WO2021015555A1 - Compound for organic electric element, organic electric element using same, and electronic device comprising same organic electric element - Google Patents

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

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WO2021015555A1
WO2021015555A1 PCT/KR2020/009674 KR2020009674W WO2021015555A1 WO 2021015555 A1 WO2021015555 A1 WO 2021015555A1 KR 2020009674 W KR2020009674 W KR 2020009674W WO 2021015555 A1 WO2021015555 A1 WO 2021015555A1
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김원삼
이중근
이가은
한승훈
이학영
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덕산네오룩스 주식회사
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Definitions

  • the present invention relates to a compound for an organic electric device, an organic electric device using the same, and an electronic device thereof.
  • the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material.
  • An organic electric device using an organic light emission phenomenon has a structure including an anode, a cathode, and an organic material layer therebetween.
  • the organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may be formed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.
  • Materials used as an organic material layer in an organic electric device can be classified into light-emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, according to their functions.
  • Efficiency, lifespan, and driving voltage are related to each other, and when the efficiency is increased, the driving voltage decreases relatively, and as the driving voltage decreases, crystallization of organic materials by Joule heating generated during driving decreases. It shows a tendency to increase the lifespan.
  • a light emission auxiliary layer must exist between the hole transport layer and the light emission layer, and different light emission auxiliary layers for each light emission layer (R, G, B) It is the time when layer development is necessary.
  • 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, thereby generating excitons through recombination.
  • materials that make up the organic material layer in the device such as hole injection materials, hole transport materials, light-emitting materials, electron transport materials, electron injection materials, and light-emitting auxiliary layer materials, are stable and efficient. Supported by the material must precede, but the development of a stable and efficient organic material layer material for organic electric devices has not been sufficiently achieved. Accordingly, development of new materials is continuously required, and in particular, development of materials for light-emitting auxiliary layers is urgently required.
  • KR1020130076842 A was used as prior literature.
  • the embodiments of the present invention for solving the problems of the background art described above have revealed a compound having a novel structure, and when the compound is applied to an organic electric device, the luminous efficiency, stability, and lifespan of the device are greatly improved. It turns out that you can.
  • an object of the present invention is to provide a novel compound and an organic electric device and an electronic device using the same.
  • the present invention provides a compound represented by the following formula (1).
  • the present invention provides an organic electric device and an electronic device using the compound represented by Formula 1 above.
  • 1 to 3 are exemplary views of an organic electroluminescent device according to the present invention.
  • organic electric device 110 first electrode
  • first hole transport layer 340 first emission layer
  • second charge generation layer 420 second hole injection layer
  • first, second, A, B, (a), (b) may be used. These terms are only used to distinguish the component from other components, and the nature, order, or order of the component is not limited by the term.
  • halo or halogen is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I) unless otherwise specified.
  • alkyl or “alkyl group” has a single bond of 1 to 60 carbon atoms unless otherwise specified, and is a straight-chain alkyl group, a branched-chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cyclo It means a radical of saturated aliphatic functional groups, including alkyl groups and cycloalkyl-substituted alkyl groups.
  • alkenyl group each have a double bond or triple bond of 2 to 60 carbon atoms, unless otherwise specified, and include a straight or branched chain group, , Not limited to this.
  • cycloalkyl as used in the present invention means an alkyl forming a ring having 3 to 60 carbon atoms, unless otherwise specified, and is not limited thereto.
  • alkoxyl group means an alkyl group to which an oxygen radical is attached, and has a carbon number of 1 to 60 unless otherwise specified, and is limited thereto. It is not.
  • aryloxyl group or “aryloxy group” used in the present invention refers to an aryl group to which an oxygen radical is attached, and has 6 to 60 carbon atoms, and is not limited thereto.
  • aryl group and arylene group used in the present invention each have 6 to 60 carbon atoms, and are not limited thereto, unless otherwise specified.
  • an aryl group or an arylene group means a single ring or multiple ring aromatics, and includes an aromatic ring formed by neighboring substituents participating in a bond or reaction.
  • the aryl group may be a phenyl group, a biphenyl group, a fluorene group, or a spirofluorene group.
  • aryl or "ar” means a radical substituted with an aryl group.
  • an arylalkyl group is an alkyl group substituted with an aryl group
  • an arylalkenyl group is an alkenyl group substituted with an aryl group
  • a radical substituted with an aryl group has the number of carbon atoms described herein.
  • arylalkoxy group it means an alkoxy group substituted with an aryl group
  • alkoxylcarbonyl group it means a carbonyl group substituted with an alkoxyl group
  • arylcarbonylalkenyl group it means an alkenyl group substituted with an arylcarbonyl group.
  • the arylcarbonyl group is a carbonyl group substituted with an aryl group.
  • heterocyclic group includes one or more heteroatoms, has 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, and includes heteroaliphatic rings and heterocyclic rings. It contains an aromatic ring. It may be formed by combining adjacent functional groups.
  • heteroatom refers to N, O, S, P, or Si unless otherwise specified.
  • heterocyclic group may also include a ring including SO 2 instead of carbon forming the ring.
  • heterocyclic group includes the following compounds.
  • fluorenyl group or "fluorenylene group” as used in the present invention means a monovalent or divalent functional group in which R, R'and R" are all hydrogen in each of the following structures, unless otherwise specified, " Substituted fluorenyl group” or “substituted fluorenylene group” means that at least one of the substituents R, R', and R" is a substituent other than hydrogen, and R and R'are bonded to each other and the carbon to which they are bonded It includes the case of forming a compound by spy together.
  • spiro compound used in the present invention has a'spiro union', and the spiro linkage refers to a connection made by two rings sharing only one atom. At this time, the atoms shared in the two rings are referred to as'spiro atoms', and these are respectively referred to as'monospiro-','dispiro-', and'trispyro-' depending on the number of spiro atoms in a compound. 'It is called a compound.
  • aliphatic refers to an aliphatic hydrocarbon having 1 to 60 carbon atoms
  • aliphatic ring refers to an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.
  • ring refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a hetero ring having 2 to 60 carbon atoms or a combination thereof, It contains saturated or unsaturated rings.
  • hetero compounds or hetero radicals other than the aforementioned hetero compounds include one or more heteroatoms, but are not limited thereto.
  • substituted or unsubstituted used in the present invention means “substituted” deuterium, halogen, amino group, nitrile group, nitro group, C 1 to C 20 alkyl group, C 1 to C 20 alkoxyl group, C 1 to C 20 alkylamine group, C 1 to C 20 alkylthiophene group, C 6 to C 20 arylthiophene group, C 2 to C 20 alkenyl group, C 2 to C 20 alkynyl, C 3 ⁇ C 20 cycloalkyl group, C 6 ⁇ C 20 aryl group, of a C 6 ⁇ C 20 substituted by deuterium aryl group, a C 8 ⁇ C 20 aryl alkenyl group, a silane group, a boron It means substituted with one or more substituents selected from the group consisting of a group, a germanium group, and a C 2 ⁇ C 20 heterocyclic group,
  • the substituent R 1 when a is an integer of 0, the substituent R 1 is absent, and when a is an integer of 1, one substituent R 1 is bonded to any one of the carbons forming the benzene ring, and a is an integer of 2 or 3.
  • R 1 may be the same or different from each other, and when a is an integer of 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the hydrogen bonded to the carbon forming the benzene ring is indicated. Is omitted.
  • R 1 to R 7 are each independently hydrogen; heavy hydrogen; halogen; C 6 ⁇ C 60 aryl group; Fluorenyl group; O, N, S, Si, and C 2 ⁇ C 60 heterocyclic group containing at least one heteroatom of P; A fused ring group of an aliphatic ring of C 3 to C 60 and an aromatic ring of C 6 to C 60 ; C 1 ⁇ C 60 alkyl group; C 2 ⁇ C 20 alkenyl group; Alkynyl group of C 2 ⁇ C 20 ; An alkoxyl group of C 1 to C 30 ; And C 6 ⁇ C 30 aryloxy group; is selected from the group consisting of, and when a, b, c, d, e, f, and g are 2 or more, each is the same as or different from each other as a plurality, and a plurality of R 1 each other or are together a plurality of R 2 to each other or a plurality of R 3 to each other or a plurality
  • R 1 to R 7 is an aryl group, it is preferably an aryl group of C 6 to C 25 , and when the R 1 to R 7 is a heterocyclic group, at least one heteroatom of O, N, S, Si and P preferably a heterocyclic group of C 2 ⁇ C 30, and including the R 1 to R 7 are fused when ring group, a fusion ring group of the aromatic ring of C 3 ⁇ C 30 of aliphatic rings and C 6 ⁇ C 30 to Preferably, when the R 1 to R 7 is an alkyl group, it is preferably a C 1 to C 30 alkyl group.
  • L 1 to L 3 are each independently a single bond; C 6 -C 60 arylene group; Fluorenyl group; C 2 ⁇ C 60 heterocyclic group; And a fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; and R 4 and L 1 may be bonded to each other to form a ring.
  • the L 1 to L 3 is an arylene group
  • the L 1 to L 3 is a heterocyclic group, at least one of O, N, S, Si and P preferably a heterocyclic group of C 2 ⁇ C 30 containing a hetero atom, and wherein L 1 to L 3 in this case fused ring group, a fused ring of an aromatic ring of C 3 -C 30 aliphatic and C 6 -C 30 ring It is preferable that it is a group.
  • Ar1 is a C 6 ⁇ C 60 aryl group; Fluorenyl group; O, N, S, Si, and C 2 -C 60 heterocyclic group containing at least one heteroatom of P; And a fused ring group of a C 3 -C 60 aliphatic ring and a C 6 -C 60 aromatic ring.
  • Ar1 is an aryl group, it is preferable that it is an aryl group of C 6 to C 25 , and when Ar1 is a heterocyclic group, C 2 -C 30 including at least one heteroatom of O, N, S, Si and P It is preferably a heterocyclic group of, and when Ar1 is a fused cyclic group, it is preferably a fused cyclic group of a C 3 -C 30 aliphatic ring and a C 6 -C 30 aromatic ring.
  • A is represented by the general formula (2), at least one of the formula 2 R 5 to R 7 binds to N of formula (I) if combined with L 3, however, and the L 3 il single bond, R 5 to R 7 may each independently form a ring with L 3 .
  • R'and R are each independently a C 6 ⁇ C 60 aryl group; Fluorenyl group; O, N, S, Si, and C 2 ⁇ C 60 heterocyclic group containing at least one heteroatom of P; And C 1 ⁇ C 60 Alkyl group; is selected from the group consisting of, R'and R” may be bonded to each other to form a spy ring.
  • R'and R are an aryl group, it is preferably an aryl group of C 6 to C 25 , and when the R'and R” are heterocyclic groups, at least one heteroatom of O, N, S, Si and P It is preferably a C 2 ⁇ C 30 heterocyclic group containing, and when R'and R” are an alkyl group, it is preferably a C 1 ⁇ C 30 alkyl group.
  • X is NR a , O, S or CR b R c .
  • R a to R c are each independently a C 6 to C 60 aryl group; Fluorenyl group; O, N, S, Si, and C 2 ⁇ C 60 heterocyclic group containing at least one heteroatom of P; And C 1 ⁇ C 60 Alkyl group; is selected from the group consisting of.
  • R a to R c is an aryl group, it is preferable that it is an aryl group of C 6 to C 25 , and when R a to R c is a heterocyclic group, at least one heteroatom of O, N, S, Si and P It is preferably a C 2 ⁇ C 30 heterocyclic group, and when R a to R c is an alkyl group, it is preferably a C 1 ⁇ C 30 alkyl group.
  • a is an integer of 0 to 5
  • b, c, d, e and g are each independently an integer of 0 to 4
  • f is an integer of 0 to 2.
  • the aryl group, fluorenyl group, arylene group, heterocyclic group, fluorenylene group, fused ring group, alkyl group, alkenyl group, alkoxyl group and aryloxy group are each deuterium; halogen; Silane group; Siloxane group; Boron group; Germanium group; Cyano group; Nitro group; C 1 -C 20 alkylthio group; An alkoxyl group of C 1 -C 20 ; A C 1 -C 20 alkyl group; An alkenyl group of C 2 -C 20 ; Alkynyl group of C 2 -C 20 ; C 6 -C 20 aryl group; A C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group; A C 3 -C 20 cycloalkyl group; C 7 -C 20 arylalkyl group and C 8 -C 20 arylalkenyl
  • R 1 to R 4 , L 1 , L 2 , Ar1, a, b, c and d are the same as defined in Formula 1,
  • R 11 , R 12 and R 13 are each independently hydrogen; heavy hydrogen; halogen; C 6 ⁇ C 60 aryl group; Fluorenyl group; O, N, S, Si, and C 2 ⁇ C 60 heterocyclic group containing at least one heteroatom of P; A fused ring group of an aliphatic ring of C 3 to C 60 and an aromatic ring of C 6 to C 60 ; C 1 ⁇ C 60 alkyl group; C 2 ⁇ C 20 alkenyl group; Alkynyl group of C 2 ⁇ C 20 ; An alkoxyl group of C 1 to C 30 ; And C 6 ⁇ C 30 aryloxy group; is selected from the group consisting of, and when x, y and z are 2 or more, each is the same as or different from each other as a plurality, and a plurality of R 11 or a plurality of R 12 or A plurality of R 13 can be bonded to each other to form a ring,
  • R 14 and R 15 are the same as R'and R” defined in Formula 2,
  • x is an integer from 0 to 3
  • y is an integer from 0 to 2
  • z is an integer from 0 to 4.
  • the present invention includes the compound represented by Formula 1 or Formula 1-2 below.
  • R 1 to R 7 , L 1 to L 3 , R', R”, Ar1, X, a, b, c, d, e, f and g are as defined in Formulas 1 and 2, and ,
  • R 15 and R 17 are hydrogen; heavy hydrogen; An alkoxyl group of C 1 -C 60 ; A C 1 -C 60 alkyl group; An alkenyl group of C 2 -C 60 ; Alkynyl group of C 2 -C 60 ; C 6 -C 60 aryl group; A C 6 -C 60 aryl group substituted with deuterium; Fluorenyl group; O, N, S, Si, and C 2 -C 60 heterocyclic group containing at least one heteroatom of P; A C 3 -C 60 cycloalkyl group; C 7 -C 60 arylalkyl group; And C 8 -C 60 arylalkenyl group; selected from the group consisting of, a plurality of R 15 to each other or a plurality of R 17 to each other can form a ring,
  • e'and g' are each independently an integer of 0 to 3. ⁇
  • the present invention includes compounds represented by the following Formulas 1-3 to 1-5, wherein the compound represented by Formula 1 above.
  • R 1 to R 4 , L 1 to L 3 , Ar1, A, a, b, c and d are the same as defined in Chemical Formula 1. ⁇
  • the formula 2 of the present invention includes a compound represented by the following formulas 2-1 to 2-4.
  • R 5 , R 6 , R 7 , R', R”, R a , R b , R c , e, f and g are the same as defined in Formula 2 above. ⁇
  • the formula 2 of the present invention includes a compound represented by the following formulas 2-5 to 2-10.
  • R 5 , R 6 , R 7 , X, R', R”, e, f and g are the same as defined in Chemical Formula 2. ⁇
  • the present invention includes a compound represented by Formula 1 to Formula 1-11 below.
  • R 1 to R 7 , L 1 to L 3 , R', R”, Ar1, X, a, b, c, d, e, f and g are the same as defined in Formulas 1 and 2,
  • R 15 , R 17 , e'and g' are the same as defined in Chemical Formulas 1-1 and 1-2. ⁇
  • the compound represented by Formula 1 may be any one of Compounds P-1 to P-128 below, but is not limited thereto.
  • the organic electric device 100 has a formula 1 between the first electrode 110, the second electrode 170, and the first electrode 110 and the second electrode 170.
  • a single compound represented by or an organic material layer including two or more compounds is provided.
  • the first electrode 110 may be an anode or an anode
  • the second electrode 170 may be a cathode or 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.
  • the organic material layer may sequentially 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 on the first electrode 110. In this case, other layers other than the emission layer 140 may not be formed.
  • a hole blocking layer, an electron blocking layer, a light emission auxiliary layer 220, and a buffer layer 210 may be further included, and the electron transport layer 150 may serve as a hole blocking layer. (See Fig. 2)
  • the organic electric device may further include a protective layer or a light efficiency improvement layer 180.
