Organic electric element comprising compound for organic electric element, and electronic device comprising same

Abstract

The present invention relates to an organic electric element comprising: a first electrode; a second electrode; and an organic material layer including a light-emitting layer formed between the first electrode and the second electrode. The organic material layer includes a hole transport layer formed between the first electrode and the light-emitting layer and a light-emitting auxiliary layer formed between the hole transport layer and the light-emitting layer, wherein the light-emitting auxiliary layer comprises a composition in which a compound represented by chemical formula 1 below and a compound represented by chemical formula 2 below are mixed, and the hole transport layer comprises a compound represented by chemical formula 3 below, thereby making it possible to lower the driving voltage of the organic electric element and improve luminous efficiency and lifespan.

Description

Organic electric device comprising a compound for organic electric device and electronic device thereof

[0001] The present invention relates to an organic electric device using a compound for an organic electric device and an electronic device thereof.

[0002] Generally, organic light emitting diodes (OLEDs) are devices that convert electrical energy into light energy using organic materials. Organic electronic devices utilizing the organic light emitting diode (OLED) phenomenon typically have a structure comprising an anode, a cathode, and an organic layer between them. These organic layers are often multilayered with different materials to enhance the efficiency and stability of the device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

[0003] Typically, 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 through recombination.

[0004] Among these, the material used in the hole transport layer must have a high HOMO value because holes must be injected from the ITO, and the emitting layer usually requires a low HOMO value due to charge balance. Therefore, a large energy gap inevitably occurs between the hole transport layer and the emitting layer, which causes charge accumulation at the interface between the hole transport layer and the emitting layer, adversely affecting the lifespan of the OLED device. Therefore, an organic electronic device that inserts a light-emitting auxiliary layer to buffer the large energy gap between the hole transport layer and the emitting layer is usually proposed.

[0005] These organic electroluminescent devices form a light-emitting auxiliary layer with a predetermined thickness between the hole transport layer and the light-emitting layer, and by appropriately controlling the HOMO energy level of the light-emitting auxiliary layer in consideration of the HOMO energy level of the adjacent organic layer, they attempted to improve the luminous efficiency and lifespan characteristics when forming the light-emitting auxiliary layer. However, if a light-emitting auxiliary layer with a HOMO value close to the light-emitting layer is inserted to improve the lifespan, the driving voltage increases due to the charge accumulation phenomenon from the hole transport layer to the light-emitting auxiliary layer. In addition, if a light-emitting auxiliary layer with a HOMO value similar to that of the hole transport layer is inserted to lower the driving voltage, the energy gap between the light-emitting auxiliary layer and the light-emitting layer causes an increase in charge accumulation at the interface between the light-emitting auxiliary layer and the light-emitting layer, which reduces the lifespan. In addition, if a light-emitting auxiliary layer with a HOMO value exactly in the middle of the energy gap between the hole transport layer and the light-emitting layer is inserted, the improvement in both the driving voltage and the lifespan is small. Therefore, active research on such light-emitting auxiliary layers is necessary.

[0006] The present invention aims to provide an organic electric device and an electronic device thereof including a compound capable of lowering the driving voltage of the device and improving the luminous efficiency, color purity, stability and lifespan of the device.

[0007] In one aspect, the present invention provides an organic electroluminescent device comprising: an organic layer including a first electrode; a second electrode; and a light-emitting layer formed between the first electrode and the second electrode; wherein the organic layer includes a hole transport layer formed between the first electrode and the light-emitting layer, and an light-emitting auxiliary layer formed between the hole transport layer and the light-emitting layer, wherein the light-emitting auxiliary layer includes a composition in which a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2 are mixed, and the hole transport layer includes a compound represented by the following chemical formula 3.

[0008] <Chemical Formula 1> <Chemical Formula 2> <Chemical Formula 3>

[0009]

[0010] In another aspect, the present invention provides an electronic device including the organic electric element.

[0011] 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 the color purity and lifespan of the device can be greatly improved.

[0012] Figures 1 to 3 are exemplary diagrams of an organic light-emitting device according to the present invention.

[0013] 100, 200, 300: Organic electric element 110: First electrode

[0014] 120: hole injection layer 130: hole transport layer

[0015] 140: Emitting layer 150: Electron transport layer

[0016] 160: Electron injection layer 170: Second electrode

[0017] 180: Light efficiency improvement layer 210: Buffer layer

[0018] 220: Light-emitting auxiliary layer 320: First hole injection layer

[0019] 330: First hole transport layer 340: First light-emitting layer

[0020] 350: First electron transport layer 360: First charge generation layer

[0021] 361: Second charge generation layer 420: Second hole injection layer

[0022] 430: Second hole transport layer 440: Second light-emitting layer

[0023] 450: Second electron transport layer CGL: Charge generation layer

[0024] ST1: First stack ST2: Second stack

[0025] Hereinafter, the present invention will be described in detail with reference to embodiments. In describing the present invention, if a detailed description of a related known configuration or function is judged to obscure the gist of the present invention, such detailed description will be omitted.

[0026] Additionally, terms such as first, second, A, B, (a), (b), etc. may be used to describe components of the present invention. These terms are only intended to distinguish the components from other components, and the nature, order, or sequence of the components are not limited by the terms. When it is described that a component is "connected," "coupled," or "connected" to another component, it should be understood that the component may be directly connected or connected to the other component, but another component may also be "connected," "coupled," or "connected" between each component.

[0027] As used in this specification and the appended claims, unless otherwise stated, the following terms have the following meanings:

[0028] The term “halo” or “halogen” as used herein, unless otherwise stated, means fluorine (F), bromine (Br), chlorine (Cl), or iodine (I).

[0029] The term "alkyl" or "alkyl group" as used in the present invention, unless otherwise stated, means a radical of a saturated aliphatic functional group having a single bond of 1 to 60 carbon atoms, 1 to 30 carbon atoms, 1 to 25 carbon atoms, 1 to 18 carbon atoms, or 1 to 12 carbon atoms, including a straight-chain alkyl group, a branched-chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cycloalkyl group, or a cycloalkyl-substituted alkyl group.

[0030] The term "alkenyl group", "alkenyl group" or "alkynyl group" used in the present invention, unless otherwise stated, includes a straight-chain or branched chain group having a double bond or triple bond of 2 to 60 carbon atoms, 2 to 30 carbon atoms, 2 to 25 carbon atoms, 2 to 18 carbon atoms or 2 to 12 carbon atoms, but is not limited thereto.

[0031] The term "cycloalkyl" or "cycloalkyl" as used in the present invention means, unless otherwise stated, an alkyl forming a ring having 3 to 60 carbon atoms, 3 to 30 carbon atoms, 3 to 25 carbon atoms, 3 to 18 carbon atoms or 3 to 12 carbon atoms, but is not limited thereto.

[0032] The term “alkoxyl group,” “alkoxy group,” or “alkyloxy group” used in the present invention means an alkyl group having an oxygen radical attached thereto, and unless otherwise specified, has, but is not limited to, 1 to 60 carbon atoms, 1 to 30 carbon atoms, 1 to 25 carbon atoms, 1 to 18 carbon atoms, or 1 to 12 carbon atoms.

[0033] The term "aryloxyl group" or "aryloxy group" used in the present invention means an aryl group having an oxygen radical attached thereto, and unless otherwise specified, has, but is not limited to, 6 to 60 carbon atoms, 6 to 30 carbon atoms, 6 to 25 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms.

[0034] The terms "aryl group" and "arylene group" used in the present invention, unless otherwise stated, have, but are not limited to, 6 to 60 carbon atoms, 6 to 30 carbon atoms, 6 to 25 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms, respectively. In the present invention, the aryl group or arylene group refers to a single ring or multi-ring aromatic group, and includes an aromatic ring formed by the participation of adjacent substituents in a bond or reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, or a spirofluorene group.

[0035] The prefix "aryl" or "ar" refers to a radical substituted with an aryl group. For example, an arylalkyl group is an alkyl group substituted with an aryl group, an arylalkenyl group is an alkenyl group substituted with an aryl group, and the aryl-substituted radical has the number of carbon atoms described herein.

[0036] Also, when prefixes are named consecutively, it means that the substituents are listed in the order they were first written. For example, in the case of arylalkoxy group, it means an alkoxy group substituted with an aryl group, in the case of alkoxylcarbonyl group, it means a carbonyl group substituted with an alkoxyl group, and in the case of 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.

[0037] The term "heterocyclic group" used in the present invention, unless otherwise stated, includes one or more heteroatoms, has 2 to 60 carbon atoms, 2 to 30 carbon atoms, 2 to 25 carbon atoms, 2 to 18 carbon atoms, or 2 to 12 carbon atoms, includes at least one of a single ring and a multiple ring, and includes a heteroaliphatic ring and a heteroaromatic ring. It may also be formed by bonding adjacent functional groups.

[0038] The term “heteroatom” as used herein refers to N, O, S, P or Si unless otherwise stated.

[0039] Additionally, the term "heterocyclic group" refers to a single ring, a ring aggregate, a fused multiple ring system, a spiro compound, etc. containing a heteroatom. In addition, compounds containing a heteroatom group such as SO2, P=O, etc. instead of carbon forming a ring, such as the compounds below, may also be included in the heterocyclic group. For example, the term "heterocyclic group" includes the following compounds.

[0040]

[0041] The term "aliphatic ring" used in the present invention means a cyclic hydrocarbon other than an aromatic hydrocarbon, and includes a single ring, a ring aggregate, a fused multiple ring system, a spiro compound, etc., and unless otherwise specified, means a ring having 3 to 60 carbon atoms, a ring having 3 to 30 carbon atoms, a ring having 3 to 25 carbon atoms, a ring having 3 to 18 carbon atoms, or a ring having 3 to 12 carbon atoms, but is not limited thereto. For example, even when an aromatic ring, benzene, and a non-aromatic ring, cyclohexane, are fused, it is considered an aliphatic ring.

[0042] The term "ring assemblies" as used herein means two or more ring systems (single ring or fused ring systems) directly connected to each other via single or double bonds, wherein the number of such direct links between rings is one less than the total number of ring systems in the compound. Ring assemblies may be formed by the same or different ring systems being directly connected to each other via single or double bonds.

[0043] The term "fluorenyl group", "fluorenylene group" or "fluorenetriyl group" used in the present invention, unless otherwise stated, means a monovalent, divalent or trivalent functional group in which R, R' and R" in the structure below are all hydrogen, and a "substituted fluorenyl group", "substituted fluorenylene group" or "substituted fluorenetriyl group" means that at least one of the substituents R, R' and R" is a substituent other than hydrogen, and includes a case where R and R' are bonded to each other to form a spiro compound together with the carbon to which they are bonded. In the present specification, regardless of valence, a fluorenyl group, a fluorenylene group and a fluorenetriyl group may all be referred to as a fluorene group.

[0044]

[0045] The term "spiro compound" used in the present invention has a "spiro union," and a spiro union means a connection formed by two rings sharing only one atom. In this case, the atom shared between the two rings is called a "spiro atom," and depending on the number of spiro atoms contained in a compound, these are called "monospiro-," "dicepiro-," and "trispiro-" compounds, respectively.

[0046] Unless otherwise stated, the term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms, 1 to 30 carbon atoms, 1 to 25 carbon atoms, 1 to 18 carbon atoms or 1 to 12 carbon atoms, and "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms, 3 to 30 carbon atoms, 3 to 25 carbon atoms, 3 to 18 carbon atoms or 3 to 12 carbon atoms.

[0047] Unless otherwise stated, the term "ring" as used herein means an aliphatic ring having 3 to 60 carbon atoms, 3 to 30 carbon atoms, 3 to 25 carbon atoms, 3 to 18 carbon atoms, or 3 to 12 carbon atoms; or an aromatic ring having 6 to 60 carbon atoms, 6 to 30 carbon atoms, 6 to 25 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms; or a heterocycle having 2 to 60 carbon atoms, 2 to 30 carbon atoms, 2 to 25 carbon atoms, 2 to 18 carbon atoms, or 2 to 12 carbon atoms; or a fused ring composed of a combination thereof, including a saturated or unsaturated ring.

[0048] Other heterocyclic compounds or heteroradicals other than the aforementioned heterocyclic compounds include, but are not limited to, one or more heteroatoms.

[0049] Also, unless explicitly stated otherwise, the term "substituted" in the term "substituted or unsubstituted" used in the present invention means deuterium, halogen, amino group, nitrile group, nitro group, C1~C 20 Alkyl group of C1~C 20 Alkoxyl group, C1~C 20 Alkylamine group of C1~C 20 Alkylthiophene group, C6~C 20 Arylthiophene group, C2~C 20 Alkenyl group, C2~C 20 Alkyne group, C3~C 20 Cycloalkyl group of C6~C 20 Aryl group of C6~C substituted with deuterium 20 Aryl group of C8~C 20 Arylalkenyl group, silane group, boron group, germanium group, and C2~C 20 It means that it is substituted with one or more substituents selected from the group consisting of heterocyclic groups, but is not limited to these substituents.

[0050] In this specification, the 'group name' corresponding to the aryl group, arylene group, heterocyclic group, etc., which are exemplified as examples of each symbol and its substituent, may be described as the 'group name reflecting the valence', but may also be described as the 'parent compound name'. For example, in the case of 'phenanthrene', which is a type of aryl group, the name of the group may be described by distinguishing the valence, such as 'phenanthryl' for the monovalent 'group' and 'phenantrylene' for the divalent group, but it may also be described as the parent compound name 'phenanthrene' regardless of the valence. Similarly, in the case of pyrimidine, it may be described as 'pyrimidine' regardless of the valence, or it may be described as the 'group name' of the corresponding valence, such as pyrimidinyl group for monovalent and pyrimidinylene for divalent. In addition, in this specification, numbers or alphabets indicating positions may be omitted when describing the compound name or substituent name. For example, pyrido[4,3-d]pyrimidine can be written as pyridopyrimidine, benzofuro[2,3-d]pyrimidine can be written as benzofuropyrimidine, 9,9-dimethyl-9H-fluorene can be written as dimethylfluorene, etc. Accordingly, both benzo[g]quinoxaline and benzo[f]quinoxaline can be written as benzoquinoxaline.

[0051] Additionally, unless explicitly stated otherwise, the chemical formulas used in the present invention are applied in the same manner as the substituent definitions by the index definitions of the chemical formulas below.

