referred to below, the accumulation ratio is not applied.

In describing the constituent elements of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are for distinguishing the constituent element from other constituent elements, and the nature, order, or order of the constituent element is not limited by the term.

When a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected or connected to that other component, but another component between each component It will be understood that elements may be “connected”, “coupled” or “connected”.

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

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

The term "halo" or "halogen" as used in this application includes fluorine (F), chlorine (Cl), bromine (Br), and iodine (I) unless otherwise specified.

The term "alkyl" or "alkyl group" as used in the present application has 1 to 60 carbons connected by a single bond, unless otherwise stated, a straight-chain alkyl group, a branched-chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted It means a radical of a saturated aliphatic functional group including a cycloalkyl group and a cycloalkyl-substituted alkyl group.

The term "haloalkyl group" or "halogenalkyl group" as used in the present application means an alkyl group in which halogen is substituted unless otherwise specified.

The terms "alkenyl" or "alkynyl" as used in the present application each have a double bond or a triple bond, unless otherwise specified, include a straight or branched chain group, and have a carbon number of 2 to 60, but are limited thereto. It does not become.

The term "cycloalkyl" as used in the present application means an alkyl forming a ring having 3 to 60 carbon atoms unless otherwise specified, and is not limited thereto.

The term "alkoxy group" or "alkyloxy group" used in the present application refers to an alkyl group to which an oxygen radical is bonded, and has a carbon number of 1 to 60 unless otherwise specified, but is not limited thereto.

The terms "alkenyl group", "alkenoxy group", "alkenyloxy group", or "alkenyloxy group" as used in the present application mean an alkenyl group to which an oxygen radical is attached, and unless otherwise specified, 2 to 60 It has a carbon number of, but is not limited thereto.

The terms "aryl group" and "arylene group" used in the present application each have 6 to 60 carbon atoms, but are not limited thereto. In the present application, the aryl group or the arylene group includes a single cyclic type, a group of rings, a conjugated cyclic compound, and the like. For example, the aryl group may include a phenyl group, a biphenyl monovalent functional group, a naphthalene monovalent functional group, a fluorenyl group, a substituted fluorenyl group, and the arylene group may include a fluorenylene group, a substituted fluorenylene group It may contain a group.

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

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

The term "conjugated multiple ring systems" as used in the present application refers to a fused ring form sharing at least two atoms, and includes a form in which two or more hydrocarbon ring systems are fused and at least one heteroatom And the like in which at least one heterocyclic system is conjugated. Several such fused ring systems may be an aromatic ring, a heteroaromatic ring, an aliphatic ring, or a combination of these rings. For example, the aryl group may be a naphthalenyl group, a phenanthrenyl group, or a fluorenyl group, but is not limited thereto.

The term "spyro compound" as used in the present application has a'spiro union', and the spiro linkage refers to a connection made by two rings sharing only one atom. At this time, the atoms shared in the two rings are referred to as'spyro atoms', and depending on the number of spyro atoms in one compound, these are respectively referred to as'monospiro-','dispiro-', and'trispyro-'. 'It is called a compound.

The terms "fluorenyl group", "fluorenylene group", and "fluorentriyl group" as used in the present application are all hydrogen in the following structures, unless otherwise specified. It means 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' It means that at least one of "is a substituent other than hydrogen, and includes the case where R and R'are bonded to each other to form a spy compound together with the carbon to which they are bonded. In the present specification, a fluorenyl group, a fluorenylene group, and a fluorenetriyl group may all be referred to as fluorene groups regardless of a valence such as monovalent, divalent, or trivalent.

In addition, the R, R', R" and R'" are each independently an alkyl group having a carbon number of 1 to 20, an alkenyl group having a carbon number of 1 to 20, an aryl group having a carbon number of 6 to 30, 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 fluorenylene group are monovalent of 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 the present application includes not only an aromatic ring such as a "heteroaryl group" or a "heteroarylene group", but also a non-aromatic ring, and unless otherwise stated, each carbon number including one or more heteroatoms It means a ring of 2 to 60, but is not limited thereto. The term "heteroatom" used in the present application represents N, O, S, P, or Si unless otherwise specified, and the heterocyclic group is a monocyclic type containing a heteroatom, a ring aggregate, a conjugated ring system, spy It means a compound and the like.

For example, the “heterocyclic group” may also include a compound including a heteroatom group such as _{SO 2} , P=O, and the like, as in the following compounds instead of carbon forming a ring.

The term "ring" as used in the present application includes monocyclic and polycyclic rings, including hydrocarbon rings as well as heterocycles including at least one heteroatom, and includes aromatic and non-aromatic rings.

The term "polycyclic" used in the present application includes ring assemblies such as biphenyl, terphenyl, etc., several fused ring systems and spiro compounds, and includes not only aromatic but also non-aromatic, hydrocarbon Rings of course include heterocycles containing at least one heteroatom.

The term "aliphatic ring group" as used in the present application refers to cyclic hydrocarbons excluding aromatic hydrocarbons, and includes monocyclic types, cyclic aggregates, conjugated cyclic systems, spiro compounds, etc., unless otherwise stated, It means a ring of 3 to 60, but is not limited thereto. For example, even when benzene, which is an aromatic ring, and cyclohexane, which is a non-aromatic ring, are fused, it corresponds to an aliphatic ring.

In addition, when the prefixes are named consecutively, it means that the substituents are listed in the order described first. For example, in the case of an arylalkoxy group, it means an alkoxy group substituted with an aryl group, in the case of an alkoxycarbonyl group, it means a carbonyl group substituted with an alkoxy group, and in the case of an arylcarbonylalkenyl group, it 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 expressly stated otherwise, the term "substituted or unsubstituted" used in the present application "substituted" refers to deuterium, halogen, amino group, nitrile group, nitro group, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₁ -C ₂₀ alkylamine group, C ₁ -C ₂₀ alkylthiophene group, C ₆ -C ₂₀ arylthiophene group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl group of, C ₆ -C ₂₀ aryl group, of a C ₆ -C ₂₀ aryl group substituted with a heavy hydrogen, C ₈ -C ₂₀ aryl alkenyl group, a silane group, a boron It means substituted with one or more substituents selected from the group consisting of _{a C 2} -C ₂₀ heterocyclic group including a group, a germanium group, and at least one heteroatom selected from the group consisting of O, N, S, Si and P And, it 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 substituent may describe'the name of the functional group reflecting the number', but it is described as the'parent compound name' You may. For example, in the case of'phenanthrene', which is a kind of aryl group, the monovalent'group' is'phenanthryl (group)', and the divalent group is named by dividing the valences such as'phenanthrylene (group)', etc. Although it may be described, 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, it is described as'pyrimidine' regardless of the valence, or in the case of monovalent, it is referred to as pyrimidinyl (group), and in the case of divalent, the'group of the corresponding valency is expressed as pyrimidinylene (group). It can also be written as'name of'. Accordingly, 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 desorption of a hydrogen atom bonded to a carbon atom and/or a heteroatom of the parent compound.

In addition, in the present specification, when describing the name of the compound or the name of the substituent, 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 or the like. Therefore, both benzo[g]quinoxaline and benzo[f]quinoxaline can be described as benzoquinoxaline.

In addition, unless there is an explicit description, the formula used in this application is applied in the same way as the definition of the substituent group defined by the index definition of the following formula.

Here, when a is an integer of 0, the substituent R ¹ means that the substituent R 1 is absent, that is, when a is 0, it means that all hydrogens are bonded to the carbon forming the benzene ring. It may be omitted and the formula or compound may be described. In addition, when a is an integer of 1, one substituent R ¹ is bonded to any one of carbons forming a benzene ring, and when a is an integer of 2 or 3, it may be bonded, for example, as follows, and a is 4 to 6 In the case of 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 or different from each other.

Unless otherwise stated in the present application, to form a ring means that adjacent groups are bonded to each other to form a single ring or several conjugated rings, and a single ring and a plurality of conjugated rings formed are hydrocarbon rings as well as at least one It includes a heterocycle including a heteroatom, and may include aromatic and non-aromatic rings.

In addition, unless otherwise specified in the present specification, when indicating a condensed ring, a number in'number-condensed ring' indicates the number of condensed rings. For example, a form in which three rings are condensed with each other, such as anthracene, phenanthrene, benzoquinazoline, etc., can 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. At this time, the shared atoms may include carbon or heteroatoms.

Hereinafter, a stacked structure of an organic electric device including 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, a first electrode may be a cathode and a 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, 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 may be sequentially formed on the first electrode 110.

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

For example, the 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 so that the capping layer 180 is formed on the second electrode 170. Optical energy loss due to surface plasmon polaritons (SPPs) can be reduced, and in the case of a bottom emission organic light emitting device, the capping layer 180 can function as a buffer for the second electrode 170 .

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

Referring to FIG. 2, an organic electric device 200 according to another embodiment of the present invention includes a hole injection layer 120, a hole transport layer 130, a buffer layer 210 formed sequentially 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. I 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 plurality of stacks including a hole transport layer, a light emitting layer, and an electron transport layer. This will be described with reference to FIG. 3.

Referring to FIG. 3, in an organic electric device 300 according to another embodiment of the present invention, two stacks ST1 and ST2 formed of a multi-layered organic material layer are disposed between the first electrode 110 and the second electrode 170. A set or more may be formed, and a charge generation layer CGL may be formed between the 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).

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 laminated structure, but may be organic material layers having different laminated 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 generation layer CGL is formed between the first emission layer 340 and the second emission layer 440 to increase current efficiency generated in each emission layer and smoothly distribute electric charges.

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

In this case, the second hole transport layer 430 includes a second stack ST2 in which the energy level is set higher than the triplet excitation energy level of the second emission layer 440.

Since the energy level of the second hole transport layer 430 is higher than that of the second light emitting layer 440, the triplet exciton of the second light emitting layer 440 passes to the second hole transport layer 430, resulting in lower luminous efficiency. Can be prevented. That is, the second hole transport layer 430 may function as an exciton blocking layer that prevents tripping of triplet excitons while transporting holes from the inherent second emission layer 440. .

In addition, the first hole transport layer 330 may also be set to an energy level higher than the triplet excitation energy level of the first emission layer 340 for the function of the exciton blocking layer. 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 emission layer 340, and the second electron transport layer 450 is also triplet excitation of the second emission layer 440. It is preferable to set the 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, a charge generation layer CGL and a third stack may be additionally stacked on the second stack ST2.

When a plurality of light-emitting layers are formed by the multi-layer stack structure method as shown in FIG. 3, it is possible to manufacture an organic electroluminescent device in which white light is emitted by the mixing effect of light emitted from each of the light-emitting layers, as well as various colors of light. 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 emission 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, but preferably, the hole transport layer 130, 330, 430, the light emission auxiliary layer 220 ), the light emitting layers 140, 340, and 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 located on the capping layer, the encapsulation layer is located on the capping layer, and at least one side portion 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 It can be formed to cover.

The protective layer may provide a flattened surface so that the encapsulation layer can be uniformly formed, and may serve to protect the first electrode, the second electrode, and the organic material layer in the manufacturing process of the encapsulation layer.

The encapsulation layer may play a role of preventing external oxygen and moisture from penetrating into the organic electric device.

On the other hand, even with the same and similar core, the band gap, electrical characteristics, and interface characteristics may vary depending on which substituent is bonded to a certain position, so the selection of the core and the combination of the sub-substituents bonded thereto may vary. In particular, long life and high efficiency can be achieved at the same time when the optimum combination of the energy level and T1 value between each organic material layer and the intrinsic properties of the material (mobility, interfacial properties, etc.) is achieved.

Therefore, in the present invention, by using the compound represented by Formula 1 as a material for the auxiliary light emitting layer 220, the light emitting layers 140, 340, and 440, and/or the capping layer 180, the energy level and the T1 value between each organic material layer, By optimizing the intrinsic properties of the material (mobility, interfacial properties, etc.), it was possible to simultaneously improve the life and efficiency of the organic electric device.

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using various deposition methods. It can be manufactured using a deposition method such as PVD or CVD. For example, a metal or a conductive metal oxide or an alloy thereof is deposited on a substrate to form the anode 110, and a hole injection layer 120 thereon. 320, 420), hole transport layers (130, 330, 430), light emitting layers (140, 340, 440), electron transport layers (150, 350, 450), and after forming an organic material layer including the electron injection layer 160, It can be manufactured by depositing a material that can be used as the cathode 170 thereon. In addition, a light emission auxiliary layer 220 between the hole transport layers 130, 330, and 430 and the emission layers 140, 340, and 440, and an electron transport auxiliary layer between the emission 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 material layer is a solution process or a solvent process other than a vapor deposition method using various polymer materials, such as a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, a roll-to-roll process, and a doctor blaze. It can be manufactured with fewer layers by a method such as a ding 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 forming method.

The organic electric device according to an embodiment of the present invention may be a top emission type, a bottom emission type, or a double-sided emission type depending on the 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 monochromatic lighting device, and a quantum dot display device.

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 or wireless communication terminal, and includes all electronic devices such as mobile communication terminals such as mobile phones, PDAs, electronic dictionaries, PMPs, remote controls, navigation, game consoles, various TVs, and various computers.

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

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

<Formula 1>

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

In Formula 1,

1) Ar ¹ to Ar ⁵ are each independently a C ₆ to C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of an aliphatic ring of C ₃ to C _{60 and an aromatic ring of C 6} to C _60; A C ₁ to C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C _20; An alkoxyl group of C ₁ to C _30; C ₆ ~ C ₃₀ aryloxy group; Or a combination thereof; Or neighboring groups can be bonded to each other to form a ring,

2) ^{At least one of Ar 1} to Ar ⁵ is Formula A-1 or Formula A-2; When the formula A-1 or formula A-2 is bonded, it is bonded to one of R ³ to R ⁷ ,

3) Z is O or S,

4) X ¹ and X ² are each independently O, S, NR' or CR'R'',

5) Y ¹ and Y ² are each independently a single bond, O, S, NR' or CR'R''; However, the ^{case where both Y 1} and Y ² are single bonds is excluded,

6) R ¹ to R ⁹ , R'and R'' are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Nitro group; Amanogi; C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of an aliphatic ring of C ₃ to C _{60 and an aromatic ring of C 6} to C _60; A C ₁ to C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C _20; An alkoxyl group of C ₁ to C _30; C ₆ ~ C ₃₀ aryloxy group; C ₆ ~ C ₃₀ arylthio group; Or neighboring groups can be bonded to each other to form a ring,

7) n is an integer of 0-4; m is an integer of 0 to 3; p, q, s, t, u, v, and w are each independently an integer of 0-4,

8) L ¹ to L ³ are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of an aliphatic ring of C ₃ to C _{60 and an aromatic ring of C 6} to C _60; C ₃ ~ C ₆₀ aliphatic ring group; A divalent aliphatic hydrocarbon group; Or a combination thereof,

In the above, when Ar ¹ to Ar ⁵ , R ¹ to R ⁹ , R'and R'' are an _{aryl group, preferably an aryl group of C 6} to C ₃₀ , more preferably an aryl group of C ₆ to C ₁₈ , For example, may be phenyl, biphenyl, naphthyl, terphenyl, etc.,

When L ¹ to L ³ , Ar ¹ to Ar ⁵ , R ¹ to R ⁹ , R'and R'' are heterocyclic _{groups, preferably a C 2} to C ₃₀ heterocyclic group, more preferably C ₂ to It may be a C ₁₈ heterocyclic group, such as dibenzofuran, dibenzothiophene, naphthobenzothiophene, naphthobenzofuran, and the like,

When L ¹ to L ³ , Ar ¹ to Ar ⁵ , R ¹ to R ⁹ , R'and R'' are fluorenyl groups, preferably 9,9-dimethyl-9H-fluorene, 9,9- It may be a diphenyl-9H-fluorenyl group, 9,9'-spirobifluorene, etc.,

When L ¹ to L ³ are an arylene group, preferably a C ₆ to C ₃₀ arylene group, more preferably a C ₆ to C ₁₈ arylene group, such as phenyl, biphenyl, naphthyl, terphenyl, etc. ,

When Ar ¹ to Ar ⁵ , R ¹ to R ⁹ , R'and R'' are alkyl groups, preferably C ₁ to C ₁₀ may be an alkyl group, such as methyl, t-butyl, and the like,

When Ar ¹ to Ar ⁵ , R ¹ to R ⁹ , R'and R'' are alkoxy _{groups, preferably a C 1} to C ₂₀ alkoxyl group, more preferably a C ₁ to C ₁₀ alkoxyl group, such as me May be oxy, t-butoxy, etc.,

Ar ¹ to Ar ⁵ , R ¹ to R ⁹ , R'and R ″The ring formed by bonding with each other adjacent to each other is an aromatic ring group of _{C 6} to C _60; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; Or it _{may be an aliphatic ring group of C 3} ~ C ₆₀ , for example, when adjacent groups are bonded to each other to form an aromatic ring, preferably an aromatic ring of C ₆ ~ C ₂₀ , more preferably C ₆ ~ C ₁₄ Aromatic rings of, such as benzene, naphthalene, phenanthrene, etc. can be formed,

9) Ar ¹ to Ar ⁵ , L ¹ to L ³ , R ¹ to R ⁹ , R', R'' and the rings formed by bonding of adjacent groups to each other are deuterium, respectively; halogen; A silane group unsubstituted or substituted with a C ₁ to C ₂₀ alkyl group or a C ₆ to C _{20 aryl group;} Siloxane group; Boron group; Germanium group; Cyano group; Nitro group; C ₁ ~ C ₂₀ alkylthio group; C ₁ ~ C ₂₀ alkoxy group; C ₆ ~ C ₂₀ arylalkoxy group; C ₆ ~ C ₂₀ aryloxy group; C ₆ ~ C ₂₀ arylthio group; A C ₁ to C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C _20; C ₆ ~ C ₂₀ aryl group; _{C 6} ~ C ₂₀ aryl group unsubstituted or substituted with deuterium; Fluorenyl group; _{O, N, S, Si, and C 2} ~ C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of P; C ₃ ~ C ₂₀ aliphatic ring group; C ₇ ~ C ₂₀ arylalkyl group; C ₈ ~ C ₂₀ arylalkenyl group; And it may be further substituted with one or more substituents selected from the group consisting of a combination thereof.

