Compound for organic electric element, organic electric element using same, and electronic device comprising same

Abstract

The present invention provides a compound represented by chemical formula 1, a method for recovering same, an organic electric element comprising a first electrode, a second electrode, and an organic material layer between the first electrode and the second electrode, and an electronic device comprising the organic electric element. By containing the compound of chemical formula 1 in the organic material layer, the driving voltage of the organic electric element can be lowered, and the luminous efficiency and lifespan of the organic electric element can be improved.

Description

Compounds for organic electric devices, organic electric devices using the same, and electronic devices thereof

[0001] The present invention relates to a compound for an organic electric device, an organic electric device using the same, 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, composed of different materials, to enhance the efficiency and stability of the device. For example, these layers may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

[0003] The biggest issues with organic light-emitting diodes are their lifespan and efficiency, and as displays become larger in size, these efficiency and lifespan issues must be resolved.

[0004] Efficiency, lifespan, and operating voltage are interrelated. As efficiency increases, the operating voltage decreases relatively. As the operating voltage decreases, the crystallization of organic substances due to Joule heating generated during operation decreases, which results in a tendency for the lifespan to increase.

[0005] However, simply improving the organic layers cannot maximize efficiency. This is because long life and high efficiency can be achieved simultaneously only 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] Therefore, in order to fully utilize the excellent characteristics of organic electronic devices, it is necessary to develop materials that form the organic layer within the device, especially the light-emitting auxiliary layer.

[0007] The purpose of the present invention is to provide a compound for an organic electric device that can lower the driving voltage of the device and improve the luminous efficiency and lifespan of the device, an organic electric device using the same, and an electronic device thereof.

[0008] In one aspect, the present invention provides a compound represented by the following chemical formula:

[0009]

[0010] In another aspect, the present invention provides an organic electric element and an electronic device thereof comprising a compound represented by the above chemical formula.

[0011] By using the compound according to an embodiment of the present invention as a material for an organic electric device, the driving voltage of the device can be lowered, and the luminous efficiency and lifespan can be improved.

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

[0013] [Explanation of symbols]

[0014] 100, 200, 300: Organic electroluminescent element 110: First electrode

[0015] 120: Hole injection layer 130: Hole transport layer

[0016] 140: Emitting layer 150: Electron transport layer

[0017] 160: Electron injection layer 170: Second electrode

[0018] 180: Light efficiency improvement layer 210: Buffer layer

[0019] 220: Light-emitting auxiliary layer 320: First hole injection layer

[0020] 330: First hole transport layer 340: First light-emitting layer

[0021] 350: First electron transport layer 360: First charge generation layer

[0022] 361: Second charge generation layer 420: Second hole injection layer

[0023] 430: Second hole transport layer 440: Second light-emitting layer

[0024] 450: Second electron transport layer CGL: Charge generation layer

[0025] ST1: First stack ST2: Second stack

[0026] The terms "aryl group," "arylene group," and "aromatic ring" used herein mean a hydrocarbon aromatic ring group, each having 6 to 60 carbon atoms unless otherwise specified, but is not limited thereto. In the present invention, the aryl group or arylene group includes a monocyclic ring, a polycyclic ring, a condensed ring, and the like.

[0027] As used herein, the term "fluorenyl group" means a substituted or unsubstituted fluorenyl group, and "fluorenylene group" means a substituted or unsubstituted fluorenylene group. The fluorenyl group or fluorenylene group used in the present invention includes a spiro compound formed by R and R' bonding to each other in the structure below, and also includes a compound in which adjacent R" bonds to each other to form a ring. The "substituted fluorenyl group" and the "substituted fluorenylene group" mean that at least one of R, R', and R" in the structure below is a substituent other than hydrogen, and the number of R" in the chemical formula below may be 1 to 8. In the present specification, regardless of the valence, a fluorenyl group, a fluorenylene group, etc. may be described as a fluorene group or fluorene.

[0028]

[0029] The term "spiro compound" as used herein has a "spiro linkage," which means a linkage formed by two rings sharing only one atom. 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.

[0030] The term "heterocyclic group" used herein includes not only aromatic heterocycles such as "heteroaryl group" or "heteroarylene group" but also non-aromatic heterocycles, and unless otherwise stated means, but is not limited to, a ring having 2 to 60 carbon atoms each containing one or more heteroatoms. The term "heteroatom" used herein, unless otherwise stated, represents an element other than carbon, such as N, O, S, P, or Si, and may include a heteroatom group such as SO2, P=O, etc. instead of carbon forming the ring, as in the following compounds.

[0031]

[0032] In addition, a heterocyclic group includes a monocyclic ring, polycyclic ring, or condensed ring containing a heteroatom, and in the case of a condensed ring, if at least one of the condensed rings is a ring containing a heteroatom, it is defined as a heterocyclic ring. For example, a condensed ring in which a heterocyclic ring such as furan, dihydrofuran, thiophene, pyrrole, pyridine, etc. and an aromatic ring such as benzene, naphthalene, phenanthrene, etc. are condensed, or an aliphatic ring such as cyclopentane, cyclohexane, etc. are condensed is also considered a heterocyclic ring, and a spiro compound in which at least one ring contains a heteroatom is also considered a heterocyclic ring.

[0033] The term "aliphatic ring" used in this specification refers to a cyclic hydrocarbon other than an aromatic hydrocarbon, including a monocyclic ring, a polycyclic ring, a condensed ring, a spiro compound, etc., and unless otherwise stated, refers to a ring having 3 to 60 carbon atoms, but is not limited thereto. In particular, an aliphatic ring (group) in this specification is defined as a hydrocarbon ring that does not contain any aromatic rings. Therefore, not only a saturated hydrocarbon ring such as a cycloalkyl group, but also a ring having one or more double bonds in the ring is considered to be an aliphatic ring as long as it is not an aromatic hydrocarbon.

[0034] The term "fused ring(group)" or "condensed ring(group)" used herein, unless otherwise stated, means a ring in which an aliphatic ring and an aromatic hydrocarbon (aromatic ring group or aryl ring) are condensed with each other, and unless otherwise stated, means a ring in which an aliphatic ring having 3 to 60 carbon atoms and an aromatic hydrocarbon having 6 to 60 carbon atoms are condensed with each other.

[0035] 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, or it may 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.

[0036] In addition, in this specification, numbers or alphabets indicating positions may be omitted when describing compound names or substituent names. For example, pyrido[4,3-d]pyrimidine may be described as pyridopyrimidine, benzofuro[2,3-d]pyrimidine as benzofuropyrimidine, 9,9-dimethyl-9H-fluorene as dimethylfluorene, etc. Accordingly, both benzo[g]quinoxaline and benzo[f]quinoxaline may be described as benzoquinoxaline.

[0037] 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.

[0038]

[0039] Here, if a is an integer of 0, the substituent R 1means that it is absent, that is, when a is 0, it means that all the carbons forming the benzene ring are bonded with hydrogen, and in this case, the indication of hydrogen bonded to carbon can be omitted and the chemical formula or compound can be described. In addition, when a is an integer of 1, one substituent R 1 It binds to one of the carbons forming the benzene ring, and when a is an integer of 2 or 3, it can bind as follows, for example, and when a is an integer of 4 to 6, it binds to the carbon of the benzene ring in a similar manner, and when a is an integer of 2 or more, R 1 may be the same or different.

[0040]

[0041] In addition, unless otherwise stated herein, a ring refers to an aryl ring, a heteroaryl ring, a fluorene ring, an aliphatic ring, a fused ring, etc., and a number-ring refers to a condensed ring, and a number-atom ring refers to a ring shape. For example, naphthalene corresponds to a two-ring condensed ring, anthracene corresponds to a three-ring condensed ring, thiophene and furan correspond to a five-membered heterocycle, and benzene and pyridine correspond to a six-membered aromatic ring.

[0042] In addition, unless otherwise stated in this specification, the rings formed by bonding adjacent groups to each other are C6~C 60 Aromatic ring group; 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; and C3~C 60 Aliphatic ring and C6~C 60 The aromatic ring may be selected from the group consisting of a fused ring group. Here, the aromatic ring group may be an aryl ring, and the heterocyclic group may include a heteroaryl ring.

[0043] Unless otherwise stated herein, 'neighboring groups' includes, for example, R1 and R2, R2 and R3, R3 and R4, R5 and R6, as well as R7 and R8 sharing a carbon, and may also include substituents bonded to non-adjacent ring elements (carbon, nitrogen, etc.), such as R1 and R7, R1 and R8, or R4 and R5. That is, when there is a substituent on a ring element such as a carbon or nitrogen that is immediately adjacent, they can be neighboring groups, but when no substituent is bonded to the ring element at the immediately adjacent position, the substituent bonded to the next ring element can be a neighboring group, and substituents bonded to the same ring carbon can also be neighboring groups. In the following chemical formula, when substituents bonded to the same carbon, such as R7 and R8, bond to each other to form a ring, a compound including a spiro moiety can be formed.

[0044]

[0045] Additionally, in this specification, the expression 'adjacent groups can combine with each other to form a ring' is used with the same meaning as 'adjacent groups combine with each other to selectively form a ring', and means a case where at least one pair of adjacent groups combine with each other to form a ring.

[0046] In addition, unless otherwise stated herein, substituents such as aryl group, arylene group, fluorenyl group, fluorenylene group, heterocyclic group, aliphatic ring group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, etc., rings formed by bonding adjacent groups to each other, etc., are each deuterium; halogen; cyano group; nitro group; siloxane group; C6-C 30Aryl group of; Fluorenyl group; C2-C containing at least one heteroatom selected from the group consisting of O, N, S, Si and P 30 Heterocyclic group of; C3-C 30 Aliphatic ring group; C3~C 60 Aliphatic ring and C6~C 60 Fused ring group of aromatic ring; C1-C 20 alkyl group of; C2-C 20 alkenyl group of; C2-C 20 Alkynyl group of; C1-C 20 Alkoxy group of; C6-C 20 Aryloxy group of; C1-C 20 Alkylthio group of; C6-C 20 Arylthio group of; C1-C 20 Alkyl group or C6-C 20 A silane group substituted or unsubstituted with an aryl group; and C1-C 20 Alkyl group or C6-C 20 It may be substituted with one or more substituents selected from the group consisting of phosphine oxide groups substituted or unsubstituted with an aryl group.

[0047] Unless otherwise stated in this specification, the symbols "*" or " " represents the joining part.

[0048] 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.

[0049] 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.

[0050] When describing components of the present invention, terms such as first, second, A, B, (a), (b), etc. may be used. 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.

[0051] Furthermore, when a component such as a layer, membrane, region, or plate is said to be "on" or "over" another component, it should be understood that this includes not only the case where it is "directly on" the other component, but also the case where there are other components in between. Conversely, when a component is said to be "directly on" another part, it should be understood that there are no other components in between.

[0052] Figures 1 to 3 are exemplary diagrams of organic electric devices according to embodiments of the present invention.