  • the light efficiency improvement layer may be formed on a surface not in contact with the organic material layer among both surfaces of the first electrode or on a surface not in contact with the organic material layer among both surfaces of the second electrode.
  • the compound according to an embodiment of the present invention applied to the organic material layer is Hole injection layer 120, hole transport layer 130, light emission auxiliary layer 220, electron transport auxiliary layer, electron transport layer 150, electron injection layer 160, host or dopant of emission layer 140, or light efficiency improvement It could be used as a layer material.
  • the compound according to Formula 1 of the present invention may be used as a material for the light emitting auxiliary layer.
  • it can be used as a material for the red light emission auxiliary layer.
  • the organic material layer may include two or more stacks including a hole transport layer, an emission layer, and an electron transport layer sequentially formed on the anode, and may further include a charge generation layer formed between the two or more stacks (see FIG. 3 ). )
  • the band gap, electrical characteristics, and interfacial characteristics may vary depending on which substituent is bonded to any position, so the selection of the core and the combination of sub-substituents bonded thereto are also very It is important, and in particular, long life and high efficiency can be achieved at the same time when the energy level and T1 value between each organic material layer and the intrinsic properties of materials (mobility, interfacial properties, etc.) are optimally combined.
  • the organic electroluminescent device may be manufactured using a physical vapor deposition (PVD) method.
  • PVD physical vapor deposition
  • an anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and a hole injection layer 120, a hole transport layer 130, a light emitting layer 140, an electron transport layer 150, and After forming an organic material layer including the electron injection layer 160, it may be manufactured by depositing a material that can be used as a cathode thereon.
  • the organic material layer is formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, and a roll-to-roll process, and the organic material layer contains the compound as an electron transport material. It provides an organic electric device characterized in that.
  • the present invention provides an organic electric device, characterized in that the organic material layer is used by mixing the same or different compounds of the compound represented by Formula 1 above.
  • the present invention provides a light emission auxiliary layer composition comprising the compound represented by Formula 1, and provides an organic electric device including the light emission auxiliary layer.
  • the present invention is a display device including the organic electric device; And a controller for driving the display device.
  • the present invention provides an electronic device, characterized in that the organic electric device is at least one of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, and a single color or white lighting device.
  • the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as mobile communication terminals such as mobile phones, PDAs, electronic dictionaries, PMPs, remote controls, navigation, game consoles, various TVs, and various computers.
  • the compound belonging to Sub 1 may be a compound as follows, but is not limited thereto, and Table 1 below shows FD-MS (Field Desorption-Mass Spectrometry) values of the compound belonging to Sub 1.
  • the compound belonging to Sub 2 may be a compound as follows, but is not limited thereto, and Table 2 below shows the FD-MS (Field Desorption-Mass Spectrometry) values of the compound belonging to Sub 2.
  • An organic electroluminescent device was manufactured according to a conventional method by using the compound of the present invention as a light emitting auxiliary layer material.
  • N1-(naphthalen-2-yl)-N4,N4-bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N1 as a hole injection layer on the ITO layer (anode) formed on the glass substrate.
  • a -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) film was vacuum-deposited to form a thickness of 60 nm.
  • -NPD 4,4-bis[N-(1-naphthyl)-N-phenylamino]biphenyl
  • BAlq (1,1'-bisphenyl)-4-oleato)bis(2-methyl-8-quinolinoleato)aluminum
  • BAlq tris(8-quinolinol) aluminum
  • Alq3 tris(8-quinolinol) aluminum
  • LiF which is an alkali metal halide
  • Al was deposited to a thickness of 150 nm and used as a cathode, thereby manufacturing an organic light emitting diode.
  • An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compound of the present invention described in Table 4 was used instead of the compound P-1 of the present invention as the light emitting auxiliary layer material.
  • An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the light emission auxiliary layer was not formed.
  • An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound A to Comparative Compound D were used as the light emitting auxiliary layer material.
  • the electroluminescence (EL) characteristics were measured with a PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared as described above, and the measurement result was based on 5000 cd/m 2 In the luminance, the T95 life was measured using a life measurement equipment manufactured by McScience. Table 4 below shows the results of device fabrication and evaluation.
  • Comparative compounds A to C are similar to the compounds of the present invention in that an amino group is substituted with the phenyl of diphenylfluorene, but the compounds of the present invention are condensed in which at least one of the substituents of the amino group contains a fluorene moiety. It differs in that the polycyclic ring is substituted.
  • the compound of the present invention when comparing the compound of the present invention with the comparative compound A, the compound of the present invention in which the structure in which benzofuran, benzothiophene, indole, and indene is condensed in a fluorene moiety is substituted rather than a simple fluorene-substituted comparative compound A, The efficiency and lifespan have been remarkably improved.This is because when the structures such as benzofuran and benzothiophene are further condensed with the fluorene moiety, the planarity of the molecule increases and the hole mobility is improved. By injection, the interfacial light emission between the light emitting auxiliary layer and the host is reduced, and since light is mainly emitted in the host, the charge balance is improved and driving, efficiency, and lifespan are improved.
  • the comparative compound B is similar to the compound of the present invention, but the amino group further substituted with the compound of the present invention is further substituted. Therefore, it has a higher molecular weight than the compound of the present invention, and thus, the Tg value increases, requiring too high a deposition temperature, and it is determined that the device life and efficiency are affected in the process.
  • Comparative Compound C has an amino group substituted with bisnaphthobenzofuran
  • Comparative Compound D has an amino group substituted at the position where the amino group is substituted is not phenyl of diphenylfluorene.
  • Table 5 it can be seen that the LUMO level of Comparative Compound C and Comparative Compound D is lower than that of the compound of the present invention. Accordingly, Comparative Compound C and Comparative Compound D Since the electrons cannot be effectively blocked, it is judged that there is a significant difference in the device results.

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Abstract

The present invention provides: a novel compound which can improve the luminous efficiency, stability, and service life of an element; an organic electric element using same; and an electronic device comprising the organic electric element.

Description

유기전기소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치Compound for organic electric device, organic electric device using same, and electronic device thereof
본 발명은 유기전기소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치에 관한 것이다.The present invention relates to a compound for an organic electric device, an organic electric device using the same, and an electronic device thereof.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기전기소자는 통상 양극과 음극 및 이 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물층은 유기전기소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 등으로 이루어질 수 있다.In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic electric device using an organic light emission phenomenon has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may be formed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.
유기전기소자에서 유기물층으로 사용되는 재료는 기능에 따라, 발광 재료와 전하수송 재료, 예컨대 정공주입 재료, 정공수송 재료, 전자수송 재료, 전자주입 재료 등으로 분류될 수 있다.Materials used as an organic material layer in an organic electric device can be classified into light-emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, according to their functions.
유기 전기 발광소자에 있어 가장 문제시되는 것은 수명과 효율인데, 디스플레이가 대면적화되면서 이러한 효율이나 수명 문제는 반드시 해결해야 하는 상황이다.Lifespan and efficiency are the most problematic in organic electroluminescent devices, and as displays become larger, these efficiency and lifetime problems must be solved.
효율과 수명, 구동전압 등은 서로 연관이 있으며, 효율이 증가되면 상대적으로 구동전압이 떨어지고, 구동전압이 떨어지면서 구동시 발생되는 주울열(Joule heating)에 의한 유기물질의 결정화가 적어져 결과적으로 수명이 높아지는 경향을 나타낸다.Efficiency, lifespan, and driving voltage are related to each other, and when the efficiency is increased, the driving voltage decreases relatively, and as the driving voltage decreases, crystallization of organic materials by Joule heating generated during driving decreases. It shows a tendency to increase the lifespan.
하지만 상기 유기물층을 단순히 개선한다고 하여 효율을 극대화시킬 수는 없다. 왜냐하면 각 유기물층 간의 에너지 준위 및 T1 값, 물질의 고유특성(이동도, 계면특성 등) 등이 최적의 조합을 이루었을 때 긴 수명과 높은 효율을 동시에 달성할 수 있기 때문이다.However, simply improving the organic material layer cannot maximize efficiency. This is because the long life and high efficiency can be achieved at the same time when the optimum combination of the energy level and T1 value between each organic material layer and the intrinsic properties of the material (mobility, interfacial properties, etc.) is achieved.
또한, 최근 유기 전기 발광소자에 있어 정공수송층에서의 발광 문제를 해결하기 위해서는 반드시 정공수송층과 발광층 사이에 발광보조층이 존재하여야 하며, 각각의 발광층(R, G, B)에 따른 서로 다른 발광보조층의 개발이 필요한 시점이다.In addition, in order to solve the problem of light emission in the hole transport layer in recent organic electroluminescent devices, a light emission auxiliary layer must exist between the hole transport layer and the light emission layer, and different light emission auxiliary layers for each light emission layer (R, G, B) It is the time when layer development is necessary.
일반적으로 전자수송층에서 발광층으로 전자(electron)가 전달되고 정공(hole)이 정공수송층에서 발광층으로 전달되어 재조합(recombination)에 의해 엑시톤(exciton)이 생성된다.In general, electrons are transferred from the electron transport layer to the light emitting layer, and holes are transferred from the hole transport layer to the light emitting layer, thereby generating excitons through recombination.
하지만 정공수송층에 사용되는 물질의 경우 낮은 HOMO 값을 가져야 하기 때문에 대부분 낮은 T1 값을 가지며, 이로 인해 발광층에서 생성된 엑시톤(exciton)이 정공수송층으로 넘어가게 되어 결과적으로 발광층 내 전하 불균형(charge unbalance)을 초래하여 정공수송층 계면에서 발광하게 된다.However, in the case of a material used for the hole transport layer, since it must have a low HOMO value, most have a low T1 value, and this causes excitons generated in the emission layer to pass to the hole transport layer, resulting in charge unbalance in the emission layer. This results in light emission at the hole transport layer interface.
정공수송층 계면에서 발광될 경우, 유기전기소자의 색순도 및 효율이 저하되고 수명이 짧아지는 문제점이 발생하게 된다. 따라서 높은 T1 값을 가지며, 정공 수송층 HOMO 에너지 준위와 발광층의 HOMO 에너지 준위 사이의 HOMO 준위를 갖는 발광보조층의 개발이 절실히 요구된다.When light is emitted at the hole transport layer interface, the color purity and efficiency of the organic electronic device are deteriorated, and the lifespan is shortened. Therefore, development of a light emission auxiliary layer having a high T1 value and having a HOMO level between the HOMO energy level of the hole transport layer and the HOMO energy level of the light emitting layer is urgently required.
한편, 유기전기소자의 수명단축 원인 중 하나인 양극전극(ITO)으로부터 금속 산화물이 유기층으로 침투확산되는 것을 지연시키면서, 소자 구동시 발생되는 주울열(Joule heating)에 대해서도 안정된 특성, 즉 높은 유리 전이온도를 갖는 정공 주입층 재료에 대한 개발이 필요하다. 정공수송층 재료의 낮은 유리전이 온도는 소자 구동시, 박막 표면의 균일도를 저하시키는 특성이 있는바, 이는 소자수명에 큰 영향을 미치는 것으로 보고되고 있다. 또한, OLED 소자는 주로 증착 방법에 의해 형성되는데, 증착시 오랫동안 견딜 수 있는 재료, 즉 내열특성이 강한 재료 개발이 필요한 실정이다.On the other hand, while delaying penetration and diffusion of metal oxides from the anode electrode (ITO) into the organic layer, which is one of the causes of shortening the lifespan of organic electronic devices, stable characteristics against Joule heating generated when the device is driven, that is, high glass transition There is a need to develop a material for a hole injection layer having a temperature. The low glass transition temperature of the hole transport layer material has a property of lowering the uniformity of the thin film surface when the device is driven, and it is reported that it has a great effect on the life of the device. In addition, OLED devices are mainly formed by a vapor deposition method, and it is necessary to develop a material that can withstand a long time during deposition, that is, a material having strong heat resistance.
즉, 유기전기소자가 갖는 우수한 특징들을 충분히 발휘하기 위해서는 소자 내 유기물층을 이루는 물질, 예컨대 정공주입 물질, 정공수송 물질, 발광 물질, 전자수송 물질, 전자주입 물질, 발광보조층 물질 등이 안정하고 효율적인 재료에 의하여 뒷받침되는 것이 선행되어야 하나, 아직까지 안정되고 효율적인 유기전기소자용 유기물층 재료의 개발이 충분히 이루어지지 않은 상태이다. 따라서, 새로운 재료의 개발이 계속 요구되고 있으며, 특히 발광보조층의 재료에 대한 개발이 절실히 요구되고 있다.In other words, in order to fully exhibit the excellent characteristics of organic electronic devices, materials that make up the organic material layer in the device, such as hole injection materials, hole transport materials, light-emitting materials, electron transport materials, electron injection materials, and light-emitting auxiliary layer materials, are stable and efficient. Supported by the material must precede, but the development of a stable and efficient organic material layer material for organic electric devices has not been sufficiently achieved. Accordingly, development of new materials is continuously required, and in particular, development of materials for light-emitting auxiliary layers is urgently required.
참고 선행문헌으로는 KR1020130076842 A를 이용하였다.For reference, KR1020130076842 A was used as prior literature.
상술한 배경기술의 문제점을 해결하기 위한 본 발명의 실시예는, 신규한 구조를 갖는 화합물을 밝혀내었으며, 또한 이 화합물을 유기전기소자에 적용시 소자의 발광효율, 안정성 및 수명을 크게 향상시킬 수 있다는 사실을 밝혀내었다.The embodiments of the present invention for solving the problems of the background art described above have revealed a compound having a novel structure, and when the compound is applied to an organic electric device, the luminous efficiency, stability, and lifespan of the device are greatly improved. It turns out that you can.
이에 본 발명은 신규한 화합물 및 이를 이용한 유기전기소자, 전자장치를 제공하는 것을 목적으로 한다.Accordingly, an object of the present invention is to provide a novel compound and an organic electric device and an electronic device using the same.
일 측면에서, 본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다.In one aspect, the present invention provides a compound represented by the following formula (1).
화학식 1Formula 1
Figure PCTKR2020009674-appb-I000001
Figure PCTKR2020009674-appb-I000001
다른 측면에서, 본 발명은 상기 화학식 1로 표시되는 화합물을 이용한 유기전기소자 및 그 전자장치를 제공한다.In another aspect, the present invention provides an organic electric device and an electronic device using the compound represented by Formula 1 above.
본 발명에 따른 화합물을 이용함으로써 소자의 높은 발광효율, 낮은 구동전압, 고내열성을 달성할 수 있고, 소자의 색순도 및 수명을 크게 향상시킬 수 있다.By using the compound according to the present invention, high luminous efficiency, low driving voltage, and high heat resistance of the device can be achieved, and color purity and lifetime of the device can be greatly improved.
도 1 내지 도 3은 본 발명에 따른 유기전기발광소자의 예시도이다.1 to 3 are exemplary views of an organic electroluminescent device according to the present invention.
도 4는 본 발명의 일 측면에 따른 화학식을 나타낸다.4 shows a chemical formula according to an aspect of the present invention.
100, 200, 300 : 유기전기소자 110 : 제 1전극100, 200, 300: organic electric device 110: first electrode
120 : 정공주입층 130 : 정공수송층120: hole injection layer 130: hole transport layer
140 : 발공층 150 : 전자수송층140: pore layer 150: electron transport layer
160 : 전자주입층 170 : 제 2전극160: electron injection layer 170: second electrode
180 : 광효율 개선층 210 : 버퍼층180: light efficiency improvement layer 210: buffer layer
220 : 발광보조층 320 : 제1 정공주입층220: light emission auxiliary layer 320: first hole injection layer
330 : 제1 정공수송층 340 : 제1 발광층330: first hole transport layer 340: first emission layer
350 : 제1 전자수송층 360 : 제1 전하생성층350: first electron transport layer 360: first charge generation layer
361 : 제2 전하생성층 420 : 제2 정공주입층361: second charge generation layer 420: second hole injection layer
430 : 제2 정공수송층 440 : 제2 발광층430: second hole transport layer 440: second emission layer
450 : 제2 전자수송층 CGL : 전하생성층450: second electron transport layer CGL: charge generation layer
ST1 : 제1 스택 ST2 : 제2 스택ST1: 1st stack ST2: 2nd stack
이하, 본 발명의 실시예를 참조하여 상세하게 설명한다. 본 발명을 설명함에 있어, 관련된 공지 구성 또는 기능에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명은 생략한다.Hereinafter, it will be described in detail with reference to an embodiment of the present invention. In describing the present invention, when it is determined that a detailed description of a related known configuration or function may obscure the subject matter of the present invention, a detailed description thereof will be omitted.