Preferably, Formula 1 may be represented by the following Formula 2 or Formula 3, but is not limited thereto.

<Formula 2> <Formula 3>

In Chemical Formulas 2 and 3, R ¹ , R ² , Ar ¹ to Ar ⁵ , L ¹ to L ³ , n, m, and Z are the same as defined in Chemical Formula 1.

More preferably, Formula 1 may be represented by any one of Formulas 4 to 31 below, but is not limited thereto.

<Formula 4> <Formula 5> <Formula 6>

<Formula 7> <Formula 8> <Formula 9>

<Formula 10> <Formula 11> <Formula 12>

<Formula 13> <Formula 14> <Formula 15>

<Formula 16> <Formula 17> <Formula 18>

<Formula 19> <Formula 20> <Formula 21>

<Formula 22> <Formula 23> <Formula 24>

<Formula 25> <Formula 26> <Formula 27>

<Formula 28> <Formula 29> <Formula 30>

<Formula 31>

In Chemical Formulas 4 to 31, R ¹ , R ² , Ar ¹ to Ar ⁵ , L ¹ to L ³ , n, m, and Z are the same as defined in Chemical Formula 1.

Even more preferably, Formula 1 may be represented by any one of Formulas 32 to 61 below, but is not limited thereto.

<Formula 32> <Formula 33> <Formula 34>

<Formula 35> <Formula 36> <Formula 37>

<Formula 38> <Formula 39> <Formula 40>

<Formula 41> <Formula 42> <Formula 43>

<Formula 44> <Formula 45> <Formula 46>

<Formula 47> <Formula 48> <Formula 49>

<Formula 50> <Formula 51> <Formula 52>

<Formula 53> <Formula 54> <Formula 55>

<Formula 56> <Formula 57> <Formula 58>

<Formula 59> <Formula 60> <Formula 61>

In Formulas 32 to 61, R ¹ , R ² , Ar ¹ to Ar ⁵ , L ¹ to L ³ , n, m, Z are the same as defined in Formula 1; a and b are each independently an integer of 0-6.

Meanwhile, the compound represented by Formula A-1 may be represented by any one of Formulas A-1-1 to A-1-6, but is not limited thereto.

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

<Formula A-1-4> <Formula A-1-5> <Formula A-1-6>

In Formulas A-1-1 to A-1-6, R ³ to R ⁵ , p, q, s, X ¹ and X ² are as defined in Formula A-1.

Meanwhile, the compound represented by Formula A-2 may be represented by any one of Formulas A-2-1 to A-2-2 below, but is not limited thereto.

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

In Formula A-2-1 or Formula A-2-2,

R ⁶ ~ R ⁹ , t, u, v, w are the same as defined in Formula 1,

Y ³ is O, S, NR' or CR'R''; Y ⁴ is a single bond, O, S, NR' or CR'R'';R'and R” are the same as defined in Chemical Formula 1.

Meanwhile, the compound represented by Formula 1 may be one of the following P-1 to P-160, 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 a 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 compound to be used alone or as a mixture is included.

The organic material layer includes at least one of a hole injection layer, a hole transport layer, a light emission auxiliary layer, a light emission layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer. That is, at least one of a hole injection layer, a hole transport layer, a light emission auxiliary layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer, or an electron injection layer included in the organic material layer may include a compound represented by Formula (1). .

Preferably, the organic material layer includes at least one of the hole transport layer, an emission auxiliary layer, and an emission 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.

The organic material layer includes two or more stacks including a hole transport layer, an emission layer, and an electron transport layer sequentially formed on the anode.

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

As another specific embodiment of the present invention, the present invention is to provide an electronic device including a display device including an organic electric device including a compound represented by Formula 1 and a control unit 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 from each other, or the compound may be included in a combination of two or more with another compound.

Hereinafter, examples for synthesizing the compound represented by Formula 1 according to the present invention and an example for preparing an organic electric device according to the present invention will be described in detail, but the present invention is not limited to the following examples.

< Synthesis example >

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

In the following Scheme 1, R ¹ , R ² , Ar ¹ to Ar ⁵ , L ¹ , L ² , L ³ , n, m and Z are the same as defined in Formula 1, and Hal ¹ and Hal ² are independently of each other Br Or Cl.

<Reaction Scheme 1>

I. Synthesis of Sub 1

Sub1 of Scheme 1 may be synthesized by the reaction route of Scheme 2-1 or 2-2, but is not limited thereto. When Z is S, it can be synthesized according to the following Reaction Scheme 2-1, and when Z is O, it can be synthesized according to the following Reaction Scheme 2-2.

Here, Hal ¹ and Hal ² are each independently I, Br or Cl,

x and y are each independently 0 or 1; x+y is necessarily 1.

<Reaction Scheme 2-1>

<Reaction Scheme 2-2>

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

1.Sub 1-1 and Sub 1-17 Synthesis example

(1) Sub 1-1-c synthesis example

After dissolving (3-chlorophenyl)boronic acid (30.0 g, 191.9 mmol) in THF (960 mL), 3-bromo-2-iodophenol (57.3 g, 191.9 mmol), NaOH (23 g, 575.6 mmol), Pd( PPh ₃ ) ₄ (13.3 g, 11.51 mmol) and water (480 mL) were added, followed by stirring at 80°C. When the reaction was completed, the _{mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 46.8 g (yield: 86%) of the product.

(2) Example of Sub 1-35 Synthesis

Sub 1-1-c (46.8 g, 136.1 mmol) in Pd(OAc) ₂ (1.53 g, 6.81 mmol), 3-nitropyridine (0.845 g, 6.81 mmol), BzOOt-Bu (tert-butyl peroxybenzoate) (52.9 g , 272.3 mmol), C ₆ F ₆ (hexafluorobenzene) (203 mL), and DMI (N,N'-dimethylimidazolidinone) (136 mL) were added and refluxed at 90°C for 3 hours. When the reaction was completed, the temperature of the reaction product was cooled to room temperature, and extracted with EA and water. The organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was recrystallized using a silica gel column to obtain 13.4 g (yield: 35%) of the product Sub 1-1 and 16.1 g (yield: 42%) of the product Sub 1-17. .

2. Sub 1-6 Synthesis example

(1) Sub 1-4-c synthesis example

(4-chloro-[1,1'-biphenyl]-2-yl)boronic acid (30.0 g, 129 mmol), 4-bromo-2-iodophenol (38.6 g, 129 mmol), NaOH (15.5 g, 387.1 mmol ), Pd(PPh ₃ ) ₄ (8.95 g, 7.74 mmol) was obtained using the synthesis method of Sub 1-1-c, to obtain a product 36.2 g (yield: 78%).

(2) Example of Sub 1-4 synthesis

Sub 1-4-c (36.2 g, 100.7 mmol) obtained in the above synthesis Pd(OAc) ₂ (1.13 g, 5.03 mmol), 3-nitropyridine (0.625 g, 5.03 mmol), BzOOt-Bu (tert-butyl peroxybenzoate) ) (39.1 g, 201.3 mmol), C ₆ F ₆ (hexafluorobenzene) (150 mL), DMI (N,N'-dimethylimidazolidinone) (101 mL) was added, and the product 26.3 using the synthesis method of Sub 1-1. g (73% yield) was obtained.

3.Sub 1-29 Synthesis example

(1) Example of Sub 1-29-c synthesis

(2-chlorophenyl)boronic acid (30.0 g, 191.9 mmol), 5-bromo-2-iodophenol (57.3 g, 191.9 mmol), NaOH (23 g, 575.6 mmol), Pd(PPh ₃ ) ₄ (13.3 g, 11.51 mmol) was obtained by using the synthesis method of Sub 1-1-c as the product 43.5 g (yield: 80%).

(2) Sub 1-29 synthesis example

Sub 1-29-c (43.5 g, 153.5 mmol) obtained in the above synthesis Pd(OAc) ₂ (1.72 g, 7.67 mmol), 3-nitropyridine (0.95 g, 7.67 mmol), BzOOt-Bu (tert-butyl peroxybenzoate) ) (59.6 g, 205 mmol), C ₆ F ₆ (hexafluorobenzene) (229 mL), and DMI (N,N'-dimethylimidazolidinone) (153 mL) were added, and the product 32 using the synthesis method of Sub 1-1 g (yield 74%) was obtained.

4.Sub 1-37 Synthesis example

(1) Sub 1-37-c synthesis example

(2-bromo-5-chlorophenyl)boronic acid (30.0 g, 127.5 mmol), 2-iodophenol (28.1 g, 127.5 mmol), NaOH (15 g, 382.5 mmol), Pd(PPh ₃ ) ₄ (8.84 g, 7.65 mmol) was obtained by using the synthesis method of Sub 1-1-c above to obtain 29.6 g (yield: 82%) of the product.

(2) Example of Sub 1-35 Synthesis

Sub 1-37-c (29.6 g, 104.6 mmol) Pd(OAc)2 (1.17 g, 5.23 mmol), 3-nitropyridine (0.649 g, 5.23 mmol), BzOOt-Bu (tert-butyl peroxybenzoate) (40.6 g , 209.1 mmol), C ₆ F ₆ (hexafluorobenzene) (156 mL), DMI (N,N'-dimethylimidazolidinone) (105 mL) was added and the product 23.3 g (yield: 79%).

5.Sub 1-71 Synthesis example

(1) Synthesis example of Sub 1-71-a

After dissolving (2-chlorophenyl)boronic acid (30.0 g, 191.9 mmol) in THF (960 mL), (4-bromo-2-iodophenyl)(ethyl)sulfane (65.8 g, 191.9 mmol), NaOH (23.02 g, 575.6 mmol), Pd(PPh ₃ ) ₄ (13.3 g, 11.51 mmol), and water (480 mL) were added, followed by stirring at 80°C. When the reaction was completed, the _{mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 50.9 g (yield: 81%) of the product.

(2) Synthesis example of Sub 1-71-b

Add acetic acid (622 mL) to Sub 1-71-a (50.9 g, 155.4 mmol) obtained in the above synthesis, add 35% Hydrogen peroxide (H ₂ O ₂ ) (44.4 mL), and stir at room temperature. When the reaction was completed, it was neutralized with an aqueous NaOH solution, followed by extraction with ethylacetate (EA) and water. The organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was recrystallized using a silica gel column to obtain 67.9 g (yield: 93%) of the product.

(3) Example of Sub 1-71 synthesis

_{Sulfuric acid (H 2} SO ₄ ) (203.7 ml) was added to Sub 1-71-b (67.9 g, 144.5 mmol) obtained in the above synthesis and stirred at room temperature. When the reaction was completed, the mixture was neutralized with an aqueous NaOH solution, CH ₂ Cl ₂ and water were added to extract the organic layer. The organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was separated and purified through a silica gel column to obtain 47.2 g (yield: 77%) of the product.

6.Sub 1-76 Synthesis example

(1) Synthesis example of Sub 1-76-a

(3-chloronaphthalen-2-yl)boronic acid (30.0 g, 145.3 mmol), (2-bromo-6-iodophenyl)(ethyl)sulfane (49.9 g, 145.3 mmol), NaOH (17.44 g, 436 mmol), Pd (PPh ₃ ) ₄ (10.08 g, 8.72 mmol) was obtained using the synthesis method of Sub 1-71-a, the product 43.9 g (yield: 80%).

(2) Synthesis example of Sub 1-76-b

Sub 1-76-a (43.9 g, 116.3 mmol), acetic acid (465 mL), 35% Hydrogen peroxide (H ₂ O ₂ ) (33.22 mL) was added to the product 41.7 using the synthesis method of Sub 1-71-b. g (yield: 91%) was obtained.

(3) Example of Sub 1-76 synthesis

Sub 1-1-76-b (28.5 g, 72.5 mmol) was obtained by using the synthesis method of Sub 1-71 above to obtain a product 26.9 g (yield: 73%).

7.Sub 1-81 Synthesis example

(1) Synthesis example of Sub 1-81-a

(2-bromo-5-chlorophenyl)boronic acid (30.0 g, 127.5 mmol), ethyl(2-iodophenyl)sulfane (31.9 g, 127.5 mmol), NaOH (15.3 g, 382.5 mmol), Pd(PPh ₃ ) ₄ ( 8.84 g, 7.65 mmol) was obtained by using the synthesis method of Sub 1-71-a, to obtain 34 g (yield: 85%) of the product.

(2) Synthesis example of Sub 1-81-b

Sub 1-81-a (34 g, 108.4 mmol), acetic acid (434 mL), 35% Hydrogen peroxide (H ₂ O ₂ ) (30.97 mL) was added to the product 32.2 using the synthesis method of Sub 1-71-b. g (yield: 90%) was obtained.

(3) Example of Sub 1-81 synthesis

Sub 1-81-b (32.2 g, 97.5 mmol) was obtained by using the synthesis method of Sub 1-71 above to obtain 24.1 g (yield: 83%) of the product.

The compound belonging to Sub 1 may be the following compound, but is not limited thereto.