[0053] 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), and an organic layer formed between the first electrode (110) and the second electrode (170) formed on a substrate (not shown), and an inorganic layer may be included between the first electrode (110) and the second electrode (120).

[0054] For example, the first electrode (110) may be an anode, the second electrode (170) may be a cathode, and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

[0055] The above organic layer refers to a layer containing at least one organic material. For example, the 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). However, the electron injection layer (160) may be an inorganic layer that does not contain an organic material.

[0056] Specifically, a hole injection layer (120), a hole transport layer (130), a light-emitting layer (140), an electron transport layer (150), and an electron injection layer (160) can be sequentially formed on a first electrode (110).

[0057] 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 or the inorganic layer, and when the light efficiency improvement layer (180) is formed, the light efficiency of the organic electric element may be improved.

[0058] 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).

[0059] 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.

[0060] Referring to FIG. 2, an organic electric element (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.

[0061] 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).

[0062] 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.

[0063] 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 of 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.

[0064] 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).

[0065] 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.

[0066] 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.

[0067] The first light-emitting layer (340) may include a light-emitting material including a blue fluorescent dopant in a blue host, and the second light-emitting layer (440) may include a material doped with a greenish yellow dopant and a red dopant in a green host, but the materials of the first light-emitting layer (340) and the second light-emitting layer (440) according to the embodiment of the present invention are not limited thereto.

[0068] In FIG. 3, n can be an integer from 1 to 5, and when n is 2, a charge generation layer (CGL) and a third stack can be additionally stacked on the second stack (ST2).

[0069] 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.

[0070] The compound represented by the chemical formula 1 of the present invention may be included in an organic layer. For example, the compound represented by the chemical formula 1 of the present invention may 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), a light-emitting layer (140, 340, 440), or a light efficiency improvement layer (180), but may preferably be used as a material for a light-emitting auxiliary layer (220).

[0071] 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.

[0072] Therefore, in the present invention, by using the compound represented by chemical formula 1 as a material of the light-emitting auxiliary layer (220), the energy level and T1 value between each organic layer, and the inherent characteristics of the material (mobility, interface characteristics, etc.) can be optimized, thereby simultaneously improving the lifespan and efficiency of the organic electric device.

[0073] 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.

[0074] 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.

[0075] An organic electric device according to one embodiment of the present invention may be a front-emitting, back-emitting, or double-sided emitting type depending on the material used.

[0076] 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.

[0077] 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, navigation systems, game consoles, various TVs, and various computers.

[0078] Hereinafter, a compound according to one aspect of the present invention will be described.

[0079] A compound according to one aspect of the present invention is represented by the following chemical formula 1.

[0080] <Chemical Formula 1> <Chemical Formula A>

[0081]

[0082] In the above chemical formula, each symbol is defined as follows.

[0083] A is chemical formula A, and X is C(R a )(R b ), O, S or N(R c )am.

[0084] Ak is selected from the group consisting of the following chemical formulas Ak-1 to Ak-3.

[0085] <Chemical Formula Ak-1> <Chemical Formula Ak-2> <Chemical Formula Ak-3>

[0086]

[0087] In the above chemical formulas Ak-1 to Ak-3, hydrogen can be replaced with deuterium.

[0088] Ar 1 Silver 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; C6~C 60 Aromatic ring and C3~C 60A fused ring group of an aliphatic ring; and a combination thereof. Here, the combination thereof may be, for example, a combination of an arylene group and an arylene group, a combination of an arylene group and a fluorenylene group, a combination of an arylene group and a heterocyclic group, a combination of a fluorenylene group and a heterocyclic group, a combination of a heterocyclic group and a heterocyclic group, etc.

[0089] Ar a is C6~C 60 is an aryl group or fluorenyl group.

[0090] R 1 and R 2 is C1~C 20 is an alkyl group, and the hydrogen of the alkyl group can be replaced with deuterium, and R 1 and R 2 Except when they combine with each other to form a ring.

[0091] R 3 Inland R 6 are independently hydrogen; deuterium; halogen; cyano group; nitro group; silane 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; C6~C 60 Aromatic ring and C3~C 60 Fused ring group of aliphatic ring; C1~C 20 Alkyl group of; C2~C 20 Alkenyl group of; C2~C 20 Alkynyl group of; C1~C 20 Alkoxy group of; and C6~C 60 It is selected from the group consisting of aryloxy groups, and adjacent groups can combine with each other to form a ring.

[0092] a and d are integers from 0 to 4, b is an integer from 0 to 2, c is an integer from 0 to 3, n is an integer of 0 or 1, and if these are integers greater than or equal to 2, a plurality of R 3Each, multiple R 4 Each, multiple R 5 Each, multiple R 6 Each is either the same or different from the other.

[0093] Neighboring units, for example, neighboring R 3 Kiri, neighboring R 4 Kiri, neighboring R 5 Kiri, neighboring R 6 When they combine with each other to form a ring, the ring is C6~C 60 Aromatic ring group; Fluorenyl group; C3~C 60 Aliphatic ring 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 It can be selected from the group consisting of fused ring groups of aromatic rings.

[0094] When adjacent groups combine with each other to form an aromatic ring, the aromatic ring is, for example, C6~C 20 , C6~C 18 , C6~C 16 , C6~C 14 , C6~C 13 , C6~C 12 , C6~C 10 , C6, C 10 , C 12 , C 14 , C 15 , C 16 , C 18 It may be an aromatic ring, such as benzene, naphthalene, anthracene, phenanthrene, pyrene, triphenylene, etc.

[0095] n is an integer of 0 or 1. When n is 0, the amine group is directly bonded to the benzene ring of fluorene, and when n is 1, the amine group is bonded to the benzene ring of fluorene through a phenylene linker.

[0096] R a , R bare independently 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; C6~C 60 Aromatic ring and C3~C 60 Fused ring group of aliphatic ring; C1~C 20 Alkyl group of; C2~C 20 Alkenyl group of; C2~C 20 Alkynyl group of; C1~C 20 Alkoxy group of; and C6~C 60 is selected from the group consisting of aryloxy groups, R a Wow R b Except when they combine with each other to form a ring.

[0097] R c is 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 C6~C 60 Aromatic ring and C3~C 60 It is selected from the group consisting of fused ring groups of aliphatic rings.

[0098] The above Ar a , R 3 Inland R 6 , R a Inland R c At least one of them is an aryl group, or Ar 1 In the case of this arylene group, the aryl group or arylene group is, for example, C6~C 30 , C6~C 29 , C6~C 28 , C6~C 27 , C6~C 26 , C6~C 25 , C6~C 24 , C6~C 23 , C6~C 22 , C6~C 21, C6~C 20 , C6~C 19 , C6~C 18 , C6~C 17 , C6~C 16 , C6~C 15 , C6~C 14 , C6~C 13 , C6~C 12 , C6~C 11 , C6~C 10 , C6, C 10 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 It may be an aryl group or an arylene group, and specifically, it may be phenyl, biphenyl, naphthyl, terphenyl, phenanthrene, triphenylene, etc.

[0099] The above Ar 1 In the case of this heterocyclic group, the heterocyclic group is, for example, C2~C 30 , C2~C 29 , C2~C 28 , C2~C 27 , C2~C 26 , C2~C 25 , C2~C 24 , C2~C 23 , C2~C 22 , C2~C 21 , C2~C 20 , C2~C 19 , C2~C 18 , C2~C 17 , C2~C 16 , C2~C 15 , C2~C 14 , C2~C 13 , C2~C 12 , C2~C 11 , C2~C 10 , C2~C9, C2~C8, C2~C7, C2~C6, C2~C5, C2~C4, C2~C3, C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 , C12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 , C 20 , C 21 , C 22 , C 23 , C 24 , C 25 , C 26 , C 27 , C 28 , C 29 It may be a heterocyclic group such as, and specifically, pyridine, pyrimidine, pyrazine, pyridazine, triazine, furan, pyrrole, indene, indole, phenyl-indole, benzoindole, phenyl-benzoindole, pyrazinoindole, quinoline, isoquinoline, benzoquinoline, pyridoquinoline, quinazoline, benzoquinazoline, dibenzoquinazoline, phenanthroquinazoline, quinoxaline, benzoquinoxaline, dibenzoquinoxaline, benzofuran, naphthobenzofuran, dibenzofuran, dinaphthofuran, phenanthrobenzofuran, thiophene, benzothiophene, dibenzothiophene, naphthobenzothiophene, dinaphthothiophene, phenantrobenzothiophene, carbazole, phenyl-carbazole, Benzocarbazole, phenyl-benzocarbazole, naphthyl-benzocarbazole, dibenzocarbazole, indolocarbazole, benzofuropyridine, benzothiopyridine, benzofuropyridine, benzothiopyrimidine, benzofuropyrimidine, benzothiopyrazine, benzofuropyrazine, benzimidazole, benzothiazole, benzosilole, phenanthroline, dihydro-phenylphenazine, 10-phenyl-10H-phenoxazine, phenoxazine, phenothiazine, dibenzodioxin, benzodibenzodioxin, thianthrene, oxazole, benzoxazole, naphthooxazole, phenanthrooxazole, dibenzothiobenzoxazole, dibenzofurobenzoxazole, It may be 9,9-dimethyl-9H-xanthrene, 9,9-dimethyl-9H-thioxanthrene, dihydrodimethylphenylacridine, spiro[fluorene-9,9'-xanthrene], etc.

[0100] The above R 3 Inland R 6If at least one of them is an aliphatic ring group, the aliphatic ring group is, for example, C3~C 30 , C3~C 29 , C3~C 28 , C3~C 27 , C3~C 26 , C3~C 25 , C3~C 24 , C3~C 23 , C3~C 22 , C3~C 21 , C3~C 20 , C3~C 19 , C3~C 18 , C3~C 17 , C3~C 16 , C3~C 15 , C3~C 14 , C3~C 13 , C3~C 12 , C3~C 11 , C3~C 10 , C3~C8, C3~C6, C6, C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 It may be an aliphatic ring group such as cyclobutane, cyclopentane, cyclohexane, cyclohexene, bicycloheptane, adamantyl, etc.

[0101] The above Ar a is fluorenyl or Ar 1 In the case of this fluorenylene group, the fluorenyl group or fluorenylene group may be 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorene, 9,9'-spirobifluorene, spiro[benzo[b]fluorene-11,9'-fluorene], benzo[b]fluorene, 11,11-diphenyl-11H-benzo[b]fluorene, 9-(naphthalen-2-yl)9-phenyl-9H-fluorene, etc.

[0102] The above R 1 Inland R 6 , Ra , R b If at least one of them is an alkyl group, the alkyl group is, for example, C1~C 20 , C1~C 10 , C1~C4, C1, C2, C3, C4, etc., and for example, it can be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, etc., and the hydrogen of the alkyl group can be replaced with deuterium.

