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

Abstract

The present invention provides a composition for stacking a second light-emitting auxiliary layer of an organic electric element comprising a compound represented by chemical formula 1, an organic electric element using same, and an electronic device comprising same, and can lower a 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] Materials used as organic layers in organic electronic devices can be classified according to their function into light-emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials.

[0004] The biggest challenges facing organic light-emitting diodes (OLEDs) are their lifespan and efficiency. As displays become larger, these efficiency and lifespan issues become increasingly crucial. Efficiency, lifespan, and operating voltage are interrelated. As efficiency increases, operating voltage decreases. As operating voltage decreases, crystallization of organic materials due to Joule heating during operation decreases, ultimately leading to longer lifespan.

[0005] However, simply improving the organic layers does not maximize efficiency. This is because long life and high efficiency can be achieved simultaneously when the energy levels and T1 values ​​between each organic layer, as well as the material's inherent properties (mobility, interfacial properties, etc.) are optimally combined.

[0006] In addition, in order to solve the problem of light emission in the hole transport layer in recent organic light emitting devices, a light emitting auxiliary layer must exist between the hole transport layer and the light emitting layer, and it is time to develop different light emitting auxiliary layers for each light emitting layer (R, G, B).

[0007] 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.

[0008] However, since the material used in the hole transport layer must have a low HOMO value, most of them have a low T1 value, which causes excitons generated in the light-emitting layer to move to the hole transport layer, resulting in charge imbalance within the light-emitting layer and causing light emission at the hole transport layer interface.

[0009] When light is emitted at the interface of the hole transport layer, the color purity and efficiency of the organic electronic device are reduced, and its lifespan is shortened. Therefore, there is an urgent need to develop a light-emitting auxiliary layer with a high T1 value and a HOMO energy level between the HOMO energy level of the hole transport layer and the HOMO energy level of the light-emitting layer.

[0010] Meanwhile, there is a need to develop a hole injection layer material that has stable properties, i.e., a high glass transition temperature, against Joule heating generated during device operation while delaying the penetration and diffusion of metal oxides from the anode electrode (ITO), which is one of the causes of shortened lifespan of organic electronic devices. The low glass transition temperature of the hole transport layer material has the characteristic of reducing the uniformity of the thin film surface during device operation, which is reported to have a significant impact on the device lifespan. In addition, OLED devices are mainly formed by a deposition method, and there is a need to develop materials that can withstand the deposition process for a long time, i.e., materials with strong heat resistance.

[0011] In other words, in order to fully demonstrate the excellent characteristics of organic electronic devices, the materials forming the organic layers within the devices, such as hole injection materials, hole transport materials, luminescent materials, electron transport materials, electron injection materials, and luminescent auxiliary layer materials, must first be supported by stable and efficient materials. However, the development of stable and efficient organic layer materials for organic electronic devices has not yet been sufficiently accomplished. Therefore, the development of new materials continues to be required, and in particular, the development of materials for luminescent auxiliary layers is urgently required.

[0012] As reference prior art documents, Korean Patent Publication No. 10-2021-0098447 A, Korean Patent Publication No. 10-2022-0048498 A, Korean Patent Publication No. 10-2022-0110056 A, and Korean Patent Publication No. 10-2023-0096155 A were used.

[0013] 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.

[0014] In one aspect, the present invention provides a composition for laminating a second light-emitting auxiliary layer of an organic electric device, comprising a compound represented by the following chemical formula 1.

[0015] <Chemical Formula 1>

[0016]

[0017] In another aspect, the present invention provides an organic electric device comprising a first electrode; a second electrode; and an organic layer including a light-emitting layer between the first electrode and the second electrode, wherein the organic layer includes a hole transport region, the hole transport region is disposed between the first electrode and the light-emitting layer, and the hole transport region is disposed in the order of a hole transport layer, a first light-emitting auxiliary layer, and a second light-emitting auxiliary layer, wherein the second light-emitting auxiliary layer includes a compound according to claim 1.

[0018] In addition, in another aspect, the present invention provides an electronic device including a display device including the organic electric element; and a control unit for driving the display device.

[0019] 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.

[0020] Figures 1 to 3 are exemplary diagrams of an organic light-emitting device according to the present invention.

[0021] 100, 200, 300: Organic electric element 110: First electrode

[0022] 120: hole injection layer 130: hole transport layer

[0023] 140: Emitting layer 150: Electron transport layer

[0024] 160: Electron injection layer 170: Second electrode

[0025] 180: Light efficiency improvement layer 210: Buffer layer

[0026] 220: Light-emitting auxiliary layer 320: First hole injection layer

[0027] 330: First hole transport layer 340: First light-emitting layer

[0028] 350: First electron transport layer 360: First charge generation layer

[0029] 361: Second charge generation layer 420: Second hole injection layer

[0030] 430: Second hole transport layer 440: Second light-emitting layer

[0031] 450: Second electron transport layer CGL: Charge generation layer

[0032] ST1: 1st stack ST2: 2nd stack

[0033] 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.

[0034] 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.

[0035] As used in this specification and the appended claims, unless otherwise stated, the following terms have the following meanings:

[0036] The term “halo” or “halogen” as used herein, unless otherwise stated, means fluorine (F), bromine (Br), chlorine (Cl), or iodine (I).

[0037] 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.

[0038] 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, respectively, and is not limited thereto.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] The term “heteroatom” as used herein refers to N, O, S, P or Si unless otherwise stated.

[0047] 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.

[0048]

[0049] 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.

[0050] 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.

[0051]

[0052] 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.

[0053] 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.

[0054] 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.

[0055] Other heterocyclic compounds or heteroradicals other than the aforementioned heterocyclic compounds include, but are not limited to, one or more heteroatoms.

[0056] 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~C20 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.

[0057] 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', or may 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.

[0058] 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.

[0059]

[0060] 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 1 may 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.

[0061]

[0062] 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 where 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 when benzene is taken 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 when benzene is taken 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.

[0063] [Example of ortho-position]

[0064]

[0065] [Example of meta-position]

[0066]

[0067] [Example of para-location]

[0068]

[0069] 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.

[0070]

[0071] 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.

[0072] 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.

[0073] Figures 1 to 3 are exemplary diagrams of organic electric devices according to embodiments of the present invention.

[0074] 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).

[0075] 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.

[0076] 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).

[0077] 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.

[0078] 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).

[0079] 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.

[0080] 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.

[0081] 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).

[0082] 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.

[0083] 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.

[0084] 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).

[0085] 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.

[0086] 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.

[0087] 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.

[0088] The compound represented by the chemical formula 1 of the present invention can be used as a material 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), but preferably, the compound represented by the chemical formula 1 of the present invention can be used as the light-emitting auxiliary layer (220).

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094]

[0095] Hereinafter, an organic electric device according to one aspect of the present invention will be described.

[0096] The present invention provides a composition for laminating a second light-emitting auxiliary layer of an organic electric device, comprising a compound represented by the following chemical formula 1.

[0097] <Chemical Formula 1>

[0098]

[0099] In the above chemical formula 1, each symbol can be defined as follows.

[0100] 1) X and Y are independently O or S,

[0101] 2) R 1 , R 2 , R 3 , R 4 and R 5 are each the same or different, and independently of each other, hydrogen; deuterium; halogen; cyano group; nitro group; 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 group; C1~C 20 Alkyl group of; C2~C 20 Alkenyl group of; C1~C 20 Alkoxyl group of; and C6~C 20 is selected from the group consisting of aryloxy groups; or adjacent groups can be combined with each other to form an aromatic ring,

[0102] The above R 1 , R 2 , R 3 , R 4 and R 5 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.