또한, 본 발명의 구성 요소를 설명하는 데 있어서, 제 1, 제 2, A, B, (a), (b) 등의 용어를 사용할 수 있다. 이러한 용어는 그 구성 요소를 다른 구성 요소와 구별하기 위한 것일 뿐, 그 용어에 의해 해당 구성 요소의 본질이나 차례 또는 순서 등이 한정되지 않는다. 어떤 구성 요소가 다른 구성 요소에 "연결", "결합" 또는 "접속"된다고 기재된 경우, 그 구성 요소는 그 다른 구성 요소에 직접적으로 연결되거나 또는 접속될 수 있지만, 각 구성 요소 사이에 또 다른 구성 요소가 "연결", "결합" 또는 "접속"될 수도 있다고 이해되어야 할 것이다.In addition, in describing the constituent elements of the present invention, terms such as first, second, A, B, (a), (b) may be used. These terms are only used to distinguish the component from other components, and the nature, order, or order of the component is not limited by the term. When a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected or connected to that other component, but another component between each component It will be understood that elements may be "connected", "coupled" or "connected".
본 명세서 및 첨부된 청구의 범위에서 사용된 바와 같이, 달리 언급하지 않는 한, 하기 용어의 의미는 하기와 같다:As used in this specification and the appended claims, unless stated otherwise, the meaning of the following terms is as follows:
본 명세서에서 사용된 용어 "할로" 또는 "할로겐"은 다른 설명이 없는 한 불소(F), 브롬(Br), 염소(Cl) 또는 요오드(I)이다.As used herein, the term "halo" or "halogen" is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I) unless otherwise specified.
본 발명에 사용된 용어 "알킬" 또는 "알킬기"는 다른 설명이 없는 한 1 내지 60의 탄소수의 단일결합을 가지며, 직쇄 알킬기, 분지쇄 알킬기, 사이클로알킬(지환족)기, 알킬-치환된 사이클로알킬기, 사이클로알킬-치환된 알킬기를 비롯한 포화 지방족 작용기의 라디칼을 의미한다.As used herein, the term "alkyl" or "alkyl group" has a single bond of 1 to 60 carbon atoms unless otherwise specified, and is a straight-chain alkyl group, a branched-chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cyclo It means a radical of saturated aliphatic functional groups, including alkyl groups and cycloalkyl-substituted alkyl groups.
본 발명에 사용된 용어 "알켄일기", "알케닐기" 또는 "알킨일기"는 다른 설명이 없는 한 각각 2 내지 60의 탄소수의 이중결합 또는 삼중결합을 가지며, 직쇄형 또는 측쇄형 사슬기를 포함하며, 여기에 제한되는 것은 아니다.The terms "alkenyl group", "alkenyl group" or "alkynyl group" used in the present invention each have a double bond or triple bond of 2 to 60 carbon atoms, unless otherwise specified, and include a straight or branched chain group, , Not limited to this.
본 발명에 사용된 용어 "시클로알킬"은 다른 설명이 없는 한 3 내지 60의 탄소수를 갖는 고리를 형성하는 알킬을 의미하며, 여기에 제한되는 것은 아니다.The term "cycloalkyl" as used in the present invention means an alkyl forming a ring having 3 to 60 carbon atoms, unless otherwise specified, and is not limited thereto.
본 발명에 사용된 용어 "알콕실기", "알콕시기", 또는 "알킬옥시기"는 산소 라디칼이 부착된 알킬기를 의미하며, 다른 설명이 없는 한 1 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다.The terms "alkoxyl group", "alkoxy group", or "alkyloxy group" as used in the present invention means an alkyl group to which an oxygen radical is attached, and has a carbon number of 1 to 60 unless otherwise specified, and is limited thereto. It is not.
본 발명에 사용된 용어 "아릴옥실기" 또는 "아릴옥시기"는 산소 라디칼이 부착된 아릴기를 의미하며, 다른 설명이 없는 한 6 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다.The term "aryloxyl group" or "aryloxy group" used in the present invention refers to an aryl group to which an oxygen radical is attached, and has 6 to 60 carbon atoms, and is not limited thereto.
본 발명에 사용된 용어 "아릴기" 및 "아릴렌기"는 다른 설명이 없는 한 각각 6 내지 60의 탄소수를 가지며, 이에 제한되는 것은 아니다. 본 발명에서 아릴기 또는 아릴렌기는 단일 고리 또는 다중 고리의 방향족을 의미하며, 이웃한 치환기가 결합 또는 반응에 참여하여 형성된 방향족 고리를 포함한다. 예컨대, 아릴기는 페닐기, 비페닐기, 플루오렌기, 스파이로플루오렌기일 수 있다.The terms "aryl group" and "arylene group" used in the present invention each have 6 to 60 carbon atoms, and are not limited thereto, unless otherwise specified. In the present invention, an aryl group or an arylene group means a single ring or multiple ring aromatics, and includes an aromatic ring formed by neighboring substituents participating 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.
접두사 "아릴" 또는 "아르"는 아릴기로 치환된 라디칼을 의미한다. 예를 들어 아릴알킬기는 아릴기로 치환된 알킬기이며, 아릴알켄일기는 아릴기로 치환된 알켄일기이며, 아릴기로 치환된 라디칼은 본 명세서에서 설명한 탄소수를 가진다. The prefix "aryl" or "ar" means 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 a radical substituted with an aryl group has the number of carbon atoms described herein.
또한 접두사가 연속으로 명명되는 경우 먼저 기재된 순서대로 치환기가 나열되는 것을 의미한다. 예를 들어, 아릴알콕시기의 경우 아릴기로 치환된 알콕시기를 의미하며, 알콕실카르보닐기의 경우 알콕실기로 치환된 카르보닐기를 의미하며, 또한 아릴카르보닐알켄일기의 경우 아릴카르보닐기로 치환된 알켄일기를 의미하며 여기서 아릴카르보닐기는 아릴기로 치환된 카르보닐기이다.In addition, when prefixes are named consecutively, it means that the substituents are listed in the order described first. For example, in the case of an arylalkoxy group, it means an alkoxy group substituted with an aryl group, in the case of an alkoxylcarbonyl group, it means a carbonyl group substituted with an alkoxyl group, and in the case of an arylcarbonylalkenyl group, it means an alkenyl group substituted with an arylcarbonyl group. And the arylcarbonyl group is a carbonyl group substituted with an aryl group.
본 발명에 사용된 용어 "헤테로고리기"는 다른 설명이 없는 한 하나 이상의 헤테로원자를 포함하고, 2 내지 60의 탄소수를 가지며, 단일 고리 및 다중 고리 중 적어도 하나를 포함하며, 헤테로지방족 고리 및 헤테로방향족 고리를 포함한다. 이웃한 작용기가 결합하여 형성될 수도 있다.The term "heterocyclic group" as used herein, unless otherwise specified, includes one or more heteroatoms, has 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, and includes heteroaliphatic rings and heterocyclic rings. It contains an aromatic ring. It may be formed by combining adjacent functional groups.
본 명세서에서 사용된 용어 "헤테로원자"는 다른 설명이 없는 한 N, O, S, P 또는 Si를 나타낸다.The term "heteroatom" as used herein refers to N, O, S, P, or Si unless otherwise specified.
또한 "헤테로고리기"는 고리를 형성하는 탄소 대신 SO2를 포함하는 고리도 포함할 수 있다. 예컨대, "헤테로고리기"는 다음 화합물을 포함한다. In addition, the "heterocyclic group" may also include a ring including SO 2 instead of carbon forming the ring. For example, "heterocyclic group" includes the following compounds.
Figure PCTKR2020009674-appb-I000002
Figure PCTKR2020009674-appb-I000002
본 발명에 사용된 용어 "플루오렌일기" 또는 "플루오렌일렌기"는 다른 설명이 없는 한 각각 하기 구조에서 R, R' 및 R"이 모두 수소인 1가 또는 2가 작용기를 의미하며, "치환된 플루오렌일기" 또는 "치환된 플루오렌일렌기"는 치환기 R, R', R" 중 적어도 하나가 수소 이외의 치환기인 것을 의미하며, R과 R'이 서로 결합되어 이들이 결합된 탄소와 함께 스파이로 화합물을 형성한 경우를 포함한다.The term "fluorenyl group" or "fluorenylene group" as used in the present invention means a monovalent or divalent functional group in which R, R'and R" are all hydrogen in each of the following structures, unless otherwise specified, " Substituted fluorenyl group" or "substituted fluorenylene group" means that at least one of the substituents R, R', and R" is a substituent other than hydrogen, and R and R'are bonded to each other and the carbon to which they are bonded It includes the case of forming a compound by spy together.
Figure PCTKR2020009674-appb-I000003
Figure PCTKR2020009674-appb-I000003
본 발명에서 사용된 용어 "스파이로 화합물"은 '스파이로 연결(spiro union)'을 가지며, 스파이로 연결은 2개의 고리가 오로지 1개의 원자를 공유함으로써 이루어지는 연결을 의미한다. 이때, 두 고리에 공유된 원자를 '스파이로 원자'라 하며, 한 화합물에 들어 있는 스파이로 원자의 수에 따라 이들을 각각 '모노스파이로-', '다이스파이로-', '트라이스파이로-' 화합물이라 한다.The term "spiro compound" used in the present invention has a'spiro union', and the spiro linkage refers to a connection made by two rings sharing only one atom. At this time, the atoms shared in the two rings are referred to as'spiro atoms', and these are respectively referred to as'monospiro-','dispiro-', and'trispyro-' depending on the number of spiro atoms in a compound. 'It is called a compound.
다른 설명이 없는 한, 본 발명에 사용된 용어 "지방족"은 탄소수 1 내지 60의 지방족 탄화수소를 의미하며, "지방족고리"는 탄소수 3 내지 60의 지방족 탄화수소 고리를 의미한다.Unless otherwise specified, the term "aliphatic" as used herein refers to an aliphatic hydrocarbon having 1 to 60 carbon atoms, and "aliphatic ring" refers to an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.
다른 설명이 없는 한, 본 발명에 사용된 용어 "고리"는 탄소수 3 내지 60의 지방족고리 또는 탄소수 6 내지 60의 방향족고리 또는 탄소수 2 내지 60의 헤테로고리 또는 이들의 조합으로 이루어진 융합 고리를 말하며, 포화 또는 불포화고리를 포함한다.Unless otherwise specified, the term "ring" used in the present invention refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a hetero ring having 2 to 60 carbon atoms or a combination thereof, It contains saturated or unsaturated rings.
전술한 헤테로화합물 이외의 그 밖의 다른 헤테로화합물 또는 헤테로라디칼은 하나 이상의 헤테로원자를 포함하며, 여기에 제한되는 것은 아니다.Other hetero compounds or hetero radicals other than the aforementioned hetero compounds include one or more heteroatoms, but are not limited thereto.
또한 명시적인 설명이 없는 한, 본 발명에서 사용된 용어 "치환 또는 비치환된"에서 "치환"은 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C1~C20의 알콕실기, C1~C20의 알킬아민기, C1~C20의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20의 알켄일기, C2~C20의 알킨일기, C3~C20의 시클로알킬기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C8~C20의 아릴알켄일기, 실란기, 붕소기, 게르마늄기, 및 C2~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환됨을 의미하며, 이들 치환기에 제한되는 것은 아니다.In addition, unless explicitly stated, the term "substituted or unsubstituted" used in the present invention means "substituted" deuterium, halogen, amino group, nitrile group, nitro group, C 1 to C 20 alkyl group, C 1 to C 20 alkoxyl group, C 1 to C 20 alkylamine group, C 1 to C 20 alkylthiophene group, C 6 to C 20 arylthiophene group, C 2 to C 20 alkenyl group, C 2 to C 20 alkynyl, C 3 ~ C 20 cycloalkyl group, C 6 ~ C 20 aryl group, of a C 6 ~ C 20 substituted by deuterium aryl group, a C 8 ~ C 20 aryl alkenyl group, a silane group, a boron It means substituted with one or more substituents selected from the group consisting of a group, a germanium group, and a C 2 ~ C 20 heterocyclic group, and is not limited to these substituents.
또한 명시적인 설명이 없는 한, 본 발명에서 사용되는 화학식은 하기 화학식의 지수 정의에 의한 치환기 정의와 동일하게 적용된다.In addition, unless explicitly stated, the chemical formula used in the present invention is applied in the same manner as the definition of the substituent by the index definition of the following formula.
Figure PCTKR2020009674-appb-I000004
Figure PCTKR2020009674-appb-I000004
여기서, a가 0의 정수인 경우 치환기 R1은 부존재하며, a가 1의 정수인 경우 하나의 치환기 R1은 벤젠 고리를 형성하는 탄소 중 어느 하나의 탄소에 결합하며, a가 2 또는 3의 정수인 경우 각각 다음과 같이 결합하며 이때 R1은 서로 동일하거나 다를 수 있으며, a가 4 내지 6의 정수인 경우 이와 유사한 방식으로 벤젠 고리의 탄소에 결합하며, 한편 벤젠 고리를 형성하는 탄소에 결합된 수소의 표시는 생략한다.Here, when a is an integer of 0, the substituent R 1 is absent, and when a is an integer of 1, one substituent R 1 is bonded to any one of the carbons forming the benzene ring, and a is an integer of 2 or 3. Each is bonded as follows, wherein R 1 may be the same or different from each other, and when a is an integer of 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the hydrogen bonded to the carbon forming the benzene ring is indicated. Is omitted.
Figure PCTKR2020009674-appb-I000005
Figure PCTKR2020009674-appb-I000005
이하, 본 발명의 일 측면에 따른 화합물 및 이를 포함하는 유기전기소자에 대하여 설명한다.Hereinafter, a compound according to an aspect of the present invention and an organic electric device including the same will be described.
본 발명의 구체적인 예에 따르면, 하기 화학식 1로 표시되는 화합물을 제공한다.According to a specific example of the present invention, a compound represented by the following formula (1) is provided.
화학식 1 화학식 2Formula 1 Formula 2
Figure PCTKR2020009674-appb-I000006
Figure PCTKR2020009674-appb-I000006
상기 화학식 1 및 화학식 2에서, 각 기호는 하기와 같이 정의될 수 있다.In Formulas 1 and 2, each symbol may be defined as follows.
1) R1 내지 R7은 서로 독립적으로 수소; 중수소; 할로겐; C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C60의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕실기; 및 C6~C30의 아릴옥시기;로 이루어진 군에서 선택되며, 또한 상기 a, b, c, d, e, f 및 g가 2 이상인 경우 각각 복수로서 서로 동일하거나 상이하며, 복수의 R1끼리 혹은 복수의 R2끼리 혹은 복수의 R3끼리 혹은 복수의 R4끼리 혹은 복수의 R5끼리 혹은 복수의 R6끼리 혹은 복수의 R7끼리 서로 결합하여 고리를 형성할 수 있다. 이때 상기 고리는 벤젠, 나프틸, 벤조퓨란, 벤조싸이오펜, 인돌 또는 인덴일 수 있다.1) R 1 to R 7 are each independently hydrogen; heavy hydrogen; halogen; C 6 ~ C 60 aryl group; Fluorenyl group; O, N, S, Si, and C 2 ~ C 60 heterocyclic group containing at least one heteroatom of P; A fused ring group of an aliphatic ring of C 3 to C 60 and an aromatic ring of C 6 to C 60 ; C 1 ~ C 60 alkyl group; C 2 ~ C 20 alkenyl group; Alkynyl group of C 2 ~ C 20 ; An alkoxyl group of C 1 to C 30 ; And C 6 ~ C 30 aryloxy group; is selected from the group consisting of, and when a, b, c, d, e, f, and g are 2 or more, each is the same as or different from each other as a plurality, and a plurality of R 1 each other or are together a plurality of R 2 to each other or a plurality of R 3 to each other or a plurality of R 4 or R 5 together with each other a plurality of or a plurality of R 6 to each other or a plurality of R 7 may bond to one another to form a ring. At this time, the ring may be benzene, naphthyl, benzofuran, benzothiophene, indole, or indene.