[0103] The above Ar 1 , Ar a , R 3 Inland R 6 , R a Inland R c are respectively deuterium; halogen; C1-C 20 Alkyl group or C6-C 20 Silane group substituted or unsubstituted with an aryl group; C1-C 20 Alkyl group or C6-C 20 Phosphine oxide substituted or unsubstituted with an aryl group; cyano group; nitro group; C1-C 20 Alkylthio group of; C1-C 20 Alkoxy group of; C6-C 30 Aryloxy group of; C6-C 30 Arylthio group of; C1-C 20 alkyl group of; C2-C 20 alkenyl group of; C2-C 20 Alkynyl group of; C6-C 30 Aryl group of; C6-C substituted with deuterium 30 Aryl group of; C3-C 30 Aliphatic ring group; C6-C 30 Aromatic ring and C3-C 30 A fused ring group of an aliphatic ring; and C2-C containing at least one heteroatom among O, N, S, Si and P. 30 It can be substituted with one or more substituents selected from the group consisting of heterocyclic groups, and the adjacent substituents can be combined with each other to form a ring, and the hydrogen of the substituent can be replaced with deuterium. However, Ra , R b Except when the substituents of form a ring.

[0104] The above Ar 1 , Ar a , R 3 Inland R 6 , R a Inland R c When at least one of them is substituted with an aryl group, the aryl group is, for example, C6~C 30 , C6~C 29 , C6~C 28 , C6~C 27 , C6~C 26 , C6~C 25 , C6~C 24 , C6~C 23 , C6~C 22 , C6~C 21 , C6~C 20 , C6~C 19 , C6~C 18 , C6~C 17 , C6~C 16 , C6~C 15 , C6~C 14 , C6~C 13 , C6~C 12 , C6~C 11 , C6~C 10 , C6, C 10 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 It can be an aryl group such as .

[0105] The above Ar 1 , Ar a , R 3 Inland R 6 , R a Inland R c When at least one of them is substituted with an aliphatic ring group, the aliphatic ring group is, for example, C3~C 30 , C3~C 29 , C3~C 28 , C3~C 27, C3~C 26 , C3~C 25 , C3~C 24 , C3~C 23 , C3~C 22 , C3~C 21 , C3~C 20 , C3~C 19 , C3~C 18 , C3~C 17 , C3~C 16 , C3~C 15 , C3~C 14 , C3~C 13 , C3~C 12 , C3~C 11 , C3~C 10 , C3~C8, C3~C6, C6, C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 It may be an aliphatic ring such as the back.

[0106] The above Ar 1 , Ar a , R 3 Inland R 6 , R a Inland R c When at least one of them is substituted with an alkyl group, the alkyl group is, for example, C1~C 20 , C1~C 10 , C1~C4, C1, C2, C3, C4, etc., and may be, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, etc.

[0107] The above chemical formula 1 can be represented by one of the following chemical formulas 1-1 to 1-4.

[0108] <Chemical Formula 1-1> <Chemical Formula 1-2>

[0109]

[0110] <Chemical Formula 1-3> <Chemical Formula 1-4>

[0111]

[0112] In the above chemical formulas 1-1 to 1-4, A, R 1 Inland R 4 , Ar 1 , Ar a , Ak, a, and b are as defined in chemical formula 1.

[0113] The above chemical formula A can be represented by one of the following chemical formulas A-1 to A-4.

[0114] <Chemical Formula A-1> <Chemical Formula A-2>

[0115]

[0116] <Chemical Formula A-3> <Chemical Formula A-4>

[0117]

[0118] In the above chemical formulas A-1 to A-4, X, R 5 , R 6 , c, d are as defined in chemical formula 1.

[0119] Ar 1 is selected from the group consisting of the following chemical formulas L-1 to L-27, and L 1 may be selected from a group consisting of a single bond or the following chemical formulas L-1 to L-27.

[0120] <Chemical Formula L-1> <Chemical Formula L-2> <Chemical Formula L-3> <Chemical Formula L-4>

[0121]

[0122] <Chemical Formula L-5> <Chemical Formula L-6> <Chemical Formula L-7> <Chemical Formula L-8>

[0123]

[0124] <Chemical Formula L-9> <Chemical Formula L-10> <Chemical Formula L-11> <Chemical Formula L-12>

[0125]

[0126] <Chemical Formula L-13> <Chemical Formula L-14> <Chemical Formula L-15>

[0127]

[0128] <Chemical Formula L-16> <Chemical Formula L-17> <Chemical Formula L-18>

[0129]

[0130] <Chemical Formula L-19> <Chemical Formula L-20> <Chemical Formula L-21>

[0131]

[0132] <Chemical Formula L-22> <Chemical Formula L-23> <Chemical Formula L-24>

[0133]

[0134] <Chemical Formula L-25> <Chemical Formula L-26> <Chemical Formula L-27>

[0135]

[0136] In the above chemical formulas L-1 to L-27, each symbol is defined as follows.

[0137] W is O, S, C(R1), C(R2)(R3), N, or N(Ar1). However, if L-14 and L-15 are connected through W, W is C(R1) or N.

[0138] R 9 Inland R 18 , R1 to R3 are each independently hydrogen; deuterium; halogen; C1-C 20 Alkyl group or C6-C 20 Silane group substituted or unsubstituted with an aryl group; C1-C 20 Alkyl group or C6-C 20 Phosphine oxide substituted or unsubstituted with an aryl group; cyano group; nitro group; C1-C 20 Alkylthio group of; C1-C 20 Alkoxy group of; C6-C 30 Aryloxy group of; C6-C30 Arylthio group of; C1-C 20 alkyl group of; C2-C 20 alkenyl group of; C2-C 20 Alkynyl group of; C6-C 30 Aryl group of; C6-C substituted with deuterium 30 Aryl group of; C3-C 30 Aliphatic ring group; C6-C 30 Aromatic ring and C3-C 30 A fused ring group of an aliphatic ring; and C2-C containing at least one heteroatom among O, N, S, Si and P. 30 is selected from the group consisting of heterocyclic groups, and adjacent groups can combine with each other to form a ring, and i, k, m, n, o, and p are each an integer from 0 to 4, j is an integer from 0 to 6, l is an integer from 0 to 2, q is an integer from 0 to 3, and r is an integer from 0 to 5.

[0139] Ar1 is C1-C 20 alkyl group of; C6-C 30 Aryl group of; C6-C substituted with deuterium 30 Aryl group of; C3-C 30 Aliphatic ring group; C6-C 30 Aromatic ring and C3-C 30 A fused ring group of an aliphatic ring; and C2-C containing at least one heteroatom among O, N, S, Si and P. 30 is selected from the group consisting of heterocyclic groups.

[0140] Specifically, the compound represented by the above chemical formula 1 may be one of the following compounds, but is not limited thereto.

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166] .

[0167] In another aspect, the present invention provides an organic electric device comprising a first electrode, a second electrode, and an organic layer formed between the first electrode and the second electrode, wherein the organic layer comprises a compound of formula 1, and preferably, the compound is included in a light-emitting auxiliary layer.

[0168] In another aspect, the present invention provides an electronic device including a display device including an organic electric element and a control unit for driving the display device, wherein the organic electric element includes a compound represented by the chemical formula 1.

[0169] The rearrangement energy of a compound used as a material for a light-emitting auxiliary layer can affect the performance of an organic light-emitting device, and the rearrangement energy is described below.

[0170] Reorganization energy (RE) refers to the energy lost due to changes in molecular structure during charge transfer (electrons and holes). It depends on molecular geometry and has the characteristic of decreasing as the difference between the neutral PES (Potential Energy Surface) and the charged PES decreases. The RE value can be calculated using the following formula.

[0171]

[0172] NONE: Neutral geometry of the molecule (= NO opt.)

[0173] NOAE: Anion geometry of neutral molecules

[0174] NOCE: Cation geometry of a neutral molecule

[0175] AONE: Neutral geometry of anion molecules

[0176] AOAE: Anion geometry of anion molecules (= AO opt.)

[0177] CONE: Neutral geometry of cation molecules

[0178] COCE: Cation geometry of the cation molecule (= CO opt.)

[0179] The rearrangement energy value and the mobility of charges are inversely proportional, and under the condition that they have the same r and T values, the RE value of each material directly affects the mobility.

[0180] The relationship between RE value and mobility is expressed as follows and is described by the charge transfer matrix element.

[0181]

[0182] (λ: Reorganization energy, μ: mobility, r: dimer displacement, t: intermolecular charge transfer matrix element)

[0183] According to the above equation, it can be seen that the smaller the RE value, the faster the mobility of charges.

[0184] To obtain rearrangement energy values, a simulation tool capable of calculating potential energy based on molecular structure is required. For example, Gaussian09 (G09) and Schrödinger Materials Science's Jaguar (JG) modules can be used. Both G09 and JG analyze molecular properties through quantum mechanical (QM) calculations and offer the ability to optimize molecular structures or calculate single-point energy for a given molecular structure.

[0185] Performing QM calculations on molecular structures requires significant computational resources. For example, two cluster servers could be used for these calculations. Each cluster server consists of four node workstations and one master workstation, with each node using CPUs with 36 or more cores, enabling molecular QM calculations through parallel computing via symmetric multiprocessing (SMP).

[0186] Using G09, we calculate the molecular structures optimized for neutral / charge states and their potential energies (NONE / COCE) required for rearrangement energy. By changing only the charges of the two optimized structures, we calculate the charge-state potential energy (NOCE) of the structure optimized for the neutral state and the neutral-state potential energy (CONE) of the structure optimized for the charge state. Then, we calculate the rearrangement energy according to the following equation.

[0187]

[0188] Since Schrödinger provides a function to automatically perform this calculation process, the JG module can sequentially calculate the potential energy for each state and calculate the RE value simply by providing the molecular structure (NO) of the basic state.

[0189] In another aspect, the present invention provides a compound represented by the chemical formula 1 obtained by recovering and purifying the material of an organic layer from a deposition device after depositing the organic layer in a manufacturing process of an organic electric device. The purity of the compound obtained by recovery and purification is 99.9% or higher.

[0190] In another aspect, the present invention provides a method for recovering a compound, comprising the steps of depositing an organic layer material including a compound represented by Chemical Formula 1, recovering the organic layer material attached to a deposition device, and purifying the recovered organic layer material to obtain a compound represented by Chemical Formula 1 having a purity of 99.9% or higher.

[0191] The above purification step may include a step of recrystallizing the recovered organic layer material using a recrystallization solvent, a step of adsorption separation using an adsorbent, and a step of sublimation purification.

[0192] The above recrystallization step may include a preliminary purification process for obtaining a compound represented by the above chemical formula 1 with a purity of 98% using a recrystallization solvent.

[0193] A polar solvent having a polarity index (PI) of 5.5 to 7.2 is preferably used as the recrystallization solvent, or a mixture of a polar solvent having a polarity index of 5.5 to 7.2 and a non-polar solvent having a polarity index of 2.0 to 4.7 may be used.