[0103] The above R 1 , R 2 , R 3 , R 4 and R 5 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, naphthobenzofuran, naphthobenzothiophene, etc.

[0104] The above R 1 , R 2 , R 3 , R 4 and R 5 If it is an aliphatic ring, preferably C3~C 30 aliphatic 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.

[0105] 3) Ar 1 Silver 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 60 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;

[0106] The above Ar 1 In this case, aryl group is preferably C6~C 30 Aryl group of, more preferably C6~C 25 , C6~C 18 or C6~C12 The aryl group may be, for example, phenyl, biphenyl, terphenyl, naphthalene, phenanthrene, chrysene, etc.

[0107] The above Ar 1 In this case, 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, naphthobenzofuran, naphthobenzothiophene, etc.

[0108] The above Ar 1 In this case, the fusion ring is 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.

[0109] The above Ar 1 In this case, it is 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.

[0110] The above Ar 1 In the case of this alkoxyl group, preferably C1~C 25 , C1~C 18 or C1~C 12 It may be an alkoxyl group.

[0111] The above Ar 1 In the case of this aryloxy group, preferably C6~C 25 , C6~C 18 or C6~C 12 It may be an aryloxy group.

[0112] a, c and e are independently integers from 0 to 4, b and d are independently integers from 0 to 3,

[0113] Here, the aryl group, heterocyclic group, fluorenyl group, aliphatic ring group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group and aryloxy group are each deuterium; halogen; C6~C 20 Silane group substituted or unsubstituted with an aryl 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 Aliphatic ring group; C7~C 20 Arylalkyl group of; C8~C 20 Aryl alkenyl group of; and C7~C 20 It may be further substituted with one or more substituents selected from the group consisting of alkylaryl groups; and further, the hydrogen of these substituents may be further substituted with one or more deuteriums, and further, these substituents may be combined with each other to form a ring, wherein the 'ring' means C3~C 60 Aliphatic ring or C6~C 60 Aromatic ring or C2~C 60 It refers to a fused ring composed of a heterocycle or a combination thereof, and includes a saturated or unsaturated ring.

[0114]

[0115] In addition, the present invention provides a composition for laminating a second light-emitting auxiliary layer of an organic electric device, characterized in that the compound represented by the above chemical formula 1 is represented by any one of the following chemical formulas 1-1 to 1-3.

[0116] <Chemical Formula 1-1> <Chemical Formula 1-2> <Chemical Formula 1-3>

[0117]

[0118] {In the above chemical formulas 1-1 to 1-3, X, Y, Ar 1 , R 1 , R 2 , R 3 , R 4 , R 5 , a, b, c, d and e are as defined above.}

[0119]

[0120] In addition, the present invention provides the R 4 Inland R 5 At least one of the compositions comprises a second light-emitting auxiliary layer for an organic electroluminescent device including deuterium.

[0121] Specifically, the compound represented by the above chemical formula 1 may be any one of the following compounds, but is not limited thereto.

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153] In addition, in another aspect, the present invention provides an organic electric device comprising: a first electrode; a second electrode; and an organic layer including a light-emitting layer between the first electrode and the second electrode; wherein the organic layer includes a hole transport region, the hole transport region is disposed between the first electrode and the light-emitting layer, and the hole transport region is disposed in the order of a hole transport layer, a first light-emitting auxiliary layer, and a second light-emitting auxiliary layer, wherein the second light-emitting auxiliary layer includes a compound represented by the chemical formula 1.

[0154] 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.

[0155] 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.

[0156] 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.

[0157]

[0158] Hereinafter, examples of synthesis of compounds represented by chemical formulas according to the present invention and examples of manufacturing organic electric devices are described in detail, but the present invention is not limited to the following examples.

[0159] [Synthesis example]

[0160] The compound represented by chemical formula 1 according to the present invention (final product) can be prepared by a reaction as shown in the following reaction scheme 1, but is not limited thereto. (Hal = Br, I or Cl)

[0161] <Reaction Scheme 1>

[0162]

[0163] {In the above reaction formula 1, X, Y, Ar 1 , R 1 , R 2 , R 3 , R 4 , R 5 , a, b, c, d and e are as defined above.}

[0164]

[0165] I. Synthesis of Sub1

[0166] Sub1 of reaction scheme 1 can be synthesized by the reaction path of reaction scheme 2 below, but is not limited thereto.

[0167] <Reaction Formula 2>

[0168]

[0169] {In the above reaction formula 2, X, Y, R 1 , R 2 , R 3 , R 4 , R 5 , a, b, c, d and e are as defined above.}

[0170]

[0171] 1. Synthesis example of Sub1-1

[0172]

[0173] 4-(dibenzo[b,d]furan-2-yl)aniline (50 g, 192.82 mmol) and 1-bromodibenzo[b,d]furan (47.6 g, 192.82 mmol) were dissolved in 650 mL of toluene in a round-bottom flask, and then Pd2(dba)3 (5.30 g, 5.78 mmol), P(t-bu)3 (2.34 g, 11.57 mmol), and t-BuONa (37.1 g, 385.64 mmol) were added and stirred at 25°C. After the reaction was completed, the organic layer was extracted with toluene and water, dried with MgSO4, concentrated, and the resulting compound was purified by silica gel column and recrystallized to obtain 76.4 g (yield: 93.1%) of the product Sub1-1 N-(4-(dibenzo[b,d]furan-2-yl)phenyl)dibenzo[b,d]furan-1-amine.

[0174]

[0175] 2. Synthesis example of Sub1-2

[0176]

[0177] 4-(9-phenyldibenzo[b,d]furan-2-yl)aniline (50 g, 149.07 mmol) and 1-bromodibenzo[b,d]furan (36.8 g, 149.07 mmol) were dissolved in 500 mL of toluene in a round-bottomed flask, and Pd2(dba)3 (4.09 g, 4.47 mmol), P(t-bu)3 (1.8 g, 8.94 mmol), and t-BuONa (28.7 g, 298.1 mmol) were added and stirred at 25°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 62.5 g (yield: 83.6%) of the product Sub1-2.

[0178]

[0179] 3. Synthesis example of Sub1-9

[0180]

[0181] 4-(dibenzo[b,d]furan-2-yl)aniline (50 g, 192.81 mmol) and 1-bromo-8-phenyldibenzo[b,d]furan (62.3 g, 192.82 mmol) were dissolved in 650 mL of toluene in a round-bottomed flask, and Pd2(dba)3 (5.30 g, 5.78 mmol), P(t-bu)3 (2.34 g, 11.57 mmol), and t-BuONa (37.06 g, 385.63 mmol) were added and stirred at 25°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 80.5 g (yield: 83.2%) of the product Sub1-9.

[0182]

[0183] 4. Synthesis example of Sub1-27

[0184]

[0185] (1) Synthesis example of Sub1-27-1

[0186] Dibenzo[b,d]furan-2-ylboronic acid (50 g, 235.84 mmol) and 4-bromo-3-methylaniline (43.9 g, 235.84 mmol) were dissolved in 600 mL of THF in a round-bottomed flask, and Pd(PPh3)4 (8.2 g, 7.07 mmol) and K2CO3 (65.2 g, 471.68 mmol) dissolved in 200 mL of H2O were added, and the mixture was 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 41.5 g (yield: 64.4%) of the product Sub1-27-1.