[0052]

[0053] Here, if a is an integer of 0, the substituent R 1 is absent, and if a is an integer of 1, there is one substituent R 1 is bonded to one of the carbons forming the benzene ring, and when a is an integer of 2 or 3, it is bonded as follows, in which case R 1may be the same or different, and when a is an integer from 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the indication of the hydrogen bonded to the carbon forming the benzene ring is omitted.

[0054]

[0055] In addition, unless explicitly stated otherwise, the terms "ortho", "meta", and "para" used in the present invention mean the substitution positions of all substituents, and the ortho position refers to a compound in which the positions of the substituents are immediately adjacent, for example, in the case of benzene, it refers to the 1st and 2nd positions, the meta position refers to the substitution position next to the immediately adjacent substitution position, and refers to the 1st and 3rd positions in the case of benzene as an example, and the para position refers to the substitution position next to the meta position, and refers to the 1st and 4th positions in the case of benzene as an example. A more detailed description of examples of substitution positions is as follows, and it can be confirmed that the ortho- and meta- positions are substituted in a non-linear type, and the para- position is substituted in a linear type.

[0056] [Example of ortho-position]

[0057]

[0058] [Example of meta-position]

[0059]

[0060] [Example of para-location]

[0061]

[0062] The term "composition" as used herein is intended to be broadly interpreted to include not only compounds but also solutions, dispersions, liquids, and solid mixtures (mixtures, admixtures). The composition of the present invention may contain the compound of the present invention alone, or may contain two or more different compounds in combination, or may contain the compound in combination with two or more other compounds. In other words, the composition may contain the compound corresponding to Chemical Formula 1 alone, may contain a mixture of two or more compounds of Chemical Formula 1, or may contain a mixture of the compound of Chemical Formula 1 and a compound not corresponding to the present invention. Here, the compound not corresponding to the present invention may be a single compound, or may be two or more compounds. In this case, when the compound is contained in a combination of two or more other compounds, the other compounds may be already known compounds of each organic layer, or may be compounds to be developed in the future. In this case, the compounds contained in the organic layer may be composed solely of compounds of the same type, but may also be a mixture of two or more heterogeneous compounds represented by Chemical Formula 1.

[0063]

[0064] Hereinafter, the laminated structure of an organic electric device including the compound of the present invention will be described with reference to FIGS. 1 to 3.

[0065] When assigning reference numerals to components in each drawing, it should be noted that identical components are assigned the same numerals whenever possible, even if they appear on different drawings. Furthermore, when describing the present invention, if a detailed description of a related known configuration or function is deemed likely to obscure the gist of the present invention, such detailed description will be omitted.

[0066] Figures 1 to 3 are exemplary diagrams of organic electric devices according to embodiments of the present invention.

[0067] Referring to FIG. 1, an organic electric element (100) according to one embodiment of the present invention includes a first electrode (110), a second electrode (170) formed on a substrate (not shown), and an organic layer formed between the first electrode (110) and the second electrode (170).

[0068] The above first electrode (110) may be an anode, and the second electrode (170) may be a cathode. In the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

[0069] The above organic layer may include a hole injection layer (120), a hole transport layer (130), a light emitting layer (140), an electron transport layer (150), and an electron injection layer (160). Specifically, the hole injection layer (120), the hole transport layer (130), the light emitting layer (140), the electron transport layer (150), and the electron injection layer (160) may be sequentially formed on the first electrode (110).

[0070] Preferably, a light efficiency improvement layer (180) may be formed on one side of the first electrode (110) or the second electrode (170) that is not in contact with the organic layer, and when the light efficiency improvement layer (180) is formed, the light efficiency of the organic electric element may be improved.

[0071] For example, a light efficiency improvement layer (180) can be formed on the second electrode (170). In the case of a top emission organic light emitting device, the formation of the light efficiency improvement layer (180) can reduce optical energy loss due to SPPs (surface plasmon polaritons) in the second electrode (170), and in the case of a bottom emission organic light emitting device, the light efficiency improvement layer (180) can serve as a buffer for the second electrode (170).

[0072] A buffer layer (210) or a light-emitting auxiliary layer (220) may be further formed between the hole transport layer (130) and the light-emitting layer (140), which will be described with reference to FIG. 2.

[0073] Referring to FIG. 2, an organic electric device (200) according to another embodiment of the present invention may include a hole injection layer (120), a hole transport layer (130), a buffer layer (210), 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) sequentially formed on a first electrode (110), and a light efficiency improvement layer (180) may be formed on the second electrode. As can be seen in FIG. 2, a buffer layer (210) may be further laminated between the light-emitting auxiliary layer (220) and the hole transport layer (130).

[0074] 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).

[0075] Additionally, according to another embodiment of the present invention, the organic layer may be formed in a form in which a plurality of stacks including a hole transport layer, a light-emitting layer, and an electron transport layer are formed. This will be described with reference to FIG. 3.

[0076] Referring to FIG. 3, an organic electric element (300) according to another embodiment of the present invention may have two or more sets of stacks (ST1, ST2) of organic layers formed in multiple layers formed between a first electrode (110) and a second electrode (170), and a charge generation layer (CGL) may be formed between the stacks of organic layers.

[0077] Specifically, an organic electric device according to one embodiment of the present invention may include a first electrode (110), a first stack (ST1), a charge generation layer (CGL: Charge Generation Layer), a second stack (ST2), a second electrode (170), and a light efficiency improvement layer (180).

[0078] The first stack (ST1) is an organic layer formed on the first electrode (110), which may include a first hole injection layer (320), a first hole transport layer (330), a first light-emitting layer (340), and a first electron transport layer (350), and the second stack (ST2) may include a second hole injection layer (420), a second hole transport layer (430), a second light-emitting layer (440), and a second electron transport layer (450). In this way, the first stack and the second stack may be organic layers having the same stacked structure, but may also be organic layers having different stacked structures.

[0079] 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). This charge generation layer (CGL) is formed between the first light-emitting layer (340) and the second light-emitting layer (440) to increase the current efficiency generated in each light-emitting layer and to smoothly distribute charges.

[0080] When a plurality of light-emitting layers are formed by a multi-layer stack structure as shown in Fig. 3, not only can an organic light-emitting device that emits white light be manufactured by the mixing effect of the light emitted from each light-emitting layer, but an organic light-emitting device that emits light of various colors can also be manufactured.

[0081] The compounds represented by chemical formulas 1 to 3 of the present invention can be used as materials for a hole injection layer (120, 320, 420), a hole transport layer (130, 330, 430), a buffer layer (210), a light-emitting auxiliary layer (220), an electron transport layer (150, 350, 450), an electron injection layer (160), a light-emitting layer (140, 340, 440), or a light efficiency improvement layer (180). However, preferably, a composition in which a compound represented by chemical formula 1 of the present invention and a compound represented by chemical formula 2 below are mixed can be used as a light-emitting auxiliary layer (220), and a compound represented by chemical formula 3 of the present invention can be used as a hole transport layer (130, 330, 430).

[0082] Even if the core is identical or similar, the band gap, electrical properties, and interface properties can vary depending on which substituent is bonded at which position. Therefore, research on the selection of the core and the combination of sub-substituents bonded to it is necessary. In particular, when the energy level and T1 value between each organic layer and the intrinsic properties of the material (mobility, interface properties, etc.) are optimally combined, long life and high efficiency can be achieved simultaneously.

[0083] An organic light emitting diode according to an embodiment of the present invention may be manufactured using various deposition methods. It may be manufactured using a deposition method such as PVD or CVD. For example, it may be manufactured by forming an anode (110) by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, forming an organic layer including 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) thereon, and then depositing a material that can be used as a cathode (170) thereon. In addition, an emission auxiliary layer (220) may be further formed between the hole transport layer (130) and the light emitting layer (140), and an electron transport auxiliary layer (not shown) may be further formed between the emission layer (140) and the electron transport layer (150), or may be formed in a stack structure as described above.

[0084] In addition, the organic layer can be manufactured with a smaller number of layers by using various polymer materials and a solution process or solvent process other than a deposition method, 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, a doctor blading process, a screen printing process, or a thermal transfer method. Since the organic layer according to the present invention can be formed by various methods, the scope of the present invention is not limited by the formation method.

[0085] In addition, the organic electric device according to one embodiment of the present invention may be selected from the group consisting of an organic light-emitting device, an organic solar cell, an organic photoconductor, an organic transistor, a device for monochrome lighting, and a device for quantum dot display.

[0086] Another embodiment of the present invention may include a display device including the organic electric element of the present invention described above, and an electronic device including a control unit for controlling the display device. In this case, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as mobile communication terminals such as cell phones, PDAs, electronic dictionaries, PMPs, remote controls, navigation systems, game consoles, various TVs, and various computers.

[0087] The light-emitting auxiliary layer according to an embodiment of the present invention is formed of a mixture of an organic material having a low HOMO energy level and an organic material having a high HOMO energy level or a mixture of Compound 1 and Compound 2. Preferably, the difference between the HOMO energy level of the compound represented by Chemical Formula 1 and the HOMO energy level of the compound represented by Chemical Formula 2 should be 0.05 to 0.12. Furthermore, it is preferable that it is 0.05 to 0.1. If the difference in the HOMO energy levels of the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 is large as described above, the hole transport characteristics of the device are reduced. In particular, the driving voltage is reduced as the hole transport characteristics are reduced. In addition, if the difference in the HOMO energy level is small, holes are injected into the host through the compound having a deep HOMO energy level, but there is a disadvantage in that the hole injection characteristics are reduced and the efficiency is not increased. Therefore, it is desirable to have a HOMO energy level difference in an appropriate range, and if it has an appropriate value, it can provide a device with excellent driving voltage and efficiency.

[0088] According to the present invention, the light-emitting auxiliary layer is formed by mixing compounds represented by Chemical Formula 1 and Chemical Formula 2. The light-emitting auxiliary layer formed in this way can provide a device with excellent driving voltage, efficiency, and lifespan. In particular, when Chemical Formula 1 and Chemical Formula 2 are mixed, excellent characteristics are exhibited in terms of lifespan. This phenomenon can provide a device with both excellent driving voltage and lifespan by mixing a compound that can improve lifespan and a compound that can assist charge injection.

[0089]

[0090] Hereinafter, an organic electric device according to one aspect of the present invention will be described.

[0091] According to one embodiment of the present invention, an organic electric device includes an organic layer including a first electrode; a second electrode; and a light-emitting layer formed between the first electrode and the second electrode; wherein the organic layer includes a hole transport layer formed between the first electrode and the light-emitting layer, and an light-emitting auxiliary layer formed between the hole transport layer and the light-emitting layer, wherein the light-emitting auxiliary layer includes a composition in which a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2 are mixed, and the hole transport layer includes a compound represented by the following chemical formula 3.

[0092] <Chemical Formula 1> <Chemical Formula 2> <Chemical Formula 3>

[0093]

[0094] In the above chemical formulas 1 to 3, each symbol can be defined as follows.

[0095] Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 , Ar 7 , Ar a and Ar b are independently C6~C60 Aryl group of; fluorenyl group; C2~C containing at least one heteroatom among O, N, S, Si and P 60 Heterocyclic group of; C3~C 60 Cycloalkyl group of; and C3~C 60 Aliphatic ring and C6~C 60 A fused ring group of an aromatic ring is selected from the group consisting of;

[0096] The above Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 , Ar 7 , Ar a and Ar b If it is an aryl group, preferably C6~C 30 Aryl group of, more preferably C6~C 25 , C6~C 18 or C6~C 12 The aryl group may be, for example, phenyl, biphenyl, terphenyl, naphthalene, phenanthrene, chrysene, etc.

[0097] The above Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 , Ar 7 , Ar a and Ar b If it is a heterocyclic group, preferably C2~C 30 A heterocyclic group, more preferably C2~C 25 , C2~C 18 or C2~C 12It may be a heterocyclic group, and examples thereof include pyrazine, thiophene, pyridine, pyrimidine, quinoline, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, quinoxaline, benzoquinazoline, carbazole, dibenzoquinazoline, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, benzothioenopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine, benzocarbazole, naphthobenzofuran, naphthobenzothiophene, etc.

[0098] The above Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 , Ar 7 , Ar a and Ar b If it is a fusion ring, preferably C3~C 30 Aliphatic ring and C6~C 30 A fused ring group of an aromatic ring, more preferably C3~C 25 Aliphatic ring and C6~C 25 It may be a fused ring group of an aromatic ring.

[0099] The above Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 , Ar 7 , Ar a and Ar b If it is a cycloalkyl group, preferably C3~C 30 Cycloalkyl group, more preferably C3~C 25 , C3~C 18 or C3~C 12 It may be a cycloalkyl group, and specifically, it may be cyclobutane, cyclopentane, cyclohexane, bicycloheptane, adamantyl, etc.

[0100] L 1 , L 2 , L 3 , L4 , L 5 , L 6 , L 7 , L a , L b and L c are independently of each other and are single bonds; C6~C 60 Arylene group; Fluorenylene group; C2~C containing at least one heteroatom among O, N, S, Si and P 60 Heterocyclic group of; and C3~C 60 Aliphatic ring and C6~C 60 A fused ring group of an aromatic ring is selected from the group consisting of;

[0101] Above L 1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 7 , L a , L b and L c If it is an arylene group, preferably C6~C 30 Arylene group, more preferably C6~C 25 , C6~C 18 or C6~C 12 It may be an arylene group, such as phenylene, biphenylene, naphthylene, terphenylene, anthracenylene, phenanthrenylene, etc.

[0102] Above L 1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 7 , L a , L b and L c If it is a heterocyclic group, preferably C2~C 30 A heterocyclic group, more preferably C2~C 25 , C2~C 18 or C2~C 12It may be a heterocyclic group, and examples thereof include pyrazine, thiophene, pyridine, pyrimidine, quinoline, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, quinoxaline, benzoquinazoline, carbazole, dibenzoquinazoline, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, benzothioenopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine, benzocarbazole, naphthobenzofuran, naphthobenzothiophene, etc.

[0103] Above L 1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 7 , L a , L b and L c If it is a fusion ring, preferably C3~C 30 Aliphatic ring and C6~C 30 A fused ring group of an aromatic ring, more preferably C3~C 25 Aliphatic ring and C6~C 25 It may be a fused ring group of an aromatic ring.