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

compound FD-MS compound FD-MS Sub 1-1 m/z=279.93 (C ₁₂ H ₆ BrClO=281.53) Sub 1-2 m/z=304.92 (C ₁₃ H ₅ BrClNO=306.54) Sub 1-3 m/z=279.93 (C ₁₂ H ₆ BrClO=281.53) Sub 1-4 m/z=293.94 (C ₁₃ H ₈ BrClO=295.56) Sub 1-5 m/z=279.93 (C ₁₂ H ₆ BrClO=281.53) Sub 1-6 m/z=355.96 (C ₁₈ H ₁₀ BrClO=357.63) Sub 1-7 m/z=279.93 (C ₁₂ H ₆ BrClO=281.53) Sub 1-8 m/z=309.94 (C ₁₃ H ₈ BrClO ₂ =311.56) Sub 1-9 m/z=279.93 (C ₁₂ H ₆ BrClO=281.53) Sub 1-10 m/z=355.96 (C ₁₈ H ₁₀ BrClO=357.63) Sub 1-11 m/z=279.93 (C ₁₂ H ₆ BrClO=281.53) Sub 1-12 m/z=329.94 (C ₁₆ H ₈ BrClO=331.59) Sub 1-13 m/z=279.93 (C ₁₂ H ₆ BrClO=281.53) Sub 1-14 m/z=379.96 (C ₂₀ H ₁₀ BrClO=381.65) Sub 1-15 m/z=279.93 (C ₁₂ H ₆ BrClO=281.53) Sub 1-16 m/z=293.94 (C ₁₃ H ₈ BrClO=295.56) Sub 1-17 m/z=279.93 (C ₁₂ H ₆ BrClO=281.53) Sub 1-18 m/z=355.96 (C ₁₈ H ₁₀ BrClO=357.63) Sub 1-19 m/z=279.93 (C ₁₂ H ₆ BrClO=281.53) Sub 1-20 m/z=461.95 (C ₂₄ H ₁₂ BrClOS=463.77) Sub 1-21 m/z=279.93 (C ₁₂ H ₆ BrClO=281.53) Sub 1-22 m/z=405.98 (C ₂₂ H ₁₂ BrClO=407.69) Sub 1-23 m/z=279.93 (C ₁₂ H ₆ BrClO=281.53) Sub 1-24 m/z=379.96 (C ₂₀ H ₁₀ BrClO=381.65) Sub 1-25 m/z=279.93 (C ₁₂ H ₆ BrClO=281.53) Sub 1-26 m/z=304.92 (C ₁₃ H ₅ BrClNO=306.54) Sub 1-27 m/z=279.93 (C ₁₂ H ₆ BrClO=281.53) Sub 1-28 m/z=329.94 (C ₁₆ H ₈ BrClO=331.59) Sub 1-29 m/z=279.93 (C ₁₂ H ₆ BrClO=281.53) Sub 1-30 m/z=355.96 (C ₁₈ H ₁₀ BrClO=357.63) Sub 1-31 m/z=279.93 (C ₁₂ H ₆ BrClO=281.53) Sub 1-32 m/z=293.94 (C ₁₃ H ₈ BrClO=295.56) Sub 1-33 m/z=279.93 (C ₁₂ H ₆ BrClO=281.53) Sub 1-34 m/z=405.98 (C ₂₂ H ₁₂ BrClO=407.69) Sub 1-35 m/z=279.93 (C ₁₂ H ₆ BrClO=281.53) Sub 1-36 m/z=329.94 (C ₁₆ H ₈ BrClO=331.59) Sub 1-37 m/z=279.93 (C ₁₂ H ₆ BrClO=281.53) Sub 1-38 m/z=355.96 (C ₁₈ H ₁₀ BrClO=357.63) Sub 1-39 m/z=279.93 (C ₁₂ H ₆ BrClO=281.53) Sub 1-40 m/z=297.92 (C ₁₂ H ₅ BrClFO=299.52) Sub 1-41 m/z=279.93 (C ₁₂ H ₆ BrClO=281.53) Sub 1-42 m/z=304.92 (C ₁₃ H ₅ BrClNO=306.54) Sub 1-43 m/z=279.93 (C ₁₂ H ₆ BrClO=281.53) Sub 1-44 m/z=309.94 (C ₁₃ H ₈ BrClO ₂ =311.56) Sub 1-45 m/z=295.91 (C ₁₂ H ₆ BrClS=297.59) Sub 1-46 m/z=320.9 (C ₁₃ H ₅ BrClNS=322.6) Sub 1-47 m/z=295.91 (C ₁₂ H ₆ BrClS=297.59) Sub 1-48 m/z=421.95 (C ₂₂ H ₁₂ BrClS=423.75) Sub 1-49 m/z=295.91 (C ₁₂ H ₆ BrClS=297.59) Sub 1-50 m/z=371.94 (C ₁₈ H ₁₀ BrClS=373.69) Sub 1-51 m/z=295.91 (C ₁₂ H ₆ BrClS=297.59) Sub 1-52 m/z=395.94 (C ₂₀ H ₁₀ BrClS=397.71) Sub 1-53 m/z=295.91 (C ₁₂ H ₆ BrClS=297.59) Sub 1-54 m/z=295.91 (C ₁₂ H ₆ BrClS=297.59) Sub 1-55 m/z=295.91 (C ₁₂ H ₆ BrClS=297.59) Sub 1-56 m/z=309.92 (C ₁₃ H ₈ BrClS=311.62) Sub 1-57 m/z=295.91 (C ₁₂ H ₆ BrClS=297.59) Sub 1-58 m/z=325.92 (C ₁₃ H ₈ BrClOS=327.62) Sub 1-59 m/z=295.91 (C ₁₂ H ₆ BrClS=297.59) Sub 1-60 m/z=537 (C ₃₀ H ₁₇ BrClNS=538.89) Sub 1-61 m/z=295.91 (C ₁₂ H ₆ BrClS=297.59) Sub 1-62 m/z=421.95 (C ₂₂ H ₁₂ BrClS=423.75) Sub 1-63 m/z=295.91 (C ₁₂ H ₆ BrClS=297.59) Sub 1-64 m/z=395.94 (C ₂₀ H ₁₀ BrClS=397.71) Sub 1-65 m/z=295.91 (C ₁₂ H ₆ BrClS=297.59) Sub 1-66 m/z=345.92 (C ₁₆ H ₈ BrClS=347.65) Sub 1-67 m/z=295.91 (C ₁₂ H ₆ BrClS=297.59) Sub 1-68 m/z=371.94 (C ₁₈ H ₁₀ BrClS=373.69) Sub 1-69 m/z=295.91 (C ₁₂ H ₆ BrClS=297.59) Sub 1-70 m/z=371.94 (C ₁₈ H ₁₀ BrClS=373.69) Sub 1-71 m/z=295.91 (C ₁₂ H ₆ BrClS=297.59) Sub 1-72 m/z=371.94 (C ₁₈ H ₁₀ BrClS=373.69) Sub 1-73 m/z=295.91 (C ₁₂ H ₆ BrClS=297.59) Sub 1-74 m/z=461.95 (C ₂₄ H ₁₂ BrClOS=463.77) Sub 1-75 m/z=295.91 (C ₁₂ H ₆ BrClS=297.59) Sub 1-76 m/z=345.92 (C ₁₆ H ₈ BrClS=347.65) Sub 1-77 m/z=295.91 (C ₁₂ H ₆ BrClS=297.59) Sub 1-78 m/z=313.9 (C ₁₂ H ₅ BrClFS=315.58) Sub 1-79 m/z=295.91 (C ₁₂ H ₆ BrClS=297.59) Sub 1-80 m/z=320.9 (C ₁₃ H ₅ BrClNS=322.6) Sub 1-81 m/z=295.91 (C ₁₂ H ₆ BrClS=297.59) Sub 1-82 m/z=325.92 (C ₁₃ H ₈ BrClOS=327.62) Sub 1-83 m/z=295.91 (C ₁₂ H ₆ BrClS=297.59) Sub 1-84 m/z=345.92 (C ₁₆ H ₈ BrClS=347.65) Sub 1-85 m/z=295.91 (C ₁₂ H ₆ BrClS=297.59) Sub 1-86 m/z=396.93 (C ₁₉ H ₉ BrClNS=398.7) Sub 1-87 m/z=295.91 (C ₁₂ H ₆ BrClS=297.59) Sub 1-88 m/z=371.94 (C ₁₈ H ₁₀ BrClS=373.69) Sub 1-89 m/z=355.96 (C ₁₈ H ₁₀ BrClO=357.63) Sub 1-90 m/z=355.96 (C ₁₈ H ₁₀ BrClO=357.63)

II. Synthesis of Sub 2

Sub 2 of Scheme 1 may be synthesized (initiated in Korean Patent Registration No. 10-1251451 (registered on April 5, 2013) of the applicant) by the reaction route of Scheme 3 below, but is not limited thereto. Hal ^{3 below} is Br or Cl.

<Reaction Scheme 3>

When Ar ⁴ is represented by Formula A-1, Ar ⁴ -Hal ³ of Scheme 3 may be synthesized by the reaction route of Scheme 4-1,

When Ar ⁴ is represented by Formula A-2, Ar ⁴ -Hal ³ of Scheme 3 may be synthesized by the reaction route of Scheme 4-2, but is not limited thereto.

The X ¹ , X ² , Y ¹ , Y ² , R ¹ to R ⁹ , R', R'', p, q, s, t, u, v, w are in Formula A-1 or Formula A-2. Is the same as defined; X'is -OH, -S(C ₂ H ₅ ), _{-NO 2} , or -CR'R"OH;Y'is -OH, -SH or -NH ₂ ; One of ^{R 3} to R ⁵ in Scheme 4-1 ^{is Hal 3} ; In Scheme 4-2, one of ^{R 6} to R ^{9 is Hal 3} .

<Reaction Scheme 4-1>

When X'is OH, it follows the synthetic route of (1); When X'is S(C ₂ H ₅ ), it follows the synthetic route of (2); When X'is NO ₂ , it follows the synthetic route of (3); When X'is CR'R''OH, it follows the synthesis route of (4).

<Reaction Scheme 4-2>

When Y'is -OH, it follows the synthetic route of (5); When Y'is -SH, it follows the synthetic route of (6); When Y'is -NH ₂ , it follows the synthesis route of (7). In addition, when Y ¹ in Sub 2-e is CR'R'', it can be synthesized according to the synthesis route of (8).

1.Sub 2-24 Synthesis example

(1) Synthesis example of Sub 2-24-a

After dissolving dibenzo[b,d]thiophen-2-ylboronic acid (50.0 g, 219.2 mmol) in THF (1.1 L), 3-chloro-2-iodophenol (55.8 g, 219.2 mmol), K ₂ CO ₃ (90.9 g, 657.7 mmol), Pd(PPh ₃ ) ₄ (15.2 g, 13.15 mmol), and water (550 mL) were added, followed by stirring at 80°C. When the reaction was completed, the _{mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Then, the resulting compound was recrystallized after applying a silica gel column to obtain 62 g (yield: 91%) of the product.

(2) Synthesis example of Sub 2-24-b

Sub 2-24-a (62 g, 199.5 mmol) in Pd(OAc) ₂ (2.24 g, 9.98 mmol), 3-nitropyridine (1.238 g, 9.98 mmol), BzOOt-Bu (tert-butyl peroxybenzoate) (77.5 g , 399 mmol), C ₆ F ₆ (hexafluorobenzene) (298 mL), and DMI (N,N'-dimethylimidazolidinone) (200 mL) were added and refluxed at 90° C. for 3 hours. When the reaction was completed, the temperature of the reaction product was cooled to room temperature, and extracted with EA and water. The organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was recrystallized using a silica gel column to obtain 25.3 g (yield: 41%) of the product Sub 2-24-b.

(3) Synthesis example of Sub 2-24

Sub 2-24-b (25.3 g, 81.9 mmol) was put in a round bottom flask and dissolved with toluene (410 mL), then [1,1'-biphenyl]-3-amine (20.8 g, 122.9 mmol), Pd ₂ (dba) ₃ (2.25 g, 2.46 mmol), P(t-Bu) ₃ (0.99 g, 4.92 mmol), and NaOt-Bu (15.7 g, 163.9 mmol) were added, followed by reflux stirring at 125°C. When the reaction was completed, _{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 a silica gel column to obtain 27.5 g (yield 76%) of the product.

2.Sub 2-25 Synthesis example

(1) Synthesis example of Sub 2-25-a

dibenzo[b,d]furan-2-ylboronic acid (50.0 g, 235.8 mmol), 2-(2-bromo-4-chlorophenyl)propan-2-ol (58.8 g, 235.8 mmol), K ₂ CO ₃ (97.8 g, 707.5 mmol), Pd(PPh ₃ ) ₄ (16.35 g, 14.15 mmol) was obtained using the synthesis method of Sub 2-24a, to obtain 68.3 g (yield: 86%) of the product.

(2) Synthesis example of Sub 2-25-b

Sub 2-25-a (68.3 g, 202.8 mmol) obtained in the above synthesis and _{150 ml of H 3} PO ₄ were put into a round bottom flask and stirred at room temperature for 12 hours. After the reaction was completed, the organic layer was extracted and concentrated, separated by a silica column, and dried to obtain 22.0 g (yield: 34%) of the product.

(3) Synthesis example of Sub 2-25

Sub 2-25-b (22.0 g, 69.0 mmol), aniline (9.6 g, 103.5 mmol), Pd ₂ (dba) ₃ (1.90 g, 2.07 mmol), P(t-Bu) ₃ (0.84 g, 4.14 mmol) ), NaOt-Bu (13.3 g, 138.0 mmol) was obtained as a product 18.4 g (yield: 71%) using the synthesis method of Sub 2-24.

3.Sub 2-32 Synthesis example

(1) Example of Sub 2-32-a synthesis

(9,9-dimethyl-9H-fluoren-1-yl)boronic acid (30.0 g, 126 mmol), 2-(2-bromo-5-chlorophenyl)propan-2-ol (31.4 g, 126 mmol), K ₂ CO ₃ (52.2 g, 378.0 mmol), Pd(PPh ₃ ) ₄ (8.74 g, 7.56 mmol) was obtained by using the synthesis method of Sub 2-24-a, 38 g (yield: 83%) of the product.

(2) Example of Sub 2-32-b synthesis

Sub 2-32-a (38 g, 104.7 mmol) obtained in the above synthesis, _{75 ml of H 3} PO ₄ was obtained by using the synthesis method of Sub 2-25-b to obtain 27.4 g (yield 76%) of the product.

(3) Example of Sub 2-32 synthesis

Sub 2-32-b (27.4 g, 79.4 mmol), aniline (11.1 g, 119.2 mmol), Pd ₂ (dba) ₃ (2.18 g, 2.38 mmol), P(t-Bu) ₃ (0.96 g, 4.77 mmol) ), NaOt-Bu (15.3 g, 158.9 mmol) was obtained by using the synthesis method of Sub 2-24, the product 22.1 g (yield: 74%).

4.Sub 2-57 Synthesis example

(1) Synthesis example of Sub 2-57-a

dibenzo[b,d]furan-2-ylboronic acid (50.0 g, 235.8 mmol), 3-chloro-2-iodophenol (60.0 g, 235.8 mmol), K ₂ CO ₃ (97.8 g, 707.5 mmol), Pd(PPh ₃ ) ₄ (16.35 g, 14.15 mmol) was obtained as a product 54.9 g (yield: 79%) using the synthesis method of Sub 2-24-a.

(2) Synthesis example of Sub 2-57-b

Sub 2-57-a (54.9 g, 186.3 mmol), Pd(OAc) ₂ (2.09 g, 9.32 mmol), 3-nitropyridine (1.156 g, 9.32 mmol), BzOOt-Bu (tert-butyl peroxybenzoate) (72.4 g , 372.6 mmol), C ₆ F ₆ (hexafluorobenzene) (278 mL), DMI (N,N'-dimethylimidazolidinone) (186 mL) using the synthesis method of Sub 2-24-b, product 21.3 g (yield: 39%).

(3) Example of Sub 2-57 synthesis

Sub 2-57-b (21.3 g, 72.8 mmol), dibenzo[b,d]thiophen-4-amine (21.8 g, 109.1 mmol), Pd ₂ (dba) ₃ (2.0 g, 2.18 mmol), P(t -Bu) ₃ (0.88 g, 4.37 mmol), NaOt-Bu (14.0 g, 145.5 mmol) was obtained by using the synthesis method of Sub 2-24, the product 23.9 g (yield: 72%).

5.Sub 2-62 Synthesis example

(1) Synthesis example of Sub 2-62-a

After dissolving (9,9-dimethyl-9H-fluoren-3-yl)boronic acid (30.0 g, 210 mmol) in THF (1050 mL), (3-bromo-2-iodophenyl)(ethyl)sulfane (72 g , 210 mmol), K ₂ CO ₃ (87.1 g, 630 mmol), Pd(PPh ₃ ) ₄ (14.56 g, 12.60 mmol), water (525 mL) were added and stirred at 80°C. When the reaction was completed, the _{mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 71.4 g (yield: 83%) of the product.

(2) Example of Sub 2-62-s synthesis

Add acetic acid (697 mL) to Sub 2-62-a (71.4 g, 174.3 mmol) obtained in the above synthesis, add 35% Hydrogen peroxide (H ₂ O ₂ ) (49.80 mL), and stir at room temperature. When the reaction was completed, it was neutralized with an aqueous NaOH solution, followed by extraction with ethylacetate (EA) and water. The organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was subjected to silica gel column and recrystallized to obtain 69 g (yield: 93%) of the product.

(3) Synthesis example of Sub 2-62-b

_{Sulfuric acid (H 2} SO ₄ ) (206.9 ml) was added to Sub 2-62-s (69 g, 162.1 mmol) obtained in the above synthesis and stirred at room temperature. When the reaction was completed, the mixture was neutralized with an aqueous NaOH solution, CH ₂ Cl ₂ and water were added to extract the organic layer. The organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was separated and purified through a silica gel column to obtain 23.4 g (yield: 38%) of Sub 2-62-b.

(4) Synthesis example of Sub 2-62

After dissolving Sub 2-62-b (23.4 g, 61.7 mmol) obtained in the above synthesis with Toluene (308 mL) in a round bottom flask, dibenzo[b,d]thiophen-4-amine (18.4 g, 92.5 mmol), Pd ₂ (dba) ₃ (1.69 g, 1.85 mmol), P(t-Bu) ₃ (0.75 g, 3.70 mmol), NaOt-Bu (11.9 g, 123.4 mmol) was added, and the synthesis method of Sub 2-24 was Using the product, 36.4 g (86% yield) was obtained.

6.Sub 2-76 Synthesis example

(1) Synthesis example of Sub 2-76-a

After dissolving (9-phenyl-9H-carbazol-1-yl)boronic acid (30.0 g, 104.5 mmol) in THF (522 mL), 5-bromo-2-iodophenol (31.2 g, 104.5 mmol), K ₂ CO ₃ (43.3 g, 313.4 mmol), Pd(PPh ₃ ) ₄ (7.24 g, 6.27 mmol), and water (261 mL) were added, followed by stirring at 80°C. When the reaction was completed, the _{mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 39.4 g (yield: 91%) of the product.

(2) Synthesis example of Sub 2-76-b

Sub 2-76-a (39.4 g, 95.1 mmol) in Pd(OAc) ₂ (1.07 g, 4.75 mmol), 3-nitropyridine (0.590 g, 4.75 mmol), BzOOt-Bu (tert-butyl peroxybenzoate) (36.9 g , 190.2 mmol), C ₆ F ₆ (hexafluorobenzene) (142 mL), and DMI (N,N'-dimethylimidazolidinone) (95 mL) were added and refluxed at 90° C. for 3 hours. When the reaction was completed, the temperature of the reaction product was cooled to room temperature, and extracted with EA and water. The organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was recrystallized through a silica gel column to obtain 27.4 g (yield: 70%) of the product.

(3) Synthesis example of Sub 2-76

After dissolving Sub 2-76-b (27.4 g, 66.5 mmol) obtained in the above synthesis with Toluene (332 mL) in a round bottom flask, 3-(tert-butyl)aniline (14.9 g, 99.7 mmol), Pd ₂ ( dba) ₃ (1.83 g, 1.99 mmol), P(t-Bu) ₃ (0.81 g, 3.99 mmol), NaOt-Bu (12.8 g, 132.9 mmol) was added and the product 27.5 using the synthesis method of Sub 2-24 g (yield 86%) was obtained.

7.Sub 2-82 Synthesis example

(1) Synthesis example of Sub 2-82-d

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

(2) Example of Sub 2-82-e synthesis

Sub 2-82-d (28.5 g, 107.7 mmol) obtained in the above synthesis was added to a round bottom flask, and H ₂ SO ₄ (770 mL) was added, followed by refluxing until all the starting materials were dissolved. When all the starting materials are dissolved, cool to room temperature and then add ice water to precipitate. Thereafter, the precipitate was washed with water and dried _{, dissolved in CH 2} Cl _2, and then recrystallized with a silica gel column to obtain 19.4 g (yield 68%) of the product.