[0187] (2) Synthesis example of Sub1-27

[0188] Sub1-27-1 (25 g, 91.46 mmol) and 1-bromodibenzo[b,d]furan (22.6 g, 91.46 mmol) were dissolved in 310 mL of toluene in a round-bottomed flask, and Pd2(dba)3 (2.5 g, 2.74 mmol), P(t-bu)3 (1.1 g, 5.48 mmol), and t-BuONa (17.6 g, 182.93 mmol) were added and stirred at 25°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 31.0 g of the product Sub1-27 (yield: 77.1%).

[0189]

[0190] 5. Synthesis example of Sub1-42

[0191]

[0192] (1) Synthesis example of Sub1-42-1

[0193] 4-Bromo-1-chlorodibenzo[b,d]thiophene (50 g, 168.02 mmol) and phenylboronic acid (20.5 g, 168.02 mmol) were dissolved in 420 mL of THF in a round-bottomed flask, and Pd(PPh3)4 (5.83 g, 5.04 mmol) and K2CO3 (46.5 g, 336.03 mmol) dissolved in 140 mL of H2O were added, and the mixture was 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 40.5 g (yield: 81.8%) of the product Sub1-42-1.

[0194] (2) Synthesis example of Sub1-42

[0195] 4-(dibenzo[b,d]furan-2-yl)aniline (25 g, 96.41 mmol) and Sub1-42-1 (28.4 g, 96.41 mmol) were dissolved in 320 mL of toluene in a round-bottomed flask, and Pd2(dba)3 (1.17 g, 2.89 mmol), X-Phos (2.8 g, 5.78 mmol), and t-BuONa (18.5 g, 192.82 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 35.2 g (yield: 70.5%) of the product Sub1-42.

[0196]

[0197] 6. Synthesis example of Sub1-57

[0198]

[0199] 3-(dibenzo[b,d]thiophen-2-yl)aniline (25 g, 90.79 mmol) and 1-chloro-8-phenyldibenzo[b,d]furan (25.3 g, 90.79 mmol) were dissolved in 300 mL of toluene in a round-bottom flask, and then Pd2(dba)3 (2.5 g, 2.72 mmol), X-Phos (2.6 g, 5.45 mmol), t-BuONa (17.5 g, 181.57 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 33.5 g of the product Sub1-57 (yield: 71.3%).

[0200]

[0201] 7. Synthesis example of Sub1-72

[0202]

[0203] 4-(dibenzo[b,d]furan-2-yl)aniline (50 g, 192.82 mmol) and 1-bromodibenzo[b,d]furan-2,3,4,6,7,8,9-d7 (47.6 g, 192.82 mmol) were dissolved in 650 mL of toluene in a round-bottomed flask, and Pd2(dba)3 (5.30 g, 5.78 mmol), P(t-bu)3 (2.34 g, 11.57 mmol), and t-BuONa (37.1 g, 385.64 mmol) were added and stirred at 25°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 72.3 g (yield: 86.7%) of the product Sub1-72.

[0204]

[0205] 8. Synthesis example of Sub1-73

[0206]

[0207] 4-(dibenzo[b,d]furan-2-yl-d7)benzen-2,3,5,6-d4-amine (50 g, 184.92 mmol) and 1-bromodibenzo[b,d]furan-2,3,4,6,7,8,9-d7 (47.0 g, 184.92 mmol) were dissolved in 650 mL of toluene in a round-bottom flask, and then Pd2(dba)3 (5.08 g, 5.55 mmol), P(t-bu)3 (2.3 g, 11.10 mmol), and t-BuONa (35.5 g, 369.85 mmol) were added and stirred at 25°C. After the reaction was completed, the organic layer was extracted with toluene and water, dried with MgSO4, concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 63.5 g of the product Sub1-73 (yield: 77.4%).

[0208]

[0209] 9. Synthesis example of Sub1-76

[0210]

[0211] 4-(dibenzo[b,d]furan-2-yl)aniline (50 g, 192.82 mmol) and 1-bromo-8-(phenyl-d5)dibenzo[b,d]furan-2,3,4,6,7,9-d6 (64.5 g, 192.82 mmol) were dissolved in 650 mL of toluene in a round-bottom flask, and Pd2(dba)3 (5.30 g, 5.78 mmol), P(t-bu)3 (2.34 g, 11.57 mmol), and t-BuONa (37.1 g, 385.64 mmol) were added and stirred at 25°C. After the reaction was completed, the organic layer was extracted with toluene and water, dried with MgSO4, concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 76.5 g of the product Sub1-76 (yield: 77.4%).

[0212]

[0213] Meanwhile, compounds belonging to Sub1 may be, but are not limited to, the compounds below, and Table 1 below shows the FD-MS (Field Desorption-Mass Spectrometry) values ​​of compounds belonging to Sub1.

[0214]

[0215]