[0194] When using a mixture of a polar solvent and a non-polar solvent as a recrystallization solvent, the non-polar solvent may be used in a ratio of 15% (v / v) or less compared to the polar solvent.

[0195] In addition, as a recrystallization solvent, a single solvent of methylpyrrolidone (N-methylpyrrolidone: NMP) is preferably used; or a mixed polar solvent in which any one selected from the group consisting of methylpyrrolidone, dimethyl imidazolidinone (1,3-dimethyl-2-imidazolidinone), 2-pyrrolidone, dimethylformamide (N,N-dimethyl formamide), dimethyl acetamide, and dimethyl sulfoxide is mixed; or a single or mixed nonpolar solvent selected from the group consisting of toluene, dichloromethane (DCM), dichloroethane (DCE), tetrahydrofuran (THF), chloroform, ethyl acetate, and butanone, or a mixture of polar solvents and nonpolar solvents can be used.

[0196] The above preliminary purification process may include a step of dissolving the unrefined organic light-emitting material recovered from the deposition equipment in a polar solvent at 90°C to 120°C and then cooling it to 0°C to 5°C to precipitate crystals.

[0197] The above preliminary purification process may include a step of dissolving an unrefined organic light-emitting material recovered from a deposition device in a polar solvent at 90°C to 120°C, cooling to 35°C to 40°C, adding a non-polar solvent, and then cooling to 0°C to 5°C to precipitate a crystal.

[0198] The above preliminary purification process may include a step of dissolving the crude organic light-emitting material recovered from the deposition equipment in a non-polar solvent, concentrating the solvent, and precipitating crystals while removing the non-polar solvent.

[0199] The above preliminary purification process may include a step of first recrystallizing with a polar solvent and then recrystallizing again with a non-polar solvent.

[0200] In the adsorption separation step using the above adsorbent, activated carbon, silica gel, alumina or a known material for adsorption purposes can be used as the adsorbent.

[0201] Hereinafter, examples of synthesis of a compound represented by Chemical Formula 1 according to the present invention and examples of manufacturing an organic electric device will be described in detail with reference to examples, but the present invention is not limited thereto.

[0202] [Synthesis Example 1]

[0203] The compound represented by chemical formula 1 according to the present invention (Final Product) can be synthesized as in the following reaction scheme 1, but is not limited thereto.

[0204] <Reaction Scheme 1> (Hal 1 is Cl, Br or I)

[0205]

[0206] I. Synthesis example of Sub1

[0207] Sub1 of the above reaction scheme 1 can be synthesized by the following reaction scheme 2, but is not limited thereto.

[0208] <Reaction Formula 2>

[0209]

[0210] Compounds belonging to Sub1 may include, but are not limited to, the compounds below, and the FD-MS (Field Desorption-Mass Spectrometry) values ​​of the compounds below are as shown in Table 1.

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219]

[0220] 화합물FD-MS화합물FD-MSSub 1-1m / z=304.1(C 21 H 17 Cl=304.82)Sub 1-2m / z=380.13(C 27 H 21 Cl=380.92)Sub 1-3m / z=380.13(C 27 H 21 Cl=380.92)Sub 1-4m / z=380.13(C 27 H 21 Cl=380.92)Sub 1-5m / z=354.12(C 25 H 19 Cl=354.88)Sub 1-6m / z=354.12(C 25 H 19 Cl=354.88)Sub 1-7m / z=404.13(C 29 H 21 Cl=404.94)Sub 1-8m / z=456.16(C 33 H 25 Cl=457.01)Sub 1-9m / z=456.16(C 33 H 25 Cl=457.01)Sub 1-10m / z=456.16(C 33 H 25 Cl=457.01)Sub 1-11m / z=456.16(C 33 H 25 Cl=457.01)Sub 1-12m / z=456.16(C 33 H 25 Cl=457.01)Sub 1-13m / z=420.16(C 30 H 25 Cl=420.98)Sub 1-14m / z=420.16(C 30 H 25 Cl=420.98)Sub 1-15m / z=420.16(C 30 H25 Cl=420.98)Sub 1-16m / z=420.16(C 30 H 25 Cl=420.98)Sub 1-17m / z=309.13(C 21 H 12 D5Cl=309.85)Sub 1-18m / z=389.19(C 27 H 12 D9Cl=389.97)Sub 1-19m / z=476.22(C 34 H 21 D6Cl=477.08)Sub 1-20m / z=354.12(C 25 H 19 Cl=354.88)Sub 1-21m / z=310.14(C 21 H 11 D6Cl=310.85)Sub 1-22m / z=315.17(C 21 H6D 11 Cl=315.88)Sub 1-23m / z=380.13(C 27 H 21 Cl=380.92)Sub 1-24m / z=456.16(C 33 H 25 Cl=457.01)Sub 1-25m / z=380.13(C 27 H 21 Cl=380.92)Sub 1-26m / z=456.16(C 33 H 25 Cl=457.01)Sub 1-27m / z=532.2(C 39 H 29 Cl=533.11)Sub 1-28m / z=430.15(C 31 H 23 Cl=430.98)Sub 1-29m / z=380.13(C 27 H 21 Cl=380.92)Sub 1-30m / z=456.16(C 33 H 25 Cl=457.01)Sub 1-31m / z=496.2(C 36 H 29 Cl=497.08)Sub 1-32m / z=456.16(C 33 H 25Cl=457.01)Sub 1-33m / z=385.16(C 27 H 16 D5Cl=385.95)Sub 1-34m / z=465.22(C 33 H 16 D9Cl=466.07)Sub 1-35m / z=385.16(C 27 H 16 D5Cl=385.95)Sub 1-36m / z=465.22(C 33 H 16 D9Cl=466.07)Sub 1-37m / z=465.22(C 33 H 16 D9Cl=466.07)Sub 1-38m / z=430.15(C 31 H 23 Cl=430.98)Sub 1-39m / z=430.15(C 31 H 23 Cl=430.98)Sub 1-40m / z=430.15(C 31 H 23 Cl=430.98)Sub 1-41m / z=386.17(C 27 H 15 D6Cl=386.95)Sub 1-42m / z=386.17(C 27 H 15 D6Cl=386.95)Sub 1-43m / z=391.2(C 27 H 10 D 11 Cl=391.98)

[0221] II. Synthesis example of Sub2

[0222] Sub2 of the above reaction scheme 1 can be synthesized according to the following reaction scheme 3, but is not limited thereto.

[0223] <Reaction Scheme 3> (Hal 2 is Br or Cl)

[0224]

[0225] Compounds belonging to Sub2 may include, but are not limited to, the compounds below, and the FD-MS values ​​of the compounds below are as shown in Table 2.

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250] 화합물FD-MS화합물FD-MSSub 2-1m / z=443.26(C 33 H 33 N=443.63)Sub 2-2m / z=455.26(C 34 H 33 N=455.65)Sub 2-3m / z=455.26(C 34 H 33 N=455.65)Sub 2-4m / z=443.26(C 33 H 33 N=443.63)Sub 2-5m / z=455.26(C 34 H 33 N=455.65)Sub 2-6m / z=455.26(C 34 H 33 N=455.65)Sub 2-7m / z=443.26(C 33 H 33 N=443.63)Sub 2-8m / z=531.29(C 40 H 37 N=531.74)Sub 2-9m / z=531.29(C 40 H 37 N=531.74)Sub 2-10m / z=493.24(C 36 H 31 NO=493.65)Sub 2-11m / z=505.24(C 37 H 31 NO=505.66)Sub 2-12m / z=505.24(C 37 H 31 NO=505.66)Sub 2-13m / z=493.24(C 36 H 31 NO=493.65)Sub 2-14m / z=521.22(C 37 H 31 NS=521.72)Sub 2-15m / z=521.22(C 37 H 31 NS=521.72)Sub 2-16m / z=549.25(C 39 H 35 NS=549.78)Sub 2-17m / z=535.2(C 37 H 29 NOS=535.71)Sub 2-18m / z=610.24(C 43 H34 N2S=610.82)Sub 2-19Mass:733.35C54H43N3733.96)Sub 2-20m / z=619.32(C 47 H 41 N=619.85)Sub 2-21m / z=833.37(C 63 H 47 NO=834.08)Sub 2-22m / z=457.24(C 33 H 31 NO=457.62)Sub 2-23m / z=535.2(C 37 H 29 NOS=535.71)Sub 2-24m / z=727.29(C 52 H 41 NOS=727.97)Sub 2-25m / z=866.37(C 63 H 50 N2S=867.17)Sub 2-26m / z=717.4(C 53 H 51 NO=718)Sub 2-27m / z=587.36(C 44 H 45 N=587.85)Sub 2-28m / z=615.39(C 46 H 49 N=615.91)Sub 2-29m / z=483.29(C 36 H 37 N=483.7)Sub 2-30m / z=461.3(C 34 H 27 D6N=461.68)Sub 2-31m / z=537.33(C 40 H 31 D6N=537.78)Sub 2-32m / z=509.22(C 36 H 31 NS=509.71)Sub 2-33m / z=429.25(C 32 H 31 N=429.61)Sub 2-34m / z=429.25(C 32 H 31 N=429.61)Sub 2-35m / z=417.25(C 31 H 31 N=417.6)Sub 2-36m / z=511.31(C 38 H29 D6N=511.74)Sub 2-37m / z=531.29(C 40 H 37 N=531.74)Sub 2-38m / z=531.29(C 40 H 37 N=531.74)Sub 2-39m / z=526.34(C 39 H 30 D7N=526.77)Sub 2-40m / z=537.33(C 40 H 31 D6N=537.78)Sub 2-41m / z=569.24(C 41 H 31 NO2=569.7)Sub 2-42m / z=641.18(C 43 H 31 NOS2=641.85)Sub 2-43m / z=483.29(C 36 H 37 N=483.7)Sub 2-44m / z=429.25(C 32 H 31 N=429.61)Sub 2-45m / z=429.21(C 31 H 27 NO=429.56)Sub 2-46m / z=373.27(C 27 H 23 D6N=373.57)Sub 2-47m / z=392.31(C 28 H 16 D 13 N=392.63)Sub 2-48m / z=463.31(C 34 H 25 D8N=463.69)Sub 2-49m / z=367.23(C 27 H 29 N=367.54)Sub 2-50m / z=379.23(C 28 H 29 N=379.55)Sub 2-51m / z=379.23(C 28 H 29 N=379.55)Sub 2-52m / z=443.26(C 33 H 33 N=443.63)Sub 2-53m / z=455.26(C 34 H 33N=455.65)Sub 2-54m / z=455.26(C 34 H 33 N=455.65)Sub 2-55m / z=443.26(C 33 H 33 N=443.63)Sub 2-56m / z=531.29(C 40 H 37 N=531.74)Sub 2-57m / z=493.24(C 36 H 31 NO=493.65)Sub 2-58m / z=485.27(C 35 H 35 NO=485.67)Sub 2-59m / z=429.21(C 31 H 27 NO=429.56)Sub 2-60m / z=493.24(C 36 H 31 NO=493.65)Sub 2-61m / z=521.22(C 37 H 31 NS=521.72)Sub 2-62m / z=521.22(C 37 H 31 NS=521.72)Sub 2-63m / z=509.22(C 36 H 31 NS=509.71)Sub 2-64m / z=521.22(C 37 H 31 NS=521.72)Sub 2-65m / z=580.29(C 43 H 36 N2=580.78)Sub 2-66m / z=568.29(C 42 H 36 N2=568.76)Sub 2-67m / z=655.32(C 50 H 41 N=655.88)Sub 2-68m / z=745.33(C 56 H 43 NO=745.97)Sub 2-69m / z=535.2(C 37 H 29 NOS=535.71)Sub 2-70m / z=711.31(C 52 H 41 NO2=711.91)Sub 2-71m / z=655.24(C45 H 37 NS2=655.92)Sub 2-72m / z=455.26(C 34 H 33 N=455.65)Sub 2-73m / z=643.42(C 48 H 53 N=643.96)Sub 2-74m / z=575.36(C 43 H 45 N=575.84)Sub 2-75m / z=497.31(C 37 H 39 N=497.73)Sub 2-76m / z=537.33(C 40 H 31 D6N=537.78)Sub 2-77m / z=537.33(C 40 H 31 D6N=537.78)Sub 2-78m / z=549.25(C 39 H 35 NS=549.78)Sub 2-79m / z=479.26(C 36 H 33 N=479.67)Sub 2-80m / z=479.26(C 36 H 33 N=479.67)Sub 2-81m / z=455.26(C 34 H 33 N=455.65)Sub 2-82m / z=511.31(C 38 H 29 D6N=511.74)Sub 2-83m / z=455.26(C 34 H 33 N=455.65)Sub 2-84m / z=587.36(C 44 H 45 N=587.85)Sub 2-85m / z=450.31(C 33 H 26 D7N=450.68)Sub 2-86m / z=593.39(C 44 H 39 D6N=593.89)Sub 2-87m / z=595.25(C 43 H 33 NO2=595.74)Sub 2-88m / z=641.18(C 43 H 31NOS2=641.85)Sub 2-89m / z=497.31(C 37 H 39 N=497.73)Sub 2-90m / z=505.28(C 38 H 35 N=505.71)Sub 2-91m / z=485.27(C 35 H 35 NO=485.67)Sub 2-92m / z=373.27(C 27 H 23 D6N=373.57)Sub 2-93m / z=468.34(C 34 H 20 D 13 N=468.72)