[0104] L 8 Silver C6~C 60 Arylene group; Fluorenylene group; C2~C containing at least one heteroatom among O, N, S, Si and P 60 is selected from the group consisting of heterocyclic groups; and ring aggregates thereof;

[0105] Above L 8 If it is an arylene group, preferably C6~C 30 Arylene group, more preferably C6~C 25 , C6~C 18 or C6~C 12 It may be an arylene group, such as phenylene, biphenylene, naphthylene, terphenylene, anthracenylene, phenanthrenylene, etc.

[0106] Above L 8If it is a heterocyclic group, preferably C2~C 30 A heterocyclic group, more preferably C2~C 25 , C2~C 18 or C2~C 12 It may be a heterocyclic group, and examples thereof include pyrazine, thiophene, pyridine, pyrimidine, quinoline, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, quinoxaline, benzoquinazoline, carbazole, dibenzoquinazoline, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, benzothioenopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine, benzocarbazole, naphthobenzofuran, naphthobenzothiophene, etc.

[0107] R a and R b are independently C6~C 60 Aryl group of; fluorenyl group; C2~C containing at least one heteroatom among O, N, S, Si and P 60 Heterocyclic group of; C3~C 60 Aliphatic ring and C6~C 60 Fused ring group of aromatic ring; C1~C 50 Alkyl group of; C2~C 20 Alkenyl group of; C2~C 20 Alkynyl group of; C1~C 30 Alkoxyl group of; and C6~C 30 is selected from the group consisting of aryloxy group of R, or a and R b can combine with each other to form spy rings,

[0108] R c and R d are identical or different from each other, and independently of each other, hydrogen; deuterium; C6~C 60 Aryl group of; fluorenyl group; C2~C containing at least one heteroatom among O, N, S, Si and P 60 Heterocyclic group of; C3~C 60 Aliphatic ring and C6~C 60Fused ring group of aromatic ring; C1~C 50 Alkyl group of; C2~C 20 Alkenyl group of; C2~C 20 Alkynyl group of; C1~C 30 Alkoxyl group of; and C6~C 30 is selected from the group consisting of aryloxy groups; or adjacent multiple R c R's or multiple R's d They can combine with each other to form rings,

[0109] The above R a , R b , R c and R d If it is an aryl group, preferably C6~C 30 Aryl group of, more preferably C6~C 25 , C6~C 18 or C6~C 12 The aryl group may be, for example, phenyl, biphenyl, terphenyl, naphthalene, phenanthrene, chrysene, etc.

[0110] The above R a , R b , R c and R d If it is a heterocyclic group, preferably C2~C 30 A heterocyclic group, more preferably C2~C 25 , C2~C 18 or C2~C 12 It may be a heterocyclic group, and examples thereof include pyrazine, thiophene, pyridine, pyrimidine, quinoline, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, quinoxaline, benzoquinazoline, carbazole, dibenzoquinazoline, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, benzothioenopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine, benzocarbazole, naphthobenzofuran, naphthobenzothiophene, etc.

[0111] The above R a , R b , R c and R dIf it is a fusion ring, preferably C3~C 30 Aliphatic ring and C6~C 30 A fused ring group of an aromatic ring, more preferably C3~C 25 Aliphatic ring and C6~C 25 It may be a fused ring group of an aromatic ring.

[0112] The above R a , R b , R c and R d If it is an alkyl group, preferably C1~C 30 It may be an alkyl group of, more preferably C1~C 25 , C1~C 18 or C1~C 12 It may be an alkyl group, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, etc.

[0113] The above R a , R b , R c and R d If it is an alkoxyl group, preferably C1~C 25 , C1~C 18 or C1~C 12 It may be an alkoxyl group.

[0114] The above R a , R b , R c and R d If it is an aryloxy group, preferably C6~C 25 , C6~C 18 or C6~C 12 It may be an aryloxy group.

[0115] a is an integer from 0 to 4, b is an integer from 0 to 3,

[0116] Here, the aryl group, arylene group, heterocyclic group, fluorenyl group, fluorenylene group, cycloalkyl group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group and aryloxy group are each deuterium; halogen; silane group; siloxane group; boron group; germanium group; cyano group; nitro group; C1~C 20 Alkylthio group of; C1~C 20 Alkoxyl group of; C6~C 20 Aryloxy group of; C1~C 20 Alkyl group of; C2~C 20 Alkenyl group of; C2~C 20 Alkyne group of; C6~C 20 Aryl group of; C6~C substituted with deuterium 20 Aryl group of; Fluorenyl group; C2~C 20 Heterocyclic group of; C3~C 20 Cycloalkyl group of; C7~C 20 Arylalkyl group of; C8~C 20 Aryl alkenyl group of; and -L'-R'R"; may be further substituted with one or more substituents selected from the group consisting of, and further, the hydrogen of these substituents is one or more deuterium, C6~C 20 Aryl group or C1~C 20 It can be further substituted with an alkyl group, and these substituents can also combine with each other to form a ring, where the 'ring' means C3~C 60 Aliphatic ring or C6~C 60 Aromatic ring or C2~C 60 A fused ring composed of a heterocycle or a combination thereof, and containing a saturated or unsaturated ring,

[0117] The above L' is a single bond; C6~C 60 Aryl group of; fluorenyl group; C2~C containing at least one heteroatom among O, N, S, Si and P 60 Heterocyclic group of; and C3~C 60 is selected from the group consisting of aliphatic rings;

[0118] The above R' and R" are independently C6~C 60 Aryl group of; fluorenyl group; C2~C containing at least one heteroatom among O, N, S, Si and P 60 Heterocyclic group of; C1~C 50 alkyl group; and C2~C 20 is selected from the group consisting of alkenyl groups;

[0119] The above L' is a single bond; C6~C 60 Aryl group of; fluorenyl group; C2~C containing at least one heteroatom among O, N, S, Si and P 60 Heterocyclic group of; and C3~C 60 is selected from the group consisting of aliphatic rings;

[0120] If the above L' is an arylene group, preferably C6~C 30 Arylene group, more preferably C6~C 25 , C6~C 18 or C6~C 12 It may be an arylene group, such as phenylene, biphenylene, naphthylene, terphenylene, anthracenylene, phenanthrenylene, etc.

[0121] If the above L' is a heterocyclic group, it is preferably C2~C 30 A heterocyclic group, more preferably C2~C 25 , C2~C 18 or C2~C 12 It may be a heterocyclic group, and examples thereof include pyrazine, thiophene, pyridine, pyrimidine, quinoline, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, quinoxaline, benzoquinazoline, carbazole, dibenzoquinazoline, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, benzothioenopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine, benzocarbazole, naphthobenzofuran, naphthobenzothiophene, etc.

[0122] If the above L' is an aliphatic ring group, preferably C3~C 30aliphatic ring, more preferably C3~C 25 , C3~C 18 or C3~C 12 It may be an aliphatic ring group, and specifically, it may be cyclobutane, cyclopentane, cyclohexane, bicycloheptane, adamantyl, etc.

[0123] The above R' and R" are independently C6~C 60 Aryl group of; fluorenyl group; C2~C containing at least one heteroatom among O, N, S, Si and P 60 Heterocyclic group of; C1~C 50 alkyl group; and C2~C 20 is selected from the group consisting of alkenyl groups;

[0124] In the case where the above R' and R" are aryl groups, preferably C6~C 30 Aryl group of, more preferably C6~C 25 , C6~C 18 or C6~C 12 The aryl group may be, for example, phenyl, biphenyl, terphenyl, naphthalene, phenanthrene, chrysene, etc.

[0125] In the case where the above R' and R" are heterocyclic groups, preferably C2~C 30 A heterocyclic group, more preferably C2~C 25 , C2~C 18 or C2~C 12 It may be a heterocyclic group, and examples thereof include pyrazine, thiophene, pyridine, pyrimidine, quinoline, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, quinoxaline, benzoquinazoline, carbazole, dibenzoquinazoline, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, benzothioenopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine, benzocarbazole, naphthobenzofuran, naphthobenzothiophene, etc.

[0126] In the case where the above R' and R" are alkyl groups, preferably C1~C30 It may be an alkyl group of, more preferably C1~C 25 , C1~C 18 or C1~C 12 It may be an alkyl group, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, etc.

[0127]

[0128] In addition, the present invention comprises the Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 , Ar 7 , Ar a and Ar b At least one of the organic electric devices comprises a compound represented by any one of the following chemical formulae Ar-a to Ar-d.

[0129] Chemical formula Ar-a Chemical formula Ar-b

[0130]

[0131] Chemical formula Ar-c Chemical formula Ar-d

[0132]

[0133] In the above chemical formulas Ar-a to Ar-d, each symbol can be defined as follows.

[0134] Y A , Y B and Y C are O, S, NR independently of each other 1A , SiR 1B R 1B or CR 1B R 1C and,

[0135] R A , R B , R C , R D , R E , R F , R 1A , R1B and R 1C are independently the same or different from each other, and independently hydrogen; deuterium; halogen; cyano group; C6~C 20 Aryl group of; C6~C substituted with deuterium 20 Aryl group of; fluorenyl group; C2~C containing at least one heteroatom among O, N, S, Si and P 20 Heterocyclic group of; C1~C 20 Alkyl group of; C2~C 20 Alkenyl group of; C2~C 20 Alkynyl group of; C1~C 20 Alkoxyl group of; C6~C 20 An aryloxy group of; and -L'-NR'R"; is selected from the group consisting of, or a plurality of adjacent R A R's or multiple R's B R's or multiple R's C R's or multiple R's D R's or multiple R's E R's or multiple R's F They can combine with each other to form a ring, or R 1B and R 1C can combine with each other to form spy rings,

[0136] ta and tc are independently integers from 0 to 3, tb and td are independently integers from 0 to 4, te is an integer from 0 to 5, tf is an integer from 0 to 7,

[0137] The above L', R' and R" are the same as defined above,

[0138] means the position of joining.

[0139]

[0140] The above chemical formula Ar-a can be represented by any one of the following chemical formulas Ar-a-1 to Ar-a-4.

[0141] <Chemical formula Ar-a-1> <Chemical formula Ar-a-2>

[0142]

[0143] <Chemical formula Ar-a-3> <Chemical formula Ar-a-4>

[0144]

[0145] {In the above chemical formulas Ar-a-1 to Ar-a-4, R A , R B , Y A , ta, tb and is as defined in the above chemical formula Ar-a.}

[0146]

[0147] The above chemical formula Ar-b can be represented by the following chemical formula Ar-b-1 or chemical formula Ar-b-2.

[0148] <Chemical formula Ar-b-1> <Chemical formula Ar-b-2>

[0149]

[0150] {In the above chemical formula Ar-b-1 and chemical formula Ar-b-2, R C , R D , Y B , Y C , tc, td and is as defined in the above chemical formula Ar-b.}

[0151]

[0152] The above chemical formula Ar-d can be represented by the following chemical formula Ar-d-1 or chemical formula Ar-d-2.

[0153] <Chemical formula Ar-d-1> <Chemical formula Ar-d-2>

[0154]

[0155] {In the above chemical formula Ar-d-1 and chemical formula Ar-d-2, R F , tf and is as defined in the above chemical formula Ar-d.}

[0156]

[0157] Above L 1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 7 , L a , L b and L c can be represented by a single bond or any one of the following chemical formulas b-1 to b-13, L 8 can be represented by any one of the following chemical formulas b-1 to b-13.

[0158] Chemical formula b-1 Chemical formula b-2 Chemical formula b-3 Chemical formula b-4 Chemical formula b-5 Chemical formula b-6

[0159]

[0160] Chemical formula b-7 Chemical formula b-8 Chemical formula b-9 Chemical formula b-10

[0161]

[0162] Chemical formula b-11 Chemical formula b-12 Chemical formula b-13

[0163]

[0164] {In the above chemical formulas b-1 to b-13,

[0165] Z 10 Silver O, S, NR 1D or CR 1E R 1F and,

[0166] a”, c”, d”, e” and i” are each independently an integer from 0 to 4, b” is an integer from 0 to 6, f” and g” are each independently an integer from 0 to 3, h” is an integer from 0 to 2, and j” is an integer of 0 or 1,

[0167] R a1 , R a2 , R a3 , R a4 , R a5 , R a6, R a7 , R 1D , R 1E and R 1F are independently the same or different from each other, and independently hydrogen; deuterium; C6~C 20 Aryl group of; fluorenyl group; C2~C containing at least one heteroatom among O, N, S, Si and P 20 Heterocyclic group of; C1~C 50 Alkyl group of; C2~C 20 Alkenyl group of; C2~C 20 Alkynyl group of; C1~C 30 Alkoxyl group of; and C6~C 30 is selected from the group consisting of aryloxy groups; or adjacent groups can be combined with each other to form a ring,

[0168] Z 49 , Z 50 and Z 51 are independently of each other 1G or N,

[0169] But, Z 49 , Z 50 and Z 51 At least one of them is N,

[0170] R 1G is the above R A is identical to the definition of

[0171] means the position where it is combined.}

[0172]

[0173] Specifically, the compound of the above chemical formula 1 may be any one of the following compounds P1-1 to P1-97, but is not limited thereto.

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200] Specifically, the compound of the above chemical formula 2 may be any one of the following compounds P2-1 to P2-79, but is not limited thereto.

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224] Specifically, the compound of the above chemical formula 3 may be any one of the following compounds P3-1 to P3-80, but is not limited thereto.

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246] In addition, the present invention provides an organic electric device in which the light-emitting layer includes a host and a dopant.

[0247] In addition, the present invention provides an organic electric device in which the dopant includes iridium (Ir) or platinum (Pt).

[0248] In addition, the present invention provides an organic electric device in which the difference between the HOMO energy level of the compound represented by the chemical formula 1 and the HOMO energy level of the compound represented by the chemical formula 2 is 0.05 to 0.12 eV.

[0249] The present invention may further include a light efficiency improvement layer formed on at least one surface of the first electrode and the second electrode, which is opposite to the organic layer.

[0250] In addition, the organic layer may include two or more stacks including a hole transport layer, a light-emitting layer, and an electron transport layer sequentially formed on the anode, and the organic layer may further include a charge generation layer formed between the two or more stacks.

[0251] In addition, the organic electric device of the present invention may further include a buffer layer between the light-emitting auxiliary layer and the hole transport layer.

[0252] In another aspect, the present invention provides an electronic device including a display device including the organic electroluminescent element; and a control unit for driving the display device. In this case, the organic electroluminescent element may be at least one of an organic electroluminescent element, an organic solar cell, an organic photoconductor, an organic transistor, and a monochrome or white lighting element.