[0216]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232] 화합물FD-MS화합물FD-MSSub1-1m / z=425.14(C 30 H 19 NO2=425.49)Sub1-2m / z=501.17(C 36 H 23 NO2=501.58)Sub1-3m / z=501.17(C 36 H 23 NO2=501.58)Sub1-4m / z=501.17(C 36 H 23 NO2=501.58)Sub1-5m / z=501.17(C 36 H 23 NO2=501.58)Sub1-6m / z=501.17(C 36 H 23 NO2=501.58)Sub1-7m / z=501.17(C 36 H 23 NO2=501.58)Sub1-8m / z=501.17(C 36 H 23 NO2=501.58)Sub1-9m / z=501.17(C 36 H 23 NO2=501.58)Sub1-10m / z=501.17(C 36 H 23 NO2=501.58)Sub1-11m / z=501.17(C 36 H 23NO2=501.58)Sub1-12m / z=577.20(C 42 H 27 NO2=577.68)Sub1-13m / z=577.20(C 42 H 27 NO2=577.68)Sub1-14m / z=577.20(C 42 H 27 NO2=577.68)Sub1-15m / z=577.20(C 42 H 27 NO2=577.68)Sub1-16m / z=577.20(C 42 H 27 NO2=577.68)Sub1-17m / z=443.13(C 30 H 18 FNO2=443.48)Sub1-18m / z=775.10(C 42 H 16 F 11 NO2=775.58)Sub1-19m / z=565.09(C 31 H 14 F7NO2=565.45)Sub1-20m / z=591.18(C 42 H 25 NO3=591.67)Sub1-21m / z=491.13(C 34 H 21 NOS=491.61)Sub1-22m / z=453.17(C 32 H 23 NO2=453.54)Sub1-23m / z=526.17(C 37 H 22 N2O2=526.60)Sub1-24m / z=546.16(C 36 H 22 N2O4=546.58)Sub1-25m / z=557.24(C 40 H 31 NO2=557.69)Sub1-26m / z=529.20(C 38 H 27 NO2=529.64)Sub1-27m / z=439.16(C 31 H 21 NO2=439.51)Sub1-28m / z=617.24(C 45 H 31NO2=617.75)Sub1-29m / z=439.16(C 31 H 21 NO2=439.51)Sub1-30m / z=507.22(C 36 H 29 NO2=507.63)Sub1-31m / z=741.27(C 55 H 35 NO2=741.89)Sub1-32m / z=757.24(C 55 H 35 NOS=757.95)Sub1-33m / z=665.24(C 49 H 31 NO2=665.79)Sub1-34m / z=591.18(C 42 H 25 NO3=591.67)Sub1-35m / z=551.19(C 40 H 25 NO2=551.64)Sub1-36m / z=601.20(C 44 H 27 NO2=601.70)Sub1-37m / z=469.15(C 32 H 23 NOS=469.60)Sub1-38m / z=759.26(C 54 H 37 NO2Si=759.98)Sub1-39m / z=517.15(C 36 H 23 NOS=517.65)Sub1-40m / z=517.15(C 36 H 23 NOS=517.65)Sub1-41m / z=593.18(C 42 H 27 NOS=593.18)Sub1-42m / z=517.15(C 36 H 23 NOS=517.65)Sub1-43m / z=517.15(C 36 H 23 NOS=517.65)Sub1-44m / z=471.11(C 31 H 21 NS2=471.64)Sub1-45m / z=425.14(C 30 H 19 NO2=425.49)Sub1-46m / z=501.17(C36 H 23 NO2=501.58)Sub1-47m / z=501.17(C 36 H 23 NO2=501.58)Sub1-48m / z=623.14(C 42 H 25 NOS2=623.79)Sub1-49m / z=515.19(C 37 H 25 NO2=515.61)Sub1-50m / z=591.18(C 42 H 25 NO3=591.67)Sub1-51m / z=571.15(C 36 H 23 NOS=517.65)Sub1-52m / z=455.13(C 31 H 21 NOS=455.57)Sub1-53m / z=571.15(C 36 H 23 NOS=517.65)Sub1-54m / z=593.18(C 42 H 27 NOS=593.74)Sub1-55m / z=517.15(C 36 H 23 NOS=517.65)Sub1-56m / z=533.13(C 36 H 23 NS2=533.71)Sub1-57m / z=517.15(C 36 H 23 NOS=517.65)Sub1-58m / z=425.14(C 30 H 19 NO2=425.49)Sub1-59m / z=501.17(C 36 H 23 NO2=501.58)Sub1-60m / z=507.22(C 36 H 29 NO2=507.63)Sub1-61m / z=501.17(C 36 H 23 NO2=501.58)Sub1-62m / z=455.13(C 31 H 21 NOS=455.57)Sub1-63m / z=481.20(C 34 H 27NO2=481.59)Sub1-64m / z=501.17(C 36 H 23 NO2=501.58)Sub1-65m / z=593.20(C 42 H 27 NO3=593.68)Sub1-66m / z=617.24(C 45 H 31 NO2=617.75)Sub1-67m / z=593.18(C 42 H 27 NOS=593.74)Sub1-68m / z=517.15(C 36 H 23 NOS=517.65)Sub1-69m / z=517.15(C 36 H 23 NOS=517.65)Sub1-70m / z=557.24(C 40 H 31 NO2=557.69)Sub1-71m / z=428.16(C 30 H 16 D3NO2=428.51)Sub1-72m / z=432.19(C 30 H 12 D7NO2=432.53)Sub1-73m / z=443.25(C 30 HD 18 NO2=443.60)Sub1-74m / z=506.20(C 36 H 18 D5NO2=506.62)Sub1-75m / z=508.22(C 36 H 16 D7NO2=508.63)Sub1-76m / z=512.24(C 36 H 12 D 11 NO2=512.65)Sub1-77m / z=523.31(C 36 HD 22 NO2=523.72)Sub1-78m / z=507.21(C 36 H 17 D6NO2=507.62)Sub1-91m / z=528.22(C 36 H 12 D 11 NOS=528.71)Sub1-80m / z=528.22(C 36 H12 D 11 NOS=528.71)Sub1-81m / z=512.24(C 36 H 12 D 11 NO2=512.65)Sub1-82m / z=432.19(C 30 H 12 D7NO2=432.53)Sub1-83m / z=528.22(C 36 H 12 D 11 NOS=528.71)Sub1-84m / z=512.24(C 36 H 12 D 11 NO2=512.65)Sub1-85m / z=528.22(C 36 H 12 D 11 NOS=528.71)Sub1-86m / z=583.24(C 42 H 21 D6NO2=583.72)Sub1-87m / z=514.26(C 36 H 22 D7NO2=514.68)Sub1-88m / z=508.22(C 36 H 16 D7NO2=508.63)Sub1-89m / z=528.22(C 36 H 12 D 11 NOS=528.71)Sub1-90m / z=432.19(C 30 H 12 D7NO2=432.53)

[0233]

[0234] II. Synthesis of Sub2

[0235] 1. Synthesis of Sub2-18

[0236]

[0237] 1-Bromo-7-chlorodibenzo[b,d]furan (50 g, 177.60 mmol) and phenylboronic acid (21.7 g, 177.60 mmol) were dissolved in 450 mL of THF in a round-bottomed flask, and Pd(PPh3)4 (6.2 g, 5.33 mmol) and K2CO3 (49.1 g, 355.20 mmol) dissolved in 150 mL of H2O were added, and the mixture was 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 40.5 g (yield: 81.8%) of the product Sub2-18.

[0238]

[0239] 2. Synthesis example of Sub2-32

[0240]

[0241] 1-Bromo-8-chlorodibenzo[b,d]thiophene (50 g, 168.02 mmol) and (3-(9-phenyl-9H-fluoren-9-yl)phenyl)boronic acid (60.9 g, 168.02 mmol) were dissolved in 420 mL of THF in a round-bottomed flask, and Pd(PPh3)4 (5.8 g, 5.04 mmol) and K2CO3 (46.4 g, 336.03 mmol) dissolved in 140 mL of H2O were added, and the mixture was 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 69.9 g (yield: 77.7%) of the product Sub2-32.

[0242]

[0243] 3. Synthesis example of Sub2-71

[0244]

[0245] 8-Bromo-1-chlorodibenzo[b,d]furan (50 g, 177.60 mmol) and (phenyl-d5)boronic acid (22.6 g, 177.60 mmol) were dissolved in 420 mL of THF in a round-bottomed flask, and Pd(PPh3)4 (6.2 g, 5.33 mmol) and K2CO3 (49.1 g, 355.20 mmol) dissolved in 150 mL of H2O were added, and the mixture was 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 38.5 g of the product Sub2-71 (yield: 76.4%).

[0246]

[0247] Compounds belonging to Sub2 of Scheme 1 may be, but are not limited to, the compounds below, and Table 2 below shows the FD-MS (Field Desorption-Mass Spectrometry) values ​​of compounds belonging to Sub2.

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262]

[0263]