[0251] III. Synthesis examples of final compounds

[0252] 1. P-1 synthesis example

[0253]

[0254] 1) Synthesis of Sub1-1

[0255] 3-Bromo-2-chloro-9,9-dimethyl-9H-fluorene (50.0 g, 162.5 mmol) was dissolved in THF (542 mL), and phenylboronic acid (21.8 g, 178.8 mmol), NaOH (19.5 g, 487.6 mmol), Pd(PPh3)4 (9.39 g, 8.13 mmol), and water (181 mL) were added. The mixture was refluxed and stirred at 80 °C. Upon completion of the reaction, the mixture was extracted with CH2Cl2 and water, and the organic layer was dried over MgSO4 and concentrated. The concentrate was then purified by silica gel column chromatography and recrystallized to obtain 39.6 g of the product (yield: 80%).

[0256] 2) Synthesis of Sub2-1

[0257] 4-Bromo-4'-cyclohexyl-1,1'-biphenyl (50.0 g, 158.6 mmol) was dissolved in toluene (529 mL), and 9,9-dimethyl-9H-fluoren-2-amine (39.8 g, 209.29 mmol), Pd2(dba)3 (4.36 g, 4.76 mmol), P(t-Bu)3 (1.93 g, 9.52 mmol), and NaOt-Bu (30.5 g, 317.2 mmol) were added and stirred at 60 °C. Upon completion of the reaction, the mixture was extracted with CH2Cl2 and water, and the organic layer was dried over MgSO4 and concentrated. The concentrate was then separated through a silica gel column and recrystallized to obtain 58.4 g of the product (yield 83%).

[0258] 3) Synthesis of P-1

[0259] Sub1-1 (30.0 g, 98.4 mmol) was dissolved in toluene (492 mL), and Sub2-1 (43.7 g, 98.4 mmol), Pd2(dba)3 (2.70 g, 2.95 mmol), P(t-Bu)3 (1.19 g, 5.91 mmol), and NaOt-Bu (28.4 g, 295.3 mmol) were added, and the mixture was refluxed at 125 °C. Upon completion of the reaction, the mixture was extracted with CH2Cl2 and water, and the organic layer was dried over MgSO4 and concentrated. The concentrate was then separated through a silica gel column and recrystallized to obtain 54 g of the product (yield 77%).

[0260] 2. P-11 Synthetic Example

[0261]

[0262] 1) Synthesis of Sub1-11

[0263] 3-bromo-2-chloro-9,9-dimethyl-9H-fluorene (50.0 g, 162.5 mmol) was dissolved in THF (542 mL), and [1,1':4',1"-terphenyl]-2-ylboronic acid (49 g, 178.8 mmol), NaOH (19.5 g, 487.6 mmol), Pd(PPh3)4 (9.39 g, 8.13 mmol), and water (181 mL) were added. The reaction was carried out in the same manner as in the synthesis example of Sub1-1, to obtain 60.2 g of the product (yield: 81%).

[0264] 2) Synthesis of Sub2-11

[0265] 2-(5'-bromo-[1,1':3',1"-terphenyl]-4-yl)bicyclo[2.2.1]heptane (50.0 g, 124.0 mmol) was dissolved in toluene (529 mL), and dibenzo[b,d]furan-2-amine (27.3 g, 148.8 mmol), Pd2(dba)3 (3.41 g, 3.72 mmol), P(t-Bu)3 (1.50 g, 7.44 mmol), and NaOt-Bu (23.8 g, 247.9 mmol) were added, and the same method as the synthesis example of Sub2-1 was followed to obtain 47.6 g of the product (yield 76%).

[0266] 3) Synthesis of P-11

[0267] After dissolving Sub1-11 (30.0 g, 65.6 mmol) in toluene (328 mL), Sub2-11 (33.2 g, 65.6 mmol), Pd2(dba)3 (1.80 g, 1.97 mmol), P(t-Bu)3 (0.80 g, 3.94 mmol), and NaOt-Bu (18.9 g, 196.9 mmol) were added, and the same method as the synthesis example of P-1 was followed to obtain 45.6 g of the product (yield 75%).

[0268] 3. P-16 synthetic example

[0269]

[0270] 1) Synthesis of Sub1-3

[0271] 3-bromo-2-chloro-9,9-dimethyl-9H-fluorene (50.0 g, 162.5 mmol) was dissolved in THF (542 mL), and [1,1'-biphenyl]-3-ylboronic acid (35.4 g, 178.8 mmol), NaOH (19.5 g, 487.6 mmol), Pd(PPh3)4 (9.39 g, 8.13 mmol), and water (181 mL) were added. The same method as the synthesis example of Sub1-1 was followed to obtain 46.4 g of the product (yield: 75%).

[0272] 2) Synthesis of Sub2-16

[0273] 2-bromo-5-(4-cyclohexylphenyl)-9,9-dimethyl-9H-fluorene (50.0 g, 115.9 mmol) was dissolved in toluene (386 mL), and then dibenzo[b,d]thiophen-3-amine (27.7 g, 139.1 mmol), Pd2(dba)3 (3.48 g, 3.48 mmol), P(t-Bu)3 (1.41 g, 6.95 mmol), and NaOt-Bu (22.3 g, 231.8 mmol) were added, and the same method as the synthesis example of Sub2-1 was followed to obtain 45.2 g of the product (yield 71%).

[0274] 3) Synthesis of P-16

[0275] After dissolving Sub1-3 (20.0 g, 65.0 mmol) in toluene (325 mL), Sub2-16 (35.7 g, 65.0 mmol), Pd2(dba)3 (1.79 g, 1.95 mmol), P(t-Bu)3 (0.79 g, 3.90 mmol), and NaOt-Bu (18.7 g, 195.1 mmol) were added, and the reaction was carried out in the same manner as in the synthesis example of P-1, to obtain 42.4 g of the product (yield 73%).

[0276] 4. P-22 synthetic example

[0277]

[0278] 1) Synthesis of Sub1-14

[0279] 3-bromo-2-chloro-9,9-dimethyl-9H-fluorene (50.0 g, 162.5 mmol) was dissolved in THF (542 mL), and (9,9-dimethyl-9H-fluoren-3-yl)boronic acid (42.6 g, 178.8 mmol), NaOH (19.5 g, 487.6 mmol), Pd(PPh3)4 (9.39 g, 8.13 mmol), and water (181 mL) were added. The reaction was carried out in the same manner as in the synthesis example of Sub1-1, to obtain 56.1 g of the product (yield: 82%).

[0280] 2) Synthesis of Sub2-22

[0281] After dissolving 7-bromo-1-cyclohexyldibenzo[b,d]furan (50.0 g, 151.9 mmol) in toluene (506 mL), 9,9-dimethyl-9H-fluoren-2-amine (38.1 g, 182.2 mmol), Pd2(dba)3 (4.17 g, 4.56 mmol), P(t-Bu)3 (1.84 g, 9.11 mmol), and NaOt-Bu (29.2 g, 303.7 mmol) were added, and the same method as the synthesis example of Sub2-1 was followed to obtain 52.8 g of the product (yield 76%).

[0282] 3) Synthesis of P-22

[0283] After dissolving Sub1-14 (30.0 g, 71.3 mmol) in toluene (380 mL), Sub2-22 (32.6 g, 71.3 mmol), Pd2(dba)3 (1.96 g, 2.14 mmol), P(t-Bu)3 (0.87 g, 2.14 mmol), and NaOt-Bu (20.5 g, 213.8 mmol) were added, and the same method as the synthesis example of P-1 was followed to obtain 47.4 g of the product (yield 79%).

[0284] 5. P-30 synthetic example

[0285]

[0286] 1) Synthesis of Sub1-17

[0287] 3-bromo-2-chloro-9,9-dimethyl-9H-fluorene (50.0 g, 162.5 mmol) was dissolved in THF (542 mL), and (phenyl-d5)boronic acid (22.7 g, 178.8 mmol), NaOH (19.5 g, 487.6 mmol), Pd(PPh3)4 (9.39 g, 8.13 mmol), and water (181 mL) were added. The reaction was carried out in the same manner as in the synthesis example of Sub1-1, to obtain 41.8 g of the product (yield: 83%).

[0288] 2) Synthesis of Sub2-30

[0289] 2-(2'-bromo-[1,1'-biphenyl]-4-yl)bicyclo[2.2.1]heptane (50.0 g, 152.8 mmol) was dissolved in toluene (509 mL), and 9,9-bis(methyl-d3)-9H-fluoren-2-amine (39.5 g, 183.3 mmol), Pd2(dba)3 (4.20 g, 4.58 mmol), P(t-Bu)3 (1.85 g, 9.17 mmol), and NaOt-Bu (29.4 g, 305.6 mmol) were added, and the same method as the synthesis example of Sub2-1 was followed to obtain 55.0 g of the product (yield 78%).