[0253]

[0254] Hereinafter, examples of synthesis of compounds represented by chemical formulas 1 to 3 and examples of manufacturing organic electric devices according to the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.

[0255]

[0256] [Synthesis Example 1] Synthesis Example of Chemical Formula 1

[0257] The compound represented by chemical formula 1 according to the present invention (final product 1) is Hal according to the reaction path of the following reaction formula 1. 1 is I, Br or Cl.)

[0258]

[0259]

[0260] I. Synthesis of Sub 1

[0261] Compounds belonging to Sub 1 of the above reaction scheme 1 may be, but are not limited to, the compounds below, and Table 1 below shows the FD-MS (Field Desorption-Mass Spectrometry) values ​​of the compounds below.

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274]

[0275]

[0276]

[0277]

[0278]

[0279]

[0280]

[0281]

[0282] 화합물FD-MS화합물FD-MSSub 1-1m / z=354.08(C 24 H 15 ClO=354.83)Sub 1-2m / z=238.05(C 16 H 11 Cl=238.71)Sub 1-3m / z=364.10(C 26 H 17 Cl=364.87)Sub 1-4m / z=241.05(C 12 D9Br=242.16)Sub 1-5m / z=278.05(C 18 H 11 ClO=278.74)Sub 1-6m / z=278.05(C 18 H 11 ClO=278.74)Sub 1-7m / z=288.07(C 20 H 13 Cl=288.77)Sub 1-8m / z=278.05(C 18 H 11 ClO=278.74)Sub 1-9m / z=354.08(C 24 H 15 ClO=354.83)Sub 1-10m / z=304.10(C 21 H 17 Cl=304.82)Sub 1-11m / z=278.05(C 18 H 11 ClO=278.74)Sub 1-12m / z=402.12(C 29 H 19 Cl=402.92)Sub 1-13m / z=402.12(C 29 H 19 Cl=402.92)Sub 1-14m / z=402.12(C 29 H 19 Cl=402.92)Sub 1-15m / z=354.08(C 24 H 15 ClO=354.83)Sub 1-16m / z=328.07(C 22 H 13ClO=328.79)Sub 1-17m / z=428.13(C 31 H 21 Cl=428.96)Sub 1-18m / z=353.10(C 24 H 16 ClN=353.85)Sub 1-19m / z=277.07(C 18 H 12 ClN=277.75)Sub 1-20m / z=426.12(C 31 H 19 Cl=426.94)Sub 1-21m / z=353.10(C 24 H 16 ClN=353.85)Sub 1-22m / z=353.10(C 24 H 16 ClN=353.85)Sub 1-23m / z=294.03(C 18 H 11 ClS=294.80)Sub 1-24m / z=278.05(C 18 H 11 ClO=278.74)Sub 1-25m / z=458.09(C 31 H 19 ClS=459.00)Sub 1-26m / z=476.13(C 35 H 21 Cl=477.00)Sub 1-27m / z=442.11(C 31 H 19 ClO=442.94)Sub 1-28m / z=278.05(C 18 H 11 ClO=278.74)Sub 1-29m / z=294.03(C 18 H 11 ClS=294.80)Sub 1-30m / z=258.12(C 18 H 14 N2=258.32)Sub 1-31m / z=278.05(C 18 H 11 ClO=278.74)Sub 1-32m / z=410.03(C 25 H 15 BrO=411.30)Sub 1-33m / z=396.05(C 25 H 17Br=397.31)Sub 1-34m / z=278.05(C 18 H 11 ClO=278.74)Sub 1-35m / z=428.13(C 31 H 21 Cl=428.96)Sub 1-36m / z=278.05(C 18 H 11 ClO=278.74)Sub 1-37m / z=408.16(C 29 H 25 Cl=408.97)Sub 1-38m / z=462.21(C 33 H 31 Cl=463.06)Sub 1-39m / z=442.11(C 31 H 19 ClO=442.94)Sub 1-40m / z=441.13(C 31 H 20 ClN=441.96)Sub 1-41m / z=278.09(C 19 H 15 Cl=278.78)Sub 1-42m / z=508.18(C 33 H 33 Br=509.53)Sub 1-43m / z=278.05(C 18 H 11 ClO=278.74)Sub 1-44m / z=278.05(C 18 H 11 ClO=278.74)Sub 1-45m / z=278.05(C 18 H 11 ClO=278.74)Sub 1-46m / z=368.08(C 24 H 17 ClSi=368.94)Sub 1-47m / z=396.05(C 25 H 17 Br=397.31)Sub 1-48m / z=244.05(C 14 H 13 ClSi=244.79)Sub 1-49m / z=302.03(C 16 H 15 BrO=303.20)Sub 1-50m / z=300.05(C 17 H 17Br=301.23)Sub 1-51m / z=396.05(C 25 H 17 Br=397.31)Sub 1-52m / z=410.07(C 26 H 19 Br=411.34)Sub 1-53m / z=246.12(C 16 H 19 Cl=246.78)Sub 1-54m / z=278.05(C 18 H 11 ClO=278.74)Sub 1-55m / z=242.09(C 16 H 15 Cl=242.75)Sub 1-56m / z=428.13(C 31 H 21 Cl=428.96)Sub 1-57m / z=314.09(C 22 H 15 Cl=314.81)Sub 1-58m / z=352.10(C 25 H 17 Cl=352.86)Sub 1-59m / z=428.13(C 31 H 21 Cl=428.96)Sub 1-60m / z=380.13(C 27 H 21 Cl=380.91)Sub 1-61m / z=428.13(C 31 H 21 Cl=428.96)Sub 1-62m / z=428.13(C 31 H 21 Cl=428.96)Sub 1-63m / z=389.19(C 26 H 28 ClN=389.97)Sub 1-64m / z=358.13(C 24 H 11 D5ClN=358.88)Sub 1-65m / z=314.09(C 22 H 15 Cl=314.81)Sub 1-66m / z=320.13(C 22 H 21 Cl=320.86)Sub 1-67m / z=508.18(C 33 H 33Br=509.53)Sub 1-68m / z=370.15(C 26 H 23 Cl=370.92)Sub 1-69m / z=194.09(C 12 H 15 Cl=194.70)Sub 1-70m / z=394.11(C 27 H 19 ClO=394.90)Sub 1-71m / z=384.04(C 24 H 13 ClOS=384.88)Sub 1-72m / z=443.11(C 30 H 18 ClNO=443.93)Sub 1-73m / z=442.12(C 30 H 19 ClN2=442.95)Sub 1-74m / z=442.12(C 30 H 19 ClN2=442.95)Sub 1-75m / z=278.05(C 18 H 11 ClO=278.74)Sub 1-76m / z=283.08(C 18 H6D5ClO=283.77)Sub 1-77m / z=364.10(C 26 H 17 Cl=364.87)Sub 1-78m / z=400.10(C 29 H 17 Cl=400.90)Sub 1-79m / z=402.12(C 29 H 19 Cl=402.92)Sub 1-80m / z=554.18(C 41 H 27 Cl=555.12)Sub 1-81m / z=394.04(C 25 H 15 Br=395.30)Sub 1-82m / z=416.04(C 24 H 19 BrSi=415.40)Sub 1-83m / z=410.03(C 25 H 15 BrO=411.30)Sub 1-84m / z=188.04(C 12 H9Cl=188.65)Sub 1-85m / z=334.11(C22 H 19 ClO=334.84)Sub 1-86m / z=272.02(C 15 H 13 Br=273.17)Sub 1-87m / z=322.04(C 19 H 15 Br=323.23)Sub 1-88m / z=322.00(C 18 H 11 BrO=323.19)Sub 1-89m / z=322.00(C 18 H 11 BrO=323.19)Sub 1-90m / z=318.08(C 21 H 15 ClO=318.80)Sub 1-91m / z=278.05(C 18 H 11 ClO=278.74)Sub 1-92m / z=322.00(C 18 H 11 BrO=323.19)Sub 1-93m / z=327.08(C 22 H 14 ClN=327.81)Sub 1-94m / z=277.07(C 18 H 12 ClN=277.75)Sub 1-95m / z=264.07(C 18 H 13 Cl=264.75)Sub 1-96m / z=238.05(C 16 H 11 Cl=238.71)Sub 1-97m / z=400.1(C 29 H 17 Cl=400.91)

[0283] II. Synthesis of Sub 2

[0284] Compounds belonging to Sub 2 of the above reaction scheme 1 may be, but are not limited to, the compounds below, and Table 2 shows the FD-MS values ​​of the compounds below.

[0285]

[0286]

[0287]

[0288]

[0289]

[0290]

[0291]

[0292]

[0293]

[0294]

[0295]

[0296]

[0297]

[0298]

[0299]

[0300]

[0301]

[0302]

[0303]

[0304]

[0305]

[0306]

[0307] Compound FD-MS Compound FD-MS Sub 2-1 m / z = 321.15 (C 24 H 19 N=321.42)Sub 2-2m / z=397.18(C 30 H 23 N=397.52)Sub 2-3m / z=345.15(C 26 H 19 N=345.44)Sub 2-4m / z=371.17(C 28 H21 N = 371.48) Sub 2-5m / z = 321.15 (C 24 H 19 N = 321.42) Sub 2-6m / z = 345.15 (C 26 H 19 N = 345.44) Sub 2-7m / z = 371.17 (C 28 H 21 N = 371.48) Sub 2-8m / z = 397.18 (C 30 H 23 N = 397.52) Sub 2-9m / z = 447.20 (C 34 H 25 N = 447.58) Sub 2-10m / z = 295.14 (C 22 H 17 N = 295.38) Sub 2-11m / z = 245.12 (C 18 H 15 N = 245.32) Sub 2-12m / z = 169.09 (C 12 H 11 N = 169.23) Sub 2-13m / z = 395.17 (C 30 H 21 N = 395.50) Sub 2-14m / z = 219.10 (C 16 H 13 N = 219.29) Sub 2-15m / z = 219.10 (C 16 H 13 N = 219.29) Sub 2-16m / z = 219.10 (C 16 H 13 N = 219.29) Sub 2-17m / z = 319.14 (C 24 H 17 N = 319.41) Sub 2-18m / z = 523.23 (C 40 H 29 N = 523.68) Sub 2-19m / z = 369.15 (C 28 H 19 N = 369.47) Sub 2-20m / z = 345.15 (C 26 H 19 N = 345.44) Sub 2-21m / z = 174.12 (C 12 H6D5N=174.26)Sub 2-22m / z=339.26(C 24 HD18 N=339.53)Sub 2-23m / z=351.20(C 26 H 25 N=351.49)Sub 2-24m / z=291.14(C 19 H 21 NSi=291.47)Sub 2-25m / z=361.18(C 27 H 23 N=361.49)Sub 2-26m / z=361.18(C 27 H 23 N=361.49)Sub 2-27m / z=401.21(C 30 H 27 N=401.55)Sub 2-28m / z=401.21(C 30 H 27 N=401.55)Sub 2-29m / z=401.21(C 30 H 27 N=401.55)Sub 2-30m / z=361.18(C 27 H 23 N=361.49)Sub 2-31m / z=401.21(C 30 H 27 N=401.55)Sub 2-32m / z=401.21(C 30 H 27 N=401.55)Sub 2-33m / z=401.21(C 30 H 27 N=401.55)Sub 2-34m / z=457.28(C 34 H 35 N=457.66)Sub 2-35m / z=477.25(C 36 H 31 N=477.65)Sub 2-36m / z=319.14(C 24 H 17 N=319.41)Sub 2-37m / z=217.09(C 16 H 11 N=217.27)Sub 2-38m / z=334.15(C 24 H 18 N2=334.42)Sub 2-39m / z=334.15(C 24 H 18 N2=334.42)Sub 2-40m / z=450.21(C33 H 26 N2=450.59)Sub 2-41m / z=651.27(C 48 H 33 N3=651.81)Sub 2-42m / z=526.24(C 39 H 30 N2=526.68)Sub 2-43m / z=500.19(C 36 H 24 N2O=500.60)Sub 2-44m / z=440.13(C 30 H 20 N2S=440.56)Sub 2-45m / z=451.19(C 33 H 25 NO=451.57)Sub 2-46m / z=451.19(C 33 H 25 NO=451.57)Sub 2-47m / z=451.19(C 33 H 25 NO=451.57)Sub 2-48m / z=451.19(C 33 H 25 NO=451.57)Sub 2-49m / z=501.21(C 37 H 27 NO=501.63)Sub 2-50m / z=375.16(C 27 H 21 NO=375.47)Sub 2-51m / z=375.16(C 27 H 21 NO=375.47)Sub 2-52m / z=375.16(C 27 H 21 NO=375.47)Sub 2-53m / z=375.16(C 27 H 21 NO=375.47)Sub 2-54m / z=425.18(C 31 H 23 NO=425.53)Sub 2-55m / z=437.18(C 32 H 23 NO=437.54)Sub 2-56m / z=259.10(C 18 H 13 NO=259.31)Sub 2-57m / z=259.10(C 18 H 13NO=259.31)Sub 2-58m / z=259.10(C 18 H 13 NO=259.31)Sub 2-59m / z=335.13(C 24 H 17 NO=335.41)Sub 2-60m / z=335.13(C 24 H 17 NO=335.41)Sub 2-61m / z=335.13(C 24 H 17 NO=335.41)Sub 2-62m / z=335.13(C 24 H 17 NO=335.41)Sub 2-63m / z=309.12(C 22 H 15 NO=309.37)Sub 2-64m / z=309.12(C 22 H 15 NO=309.37)Sub 2-65m / z=385.15(C 28 H 19 NO=385.47)Sub 2-66m / z=411.16(C 30 H 21 NO=411.50)Sub 2-67m / z=359.13(C 26 H 17 NO=359.43)Sub 2-68m / z=411.16(C 30 H 21 NO=411.50)Sub 2-69m / z=411.16(C 30 H 21 NO=411.50)Sub 2-70m / z=411.16(C 30 H 21 NO=411.50)Sub 2-71m / z=335.13(C 24 H 17 NO=335.41)Sub 2-72m / z=411.16(C 30 H 21 NO=411.50)Sub 2-73m / z=385.15(C 28 H 19 NO=385.47)Sub 2-74m / z=411.16(C 30 H 21 NO=411.50)Sub 2-75m / z=349.11(C24 H 15 NO2=349.39)Sub 2-76m / z=441.12(C 30 H 19 NOS=441.55)Sub 2-77m / z=529.15(C 37 H 23 NOS=529.66)Sub 2-78m / z=499.19(C 37 H 25 NO=499.61)Sub 2-79m / z=499.19(C 37 H 25 NO=499.61)Sub 2-80m / z=517.15(C 36 H 23 NOS=517.65)Sub 2-81m / z=517.15(C 36 H 23 NOS=517.65)Sub 2-82m / z=275.08(C 18 H 13 NS=275.37)Sub 2-83m / z=351.11(C 24 H 17 NS=351.47)Sub 2-84m / z=275.08(C 18 H 13 NS=275.37)Sub 2-85m / z=325.09(C 22 H 15 NS=325.43)Sub 2-86m / z=325.09(C 22 H 15 NS=325.43)Sub 2-87m / z=351.11(C 24 H 17 NS=351.47)Sub 2-88m / z=391.14(C 27 H 21 NS=391.53)Sub 2-89m / z=409.18(C 31 H 23 N=409.53)Sub 2-90m / z=485.21(C 37 H 27 N=485.63)Sub 2-91m / z=485.21(C 37 H 27 N=485.63)Sub 2-92m / z=485.21(C 37 H 27N = 485.63) Sub 2-93m / z = 485.21 (C 37 H 27 N = 485.63) Sub 2-94m / z = 485.21 (C 37 H 27 N = 485.63) Sub 2-95 m / z = 423.16 (C 31 H 21 NO=423.51)Sub 2-96m / z=423.16(C 31 H 21 NO=423.51)Sub 2-97m / z=379.23(C 28 H 29 N = 379.55) Sub 2-98m / z = 367.23 (C 27 H 29 N = 367.54) Sub 2-99m / z = 367.23 (C 27 H 29 N = 367.54) Sub 2-100m / z = 341.18 (C 24 H 23 NO=341.45)Sub 2-101m / z=385.28(C 28 H 35 N = 385.59) Sub 2-102m / z = 345.25 (C 25 H 31 N = 345.53) Sub 2-103m / z = 397.28 (C 29 H 35 N = 397.61) Sub 2-104m / z = 209.12 (C 15 H 15 N = 209.29) Sub 2-105m / z = 411.16 (C 30 H 21 NO = 411.50) Sub 2-106m / z = 409.18 (C 31 H 23 N = 409.53) Sub 2-107m / z = 485.21 (C 37 H 27 N = 485.63) Sub 2-108m / z = 553.28 (C 42 H 35 N = 553.75)