[0264] 화합물FD-MS화합물FD-MSSub2-1m / z=231.99(C 12 H9Br=233.11)Sub2-2m / z=231.99(C 12 H9Br=233.11)Sub2-3m / z=231.99(C 12 H9Br=233.11)Sub2-4m / z=308.02(C 18 H 13 Br=309.21)Sub2-5m / z=308.02(C 18 H 13 Br=309.21)Sub2-6m / z=308.02(C 18 H 13 Br=309.21)Sub2-7m / z=288.05(C 16 H 17 Br=289.22)Sub2-8m / z=238.04(C 12 H 15 Br=239.16)Sub2-9m / z=250.04(C 13 H 15 Br=251.17)Sub2-10m / z=290.07(C 16 H 19 Br=291.23)Sub2-11m / z=245.97(C 12 H7BrO=247.09)Sub2-12m / z=245.97(C 12 H7BrO=247.09)Sub2-13m / z=245.97(C 12 H7BrO=247.09)Sub2-14m / z=278.05(C 18 H 11 ClO=278.74)Sub2-15m / z=278.05(C 18 H 11 ClO=278.74)Sub2-16m / z=278.05(C18 H 11 ClO=278.74)Sub2-17m / z=278.05(C 18 H 11 ClO=278.74)Sub2-18m / z=278.05(C 18 H 11 ClO=278.74)Sub2-19m / z=278.05(C 18 H 11 ClO=278.74)Sub2-20m / z=295.98(C 16 H9BrO=297.15)Sub2-21m / z=292.07(C 19 H 13 ClO=292.76)Sub2-22m / z=302.03(C 16 H 15 BrO=303.20)Sub2-23m / z=259.98(C 13 H9BrO=261.12)Sub2-24m / z=259.98(C 13 H9BrO=261.12)Sub2-25m / z=328.05(C 18 H 17 BrO=329.24)Sub2-26m / z=261.95(C 12 H7BrS=263.15)Sub2-27m / z=261.95(C 12 H7BrS=263.15)Sub2-28m / z=294.03(C 18 H 11 ClS=294.80)Sub2-29m / z=294.03(C 18 H 11 ClS=294.80)Sub2-30m / z=294.03(C 18 H 11 ClS=294.80)Sub2-31m / z=294.03(C 18 H 11 ClS=294.80)Sub2-32m / z=534.12(C 37 H 23 ClS=535.10)Sub2-33m / z=458.09(C 32 H 19 ClS=459.00)Sub2-34m / z=275.96(C 13H9BrS=277.18)Sub2-35m / z=350.09(C 22 H 19 ClS=350.90)Sub2-36m / z=272.02(C 15 H 13 Br=273.17)Sub2-37m / z=272.02(C 15 H 13 Br=273.17)Sub2-38m / z=272.02(C 15 H 13 Br=273.17)Sub2-39m / z=272.02(C 15 H 13 Br=273.17)Sub2-40m / z=348.05(C 21 H 17 Br=349.27)Sub2-41m / z=348.05(C 21 H 17 Br=349.27)Sub2-42m / z=396.05(C 25 H 17 Br=397.31)Sub2-43m / z=396.05(C 25 H 17 Br=397.31)Sub2-44m / z=394.04(C 25 H 15 Br=395.30)Sub2-45m / z=394.04(C 25 H 15 Br=395.30)Sub2-46m / z=506.16(C 33 H 31 Br=507.51)Sub2-47m / z=396.05(C 25 H 17 Br=397.31)Sub2-48m / z=396.05(C 25 H 17 Br=397.31)Sub2-49m / z=396.05(C 25 H 17 Br=397.31)Sub2-50m / z=410.03(C 25 H 15 BrO=411.30)Sub2-51m / z=321.02(C 18 H 12 BrN=322.20)Sub2-52m / z=321.02(C 18 H12 BrN=322.20)Sub2-53m / z=321.02(C 18 H 12 BrN=322.20)Sub2-54m / z=397.05(C 24 H 16 BrN=398.30)Sub2-55m / z=397.05(C 24 H 16 BrN=398.30)Sub2-56m / z=288.00(C 14 H 13 BrSi=289.25)Sub2-57m / z=412.03(C 24 H 17 BrSi=413.39)Sub2-58m / z=412.03(C 24 H 17 BrSi=413.39)Sub2-59m / z=414.04(C 24 H 19 BrSi=415.40)Sub2-60m / z=414.04(C 24 H 19 BrSi=415.40)Sub2-61m / z=384.15(C 23 H 29 Br=385.39)Sub2-62m / z=410.07(C 26 H 19 Br=411.34)Sub2-63m / z=508.18(C 33 H 33 Br=509.53)Sub2-64m / z=506.16(C 33 H 31 Br=507.51)Sub2-65m / z=506.16(C 33 H 31 Br=507.51)Sub2-66m / z=241.05(C 12 D9Br=242.16)Sub2-67m / z=237.02(C 12 H4D5Br=238.14)Sub2-68m / z=248.99(C 12 H4D3BrO=250.11)Sub2-69m / z=253.01(C 12 D7BrO=254.13)Sub2-70m / z=289.12(C 18 D 11ClO=289.80)Sub2-71m / z=283.08(C 18 H6D5ClO=283.77)Sub2-72m / z=279.06(C 15 H6D7Br=280.22)Sub2-73m / z=278.06(C 15 H7D6Br=279.21)Sub2-74m / z=285.10(C 15 D 13 Br=286.25)Sub2-75m / z=279.06(C 15 H6D7Br=280.22)Sub2-76m / z=413.16(C 25 D 17 Br=414.42)Sub2-77m / z=413.16(C 25 D 17 Br=414.42)Sub2-78m / z=403.09(C 25 H6D9Br=404.35)Sub2-79m / z=405.10(C 25 H4D 11 Br=406.37)

[0265]

[0266] III. Synthesis of final products

[0267] 1. Synthesis example of P-1

[0268]

[0269] Sub1-1 (15 g, 35.25 mmol) and Sub2-1 (8.3 g, 35.25 mmol) were dissolved in 120 mL of toluene in a round-bottomed flask, and Pd2(dba)3 (1.0 g, 1.06 mmol), P(t-bu)3 (0.5 g, 2.11 mmol), and t-BuONa (6.8 g, 70.51 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 18.2 g of product P-1 (yield: 89.4%).

[0270]

[0271] 2. Synthesis example of P-16

[0272]

[0273] Sub1-26 (15 g, 28.32 mmol) and Sub2-15 (7.9 g, 28.32 mmol) were dissolved in 100 mL of toluene in a round-bottomed flask, and Pd2(dba)3 (0.8 g, 0.84 mmol), P(t-bu)3 (0.4 g, 1.70 mmol), and t-BuONa (5.5 g, 56.64 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 14.7 g of the product P-16 (yield: 67.2%).

[0274]

[0275] 3. Synthetic example of P-29

[0276]

[0277] Sub1-1 (15 g, 35.25 mmol) and Sub2-40 (10.8 g, 35.25 mmol) were dissolved in 120 mL of toluene in a round-bottomed flask, and Pd2(dba)3 (1.0 g, 1.06 mmol), P(t-bu)3 (0.5 g, 2.12 mmol), and t-BuONa (6.8 g, 70.51 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 20.0 g of the product P-29 (yield: 81.8%).

[0278]

[0279] 4. Synthetic example of P-35

[0280]

[0281] Sub1-9 (15 g, 29.91 mmol) and Sub2-47 (11.9 g, 29.91 mmol) were dissolved in 100 mL of toluene in a round-bottomed flask, and Pd2(dba)3 (0.8 g, 0.90 mmol), P(t-bu)3 (0.4 g, 1.79 mmol), and t-BuONa (5.7 g, 59.81 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 22.4 g of the product P-35 (yield: 91.6%).

[0282]

[0283] 5. Synthetic example of P-48

[0284]

[0285] Sub1-7 (15 g, 29.91 mmol) and Sub2-59 (12.4 g, 29.91 mmol) were dissolved in 100 mL of toluene in a round-bottomed flask, and Pd2(dba)3 (0.8 g, 0.90 mmol), P(t-bu)3 (0.4 g, 1.79 mmol), and t-BuONa (5.7 g, 59.81 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 20.5 g of the product P-48 (yield: 82.0%).

[0286]

[0287] 6. Synthetic example of P-54

[0288]

[0289] Sub1-42 (15 g, 28.98 mmol) and Sub2-29 (8.6 g, 28.98 mmol) were dissolved in 100 mL of toluene in a round-bottomed flask, and Pd2(dba)3 (0.8 g, 0.90 mmol), P(t-bu)3 (0.4 g, 1.79 mmol), and t-BuONa (5.7 g, 59.81 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 16.5 g of the product P-54 (yield: 73.4%).