[0290] 3) Synthesis of P-30

[0291] After dissolving Sub1-17 (30.0 g, 96.8 mmol) in toluene (484 mL), Sub2-30 (44.7 g, 96.8 mmol), Pd2(dba)3 (2.66 g, 2.90 mmol), P(t-Bu)3 (1.18 g, 5.81 mmol), and NaOt-Bu (27.9 g, 290.5 mmol) were added, and the same method as the synthesis example of P-1 was followed to obtain 56.9 g of the product (yield 80%).

[0292] 6. P-44 synthetic example

[0293]

[0294] 1) Synthesis of Sub1-20

[0295] 3-bromo-2-chloro-11,11-dimethyl-11H-benzo[b]fluorene (50.0 g, 139.8 mmol) was dissolved in THF (466 mL), and phenylboronic acid (18.7 g, 153.8 mmol), NaOH (16.8 g, 419.4 mmol), Pd(PPh3)4 (8.08 g, 6.99 mmol), and water (155 mL) were added. The reaction was carried out in the same manner as in the synthesis example of Sub1-1, to obtain 42.2 g of the product (yield: 85%).

[0296] 2) Synthesis of Sub2-44

[0297] After dissolving 2-(2-bromophenyl)bicyclo[2.2.1]heptane (50.0 g, 199.1 mmol) in toluene (664 mL), 11,11-dimethyl-11H-benzo[b]fluoren-2-amine (62.0 g, 238.9 mmol), Pd2(dba)3 (5.47 g, 5.97 mmol), P(t-Bu)3 (2.42 g, 11.94 mmol), and NaOt-Bu (38.3 g, 398.1 mmol) were added, and the same method as the synthesis example of Sub2-1 was followed to obtain 65.0 g of the product (yield 76%).

[0298] 3) Synthesis of P-44

[0299] After dissolving Sub1-20 (30.0 g, 84.5 mmol) in toluene (423 mL), Sub2-44 (36.3 g, 84.5 mmol), Pd2(dba)3 (2.32 g, 2.54 mmol), P(t-Bu)3 (1.03 g, 5.07 mmol), and NaOt-Bu (24.4 g, 253.6 mmol) were added, and the same method as the synthesis example of P-1 was followed to obtain 51.2 g of the product (yield 81%).

[0300] 7. P-49 synthetic example

[0301]

[0302] 1) Synthesis of Sub1-23

[0303] 3-bromo-2-(4-chlorophenyl)-9,9-dimethyl-9H-fluorene (50.0 g, 130.3 mmol) was dissolved in THF (434 mL), and phenylboronic acid (17.5 g, 143.3 mmol), NaOH (15.6 g, 390.9 mmol), Pd(PPh3)4 (7.53 g, 6.52 mmol), and water (145 mL) were added. The same method as the synthesis example of Sub1-1 was followed to obtain 41.2 g of the product (yield: 83%).

[0304] 2) Synthesis of Sub2-49

[0305] After dissolving 1-bromo-4-cyclohexylbenzene (50.0 g, 209.1 mmol) in toluene (697 mL), 9,9-dimethyl-9H-fluoren-2-amine (52.5 g, 250.9 mmol), Pd2(dba)3 (5.74 g, 6.27 mmol), P(t-Bu)3 (2.54 g, 12.54 mmol), and NaOt-Bu (40.2 g, 418.1 mmol) were added, and the same method as the synthesis example of Sub2-1 was followed to obtain 62.2 g of the product (yield 81%).

[0306] 3) Synthesis of P-49

[0307] After dissolving Sub1-23 (30.0 g, 78.8 mmol) in toluene (394 mL), Sub2-49 (28.9 g, 78.8 mmol), Pd2(dba)3 (2.16 g, 2.36 mmol), P(t-Bu)3 (0.96 g, 4.73 mmol), and NaOt-Bu (22.7 g, 236.3 mmol) were added, and the reaction was carried out in the same manner as in the synthesis example of P-1, to obtain 46.0 g of the product (yield 82%).

[0308] 8. P-74 synthetic example

[0309]

[0310] 1) Synthesis of Sub1-32

[0311] 3-bromo-2-(3-chlorophenyl)-9,9-dimethyl-9H-fluorene (50.0 g, 130.3 mmol) was dissolved in THF (434 mL), and [1,1'-biphenyl]-3-ylboronic acid (28.4 g, 198.03 mmol), NaOH (15.6 g, 390.9 mmol), Pd(PPh3)4 (7.53 g, 6.52 mmol), and water (145 mL) were added. The reaction was carried out in the same manner as in the synthesis example of Sub1-1, to obtain 44.7 g of the product (yield: 75%).

[0312] 2) Synthesis of Sub2-72

[0313] 2-(3-bromo-[1,1'-biphenyl]-4-yl)bicyclo[2.2.1]heptane (50.0 g, 152.8 mmol) was dissolved in toluene (509 mL), and 9,9-dimethyl-9H-fluoren-2-amine (38.4 g, 183.3 mmol), Pd2(dba)3 (4.20 g, 4.58 mmol), P(t-Bu)3 (1.85 g, 9.17 mmol), and NaOt-Bu (29.4 g, 305.6 mmol) were added, and the same method as the synthesis example of Sub2-1 was followed to obtain 57.8 g of the product (yield 83%).

[0314] 3) Synthesis of P-74

[0315] After dissolving Sub1-32 (30.0 g, 78.2 mmol) in toluene (391 mL), Sub2-72 (35.6 g, 78.2 mmol), Pd2(dba)3 (2.15 g, 2.35 mmol), P(t-Bu)3 (0.95 g, 4.69 mmol), and NaOt-Bu (22.5 g, 234.6 mmol) were added, and the reaction was carried out in the same manner as in the synthesis example of P-1, to obtain 48.6 g of the product (yield 71%).

[0316] 9. P-86 synthetic example

[0317]

[0318] 1) Synthesis of Sub1-37

[0319] 3-bromo-2-(4-chlorophenyl)-9,9-dimethyl-9H-fluorene (50.0 g, 130.3 mmol) was dissolved in THF (434 mL), and ([1,1'-biphenyl]-4-yl-d9)boronic acid (29.7 g, 143.3 mmol), NaOH (15.6 g, 390.9 mmol), Pd(PPh3)4 (7.53 g, 6.52 mmol), and water (145 mL) were added. The reaction was carried out in the same manner as in the synthesis example of Sub1-1, to obtain 46.8 g of the product (yield: 77%).

[0320] 2) Synthesis of Sub2-84

[0321] 1-(3'-bromo-[1,1'-biphenyl]-4-yl)bicyclo[2.2.1]heptane (50.0 g, 152.8 mmol) was dissolved in toluene (509 mL), and 5-(4-(tert-butyl)phenyl)-9,9-dimethyl-9H-fluoren-2-amine (62.6 g, 183.3 mmol), Pd2(dba)3 (4.20 g, 4.58 mmol), P(t-Bu)3 (1.85 g, 9.17 mmol), NaOt-Bu (29.4 g, 305.6 mmol) were added, and the same method as the synthesis example of Sub2-1 was followed to obtain 67.4 g of the product (yield 75%).

[0322] 3) Synthesis of P-86

[0323] After dissolving Sub1-37 (30.0 g, 64.4 mmol) in toluene (322 mL), Sub2-84 (37.8 g, 64.4 mmol), Pd2(dba)3 (1.77 g, 1.93 mmol), P(t-Bu)3 (0.78 g, 3.86 mmol), and NaOt-Bu (18.6 g, 193.1 mmol) were added, and the same method as the synthesis example of P-1 was followed to obtain 50.4 g of the product (yield 77%).

[0324] The FD-MS values ​​of compounds P-1 to P-100 of the present invention manufactured according to the above synthetic examples are as shown in Table 3 below.