(3) Synthesis example of Sub 2-82-f

2-bromo-1,1'-biphenyl (17.1 g, 73.28 mmol) was dissolved in THF (130 mL) in a round bottom flask under a nitrogen atmosphere, and then cooled to -78°C. After that, n-BuLi (29 mL) was slowly added dropwise, and the mixture was stirred for 30 minutes. Subsequently, Sub 2-82-e (19.4 g, 73.28 mmol) obtained in the above synthesis was dissolved in THF (120 mL), and then slowly added dropwise to the reaction round bottom flask. After stirring for an additional 1 hour at -78 ℃, it is gradually raised to room temperature. When the reaction was completed, ethyl acetate and water were extracted, the organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 24.4 g (yield 83%) of the product.

(4) Synthesis example of Sub 2-82-g

Sub 2-82-f (24.4 g, 60.83 mmol) obtained in the above synthesis, acetic acid (152 mL), and concentrated hydrochloric acid (24 mL) were added to a round bottom flask, followed by stirring at 60 to 80°C for 3 hours under a nitrogen atmosphere. . When the reaction was completed, the product was _{extracted with CH 2} Cl ₂ and water, and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized through a silica gel column to obtain 20.7 g (yield 89%) of the product.

(5) Synthesis example of Sub 2-82

After dissolving Sub 2-82-g (20.7 g, 54.1 mmol) obtained in the above synthesis with Toluene (270 mL) in a round bottom flask, 9,9-dimethyl-9H-fluoren-2-amine (17 g, 81.1 mmol) ), Pd ₂ (dba) ₃ (1.49 g, 1.62 mmol), P(t-Bu) ₃ (0.66 g, 3.24 mmol), NaOt-Bu (10.4 g, 108.1 mmol) was added, followed by 5 hours at 125°C. It was stirred while refluxing. When the reaction was completed, the product was _{extracted with CH 2} Cl ₂ and water, and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 21.3 g (yield 71%) of the product.

8.Sub 2-92 Synthesis example

(1) Synthesis example of Sub 2-92-d

2-iodobenzoic acid (30.0 g, 120.96 mmol), Phenol (22.8 g, 241.92 mmol), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (54.3 g, 362.67 mmol), pyridine (1.9 mL), copper powder (1.0 g, 15.72 mmol), and CuI (1.0 g, 5.44 mmol) in a round flask, DMF (968 mL) was added and refluxed for 3 hours. When the reaction is complete, after cooling to room temperature, 3M HCl is added until precipitation is completed. Thereafter, the precipitate was washed with water and dried to obtain 22.5 g (yield 87%) of the product.

(2) Synthesis example of Sub 2-92-e

Su b2-92-d (22.5 g, 105 mmol) and H ₂ SO ₄ (750 mL) obtained in the above synthesis were obtained using the synthesis method of Sub 2-82-b, to obtain 14 g (68% yield) of the product.

(3) Synthesis example of Sub 2-92-f

2-bromo-4'-chloro-1,1'-biphenyl (19.1 g, 71.35 mmol), n-BuLi (29 mL), Sub 2-92-e (14.0 g, 71.35 mmol) obtained in the above synthesis was added to the above. Using the synthesis method of Sub 2-82-c, the product 23.1 g (84% yield) was obtained.

(4) Synthesis example of Sub 2-92-g

Sub 2-92-f (23.1 g, 59.94 mmol) obtained in the above synthesis, acetic acid (150 mL) and concentrated hydrochloric acid (24 mL) were added to the product 19.8 g (yield 90%) using the synthesis method of Sub 2-82-d. ) Got it.

(5) Synthesis example of Sub 2-92

Sub 2-92-g (19.8 g, 54.0 mmol), aniline (7.5 g, 81.0 mmol), Pd ₂ (dba) ₃ (1.48 g, 1.62 mmol), P(t-Bu) ₃ (0.66) obtained in the above synthesis g, 3.24 mmol), NaOt-Bu (10.4 g, 107.9 mmol) was obtained by using the synthesis method of Sub 2-82, 22.8 g (yield 76%) of the product.

9.Sub 2-100 Synthesis example

(1) Example of Sub 2-100-h synthesis

9H-carbazole (20.0 g, 119.61 mmol), 2-bromo-1-iodonaphthalene (43.8 g, 131.57 mmol), Copper powder (7.6 g, 119.61 mmol), 18-Crown-6 (9.48 g, 35.88 g), Nitrobenzene (600 ml) was put in a round bottom flask and stirred at 220° C. for 12 hours. When the reaction is complete, distillation under reduced pressure to remove the solvent, dissolve in Toluene, put in a separatory funnel with water, and separate the organic matter. The organic material was subjected to silica gel column and recrystallized to obtain 35.62 g of the product.

(2) Example of Sub 2-100-i synthesis

To Sub 2-100-h (35.62 g, 95.68 mmol) obtained in the above synthesis, 3-chloro-9H-fluoren-9-one (20.5 g, 95.68 mmol), n-BuLi (38 mL) was added, and the Sub was added. Using the synthesis method of 2-82-c, the product 39.4 g (yield 87%) was obtained.

(3) Example of Sub 2-100-j synthesis

Acetic acid (208 mL) and concentrated hydrochloric acid (33 mL) were added to Sub 2-100-i (39.4 g, 83.2 mmol) obtained in the above synthesis, and the product 35.9 g (yield 88%).

(4) Synthesis example of Sub 2-100

Sub 2-100-j (36 g, 73.2 mmol), anilline (10.2 g, 109.8 mmol), Pd ₂ (dba) ₃ (2.01 g, 2.20 mmol), P(t-Bu) ₃ (0.89) obtained in the above synthesis g, 4.40 mmol), NaOt-Bu (14.1 g, 146.5 mmol) was obtained by using the synthesis method of Sub2-82, 30.4 g (yield 76%) of the product.

10. Sub 2-104 Synthesis example

(1) Synthesis example of Sub 2-104-c

2-(2-bromo-5-chlorophenyl)propan-2-ol (50.0 g, 200.4 mmol), benzylboronic acid (27.2 g, 200.4 mmol), K ₂ CO ₃ (83.1 g, 601.1 mmol), Pd(PPh ₃ ) ₄ (13.89 g, 12.02 mmol) was obtained as a product 44.9 g (yield: 86%) using the synthesis method of Sub 2-24-a.

(2) Synthesis example of Sub 2-104-c'

Sub 2-104-c (44.9 g, 172.3 mmol) obtained in the above synthesis was put into a reaction flask, 270 mL of sulfuric acid was added, and the mixture was stirred at room temperature for 2 hours. After the reaction was completed, purified water was slowly added, and NaOH aqueous solution was slowly added to adjust the pH to 7. After extraction with ethyl acetate and distilled water, it was treated with anhydrous magnesium sulfate. Crystallization from dichloromethane and nucleic acid gave the product 35.1 g (84% yield).

(3) Synthesis example of Sub 2-104-e

Sub 2-104-c' (35.1 g, 144.75 mmol) obtained in the above synthesis was added to acetic acid, heated to 58° C., and chromium trioxide (23.16 g, 231.6 mmol) dissolved in 1052 mL of acetic acid was added dropwise to the reaction. And stirred for 4 hours. After the reaction was completed, the solvent was removed, water was added to make crystals, extracted with dichloromethane and water, and the separated organic layer was treated with anhydrous magnesium sulfate and filtered. After distillation under reduced pressure to remove the solvent, ethanol and water were 3:1 and recrystallized to obtain 30 g (yield 81%) of the product.

(4) Synthesis example of Sub 2-104-f

2-bromo-1,1'-biphenyl (27.2 g, 116.85 mmol), n-BuLi (47 mL) was added to Sub 2-104-e (30 g, 116.85 mmol) obtained in the above synthesis, and the Sub 2- Using the synthesis method of 82-c, the product 41.3 g (86% yield) was obtained.

(5) Synthesis example of Sub 2-104-g

Sub 2-104-f (41.3 g, 100.49 mmol) obtained in the above synthesis, acetic acid (251 mL) and concentrated hydrochloric acid (40 mL) were added to the product 34.4 g (yield 87%) using the synthesis method of Sub2-82-d. Got it.

(6) Synthesis example of Sub 2-104

Sub 2-104-g (34.4 g, 87.5 mmol), [1,1'-biphenyl]-4-amine (22.2 g, 131.3 mmol), Pd ₂ (dba) ₃ (2.41 g, 2.63 mmol) obtained in the above synthesis ), P(t-Bu) ₃ (1.06 g, 5.25 mmol), NaOt-Bu (16.8 g, 175.1 mmol) was obtained using the synthesis method of Sub 2-82, to obtain a product 33.1 g (72% yield).

Examples of Sub 2 are as follows, but are not limited thereto.

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

compound FD-MS compound FD-MS Sub 2-1 m/z=169.09 (C ₁₂ H ₁₁ N=169.23) Sub 2-2 m/z=219.1 (C ₁₆ H ₁₃ N=219.29) Sub 2-3 m/z=245.12 (C ₁₈ H ₁₅ N=245.33) Sub 2-4 m/z=303.11 (C ₂₀ H ₁₇ NS=303.42) Sub 2-5 m/z=259.1 (C ₁₈ H ₁₃ NO=259.31) Sub 2-6 m/z=285.15 (C ₂₁ H ₁₉ N=285.39) Sub 2-7 m/z=219.1 (C ₁₆ H ₁₃ N=219.29) Sub 2-8 m/z=195.1 (C ₁₄ H ₁₃ N=195.27) Sub 2-9 m/z=205.07 (C ₁₂ H ₉ F ₂ N=205.21) Sub 2-10 m/z=321.15 (C ₂₄ H ₁₉ N=321.42) Sub 2-11 m/z=275.08 (C ₁₈ H ₁₃ NS=275.37) Sub 2-12 m/z=349.11 (C ₂₄ H ₁₅ NO ₂ =349.39) Sub 2-13 m/z=425.14 (C ₃₀ H ₁₉ NO ₂ =425.49) Sub 2-14 m/z=425.14 (C ₃₀ H ₁₉ NO ₂ =425.49) Sub 2-15 m/z=421.15 (C ₂₇ H ₂₃ NO ₂ Si=421.57) Sub 2-16 m/z=455.1 (C ₃₀ H ₁₇ NO ₂ S=455.53) Sub 2-17 m/z=365.09 (C ₂₄ H ₁₅ NOS=365.45) Sub 2-18 m/z=501.21 (C ₃₇ H ₂₇ NO=501.63) Sub 2-19 m/z=731.24 (C ₅₂ H ₃₃ N ₃ S=731.92) Sub 2-20 m/z=441.16 (C ₃₁ H ₂₃ NS=441.59) Sub 2-21 m/z=552.26 (C ₄₁ H ₃₂ N ₂ =552.72) Sub 2-22 m/z=451.19 (C ₃₃ H ₂₅ NO=451.57) Sub 2-23 m/z=590.24 (C ₄₃ H ₃₀ N ₂ O=590.73) Sub 2-24 m/z=441.12 (C ₃₀ H ₁₉ NOS=441.55) Sub 2-25 m/z=375.16 (C ₂₇ H ₂₁ NO=375.47) Sub 2-26 m/z=440.13 (C ₃₀ H ₂₀ N ₂ S=440.56) Sub 2-27 m/z=391.14 (C ₂₇ H ₂₁ NS=391.53) Sub 2-28 m/z=481.15 (C ₃₃ H ₂₃ NOS=481.61) Sub 2-29 m/z=797.35 (C ₅₇ H ₄₃ N ₅ =798.01) Sub 2-30 m/z=381.06 (C ₂₄ H ₁₅ NS ₂ =381.51) Sub 2-31 m/z=552.2 (C ₃₈ H ₂₄ N ₄ O=552.64) Sub 2-32 m/z=401.21 (C ₃₀ H ₂₇ N=401.55) Sub 2-33 m/z=732.26 (C ₅₃ H ₃₆ N ₂ S=732.95) Sub 2-34 m/z=405.08 (C ₂₆ H ₁₅ NO ₂ S=405.47) Sub 2-35 m/z=711.3 (C ₅₂ H ₄₁ NS=711.97) Sub 2-36 m/z=673.25 (C ₅₀ H ₃₁ N ₃ =673.82) Sub 2-37 m/z=321.15 (C ₂₄ H ₁₉ N=321.42) Sub 2-38 m/z=323.02 (C ₁₈ H ₁₃ NSe=322.27) Sub 2-39 m/z=332.13 (C ₂₄ H ₁₆ N ₂ =332.41) Sub 2-40 m/z=219.08 (C ₁₄ H ₉ N ₃ =219.25) Sub 2-41 m/z=321.15 (C ₂₄ H ₁₉ N=321.42) Sub 2-42 m/z=369.13 (C ₂₄ H ₂₀ NOP=369.4) Sub 2-43 m/z=401.21 (C ₃₀ H ₂₇ N=401.55) Sub 2-44 m/z=335.13 (C ₂₄ H ₁₇ NO=335.41) Sub 2-45 m/z=269.12 (C ₂₀ H ₁₅ N=269.35) Sub 2-46 m/z=251.08 (C ₁₆ H ₁₃ NS=251.35) Sub 2-47 m/z=349.11 (C ₂₄ H ₁₅ NO ₂ =349.39) Sub 2-48 m/z=514.15 (C ₃₆ H ₂₂ N ₂ S=514.65) Sub 2-49 m/z=523.23 (C ₄₀ H ₂₉ N=523.68) Sub 2-50 m/z=349.11 (C ₂₄ H ₁₅ NO ₂ =349.39) Sub 2-51 m/z=620.23 (C ₄₄ H ₃₂ N ₂ S=620.81) Sub 2-52 m/z=349.11 (C ₂₄ H ₁₅ NO ₂ =349.39) Sub 2-53 m/z=477.25 (C ₃₆ H ₃₁ N=477.65) Sub 2-54 m/z=511.14 (C ₃₄ H ₂₅ NS ₂ =511.7) Sub 2-55 m/z=425.18 (C ₃₁ H ₂₃ NO=425.53) Sub 2-56 m/z=465.13 (C ₃₁ H ₁₉ N ₃ S=465.57) Sub 2-57 m/z=455.1 (C ₃₀ H ₁₇ NO ₂ S=455.53) Sub 2-58 m/z=481.15 (C ₃₃ H ₂₃ NOS=481.61) Sub 2-59 m/z=576.11 (C ₃₂ H ₁₈ F ₆ N ₂ S=576.56) Sub 2-60 m/z=526.24 (C ₃₉ H ₃₀ N ₂ =526.68) Sub 2-61 m/z=492.16 (C ₃₄ H ₂₁ FN ₂ O=492.55) Sub 2-62 m/z=497.13 (C ₃₃ H ₂₃ NS ₂ =497.67) Sub 2-63 m/z=619.16 (C ₄₃ H ₂₅ NO ₂ S=619.74) Sub 2-64 m/z=375.16 (C ₂₇ H ₂₁ NO=375.47) Sub 2-65 m/z=493.19 (C ₃₅ H ₂₇ NS=493.67) Sub 2-66 m/z=490.15 (C ₃₄ H ₂₂ N ₂ S=490.62) Sub 2-67 m/z=515.24 (C ₃₇ H ₂₉ N ₃ =515.66) Sub 2-68 m/z=426.15 (C ₂₈ H ₁₈ N ₄ O=426.48) Sub 2-69 m/z=646.21 (C ₄₅ H ₃₀ N ₂ OS=646.81) Sub 2-70 m/z=365.09 (C ₂₄ H ₁₅ NOS=365.45) Sub 2-71 m/z=391.14 (C ₂₇ H ₂₁ NS=391.53) Sub 2-72 m/z=351.11 (C ₂₄ H ₁₇ NS=351.47) Sub 2-73 m/z=195.1 (C ₁₄ H ₁₃ N=195.27) Sub 2-74 m/z=401.21 (C ₃₀ H ₂₇ N=401.55) Sub 2-75 m/z=487.05 (C ₃₀ H ₁₇ NS ₃ =487.65) Sub 2-76 m/z=480.22 (C ₃₄ H ₂₈ N ₂ O=480.61) Sub 2-77 m/z=455.1 (C ₃₀ H ₁₇ NO ₂ S=455.53) Sub 2-78 m/z=557.22 (C ₄₀ H ₃₁ NS=557.76) Sub 2-79 m/z=471.11 (C ₃₁ H ₂₁ NS ₂ =471.64) Sub 2-80 m/z=742.33 (C ₅₆ H ₄₂ N ₂ =742.97) Sub 2-81 m/z=515.17 (C ₃₇ H ₂₅ NS=515.67) Sub 2-82 m/z=555.2 (C ₄₀ H ₂₉ NS=555.74) Sub 2-83 m/z=361.18 (C ₂₇ H ₂₃ N=361.49) Sub 2-84 m/z=439.14 (C ₃₁ H ₂₁ NS=439.58) Sub 2-85 m/z=269.12 (C ₂₀ H ₁₅ N=269.35) Sub 2-86 m/z=440.13 (C ₃₀ H ₂₀ N ₂ S=440.56) Sub 2-87 m/z=439.14 (C ₃₁ H ₂₁ NS=439.58) Sub 2-88 m/z=535.17 (C ₃₇ H ₂₃ F ₂ NO=535.59) Sub 2-89 m/z=513.17 (C ₃₇ H ₂₃ NO ₂ =513.6) Sub 2-90 m/z=439.19 (C ₃₂ H ₂₅ NO=439.56) Sub 2-91 m/z=423.16 (C ₃₁ H ₂₁ NO=423.52) Sub 2-92 m/z=423.16 (C ₃₁ H ₂₁ NO=423.52) Sub 2-93 m/z=681.25 (C ₅₀ H ₃₂ FNO=681.81) Sub 2-94 m/z=423.16 (C ₃₁ H ₂₁ NO=423.52) Sub 2-95 m/z=574.24 (C ₄₃ H ₃₀ N ₂ =574.73) Sub 2-96 m/z=548.23 (C ₄₁ H ₂₈ N ₂ =548.69) Sub 2-97 m/z=654.21 (C ₄₇ H ₃₀ N ₂ S=654.83) Sub 2-98 m/z=514.24 (C ₃₈ H ₃₀ N ₂ =514.67) Sub 2-99 m/z=664.25 (C ₄₉ H ₃₂ N ₂ O=664.81) Sub 2-100 m/z=546.21 (C ₄₁ H ₂₆ N ₂ =546.67) Sub 2-101 m/z=498.21 (C ₃₇ H ₂₆ N ₂ =498.63) Sub 2-102 m/z=565.28 (C ₄₃ H ₃₅ N=565.76) Sub 2-103 m/z=449.21 (C ₃₄ H ₂₇ N=449.6) Sub 2-104 m/z=525.25 (C ₄₀ H ₃₁ N=525.7) Sub 2-105 m/z=335.13 (C ₂₄ H ₁₇ NO=335.41) Sub 2-106 m/z=631.23 (C ₄₆ H ₃₃ NS=631.84) Sub 2-107 m/z=655.29 (C ₄₉ H ₃₇ NO=655.84) Sub 2-108 m/z=859.38 (C ₆₅ H ₄₉ NO=860.11) Sub 2-109 m/z=649.28 (C ₅₀ H ₃₅ N=649.84) Sub 2-110 m/z=449.21 (C ₃₄ H ₂₇ N=449.6) Sub 2-111 m/z=574.24 (C ₄₃ H ₃₀ N ₂ =574.73) Sub 2-112 m/z=449.21 (C ₃₄ H ₂₇ N=449.6) Sub 2-113 m/z=499.19 (C ₃₇ H ₂₅ NO=499.61) Sub 2-114 m/z=375.16 (C ₂₇ H ₂₁ NO=375.47) Sub 2-115 m/z=365.09 (C ₂₄ H ₁₅ NOS=365.45) Sub 2-116 m/z=361.18 (C ₂₇ H ₂₃ N=361.49) Sub 2-117 m/z=335.13 (C ₂₄ H ₁₇ NO=335.41) Sub 2-118 m/z=515.17 (C ₃₇ H ₂₅ NS=515.67) Sub 2-119 m/z=334.15 (C ₂₄ H ₁₈ N ₂ =334.42) Sub 2-120 m/z=499.19 (C ₃₇ H ₂₅ NO=499.61) Sub 2-121 m/z=259.1 (C ₁₈ H ₁₃ NO=259.31) Sub 2-122 m/z=455.1 (C ₃₀ H ₁₇ NO ₂ S=455.53)