[0290]

[0291] 7. Synthetic example of P-68

[0292]

[0293] Sub1-45 (15 g, 35.25 mmol) and Sub2-62 (14.5 g, 35.25 mmol) were dissolved in 120 mL of toluene in a round-bottomed flask, and Pd2(dba)3 (1.0 g, 1.06 mmol), P(t-bu)3 (0.4 g, 2.11 mmol), and t-BuONa (6.8 g, 70.51 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 21.5 g of the product P-68 (yield: 80.7%).

[0294]

[0295] 8. Synthetic example of P-77

[0296]

[0297] Sub1-61 (15 g, 29.91 mmol) and Sub2-44 (11.9 g, 29.91 mmol) were dissolved in 110 mL of toluene in a round-bottomed flask, and Pd2(dba)3 (0.8 g, 0.89 mmol), P(t-bu)3 (0.4 g, 2.11 mmol), and t-BuONa (5.7 g, 59.81 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 22.5 g of the product P-77 (yield: 92.2%).

[0298]

[0299] 9. Synthetic example of P-90

[0300]

[0301] Sub1-72 (15 g, 34.68 mmol) and Sub2-1 (8.1 g, 34.68 mmol) were dissolved in 120 mL of toluene in a round-bottomed flask, and Pd2(dba)3 (1.0 g, 1.04 mmol), P(t-bu)3 (0.4 g, 2.08 mmol), and t-BuONa (6.7 g, 69.36 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 16.2 g of the product P-90 (yield: 79.9%).

[0302]

[0303] 10. Synthetic example of P-99

[0304]

[0305] Sub1-72 (15 g, 34.68 mmol) and Sub2-76 (14.4 g, 34.68 mmol) were dissolved in 120 mL of toluene in a round-bottomed flask, and Pd2(dba)3 (1.0 g, 1.04 mmol), P(t-bu)3 (0.4 g, 2.08 mmol), and t-BuONa (6.7 g, 69.36 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 22.8 g of the product P-99 (yield: 85.8%).

[0306]

[0307] 11. Synthesis example of P-102

[0308]

[0309] Sub1-76 (15 g, 29.26 mmol) and Sub2-36 (8.0 g, 29.26 mmol) were dissolved in 100 mL of toluene in a round-bottomed flask, and Pd2(dba)3 (0.8 g, 0.88 mmol), P(t-bu)3 (0.4 g, 1.76 mmol), and t-BuONa (5.6 g, 58.52 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 15.5 g of the product P-102 (yield: 75.2%).

[0310]

[0311] 12. Synthesis example of P-120

[0312]

[0313] Sub1-79 (15 g, 28.37 mmol) and Sub2-48 (11.3 g, 28.37 mmol) were dissolved in 100 mL of toluene in a round-bottomed flask, and Pd2(dba)3 (0.8 g, 0.88 mmol), P(t-bu)3 (0.4 g, 1.76 mmol), and t-BuONa (5.6 g, 58.52 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 14.7 g of the product P-120 (yield: 61.3%).

[0314]

[0315] Meanwhile, the FD-MS values ​​of compounds P-1 to P-120 of the present invention manufactured according to the above-described synthetic examples are as shown in Table 3 below.

[0316] Compound FD-MS Compound FD-MSP-1 m / z = 577.20 (C 42 H 27 NO2=577.68)P-2m / z=653.24(C 48 H 31 NO2=653.78)P-3m / z=729.27(C 54 H 35 NO2=729.88)P-4m / z=745.26(C 54 H 35 NO3=745.88)P-5m / z=727.29(C 52 H 38 FNO2=727.88)P-6m / z=749.24(C 48 H 32 F5NO2=749.78)P-7m / z=945.21(C 55 H 30 F 11 NO2=945.83)P-8m / z=775.23(C 47 H 32 F7NO2=775.77)P-9m / z=757.23(C 54 H 31 NO4=757.84)P-10m / z=707.19(C 50 H29 NO2S=707.85)P-11m / z=695.25(C 50 H 33 NO3=695.82)P-12m / z=667.21(C 48 H 29 NO3=667.76)P-13m / z=782.26(C 56 H 34 N2O3=782.90)P-14m / z=788.23(C 54 H 32 N2O5=788.86)P-15m / z=799.31(C 58 H 41 NO3=799.97)P-16m / z=771.28(C 56 H 37 NO3=771.92)P-17m / z=661.26(C 47 H 35 NO3=661.80)P-18m / z=783.28(C 57 H 37 NO3=783.93)P-19m / z=619.21(C 44 H 29 NO3=619.72)P-20m / z=687.28(C 49 H 37 NO3=687.84)P-21m / z=923.29(C 67 H 42 NO2S=924.13)P-22m / z=607.16(C 42 H 25 NO2S=607.73)P-23m / z=999.32(C 73 H 45 NO2S=1000.23)P-24m / z=923.29(C 67 H 42 NO2S=924.13)P-25m / z=617.24(C 45 H 31 NO2=617.75)P-26m / z=783.28(C 57 H 37 NO3=783.93)P-27m / z=743.28(C 55 H 37 NO2=743.91)P-28m / z=793.30(C 59 H 39NO2=793.97)P-29m / z=693.27(C 51 H 35 NO2=693.85)P-30m / z=741.27(C 55 H 35 NO2=741.89)P-31m / z=791.28(C 59 H 37 NO2=791.95)P-32m / z=739.25(C 55 H 33 NO2=739.87)P-33m / z=741.27(C 55 H 35 NO2=741.89)P-34m / z=817.30(C 61 H 39 NO2=817.99)P-35m / z=817.30(C 61 H 39 NO2=817.99)P-36m / z=817.30(C 61 H 39 NO2=817.99)P-37m / z=815.28(C 61 H 37 NO2=815.97)P-38m / z=851.38(C 63 H 49 NO2=852.09)P-39m / z=755.25(C 55 H 33 NO3=755.87)P-40m / z=799.25(C 57 H 37 NO2S=799.99)P-41m / z=666.23(C 48 H 30 N2O2=666.78)P-42m / z=666.23(C 48 H 30 N2O2=666.78)P-43m / z=831.29(C 60 H 37 N3O2=831.98)P-44m / z=742.26(C 54 H 34 N2O2=742.88)P-45m / z=633.21(C 44 H 31 NO2Si=633.82)P-46m / z=833.28(C 60 H 39NO2Si=834.06)P-47m / z=833.28(C 60 H 39 NO2Si=834.06)P-48m / z=835.29(C 60 H 41 NO2Si=836.08)P-49m / z=911.32(C 66 H 45 NO2Si=912.18)P-50m / z=785.28(C 57 H 39 NOS=786.00)P-51m / z=709.24(C 51 H 35 NOS=709.91)P-52m / z=785.28(C 57 H 39 NOS=786.00)P-53m / z=759.22(C 54 H 34 NO2S=759.92)P-54m / z=775.20(C 54 H 33 NOS2=775.98)P-55m / z=775.20(C 54 H 33 NSO2=775.98)P-56m / z=729.16(C 49 H 31 NS3=729.97)P-57m / z=577.20(C 42 H 27 NO2=577.68)P-58m / z=693.27(C 51 H 35 NO2=693.85)P-59m / z=693.27(C 51 H 35 NO2=693.85)P-60m / z=799.25(C 57 H 37 NO2S=799.99)P-61m / z=783.31(C 58 H 41 NO2=783.97)P-62m / z=743.25(C 54 H 33 NO3=743.86)P-63m / z=847.25(C 61 H 37 NO2S=848.03)P-64m / z=769.24(C 56 H 35NOS=769.96)P-65m / z=741.27(C 55 H 35 NO2=741.89)P-66m / z=817.30(C 61 H 39 NO2=817.99)P-67m / z=909.31(C 67 H 43 NOS=910.15)P-68m / z=755.28(C 56 H 37 NO2=755.92)P-69m / z=833.28(C 61 H 39 NOS=834.05)P-70m / z=961.38(C 69 H 55 NS2=962.33)P-71m / z=709.24(C 51 H 35 NOS=709.91)P-72m / z=815.28(C 61 H 37 NO2=815.97)P-73m / z=617.24(C 45 H 31 NO2=617.75)P-74m / z=693.27(C 51 H 35 NO2=693.85)P-75m / z=699.31(C 51 H 41 NO2=699.89)P-76m / z=729.36(C 53 H 47 NO2=729.96)P-77m / z=815.28(C 61 H 37 NO2=815.97)P-78m / z=881.37(C 64 H 51 NOS=882.18)P-79m / z=811.31(C 59 H 41 NO3=811.98)P-80m / z=817.30(C 61 H 39 NO2=817.99)P-81m / z=759.24(C 54 H 33 NO4=759.86)P-82m / z=783.28(C 57 H 37 NO3=783.93)P-83m / z=833.28(C61 H 39 NOS=834.05)P-84m / z=831.26(C 61 H 37 NOS=832.03)P-85m / z=775.20(C 54 H 33 NOS2=775.98)P-86m / z=709.24(C 51 H 35 NOS=709.91)P-87m / z=815.28(C 61 H 37 NO2=815.97)P-88m / z=983.47(C 73 H 61 NO2=984.30)P-89m / z=580.22(C 42 H 24 D3NO2=580.70)P-90m / z=584.25(C 42 H 20 D7NO2=584.73)P-91m / z=595.32(C 42 H9D 18 NO2=595.79)P-92m / z=714.33(C 52 H 34 D5NO2=714.92)P-93m / z=666.33(C 48 H 30 D7NO2=666.87)P-94m / z=605.27(C 42 H 11 D 14 NO3=605.75)P-95m / z=685.33(C 48 H 11 D 18 NO3=685.87)P-96m / z=696.40(C 48 D 29 NO3=696.94)P-97m / z=748.31(C 55 H 28 D7NO2=748.93)P-98m / z=828.37(C 61 H 28 D 11 NO2=829.06)P-99m / z=765.42(C 55 H 11 D 24 NO2=766.04)P-100m / z=776.49(C 55 D35 NO2=777.10)P-101m / z=720.31(C 51 H 24 D 11 NOS=720.97)P-102m / z=704.34(C 51 H 24 D 11 NO2=704.91)P-103m / z=664.30(C 48 H 20 D 11 NO2=664.85)P-104m / z=746.30(C 55 H 26 D7NO2=746.92)P-105m / z=746.30(C 55 H 26 D7NO2=746.92)P-106m / z=762.29(C 55 H 26 D7NO3=762.92)P-107m / z=640.26(C 44 H 26 D7NO2Si=640.86)P-108m / z=846.36(C 60 H 30 D 11 NO2Si=847.15)P-109m / z=770.29(C 54 H 22 D 11 NO2S=770.99)P-110m / z=746.30(C 54 H 22 D 17 NO2=746.92)P-111m / z=748.31(C 55 H 28 D7NO2=748.93)P-112m / z=720.31(C 51 H 24 D 11 NOS=720.97)P-113m / z=704.34(C 51 H 24 D 11 NO2=704.91)P-114m / z=786.27(C 54 H 22 D 11 NOS2=787.05)P-115m / z=897.35(C 67 H 35D6NO2=898.11)P-116m / z=706.36(C 51 H 34 D7NO2=706.94)P-117m / z=706.35(C 51 H 22 D 13 NO2S=706.96)P-118m / z=694.26(C 48 H 18 D 11 NO2S=694.89)P-119m / z=690.24(C 48 H 22 D7NO2S=690.87)P-120m / z=844.34(C 61 H 28 D 11 NOS=845.12)