상기 R1 내지 R7이 아릴기일 경우, C6~C25의 아릴기인 것이 바람직하며, 상기 R1 내지 R7이 헤테로고리기일 경우, O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C30의 헤테로고리기인 것이 바람직하고, 상기 R1 내지 R7이 융합고리기일 경우, C3~C30의 지방족고리와 C6~C30의 방향족고리의 융합고리기인 것이 바람직하며, 상기 R1 내지 R7이 알킬기일 경우, C1~C30의 알킬기인 것이 바람직하다.When the R 1 to R 7 is an aryl group, it is preferably an aryl group of C 6 to C 25 , and when the R 1 to R 7 is a heterocyclic group, at least one heteroatom of O, N, S, Si and P preferably a heterocyclic group of C 2 ~ C 30, and including the R 1 to R 7 are fused when ring group, a fusion ring group of the aromatic ring of C 3 ~ C 30 of aliphatic rings and C 6 ~ C 30 to Preferably, when the R 1 to R 7 is an alkyl group, it is preferably a C 1 to C 30 alkyl group.
2) L1 내지 L3는 서로 독립적으로 단일결합; C6-C60의 아릴렌기; 플루오렌일기; C2~C60의 헤테로고리기; 및 C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기;로 이루어진 군에서 선택되며, R4와 L1은 서로 결합하여 고리를 형성할 수 있다.2) L 1 to L 3 are each independently a single bond; C 6 -C 60 arylene group; Fluorenyl group; C 2 ~ C 60 heterocyclic group; And a fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; and R 4 and L 1 may be bonded to each other to form a ring.
상기 L1 내지 L3이 아릴렌기일 경우, C6-C25의 아릴렌기인 것이 바람직하며, 상기 L1 내지 L3이 헤테로고리기일 경우, O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C30의 헤테로고리기인 것이 바람직하고, 상기 L1 내지 L3이 융합고리기일 경우, C3-C30의 지방족고리와 C6-C30의 방향족고리의 융합고리기인 것이 바람직하다.When the L 1 to L 3 is an arylene group, it is preferable that it is an arylene group of C 6 -C 25 , and when the L 1 to L 3 is a heterocyclic group, at least one of O, N, S, Si and P preferably a heterocyclic group of C 2 ~ C 30 containing a hetero atom, and wherein L 1 to L 3 in this case fused ring group, a fused ring of an aromatic ring of C 3 -C 30 aliphatic and C 6 -C 30 ring It is preferable that it is a group.
3) Ar1은 C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; 및 C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기;로 이루어진 군에서 선택된다.3) Ar1 is a C 6 ~ C 60 aryl group; Fluorenyl group; O, N, S, Si, and C 2 -C 60 heterocyclic group containing at least one heteroatom of P; And a fused ring group of a C 3 -C 60 aliphatic ring and a C 6 -C 60 aromatic ring.
상기 Ar1이 아릴기일 경우, C6~C25의 아릴기인 것이 바람직하며, 상기 Ar1이 헤테로고리기일 경우, O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2-C30의 헤테로고리기인 것이 바람직하고, 상기 Ar1이 융합고리기일 경우, C3-C30의 지방족고리와 C6-C30의 방향족고리의 융합고리기인 것이 바람직하다.When Ar1 is an aryl group, it is preferable that it is an aryl group of C 6 to C 25 , and when Ar1 is a heterocyclic group, C 2 -C 30 including at least one heteroatom of O, N, S, Si and P It is preferably a heterocyclic group of, and when Ar1 is a fused cyclic group, it is preferably a fused cyclic group of a C 3 -C 30 aliphatic ring and a C 6 -C 30 aromatic ring.
4) A는 상기 화학식 2로 표시되며, 상기 화학식 2의 R5 내지 R7 중 적어도 어느 하나는 L3과 결합하고, 단, L3이 단일결합일 경우 상기 화학식 1의 N과 결합하며, R5 내지 R7은 서로 독립적으로 L3과 고리를 형성할 수 있다.4) A is represented by the general formula (2), at least one of the formula 2 R 5 to R 7 binds to N of formula (I) if combined with L 3, however, and the L 3 il single bond, R 5 to R 7 may each independently form a ring with L 3 .
5) R' 및 R”은 서로 독립적으로 C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; 및 C1~C60의 알킬기;로 이루어진 군에서 선택되며, R' 및 R”은 서로 결합하여 스파이로 고리를 형성할 수 있다.5) R'and R” are each independently a C 6 ~C 60 aryl group; Fluorenyl group; O, N, S, Si, and C 2 ~ C 60 heterocyclic group containing at least one heteroatom of P; And C 1 ~ C 60 Alkyl group; is selected from the group consisting of, R'and R” may be bonded to each other to form a spy ring.
상기 R' 및 R”이 아릴기일 경우, C6~C25의 아릴기인 것이 바람직하며, 상기 R' 및 R”이 헤테로고리기일 경우, O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C30의 헤테로고리기인 것이 바람직하고, 상기 R' 및 R”이 알킬기일 경우, C1~C30의 알킬기인 것이 바람직하다.When the R'and R” are an aryl group, it is preferably an aryl group of C 6 to C 25 , and when the R'and R” are heterocyclic groups, at least one heteroatom of O, N, S, Si and P It is preferably a C 2 ~ C 30 heterocyclic group containing, and when R'and R” are an alkyl group, it is preferably a C 1 ~ C 30 alkyl group.
6) X는 NRa, O, S 또는 CRbRc이다.6) X is NR a , O, S or CR b R c .
상기 Ra 내지 Rc는 서로 독립적으로 C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; 및 C1~C60의 알킬기;로 이루어진 군에서 선택된다.R a to R c are each independently a C 6 to C 60 aryl group; Fluorenyl group; O, N, S, Si, and C 2 ~ C 60 heterocyclic group containing at least one heteroatom of P; And C 1 ~ C 60 Alkyl group; is selected from the group consisting of.
상기 Ra 내지 Rc이 아릴기일 경우, C6~C25의 아릴기인 것이 바람직하며, 상기 Ra 내지 Rc이 헤테로고리기일 경우 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C30의 헤테로고리기인 것이 바람직하고, 상기 Ra 내지 Rc이 알킬기일 경우, C1~C30의 알킬기인 것이 바람직하다.When R a to R c is an aryl group, it is preferable that it is an aryl group of C 6 to C 25 , and when R a to R c is a heterocyclic group, at least one heteroatom of O, N, S, Si and P It is preferably a C 2 ~ C 30 heterocyclic group, and when R a to R c is an alkyl group, it is preferably a C 1 ~ C 30 alkyl group.
7) a는 0 내지 5의 정수이며, b, c, d, e 및 g는 서로 독립적으로 0 내지 4의 정수이고, f는 0 내지 2의 정수이다.7) a is an integer of 0 to 5, b, c, d, e and g are each independently an integer of 0 to 4, and f is an integer of 0 to 2.
여기서, 상기 아릴기, 플루오렌일기, 아릴렌기, 헤테로고리기, 플루오렌일렌기, 융합고리기, 알킬기, 알켄일기, 알콕실기 및 아릴옥시기는 각각 중수소; 할로겐; 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; C1-C20의 알킬싸이오기; C1-C20의 알콕실기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 중수소로 치환된 C6-C20의 아릴기; 플루오렌일기; C2-C20의 헤테로고리기; C3-C20의 시클로알킬기; C7-C20의 아릴알킬기 및 C8-C20의 아릴알켄일기;로 이루어진 군에서 선택된 하나 이상의 치환기로 더욱 치환될 수 있으며, 또한 이들 치환기들은 서로 결합하여 고리를 형성할 수도 있으며, 여기서 '고리'란 C3-C60의 지방족고리 또는 C6-C60의 방향족고리 또는 C2-C60의 헤테로고리 또는 이들의 조합으로 이루어진 융합 고리를 말하며, 포화 또는 불포화 고리를 포함한다.Here, the aryl group, fluorenyl group, arylene group, heterocyclic group, fluorenylene group, fused ring group, alkyl group, alkenyl group, alkoxyl group and aryloxy group are each deuterium; halogen; Silane group; Siloxane group; Boron group; Germanium group; Cyano group; Nitro group; C 1 -C 20 alkylthio group; An alkoxyl group of C 1 -C 20 ; A C 1 -C 20 alkyl group; An alkenyl group of C 2 -C 20 ; Alkynyl group of C 2 -C 20 ; C 6 -C 20 aryl group; A C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group; A C 3 -C 20 cycloalkyl group; C 7 -C 20 arylalkyl group and C 8 -C 20 arylalkenyl group; may be further substituted with one or more substituents selected from the group consisting of, and these substituents may be bonded to each other to form a ring, wherein ' The term'ring' refers to a fused ring consisting of a C 3 -C 60 aliphatic ring or a C 6 -C 60 aromatic ring or a C 2 -C 60 hetero ring or a combination thereof, and includes a saturated or unsaturated ring.
단, 하기 화학식 11로 표시되는 화합물은 제외한다.However, compounds represented by the following formula (11) are excluded.
화학식 11Formula 11
Figure PCTKR2020009674-appb-I000007
Figure PCTKR2020009674-appb-I000007
{상기 화학식 11에서,{In Formula 11,
1) R1 내지 R4, L1, L2, Ar1, a, b, c 및 d는 상기 화학식 1에서의 정의와 동일하고,1) R 1 to R 4 , L 1 , L 2 , Ar1, a, b, c and d are the same as defined in Formula 1,
2) R11, R12 및 R13은 서로 독립적으로 수소; 중수소; 할로겐; C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C60의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕실기; 및 C6~C30의 아릴옥시기;로 이루어진 군에서 선택되며, 또한 상기 x, y 및 z가 2 이상인 경우 각각 복수로서 서로 동일하거나 상이하며, 복수의 R11끼리 혹은 복수의 R12끼리 혹은 복수의 R13끼리 서로 결합하여 고리를 형성할 수 있고,2) R 11 , R 12 and R 13 are each independently hydrogen; heavy hydrogen; halogen; C 6 ~ C 60 aryl group; Fluorenyl group; O, N, S, Si, and C 2 ~ C 60 heterocyclic group containing at least one heteroatom of P; A fused ring group of an aliphatic ring of C 3 to C 60 and an aromatic ring of C 6 to C 60 ; C 1 ~ C 60 alkyl group; C 2 ~ C 20 alkenyl group; Alkynyl group of C 2 ~ C 20 ; An alkoxyl group of C 1 to C 30 ; And C 6 ~ C 30 aryloxy group; is selected from the group consisting of, and when x, y and z are 2 or more, each is the same as or different from each other as a plurality, and a plurality of R 11 or a plurality of R 12 or A plurality of R 13 can be bonded to each other to form a ring,
3) R14 및 R15는 상기 화학식 2에서 정의된 R' 및 R”와 동일하며,3) R 14 and R 15 are the same as R'and R” defined in Formula 2,
4) x는 0 내지 3의 정수이며, y는 0 내지 2의 정수이고, z는 0 내지 4의 정수이다.}4) x is an integer from 0 to 3, y is an integer from 0 to 2, and z is an integer from 0 to 4.}
또한, 본 발명은 상기 화학식 1로 나타낸 화합물이 하기 화학식 1-1 또는 화학식 1-2로 표시되는 화합물을 포함한다.In addition, the present invention includes the compound represented by Formula 1 or Formula 1-2 below.
화학식 1-1 화학식 1-2Formula 1-1 Formula 1-2
Figure PCTKR2020009674-appb-I000008
Figure PCTKR2020009674-appb-I000009
Figure PCTKR2020009674-appb-I000008
Figure PCTKR2020009674-appb-I000009
{상기 화학식 1-1 및 화학식 1-2에서,{In Formula 1-1 and Formula 1-2,
1) R1 내지 R7, L1 내지 L3, R', R”, Ar1, X, a, b, c, d, e, f 및 g는 상기 화학식 1 및 화학식 2에 정의된 바와 같으며,1) R 1 to R 7 , L 1 to L 3 , R', R”, Ar1, X, a, b, c, d, e, f and g are as defined in Formulas 1 and 2, and ,
2) R15 및 R17은 수소; 중수소; C1-C60의 알콕실기; C1-C60의 알킬기; C2-C60의 알켄일기; C2-C60의 알킨일기; C6-C60의 아릴기; 중수소로 치환된 C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 시클로알킬기; C7-C60의 아릴알킬기; 및 C8-C60의 아릴알켄일기;로 이루어진 군에서 선택되며, 복수의 R15끼리 혹은 복수의 R17끼리 서로 결합하여 고리를 형성할 수 있고,2) R 15 and R 17 are hydrogen; heavy hydrogen; An alkoxyl group of C 1 -C 60 ; A C 1 -C 60 alkyl group; An alkenyl group of C 2 -C 60 ; Alkynyl group of C 2 -C 60 ; C 6 -C 60 aryl group; A C 6 -C 60 aryl group substituted with deuterium; Fluorenyl group; O, N, S, Si, and C 2 -C 60 heterocyclic group containing at least one heteroatom of P; A C 3 -C 60 cycloalkyl group; C 7 -C 60 arylalkyl group; And C 8 -C 60 arylalkenyl group; selected from the group consisting of, a plurality of R 15 to each other or a plurality of R 17 to each other can form a ring,
3) e' 및 g'은 서로 독립적으로 0 내지 3의 정수이다.}3) e'and g'are each independently an integer of 0 to 3.}
또한, 본 발명은 상기 화학식 1로 나타낸 화합물이 하기 화학식 1-3 내지 화학식 1-5로 표시되는 화합물을 포함한다.In addition, the present invention includes compounds represented by the following Formulas 1-3 to 1-5, wherein the compound represented by Formula 1 above.
화학식 1-3 화학식 1-4Formula 1-3 Formula 1-4
Figure PCTKR2020009674-appb-I000010
Figure PCTKR2020009674-appb-I000010
화학식 1-5Formula 1-5
Figure PCTKR2020009674-appb-I000011
Figure PCTKR2020009674-appb-I000011
{상기 화학식 1-3 내지 화학식 1-5에서,{In Formulas 1-3 to 1-5,
R1 내지 R4, L1 내지 L3, Ar1, A, a, b, c 및 d는 상기 화학식 1에서 정의한 바와 동일하다.}R 1 to R 4 , L 1 to L 3 , Ar1, A, a, b, c and d are the same as defined in Chemical Formula 1.}
또한, 본 발명의 상기 화학식 2는 하기 화학식 2-1 내지 화학식 2-4로 표시되는 화합물을 포함하는 것이 바람직하다.In addition, it is preferable that the formula 2 of the present invention includes a compound represented by the following formulas 2-1 to 2-4.
화학식 2-1 화학식 2-2Formula 2-1 Formula 2-2
Figure PCTKR2020009674-appb-I000012
Figure PCTKR2020009674-appb-I000012
화학식 2-3 화학식 2-4Formula 2-3 Formula 2-4
Figure PCTKR2020009674-appb-I000013
Figure PCTKR2020009674-appb-I000013
{상기 화학식 2-1 내지 화학식 2-4에서,{In Formula 2-1 to Formula 2-4,
R5, R6, R7, R', R”, Ra, Rb, Rc, e, f 및 g는 상기 화학식 2에서 정의한 바와 동일하다.}R 5 , R 6 , R 7 , R', R”, R a , R b , R c , e, f and g are the same as defined in Formula 2 above.}
또한, 본 발명의 상기 화학식 2는 하기 화학식 2-5 내지 화학식 2-10으로 표시되는 화합물을 포함하는 것이 바람직하다.In addition, it is preferable that the formula 2 of the present invention includes a compound represented by the following formulas 2-5 to 2-10.
화학식 2-5 화학식 2-6Formula 2-5 Formula 2-6
Figure PCTKR2020009674-appb-I000014
Figure PCTKR2020009674-appb-I000014
화학식 2-7 화학식 2-8Chemical Formula 2-7 Chemical Formula 2-8
Figure PCTKR2020009674-appb-I000015
Figure PCTKR2020009674-appb-I000015
화학식 2-9 화학식 2-10Chemical Formula 2-9 Chemical Formula 2-10
Figure PCTKR2020009674-appb-I000016
Figure PCTKR2020009674-appb-I000016
{상기 화학식 2-5 내지 화학식 2-10에서,{In Formula 2-5 to Formula 2-10,
R5, R6, R7, X, R', R”, e, f 및 g는 상기 화학식 2에서 정의한 바와 동일하다.}R 5 , R 6 , R 7 , X, R', R”, e, f and g are the same as defined in Chemical Formula 2.}
또한, 본 발명은 상기 화학식 1로 나타낸 화합물이 하기 화학식 1-6 내지 화학식 1-11로 표시되는 화합물을 포함한다.In addition, the present invention includes a compound represented by Formula 1 to Formula 1-11 below.