[0308] III. Final Product 1의 합성예

[0309] 1. P1-32 Synthesis Example

[0310]

[0311] Sub 1-21 (15 g, 40.6 mmol), Toluene (140 mL), Sub 2-19 (14.4 g, 40.6 mmol), Pd2(dba)3(1.12 g, 1.22 mmol), P(t-Bu)3(0.49 g, 2.44 mmol), NaOt-Bu (7.80 g, 81.2 mmol) were added and stirred at 100°C. Upon completion of the reaction, the mixture was extracted with Toluene and water, and the organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain the product (19.5 g, 70%).

[0312]

[0313] 2. P1-48 Synthesis Example

[0314]

[0315] Sub 1-32 (16 g, 42.6 mmol), Toluene (140 mL), Sub 2-50 (17.5 g, 42.6 mmol), Pd2(dba)3(1.17 g, 1.28 mmol), P(t-Bu)3(0.52 g, 2.56 mmol), NaOt-Bu (8.20 g, 85.2 mmol) were added and stirred at 100°C. Upon completion of the reaction, the mixture was extracted with Toluene and water, and the organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain the product (23.5 g, 78%).

[0316]

[0317] 3. P1-69 Synthesis example

[0318]

[0319] Sub 1-82 (16 g, 38.5 mmol), toluene (193 mL), Sub 2-87 (13.5 g, 38.5 mmol), Pd2(dba)3(1.06 g, 1.16 mmol), P(t-Bu)3(0.47 g, 2.31 mmol), and NaOt-Bu (7.4 g, 77.0 mmol) were added and stirred at 100°C. Upon completion of the reaction, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain the product (19.0 g, 72%).

[0320]

[0321] 4. P1-71 Synthesis Example

[0322]

[0323] Sub 1-53 (15 g, 39.5 mmol), toluene (130 mL), Sub 2-97 (9.75 g, 39.5 mmol), Pd2(dba)3(1.09 g, 1.19 mmol), P(t-Bu)3(0.48 g, 2.37 mmol), and NaOt-Bu (7.60 g, 79.0 mmol) were added and stirred at 100°C. Upon completion of the reaction, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain the product (18.9 g, 81%).

[0324]

[0325] 5. P1-95 Synthesis Example

[0326]

[0327] Sub 1-75 (10 g, 47.8 mmol), Toluene (160 mL), Sub 2-104 (26.6 g, 100.3 mmol), Pd2(dba)3(2.19 g, 2.39 mmol), P(t-Bu)3(0.97 g, 4.78 mmol), NaOt-Bu (13.8 g, 143.3 mmol) were added and stirred at 100°C. Upon completion of the reaction, the mixture was extracted with Toluene and water, and the organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain the product (25.9 g, 78%).

[0328]

[0329] 6. P1-96 Synthesis Example

[0330]

[0331] Sub 1-76 (10 g, 47.8 mmol), toluene (160 mL), Sub 2-104 (27.1 g, 100.3 mmol), Pd2(dba)3(2.19 g, 2.39 mmol), P(t-Bu)3(0.97 g, 4.78 mmol), NaOt-Bu (13.8 g, 143.3 mmol) were added and stirred at 100°C. Upon completion of the reaction, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain the product (25.2 g, 75%).

[0332]

[0333] The FD-MS values ​​of compounds P1-1 to P1-97 of the present invention manufactured according to the above synthetic examples are as shown in Table 3 below.

[0334] Compound FD-MS Compound FD-MSP1-1 m / z = 473.21 (C 36 H 27 N=473.62)P1-2m / z=471.20(C 36 H 25 N=471.60)P1-3m / z=675.29(C52 H 37 N=675.88)P1-4m / z=715.29(C 54 H 37 NO=715.90)P1-5m / z=623.26(C 48 H 33 N=623.80)P1-6m / z=649.28(C 50 H 35 N=649.84)P1-7m / z=667.39(C 50 H 17 D 18 N=667.95)P1-8m / z=749.31(C 58 H 39 N=749.96)P1-9m / z=653.24(C 48 H 31 NO2=653.78)P1-10m / z=567.17(C 40 H 25 NOS=567.71)P1-11m / z=531.13(C 36 H 21 NO2S=531.63)P1-12m / z=593.18(C 42 H 27 NOS=593.74)P1-13m / z=527.17(C 38 H 25 NS=527.68)P1-14m / z=561.21(C 42 H 27 NO=561.68)P1-15m / z=527.22(C 39 H 29 NO=527.67)P1-16m / z=769.30(C 57 H 39 NO2=769.94)P1-17m / z=643.29(C 48 H 37 NO=643.83)P1-18m / z=719.32(C 54 H 41 NO=719.93)P1-19m / z=767.32(C 58 H 41 NO=767.97)P1-20m / z=651.26(C 49 H 33 NO=651.81)P1-21m / z=717.34(C 55 H43 N=717.96)P1-22m / z=717.34(C 55 H 43 N=717.96)P1-23m / z=767.36(C 59 H 45 N=768.02)P1-24m / z=767.36(C 59 H 45 N=768.02)P1-25m / z=817.33(C 62 H 43 NO=818.03)P1-26m / z=727.29(C 55 H 37 NO=727.91)P1-27m / z=817.33(C 62 H 43 NO=818.03)P1-28m / z=703.25(C 52 H 33 NO2=703.84)P1-29m / z=869.40(C 67 H 51 N=870.15)P1-30m / z=767.36(C 59 H 45 N=768.02)P1-31m / z=562.24(C 42 H 30 N2=562.72)P1-32m / z=686.27(C 52 H 34 N2=686.86)P1-33m / z=586.24(C 44 H 30 N2=586.74)P1-34m / z=602.27(C 45 H 34 N2=602.78)P1-35m / z=602.27(C 45 H 34 N2=602.78)P1-36m / z=649.24(C 49 H 31 NO=649.79)P1-37m / z=673.24(C 51 H 31 NO=673.81)P1-38m / z=711.29(C 55 H 37 N=711.91)P1-39m / z=725.27(C 55 H 35NO=725.89)P1-40m / z=965.38(C 73 H 47 N3=966.20)P1-41m / z=815.32(C 62 H 41 NO=816.02)P1-42m / z=919.42(C 71 H 53 N=920.21)P1-43m / z=753.30(C 57 H 39 NO=753.94)P1-44m / z=758.24(C 54 H 34 N2OS=758.94)P1-45m / z=717.25(C 53 H 35 NS=717.93)P1-46m / z=891.35(C 68 H 45 NO=892.11)P1-47m / z=759.22(C 54 H 33 NO2S=759.92)P1-48m / z=705.27(C 52 H 35 NO2=705.86)P1-49m / z=691.29(C 52 H 37 NO=691.87)P1-50m / z=617.24(C 45 H 31 NO2=617.75)P1-51m / z=849.34(C 66 H 43 N=850.08)P1-52m / z=753.34(C 58 H 43 N=753.99)P1-53m / z=727.29(C 55 H 37 NO=727.91)P1-54m / z=747.35(C 56 H 45 NO=747.98)P1-55m / z=761.37(C 57 H 47 NO=762.01)P1-56m / z=781.30(C 58 H 39 NO2=781.95)P1-57m / z=766.33(C 58 H 42N2=766.99)P1-58m / z=845.28(C 62 H 39 NOS=846.06)P1-59m / z=727.32(C 56 H 41 N=727.95)P1-60m / z=945.40(C 69 H 55 NOS=946.26)P1-61m / z=643.29(C 48 H 37 NO=643.83)P1-62m / z=682.21(C 48 H 30 N2OS=682.84)P1-63m / z=707.26(C 51 H 37 NOSi=707.95)P1-64m / z=707.26(C 51 H 37 NOSi=707.95)P1-65m / z=679.38(C 50 H 49 NO=679.95)P1-66m / z=801.34(C 62 H 43 N=802.03)P1-67m / z=691.32(C 53 H 41 N=691.92)P1-68m / z=705.34(C 54 H 43 N=705.94)P1-69m / z=685.23(C 48 H 35 NSSi=685.96)P1-70m / z=695.36(C 53 H 45 N=695.95)P1-71m / z=589.37(C 44 H 47 N=589.87)P1-72m / z=603.26(C 45 H 33 NO=603.76)P1-73m / z=753.34(C 58 H 43 N=753.99)P1-74m / z=767.32(C 58 H 41 NO=767.97)P1-75m / z=753.34(C 58 H 43 N=753.99)P1-76m / z=705.30(C53 H 39 NO=705.90)P1-77m / z=829.30(C 62 H 39 NO2=830.00)P1-78m / z=993.36(C 75 H 47 NO2=994.21)P1-79m / z=763.32(C 59 H 41 N=763.98)P1-80m / z=753.34(C 58 H 43 N=753.99)P1-81m / z=639.29(C 49 H 37 N=639.84)P1-82m / z=685.33(C 51 H 43 NO=685.91)P1-83m / z=665.37(C 49 H 47 NO=665.92)P1-84m / z=651.39(C 49 H 49 N=651.94)P1-85m / z=750.49(C 55 H 62 N2=751.11)P1-86m / z=577.37(C 43 H 47 N=577.86)P1-87m / z=773.50(C 58 H 63 N=774.15)P1-88m / z=695.36(C 53 H 45 N=695.95)P1-89m / z=533.27(C 39 H 35 NO=533.71)P1-90m / z=719.32(C 54 H 41 NO=719.93)P1-91m / z=709.24(C 51 H 35 NOS=709.91)P1-92m / z=768.31(C 57 H 40 N2O=768.96)P1-93m / z=767.33(C 57 H 41 N3=767.98)P1-94m / z=767.33(C 57 H 41N3=767.98)P1-95m / z=693.27(C 51 H 35 NO2=693.85)P1-96m / z=703.33(C 51 H 25 D 10 NO2=703.91)P1-97m / z=683.33(C 51 H 33 D5N2=683.91)

[0335] [Synthesis Example 2] Synthesis Example of Chemical Formula 2

[0336] The compound represented by chemical formula 2 according to the present invention (final product 2) can be synthesized according to the reaction path of the following reaction scheme 2, but is not limited thereto.

[0337] <Reaction Scheme 2> (Hal 2 and Hal 3 are independently I, Br or Cl.)

[0338]

[0339]

[0340] I. Synthesis of Sub 3

[0341] Compounds belonging to Sub 3 of the above reaction scheme 2 may be, but are not limited to, the compounds below, and Table 4 below shows the FD-MS values ​​of the compounds below.