III. Sub 3 synthesis

Sub 3 of Scheme 1 may be synthesized by the reaction route of Scheme 5 below, but is not limited thereto. Hal ⁴ and Hal ⁵ are each independently Br or Cl; Hal ⁶ is I or Br; Ar ¹ to Ar ³ may be each independently of Formula A-1 or Formula A-2.

<Reaction Scheme 5>

1.Sub 3-5 Synthesis example

(1) Sub 3-5-a synthesis example

After dissolving Sub 2-57-b (20 g, 68.3 mmol) in Toluene (340 mL) in a round bottom flask, 9,9-dimethyl-9H-fluoren-2-amine (21.4 g, 102.5 mmol), Pd ₂ (dba) ₃ (1.88 g, 2.05 mmol), P(t-Bu) ₃ (0.83 g, 4.2 mmol), NaOt-Bu (13.1 g, 136.6 mmol) were added and stirred at 125°C. When the reaction was completed, the product was _{extracted with CH 2} Cl ₂ and water, and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 25.8 g (yield 81%) of the product.

(2) Example of Sub 3-5-b synthesis

Sub 3-5-a (25.8 g, 55.3 mmol), 1-bromo-3-chlorobenzene (10.6 g, 55.3 mmol), Pd2(dba)3 (1.52 g, 1.66 mmol), P(t-) obtained in the above synthesis Bu)3 (0.67 g, 3.32 mmol) and NaOt-Bu (10.6 g, 110.7 mmol) were stirred at 80° C. to obtain 28.7 g (yield 90%) of the product using the synthesis method of Sub 3-5-a.

(3) Sub 3-5 synthesis example

Sub 3-5-b (28.7 g, 49.8 mmol), aniline (7 g, 74.7 mmol), Pd2(dba)3 (1.37 g, 1.49 mmol), P(t-Bu)3 (0.60 g) obtained in the above synthesis , 2.99 mmol), NaOt-Bu (9.6 g, 99.6 mmol) was obtained by using the synthesis method of Sub 3-5-a, to obtain a product 25.2 g (yield 80%).

2.Sub 3-63 Synthesis example

(1) Synthesis example of Sub 3-63-a

diphenylamine (20 g, 118.2 mmol), 1-bromo-2-chlorobenzene (22.6 g, 118.2 mmol), Pd ₂ (dba) ₃ (3.25 g, 3.55 mmol), P(t-Bu) ₃ (1.43 g, 7.09 mmol) and NaOt-Bu (22.7 g, 236.4 mmol) were stirred at 80° C. to obtain 25.8 g (yield 79%) of the product using the synthesis method of Sub 3-5-a.

(2) Synthesis example of Sub 3-63-b

After dissolving Sub 3-63-a (25.8 g, 92.2 mmol) obtained in the above synthesis in THF (460 mL), (4-aminophenyl)boronic acid (16.1 g, 92.2 mmol), NaOH (11.1 g, 276.5 mmol) , Pd(PPh ₃ ) ₄ (6.39 g, 5.53 mmol) and water (230 mL) were added, followed by reflux stirring at 80°C. When the reaction was completed, the _{mixture was extracted with CH 2} Cl ₂ and water, and the organic layer was dried over _{MgSO 4 and concentrated.} Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 26.1 g (yield: 84%) of the product.

(3) Example of Sub 3-63 synthesis

Sub 3-63-b (26.1 g, 77.4 mmol), 2'-bromospiro[fluorene-9,9'-xanthene] (22.3 g, 54.2 mmol), Pd ₂ (dba) ₃ (1.49 g, obtained in the above synthesis) 1.63 mmol), P(t-Bu) ₃ (0.66 g, 3.25 mmol), NaOt-Bu (10.4 g, 108.4 mmol) was stirred at room temperature, and the product 30.0 g ( Yield 83%).

3.Sub 3-72 Synthesis example

(1) Synthesis example of Sub 3-72-a

1-bromo-4-chlorodibenzo[b,d]thiophene (20.0 g, 67.2 mmol), (9,9-dimethyl-9H-fluoren-2-yl)boronic acid (16 g, 67.2 mmol), NaOH (8.1 g , 201.6 mmol), Pd(PPh ₃ ) ₄ (4.66 g, 4.03 mmol) was obtained using the synthesis method of Sub 3-63-b, to obtain a product 24.3 g (yield: 88%).

(2) Example of Sub 3-72 synthesis

Sub 3-72-a (24.3 g, 59.1 mmol), N1,N1-diphenylbenzene-1,3-diamine (23.1 g, 88.7 mmol), Pd ₂ (dba) ₃ (1.62 g, 1.77 mmol) obtained in the above synthesis , P(t-Bu) ₃ (0.72 g, 3.55 mmol), NaOt-Bu (11.4 g, 118.3 mmol) was obtained using the synthesis method of Sub 3-5-a, to obtain a product 31.2 g (yield 83%).

4.Sub 3-120 Synthesis example

(1) Synthesis example of Sub 3-120-a

2-bromo-4-chlorodibenzo[b,d]thiophene (20 g, 68.4 mmol), diphenylamine (11.6 g, 68.4 mmol), Pd ₂ (dba) ₃ (1.88 g, 2.05 mmol), P(t-Bu) ₃ (0.83 g, 4.10 mmol) and NaOt-Bu (13.1 g, 136.7 mmol) were stirred at 80° C. to obtain 22.7 g (yield 86%) of the product using the synthesis method of Sub 3-5-a.

(2) Example of Sub 3-120 synthesis

Sub 3-120-a (22.7 g, 58.8 mmol), aniline (8.2 g, 88.2 mmol), Pd ₂ (dba) ₃ (1.61 g, 1.76 mmol), P(t-Bu) ₃ (0.71) obtained in the above synthesis g, 3.53 mmol), NaOt-Bu (11.3 g, 117.6 mmol) was obtained by using the synthesis method of Sub 3-5-a, to obtain 21.9 g (yield 84%) of the product.

5.Sub 3-122 Synthesis example

(1) Synthesis example of Sub 3-122-a

1-chloro-10,10-dimethyl-10H-spiro[anthracene-9,9'-fluorene] (30 g, 76.3 mmol), aniline (10.7 g, 114.5 mmol), Pd ₂ (dba) ₃ (2.10 g, 2.29 mmol), P(t-Bu) ₃ (0.93 g, 4.58 mmol), NaOt-Bu (14.7 g, 152.7 mmol) was added to the product 26.1 g (yield 76%) using the synthesis method of Sub 3-5-a Got it.

(2) Synthesis example of Sub 3-122-b

Sub 3-122-a (26.1 g, 58.0 mmol), 1-bromo-6-chlorodibenzo[b,d]furan (16.3 g, 58.0 mmol), Pd ₂ (dba) ₃ (1.59 g, 1.74) obtained in the above synthesis mmol), P(t-Bu) ₃ (0.70 g, 3.48 mmol), and NaOt-Bu (11.2 g, 116.1 mmol) were stirred at 80° C., and the product 26.4 g ( Yield 70%) was obtained.

(3) Synthesis example of Sub 3-122

Sub 3-122-b (26.4 g, 40.6 mmol), (3-(phenylamino)phenyl)boronic acid (8.7 g, 40.6 mmol), NaOH (4.9 g, 121.9 mmol), Pd(PPh ₃ ) obtained in the above synthesis ₄ (2.82 g, 2.44 mmol) was obtained as a product 25.8 g (yield: 81%) using the synthesis method of Sub 3-63-b.

6.Sub 3-140 Synthesis example

(1) Synthesis example of Sub 3-140-a

1-bromo-8-chlorodibenzo[b,d]furan (20 g, 71.0 mmol), diphenylamine (12.0 g, 71.0 mmol), Pd ₂ (dba) ₃ (1.95 g, 2.13 mmol), P(t-Bu) ₃ (0.86 g, 4.26 mmol) and NaOt-Bu (13.7 g, 142.1 mmol) were stirred at 80° C. to obtain 23.3 g (yield 85%) of the product using the synthesis method of Sub 3-5-a.

(2) Synthesis example of Sub 3-140

Sub 3-140-a (23.3 g, 60.4 mmol), aniline (8.4 g, 90.6 mmol), Pd ₂ (dba) ₃ (1.66 g, 1.81 mmol), P(t-Bu) ₃ (0.73) obtained in the above synthesis g, 3.62 mmol), NaOt-Bu (11.6 g, 120.8 mmol) was obtained by using the synthesis method of Sub 3-5-a, to obtain 22.2 g (yield 83%) of the product.

7.Sub 3-141 Synthesis example

(1) Synthesis example of Sub 3-141-a

1-bromo-3-chlorobenzene (50 g, 261.2 mmol), diphenylamine (44.2 g, 261.2 mmol), Pd ₂ (dba) ₃ (7.17 g, 7.83 mmol), P(t-Bu) ₃ (3.17 g, 15.67 mmol) and NaOt-Bu (50.2 g, 522.3 mmol) were stirred at 80° C. to obtain 59.9 g (82% yield) of the product using the synthesis method of Sub 3-5-a.

(2) Synthesis example of Sub 3-141

Sub 3-141-a (59.9 g, 214.2 mmol), aniline (29.9 g, 321.2 mmol), Pd ₂ (dba) ₃ (5.88 g, 6.42 mmol), P(t-Bu) ₃ (2.60) obtained in the above synthesis g, 12.85 mmol), NaOt-Bu (41.2 g, 428.3 mmol) was obtained by using the synthesis method of Sub 3-5-a, to obtain a product 55.5 g (yield 77%).

Examples of Sub 3 are as follows, but are not limited thereto.

Table 3 below shows the FD-MS values of the compounds belonging to Sub 3.