[0325] Compound FD-MS Compound FD-MSP-1 m / z = 711.39 (C 54 H 49 N=711.99)P-2m / z=799.42(C 61 H 53 N=800.1)P-3m / z=799.42(C 61 H 53 N=800.1)P-4m / z=787.42(C 60 H 53 N=788.09)P-5m / z=773.4(C 59 H 51N=774.06)P-6m / z=773.4(C 59 H 51 N=774.06)P-7m / z=811.42(C 62 H 53 N=812.11)P-8m / z=811.42(C 62 H 53 N=812.11)P-9m / z=951.48(C 73 H 61 N=952.3)P-10m / z=913.43(C 69 H 55 NO=914.2)P-11m / z=925.43(C 70 H 55 NO=926.22)P-12m / z=925.43(C 70 H 55 NO=926.22)P-13m / z=837.4(C 63 H 51 NO=838.11)P-14m / z=865.37(C 64 H 51 NS=866.18)P-15m / z=867.39(C 64 H 53 NS=868.2)P-16m / z=893.41(C 66 H 55 NS=894.23)P-17m / z=3861.73(C 288 H 226 N7OS 23 =3865.14)P-18m / z=954.4(C 70 H 54 N2S=955.28)P-19m / z=1077.5(C 81 H 63 N3=1078.42)P-20m / z=963.48(C 74 H 61 N=964.31)P-21m / z=1217.55(C 93 H 71 NO=1218.6)P-22m / z=841.43(C 63 H 55 NO=842.14)P-23m / z=919.38(C 67 H 53 NOS=920.23)P-24m / z=1111.48(C 82 H65 NOS=1112.49)P-25m / z=1210.53(C 90 H 70 N2S=1211.62)P-26m / z=1061.55(C 80 H 71 NO=1062.45)P-27m / z=931.51(C 71 H 65 N=932.31)P-28m / z=959.54(C 73 H 69 N=960.36)P-29m / z=756.45(C 57 H 48 D5N=757.09)P-30m / z=734.46(C 55 H 38 D 11 N=735.07)P-31m / z=810.49(C 61 H 42 D 11 N=811.17)P-32m / z=777.34(C 57 H 47 NS=778.07)P-33m / z=782.46(C 59 H 42 D9N=783.12)P-34m / z=697.37(C 53 H 47 N=697.97)P-35m / z=685.37(C 52 H 47 N=685.96)P-36m / z=779.44(C 59 H 45 D6N=780.1)P-37m / z=799.42(C 61 H 53 N=800.1)P-38m / z=884.51(C 67 H 48 D9N=885.25)P-39m / z=794.46(C 60 H 46 D7N=795.13)P-40m / z=805.46(C 61 H 47 D6N=806.14)P-41m / z=837.36(C 62 H 47 NO2=838.06)P-42m / z=909.31(C 64 H 47NOS2=910.21)P-43m / z=923.53(C 70 H 57 D6N=924.32)P-44m / z=747.39(C 57 H 49 N=748.03)P-45m / z=832.44(C 62 H 40 D9NO=833.13)P-46m / z=647.43(C 48 H 33 D 12 N=647.97)P-47m / z=666.47(C 49 H 26 D 19 N=667.02)P-48m / z=742.51(C 55 H 30 D 19 N=743.12)P-49m / z=711.39(C 54 H 49 N=711.99)P-50m / z=799.42(C 61 H 53 N=800.1)P-51m / z=723.39(C 55 H 49 N=724)P-52m / z=863.45(C 66 H 57 N=864.19)P-53m / z=799.42(C 61 H 53 N=800.1)P-54m / z=951.48(C 73 H 61 N=952.3)P-55m / z=837.43(C 64 H 55 N=838.15)P-56m / z=875.45(C 67 H 57 N=876.2)P-57m / z=875.45(C 67 H 57 N=876.2)P-58m / z=837.4(C 63 H 51 NO=838.11)P-59m / z=829.43(C 62 H 55 NO=830.13)P-60m / z=773.37(C 58 H 47NO=774.02)P-61m / z=837.4(C 63 H 51 NO=838.11)P-62m / z=865.37(C 64 H 51 NS=866.18)P-63m / z=865.37(C 64 H 51 NS=866.18)P-64m / z=853.37(C 63 H 51 NS=854.17)P-65m / z=924.44(C 70 H 56 N2=925.23)P-66m / z=865.37(C 64 H 51 NS=866.18)P-67m / z=988.48(C 75 H 60 N2=989.32)P-68m / z=999.48(C 77 H 61 N=1000.34)P-69m / z=1089.49(C 83 H 63 NO=1090.42)P-70m / z=877.43(C 66 H 55 NO=878.17)P-71m / z=879.35(C 64 H 49 NOS=880.16)P-72m / z=1171.53(C 88 H 69 NO2=1172.52)P-73m / z=999.39(C 72 H 57 NS2=1000.37)P-74m / z=875.45(C 67 H 57 N=876.2)P-75m / z=987.57(C 75 H 73 N=988.42)P-76m / z=919.51(C 70 H 65 N=920.3)P-77m / z=846.5(C 64 H 54 D5N=847.21)P-78m / z=966.57(C 73 H 46 D 15 N=967.39)P-79m / z=886.52(C67 H 46 D 11 N=887.27)P-80m / z=898.44(C 66 H 50 D5NS=899.26)P-81m / z=823.42(C 63 H 53 N=824.12)P-82m / z=823.42(C 63 H 53 N=824.12)P-83m / z=884.51(C 67 H 48 D9N=885.25)P-84m / z=855.47(C 65 H 49 D6N=856.2)P-85m / z=799.42(C 61 H 53 N=800.1)P-86m / z=1016.6(C 77 H 60 D9N=1017.46)P-87m / z=794.46(C 60 H 46 D7N=795.13)P-88m / z=937.55(C 71 H 59 D6N=938.34)P-89m / z=939.41(C 70 H 53 NO2=940.2)P-90m / z=985.34(C 70 H 51 NOS2=986.3)P-91m / z=891.48(C 68 H 61 N=892.24)P-92m / z=899.45(C 69 H 57 N=900.22)P-93m / z=879.44(C 66 H 57 NO=880.19)P-94m / z=723.46(C 54 H 37 D 12 N=724.07)P-95m / z=818.54(C 61 H 34 D 19 N=819.22)P-96m / z=818.54(C 61 H 34 D 19N=819.22)P-97m / z=659.32(C 49 H 41 NO=659.87)P-98m / z=793.46(C 60 H 59 N=794.14)P-99m / z=635.36(C 48 H 45 N=635.90)P-100m / z=889.61(C 67 H 45 D 18 N=900.36)

[0326] Although the above has been described with respect to exemplary synthetic examples of the present invention represented by Chemical Formula 1, 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 example is combined with another substituent defined in Chemical Formula 1.

[0327] Manufacturing and evaluation of organic electronic devices

[0328] [Example 1] Red organic light-emitting device (luminescent auxiliary layer)

[0329] N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine (hereinafter referred to as compound A) and 4,4',4"-((1E,1'E,1"E)-cyclopropane-1,2,3-triylidenetris(cyanomethaneylylidene))tris(2,3,5,6-tetrafluorobenzonitrile) (hereinafter referred to as compound B) are vacuum-deposited on an ITO layer (anode) formed on a glass substrate to form a hole injection layer having a thickness of 10 nm. At this time, compound B is doped so that the weight ratio of compound A and compound B is 98:2.

[0330] Afterwards, compound A is vacuum-deposited on the hole injection layer to form a hole transport layer with a thickness of 110 nm.

[0331] Thereafter, the compound P-1 of the present invention is vacuum-deposited on the hole transport layer to form a light-emitting auxiliary layer having a thickness of 10 nm.

[0332] Thereafter, a host 14-(4-phenylquinazolin-2-yl)-14H-benzo[c]benzo[4,5]thieno[2,3-a]carbazole and a dopant bis-(1-phenylisoquinolyl)iridium(Ⅲ)acetylacetonate (hereinafter abbreviated as '(piq)2Ir(acac)') are vacuum-deposited on the light-emitting auxiliary layer to form a light-emitting layer with a thickness of 30 nm. At this time, the dopant is doped so that the weight ratio of the host and the dopant becomes 95:5.

[0333] Afterwards, 2-(4'-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine is vacuum-deposited on the light-emitting layer to form a hole-blocking layer with a thickness of 10 nm.

[0334] Afterwards, a mixture of 2,7-bis(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphthalene and (8-quinolinolato)lithium in a weight ratio of 5:5 is vacuum-deposited on the hole-blocking layer to form an electron transport layer with a thickness of 30 nm.

[0335] Afterwards, a compound (8-quinolinolato)lithium is vacuum-deposited on the electron transport layer to form an electron injection layer with a thickness of 0.2 nm, and then Al is deposited to form a cathode with a thickness of 150 nm.

[0336] [Example 2] to [Example 20]

[0337] 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 P-1 of the present invention as a light-emitting auxiliary layer material.

[0338] [Comparative Example 1] to [Comparative Example 3]

[0339] An organic light-emitting device was manufactured in the same manner as Example 1, except that one of the following comparative compounds A to C was used instead of the compound P-1 of the present invention as the light-emitting auxiliary layer material.

[0340] Comparative Compound A Comparative Compound B Comparative Compound C

[0341]

[0342] The organic electroluminescence devices manufactured by Examples 1 to 20 and Comparative Examples 1 to 3 of the present invention were subjected to a forward bias DC voltage, and the electroluminescence (EL) characteristics were measured using PR-650 from Photoresearch, and 2500 cd / m 2 T95 was measured using a life-span measuring device manufactured by Maxscience at a reference luminance. The measurement results are shown in Table 4 below.

[0343] These measuring devices are unaffected by daily variations in deposition rate, vacuum quality, or other parameters, and can evaluate new performance compared to reference compounds under identical conditions. Since each batch contains four identically prepared OLEDs containing the reference compound, and the performance of a total of 12 OLEDs is evaluated in three batches, the experimental results obtained in this manner are statistically significant.

[0344] Compound driving voltage (V) current (mA / cm) 2 ) Luminance (cd / m 2 ) Efficiency (cd / A) T (95) Comparative Example 1 Comparative Compound A 5.5 16.9 2500.0 14.8 8 1.1 Comparative Example 2 Comparative Compound B 5.2 13.2 2500.0 18.9 9 1.6 Comparative Example 3 Comparative Compound C 5.1 14.3 2500.0 17.5 8 9.4 Example 1 P-14.26 52500.0 38.4 123.7 Example 2 P-64.16 82500.0 36.6 124.8 Example 3 P-114.57 42500.0 34.0 117.0 Example 4 P-234.57 42500.0 33.8 117.8 Example 5 P-274.26 7 250 0.037.1127.6 Example 6P-364.26.72500.037.5121.1 Example 7P-414.47.92500.031.8112.9 Example 8P-444.36.42500.039.3129.1 Example 9P-494.17.02500.035.9122.5 Example 10P-524.36.72500.037.1 121.5 Example 11P-584.57.82500.032.0114.4 Example 12P-634.47.42500.033.8120.8 Example 13P-804.58.12500.030.9110.5 Example 14P-814.27.12500.035.4123.0 Example 15P-904.47.82500.032.2111 .7 Example 16P-944.26.62500.037.9129.3 Example 17P-974.48.22500.030.6117.5 Example 18P-984.26.62500.037.6128.9 Example 19P-994.16.32500.039.6126.8 Example 20P-1004.16.72500.037.5123.4

[0345] From the above Table 4, it can be seen that when the compound of the present invention is used as a light-emitting auxiliary layer material, the driving voltage of the organic light-emitting device is significantly lowered and the efficiency and lifespan are significantly improved compared to when one of the comparative compounds A to D (Comparative Examples 1 to 3) is used. First, the structural differences between the compound of the present invention and the comparative compound A and the influence of the difference in rearrangement energy resulting therefrom on the device characteristics will be described.

[0346] Comparative compound A is similar to the compound of the present invention in that an amino group is bonded to the fluorene 2-position, but is different in that the substituents at the fluorene 9-position and 9'-position are phenyl groups, not alkyl groups, and that the fluorene 3-position is substituted with a heterocyclic group, not an aryl group.

[0347] In order to examine the influence of these structural differences on the rearrangement energy of the compounds, the rearrangement energy of the comparative compound A and the compound P-97 of the present invention having a similar structure was measured using the DFT method (B3LYP / 6-31g(D)) of the Gaussian program. The measurement results are as shown in Table 5 below, and the RE value is RE hole Indicates a value.

[0348] Compound HOMO (eV) Reorganization Energy (RE) Comparative Compound A-4.7600.226P-97-4.8680.193

[0349] From the above Table 5, it can be seen that the RE value of the compound P-97 of the present invention, which has a structure similar to that of the comparative compound A, is smaller. Therefore, when the compound of the present invention with a small RE value is used as a light-emitting auxiliary layer material, it has higher hole mobility and faster HOD (Hole on Device) than when the comparative compound A is used, so that hole movement and hole injection are significantly superior, and as a result, the charge balance in the light-emitting layer is maximized to reduce the driving voltage, so that the driving voltage and efficiency of the device are significantly improved. Next, the structural differences between the compound of the present invention and the comparative compound B and the influence of the difference in T1 energy level caused by this on the device characteristics will be described.

[0350] Comparative compound B is similar to the compound of the present invention in that one of the substituents of the amine is substituted with an aliphatic ring group, but Ar of the present invention is substituted at the 3-position of fluorene. a It differs in that there is no corresponding substituent.

[0351] In order to examine the influence of these structural differences on the T1 energy level of the compounds, the T1 energy levels of comparative compound B and compound P-98 of the present invention having a similar structure were measured using the DFT method (B3LYP / 6-31g(D)) of the Gaussian program. The measurement results are shown in Table 6 below.