[0342]

[0343]

[0344]

[0345]

[0346]

[0347]

[0348]

[0349] 화합물FD-MS화합물FD-MSSub 3-1m / z=235.87(C6H4Br2=235.91)Sub 3-2m / z=235.87(C6H4Br2=235.91)Sub 3-3m / z3=311.90(C 12 H8Br2=312.00)Sub 3-4m / z=311.90(C 12 H8Br2=312.00)Sub 3-5m / z=311.90(C 12 H8Br2=312.00)Sub 3-6m / z=311.90(C 12 H8Br2=312.00)Sub 3-7m / z=343.98(C 18 H 12 BrCl=343.65)Sub 3-8m / z=343.98(C 18 H 12 BrCl=343.65)Sub 3-9m / z=317.96(C 16 H 10 BrCl=317.61)Sub 3-10m / z=341.85(C 12 H6Br2S=342.05)Sub 3-11m / z=297.90(C 12 H6BrClS=297.59)Sub 3-12m / z=297.90(C 12 H6BrClS=297.59)Sub 3-13m / z=341.85(C 12 H6Br2S=342.05)Sub 3-14m / z=297.90(C 12 H6BrClS=297.59)Sub 3-15m / z=311.92(C 13 H8BrClS=311.62)Sub 3-16m / z=327.99(C 18 H 10 Cl2S=329.24)Sub 3-17m / z=347.92(C 16 H8BrClS=347.65)Sub 3-18m / z=347.92(C 16 H8BrClS=347.65)Sub 3-19m / z=371.94(C 18 H 10 BrClS=373.69)Sub 3-20m / z=325.88(C 12H6Br2O=325.99)Sub 3-21m / z=281.93(C 12 H6BrClO=281.53)Sub 3-22m / z=281.93(C 12 H6BrClO=281.53)Sub 3-23m / z=325.88(C 12 H6Br2O=325.99)Sub 3-24m / z=401.91(C 18 H 10 Br2O=402.08)Sub 3-25m / z=357.96(C 18 H 10 BrClO=357.63)Sub 3-26m / z=463.95(C 24 H 12 BrClOS=463.77)Sub 3-27m / z=400.92(C 18 H 11 Br2N=401.10)Sub 3-28m / z=433.01(C 24 H 15 BrClN=432.75)Sub 3-29m / z=387.06(C 24 H 15 Cl2N=388.29)Sub 3-30m / z=437.07(C 28 H 17 Cl2N=438.35)Sub 3-31m / z=351.93(C 15 H 12 Br2=352.07)Sub 3-32m / z=338.06(C 21 H 16 Cl2=339.26)Sub 3-33m / z=386.06(C 25 H 16 Cl2=387.30)Sub 3-34m / z=386.06(C 25 H 16 Cl2=387.30)

[0350] II. Final Product 2의 합성예

[0351] 1. P2-31 합성예

[0352]

[0353] Sub 2-28 (25.7 g, 64.1 mmol), toluene (105 mL), Sub 3-3 (10 g, 32.1 mmol), Pd2(dba)3(1.47 g, 1.60 mmol), P(t-Bu)3(0.65 g, 3.21 mmol), NaOt-Bu (9.24 g, 96.2 mmol) were added and stirred at 100°C. Upon completion of the reaction, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain the product (25.7 g, 84%).

[0354]

[0355] 2. P2-37 Synthesis Example

[0356]

[0357] Sub 2-12 (16 g, 94.5 mmol), Toluene (160 mL), Sub 3-9 (15 g, 47.2 mmol), Pd2(dba)3(2.16 g, 2.36 mmol), P(t-Bu)3(0.96 g, 4.72 mmol), NaOt-Bu (13.6 g, 141.7 mmol) were added and stirred at 100°C. Upon completion of the reaction, the mixture was extracted with Toluene and water, and the organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain the product (18.1 g, 71%).

[0358]

[0359] 3. P2-42 Synthesis Example

[0360]

[0361] (1) Synthesis of Inter 2-48

[0362] Sub 2-12 (30 g, 177.6 mmol), Toluene (590 mL), Sub 3-21 (50 g, 177.6 mmol), Pd2(dba)3(4.88 g, 2.36 mmol), P(t-Bu)3(2.16 g, 10.6 mmol), NaOt-Bu (34.1 g, 355.2 mmol) were added and stirred at 70°C. Upon completion of the reaction, the mixture was extracted with Toluene and water, and the organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain the product (48.6 g, 74%).

[0363] (2) Synthesis of P2-42

[0364] Inter 2-48 (18.5 g, 50.0 mmol), toluene (170 mL), Sub 2-78 (25 g, 50.0 mmol), Pd2(dba)3(1.37 g, 1.50 mmol), P(t-Bu)3(0.61 g, 3.00 mmol), and NaOt-Bu (9.62 g, 100.1 mmol) were added and stirred at 100°C. Upon completion of the reaction, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain the product (27.9 g, 67%).

[0365]

[0366] 4. P2-52 Synthesis Example

[0367]

[0368] (1) Synthesis of Inter 2-52

[0369] Sub 2-12 (15 g, 88.6 mmol), Toluene (300 mL), Sub 3-14 (26.4 g, 88.6 mmol), Pd2(dba)3(2.44 g, 2.66 mmol), P(t-Bu)3(1.08 g, 5.32 mmol), NaOt-Bu (17.0 g, 177.3 mmol) were added and stirred at 70°C. Upon completion of the reaction, the mixture was extracted with Toluene and water, and the organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain the product (23.6 g, 69%).

[0370] (2) Synthesis of P2-52

[0371] Sub 2-85 (18 g, 55.3 mmol), toluene (180 mL), Inter 2-52 (21.4 g, 55.3 mmol), Pd2(dba)3(1.52 g, 1.66 mmol), P(t-Bu)3(0.67 g, 3.32 mmol), and NaOt-Bu (10.6 g, 110.6 mmol) were added and stirred at 100°C. Upon completion of the reaction, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain the product (27.6 g, 74%).

[0372]

[0373] 5. P2-68 Synthesis Example

[0374]

[0375] (1) Synthesis of Inter 2-68

[0376] Sub 2-12 (10 g, 59.1 mmol), Toluene (200 mL), Sub 3-33 (25.5 g, 59.1 mmol), Pd2(dba)3 (1.62 g, 1.77 mmol), P(t-Bu)3 (0.72 g, 3.55 mmol), NaOt-Bu (11.4 g, 118.2 mmol) were added and stirred at 70°C. Upon completion of the reaction, the mixture was extracted with Toluene and water, and the organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain the product (20.0 g, 65%).

[0377] (2) Synthesis of P2-68

[0378] Sub 2-105 (15 g, 36.5 mmol), toluene (120 mL), Inter 2-68 (19.0 g, 36.5 mmol), Pd2(dba)3(1.0 g, 1.09 mmol), P(t-Bu)3(0.44 g, 2.19 mmol), and NaOt-Bu (7.01 g, 72.9 mmol) were added and stirred at 100°C. Upon completion of the reaction, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain the product (25.1 g, 77%).

[0379]

[0380] The FD-MS values ​​of compounds P2-1 to P2-79 of the present invention manufactured according to the above synthetic examples are as shown in Table 5 below.

[0381] Compound FD-MS Compound FD-MSP2-1 m / z = 716.32 (C 54 H 40 N2=716.93)P2-2m / z=792.35(C 60 H 44 N2=793.03)P2-3m / z=806.33(C 60 H 42 N2O=807.01)P2-4m / z=822.31(C 60 H42 N2S=823.07)P2-5m / z=881.38(C 66 H 47 N3=882.12)P2-6m / z=832.38(C 63 H 48 N2=833.09)P2-7m / z=868.38(C 66 H 48 N2=869.12)P2-8m / z=866.37(C 66 H 46 N2=867.11)P2-9m / z=842.37(C 64 H 46 N2=843.09)P2-10m / z=816.35(C 62 H 44 N2=817.05)P2-11m / z=918.40(C 70 H 50 N2=919.18)P2-12m / z=931.39(C 70 H 49 N3=932.18)P2-13m / z=790.21(C 54 H 34 N2OS2=791.00)P2-14m / z=912.32(C 66 H 44 N2OS=913.15)P2-15m / z=664.29(C 50 H 36 N2=664.85)P2-16m / z=652.25(C 48 H 32 N2O=652.80)P2-17m / z=550.20(C 40 H 26 N2O=550.66)P2-18m / z=1037.47(C 78 H 59 N3=1038.35)P2-19m / z=756.35(C 57 H 44 N2=756.99)P2-20m / z=698.20(C 48 H 30 N2O2S=698.84)P2-21m / z=894.37(C 66 H 46 N4=895.12)P2-22m / z=885.32(C 64 H 43N3S=886.13)P2-23m / z=832.32(C 60 H 40 N4O=833.01)P2-24m / z=682.23(C 48 H 30 N2O3=682.78)P2-25m / z=819.32(C 60 H 41 N3O=820.01)P2-26m / z=832.31(C 61 H 40 N2O2=833.00)P2-27m / z=743.29(C 54 H 37 N3O=743.91)P2-28m / z=818.33(C 61 H 42 N2O=819.02)P2-29m / z=791.24(C 54 H 37 N3S2=792.03)P2-30m / z=879.36(C 66 H 45 N3=880.11)P2-31m / z=952.48(C 72 H 60 N2=953.29)P2-32m / z=800.23(C 56 H 36 N2S2=801.04)P2-33m / z=780.31(C 58 H 40 N2O=780.97)P2-34m / z=904.38(C 69 H 48 N2=905.16)P2-35m / z=664.29(C 50 H 36 N2=664.85)P2-36m / z=674.19(C 46 H 30 N2S2=674.88)P2-37m / z=538.24(C 40 H 30 N2=538.69)P2-38m / z=674.19(C 46 H 30 N2S2=674.88)P2-39m / z=846.29(C 61 H 38 N2O3=846.99)P2-40m / z=888.32(C 64 H 44N2OS=889.13)P2-41m / z=830.29(C 61 H 38 N2O2=830.99)P2-42m / z=832.31(C 61 H 40 N2O2=833.00)P2-43m / z=792.39(C 57 H 52 N2Si=793.14)P2-44m / z=896.34(C 66 H 44 N2O2=897.09)P2-45m / z=694.24(C 50 H 34 N2S=694.90)P2-46m / z=608.19(C 42 H 28 N2OS=608.76)P2-47m / z=668.25(C 48 H 32 N2O2=668.80)P2-48m / z=791.24(C 54 H 37 N3S2=792.03)P2-49m / z=658.21(C 46 H 30 N2OS=658.82)P2-50m / z=624.17(C 42 H 28 N2S2=624.82)P2-51m / z=700.20(C 48 H 32 N2S2=700.92)P2-52m / z=674.19(C 46 H 30 N2S2=674.88)P2-53m / z=791.24(C 54 H 37 N3S2=792.03)P2-54m / z=638.19(C 43 H 30 N2S2=638.85)P2-55m / z=624.17(C 42 H 28 N2S2=624.82)P2-56m / z=674.19(C 46 H 30 N2S2=674.88)P2-57m / z=684.22(C 48 H 32 N2OS=684.86)P2-58m / z=775.27(C 54 H37 N3OS=775.97)P2-59m / z=848.29(C 61 H 40 N2OS=849.06)P2-60m / z=800.29(C 57 H 40 N2OS=801.02)P2-61m / z=668.25(C 48 H 32 N2O2=668.80)P2-62m / z=710.28(C 51 H 38 N2S=710.94)P2-63m / z=891.33(C 63 H 45 N3OS=892.13)P2-64m / z=848.29(C 61 H 40 N2OS=849.06)P2-65m / z=774.27(C 55 H 38 N2OS=774.98)P2-66m / z=682.23(C 48 H 30 N2O3=682.78)P2-67m / z=758.26(C 54 H 34 N2O3=758.88)P2-68m / z=894.36(C 67 H 46 N2O=895.12)P2-69m / z=1112.43(C 83 H 56 N2O2=1113.37)P2-70m / z=849.30(C 60 H 39 N3O3=849.99)P2-71m / z=834.29(C 60 H 38 N2O3=834.97)P2-72m / z=818.33(C 61 H 42 N2O=819.02)P2-73m / z=744.28(C 54 H 36 N2O2=744.89)P2-74m / z=916.39(C 67 H 52 N2S=917.23)P2-75m / z=837.34(C 61 H 35 D5N2O2=838.03)P2-76m / z=758.26(C54 H 34 N2O3=758.88)P2-77m / z=758.26(C 54 H 34 N2O3=758.88)P2-78m / z=846.29(C 61 H 38 N2O3=846.99)P2-79m / z=784.31(C 57 H 40 N2O2=784.96)

[0382] [Synthesis Example 3] Synthesis Example of Chemical Formula 3

[0383] The compound represented by chemical formula 3 according to the present invention (final product 3) can be synthesized according to the reaction path of the following reaction scheme 3, but is not limited thereto.

[0384] <Reaction Scheme 3> (Hal 4 is I, Br or Cl.)

[0385]

[0386]

[0387] 1. P3-3 Synthesis Example

[0388]

[0389] Sub 1-86 (20 g, 73.2 mmol), toluene (250 mL), Sub 2-106 (30 g, 73.2 mmol), Pd2(dba)3(2.01 g, 2.20 mmol), P(t-Bu)3(0.9 g, 4.39 mmol), NaOt-Bu (14.07 g, 146.4 mmol) were added and stirred at 90°C. Upon completion of the reaction, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain the product (36.1 g, 83%).

[0390]

[0391] 2. P3-9 Synthesis Example

[0392]

[0393] Sub 2-108 (15 g, 27.09 mmol), Toluene (100 mL), Sub 1-95 (7.17 g, 27.09 mmol), Pd2(dba)3(0.74 g, 0.81 mmol), P(t-Bu)3(0.3g, 1.63 mmol), NaOt-Bu (5.21 g, 54.18 mmol) were added and stirred at 120°C. Upon completion of the reaction, the mixture was extracted with Toluene and water, and the organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain the product (15 g, 71%).

[0394]

[0395] 3. P3-30 Synthesis Example

[0396]

[0397] Sub 2-28 (20 g, 49.81 mmol), toluene (170 mL), Sub 1-96 (14.1 g, 49.81 mmol), Pd2(dba)3(1.37 g, 1.49 mmol), P(t-Bu)3(0.6 g, 2.99 mmol), NaOt-Bu (9.57 g, 99.61 mmol) were added and stirred at 90°C. Upon completion of the reaction, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain the product (26.2 g, 87%).

[0398]

[0399] 4. P3-53 Synthesis Example

[0400]

[0401] Sub 2-39 (13 g, 38.9 mmol), toluene (130 mL), Sub 1-97 (15.6 g, 38.9 mmol), Pd2(dba)3(1.07 g, 1.17 mmol), P(t-Bu)3(0.5 g, 2.33 mmol), NaOt-Bu (7.48 g, 77.81 mmol) were added and stirred at 120°C. Upon completion of the reaction, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain the product (20.1 g, 74%).

[0402]

[0403] 5. P3-71 Synthesis Example

[0404]

[0405] Sub 2-107 (15 g, 30.9 mmol), toluene (100 mL), Sub 1-97 (12.4 g, 30.9 mmol), Pd2(dba)3(0.85 g, 0.93 mmol), P(t-Bu)3(0.4 g, 1.85 mmol), NaOt-Bu (5.94 g, 61.78 mmol) were added and stirred at 120°C. Upon completion of the reaction, the mixture was extracted with toluene and water, and the organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silica gel column chromatography and recrystallization to obtain the product (18.1 g, 6%).

[0406]

[0407] Meanwhile, the FD-MS values ​​of compounds P3-1 to P3-80 of the present invention manufactured according to the above-described synthetic examples are as shown in Table 6 below.