compound FD-MS compound FD-MS Sub 3-1 m/z=516.18 (C ₃₆ H ₂₄ N ₂ O ₂ =516.6) Sub 3-2 m/z=597.25 (C ₄₂ H ₂₃ D ₅ N ₂ O ₂ =597.73) Sub 3-3 m/z=650.24 (C ₄₅ H ₃₁ FN ₂ O ₂ =650.75) Sub 3-4 m/z=632.25 (C ₄₅ H ₃₂ N ₂ O ₂ =632.76) Sub 3-5 m/z=632.25 (C ₄₅ H ₃₂ N ₂ O ₂ =632.76) Sub 3-6 m/z=622.17 (C ₄₂ H ₂₆ N ₂ O ₂ S=622.74) Sub 3-7 m/z=516.18 (C ₃₆ H ₂₄ N ₂ O ₂ =516.6) Sub 3-8 m/z=702.23 (C ₄₈ H ₂₆ D ₄ N ₂ O ₂ S=702.86) Sub 3-9 m/z=681.24 (C ₄₈ H ₃₁ N ₃ O ₂ =681.8) Sub 3-10 m/z=592.22 (C ₄₂ H ₂₈ N ₂ O ₂ =592.7) Sub 3-11 m/z=516.18 (C ₃₆ H ₂₄ N ₂ O ₂ =516.6) Sub 3-12 m/z=632.25 (C ₄₅ H ₃₂ N ₂ O ₂ =632.76) Sub 3-13 m/z=516.18 (C ₃₆ H ₂₄ N ₂ O ₂ =516.6) Sub 3-14 m/z=592.22 (C ₄₂ H ₂₈ N ₂ O ₂ =592.7) Sub 3-15 m/z=592.22 (C ₄₂ H ₂₈ N ₂ O ₂ =592.7) Sub 3-16 m/z=361.16 (C ₂₅ H ₁₉ N ₃ =361.45) Sub 3-17 m/z=336.16 (C ₂₄ H ₂₀ N ₂ =336.44) Sub 3-18 m/z=436.19 (C ₃₂ H ₂₄ N ₂ =436.56) Sub 3-19 m/z=426.17 (C ₃₀ H ₂₂ N ₂ O=426.52) Sub 3-20 m/z=488.23 (C ₃₆ H ₂₈ N ₂ =488.63) Sub 3-21 m/z=518.18 (C ₃₆ H ₂₆ N ₂ S=518.68) Sub 3-22 m/z=552.23 (C ₃₉ H ₂₈ N ₄ =552.68) Sub 3-23 m/z=436.19 (C ₃₂ H ₂₄ N ₂ =436.56) Sub 3-24 m/z=612.24 (C ₄₃ H ₃₀ F ₂ N ₂ =612.72) Sub 3-25 m/z=426.17 (C ₃₀ H ₂₂ N ₂ O=426.52) Sub 3-26 m/z=502.2 (C ₃₆ H ₂₆ N ₂ O=502.62) Sub 3-27 m/z=484.23 (C ₃₃ H ₃₂ N ₂ Si=484.72) Sub 3-28 m/z=442.15 (C ₃₀ H ₂₂ N ₂ S=442.58) Sub 3-29 m/z=561.3 (C ₄₀ H ₁₉ D ₁₀ N ₃ =561.75) Sub 3-30 m/z=502.2 (C ₃₆ H ₂₆ N ₂ O=502.62) Sub 3-31 m/z=412.19 (C ₃₀ H ₂₄ N ₂ =412.54) Sub 3-32 m/z=518.18 (C ₃₆ H ₂₆ N ₂ S=518.68) Sub 3-33 m/z=538.24 (C ₄₀ H ₃₀ N ₂ =538.69) Sub 3-34 m/z=436.19 (C ₃₂ H ₂₄ N ₂ =436.56) Sub 3-35 m/z=578.24 (C ₄₂ H ₃₀ N ₂ O=578.72) Sub 3-36 m/z=378.21 (C ₂₇ H ₂₆ N ₂ =378.52) Sub 3-37 m/z=388.19 (C ₂₈ H ₂₄ N ₂ =388.51) Sub 3-38 m/z=336.16 (C ₂₄ H ₂₀ N ₂ =336.44) Sub 3-39 m/z=386.18 (C ₂₈ H ₂₂ N ₂ =386.5) Sub 3-40 m/z=520.21 (C ₃₆ H ₂₀ D ₄ N ₂ O ₂ =520.62) Sub 3-41 m/z=658.21 (C ₄₆ H ₃₀ N ₂ OS=658.82) Sub 3-42 m/z=684.35 (C ₅₁ H ₄₄ N ₂ =684.93) Sub 3-43 m/z=774.25 (C ₅₃ H ₃₄ N ₄ OS=774.94) Sub 3-44 m/z=682.26 (C ₄₉ H ₃₄ N ₂ O ₂ =682.82) Sub 3-45 m/z=622.17 (C ₄₂ H ₂₆ N ₂ O ₂ S=622.74) Sub 3-46 m/z=648.22 (C ₄₅ H ₃₂ N ₂ OS=648.82) Sub 3-47 m/z=713.2 (C ₄₈ H ₃₁ N ₃ S ₂ =713.92) Sub 3-48 m/z=568.29 (C ₄₂ H ₃₆ N ₂ =568.76) Sub 3-49 m/z=566.2 (C ₄₀ H ₂₆ N ₂ O ₂ =566.66) Sub 3-50 m/z=557.16 (C ₃₇ H ₂₃ N ₃ OS=557.67) Sub 3-51 m/z=742.31 (C ₅₄ H ₃₈ N ₄ =742.93) Sub 3-52 m/z=592.22 (C ₄₂ H ₂₈ N ₂ O ₂ =592.7) Sub 3-53 m/z=608.19 (C ₄₂ H ₂₈ N ₂ OS=608.76) Sub 3-54 m/z=692.28 (C ₅₁ H ₃₆ N ₂ O=692.86) Sub 3-55 m/z=412.19 (C ₃₀ H ₂₄ N ₂ =412.54) Sub 3-56 m/z=460.19 (C ₃₄ H ₂₄ N ₂ =460.58) Sub 3-57 m/z=473.17 (C ₃₁ H ₂₁ F ₂ N ₃ =473.53) Sub 3-58 m/z=532.16 (C ₃₆ H ₂₄ N ₂ OS=532.66) Sub 3-59 m/z=452.23 (C ₃₃ H ₂₈ N ₂ =452.6) Sub 3-60 m/z=476.19 (C ₃₄ H ₂₄ N ₂ O=476.58) Sub 3-61 m/z=574.24 (C ₄₃ H ₃₀ N ₂ =574.73) Sub 3-62 m/z=617.28 (C ₄₅ H ₃₅ N ₃ =617.8) Sub 3-63 m/z=666.27 (C ₄₉ H ₃₄ N ₂ O=666.82) Sub 3-64 m/z=518.18 (C ₃₆ H ₂₆ N ₂ S=518.68) Sub 3-65 m/z=616.29 (C ₄₆ H ₃₆ N ₂ =616.81) Sub 3-66 m/z=518.18 (C ₃₆ H ₂₆ N ₂ S=518.68) Sub 3-67 m/z=611.31 (C ₄₄ H ₂₁ D ₁₀ N ₃ =611.81) Sub 3-68 m/z=684.22 (C ₄₈ H ₃₂ N ₂ OS=684.86) Sub 3-69 m/z=607.21 (C ₄₂ H ₂₉ N ₃ S=607.78) Sub 3-70 m/z=558.27 (C ₄₀ H ₃₄ N ₂ O=558.73) Sub 3-71 m/z=490.22 (C ₃₄ H ₂₆ N ₄ =490.61) Sub 3-72 m/z=634.24 (C ₄₅ H ₃₄ N ₂ S=634.84) Sub 3-73 m/z=488.23 (C ₃₆ H ₂₈ N ₂ =488.63) Sub 3-74 m/z=488.23 (C ₃₆ H ₂₈ N ₂ =488.63) Sub 3-75 m/z=516.18 (C ₃₆ H ₂₄ N ₂ O ₂ =516.6) Sub 3-76 m/z=608.19 (C ₄₂ H ₂₈ N ₂ OS=608.76) Sub 3-77 m/z=658.3 (C ₄₈ H ₃₈ N ₂ O=658.85) Sub 3-78 m/z=649.16 (C ₄₃ H ₂₇ N ₃ S ₂ =649.83) Sub 3-79 m/z=813.28 (C ₅₇ H ₃₉ N ₃ OS=814.02) Sub 3-80 m/z=747.23 (C ₅₂ H ₃₃ N ₃ OS=747.92) Sub 3-81 m/z=586.28 (C ₄₂ H ₃₅ FN ₂ =586.75) Sub 3-82 m/z=702.23 (C ₄₈ H ₂₆ D ₄ N ₂ O ₂ S=702.86) Sub 3-83 m/z=723.27 (C ₅₁ H ₃₇ N ₃ S=723.94) Sub 3-84 m/z=772.31 (C ₅₆ H ₄₀ N ₂ O ₂ =772.95) Sub 3-85 m/z=724.25 (C ₅₁ H ₃₆ N ₂ OS=724.92) Sub 3-86 m/z=674.28 (C ₄₈ H ₃₈ N ₂ S=674.91) Sub 3-87 m/z=618.27 (C ₄₅ H ₃₄ N ₂ O=618.78) Sub 3-88 m/z=809.29 (C ₅₈ H ₃₉ N ₃ S=810.03) Sub 3-89 m/z=668.25 (C ₄₈ H ₃₂ N ₂ O ₂ =668.8) Sub 3-90 m/z=376.25 (C ₂₅ H ₄ D ₁₅ N ₃ =376.54) Sub 3-91 m/z=417.23 (C ₃₀ H ₁₉ D ₅ N ₂ =417.57) Sub 3-92 m/z=436.19 (C ₃₂ H ₂₄ N ₂ =436.56) Sub 3-93 m/z=542.24 (C ₃₉ H ₃₀ N ₂ O=542.68) Sub 3-94 m/z=606.23 (C ₄₃ H ₃₀ N ₂ O ₂ =606.73) Sub 3-95 m/z=698.24 (C ₄₉ H ₃₄ N ₂ OS=698.88) Sub 3-96 m/z=452.23 (C ₃₃ H ₂₈ N ₂ =452.6) Sub 3-97 m/z=617.28 (C ₄₅ H ₃₅ N ₃ =617.8) Sub 3-98 m/z=797.34 (C ₅₈ H ₄₃ N ₃ O=798) Sub 3-99 m/z=891.33 (C ₆₃ H ₄₅ N ₃ OS=892.13) Sub 3-100 m/z=858.4 (C ₆₅ H ₅₀ N ₂ =859.13) Sub 3-101 m/z=506.23 (C ₃₆ H ₂₂ D ₄ N ₂ O=506.64) Sub 3-102 m/z=952.35 (C ₆₉ H ₄₈ N ₂ OS=953.22) Sub 3-103 m/z=644.28 (C ₄₇ H ₃₆ N ₂ O=644.82) Sub 3-104 m/z=502.2 (C ₃₆ H ₂₆ N ₂ O=502.62) Sub 3-105 m/z=692.21 (C ₄₇ H ₃₀ F ₂ N ₂ S=692.83) Sub 3-106 m/z=706.24 (C ₅₁ H ₃₄ N ₂ S=706.91) Sub 3-107 m/z=558.21 (C ₃₉ H ₃₀ N ₂ S=558.74) Sub 3-108 m/z=461.14 (C ₂₉ H ₁₅ N ₇ =461.49) Sub 3-109 m/z=412.19 (C ₃₀ H ₂₄ N ₂ =412.54) Sub 3-110 m/z=620.25 (C ₄₄ H ₃₂ N ₂ O ₂ =620.75) Sub 3-111 m/z=578.25 (C ₄₁ H ₃₀ N ₄ =578.72) Sub 3-112 m/z=831.34 (C ₆₀ H ₄₁ N ₅ =832.02) Sub 3-113 m/z=758.28 (C ₅₅ H ₃₈ N ₂ S=758.98) Sub 3-114 m/z=526.2 (C ₃₈ H ₂₆ N ₂ O=526.64) Sub 3-115 m/z=426.17 (C ₃₀ H ₂₂ N ₂ O=426.52) Sub 3-116 m/z=885.39 (C ₆₁ H ₅₅ N ₃ Si ₂ =886.3) Sub 3-117 m/z=590.24 (C ₄₀ H ₃₄ N ₂ OS=590.79) Sub 3-118 m/z=442.15 (C ₃₀ H ₂₂ N ₂ S=442.58) Sub 3-119 m/z=502.2 (C ₃₆ H ₂₆ N ₂ O=502.62) Sub 3-120 m/z=442.15 (C ₃₀ H ₂₂ N ₂ S=442.58) Sub 3-121 m/z=488.23 (C ₃₆ H ₂₈ N ₂ =488.63) Sub 3-122 m/z=782.33 (C ₅₈ H ₄₂ N ₂ O=782.99) Sub 3-123 m/z=426.19 (C ₂₇ H ₂₆ N ₂ O ₃ =426.52) Sub 3-124 m/z=590.24 (C ₄₃ H ₃₀ N ₂ O=590.73) Sub 3-125 m/z=590.24 (C ₄₃ H ₃₀ N ₂ O=590.73) Sub 3-126 m/z=412.19 (C ₃₀ H ₂₄ N ₂ =412.54) Sub 3-127 m/z=874.34 (C ₆₄ H ₄₆ N ₂ S=875.15) Sub 3-128 m/z=706.24 (C ₅₁ H ₃₄ N ₂ S=706.91) Sub 3-129 m/z=732.28 (C ₅₃ H ₃₆ N ₂ O ₂ =732.88) Sub 3-130 m/z=665.28 (C ₄₉ H ₃₅ N ₃ =665.84) Sub 3-131 m/z=568.29 (C ₄₂ H ₃₆ N ₂ =568.76) Sub 3-132 m/z=590.24 (C ₄₃ H ₃₀ N ₂ O=590.73) Sub 3-133 m/z=681.28 (C ₄₉ H ₃₅ N ₃ O=681.84) Sub 3-134 m/z=616.29 (C ₄₆ H ₃₆ N ₂ =616.81) Sub 3-135 m/z=682.24 (C ₄₉ H ₃₄ N ₂ S=682.89) Sub 3-136 m/z=857.38 (C ₆₄ H ₄₇ N ₃ =858.1) Sub 3-137 m/z=590.24 (C ₄₃ H ₃₀ N ₂ O=590.73) Sub 3-138 m/z=698.24 (C ₄₉ H ₃₄ N ₂ OS=698.88) Sub 3-139 m/z=732.35 (C ₅₅ H ₄₄ N ₂ =732.97) Sub 3-140 m/z=426.17 (C ₃₀ H ₂₂ N ₂ O=426.52) Sub 3-141 m/z=336.16 (C ₂₄ H ₂₀ N ₂ =336.44)

IV. Synthesis of final compound

1.P-1 Synthesis example

(1) Inter 1-a synthesis example

After dissolving Sub 1-31 (5.00 g, 17.8 mmol) in toluene (90 mL) in a round bottom flask, Sub 2-1 (3.0 g, 17.8 mmol), Pd ₂ (dba) ₃ (0.49 g, 0.53 mmol) , P(t-Bu) ₃ (0.22 g, 1.07 mmol) and NaOt-Bu (3.4 g, 35.5 mmol) were added and stirred at 40°C. When the reaction was completed, the product was _{extracted with CH 2} Cl ₂ and water, and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 10.3 g (yield 81%) of the product.

(2) Synthesis example of P-1

Inter 1-a (5.3 g, 14.4 mmol) obtained in the above synthesis was dissolved in toluene (72 mL) in a round bottom flask, and then Sub 3-1 (7.4 g, 14.4 mmol), Pd ₂ (dba) ₃ (0.40 g , 0.43 mmol), P(t-Bu) ₃ (0.17 g, 0.86 mmol), and NaOt-Bu (2.8 g, 128.8 mmol) were added, followed by reflux stirring at 125°C. When the reaction was completed, the product was _{extracted with CH 2} Cl ₂ and water, and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 9.5 g (yield 78%) of the product.

2. P-24 Synthesis example

(1) Inter 24-a synthesis example

Sub 1-3 (5.00 g, 17.8 mmol), Sub 2-20 (7.8 g, 17.8 mmol), Pd ₂ (dba) ₃ (0.49 g, 0.53 mmol), P(t-Bu) ₃ (0.22 g, 1.07 mmol), NaOt-Bu (3.4 g, 35.5 mmol) was obtained as a product 9.1 g (yield 80%) using the synthesis method of Inter 1-a.

(2) Synthesis example of P-24

Inter 24-a (9.1 g, 14.2 mmol), Sub 3-23 (6.2 g, 14.2 mmol), Pd ₂ (dba) ₃ (0.39 g, 0.43 mmol), P(t-Bu) ₃ ( 0.17 g, 0.85 mmol), NaOt-Bu (2.7 g, 28.4 mmol) was obtained by using the synthesis method of P-1 above to obtain 11.3 g (yield 76%) of the product.

3. P-46 Synthesis example

(1) Synthesis example of Inter 46-a

Sub 1-50 (5.00 g, 13.4 mmol), Sub 3-45 (8.3 g, 13.4 mmol), Pd ₂ (dba) ₃ (0.37 g, 0.40 mmol), P(t-Bu) ₃ (0.16 g, 0.80 mmol), NaOt-Bu (2.6 g, 26.8 mmol) was obtained as a product 10.4 g (yield 85%) using the synthesis method of Inter 1-a.

(2) Synthesis example of P-46

Inter 46-a (10.4 g, 11.4 mmol), Sub 2-39 (3.8 g, 11.4 mmol), Pd ₂ (dba) ₃ (0.31 g, 0.34 mmol), P(t-Bu) ₃ ( 0.14 g, 0.68 mmol), NaOt-Bu (2.2 g, 22.7 mmol) was obtained by using the synthesis method of P-1 above to obtain 10.6 g (yield 77%) of the product.

4. P-66 Synthesis example

(1) Synthesis example of Inter 66-a

Sub 1-45 (5.00 g, 16.8 mmol), Sub 2-122 (7.7 g, 16.8 mmol), Pd ₂ (dba) ₃ (0.46 g, 0.50 mmol), P(t-Bu) ₃ (0.2 g, 1.01 mmol), NaOt-Bu (3.2 g, 33.6 mmol) was obtained as a product 9.1 g (81% yield) using the synthesis method of Inter 1-a.

(2) Synthesis example of P-66

Inter 66-a (9.1 g, 13.6 mmol), Sub 3-63 (9.1 g, 13.6 mmol), Pd ₂ (dba) ₃ (0.37 g, 0.41 mmol), P(t-Bu) ₃ ( 0.17 g, 0.82 mmol), NaOt-Bu (2.6 g, 27.2 mmol) was obtained by using the synthesis method of P-1 above to obtain 13.5 g (yield 76%) of the product.

5. P-85 Synthesis example

(1) Synthesis example of Inter 85-a

Sub 1-37 (5.00 g, 17.8 mmol), Sub 3-79 (14.5 g, 17.8 mmol), Pd ₂ (dba) ₃ (0.49 g, 0.53 mmol), P(t-Bu) ₃ (0.22 g, 1.07 mmol), NaOt-Bu (3.4 g, 35.5 mmol) was obtained as a product 14.2 g (79% yield) using the synthesis method of Inter 1-a.

(2) Synthesis example of P-85

Inter 85-a (14.2 g, 14.0 mmol), Sub 2-121 (3.6 g, 14.0 mmol), Pd ₂ (dba) ₃ (0.39 g, 0.42 mmol), P(t-Bu) ₃ ( 0.17 g, 0.84 mmol), NaOt-Bu (2.7 g, 28.1 mmol) was obtained using the synthesis method of P-1 above to obtain 13.5 g (yield 78%) of the product.

6. P-100 Synthesis example

(1) Synthesis example of Inter 100-a

Sub 1-86 (5.00 g, 12.5 mmol), Sub 2-77 (5.7 g, 12.5 mmol), Pd ₂ (dba) ₃ (0.34 g, 0.38 mmol), P(t-Bu) ₃ (0.15 g, 0.75 mmol), NaOt-Bu (2.4 g, 25.1 mmol) was obtained by using the synthesis method of Inter 1-a above to obtain 7.8 g (yield 80%) of the product.

(2) Synthesis example of P-100

Inter 100-a (7.8 g, 10.0 mmol), Sub 3-93 (5.4 g, 10.0 mmol), Pd ₂ (dba) ₃ (0.28 g, 0.30 mmol), P(t-Bu) ₃ ( 0.12 g, 0.60 mmol), NaOt-Bu (1.9 g, 20.1 mmol) was obtained using the synthesis method of P-1 above to obtain 9.5 g (yield 74%) of the product.

7. P-115 Synthesis example

(1) Synthesis example of Inter 115-a

Sub 1-13 (5.00 g, 17.8 mmol), Sub 2-86 (7.8 g, 17.8 mmol), Pd ₂ (dba) ₃ (0.49 g, 0.53 mmol), P(t-Bu) ₃ (0.22 g, 1.07 mmol), NaOt-Bu (3.4 g, 35.5 mmol) was obtained by using the synthesis method of Inter 1-a above to obtain 8.9 g (yield 78%) of the product.

(2) Synthesis example of P-115

Inter 115-a (8.9 g, 13.9 mmol), Sub 3-107 (7.7 g, 13.9 mmol), Pd ₂ (dba) ₃ (0.38 g, 0.42 mmol), P(t-Bu) ₃ ( 0.17 g, 0.83 mmol), NaOt-Bu (2.7 g, 27.7 smmol) was obtained by using the synthesis method of P-1 above to obtain 12.6 g (yield 78%) of the product.