[0352] Compound T1 (eV) Comparative compound B2.597P-982.645

[0353] From the above Table 6, it can be seen that the T1 value of the compound of the present invention is much higher than that of the comparative compound B. Therefore, when the compound of the present invention having a high T1 value is used as a light-emitting auxiliary layer material, it appears that triplet excitons coming from the light-emitting layer can be effectively blocked more effectively than the comparative compound B, thereby significantly improving the efficiency and lifespan of the device. Finally, the structural differences between the compound of the present invention and the comparative compound C and the resulting difference in hole neutral stabilization energy on the device characteristics are described.

[0354] Comparative compound C is similar to the compound of the present invention in that one of the substituents of the amine is an aliphatic ring group and an aryl group is substituted at the 3-position of fluorene, but the type of the aliphatic ring group is different from that of the compound of the present invention.

[0355] In order to examine the effect of these differences on the Hole Neutral Stabilization Energy (unit: eV, hereinafter abbreviated as HNSE) of the compound, the HNSE values ​​of comparative compound C and compound P-99 of the present invention having a similar structure were measured using molecular simulation (Schrodinger Materials Science Suite 4.9.128). The measurement results are shown in Table 7 below.

[0356] Compound HNSE(eV) Comparative compound C0.070P-990.060

[0357] From the above Table 7, it can be seen that the HNSE value of the compound P-99 of the present invention is formed lower than that of the comparative compound C. This means that when the compound of the present invention is used as a material for a light-emitting auxiliary layer, holes can be transferred to the hole transport layer within the device, or after transferring holes to the light-emitting layer, the device can reach a stable state more quickly with less energy than the comparative compound C. Therefore, it appears that the lifespan of the device is significantly improved when the compound of the present invention is used as a material for a light-emitting auxiliary layer. From the above Tables 5 to 7, it can be confirmed that even among compounds having similar structures, the compound of the present invention satisfying all complex factors such as the type of substituent and the substitution position of the substituent exhibits a remarkable effect compared to other comparative compounds in an organic electric device, and through this, it can be seen that the compound of the present invention exhibits a remarkable effect in an organic electric device compared to other compounds having similar structures not described herein.

[0358] Through this, it can be seen that even when compounds with similar structures are used as hosts, the properties of the compound, such as hole characteristics, light efficiency characteristics, energy level, hole injection and mobility characteristics, charge balance of holes and electrons, volume density, and intermolecular distance, can differ depending on the type of substituent, the substitution position of the substituent, etc., and the performance of the device can differ significantly due to these differences.

[0359] In the case of a light-emitting auxiliary layer, the relationship between the hole transport layer and the light-emitting layer (host) must be understood. Therefore, even if a similar core is used, it would be very difficult for even a person skilled in the art to infer the characteristics exhibited by the light-emitting auxiliary layer using the compound of the present invention.

[0360] In the evaluation of the above-described device fabrication, the device characteristics were described when the compound of the present invention was applied only to the light-emitting auxiliary layer, but the compound of the present invention may be applied to the hole transport layer or may be applied to both the hole transport layer and the light-emitting auxiliary layer.

[0361] 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. The scope of protection of the present invention should be construed in accordance with the claims below, and all techniques within the scope equivalent thereto should be construed as being included within the scope of the present invention.

Claims

1. A compound represented by the following chemical formula 1: <Chemical Formula 1> <Chemical Formula A> In the above chemical formula, A is chemical formula A, X is C(R a )(R b ), O, S or N(R c ) and Ak is selected from the group consisting of the following chemical formulas Ak-1 to Ak-3, <Chemical Formula Ak-1> <Chemical Formula Ak-2> <Chemical Formula Ak-3> In the above chemical formulas Ak-1 to Ak-3, hydrogen can be replaced with deuterium, Ar 1 Silver 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 ; C6~C 60 Aromatic ring and C3~C 60 A fused ring group of an aliphatic ring; and a combination thereof, selected from the group consisting of Ar a is C6~C 60 is an aryl group or a fluorenyl group, R 1 and R 2 is C1~C 20 is an alkyl group, and the hydrogen of the alkyl group can be replaced with deuterium, R 3 Inland R 6 are independently hydrogen; deuterium; halogen; cyano group; nitro group; silane 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; C6~C 60 Aromatic ring and C3~C 60 A fused ring group of an aliphatic ring; C1~C 20 Alkyl group of; C2~C 20 Alkenyl group of ; C2~C 20 Alkyne group of ; C1~C 20 Alkoxy group of; and C6~C 60 is selected from the group consisting of aryloxy groups, and adjacent groups can be combined with each other to form a ring, a and d are each an integer from 0 to 4, b is an integer from 0 to 2, c is an integer from 0 to 3, and n is an integer of 0 or 1. R a , R b are independently 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; C6~C 60 Aromatic ring and C3~C 60 A fused ring group of an aliphatic ring; C1~C 20 Alkyl group of; C2~C 20 Alkenyl group of ; C2~C 20 Alkyne group of ; C1~C 20 Alkoxy group of; and C6~C 60 is selected from the group consisting of aryloxy groups, R c is 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 C6~C 60 Aromatic ring and C3~C 60 is selected from the group consisting of fused ring groups of aliphatic rings, Above Ar 1 , Ar a , R 3 Inland R 6 , R a Inland R c are respectively deuterium; halogen; C1-C 20 Alkyl group or C6-C 20 Silane group substituted or unsubstituted with aryl group; C1-C 20 Alkyl group or C6-C 20 Phosphine oxide substituted or unsubstituted with an aryl group; Cyano group; Nitro group; C1-C 20 Alkylthio group of; C1-C 20 Alkoxy group of; C6-C 30 Aryloxy group of; C6-C 30 Arylthio group of; C1-C 20 Alkyl group of; C2-C 20 Alkenyl group of ; C2-C 20 Alkyne group of ; C6-C 30 Aryl group of; C6-C substituted with deuterium 30 Aryl group of; C3-C 30 Aliphatic ring group; C6-C 30 Aromatic ring and C3-C 30 A fused ring group of an aliphatic ring; and C2-C containing at least one heteroatom among O, N, S, Si and P. 30 It may be substituted with one or more substituents selected from the group consisting of heterocyclic groups, and adjacent substituents may be combined with each other to form a ring (provided that R a , R b (except when the substituents of the above substituents form a ring), the hydrogen of the above substituents may be replaced by deuterium.

2. In paragraph 1, The above chemical formula 1 is a compound characterized by being represented by one of the following chemical formulas 1-1 to 1-4: <Chemical Formula 1-1> <Chemical Formula 1-2> <Chemical Formula 1-3> <Chemical Formula 1-4> In the above chemical formulas 1-1 to 1-4, A, R 1 Inland R 4 , Ar 1 , Ar a , Ak, a, and b are as defined in Article 1.

3. In paragraph 1, The above chemical formula A is a compound characterized by being represented by one of the following chemical formulas A-1 to A-4: <Chemical Formula A-1> <Chemical Formula A-2> <Chemical Formula A-3> <Chemical Formula A-4> In the above chemical formulas A-1 to A-4, X, R 5 , R 6 , c, d are as defined in paragraph 1.

4. In paragraph 1, Ar 1 is selected from the group consisting of the following chemical formulas L-1 to L-27, and L 1 A compound characterized by being selected from the group consisting of a single bond or chemical formulas L-1 to L-27 below: <Chemical Formula L-1> <Chemical Formula L-2> <Chemical Formula L-3> <Chemical Formula L-4> <Chemical Formula L-5> <Chemical Formula L-6> <Chemical Formula L-7> <Chemical Formula L-8> <Chemical Formula L-9> <Chemical Formula L-10> <Chemical Formula L-11> <Chemical Formula L-12> <Chemical Formula L-13> <Chemical Formula L-14> <Chemical Formula L-15> <Chemical Formula L-16> <Chemical Formula L-17> <Chemical Formula L-18> <Chemical Formula L-19> <Chemical Formula L-20> <Chemical Formula L-21> <Chemical Formula L-22> <Chemical Formula L-23> <Chemical Formula L-24> <Chemical Formula L-25> <Chemical Formula L-26> <Chemical Formula L-27> In the chemical formulas L-1 to L-27 above, W is O, S, C(R1), C(R2)(R3), N or N(Ar1), except that when L-14 and L-15 are connected through W, W is C(R1) or N, R 9 Inland R 18 , R1 to R3 are independently hydrogen; deuterium; halogen; C1-C 20 Alkyl group or C6-C 20 Silane group substituted or unsubstituted with aryl group; C1-C 20 Alkyl group or C6-C 20 Phosphine oxide substituted or unsubstituted with an aryl group; Cyano group; Nitro group; C1-C 20 Alkylthio group of; C1-C 20 Alkoxy group of; C6-C 30 Aryloxy group of; C6-C 30 Arylthio group of; C1-C 20 Alkyl group of; C2-C 20 Alkenyl group of ; C2-C 20 Alkyne group of ; C6-C 30 Aryl group of; C6-C substituted with deuterium 30 Aryl group of; C3-C 30 Aliphatic ring group; C6-C 30 Aromatic ring and C3-C 30 A fused ring group of an aliphatic ring; and C2-C containing at least one heteroatom among O, N, S, Si and P. 30 is selected from a group consisting of heterocyclic groups, and adjacent groups can combine with each other to form a ring, Ar1 is C1-C 20 Alkyl group of; C6-C 30 Aryl group of; C6-C substituted with deuterium 30 Aryl group of; C3-C 30 Aliphatic ring group; C6-C 30 Aromatic ring and C3-C 30 A fused ring group of an aliphatic ring; and C2-C containing at least one heteroatom among O, N, S, Si and P. 30 is selected from the group consisting of heterocyclic groups, i, k, m, n, o, p are each an integer from 0 to 4, j is an integer from 0 to 6, l is an integer from 0 to 2, q is an integer from 0 to 3, and r is an integer from 0 to 5.

5. In paragraph 1, A compound represented by the above chemical formula 1 is characterized in that it is one of the following compounds: .

6. In an organic electric device including a first electrode, a second electrode, and an organic layer between the first electrode and the second electrode, An organic electric device, characterized in that the organic layer comprises the compound of claim 1.

7. In paragraph 6, An organic electric device characterized in that the organic layer includes a light-emitting auxiliary layer, and the light-emitting auxiliary layer includes the compound of claim 1.

8. In paragraph 6, An organic electric device characterized in that the organic layer includes two or more stacks including a hole transport layer, a light-emitting layer, and an electron transport layer sequentially formed on the first electrode.

9. A display device including the organic electric element of clause 6; and An electronic device including a control unit that drives the display device.

10. A step of depositing an organic layer material including a compound represented by the chemical formula 1 of paragraph 1; A step of recovering the organic layer material attached to the deposition equipment; and A method for recovering a compound, characterized by including a step of purifying the recovered organic layer material to obtain a compound represented by the chemical formula 1 having a purity of 99.9% or higher.

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