[0408] Compound FD-MS Compound FD-MSP3-1 m / z = 648.26 (C 49 H 32 N2=648.81)P3-2m / z=613.37(C 46 H 47 N=613.89)P3-3m / z=601.28(C46 H 35 N=601.79)P3-4m / z=677.31(C 52 H 39 N=677.89)P3-5m / z=758.37(C 58 H 38 D5N=759.02)P3-6m / z=837.43(C 64 H 55 N=838.15)P3-7m / z=727.32(C 56 H 41 N=727.95)P3-8m / z=755.36(C 58 H 45 N=756.01)P3-9m / z=781.37(C 60 H 47 N=782.04)P3-10m / z=755.36(C 58 H 45 N=756.01)P3-11m / z=781.37(C 60 H 47 N=782.04)P3-12m / z=781.37(C 60 H 47 N=782.04)P3-13m / z=697.37(C 53 H 47 N=697.97)P3-14m / z=645.34(C 49 H 43 N=645.89)P3-15m / z=715.32(C 55 H 41 N=715.94)P3-16m / z=679.32(C 52 H 41 N=679.91)P3-17m / z=639.29(C 49 H 37 N=639.84)P3-18m / z=715.32(C 55 H 41 N=715.94)P3-19m / z=689.31(C 53 H 39 N=689.9)P3-20m / z=571.32(C 43 H 41 N=571.81)P3-21m / z=791.36(C 61 H 45 N=792.04)P3-22m / z=715.32(C55 H 41 N=715.94)P3-23m / z=715.32(C 55 H 41 N=715.94)P3-24m / z=639.29(C 49 H 37 N=639.84)P3-25m / z=773.4(C 59 H 51 N=774.06)P3-26m / z=695.36(C 53 H 45 N=695.95)P3-27m / z=769.37(C 59 H 47 N=770.03)P3-28m / z=806.37(C 61 H 46 N2=807.05)P3-29m / z=603.29(C 46 H 37 N=603.81)P3-30m / z=603.29(C 46 H 37 N=603.81)P3-31m / z=653.31(C 50 H 39 N=653.87)P3-32m / z=679.32(C 52 H 41 N=679.91)P3-33m / z=679.32(C 52 H 41 N=679.91)P3-34m / z=679.32(C 52 H 41 N=679.91)P3-35m / z=615.29(C 47 H 37 N=615.82)P3-36m / z=615.29(C 47 H 37 N=615.82)P3-37m / z=691.32(C 53 H 41 N=691.92)P3-38m / z=691.32(C 53 H 41 N=691.92)P3-39m / z=691.32(C 53 H 41 N=691.92)P3-40m / z=691.32(C 53 H 41N=691.92)P3-41m / z=725.31(C 56 H 39 N=725.94)P3-42m / z=726.3(C 55 H 38 N2=726.92)P3-43m / z=726.3(C 55 H 38 N2=726.92)P3-44m / z=726.3(C 55 H 38 N2=726.92)P3-45m / z=677.31(C 52 H 39 N=677.89)P3-46m / z=753.34(C 58 H 43 N=753.99)P3-47m / z=770.33(C 57 H 42 N2O=770.98)P3-48m / z=755.36(C 58 H 45 N=756.01)P3-49m / z=653.27(C 49 H 35 NO=653.83)P3-50m / z=653.27(C 49 H 35 NO=653.83)P3-51m / z=639.29(C 49 H 37 N=639.84)P3-52m / z=652.29(C 49 H 36 N2=652.84)P3-53m / z=698.27(C 53 H 34 N2=698.87)P3-54m / z=690.3(C 52 H 38 N2=690.89)P3-55m / z=678.3(C 51 H 38 N2=678.88)P3-56m / z=639.29(C 49 H 37 N=639.84)P3-57m / z=698.27(C 53 H 34 N2=698.87)P3-58m / z=698.27(C 53 H 34 N2=698.87)P3-59m / z=787.42(C 60H 53 N=788.09)P3-60m / z=653.27(C 49 H 35 NO=653.83)P3-61m / z=543.2(C 39 H 29 NS=543.73)P3-62m / z=619.23(C 45 H 33 NS=619.83)P3-63m / z=593.22(C 43 H 31 NS=593.79)P3-64m / z=619.23(C 45 H 33 NS=619.83)P3-65m / z=694.3(C 51 H 38 N2O=694.88)P3-66m / z=865.33(C 66 H 43 NO=866.08)P3-67m / z=863.32(C 66 H 41 NO=864.06)P3-68m / z=678.3(C 51 H 38 N2=678.88)P3-69m / z=773.4(C 59 H 51 N=774.06)P3-70m / z=773.4(C 59 H 51 N=774.06)P3-71m / z=849.34(C 66 H 43 N=850.08)P3-72m / z=727.32(C 56 H 41 N=727.95)P3-73m / z=655.32(C 50 H 41 N=655.89)P3-74m / z=817.37(C 63 H 47 N=818.08)P3-75m / z=769.37(C 59 H 47 N=770.03)P3-76m / z=781.37(C 60 H 47 N=782.04)P3-77m / z=629.4(C 47 H 51 N=629.93)P3-78m / z=577.37(C43 H 47 N=577.86)P3-79m / z=683.36(C 52 H 45 N=683.94)P3-80m / z=697.37(C 53 H 47 N=697.97)

[0409] Meanwhile, although the exemplary synthetic examples of the present invention represented by Chemical Formulas 1 to 3 have been described above, they are all based on Buchwald-Hartwig cross coupling reaction, Miyaura boration reaction, Suzuki cross-coupling reaction, Intramolecular acid-induced cyclization reaction (J. mater. Chem. 1999, 9, 2095), Pd(II)-catalyzed oxidative cyclization reaction (Org. Lett. 2011, 13, 5504), and PPh3-mediated reductive cyclization reaction (J. Org. Chem. 2005, 70, 5014), and it will be easily understood by those skilled in the art that the above reaction proceeds even if a substituent other than the substituent specified in the specific synthetic examples is combined.

[0410]

[0411] Manufacturing and evaluation of organic electronic devices

[0412] [Example 1] Green organic light-emitting device

[0413] A hole injection layer was formed by vacuum depositing the compound P3-55 (N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine) of the present invention: NDP9 at a weight ratio of 9:1 to a thickness of 10 nm on an ITO / Ag / ITO layer (anode) formed on a glass substrate, and then the compound P3-55 of the present invention was vacuum deposited to a thickness of 110 nm on the hole injection layer to form a hole transport layer.

[0414] A light-emitting auxiliary layer was formed by vacuum-depositing the compounds P1-12 and P2-12 of the present invention on the above hole transport layer at a weight ratio of 3:7 to a thickness of 35 nm.

[0415] Next, on the light-emitting auxiliary layer, 4,4'-N,N'-dicarbazole-biphenyl (hereinafter abbreviated as CBP) was used as a host material, and tris(2-phenylpyridine)-iridium (hereinafter abbreviated as Ir(ppy)3) was used as a dopant material, and the dopant was doped at a weight ratio of 95:5 to form a light-emitting layer having a thickness of 40 nm.

[0416] Next, (1,1'-biphenyl-4-olato)bis(2-methyl-8-quinolinolato)aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 5 nm on the light-emitting layer to form a hole-blocking layer, and 2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline (hereinafter abbreviated as BCP) was vacuum-deposited to a thickness of 20 nm on the hole-blocking layer to form an electron transport layer.

[0417] Afterwards, Yb was deposited on the electron transport layer to a thickness of 0.2 nm to form an electron injection layer, and Ag:Mg was deposited on the electron injection layer to a thickness of 12 nm at a weight ratio of 9:1 to form a cathode.

[0418] [Example 2] to [Example 60]

[0419] An organic light-emitting device was manufactured in the same manner as Example 1, except that the compounds of the present invention described in Table 7 below were used as the first compound and the second compound materials.

[0420] [Comparative Example 1] to [Comparative Example 3]

[0421] An organic light-emitting device was manufactured in the same manner as Example 1, except that the compounds of the present invention described in Table 7 below were used as the first compound and the second compound materials, and the weight ratio of the light-emitting auxiliary layer was used as the weight ratio of the present invention described in Table 7 below.

[0422] [Comparative Example 4] to [Comparative Example 6]

[0423] An organic light emitting device was manufactured in the same manner as Example 1, except that the compounds described in Table 7 were used as the hole transport layer, the thickness of the hole transport layer was set to 145 nm, the weight ratio of the hole transport layer was set to the weight ratio of the present invention described in Table 7, and the light emitting auxiliary layer was not used.

[0424] Comparative Compound A <Comparative Compound B>

[0425]

[0426] The organic electroluminescence devices manufactured in this way were subjected to a direct current bias voltage and the electroluminescence (EL) characteristics were measured using a PR-650 from Photoresearch. The measured result was 5000 cd / m 2 The T95 lifespan was measured using a lifespan measuring device manufactured by Maxscience at a reference luminance. Table 7 below shows the results of the device fabrication and evaluation.

[0427] This measuring device allows the performance of new materials to be evaluated against reference compounds under identical conditions, without being affected by possible daily variations in deposition rate, vacuum quality or other parameters.

[0428] Since, during the evaluation, one batch contains four identically prepared OLEDs including a comparative compound, and the performance of a total of 12 OLEDs is evaluated in three batches, the values ​​of the experimental results obtained in this way exhibit statistical significance.

[0429] Hole transport layer, light-emitting auxiliary layer, weight ratio, driving voltage (V), current density (mA / cm) 2) Efficiency (Cd / A) Lifespan (T95) Comparative Example (1) (P3-55) Comparative Compound A: Comparative Compound B3: 73.84 19.60 76.54 115 Comparative Example (2) (P3-55) Comparative Compound A: Comparative Compound B5: 53.72 19.95 75.2094 Comparative Example (3) (P3-55) Comparative Compound A: Comparative Compound B7: 33.66 19.60 76.54 81 Comparative Example (4) (P1-12) : (P2-12)-3: 74.63 19.56 76.67 128 Comparative Example (5) (P1-12) : (P2-12)-5:54.4219.9475.21119Comparative Example (6)(P1-12) : (P2-12)-7:34.1619.8375.6597Example (1)(P3-55)(P1-12) : (P2-12)3 : 73.4017.9683.53159Example (2)(P3-55)(P1-12) : (P2-38)3 : 73.4017.7884.36164Example (3)(P3-55)(P1-12) : (P2-45)3 : 73.3817.9583.57158Example (4)(P3-55)(P1-12) : (P2-64)3 : 73.4217.6485.05156Embodiment (5)(P3-55)(P1-33) : (P2-12)3 : 73.4617.7484.56171Embodiment (6)(P3-55)(P1-33) : (P2-38)3 : 73.4717.6884.83160Embodiment (7)(P3-55)(P1-33) : (P2-45)3 : 73.4717.8184.23156Embodiment (8)(P3-55)(P1-33) : (P2-64)3 : 73.4817.6185.17151Embodiment (9)(P3-55)(P1-45) : (P2-12)3 : 73.4417.8384.15153Embodiment (10)(P3-55)(P1-45) : (P2-38)3 : 73.4217.6684.96159Embodiment (11)(P3-55)(P1-45) : (P2-45)3 : 73.4417.6085.25170Embodiment (12)(P3-55)(P1-45) : (P2-64)3 : 73.4717.9683.54148Embodiment (13)(P3-55)(P1-64) : (P2-12)3 : 73.4717.6784.90149Embodiment (14)(P3-55)(P1-64) : (P2-38)3 : 73.3917.6085.21161Embodiment (15)(P3-55)(P1-64) : (P2-45)3 : 73.4017.9183.76168Embodiment (16)(P3-55)(P1-64) : (P2-64)3 : 73.4817.6784.90151Embodiment (17)(P3-55)(P1-73) : (P2-12)3 : 73.4517.9483.59159Embodiment (18)(P3-55)(P1-73) : (P2-38)3 : 73.4017.6884.82158Embodiment (19)(P3-55)(P1-73) : (P2-45)3 : 73.4117.8284.19169Embodiment (20)(P3-55)(P1-73) : (P2-64)3 : 73.4817.6984.78150Embodiment (21)(P3-20)(P1-12) : (P2-12)3 : 73.4817.2786.85151Embodiment (22)(P3-20)(P1-12) : (P2-38)3 : 73.5117.2686.93164Embodiment (23)(P3-20)(P1-12) : (P2-45)3 : 73.5417.1687.41161Example (24)(P3-20)(P1-12) : (P2-64)3 : 73.4917.4685.92175Example (25)(P3-20)(P1-33) : (P2-12)3 : 73.5417.3086.70150Example (26)(P3-20)(P1-33) : (P2-38)3 : 73.4917.5285.61150Example (27)(P3-20)(P1-33) : (P2-45)3 : 73.5217.4486.03148 Example (28)(P3-20)(P1-33) : (P2-64)3 : 73.4817.4286.11169 Example (29)(P3-20)(P1-45) : (P2-12)3 : 73.5417.4885.82150 Example (30)(P3-20)(P1-45) : (P2-38)3 : 73.4817.3686.39168 Example (31)(P3-20)(P1-45) : (P2-45)3 : 73.4917.3886.32158 Example (32)(P3-20)(P1-45) : (P2-64)3:73.4917.1887.33176Embodiment (33)(P3-20)(P1-64) : (P2-12)3 : 73.5517.4286.11169Embodiment (34)(P3-20)(P1-64) : (P2-38)3 : 73.4517.2586.95162Embodiment (35)(P3-20)(P1-64) : (P2-45)3 : 73.4817.5085.74168Embodiment (36)(P3-20)(P1-64) : (P2-64)3 : 73.5117.2087.22157Embodiment (37)(P3-20)(P1-73) : (P2-12)3 : 73.4517.2786.88172Example (38)(P3-20)(P1-73) : (P2-38)3 : 73.4917.1887.30164Example (39)(P3-20)(P1-73) : (P2-45)3 : 73.5417.4585.96158Example (40)(P3-20)(P1-73) : (P2-64)3 : 73.4817.3286.62150Example (41)(P3-78)(P1-12) : (P2-12)3 : 73.5717.2586.95154Embodiment (42)(P3-78)(P1-12) : (P2-38)3 : 73.5017.5285.63175Embodiment (43)(P3-78)(P1-12) : (P2-45)3 : 73.5017.1887.31172Embodiment (44)(P3-78)(P1-12) : (P2-64)3 : 73.5617.4585.98169Embodiment (45)(P3-78)(P1-33) : (P2-12)3 : 73.5217.3086.69163Embodiment (46)(P3-78)(P1-33) : (P2-38)3 : 73.4917.4386.07168Example (47)(P3-78)(P1-33) : (P2-45)3 : 73.5717.5385.59174Example (48)(P3-78)(P1-33) : (P2-64)3 : 73.5617.2487.00161Example (49)(P3-78)(P1-45) : (P2-12)3 : 73.5517.3286.59176Example (50)(P3-78)(P1-45) : (P2-38)3 : 73.5317.4785.88170Example (51)(P3-78)(P1-45) : (P2-45)3 : 73.5717.5185.64170Example (52)(P3-78)(P1-45) : (P2-64)3 : 73.5017.4086.19164Example (53)(P3-78)(P1-64) : (P2-12)3 : 73.5317.3986.24161Example (54)(P3-78)(P1-64) : (P2-38)3 : 73.5617.1887.29171Example (55)(P3-78)(P1-64) : (P2-45)3 : 73.5217.5085.69153Embodiment (56)(P3-78)(P1-64) : (P2-64)3 : 73.5517.2087.23175Embodiment (57)(P3-78)(P1-73) : (P2-12)3 : 73.5217.2187.15152Embodiment (58)(P3-78)(P1-73) : (P2-38)3 : 73.5317.3486.52175Embodiment (59)(P3-78)(P1-73) : (P2-45)3 : 73.5717.5385.55165Embodiment (60)(P3-78)(P1-73) : (P2-64)3:73.5717.1587.46175.