[0317] Meanwhile, although the exemplary synthetic examples of the present invention represented by Chemical Formula 1 have been described above, these 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.

[0318]

[0319] Manufacturing and evaluation of organic electronic devices

[0320] [Example 1] Green organic light-emitting device

[0321] First, 4,4',4''-Tris[2-naphthyl(phenyl)amino]triphenylamine (hereinafter, 2-TNATA) was vacuum-deposited to a thickness of 70 nm on an ITO layer (anode) formed on a glass substrate to form a hole injection layer, and then N,N'-bis(1-naphthalenyl)-N,N'-bis-phenyl-(1,1'-biphenyl)-4,4'-diamine (hereinafter, NPB) as a hole transport compound was vacuum-deposited to a thickness of 70 nm on the hole injection layer to form a hole transport layer. Next, compound C-1 below was vacuum-deposited to a thickness of 30 nm on the hole transport layer to form a first light-emitting auxiliary layer, and then compound P2-11 of the present invention was vacuum-deposited to a thickness of 5 nm on the first light-emitting auxiliary layer to form a second light-emitting auxiliary layer. Next, on the second light-emitting auxiliary layer, a light-emitting layer was deposited with a thickness of 30 nm by doping 4,4'-N,N'-dicarbazole-biphenyl (hereinafter, CBP) as a host material and [tris(2-phenylpyridine)-iridium] (hereinafter, abbreviated as Ir(ppy)3) as a dopant material at a weight ratio of 95:5. Subsequently, (1,1'-bisphenyl)-4-oleato)bis(2-methyl-8-quinolinolato)aluminum (hereinafter, abbreviated as BAlq) was vacuum-deposited with a thickness of 10 nm as a hole-blocking layer, and Bis(10-hydroxybenzo[h]quinolinato)beryllium (hereinafter, abbreviated as BeBq2) was deposited with a thickness of 60 nm as an electron transport layer. Afterwards, LiF, a halogenated alkali metal, was deposited on the electron transport layer to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited on the electron injection layer to a thickness of 150 nm to form a cathode, thereby manufacturing an organic light emitting device.

[0322]

[0323] [Example 2] to [Example 17]

[0324] An organic light-emitting device was manufactured in the same manner as Example 1, except that the compound of the present invention described in Table 4 below was used instead of the compound P2-11 of the present invention as the second light-emitting auxiliary layer material.

[0325]

[0326] [Comparative Example 1]

[0327] An organic light-emitting device was manufactured in the same manner as Example 1, except that the chemical formula P-1 of the present invention was used as both the first light-emitting auxiliary layer and the second light-emitting auxiliary layer material.

[0328]

[0329] [Comparative Example 2]

[0330] An organic light-emitting device was manufactured in the same manner as Example 1, except that the chemical formula P-33 of the present invention was used as both the first light-emitting auxiliary layer and the second light-emitting auxiliary layer material.

[0331]

[0332] [Comparative Example 3]

[0333] An organic light-emitting device was manufactured in the same manner as in Example 1, except that the following comparative compound A was used instead of P-1 as the second light-emitting auxiliary layer material.

[0334] <c-1>Comparative Compound A

[0335]

[0336]

[0337] 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 4 below shows the results of the device fabrication and evaluation.

[0338] 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.

[0339] 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.