화학식 1-6 화학식 1-7Formula 1-6 Formula 1-7
Figure PCTKR2020009674-appb-I000017
Figure PCTKR2020009674-appb-I000017
화학식 1-8 화학식 1-9Chemical Formula 1-8 Chemical Formula 1-9
Figure PCTKR2020009674-appb-I000018
Figure PCTKR2020009674-appb-I000018
화학식 1-10 화학식 1-11Formula 1-10 Formula 1-11
Figure PCTKR2020009674-appb-I000019
Figure PCTKR2020009674-appb-I000019
{상기 화학식 1-6 내지 화학식 1-11에서,{In Formula 1-6 to Formula 1-11,
1) R1 내지 R7, L1 내지 L3, R', R”, Ar1, X, a, b, c, d, e, f 및 g는 상기 화학식 1 및 화학식 2에서 정의한 바와 동일하며,1) R 1 to R 7 , L 1 to L 3 , R', R”, Ar1, X, a, b, c, d, e, f and g are the same as defined in Formulas 1 and 2,
2) R15, R17, e' 및 g'은 상기 화학식 1-1 및 화학식 1-2에서 정의한 바와 동일하다.}2) R 15 , R 17 , e'and g'are the same as defined in Chemical Formulas 1-1 and 1-2.}
구체적으로, 상기 화학식 1로 나타내는 화합물이 하기 화합물 P-1 내지 P-128 중 어느 하나일 수 있으나, 이에 제한되는 것은 아니다.Specifically, the compound represented by Formula 1 may be any one of Compounds P-1 to P-128 below, but is not limited thereto.
Figure PCTKR2020009674-appb-I000020
Figure PCTKR2020009674-appb-I000020
Figure PCTKR2020009674-appb-I000021
Figure PCTKR2020009674-appb-I000021
Figure PCTKR2020009674-appb-I000022
Figure PCTKR2020009674-appb-I000022
Figure PCTKR2020009674-appb-I000023
Figure PCTKR2020009674-appb-I000023
Figure PCTKR2020009674-appb-I000024
Figure PCTKR2020009674-appb-I000024
Figure PCTKR2020009674-appb-I000025
Figure PCTKR2020009674-appb-I000025
Figure PCTKR2020009674-appb-I000026
Figure PCTKR2020009674-appb-I000026
Figure PCTKR2020009674-appb-I000027
Figure PCTKR2020009674-appb-I000027
Figure PCTKR2020009674-appb-I000028
Figure PCTKR2020009674-appb-I000028
Figure PCTKR2020009674-appb-I000029
Figure PCTKR2020009674-appb-I000029
Figure PCTKR2020009674-appb-I000030
Figure PCTKR2020009674-appb-I000030
Figure PCTKR2020009674-appb-I000031
Figure PCTKR2020009674-appb-I000031
Figure PCTKR2020009674-appb-I000032
Figure PCTKR2020009674-appb-I000032
Figure PCTKR2020009674-appb-I000033
Figure PCTKR2020009674-appb-I000033
Figure PCTKR2020009674-appb-I000034
Figure PCTKR2020009674-appb-I000034
Figure PCTKR2020009674-appb-I000035
Figure PCTKR2020009674-appb-I000035
Figure PCTKR2020009674-appb-I000036
Figure PCTKR2020009674-appb-I000036
Figure PCTKR2020009674-appb-I000037
Figure PCTKR2020009674-appb-I000037
Figure PCTKR2020009674-appb-I000038
Figure PCTKR2020009674-appb-I000038
Figure PCTKR2020009674-appb-I000039
Figure PCTKR2020009674-appb-I000039
Figure PCTKR2020009674-appb-I000040
Figure PCTKR2020009674-appb-I000040
Figure PCTKR2020009674-appb-I000041
Figure PCTKR2020009674-appb-I000041
Figure PCTKR2020009674-appb-I000042
Figure PCTKR2020009674-appb-I000042
Figure PCTKR2020009674-appb-I000043
Figure PCTKR2020009674-appb-I000043
Figure PCTKR2020009674-appb-I000044
Figure PCTKR2020009674-appb-I000044
Figure PCTKR2020009674-appb-I000045
Figure PCTKR2020009674-appb-I000045
Figure PCTKR2020009674-appb-I000046
Figure PCTKR2020009674-appb-I000046
Figure PCTKR2020009674-appb-I000047
Figure PCTKR2020009674-appb-I000047
Figure PCTKR2020009674-appb-I000048
Figure PCTKR2020009674-appb-I000048
Figure PCTKR2020009674-appb-I000049
Figure PCTKR2020009674-appb-I000049
Figure PCTKR2020009674-appb-I000050
Figure PCTKR2020009674-appb-I000050
Figure PCTKR2020009674-appb-I000051
Figure PCTKR2020009674-appb-I000051
도 1을 참조하여 설명하면, 본 발명에 따른 유기전기소자(100)는 제 1전극(110), 제 2전극(170) 및 제 1전극(110)과 제 2전극(170) 사이에 화학식 1로 표시되는 단독화합물 또는 2종 이상의 화합물을 포함하는 유기물층을 구비한다. 이때, 제 1전극(110)은 애노드 또는 양극이고, 제 2전극(170)은 캐소드 또는 음극일 수 있으며, 인버트형의 경우에는 제 1전극이 캐소드이고 제 2전극이 애노드일 수 있다Referring to FIG. 1, the organic electric device 100 according to the present invention has a formula 1 between the first electrode 110, the second electrode 170, and the first electrode 110 and the second electrode 170. A single compound represented by or an organic material layer including two or more compounds is provided. At this time, the first electrode 110 may be an anode or an anode, and the second electrode 170 may be a cathode or 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.
유기물층은 제 1전극(110) 상에 순차적으로 정공주입층(120), 정공수송층(130), 발광층(140), 전자수송층(150) 및 전자주입층(160)을 포함할 수 있다. 이때, 발광층(140)을 제외한 나머지 층들이 형성되지 않을 수 있다. 정공저지층, 전자저지층, 발광보조층(220), 버퍼층(210) 등을 더 포함할 수도 있고, 전자수송층(150) 등이 정공저지층의 역할을 할 수도 있을 것이다. (도 2 참조)The organic material layer may sequentially 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 on the first electrode 110. In this case, other layers other than the emission layer 140 may not be formed. A hole blocking layer, an electron blocking layer, a light emission auxiliary layer 220, and a buffer layer 210 may be further included, and the electron transport layer 150 may serve as a hole blocking layer. (See Fig. 2)
또한, 본 발명의 일 실시예에 따른 유기전기소자는 보호층 또는 광효율 개선층(180)을 더 포함할 수 있다. 이러한 광효율 개선층은 제 1전극의 양면 중 유기물층과 접하지 않는 면 또는 제 2전극의 양면 중 유기물층과 접하지 않는 면에 형성될 수 있다상기 유기물층에 적용되는 본 발명의 일 실시예에 따른 화합물은 정공주입층(120), 정공수송층(130), 발광보조층(220), 전자수송보조층, 전자수송층(150), 전자주입층(160), 발광층(140)의 호스트 또는 도펀트, 또는 광효율 개선층의 재료로 사용될 수 있을 것이다. 바람직하게는 예컨대, 본 발명의 화학식 1에 따른 화합물은 발광보조층의 재료로 사용될 수 있다. 바람직하게는 적색 발광보조층의 재료로 사용될 수 있다.In addition, the organic electric device according to an embodiment of the present invention may further include a protective layer or a light efficiency improvement layer 180. The light efficiency improvement layer may be formed on a surface not in contact with the organic material layer among both surfaces of the first electrode or on a surface not in contact with the organic material layer among both surfaces of the second electrode. The compound according to an embodiment of the present invention applied to the organic material layer is Hole injection layer 120, hole transport layer 130, light emission auxiliary layer 220, electron transport auxiliary layer, electron transport layer 150, electron injection layer 160, host or dopant of emission layer 140, or light efficiency improvement It could be used as a layer material. Preferably, for example, the compound according to Formula 1 of the present invention may be used as a material for the light emitting auxiliary layer. Preferably, it can be used as a material for the red light emission auxiliary layer.
상기 유기물층은 상기 양극 상에 순차적으로 형성된 정공수송층, 발광층 및 전자수송층을 포함하는 스택을 둘 이상 포함할 수 있으며, 상기 둘 이상의 스택 사이에 형성된 전하생성층을 더 포함할 수 있다.(도 3 참조)The organic material layer may include two or more stacks including a hole transport layer, an emission layer, and an electron transport layer sequentially formed on the anode, and may further include a charge generation layer formed between the two or more stacks (see FIG. 3 ). )
한편, 동일한 코어일지라도 어느 위치에 어느 치환기를 결합시키냐에 따라 밴드갭(band gap), 전기적 특성, 계면 특성 등이 달라질 수 있으므로, 코어의 선택 및 이에 결합된 서브(sub)-치환체의 조합도 아주 중요하며, 특히 각 유기물층 간의 에너지 level 및 T1 값, 물질의 고유특성(mobility, 계면특성 등) 등이 최적의 조합을 이루었을 때 긴 수명과 높은 효율을 동시에 달성할 수 있다.On the other hand, even with the same core, the band gap, electrical characteristics, and interfacial characteristics may vary depending on which substituent is bonded to any position, so the selection of the core and the combination of sub-substituents bonded thereto are also very It is important, and in particular, long life and high efficiency can be achieved at the same time when the energy level and T1 value between each organic material layer and the intrinsic properties of materials (mobility, interfacial properties, etc.) are optimally combined.
본 발명의 일 실시예에 따른 유기전기발광소자는 PVD(physical vapor deposition) 방법을 이용하여 제조될 수 있다. 예컨대, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고, 그 위에 정공주입층(120), 정공수송층(130), 발광층(140), 전자수송층(150) 및 전자주입층(160)을 포함하는 유기물층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다.The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a physical vapor deposition (PVD) method. For example, an anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and a hole injection layer 120, a hole transport layer 130, a light emitting layer 140, an electron transport layer 150, and After forming an organic material layer including the electron injection layer 160, it may be manufactured by depositing a material that can be used as a cathode thereon.
또한 본 발명에서 상기 유기물층은 스핀코팅 공정, 노즐 프린팅 공정, 잉크젯 프린팅 공정, 슬롯코팅 공정, 딥코팅 공정 및 롤투롤 공정 중 어느 하나에 의해 형성되며, 상기 유기물층은 전자수송재료로 상기 화합물을 포함하는 것을 특징으로 하는 유기전기소자를 제공한다.In addition, in the present invention, the organic material layer is formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, and a roll-to-roll process, and the organic material layer contains the compound as an electron transport material. It provides an organic electric device characterized in that.
또 다른 구체적인 예로서, 본 발명은 상기 유기물층에 상기 화학식 1로 표시되는 화합물의 동종 또는 이종의 화합물이 혼합되어 사용되는 것을 특징으로 하는 유기전기소자를 제공한다.As another specific example, the present invention provides an organic electric device, characterized in that the organic material layer is used by mixing the same or different compounds of the compound represented by Formula 1 above.
또한 본 발명은 상기 화학식 1로 표시되는 화합물을 포함하는 발광보조층 조성물을 제공하고, 상기 발광보조층을 포함하는 유기전기소자를 제공한다.In addition, the present invention provides a light emission auxiliary layer composition comprising the compound represented by Formula 1, and provides an organic electric device including the light emission auxiliary layer.
또한 본 발명은 상기한 유기전기소자를 포함하는 디스플레이장치; 및 상기 디스플레이장치를 구동하는 제어부;를 포함하는 전자장치를 제공한다.In addition, the present invention is a display device including the organic electric device; And a controller for driving the display device.
또 다른 측면에서 상기 유기전기소자는 유기전기발광소자, 유기태양전지, 유기감광체, 유기트랜지스터, 및 단색 또는 백색 조명용 소자 중 적어도 하나인 것을 특징으로 하는 전자장치를 본 발명에서 제공한다. 이때, 전자장치는 현재 또는 장래의 유무선 통신단말기일 수 있으며, 휴대폰 등의 이동 통신 단말기, PDA, 전자사전, PMP, 리모콘, 네비게이션, 게임기, 각종 TV, 각종 컴퓨터 등 모든 전자장치를 포함한다.In another aspect, the present invention provides an electronic device, characterized in that the organic electric device is at least one of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, and a single color or white lighting device. In this case, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as mobile communication terminals such as mobile phones, PDAs, electronic dictionaries, PMPs, remote controls, navigation, game consoles, various TVs, and various computers.
이하에서, 본 발명의 상기 화학식 1로 표시되는 화합물의 합성예 및 본 발명의 유기전기소자의 제조예에 관하여 실시예를 들어 구체적으로 설명하지만, 본 발명의 하기 실시예로 한정되는 것은 아니다.Hereinafter, examples for synthesizing the compound represented by Chemical Formula 1 of the present invention and examples for manufacturing the organic electric device of the present invention will be described in detail, but are not limited to the following examples of the present invention.
[[ 합성예Synthesis example 1] One]
본 발명에 따른 화학식 1로 표시되는 화합물(Final Product)은 하기 반응식 1과 같이 합성되며, 이에 한정되는 것은 아니다. Hal은 I, Br 또는 Cl이다.The compound (Final Product) represented by Formula 1 according to the present invention is synthesized as shown in Scheme 1 below, but is not limited thereto. Hal is I, Br or Cl.
<반응식 1><Reaction Scheme 1>
Figure PCTKR2020009674-appb-I000052
Figure PCTKR2020009674-appb-I000052
I. Sub 1의 합성I. Synthesis of Sub 1
상기 반응식 1의 Sub 1은 하기 반응식 2의 반응경로에 의해 합성되며, 이에 한정되는 것은 아니다. Hal은 I, Br 또는 Cl이다.Sub 1 of Scheme 1 is synthesized by the reaction route of Scheme 2 below, but is not limited thereto. Hal is I, Br or Cl.
<반응식 2><Reaction Scheme 2>
Figure PCTKR2020009674-appb-I000053
Figure PCTKR2020009674-appb-I000053
1. Sub 1-1 1.Sub 1-1 합성예Synthesis example
Figure PCTKR2020009674-appb-I000054
Figure PCTKR2020009674-appb-I000054
둥근바닥플라스크에 Sub 1-1-a (50 g, 125.8 mmol), Sub 1-1-b (42.6 g, 251.7 mmol), Pd2(dba)3 (3.5 g, 3.8 mmol), P(t-Bu)3 (1.5 g, 7.6 mmol), NaOt-Bu (24.2 g, 251.7 mmol), toluene (629 mL)을 넣은 후에 80℃에서 반응을 진행한다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물 49.5 g을 얻었다. (수율 : 81%)In a round bottom flask, Sub 1-1-a (50 g, 125.8 mmol), Sub 1-1-b (42.6 g, 251.7 mmol), Pd 2 (dba) 3 (3.5 g, 3.8 mmol), P(t- Bu) 3 (1.5 g, 7.6 mmol), NaOt-Bu (24.2 g, 251.7 mmol), and toluene (629 mL) were added, followed by reaction at 80°C. When the reaction was completed, the product was extracted with CH 2 Cl 2 and water, and the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 49.5 g of a product. (Yield: 81%)
2. Sub 1-27 2.Sub 1-27 합성예Synthesis example
Figure PCTKR2020009674-appb-I000055
Figure PCTKR2020009674-appb-I000055
둥근바닥플라스크에 Sub 1-27-a (50.0 g, 447.38 mmol), Sub 1-27-b (57.7 g, 223.5 mmol), Pd2(dba)3 (3.1 g, 3.4 mmol), P(t-Bu)3 (1.4 g, 6.7 mmol), NaOt-Bu (21.5 g, 223.5 mmol), toluene (559 mL)을 상기 Sub 1-1과 동일한 방법으로 실험하여 생성물 53.8 g을 얻었다. (수율 : 77%)In a round bottom flask, Sub 1-27-a (50.0 g, 447.38 mmol), Sub 1-27-b (57.7 g, 223.5 mmol), Pd 2 (dba) 3 (3.1 g, 3.4 mmol), P(t- Bu) 3 (1.4 g, 6.7 mmol), NaOt-Bu (21.5 g, 223.5 mmol), and toluene (559 mL) were tested in the same manner as in Sub 1-1 to obtain 53.8 g of a product. (Yield: 77%)
3. Sub 1-37 3.Sub 1-37 합성예Synthesis example
Figure PCTKR2020009674-appb-I000056
Figure PCTKR2020009674-appb-I000056
둥근바닥플라스크에 Sub 1-37-a (50.0 g, 487.4 mmol), Sub 1-27-b (19.1 g, 205.2 mmol), Pd2(dba)3 (2.8 g, 3.1 mmol), P(t-Bu)3 (1.3 g, 6.2 mmol), NaOt-Bu (19.7 g, 205.2 mmol), toluene (513 mL)을 상기 Sub 1-1과 동일한 방법으로 실험하여 생성물 40.5 g을 얻었다. (수율 : 79%)In a round bottom flask, Sub 1-37-a (50.0 g, 487.4 mmol), Sub 1-27-b (19.1 g, 205.2 mmol), Pd 2 (dba) 3 (2.8 g, 3.1 mmol), P(t- Bu) 3 (1.3 g, 6.2 mmol), NaOt-Bu (19.7 g, 205.2 mmol), and toluene (513 mL) were tested in the same manner as in Sub 1-1 to obtain 40.5 g of a product. (Yield: 79%)
상기 Sub 1에 속하는 화합물은 아래와 같은 화합물일 수 있으나, 이에 한정되는 것은 아니며, 하기 표 1은 Sub 1에 속하는 화합물의 FD-MS (Field Desorption-Mass Spectrometry) 값을 나타낸 것이다.The compound belonging to Sub 1 may be a compound as follows, but is not limited thereto, and Table 1 below shows FD-MS (Field Desorption-Mass Spectrometry) values of the compound belonging to Sub 1.