8. P-119 Synthesis example

(1) Synthesis example of Inter 119-a

Sub 1-27 (5.00 g, 17.8 mmol), Sub 2-90 (7.8 g, 17.8 mmol), Pd ₂ (dba) ₃ (0.49 g, 0.53 mmol), P(t-Bu) ₃ (0.22 g, 1.07 mmol), NaOt-Bu (3.4 g, 35.5 mmol) was obtained by using the synthesis method of Inter 1-a as the product 9.8 g (yield 86%).

(2) Synthesis example of P-119

Inter 119-a (9.8 g, 15.3 mmol), Sub 3-141 (5.1 g, 15.3 mmol), Pd ₂ (dba) ₃ (0.42 g, 0.46 mmol), P(t-Bu) ₃ ( 0.19 g, 0.92 mmol), NaOt-Bu (2.9 g, 30.5 mmol) was obtained by using the synthesis method of P-1, 11.3 g (yield 80%) of the product.

9. P-131 Synthesis example

(1) Synthesis example of Inter 131-a

Sub 1-17 (5.00 g, 17.8 mmol), Sub 2-100 (9.7 g, 17.8 mmol), Pd ₂ (dba) ₃ (0.49 g, 0.53 mmol), P(t-Bu) ₃ (0.22 g, 1.07 mmol), NaOt-Bu (3.4 g, 35.5 mmol) was obtained as a product 11.0 g (yield 83%) using the synthesis method of Inter 1-a.

(2) Synthesis example of P-131

Inter 131-a (11.0 g, 14.7 mmol), Sub 3-119 (7.4 g, 14.7 mmol), Pd ₂ (dba) ₃ (0.40 g, 0.44 mmol), P(t-Bu) ₃ ( 0.18 g, 0.88 mmol), NaOt-Bu (2.8 g, 29.5 mmol) was obtained by using the synthesis method of P-1 above to obtain 12.7 g (71% yield) of the product.

10. P-135 Synthesis example

(1) Synthesis example of Inter 135-a

Sub 1-9 (5.00 g, 17.8 mmol), Sub 2-104 (9.3 g, 17.8 mmol), Pd ₂ (dba) ₃ (0.49 g, 0.53 mmol), P(t-Bu) ₃ (0.22 g, 1.07 mmol), NaOt-Bu (3.4 g, 35.5 mmol) was obtained as a product 11.0 g (yield 85%) using the synthesis method of Inter 1-a.

(2) Synthesis example of P-135

Inter 135-a (11.0 g, 15.1 mmol), Sub 3-141 (5.1 g, 15.1 mmol), Pd ₂ (dba) ₃ (0.41 g, 0.45 mmol), P(t-Bu) ₃ ( 0.18 g, 0.91 mmol), NaOt-Bu (2.9 g, 30.2 mmol) was obtained by using the synthesis method of P-1 above to obtain 12.9 g (yield 83%) of the product.

11.P-150 Synthesis example

(1) Synthesis example of Inter 150-a

Sub 1-41 (5.00 g, 17.8 mmol), Sub 2-114 (6.7 g, 17.8 mmol), Pd ₂ (dba) ₃ (0.49 g, 0.53 mmol), P(t-Bu) ₃ (0.22 g, 1.07 mmol), NaOt-Bu (3.4 g, 35.5 mmol) was obtained by using the synthesis method of Inter 1-a above to obtain 8.5 g (yield 83%) of the product.

(2) Synthesis example of P-150

Inter 150-a (8.5 g, 14.7 mmol), Sub 3-132 (8.7 g, 14.7 mmol), Pd ₂ (dba) ₃ (0.40 g, 0.44 mmol), P(t-Bu) ₃ ( 0.18 g, 0.88 mmol), NaOt-Bu (2.8 g, 29.5 mmol) was obtained by using the synthesis method of P-1 above to obtain 13.0 g (yield 78%) of the product.

12. P-160 Synthesis example

(1) Synthesis example of Inter 160-a

Sub 1-87 (5.00 g, 16.8 mmol), Sub 3-140 (7.2 g, 16.8 mmol), Pd ₂ (dba) ₃ (0.46 g, 0.50 mmol), P(t-Bu) ₃ (0.20 g, 1.01 mmol), NaOt-Bu (3.2 g, 33.6 mmol) was obtained by using the synthesis method of Inter 1-a as the product 7.7 g (yield 71%).

(2) Synthesis example of P-160

Inter 160-a (7.7 g, 11.9 mmol), Sub 2-98 (5.9 g, 11.9 mmol), Pd ₂ (dba) ₃ (0.33 g, 0.36 mmol), P(t-Bu) ₃ ( 0.14 g, 0.72 mmol), NaOt-Bu (2.3 g, 23.9 mmol) was obtained by using the synthesis method of P-1 above to obtain 9.1 g (yield 69%) of the product.

Meanwhile, the FD-MS values of the compounds P-1 to P-160 of the present invention prepared according to the synthesis example as described above are shown in Table 4 below.

compound FD-MS compound FD-MS P-1 m/z=849.3 (C ₆₀ H ₃₉ N ₃ O ₃ =849.99) P-2 m/z=1005.37 (C ₇₁ H ₃₉ D ₅ N ₄ O ₃ =1006.19) P-3 m/z=1059.38 (C ₇₅ H ₅₀ FN ₃ O ₃ =1060.24) P-4 m/z=1113.4 (C ₇₈ H ₅₅ N ₃ O ₃ S=1114.38) P-5 m/z=1055.37 (C ₇₅ H ₄₉ N ₃ O ₄ =1056.23) P-6 m/z=955.29 (C ₆₆ H ₄₁ N ₃ O ₃ S=956.13) P-7 m/z=965.36 (C ₆₉ H ₄₇ N ₃ O ₃ =966.15) P-8 m/z=1141.39 (C ₇₉ H ₄₇ D ₄ N ₃ O ₄ S=1142.38) P-9 m/z=1064.37 (C ₇₆ H ₄₈ N ₄ O ₃ =1065.25) P-10 m/z=1027.38 (C ₇₄ H ₄₉ N ₃ O ₃ =1028.22) P-11 m/z=849.3 (C ₆₀ H ₃₉ N ₃ O ₃ =849.99) P-12 m/z=1001.34 (C ₆₉ H ₄₅ F ₂ N ₃ O ₃ =1002.13) P-13 m/z=899.31 (C ₆₄ H ₄₁ N ₃ O ₃ =900.05) P-14 m/z=925.33 (C ₆₆ H ₄₃ N ₃ O ₃ =926.09) P-15 m/z=1131.35 (C ₈₀ H ₄₉ N ₃ O ₃ S=1132.35) P-16 m/z=874.29 (C ₆₁ H ₃₈ N ₄ O ₃ =875) P-17 m/z=939.35 (C ₆₇ H ₄₅ N ₃ O ₃ =940.12) P-18 m/z=925.33 (C ₆₆ H ₄₃ N ₃ O ₃ =926.09) P-19 m/z=1097.4 (C ₇₇ H ₅₅ N ₃ O ₃ Si=1098.39) P-20 m/z=1045.3 (C ₇₂ H ₄₃ N ₃ O ₄ S=1046.21) P-21 m/z=1199.36 (C ₈₄ H ₅₃ N ₃ O ₂ S ₂ =1200.49) P-22 m/z=1183.42 (C ₈₅ H ₅₇ N ₃ O ₂ S=1184.47) P-23 m/z=1573.54 (C ₁₁₃ H ₇₁ N ₇ OS=1574.92) P-24 m/z=1041.38 (C ₇₅ H ₅₁ N ₃ OS=1042.31) P-25 m/z=1428.55 (C ₁₀₄ H ₇₀ F ₂ N ₄ O=1429.73) P-26 m/z=1041.39 (C ₇₅ H ₅₁ N ₃ O ₃ =1042.25) P-27 m/z=1270.48 (C ₉₂ H ₆₂ N ₄ O ₃ =1271.53) P-28 m/z=1089.38 (C ₇₅ H ₅₅ N ₃ O ₂ SSi=1090.43) P-29 m/z=1057.37 (C ₇₅ H ₅₁ N ₃ O ₂ S=1058.31) P-30 m/z=940.32 (C ₆₆ H ₄₄ N ₄ OS=941.17) P-31 m/z=1107.39 (C ₇₉ H ₅₃ N ₃ O ₂ S=1108.37) P-32 m/z=1057.37 (C ₇₅ H ₅₁ N ₃ O ₂ S=1058.31) P-33 m/z=1504.55 (C ₁₀₆ H ₇₂ N ₈ OS=1505.86) P-34 m/z=1083.33 (C ₇₆ H ₄₉ N ₃ OS ₂ =1084.37) P-35 m/z=1152.42 (C ₈₂ H ₅₂ N ₆ O ₂ =1153.36) P-36 m/z=1219.51 (C ₉₀ H ₆₅ N ₃ O ₂ =1220.53) P-37 m/z=1274.5 (C ₉₂ H ₆₆ N ₄ OS=1275.63) P-38 m/z=1033.33 (C ₇₂ H ₄₇ N ₃ O ₃ S=1034.25) P-39 m/z=1211.48 (C ₈₈ H ₆₅ N ₃ OS=1212.57) P-40 m/z=1223.46 (C ₉₀ H ₅₇ N ₅ O=1224.48) P-41 m/z=985.36 (C ₆₉ H ₄₃ D ₄ N ₃ O ₂ S=986.24) P-42 m/z=1032.3 (C ₇₁ H ₄₄ N ₄ OS ₂ =1033.28) P-43 m/z=1185.51 (C ₈₇ H ₆₇ N ₃ S=1186.57) P-44 m/z=1249.38 (C ₈₇ H ₅₅ N ₅ OS ₂ =1250.55) P-45 m/z=1185.29 (C ₇₉ H ₅₁ N ₃ O ₂ SSe=1185.32) P-46 m/z=1210.34 (C ₈₄ H ₅₀ N ₄ O ₂ S ₂ =1211.47) P-47 m/z=1103.3 (C ₇₅ H ₄₉ N ₃ OS ₃ =1104.42) P-48 m/z=1212.31 (C ₈₂ H ₄₈ N ₆ S ₃ =1213.51) P-49 m/z=1069.44 (C ₇₈ H ₅₉ N ₃ S=1070.41) P-50 m/z=865.28 (C ₆₀ H ₃₉ N ₃ O ₂ S=866.05) P-51 m/z=1156.36 (C ₇₉ H ₅₃ FN ₄ OS ₂ =1157.44) P-52 m/z=1257.44 (C ₉₀ H ₅₉ N ₅ OS=1258.56) P-53 m/z=1055.35 (C ₇₅ H ₄₉ N ₃ O ₂ S=1056.3) P-54 m/z=1063.27 (C ₇₂ H ₄₅ N ₃ OS ₃ =1064.35) P-55 m/z=1153.37 (C ₈₀ H ₅₅ N ₃ O ₂ S ₂ =1154.46) P-56 m/z=941.31 (C ₆₆ H ₄₃ N ₃ O ₂ S=942.15) P-57 m/z=1395.44 (C ₁₀₀ H ₆₁ N ₅ S ₂ =1396.74) P-58 m/z=1176.4 (C ₈₃ H ₅₄ F ₂ N ₄ S=1177.43) P-59 m/z=1187.32 (C ₈₂ H ₄₉ N ₃ O ₃ S ₂ =1188.43) P-60 m/z=1252.46 (C ₈₉ H ₆₄ N ₄ S ₂ =1253.64) P-61 m/z=865.28 (C ₆₀ H ₃₉ N ₃ O ₂ S=866.05) P-62 m/z=1158.43 (C ₈₃ H ₅₈ N ₄ OS=1159.46) P-63 m/z=1315.4 (C ₉₃ H ₆₁ N ₃ S ₃ =1316.71) P-64 m/z=1222.46 (C ₈₈ H ₆₂ N ₄ OS=1223.55) P-65 m/z=1133.36 (C ₇₉ H ₅₁ N ₅ S ₂ =1134.43) P-66 m/z=1301.37 (C ₉₁ H ₅₅ N ₃ O ₃ S ₂ =1302.58) P-67 m/z=1301.37 (C ₉₁ H ₅₅ N ₃ O ₃ S ₂ =1302.58) P-68 m/z=1388.43 (C ₉₁ H ₆₂ F ₆ N ₄ S ₂ =1389.64) P-69 m/z=1390.47 (C ₉₉ H ₆₆ N ₄ OS ₂ =1391.76) P-70 m/z=1475.58 (C ₁₀₅ H ₅₈ D ₁₀ FN ₅ OS=1476.85) P-71 m/z=1331.4 (C ₉₃ H ₆₁ N ₃ OS ₃ =1332.71) P-72 m/z=1211.36 (C ₈₅ H ₅₃ N ₃ O ₂ S ₂ =1212.5) P-73 m/z=1238.41 (C ₈₇ H ₅₈ N ₄ OS ₂ =1239.57) P-74 m/z=1231.46 (C ₈₇ H ₆₅ N ₃ OS ₂ =1232.62) P-75 m/z=1160.37 (C ₈₀ H ₅₂ N ₆ S ₂ =1161.46) P-76 m/z=1329.48 (C ₉₄ H ₆₇ N ₅ S ₂ =1330.73) P-77 m/z=942.31 (C ₆₄ H ₄₂ N ₆ OS=943.14) P-78 m/z=1314.44 (C ₉₃ H ₆₂ N ₄ OS ₂ =1315.67) P-79 m/z=1007.3 (C ₇₀ H ₄₅ N ₃ OS ₂ =1008.27) P-80 m/z=1059.37 (C ₇₅ H ₅₃ N ₃ S ₂ =1060.39) P-81 m/z=849.3 (C ₆₀ H ₃₉ N ₃ O ₃ =849.99) P-82 m/z=975.28 (C ₆₆ H ₄₂ FN ₃ OS ₂ =976.2) P-83 m/z=1117.46 (C ₈₂ H ₅₉ N ₃ O ₂ =1118.39) P-84 m/z=1205.27 (C ₈₀ H ₄₇ N ₅ S ₄ =1206.53) P-85 m/z=1236.41 (C ₈₇ H ₅₆ N ₄ O ₃ S=1237.49) P-86 m/z=1096.33 (C ₇₆ H ₄₈ N ₄ OS ₂ =1097.37) P-87 m/z=1053.45 (C ₇₅ H ₅₇ F ₂ N ₃ O=1054.3) P-88 m/z=1177.37 (C ₈₂ H ₄₇ D ₄ N ₃ O ₂ S ₂ =1178.47) P-89 m/z=1232.45(C ₈₉ H ₆₀ N ₄ OS=1233.55) P-90 m/z=1184.39 (C ₈₄ H ₅₆ N ₄ S ₂ =1185.52) P-91 m/z=849.30 (C ₆₀ H ₃₉ N ₃ O ₃ =849.99) P-92 m/z=865.28 (C ₆₀ H ₃₉ N ₃ O ₂ S=866.05) P-93 m/z=1007.39 (C ₇₂ H ₅₃ N ₃ OS=1008.3) P-94 m/z=967.36 (C ₆₉ H ₄₉ N ₃ OS=968.23) P-95 m/z=1107.35 (C ₇₈ H ₄₉ N ₃ O ₃ S=1108.33) P-96 m/z=957.47 (C ₆₇ H ₃₅ D ₁₅ N ₄ S=958.32) P-97 m/z=925.33 (C ₆₆ H ₄₃ N ₃ O ₃ =926.09) P-98 m/z=1084.28 (C ₇₂ H ₄₀ D ₅ N ₃ S ₄ =1085.44) P-99 m/z=1080.44 (C ₇₈ H ₅₆ N ₄ O ₂ =1081.33) P-100 m/z=1278.36 (C ₈₈ H ₅₄ N ₄ O ₃ S ₂ =1279.55) P-101 m/z=955.32 (C ₆₇ H ₄₅ N ₃ O ₂ S=956.18) P-102 m/z=1107.39 (C ₇₉ H ₅₃ N ₃ O ₂ S=1108.37) P-103 m/z=1189.45 (C ₈₅ H ₆₃ N ₃ S ₂ =1190.58) P-104 m/z=1266.44 (C ₈₉ H ₆₂ N ₄ OS ₂ =1267.62) P-105 m/z=1262.5 (C ₉₁ H ₆₆ N ₄ OS=1263.62) P-106 m/z=1224.44 (C ₈₇ H ₆₀ N ₄ O ₂ S=1225.52) P-107 m/z=1323.55 (C ₉₈ H ₇₃ N ₃ S=1324.74) P-108 m/z=1412.59 (C ₁₀₄ H ₆₈ D ₄ N ₄ O ₂ =1413.77) P-109 m/z=1285.46 (C ₉₃ H ₆₃ N ₃ O ₂ S=1286.61) P-110 m/z=1357.45 (C ₉₆ H ₆₄ FN ₃ OS ₂ =1358.71) P-111 m/z=1055.39 (C ₇₆ H ₅₃ N ₃ OS=1056.34) P-112 m/z=1121.35 (C ₇₉ H ₅₁ N ₃ OS ₂ =1122.42) P-113 m/z=1025.33 (C ₇₁ H ₄₅ F ₂ N ₃ OS=1026.22) P-114 m/z=1155.37 (C ₈₃ H ₅₃ N ₃ S ₂ =1156.48) P-115 m/z=1162.37 (C ₈₁ H ₅₄ N ₄ OS ₂ =1163.47) P-116 m/z=1080.28 (C ₇₂ H ₄₀ N ₈ S ₂ =1081.29) P-117 m/z=1035.36 (C ₇₃ H ₄₇ F ₂ N ₃ O ₂ =1036.19) P-118 m/z=1105.37 (C ₇₉ H ₅₁ N ₃ O ₂ S=1106.36) P-119 m/z=939.38 (C ₆₈ H ₄₉ N ₃ O ₂ =940.16) P-120 m/z=939.33 (C ₆₇ H ₄₅ N ₃ OS=940.18) P-121 m/z=1075.41 (C ₇₉ H ₅₃ N ₃ O ₂ =1076.31) P-122 m/z=939.33 (C ₆₇ H ₄₅ N ₃ OS=940.18) P-123 m/z=1423.52 (C ₁₀₃ H ₆₆ FN ₅ O ₂ =1424.69) P-124 m/z=1434.5 (C ₁₀₃ H ₆₆ N ₆ OS=1435.76) P-125 m/z=1496.54 (C ₁₁₀ H ₇₂ N ₄ OS=1497.87) P-126 m/z=1272.42 (C ₉₁ H ₅₇ FN ₄ OS=1273.54) P-127 m/z=1244.41 (C ₈₉ H ₅₆ N ₄ O ₂ S=1245.51) P-128 m/z=1234.49 (C ₈₅ H ₇₀ N ₄ SSi ₂ =1235.75) P-129 m/z=1268.51 (C ₉₀ H ₆₈ N ₄ O ₂ S=1269.62) P-130 m/z=1286.41 (C ₉₁ H ₅₈ N ₄ OS ₂ =1287.61) P-131 m/z=1212.44 (C ₈₉ H ₅₆ N ₄ O ₂ =1213.45) P-132 m/z=1014.38 (C ₇₃ H ₅₀ N ₄ S=1015.29) P-133 m/z=1171.45 (C ₈₅ H ₆₁ N ₃ OS=1172.5) P-134 m/z=1117.44 (C ₈₂ H ₅₉ N ₃ S=1118.46) P-135 m/z=1025.43 (C ₇₆ H ₅₅ N ₃ O=1026.3) P-136 m/z=1281.49 (C ₉₄ H ₆₃ N ₃ O ₃ =1282.56) P-137 m/z=1237.43 (C ₈₅ H ₆₃ N ₃ O ₃ S ₂ =1238.58) P-138 m/z=1155.48 (C ₈₅ H ₆₁ N ₃ O ₂ =1156.44) P-139 m/z=1359.57 (C ₁₀₁ H ₇₃ N ₃ O ₂ =1360.71) P-140 m/z=1073.43 (C ₈₀ H ₅₅ N ₃ O=1074.34) P-141 m/z=949.4 (C ₇₀ H ₅₁ N ₃ O=950.2) P-142 m/z=923.35 (C ₆₇ H ₄₅ N ₃ O ₂ =924.12) P-143 m/z=998.40 (C ₇₃ H ₅₀ N ₄ O=999.23) P-144 m/z=923.35 (C ₆₇ H ₄₅ N ₃ O ₂ =924.12) P-145 m/z=1115.39 (C ₈₁ H ₅₃ N ₃ OS=1116.4) P-146 m/z=1025.43 (C ₇₆ H ₅₅ N ₃ O=1026.3) P-147 m/z=1065.39 (C ₇₇ H ₅₁ N ₃ O ₃ =1066.27) P-148 m/z=1150.46 (C ₈₅ H ₅₈ N ₄ O=1151.43) P-149 m/z=1231.51 (C ₉₁ H ₆₅ N ₃ O ₂ =1232.54) P-150 m/z=1129.42 (C ₈₂ H ₅₅ N ₃ O ₃ =1130.36) P-151 m/z=1210.39 (C ₈₅ H ₅₄ N ₄ O ₃ S=1211.45) P-152 m/z=1157.47 (C ₈₅ H ₆₃ N ₃ S=1158.52) P-153 m/z=1197.38 (C ₈₅ H ₅₅ N ₃ OS ₂ =1198.52) P-154 m/z=1206.47 (C ₈₈ H ₆₂ N ₄ S=1207.55) P-155 m/z=939.33 (C ₆₇ H ₄₅ N ₃ OS=940.18) P-156 m/z=1013.36 (C ₇₃ H ₄₇ N ₃ O ₂ =1014.20) P-157 m/z=1212.39 (C ₈₅ H ₅₆ N ₄ OS ₂ =1213.53) P-158 m/z=1015.36 (C ₇₃ H ₄₉ N ₃ OS=1016.28) P-159 m/z=1081.44 (C ₇₉ H ₅₉ N ₃ S=1082.42) P-160 m/z=1104.39 (C ₇₉ H ₅₂ N ₄ OS=1105.37)