[0340] First light-emitting auxiliary layerSecond light-emitting auxiliary layerDriving voltage (V)Current (mA / cm) 2 ) Efficiency (cd / A) T (95) Comparative Example (1) Compound (P-1) Compound (P-1) 5.2 17.6 28.4 9 3.8 Comparative Example (2) Compound (P-33) Compound (P-33) 5.2 17.8 28.1 9 4.3 Comparative Example (3) Compound (C-1) Comparative Compound A5.118.127.7110.2 Example (1) Compound (C-1) Compound (P-1) 4.914.933.5122.9 Example (2) Compound (C-1) Compound (P-2) 4.914.833.9123.6 Example (3) Compound (C-1) Compound (P-12) 4.915.232.8120.8 Example (4) Compound (C-1) Compound (P-25) 4.815.831.6116.2 Example (5) Compound (C-1) Compound (P-32) 5.0 15.3 32.7 120.2 Example (6) Compound (C-1) Compound (P-33) 4.9 15.0 33.3 123.6 Example (7) Compound (C-1) Compound (P-35) 5.0 14.8 33.7 124.3 Example (8) Compound (C-1) Compound (P-45) 4.9 15.4 32.5 119.3 Example (9) Compound (C-1) Compound (P-51)4.815.931.4114.8Example (10) Compound (C-1) Compound (P-56)4.915.632.1117.8Example (11) Compound (C-1) Compound (P-57)5.015.133.2121.8Example (12) Compound (C-1) Compound (P-65)5.015.233.0122.5Example (13) Compound (C-1) Compound (P-73)5.016. 330.7112.8 Example (14) Compound (C-1) Compound (P-90) 4.914.933.6127.8 Example (15) Compound (C-1) Compound (P-97) 4.915.033.4128.5 Example (16) Compound (C-1) Compound (P-100) 4.914.933.5129.7 Example (17) Compound (C-1) Compound (P-103) 4.914.734.0128.6

[0341] As can be seen in Table 4 above, when a green organic electroluminescent device is manufactured using the material for an organic electroluminescent device of the present invention as a light-emitting auxiliary layer material, it can be confirmed that the compound and device configuration of the present invention have an effect on improving the overall performance of the device compared to the comparative example, and in particular, it can be confirmed that the lifespan is significantly improved.

[0342] Comparing the device configuration of Comparative Examples 1 and 2 with the device configuration of the present invention, Comparative Examples 1 and 2 are devices composed of a single-layer light-emitting auxiliary layer (the first light-emitting auxiliary layer and the second light-emitting auxiliary layer are made of the same material and are a single-layer light-emitting auxiliary layer), whereas the device configuration of the present invention is composed of a plurality of light-emitting auxiliary layers. In the case of the compound represented by Chemical Formula 1 of the present invention, it is composed of No. 1 dibenzofuran or dibenzothiophene and No. 2 dibenzofuran or dibenzothiophene containing a phenylene linker. While the compound composed in this way exhibits an effect of decreasing efficiency as the driving voltage increases, it is expected to have an excellent lifespan. However, as can be seen in Examples 1 to 17, when a compound expected to have a fast driving voltage is used as the first light-emitting auxiliary layer, the synergistic effect of pulling up the driving voltage and maximizing the efficiency is exhibited. In addition, when used as the second light-emitting auxiliary layer like the device configuration of the present invention, the lifespan increase effect appears to be maximized. In particular, when deuterium is further substituted in dibenzofuran or dibenzothiophene No. 1, the lifespan can be maximized (Examples 14, 15, and 17), and it can be seen that overall, similar performance is shown compared to the compound substituted with deuterium (Example 16). Furthermore, when the light-emitting region is formed close to the interface between the light-emitting auxiliary layer and the host, the lifespan effect of the second light-emitting auxiliary layer is expected to be further maximized.

[0343] Second, when comparing the configuration of Comparative Example 3 with the configuration of the present invention, the device configuration of Comparative Example 3 and the device configuration of the present invention are similar, but Comparative Example 3 uses Comparative Compound A as the second light-emitting auxiliary layer, whereas the compound of the present invention uses a compound represented by Chemical Formula 1. When comparing Comparative Compound A with the compound represented by Chemical Formula 1 of the present invention, Comparative Compound A has a substituted biphenyl group, whereas the compound represented by Chemical Formula 1 has a substituted dibenzofuran or dibenzothiophene 2 containing a phenylene linker. The compound represented by Chemical Formula 1 is expected to have a fast driving voltage compared to Comparative Compound A, but when the second light-emitting auxiliary layer compound is very slow like Comparative Compound A, it seems to have a negative effect in terms of driving voltage and efficiency, and it seems to have a negative effect on the lifespan as the efficiency decreases.

[0344] In conclusion, when the compound represented by chemical formula 1 is used as the second light-emitting auxiliary layer, the device exhibits excellent characteristics in overall performance, and in particular, it can be seen to be remarkably superior in terms of lifespan.

[0345] The above description is merely illustrative of the present invention. 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.

[0346] 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.

[0347] 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. A composition for laminating a second light-emitting auxiliary layer of an organic electric device, characterized in that it comprises a compound represented by the following chemical formula 1. <Chemical Formula 1> {In the above chemical formula 1, 1) X and Y are independently O or S, 2) R 1 , R 2 , R 3 , R 4 and R 5 are each the same or different, and independently of each other, hydrogen; deuterium; halogen; cyano group; nitro group; 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 group; C1~C 20 Alkyl group of; C2~C 20 Alkenyl group of; C1~C 20 Alkoxyl group of; and C6~C 20 is selected from the group consisting of aryloxy groups; or adjacent groups can be combined with each other to form an aromatic ring, 3) Ar 1 Silver 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 60 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; a, c and e are independently integers from 0 to 4, b and d are independently integers from 0 to 3, Here, the aryl group, heterocyclic group, fluorenyl group, aliphatic ring group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group and aryloxy group are each deuterium; halogen; C6~C 20 Silane group substituted or unsubstituted with an aryl 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 Aliphatic ring group; C7~C 20 Arylalkyl group of; C8~C 20 Aryl alkenyl group of; and C7~C 20 It may be further substituted with one or more substituents selected from the group consisting of alkylaryl groups; and further, the hydrogen of these substituents may be further substituted with one or more deuteriums, and further, these substituents may be combined with each other to form a ring, wherein 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, including a saturated or unsaturated ring.

2. A composition for laminating a second light-emitting auxiliary layer of an organic electric device, characterized in that the compound represented by the chemical formula 1 in claim 1 is represented by any one of the following chemical formulas 1-1 to 1-3. <Chemical Formula 1-1> <Chemical Formula 1-2> <Chemical Formula 1-3> {In the above chemical formulas 1-1 to 1-3, X, Y, Ar 1 , R 1 , R 2 , R 3 , R 4 , R 5 , a, b, c, d and e are the same as defined in claim 1 above.

3. In the first paragraph, the R 4 Inland R 5 A composition for laminating a second light-emitting auxiliary layer of an organic electric device, characterized in that at least one of the layers contains deuterium.

4. A composition for laminating a second light-emitting auxiliary layer of an organic electric device, characterized in that the compound of the chemical formula 1 in the first paragraph is any one of the following compounds.

5. An organic electric device comprising a first electrode; a second electrode; and an organic layer including a light-emitting layer between the first electrode and the second electrode, wherein the organic layer includes a hole transport region, the hole transport region is arranged between the first electrode and the light-emitting layer, and the hole transport region is arranged in the order of a hole transport layer, a first light-emitting auxiliary layer, and a second light-emitting auxiliary layer. An organic electric device characterized in that the second light-emitting auxiliary layer comprises a compound according to claim 1.

6. An organic electric device according to claim 5, further comprising 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.

7. An organic electric device according to claim 5, 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.

8. An organic electric device according to claim 7, characterized in that the organic layer further includes a charge generation layer formed between the two or more stacks.

9. An electronic device comprising a display device including the organic electric element of clause 5; and a control unit for driving the display device.

10. An electronic device according to claim 9, 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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