Figure PCTKR2020009674-appb-I000057
Figure PCTKR2020009674-appb-I000057
Figure PCTKR2020009674-appb-I000058
Figure PCTKR2020009674-appb-I000058
Figure PCTKR2020009674-appb-I000059
Figure PCTKR2020009674-appb-I000059
Figure PCTKR2020009674-appb-I000060
Figure PCTKR2020009674-appb-I000060
Figure PCTKR2020009674-appb-I000061
Figure PCTKR2020009674-appb-I000061
Figure PCTKR2020009674-appb-I000062
Figure PCTKR2020009674-appb-I000062
Figure PCTKR2020009674-appb-I000063
Figure PCTKR2020009674-appb-I000063
Figure PCTKR2020009674-appb-I000064
Figure PCTKR2020009674-appb-I000064
Figure PCTKR2020009674-appb-I000065
Figure PCTKR2020009674-appb-I000065
Figure PCTKR2020009674-appb-I000066
Figure PCTKR2020009674-appb-I000066
Figure PCTKR2020009674-appb-I000067
Figure PCTKR2020009674-appb-I000067
Figure PCTKR2020009674-appb-I000068
Figure PCTKR2020009674-appb-I000068
Figure PCTKR2020009674-appb-I000069
Figure PCTKR2020009674-appb-I000069
Figure PCTKR2020009674-appb-I000070
Figure PCTKR2020009674-appb-I000070
Figure PCTKR2020009674-appb-I000071
Figure PCTKR2020009674-appb-I000071
Figure PCTKR2020009674-appb-I000072
Figure PCTKR2020009674-appb-I000072
화합물compound FD-MSFD-MS 화합물compound FD-MSFD-MS
Sub 1-1Sub 1-1 m/z=485.21(C37H27N=485.63)m/z=485.21 (C 37 H 27 N=485.63) Sub 1-2Sub 1-2 m/z=485.21(C37H27N=485.63)m/z=485.21 (C 37 H 27 N=485.63)
Sub 1-3Sub 1-3 m/z=485.21(C37H27N=485.63)m/z=485.21 (C 37 H 27 N=485.63) Sub 1-4Sub 1-4 m/z=409.18(C31H23N=409.53)m/z=409.18 (C 31 H 23 N=409.53)
Sub 1-5Sub 1-5 m/z=561.25(C43H31N=561.73)m/z=561.25 (C 43 H 31 N=561.73) Sub 1-6Sub 1-6 m/z=485.21(C37H27N=485.63)m/z=485.21 (C 37 H 27 N=485.63)
Sub 1-7Sub 1-7 m/z=409.18(C31H23N=409.53)m/z=409.18 (C 31 H 23 N=409.53) Sub 1-8Sub 1-8 m/z=549.21(C41H27NO=549.67)m/z=549.21 (C 41 H 27 NO=549.67)
Sub 1-9Sub 1-9 m/z=535.23(C41H29N=535.69)m/z=535.23 (C 41 H 29 N=535.69) Sub 1-10Sub 1-10 m/z=611.26(C47H33N=611.79)m/z=611.26 (C 47 H 33 N=611.79)
Sub 1-11Sub 1-11 m/z=525.25(C40H31N=525.7)m/z=525.25 (C 40 H 31 N=525.7) Sub 1-12Sub 1-12 m/z=499.19(C37H25NO=499.61)m/z=499.19 (C 37 H 25 NO=499.61)
Sub 1-13Sub 1-13 m/z=485.21(C37H27N=485.63)m/z=485.21 (C 37 H 27 N=485.63) Sub 1-14Sub 1-14 m/z=515.17(C37H25NS=515.67)m/z=515.17 (C 37 H 25 NS=515.67)
Sub 1-15Sub 1-15 m/z=727.29(C55H37NO=727.91)m/z=727.29 (C 55 H 37 NO=727.91) Sub 1-16Sub 1-16 m/z=549.21(C41H27NO=549.67)m/z=549.21 (C 41 H 27 NO=549.67)
Sub 1-17Sub 1-17 m/z=485.21(C37H27N=485.63)m/z=485.21 (C 37 H 27 N=485.63) Sub 1-18Sub 1-18 m/z=525.25(C40H31N=525.7)m/z=525.25 (C 40 H 31 N=525.7)
Sub 1-19Sub 1-19 m/z=574.24(C43H30N2=574.73)m/z=574.24 (C 43 H 30 N 2 =574.73) Sub 1-20Sub 1-20 m/z=487.2(C35H25N3=487.61)m/z=487.2 (C 35 H 25 N 3 =487.61)
Sub 1-21Sub 1-21 m/z=601.28(C46H35N=601.79)m/z=601.28 (C 46 H 35 N=601.79) Sub 1-22Sub 1-22 m/z=486.21(C36H26N2=486.62)m/z=486.21 (C 36 H 26 N 2 =486.62)
Sub 1-23Sub 1-23 m/z=535.23(C41H29N=535.69)m/z=535.23 (C 41 H 29 N=535.69) Sub 1-24Sub 1-24 m/z=485.21(C37H27N=485.63)m/z=485.21 (C 37 H 27 N=485.63)
Sub 1-25Sub 1-25 m/z=613.25(C45H31N3=613.76)m/z=613.25 (C 45 H 31 N 3 =613.76) Sub 1-26Sub 1-26 m/z=561.25(C43H31N=561.73)m/z=561.25 (C 43 H 31 N=561.73)
Sub 1-27Sub 1-27 m/z=624.26(C47H32N2=624.79)m/z=624.26 (C 47 H 32 N 2 =624.79) Sub 1-28Sub 1-28 m/z=509.21(C39H27N=509.65)m/z=509.21 (C 39 H 27 N=509.65)
Sub 1-29Sub 1-29 m/z=716.29(C52H36N4=716.89)m/z=716.29 (C 52 H 36 N 4 =716.89) Sub 1-30Sub 1-30 m/z=549.21(C41H27NO=549.67)m/z=549.21 (C 41 H 27 NO=549.67)
Sub 1-31Sub 1-31 m/z=574.24(C43H30N2=574.73)m/z=574.24 (C 43 H 30 N 2 =574.73) Sub 1-32Sub 1-32 m/z=591.2(C43H29NS=591.77)m/z=591.2 (C 43 H 29 NS=591.77)
Sub 1-33Sub 1-33 m/z=561.25(C43H31N=561.73)m/z=561.25 (C 43 H 31 N=561.73) Sub 1-34Sub 1-34 m/z=649.28(C50H35N=649.84)m/z=649.28 (C 50 H 35 N=649.84)
Sub 1-35Sub 1-35 m/z=561.25(C43H31N=561.73)m/z=561.25 (C 43 H 31 N=561.73) Sub 1-36Sub 1-36 m/z=649.28(C50H35N=649.84)m/z=649.28 (C 50 H 35 N=649.84)
Sub 1-37Sub 1-37 m/z=499.19(C37H25NO=499.61)m/z=499.19 (C 37 H 25 NO=499.61) Sub 1-38Sub 1-38 m/z=459.2(C35H25N=459.59)m/z=459.2 (C 35 H 25 N=459.59)
Sub 1-39Sub 1-39 m/z=528.22(C38H28N2O=528.66)m/z=528.22 (C 38 H 28 N 2 O=528.66) Sub 1-40Sub 1-40 m/z=537.22(C39H27N3=537.67)m/z=537.22 (C 39 H 27 N 3 =537.67)
Sub 1-41Sub 1-41 m/z=485.21(C37H27N=485.63)m/z=485.21 (C 37 H 27 N=485.63) Sub 1-42Sub 1-42 m/z=485.21(C37H27N=485.63)m/z=485.21 (C 37 H 27 N=485.63)
Sub 1-43Sub 1-43 m/z=561.25(C43H31N=561.73)m/z=561.25 (C 43 H 31 N=561.73) Sub 1-44Sub 1-44 m/z=409.18(C31H23N=409.53)m/z=409.18 (C 31 H 23 N=409.53)
Sub 1-45Sub 1-45 m/z=611.26(C47H33N=611.79)m/z=611.26 (C 47 H 33 N=611.79) Sub 1-46Sub 1-46 m/z=575.22(C43H29NO=575.71)m/z=575.22 (C 43 H 29 NO=575.71)
Sub 1-47Sub 1-47 m/z=509.21(C39H27N=509.65)m/z=509.21 (C 39 H 27 N=509.65) Sub 1-48Sub 1-48 m/z=525.25(C40H31N=525.7)m/z=525.25 (C 40 H 31 N=525.7)
Sub 1-49Sub 1-49 m/z=485.21(C37H27N=485.63)m/z=485.21 (C 37 H 27 N=485.63) Sub 1-50Sub 1-50 m/z=574.24(C43H30N2=574.73)m/z=574.24 (C 43 H 30 N 2 =574.73)
Sub 1-51Sub 1-51 m/z=561.25(C43H31N=561.73)m/z=561.25 (C 43 H 31 N=561.73) Sub 1-52Sub 1-52 m/z=575.22(C43H29NO=575.71)m/z=575.22 (C 43 H 29 NO=575.71)
Sub 1-53Sub 1-53 m/z=574.24(C43H30N2=574.73)m/z=574.24 (C 43 H 30 N 2 =574.73) Sub 1-54Sub 1-54 m/z=459.2(C35H25N=459.59)m/z=459.2 (C 35 H 25 N=459.59)
Sub 1-55Sub 1-55 m/z=459.2(C35H25N=459.59)m/z=459.2 (C 35 H 25 N=459.59) Sub 1-56Sub 1-56 m/z=561.25(C43H31N=561.73)m/z=561.25 (C 43 H 31 N=561.73)
Sub 1-57Sub 1-57 m/z=535.23(C41H29N=535.69)m/z=535.23 (C 41 H 29 N=535.69) Sub 1-58Sub 1-58 m/z=485.21(C37H27N=485.63)m/z=485.21 (C 37 H 27 N=485.63)
Sub 1-59Sub 1-59 m/z=575.22(C43H29NO=575.71)m/z=575.22 (C 43 H 29 NO=575.71) Sub 1-60Sub 1-60 m/z=499.19(C37H25NO=499.61)m/z=499.19 (C 37 H 25 NO=499.61)
Sub 1-61Sub 1-61 m/z=487.2(C35H25N3=487.61)m/z=487.2 (C 35 H 25 N 3 =487.61) Sub 1-62Sub 1-62 m/z=499.19(C37H25NO=499.61)m/z=499.19 (C 37 H 25 NO=499.61)
Sub 1-63Sub 1-63 m/z=549.21(C41H27NO=549.67)m/z=549.21 (C 41 H 27 NO=549.67) Sub 1-64Sub 1-64 m/z=485.21(C37H27N=485.63)m/z=485.21 (C 37 H 27 N=485.63)
Sub 1-65Sub 1-65 m/z=525.25(C40H31N=525.7)m/z=525.25 (C 40 H 31 N=525.7) Sub 1-66Sub 1-66 m/z=576.23(C41H28N4=576.7)m/z=576.23 (C 41 H 28 N 4 =576.7)
Sub 1-67Sub 1-67 m/z=601.28(C46H35N=601.79)m/z=601.28 (C 46 H 35 N=601.79) Sub 1-68Sub 1-68 m/z=487.2(C35H25N3=487.61)m/z=487.2 (C 35 H 25 N 3 =487.61)
Sub 1-69Sub 1-69 m/z=679.23(C50H33NS=679.88)m/z=679.23 (C 50 H 33 NS=679.88) Sub 1-70Sub 1-70 m/z=663.26(C50H33NO=663.82)m/z=663.26 (C 50 H 33 NO=663.82)
Sub 1-71Sub 1-71 m/z=738.3(C56H38N2=738.93)m/z=738.3 (C 56 H 38 N 2 =738.93) Sub 1-72Sub 1-72 m/z=814.33(C62H42N2=815.03)m/z=814.33 (C 62 H 42 N 2 =815.03)
Sub 1-73Sub 1-73 m/z=527.26(C40H33N=527.71)m/z=527.26 (C 40 H 33 N=527.71) Sub 1-74Sub 1-74 m/z=499.23(C38H29N=499.66)m/z=499.23 (C 38 H 29 N=499.66)
Sub 1-75Sub 1-75 m/z=435.2(C33H25N=435.57)m/z=435.2 (C 33 H 25 N=435.57) Sub 1-76Sub 1-76 m/z=561.25(C43H31N=561.73)m/z=561.25 (C 43 H 31 N=561.73)
Sub 1-77Sub 1-77 m/z=434.18(C32H22N2=434.54)m/z=434.18 (C 32 H 22 N 2 =434.54) Sub 1-78Sub 1-78 m/z=414.21(C31H18D5N=414.56)m/z=414.21 (C 31 H 18 D 5 N=414.56)
Sub 1-79Sub 1-79 m/z=414.21(C31H18D5N=414.56)m/z=414.21 (C 31 H 18 D 5 N=414.56)
II. Sub 2의 합성II. Synthesis of Sub 2
상기 반응식 1의 Sub 2는 하기 반응식 3의 반응경로에 의해 합성되며, 이에 한정되는 것은 아니다. Sub 2 of Scheme 1 is synthesized by the reaction route of Scheme 3 below, but is not limited thereto.
<반응식 3><Reaction Scheme 3>
Figure PCTKR2020009674-appb-I000073
Figure PCTKR2020009674-appb-I000073
상기 반응식 3에서, n 및 m은 각각 0 또는 1이며, n+m=1이다.In Scheme 3, n and m are each 0 or 1, and n+m=1.