[0430] Table 8 below shows the results of measurements made using a HOD (Hole only device) for the compounds of the examples.

[0431] The HOD configuration was formed by vacuum-depositing 2-TNATA on a TIO layer (anode) formed on a glass substrate to form a hole injection layer with a thickness of 70 nm, and then vacuum-depositing NPB with a thickness of 75 nm on the hole injection layer to form a hole transport layer. The compound of the present invention was vacuum-deposited on the hole transport layer to a thickness of 40 nm to form a light-emitting auxiliary layer. Thereafter, HATCN was deposited on the light-emitting auxiliary layer to a thickness of 0.1 nm to form an electron blocking layer, and Al was deposited on the electron blocking layer to a thickness of 150 nm to form a cathode.

[0432] V (0.01mA / cm 2 )V (20mA / cm 2 -0.01mA / cm2 )Comparative Compound A0.171.42Comparative Compound B0.221.66Compound (P1-12)0.040.74Compound (P1-33)0.031.17Compound (P1-45)0.030.78Compound (P1-64)0.041.21Compound (P1-73)0.070.93

[0433] Table 9 below shows the calculated CN Bond BDE values ​​for the compounds of the examples.

[0434] The weakest BDE was calculated using the Bond and Ligand Dissociation panel using the Jaguar module from Schrödinger Materials Science (ver. 5.0.122, 2023-2). We used the Becke, 3-parameter, Lee-Yang-Parr Method (B3LYP) and the 6-31G(d) basis set, one of the pople basis sets, for optimization and CN Bond BDE calculations.

[0435] Here, CN Bond BDE refers to the CN Bond between Amine and Bulky moiety.

[0436] Sample C-N bond BDE (eV) (@ Cation) Comparative compound-A 3.475 Comparative compound-B 3.455 Compound (P2-12) 4.258 Compound (P2-38) 3.970 Compound (P2-47) 3.965 Compound (P2-62) 4.335

[0437] As can be seen from the results in Table 7 above, when a green organic light-emitting device is manufactured by mixing the material for an organic light-emitting device of the present invention into a light-emitting auxiliary layer, the composition of the present invention exhibits remarkable characteristics in device performance compared to Comparative Examples 1 to 6, and particularly exhibits excellent characteristics in terms of lifespan.

[0438] As can be seen in Comparative Examples 4 to 6 above, when the light-emitting auxiliary layer is mixed, it can be seen that it is superior in terms of driving voltage, efficiency, and lifespan compared to when the hole transport layer is mixed and used. This is because when only the hole transport layer is used, a very slow driving voltage is shown, and the lifespan is also reduced due to the synergy effect. In order to resolve this, it can be seen that when the light-emitting auxiliary layer is mixed instead of the hole transport layer, superior characteristics are shown in terms of driving voltage and lifespan. In addition, when comparing Comparative Examples 1 to 3, there is a difference in that Comparative Compound A and Comparative Compound B are used instead of the compound of the present invention. Comparative Compound A and Comparative Compound B have a structure including carbazole, and when they are mixed, the synergy is judged not to be high. The reason is that, as can be seen from the results in Table 8 above, the voltage (V) (0.01 mA / cm) of the compound of the present invention represented by Chemical Formula 1 is higher than that of Comparative Compound A and Comparative Compound B. 2 ) can be seen to be lower. This means the voltage injected from the hole transport layer to the light-emitting auxiliary layer, and the lower the value, the better the hole injection into the light-emitting auxiliary layer. In addition, the voltage (V) (20 mA / cm 2 -0.01mA / cm 2) can be seen to be lower than that of the comparative compound, and the lower this value means that the hole transport characteristics are higher. Therefore, it can be seen that holes are well injected from the hole transport layer to the light-emitting auxiliary layer, and the hole transport characteristics are excellent, so the driving voltage is improved compared to Comparative Examples 1 to 3. In addition, as can be seen in Table 9 above, it can be seen that the bond dissociation energy (BDE) of the compound of the present invention represented by Chemical Formula 2 is higher than that of Comparative Compound A or Comparative Compound B. This is because as the driving time of the phosphorescent organic light-emitting device passes, the triplet energy of the organic light-emitting layer or a material adjacent to the organic light-emitting layer decreases, and as a result, the luminance decreases for the same current due to the acceleration of triplet energy quenching, which is considered to be one of the main causes of the reduced lifespan. This phenomenon of lowering triplet energy is generally thought to occur during the decomposition-recombination process of organic substances, and in particular, as the bulky moiety decomposes and recombines, the conjugation expands, which seems to significantly reduce the triplet energy of the recombination product. Therefore, among the BDEs of organic substances, the BDE of amine and bulky moiety, which can easily have holes, is very important and seems to play a major role in improving the lifespan. That is, when the compound represented by chemical formula 1 and the compound represented by chemical formula 2 are mixed to form a light-emitting auxiliary layer, the synergistic effect shows a rapid improvement in the driving voltage and lifespan, and in particular, it can be seen that it shows excellent characteristics in terms of lifespan.

[0439] The above description is merely illustrative of the present invention, and those skilled in the art will appreciate that various modifications may be made without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed herein are intended to illustrate, rather than limit, the present invention, and the spirit and scope of the present invention are not limited by these embodiments.

[0440] 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 interpreted as being included in the scope of the rights of the present invention.

[0441] According to the present invention, an organic device having excellent device characteristics such as high brightness, high luminescence, and long lifespan can be manufactured, and thus has industrial applicability.

Claims

1. In an organic electric device comprising: a first electrode; a second electrode; and an organic layer including a light-emitting layer formed between the first electrode and the second electrode; The organic layer includes a hole transport layer formed between the first electrode and the light-emitting layer, and includes a light-emitting auxiliary layer formed between the hole transport layer and the light-emitting layer. An organic electric device characterized in that the light-emitting auxiliary layer comprises a composition in which a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2 are mixed, and the hole transport layer comprises a compound represented by the following chemical formula 3. <Chemical Formula 1> <Chemical Formula 2> <Chemical Formula 3> {In the above chemical formulas 1 to 3, Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 , Ar 7 , Ar a and Ar b are independently C6~C 60 Aryl group of; fluorenyl group; C2~C containing at least one heteroatom among O, N, S, Si and P 60 Heterocyclic group of; C3~C 60 Cycloalkyl group of; and C3~C 60 Aliphatic ring and C6~C 60 A fused ring group of an aromatic ring is selected from the group consisting of; L 1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 7 , L a , L b and L c are independently of each other and are single bonds; C6~C 60 Arylene group; Fluorenylene group; C2~C containing at least one heteroatom among O, N, S, Si and P 60 Heterocyclic group of; and C3~C 60 Aliphatic ring and C6~C 60 A fused ring group of an aromatic ring is selected from the group consisting of; L 8 Silver C6~C 60 Arylene group; Fluorenylene group; C2~C containing at least one heteroatom among O, N, S, Si and P 60 is selected from the group consisting of heterocyclic groups; and ring aggregates thereof; R a and R b are independently C6~C 60 Aryl group of; fluorenyl group; C2~C containing at least one heteroatom among O, N, S, Si and P 60 Heterocyclic group of; C3~C 60 Aliphatic ring and C6~C 60 Fused ring group of aromatic ring; C1~C 50 Alkyl group of; C2~C 20 Alkenyl group of; C2~C 20 Alkynyl group of; C1~C 30 Alkoxyl group of; and C6~C 30 is selected from the group consisting of aryloxy group of R, or a and R b can combine with each other to form spy rings, R c and R d are identical or different from each other, and independently of each other, hydrogen; deuterium; C6~C 60 Aryl group of; fluorenyl group; C2~C containing at least one heteroatom among O, N, S, Si and P 60 Heterocyclic group of; C3~C 60 Aliphatic ring and C6~C 60 Fused ring group of aromatic ring; C1~C 50 Alkyl group of; C2~C 20 Alkenyl group of; C2~C 20 Alkynyl group of; C1~C 30 Alkoxyl group of; and C6~C 30 is selected from the group consisting of aryloxy groups; or adjacent multiple R c R's or multiple R's d They can combine with each other to form rings, a is an integer from 0 to 4, b is an integer from 0 to 3, Here, the aryl group, arylene group, heterocyclic group, fluorenyl group, fluorenylene group, cycloalkyl group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group and aryloxy group are each deuterium; halogen; silane group; siloxane group; boron group; germanium group; cyano group; nitro group; C1~C 20 Alkylthio group of; C1~C 20 Alkoxyl group of; C6~C 20 Aryloxy group of; C1~C 20 Alkyl group of; C2~C 20 Alkenyl group of; C2~C 20 Alkyne group of; C6~C 20 Aryl group of; C6~C substituted with deuterium 20 Aryl group of; Fluorenyl group; C2~C 20 Heterocyclic group of; C3~C 20 Cycloalkyl group of; C7~C 20 Arylalkyl group of; C8~C 20 Aryl alkenyl group of; and -L'-R'R"; may be further substituted with one or more substituents selected from the group consisting of, and further, the hydrogen of these substituents is one or more deuterium, C6~C 20 Aryl group or C1~C 20 It can be further substituted with an alkyl group, and these substituents can also combine with each other to form a ring, where the 'ring' means C3~C 60 Aliphatic ring or C6~C 60 Aromatic ring or C2~C 60 A fused ring composed of a heterocycle or a combination thereof, and containing a saturated or unsaturated ring, The above L' is a single bond; C6~C 60 Aryl group of; fluorenyl group; C2~C containing at least one heteroatom among O, N, S, Si and P 60 Heterocyclic group of; and C3~C 60 is selected from the group consisting of aliphatic rings; The above R' and R" are independently C6~C 60 Aryl group of; fluorenyl group; C2~C containing at least one heteroatom among O, N, S, Si and P 60 Heterocyclic group of; C1~C 50 alkyl group; and C2~C 20 is selected from the group consisting of an alkenyl group; 2. In the first paragraph, the Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 , Ar 7 , Ar a and Ar b An organic electric device characterized in that at least one of the following chemical formulae Ar-a to Ar-d is represented by one of the following chemical formulae: Chemical formula Ar-a Chemical formula Ar-b Chemical formula Ar-c Chemical formula Ar-d {In the above chemical formulas Ar-a to Ar-d, Y A , Y B and Y C are O, S, NR independently of each other 1A , SiR 1B R 1C or CR 1B R 1C and, R A , R B , R C , R D , R E , R F , R 1A , R 1B and R 1C are independently the same or different from each other, and independently hydrogen; deuterium; halogen; cyano group; C6~C 20 Aryl group of; C6~C substituted with deuterium 20 Aryl group of; fluorenyl group; C2~C containing at least one heteroatom among O, N, S, Si and P 20 Heterocyclic group of; C1~C 20 Alkyl group of; C2~C 20 Alkenyl group of; C2~C 20 Alkynyl group of; C1~C 20 Alkoxyl group of; C6~C 20 An aryloxy group of; and -L'-NR'R"; is selected from the group consisting of, or a plurality of adjacent R A R's or multiple R's B R's or multiple R's C R's or multiple R's D R's or multiple R's E R's or multiple R's F They can combine with each other to form a ring, or R 1B and R 1C can combine with each other to form spy rings, ta and tc are independently integers from 0 to 3, tb and td are independently integers from 0 to 4, te is an integer from 0 to 5, tf is an integer from 0 to 7, The above L', R' and R" are the same as defined in claim 1, means the position of joining.} 3. An organic electric device according to claim 1, wherein the chemical formula 1 is represented by any one of the compounds P1-1 to P1-97 below.

4. An organic electric device according to claim 1, wherein the chemical formula 2 is represented by any one of the compounds P2-1 to P2-79.

5. An organic electric device according to claim 1, wherein the chemical formula 3 is represented by any one of the compounds P3-1 to P3-80.

6. An organic electric device according to claim 1, wherein the light-emitting layer comprises a host and a dopant.

7. An organic electric device according to claim 6, characterized in that the dopant comprises iridium (Ir) or platinum (Pt).

8. An organic electric device according to claim 1, characterized in that the difference between the HOMO energy level of the compound represented by the chemical formula 1 and the HOMO energy level of the compound represented by the chemical formula 2 is 0.05 to 0.12 eV.

9. An organic electric device according to claim 1, characterized in that it further comprises a light efficiency improvement layer formed on at least one surface of the first electrode and the second electrode, the surface being opposite to the organic layer.

10. An organic electric device according to claim 1, characterized in that the organic layer comprises two or more stacks including a hole transport layer, a light-emitting layer, and an electron transport layer sequentially formed on the first electrode.

11. An organic electric device according to claim 10, characterized in that the organic layer further includes a charge generation layer formed between the two or more stacks.

12. An organic electric device according to claim 1, characterized in that it further comprises a buffer layer between the light-emitting auxiliary layer and the hole transport layer.

13. An electronic device comprising a display device including the organic electric element of paragraph 1; and a control unit for driving the display device.

14. An electronic device according to claim 13, wherein the organic electroluminescent element is at least one of an organic light-emitting element, an organic solar cell, an organic photoconductor, an organic transistor, and a monochrome or white lighting element.

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