Manufacturing evaluation of organic electric devices

( Example 1) Green organic electroluminescent device ( Light-emitting auxiliary layer )

An organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material.

First, on the 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 After vacuum deposition of -phenylbenzene-1,4-diamine (hereinafter, 2-TNATA) to a thickness of 60 nm to form a hole injection layer, 4,4-bis[N-(1) as a hole transport compound on the hole injection layer -Naphthyl)-N-phenylamino]biphenyl (hereinafter, abbreviated as NPB) was vacuum deposited to a thickness of 60 nm to form a hole transport layer.

Subsequently, after vacuum deposition of the compound P-1 of the present invention to a thickness of 30 nm on the hole transport layer to form a light emission auxiliary layer, CBP[4,4'-N,N'-dicarbazole-biphenyl ] As a host material and as a dopant, Ir(ppy) ₃ [tris(2-phenylpyridine)-iridium] was doped with a weight of 95:5 to deposit a light emitting layer having a thickness of 30 nm on the light emitting auxiliary layer.

Then, (1,1'-bisphenyl)-4-oleato)bis(2-methyl-8-quinolinoleato) aluminum (hereinafter abbreviated as BAlq) was vacuum deposited to a thickness of 10 nm on the light emitting layer to A blocking layer was formed, and an electron transport layer was formed by vacuum deposition of Bis(10-hydroxybenzo[h]quinolinato)beryllium (hereinafter, BeBq2) to a thickness of 40 nm on the hole blocking layer.

Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

( Example 2) to ( Example 31)

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compound of the present invention described in Table 5 below 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) to ( Comparative example 4)

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

<Comparative Compound A> <Comparative Compound B> <Comparative Compound C>

Electroluminescence (EL) characteristics were measured with a PR-650 of Photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices manufactured according to Examples 1 to 31 and Comparative Examples 1 to 4, and the measurement As a result, the T95 life was measured using a life measurement equipment manufactured by McScience at a reference luminance of 5000 ^{cd/m 2.} Table 5 below shows the results of device fabrication and evaluation.

compound Driving voltage electric current
(mA/cm ² ) Luminance
(cd/m ² ) efficiency
(cd/A) T(95) CIE x y Comparative Example (1) - 6.0 20.0 5000 25.0 62.3 0.31 0.61 Comparative Example (2) Comparative compound A 5.7 15.7 5000 31.8 99.2 0.33 0.60 Comparative Example (3) Comparative compound B 5.4 14.9 5000 33.6 105.0 0.30 0.64 Comparative Example (4) Comparative compound C 5.3 15.6 5000 32.0 103.3 0.33 0.64 Example (1) Compound (P-1) 5.5 14.7 5000 34.1 138.9 0.30 0.62 Example (2) Compound (P-11) 5.3 14.5 5000 34.4 138.6 0.30 0.61 Example (3) Compound (P-13) 5.4 13.8 5000 36.2 149.8 0.30 0.65 Example (4) Compound (P-16) 5.5 14.6 5000 34.2 139.2 0.34 0.60 Example (5) Compound (P-18) 5.4 14.2 5000 35.2 145.9 0.32 0.64 Example (6) Compound (P-20) 5.5 14.7 5000 34.0 138.3 0.32 0.64 Example (7) Compound (P-29) 5.5 14.4 5000 34.7 134.6 0.34 0.60 Example (8) Compound (P-30) 5.3 14.5 5000 34.5 136.1 0.32 0.61 Example (9) Compound (P-41) 5.4 15.4 5000 32.4 133.2 0.32 0.61 Example (10) Compound (P-49) 5.5 14.9 5000 33.5 126.8 0.34 0.65 Example (11) Compound (P-50) 5.2 15.3 5000 32.7 134.2 0.32 0.61 Example (12) Compound (P-53) 5.4 14.7 5000 33.9 145.5 0.31 0.62 Example (13) Compound (P-56) 5.4 15.3 5000 32.6 132.3 0.32 0.65 Example (14) Compound (P-61) 5.4 15.5 5000 32.3 131.5 0.35 0.60 Example (15) Compound (P-65) 5.2 15.7 5000 31.9 123.5 0.33 0.64 Example (16) Compound (P-81) 5.3 14.5 5000 34.4 132.5 0.32 0.61 Example (17) Compound (P-91) 5.3 14.3 5000 34.9 133.6 0.35 0.64 Example (18) Compound (P-92) 5.2 15.1 5000 33.2 127.3 0.33 0.60 Example (19) Compound (P-97) 5.2 14.7 5000 34.1 134.9 0.33 0.61 Example (20) Compound (P-111) 5.0 14.0 5000 35.8 123.1 0.34 0.63 Example (21) Compound (P-115) 5.1 14.6 5000 34.2 129.2 0.32 0.63 Example (22) Compound (P-119) 5.2 13.4 5000 37.4 131.3 0.30 0.64 Example (23) Compound (P-120) 5.1 14.4 5000 34.7 119.0 0.31 0.65 Example (24) Compound (P-122) 5.1 13.7 5000 36.5 130.9 0.34 0.64 Example (25) Compound (P-134) 5.1 14.4 5000 34.6 121.7 0.32 0.61 Example (26) Compound (P-135) 5.1 14.1 5000 35.5 121.3 0.32 0.64 Example (27) Compound (P-142) 5.1 13.6 5000 36.7 119.0 0.32 0.63 Example (28) Compound (P-143) 4.9 13.9 5000 36.0 116.7 0.34 0.60 Example (29) Compound (P-144) 5.0 13.5 5000 37.1 120.2 0.32 0.65 Example (30) Compound (P-156) 5.1 14.0 5000 35.6 137.7 0.33 0.62 Example (31) Compound (P-158) 4.9 14.2 5000 35.1 114.4 0.31 0.62

As can be seen from the results of Table 5, when a green organic electroluminescent device is manufactured by using the compound represented by Formula 1 of the present invention as a light emitting auxiliary layer material of an organic electroluminescent device, a light emitting auxiliary layer is not used, or Compared to the case of using Comparative Compound A to Comparative Compound C, the performance of the organic electroluminescent device can be improved.

In other words, the results of Comparative Examples 2 to 4 using Comparative Compound A to Comparative Compound C were superior to Comparative Example 1 in which the light-emitting auxiliary layer was not used, and Examples 1 to 31 of the compounds of the present invention were the driving voltage. Or it showed remarkably excellent results in the lifespan.

In particular, in the case of Examples 1 to 19 in which the pentacyclic ring was substituted, remarkable results were shown in the lifespan compared to Comparative Examples 1 to 4, and spiro [fluorene-9,9'-xanthene], spiro [flu Examples 20 to 31 in which orene-9,9'-thioxanthene], spiro[acridine-9,9'-fluorene], and spiro[anthracene-9,9'-fluorene] were substituted In the case of, compared to Comparative Examples 1 to 4, the result was remarkable in the driving voltage.

Table 6 below shows the physical property values of Comparative Compound B, Compound P-61 of the present invention, and Compound P-120 of the present invention.

Comparative compound B Compound P-61 of the present invention Compound P-120 of the present invention G.HOMO -4.82 -4.82 -4.72 G. LUMO -1.12 -1.21 -0.99 G. Bandgap 3.70 3.61 3.73

Comparing Comparative Compound B with Compound P-61 of the present invention and Compound P-120 of the present invention, in the case of Comparative Compound B, dibenzofuran was substituted, but in the case of Compound P-61 of the present invention, the pentacyclic ring was substituted. In the case of the compound P-120 of the present invention, spiro [fluorene-9,9'-xanthene] is substituted. As shown in Table 6, when the pentacyclic ring is substituted, it can be confirmed that LUMO is lower than when dibenzofuran was introduced.Compared to Comparative Compound B, electrons accumulated in the host were converted to Compound P-61 of the present invention. This can be better resolved, and thus it is judged to reduce the damage of the host, which is unstable to the electron. That is, it is determined that this increases the life of the device.

In addition, when spiro [fluorene-9,9'-xanthene] is substituted, it can be seen that the HOMO value is higher than when dibenzofuran is introduced. Is injected, and it is determined that the driving voltage decreases.

In the case of the light-emitting auxiliary layer, it is necessary to grasp the correlation between the hole transport layer and the light-emitting layer (host). Even if a similar core is used, it is possible for a person skilled in the art to infer the characteristics of the light-emitting auxiliary layer in which the compound of the present invention is used. It will be very difficult.

In addition, in the evaluation results of the device fabrication described above, the device characteristics in which the compound of the present invention is applied only to the light-emitting auxiliary layer have 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-emitting auxiliary layer may be used.

The above description is only illustrative of the present invention, and those of ordinary skill in the art to which the present invention pertains can include various methods for improving performance including other compounds within the range not departing from the essential characteristics of the present invention. Transformation will be possible.

Accordingly, the embodiments disclosed in the present specification are not intended to limit the present invention, but to describe the present invention, and the scope of the spirit of the present invention is not limited by these embodiments. The scope of protection of the present invention should be interpreted by the claims below, and all technologies within the scope equivalent thereto should be construed as being included in the scope of the present invention.

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

Claims (12)

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

<Formula A-1><FormulaA-2>

In Formula 1,
1) Ar ¹ to Ar ⁵ are each independently a C ₆ to C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of an aliphatic ring of C ₃ to C _{60 and an aromatic ring of C 6} to C _60; A C ₁ to C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C _20; An alkoxyl group of C ₁ to C _30; C ₆ ~ C ₃₀ aryloxy group; Or a combination thereof; Or neighboring groups can be bonded to each other to form a ring,
2) ^{At least one of Ar 1} to Ar ⁵ is Formula A-1 or Formula A-2; When the formula A-1 or formula A-2 is bonded, it is bonded to one of R ³ to R ⁷ ,
3) Z is O or S,
4) X ¹ and X ² are each independently O, S, NR' or CR'R'',
5) Y ¹ and Y ² are each independently a single bond, O, S, NR' or CR'R''; However, the ^{case where both Y 1} and Y ² are single bonds is excluded,
6) R ¹ to R ⁹ , R'and R'' are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Nitro group; Amanogi; C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of an aliphatic ring of C ₃ to C _{60 and an aromatic ring of C 6} to C _60; A C ₁ to C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C _20; An alkoxyl group of C ₁ to C _30; C ₆ ~ C ₃₀ aryloxy group; C ₆ ~ C ₃₀ arylthio group; Or neighboring groups can be bonded to each other to form a ring,
7) n is an integer of 0-4; m is an integer from 0 to 3; p, q, s, t, u, v, and w are each independently an integer of 0-4,
8) L ¹ to L ³ are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; A fused ring group of an aliphatic ring of C ₃ to C _{60 and an aromatic ring of C 6} to C _60; C ₃ ~ C ₆₀ aliphatic ring group; A divalent aliphatic hydrocarbon group; Or a combination thereof,
9) Ar ¹ to Ar ⁵ , L ¹ to L ³ , R ¹ to R ⁹ , R', R'' and the rings formed by bonding of adjacent groups to each other are deuterium, respectively; halogen; A silane group unsubstituted or substituted with a C ₁ to C ₂₀ alkyl group or a C ₆ to C _{20 aryl group;} Siloxane group; Boron group; Germanium group; Cyano group; Nitro group; C ₁ ~ C ₂₀ alkylthio group; C ₁ ~ C ₂₀ alkoxy group; C ₆ ~ C ₂₀ arylalkoxy group; C ₆ ~ C ₂₀ aryloxy group; C ₆ ~ C ₂₀ arylthio group; A C ₁ to C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C _20; C ₆ ~ C ₂₀ aryl group; _{C 6} ~ C ₂₀ aryl group unsubstituted or substituted with deuterium; Fluorenyl group; _{O, N, S, Si, and C 2} ~ C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of P; C ₃ ~ C ₂₀ aliphatic ring group; C ₇ ~ C ₂₀ arylalkyl group; C ₈ ~ C ₂₀ arylalkenyl group; And it may be further substituted with one or more substituents selected from the group consisting of a combination thereof. The compound according to claim 1, wherein Formula 1 is represented by the following Formula 2 or Formula 3:
<Formula 2><Formula3>

In Formulas 2 and 3, R ¹ , R ² , Ar ¹ to Ar ⁵ , L ¹ to L ³ , n, m, and Z are as defined in claim 1. The compound according to claim 1, wherein the formula 1 is represented by any one of the following formulas 4 to 31:
<Formula 4><Formula5><Formula6>

<Formula 7><Formula8><Formula9>

<Formula 10><Formula11><Formula12>

<Formula 13><Formula14><Formula15>

<Formula 16><Formula17><Formula18>

<Formula 19><Formula20><Formula21>

<Formula 22><Formula23><Formula24>

<Formula 25><Formula26><Formula27>

<Formula 28><Formula29><Formula30>

<Formula 31>

In Formulas 4 to 31, R ¹ , R ² , Ar ¹ to Ar ⁵ , L ¹ to L ³ , n, m and Z are as defined in claim 1. The compound of claim 1, wherein the compound represented by Formula 1 is one of the following P-1 to P-160:

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

Images