1. Sub 2-6 1.Sub 2-6 합성예Synthesis example
Figure PCTKR2020009674-appb-I000074
Figure PCTKR2020009674-appb-I000074
(1) Sub 2-6-b의 합성 (1) Synthesis of Sub 2-6-b
둥근바닥플라스크에 Sub 2-6-a (50 g, 162.5 mmol)를 넣고 THF (813 ml)에 녹인 후, Sub 2-6-a' (22.4 g, 162.5 mmol), Pd(PPh3)4 (11.3 g, 9.8 mmol), NaOH (19.5 g, 487.6 mmol), 물 (406 ml)을 첨가하고 80℃에서 반응을 진행한다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물 32.3 g을 얻었다. (수율 : 62%)Put Sub 2-6-a (50 g, 162.5 mmol) in a round bottom flask and dissolve in THF (813 ml), then Sub 2-6-a' (22.4 g, 162.5 mmol), Pd(PPh 3 ) 4 ( 11.3 g, 9.8 mmol), NaOH (19.5 g, 487.6 mmol), and water (406 ml) were added, and the reaction proceeded at 80°C. When the reaction was completed, CH 2 Cl 2 and water were extracted, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 32.3 g of a product. (Yield: 62%)
(2) Sub 2-6의 합성(2) Synthesis of Sub 2-6
상기 반응에서 얻은 Sub 2-6-b (32.3 g, 100.8 mmol)를 C6F6 (150 ml), DMI (101 ml)에 녹인 후, Pd(OAc)2 (1.1 g, 5.0 mmol), 3-nitropyridine (0.6 g, 5.0 mmol), tert-butyl peroxybenzoate (39.1 g, 201.5 mmol)를 차례대로 첨가하고 90℃에서 반응을 진행한다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물 21.8 g을 얻었다. (수율 : 68%)Sub 2-6-b (32.3 g, 100.8 mmol) obtained in the above reaction was dissolved in C 6 F 6 (150 ml) and DMI (101 ml), and then Pd(OAc) 2 (1.1 g, 5.0 mmol), 3-nitropyridine (0.6 g, 5.0 mmol), and tert- butyl peroxybenzoate (39.1 g, 201.5 mmol) were sequentially added and the reaction proceeded at 90°C. When the reaction was completed, the product was extracted with CH 2 Cl 2 and water, and the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 21.8 g of a product. (Yield: 68%)
2. Sub 2-48 2.Sub 2-48 합성예Synthesis example
Figure PCTKR2020009674-appb-I000075
Figure PCTKR2020009674-appb-I000075
(1) Sub 2-48-b의 합성(1) Synthesis of Sub 2-48-b
둥근바닥플라스크에 Sub 2-48-a (50.0 g, 162.5 mmol)을 넣고 THF (813 ml)에 녹인 후, Sub 2-48-a' (29.9 g, 162.5 mmol), Pd(PPh3)4 (11.3 g, 9.8 mmol), NaOH (19.5 g, 487.6 mmol), 물 (406 ml)을 첨가하고 상기 Sub 2-6-b와 동일한 방법으로 실험하여 생성물을 48.3 g 얻었다. (수율 : 81%)Put Sub 2-48-a (50.0 g, 162.5 mmol) in a round bottom flask and dissolve in THF (813 ml), then Sub 2-48-a' (29.9 g, 162.5 mmol), Pd(PPh 3 ) 4 ( 11.3 g, 9.8 mmol), NaOH (19.5 g, 487.6 mmol), and water (406 ml) were added, and the experiment was performed in the same manner as for Sub 2-6-b to obtain 48.3 g of the product. (Yield: 81%)
(2) Sub 2-48의 합성(2) Synthesis of Sub 2-48
상기 반응에서 얻은 Sub 2-48-b (48.3 g, 131.7 mmol)에 과량의 trifluoromethane-sulfonic acid을 넣고 상온에서 24시간 교반한 뒤, 물과 피리딘(8:1)을 첨가하고 30분간 환류시킨다. 이후 상온으로 식힌 뒤, CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물 39.7 g을 얻었다. (수율 : 90%)To Sub 2-48-b (48.3 g, 131.7 mmol) obtained in the above reaction, an excess of trifluoromethane-sulfonic acid was added, stirred at room temperature for 24 hours, water and pyridine (8:1) were added and refluxed for 30 minutes. After cooling to room temperature, extraction with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 39.7 g of a product. (Yield: 90%)
3. Sub 2-73 3.Sub 2-73 합성예Synthesis example
Figure PCTKR2020009674-appb-I000076
Figure PCTKR2020009674-appb-I000076
(1) Sub 2-73-b의 합성(1) Synthesis of Sub 2-73-b
둥근바닥플라스크에 Sub 2-73-a (50.0 g, 162.5 mmol)을 넣고 THF (813 ml)에 녹인 후, Sub 2-73-a' (27.1 g, 162.5 mmol), Pd(PPh3)4 (11.3 g, 9.8 mmol), NaOH (19.5 g, 487.6 mmol), 물(406 ml)을 첨가하고 상기 Sub 2-6-b와 동일한 방법으로 실험하여 생성물을 47.2 g 얻었다. (수율 : 83%)Put Sub 2-73-a (50.0 g, 162.5 mmol) in a round bottom flask and dissolve in THF (813 ml), then Sub 2-73-a' (27.1 g, 162.5 mmol), Pd(PPh 3 ) 4 ( 11.3 g, 9.8 mmol), NaOH (19.5 g, 487.6 mmol), and water (406 ml) were added, and the experiment was performed in the same manner as for Sub 2-6-b to obtain 47.2 g of the product. (Yield: 83%)
(2) Sub 2-73-b'의 합성(2) Synthesis of Sub 2-73-b'
상기 반응에서 얻은 Sub 2-73-b (47.2 g, 134.9 mmol)를 o-dichlorobenzene (675 mL)으로 녹인 후, triphenylphosphine (88.5 g, 337.3 mmol)을 첨가하고 200℃에서 교반하였다. 반응이 완료되면 증류를 통해 o-dichlorobenzene을 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 36.5 g을 얻었다. (수율: 85%)Sub 2-73-b (47.2 g, 134.9 mmol) obtained in the above reaction was dissolved with o- dichlorobenzene (675 mL), triphenylphosphine (88.5 g, 337.3 mmol) was added, followed by stirring at 200°C. When the reaction was completed, o- dichlorobenzene was removed through distillation and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 36.5 g of a product. (Yield: 85%)
(3) (3) Sub2Sub2 -73의 합성Synthesis of -73
상기 반응에서 얻어진 Sub 2-73-b' (36.5 g, 114.8 mmol)을 toluene (574 mL)으로 녹인 후에, bromobenzene (36.1 g, 229.7 mmol), Pd2(dba)3 (3.2 g, 3.5 mmol), P(t-Bu)3 (1.4 g, 6.9 mmol), NaOt-Bu (22.1 g, 229.7 mmol)을 넣고 120℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물을 32.6 g 얻었다. (수율 : 72%)After dissolving Sub 2-73-b' (36.5 g, 114.8 mmol) obtained in the above reaction with toluene (574 mL), bromobenzene (36.1 g, 229.7 mmol), Pd 2 (dba) 3 (3.2 g, 3.5 mmol) , P( t -Bu) 3 (1.4 g, 6.9 mmol), NaO t -Bu (22.1 g, 229.7 mmol) was added and stirred at 120°C. When the reaction was completed, CH 2 Cl 2 was extracted with water and the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was recrystallized in a silicagel column to obtain 32.6 g of the product. (Yield: 72%)
4. Sub 2-93 4.Sub 2-93 합성예Synthesis example
Figure PCTKR2020009674-appb-I000077
Figure PCTKR2020009674-appb-I000077
(1) Sub 2-93-b의 합성(1) Synthesis of Sub 2-93-b
둥근바닥플라스크에 Sub 2-93-a (50.0 g, 162.5 mmol)을 넣고 THF (813 ml)에 녹인 후, Sub 2-93-a' (29.3 g, 162.5 mmol), Pd(PPh3)4 (11.3 g, 9.8 mmol), NaOH (19.5 g, 487.6 mmol), 물(406 ml)을 첨가하고 상기 Sub 2-6-b와 동일한 방법으로 실험하여 생성물을 38.9 g 얻었다. (수율 : 66%)Put Sub 2-93-a (50.0 g, 162.5 mmol) in a round bottom flask and dissolve in THF (813 ml), then Sub 2-93-a' (29.3 g, 162.5 mmol), Pd(PPh 3 ) 4 ( 11.3 g, 9.8 mmol), NaOH (19.5 g, 487.6 mmol), and water (406 ml) were added, and the experiment was performed in the same manner as for Sub 2-6-b to obtain 38.9 g of the product. (Yield: 66%)
(2) Sub 2-93의 합성(2) Synthesis of Sub 2-93
상기 합성에서 얻어진 Sub 2-93-b (38.9 g, 107.3 mmol)를 THF (600 ml)로 녹인 후, Methylmagnesium bromide 1.0 M in THF (214.6 ml)을 적정하고 상온에서 반응시킨다. 이후, Acetic acid (600 ml), HCl (9 ml)을 넣고 상온에서 24시간 동안 교반한 뒤, 물과 피리딘(5:1)을 첨가하고 30분간 환류시킨다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물을 40.4 g 얻었다. (수율 : 72%)After dissolving Sub 2-93-b (38.9 g, 107.3 mmol) obtained in the above synthesis with THF (600 ml), Methylmagnesium bromide 1.0 M in THF (214.6 ml) was titrated and reacted at room temperature. Thereafter, Acetic acid (600 ml) and HCl (9 ml) were added and stirred at room temperature for 24 hours, then water and pyridine (5:1) were added and refluxed for 30 minutes. When the reaction was completed, the product was extracted with CH 2 Cl 2 and water, and the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was recrystallized with a silicagel column to obtain 40.4 g of the product. (Yield: 72%)
상기 Sub 2에 속하는 화합물은 아래와 같은 화합물일 수 있으나, 이에 한정되는 것은 아니며, 하기 표 2는 Sub 2에 속하는 화합물의 FD-MS (Field Desorption-Mass Spectrometry) 값을 나타낸 것이다.The compound belonging to Sub 2 may be a compound as follows, but is not limited thereto, and Table 2 below shows the FD-MS (Field Desorption-Mass Spectrometry) values of the compound belonging to Sub 2.
Figure PCTKR2020009674-appb-I000078
Figure PCTKR2020009674-appb-I000078
Figure PCTKR2020009674-appb-I000079
Figure PCTKR2020009674-appb-I000079
Figure PCTKR2020009674-appb-I000080
Figure PCTKR2020009674-appb-I000080
Figure PCTKR2020009674-appb-I000081
Figure PCTKR2020009674-appb-I000081
Figure PCTKR2020009674-appb-I000082
Figure PCTKR2020009674-appb-I000082
Figure PCTKR2020009674-appb-I000083
Figure PCTKR2020009674-appb-I000083
Figure PCTKR2020009674-appb-I000084
Figure PCTKR2020009674-appb-I000084
Figure PCTKR2020009674-appb-I000085
Figure PCTKR2020009674-appb-I000085
Figure PCTKR2020009674-appb-I000086
Figure PCTKR2020009674-appb-I000086
Figure PCTKR2020009674-appb-I000087
Figure PCTKR2020009674-appb-I000087
Figure PCTKR2020009674-appb-I000088
Figure PCTKR2020009674-appb-I000088
Figure PCTKR2020009674-appb-I000089
Figure PCTKR2020009674-appb-I000089
Figure PCTKR2020009674-appb-I000090
Figure PCTKR2020009674-appb-I000090
Figure PCTKR2020009674-appb-I000091
Figure PCTKR2020009674-appb-I000091
Figure PCTKR2020009674-appb-I000092
Figure PCTKR2020009674-appb-I000092
Figure PCTKR2020009674-appb-I000093
Figure PCTKR2020009674-appb-I000093
Figure PCTKR2020009674-appb-I000094
Figure PCTKR2020009674-appb-I000094
Figure PCTKR2020009674-appb-I000095
Figure PCTKR2020009674-appb-I000095
Figure PCTKR2020009674-appb-I000096
Figure PCTKR2020009674-appb-I000096
Figure PCTKR2020009674-appb-I000097
Figure PCTKR2020009674-appb-I000097
Figure PCTKR2020009674-appb-I000098
Figure PCTKR2020009674-appb-I000098
Figure PCTKR2020009674-appb-I000099
Figure PCTKR2020009674-appb-I000099
Figure PCTKR2020009674-appb-I000100
Figure PCTKR2020009674-appb-I000100
화합물compound FD-MSFD-MS 화합물compound FD-MSFD-MS
Sub 2-1Sub 2-1 m/z=318.08(C21H15ClO=318.8)m/z=318.08 (C 21 H 15 ClO=318.8) Sub 2-2Sub 2-2 m/z=318.08(C21H15ClO=318.8)m/z=318.08 (C 21 H 15 ClO=318.8)
Sub 2-3Sub 2-3 m/z=318.08(C21H15ClO=318.8)m/z=318.08 (C 21 H 15 ClO=318.8) Sub 2-4Sub 2-4 m/z=318.08(C21H15ClO=318.8)m/z=318.08 (C 21 H 15 ClO=318.8)
Sub 2-5Sub 2-5 m/z=318.08(C21H15ClO=318.8)m/z=318.08 (C 21 H 15 ClO=318.8) Sub 2-6Sub 2-6 m/z=318.08(C21H15ClO=318.8)m/z=318.08 (C 21 H 15 ClO=318.8)
Sub 2-7Sub 2-7 m/z=368.1(C25H17ClO=368.86)m/z=368.1 (C 25 H 17 ClO=368.86) Sub 2-8Sub 2-8 m/z=368.1(C25H17ClO=368.86)m/z=368.1 (C 25 H 17 ClO=368.86)
Sub 2-9Sub 2-9 m/z=394.11(C27H19ClO=394.9)m/z=394.11 (C 27 H 19 ClO=394.9) Sub 2-10Sub 2-10 m/z=394.11(C27H19ClO=394.9)m/z=394.11 (C 27 H 19 ClO=394.9)
Sub 2-11Sub 2-11 m/z=318.08(C21H15ClO=318.8)m/z=318.08 (C 21 H 15 ClO=318.8) Sub 2-12Sub 2-12 m/z=394.11(C27H19ClO=394.9)m/z=394.11 (C 27 H 19 ClO=394.9)
Sub 2-13Sub 2-13 m/z=442.11(C31H19ClO=442.94)m/z=442.11 (C 31 H 19 ClO=442.94) Sub 2-14Sub 2-14 m/z=318.08(C21H15ClO=318.8)m/z=318.08 (C 21 H 15 ClO=318.8)
Sub 2-15Sub 2-15 m/z=318.08(C21H15ClO=318.8)m/z=318.08 (C 21 H 15 ClO=318.8) Sub 2-16Sub 2-16 m/z=318.08(C21H15ClO=318.8)m/z=318.08 (C 21 H 15 ClO=318.8)
Sub 2-17Sub 2-17 m/z=318.08(C21H15ClO=318.8)m/z=318.08 (C 21 H 15 ClO=318.8) Sub 2-18Sub 2-18 m/z=394.11(C27H19ClO=394.9)m/z=394.11 (C 27 H 19 ClO=394.9)
Sub 2-19Sub 2-19 m/z=484.12(C33H21ClO2=484.98)m/z=484.12 (C 33 H 21 ClO 2 =484.98) Sub 2-20Sub 2-20 m/z=368.1(C25H17ClO=368.86)m/z=368.1 (C 25 H 17 ClO=368.86)
Sub 2-21Sub 2-21 m/z=318.08(C21H15ClO=318.8)m/z=318.08 (C 21 H 15 ClO=318.8) Sub 2-22Sub 2-22 m/z=418.11(C29H19ClO=418.92)m/z=418.11 (C 29 H 19 ClO=418.92)
Sub 2-23Sub 2-23 m/z=318.08(C21H15ClO=318.8)m/z=318.08 (C 21 H 15 ClO=318.8) Sub 2-24Sub 2-24 m/z=318.08(C21H15ClO=318.8)m/z=318.08 (C 21 H 15 ClO=318.8)
Sub 2-25Sub 2-25 m/z=440.1(C31H17ClO=440.93)m/z=440.1 (C 31 H 17 ClO=440.93) Sub 2-26Sub 2-26 m/z=396.1(C25H17ClN2O=396.87)m/z=396.1 (C 25 H 17 ClN 2 O=396.87)
Sub 2-27Sub 2-27 m/z=394.11(C27H19ClO=394.9)m/z=394.11 (C 27 H 19 ClO=394.9) Sub 2-28Sub 2-28 m/z=334.06(C21H15ClS=334.86)m/z=334.06 (C 21 H 15 ClS=334.86)
Sub 2-29Sub 2-29 m/z=334.06(C21H15ClS=334.86)m/z=334.06 (C 21 H 15 ClS=334.86) Sub 2-30Sub 2-30 m/z=334.06(C21H15ClS=334.86)m/z=334.06 (C 21 H 15 ClS=334.86)
Sub 2-31Sub 2-31 m/z=334.06(C21H15ClS=334.86)m/z=334.06 (C 21 H 15 ClS=334.86) Sub 2-32Sub 2-32 m/z=334.06(C21H15ClS=334.86)m/z=334.06 (C 21 H 15 ClS=334.86)
Sub 2-33Sub 2-33 m/z=334.06(C21H15ClS=334.86)m/z=334.06 (C 21 H 15 ClS=334.86) Sub 2-34Sub 2-34 m/z=384.07(C25H17ClS=384.92)m/z=384.07 (C 25 H 17 ClS=384.92)
Sub 2-35Sub 2-35 m/z=384.07(C25H17ClS=384.92)m/z=384.07 (C 25 H 17 ClS=384.92) Sub 2-36Sub 2-36 m/z=410.09(C27H19ClS=410.96)m/z=410.09 (C 27 H 19 ClS=410.96)
Sub 2-37Sub 2-37 m/z=334.06(C21H15ClS=334.86)m/z=334.06 (C 21 H 15 ClS=334.86) Sub 2-38Sub 2-38 m/z=334.06(C21H15ClS=334.86)m/z=334.06 (C 21 H 15 ClS=334.86)
Sub 2-39Sub 2-39 m/z=458.09(C31H19ClS=459)m/z=458.09 (C 31 H 19 ClS=459) Sub 2-40Sub 2-40 m/z=334.06(C21H15ClS=334.86)m/z=334.06 (C 21 H 15 ClS=334.86)
Sub 2-41Sub 2-41 m/z=486.12(C33H23ClS=487.06)m/z=486.12 (C 33 H 23 ClS=487.06) Sub 2-42Sub 2-42 m/z=532.11(C37H21ClS=533.09)m/z=532.11 (C 37 H 21 ClS=533.09)
Sub 2-43Sub 2-43 m/z=410.09(C27H19ClS=410.96)m/z=410.09 (C 27 H 19 ClS=410.96) Sub 2-44Sub 2-44 m/z=410.09(C27H19ClS=410.96)m/z=410.09 (C 27 H 19 ClS=410.96)
Sub 2-45Sub 2-45 m/z=472.07(C31H17ClOS=472.99)m/z=472.07 (C 31 H 17 ClOS=472.99) Sub 2-46Sub 2-46 m/z=384.07(C25H17ClS=384.92)m/z=384.07 (C 25 H 17 ClS=384.92)
Sub 2-47Sub 2-47 m/z=384.07(C25H17ClS=384.92)m/z=384.07 (C 25 H 17 ClS=384.92) Sub 2-48Sub 2-48 m/z=334.06(C21H15ClS=334.86)m/z=334.06 (C 21 H 15 ClS=334.86)
Sub 2-49Sub 2-49 m/z=334.06(C21H15ClS=334.86)m/z=334.06 (C 21 H 15 ClS=334.86) Sub 2-50Sub 2-50 m/z=334.06(C21H15ClS=334.86)m/z=334.06 (C 21 H 15 ClS=334.86)
Sub 2-51Sub 2-51 m/z=334.06(C21H15ClS=334.86)m/z=334.06 (C 21 H 15 ClS=334.86) Sub 2-52Sub 2-52 m/z=334.06(C21H15ClS=334.86)m/z=334.06 (C 21 H 15 ClS=334.86)
Sub 2-53Sub 2-53 m/z=411.08(C26H18ClNS=411.95)m/z=411.08 (C 26 H 18 ClNS=411.95) Sub 2-54Sub 2-54 m/z=516.08(C33H21ClS2=517.1)m/z=516.08 (C 33 H 21 ClS 2 =517.1)
Sub 2-55Sub 2-55 m/z=393.13(C27H20ClN=393.91)m/z=393.13 (C 27 H 20 ClN=393.91) Sub 2-56Sub 2-56 m/z=393.13(C27H20ClN=393.91)m/z=393.13 (C 27 H 20 ClN=393.91)
Sub 2-57Sub 2-57 m/z=469.16(C33H24ClN=470.01)m/z=469.16 (C 33 H 24 ClN=470.01) Sub 2-58Sub 2-58 m/z=393.13(C27H20ClN=393.91)m/z=393.13 (C 27 H 20 ClN=393.91)
Sub 2-59Sub 2-59 m/z=393.13(C27H20ClN=393.91)m/z=393.13 (C 27 H 20 ClN=393.91) Sub 2-60Sub 2-60 m/z=393.13(C27H20ClN=393.91)m/z=393.13 (C 27 H 20 ClN=393.91)
Sub 2-61Sub 2-61 m/z=493.16(C35H24ClN=494.03)m/z=493.16 (C 35 H 24 ClN=494.03) Sub 2-62Sub 2-62 m/z=443.14(C31H22ClN=443.97)m/z=443.14 (C 31 H 22 ClN=443.97)
Sub 2-63Sub 2-63 m/z=393.13(C27H20ClN=393.91)m/z=393.13 (C 27 H 20 ClN=393.91) Sub 2-64Sub 2-64 m/z=393.13(C27H20ClN=393.91)m/z=393.13 (C 27 H 20 ClN=393.91)
Sub 2-65Sub 2-65 m/z=531.18(C38H26ClN=532.08)m/z=531.18 (C 38 H 26 ClN=532.08) Sub 2-66Sub 2-66 m/z=519.18(C37H26ClN=520.07)m/z=519.18 (C 37 H 26 ClN=520.07)
Sub 2-67Sub 2-67 m/z=548.18(C36H25ClN4=549.07)m/z=548.18 (C 36 H 25 ClN 4 =549.07) Sub 2-68Sub 2-68 m/z=393.13(C27H20ClN=393.91)m/z=393.13 (C 27 H 20 ClN=393.91)
Sub 2-69Sub 2-69 m/z=393.13(C27H20ClN=393.91)m/z=393.13 (C 27 H 20 ClN=393.91) Sub 2-70Sub 2-70 m/z=393.13(C27H20ClN=393.91)m/z=393.13 (C 27 H 20 ClN=393.91)
Sub 2-71Sub 2-71 m/z=571.18(C39H26ClN3=572.11)m/z=571.18 (C 39 H 26 ClN 3 =572.11) Sub 2-72Sub 2-72 m/z=393.13(C27H20ClN=393.91)m/z=393.13 (C 27 H 20 ClN=393.91)
Sub 2-73Sub 2-73 m/z=393.13(C27H20ClN=393.91)m/z=393.13 (C 27 H 20 ClN=393.91) Sub 2-74Sub 2-74 m/z=393.13(C27H20ClN=393.91)m/z=393.13 (C 27 H 20 ClN=393.91)
Sub 2-75Sub 2-75 m/z=393.13(C27H20ClN=393.91)m/z=393.13 (C 27 H 20 ClN=393.91) Sub 2-76Sub 2-76 m/z=393.13(C27H20ClN=393.91)m/z=393.13 (C 27 H 20 ClN=393.91)
Sub 2-77Sub 2-77 m/z=393.13(C27H20ClN=393.91)m/z=393.13 (C 27 H 20 ClN=393.91) Sub 2-78Sub 2-78 m/z=472.15(C30H21ClN4=472.98)m/z=472.15 (C 30 H 21 ClN 4 =472.98)
Sub 2-79Sub 2-79 m/z=559.17(C39H26ClNO=560.09)m/z=559.17 (C 39 H 26 ClNO=560.09) Sub 2-80Sub 2-80 m/z=344.13(C24H21Cl=344.88)m/z=344.13 (C 24 H 21 Cl=344.88)
Sub 2-81Sub 2-81 m/z=344.13(C24H21Cl=344.88)m/z=344.13 (C 24 H 21 Cl=344.88) Sub 2-82Sub 2-82 m/z=344.13(C24H21Cl=344.88)m/z=344.13 (C 24 H 21 Cl=344.88)
Sub 2-83Sub 2-83 m/z=344.13(C24H21Cl=344.88)m/z=344.13 (C 24 H 21 Cl=344.88) Sub 2-84Sub 2-84 m/z=344.13(C24H21Cl=344.88)m/z=344.13 (C 24 H 21 Cl=344.88)
Sub 2-85Sub 2-85 m/z=344.13(C24H21Cl=344.88)m/z=344.13 (C 24 H 21 Cl=344.88) Sub 2-86Sub 2-86 m/z=394.15(C28H23Cl=394.94)m/z=394.15 (C 28 H 23 Cl=394.94)
Sub 2-87Sub 2-87 m/z=444.16(C32H25Cl=445)m/z=444.16 (C 32 H 25 Cl=445) Sub 2-88Sub 2-88 m/z=420.16(C30H25Cl=420.98)m/z=420.16 (C 30 H 25 Cl=420.98)
Sub 2-89Sub 2-89 m/z=344.13(C24H21Cl=344.88)m/z=344.13 (C 24 H 21 Cl=344.88) Sub 2-90Sub 2-90 m/z=420.16(C30H25Cl=420.98)m/z=420.16 (C 30 H 25 Cl=420.98)
Sub 2-91Sub 2-91 m/z=592.2(C44H29Cl=593.17)m/z=592.2 (C 44 H 29 Cl=593.17) Sub 2-92Sub 2-92 m/z=546.21(C40H31Cl=547.14)m/z=546.21 (C 40 H 31 Cl=547.14)
Sub 2-93Sub 2-93 m/z=344.13(C24H21Cl=344.88)m/z=344.13 (C 24 H 21 Cl=344.88) Sub 2-94Sub 2-94 m/z=509.19(C36H28ClN=510.08)m/z=509.19 (C 36 H 28 ClN=510.08)
Sub 2-95Sub 2-95 m/z=344.13(C24H21Cl=344.88)m/z=344.13 (C 24 H 21 Cl=344.88) Sub 2-96Sub 2-96 m/z=344.13(C24H21Cl=344.88)m/z=344.13 (C 24 H 21 Cl=344.88)
Sub 2-97Sub 2-97 m/z=344.13(C24H21Cl=344.88)m/z=344.13 (C 24 H 21 Cl=344.88) Sub 2-98Sub 2-98 m/z=394.15(C28H23Cl=394.94)m/z=394.15 (C 28 H 23 Cl=394.94)
Sub 2-99Sub 2-99 m/z=344.13(C24H21Cl=344.88)m/z=344.13 (C 24 H 21 Cl=344.88) Sub 2-100Sub 2-100 m/z=466.15(C34H23Cl=467.01)m/z=466.15 (C 34 H 23 Cl=467.01)
Sub 2-101Sub 2-101 m/z=344.13(C24H21Cl=344.88)m/z=344.13 (C 24 H 21 Cl=344.88) Sub 2-102Sub 2-102 m/z=420.16(C30H25Cl=420.98)m/z=420.16 (C 30 H 25 Cl=420.98)
Sub 2-103Sub 2-103 m/z=420.16(C30H25Cl=420.98)m/z=420.16 (C 30 H 25 Cl=420.98) Sub 2-104Sub 2-104 m/z=318.08(C21H15ClO=318.8)m/z=318.08 (C 21 H 15 ClO=318.8)
Sub 2-105Sub 2-105 m/z=334.06(C21H15ClS=334.86)m/z=334.06 (C 21 H 15 ClS=334.86) Sub 2-106Sub 2-106 m/z=336.07(C21H14ClFO=336.79)m/z=336.07 (C 21 H 14 ClFO=336.79)
Sub 2-107Sub 2-107 m/z=334.06(C21H15ClS=334.86)m/z=334.06 (C 21 H 15 ClS=334.86) Sub 2-108Sub 2-108 m/z=393.13(C27H20ClN=393.91)m/z=393.13 (C 27 H 20 ClN=393.91)
Sub 2-109Sub 2-109 m/z=344.13(C24H21Cl=344.88)m/z=344.13 (C 24 H 21 Cl=344.88) Sub 2-110Sub 2-110 m/z=348.09(C22H17ClO2=348.83)m/z=348.09 (C 22 H 17 ClO 2 =348.83)
Sub 2-111Sub 2-111 m/z=334.06(C21H15ClS=334.86)m/z=334.06 (C 21 H 15 ClS=334.86) Sub 2-112Sub 2-112 m/z=393.13(C27H20ClN=393.91)m/z=393.13 (C 27 H 20 ClN=393.91)
Sub 2-113Sub 2-113 m/z=344.13(C24H21Cl=344.88)m/z=344.13 (C 24 H 21 Cl=344.88) 　 　
III. Final Product의 합성III. Synthesis of Final Product
1. P-1 1.P-1 합성예Synthesis example
Figure PCTKR2020009674-appb-I000101
Figure PCTKR2020009674-appb-I000101
둥근바닥플라스크에 Sub 1-1 (10.0 g, 20.5 mmol), Sub 2-1 (13.1 g, 41.1 mmol), Pd2(dba)3 (0.6 g, 0.6 mmol), P(t-Bu)3 (0.3 g, 1.2 mmol), NaOt-Bu (4.0 g, 41.1 mmol), toluene (103 mL)을 상기 Sub 1-1과 동일한 방법으로 실험하여 생성물 12.0 g을 얻었다. (수율 : 76%)In a round bottom flask, Sub 1-1 (10.0 g, 20.5 mmol), Sub 2-1 (13.1 g, 41.1 mmol), Pd 2 (dba) 3 (0.6 g, 0.6 mmol), P(t-Bu) 3 ( 0.3 g, 1.2 mmol), NaOt-Bu (4.0 g, 41.1 mmol), and toluene (103 mL) were tested in the same manner as in Sub 1-1 to obtain 12.0 g of the product. (Yield: 76%)
2. P-6 2. P-6 합성예Synthesis example
Figure PCTKR2020009674-appb-I000102
Figure PCTKR2020009674-appb-I000102
둥근바닥플라스크에 Sub 1-6 (10.0 g, 20.5 mmol), Sub 2-6 (13.1 g, 41.1 mmol), Pd2(dba)3 (0.6 g, 0.6 mmol), P(t-Bu)3 (0.3 g, 1.2 mmol), NaOt-Bu (4.0 g, 41.1 mmol), toluene (103 mL)을 상기 Sub 1-1과 동일한 방법으로 실험하여 생성물 12.8 g을 얻었다. (수율 : 81%)In a round bottom flask, Sub 1-6 (10.0 g, 20.5 mmol), Sub 2-6 (13.1 g, 41.1 mmol), Pd 2 (dba) 3 (0.6 g, 0.6 mmol), P(t-Bu) 3 ( 0.3 g, 1.2 mmol), NaOt-Bu (4.0 g, 41.1 mmol), and toluene (103 mL) were tested in the same manner as in Sub 1-1 to obtain 12.8 g of a product. (Yield: 81%)
3. P-28 3. P-28 합성예Synthesis example
Figure PCTKR2020009674-appb-I000103
Figure PCTKR2020009674-appb-I000103
둥근바닥플라스크에 Sub 1-6 (10.0 g, 20.5 mmol), Sub 2-27 (16.3 g, 41.1 mmol), Pd2(dba)3 (0.6 g, 0.6 mmol), P(t-Bu)3 (0.3 g, 1.2 mmol), NaOt-Bu (4.0 g, 41.1 mmol), toluene (103 mL)을 상기 Sub 1-1과 동일한 방법으로 실험하여 생성물 12.3 g을 얻었다. (수율 : 71%)In a round bottom flask, Sub 1-6 (10.0 g, 20.5 mmol), Sub 2-27 (16.3 g, 41.1 mmol), Pd 2 (dba) 3 (0.6 g, 0.6 mmol), P(t-Bu) 3 ( 0.3 g, 1.2 mmol), NaOt-Bu (4.0 g, 41.1 mmol), and toluene (103 mL) were tested in the same manner as in Sub 1-1 to obtain 12.3 g of the product. (Yield: 71%)
4. P-37 4. P-37 합성예Synthesis example
Figure PCTKR2020009674-appb-I000104
Figure PCTKR2020009674-appb-I000104
둥근바닥플라스크에 Sub 1-27 (10.0 g, 16.0 mmol), Sub 2-36 (12.1 g, 32.0 mmol), Pd2(dba)3 (0.5 g, 0.5 mmol), P(t-Bu)3 (0.2 g, 1.0 mmol), NaOt-Bu (3.1 g, 32.0 mmol), toluene (80 mL)을 상기 Sub 1-1과 동일한 방법으로 실험하여 생성물 11.8 g을 얻었다. (수율 : 74%)In a round bottom flask, Sub 1-27 (10.0 g, 16.0 mmol), Sub 2-36 (12.1 g, 32.0 mmol), Pd 2 (dba) 3 (0.5 g, 0.5 mmol), P(t-Bu) 3 ( 0.2 g, 1.0 mmol), NaOt-Bu (3.1 g, 32.0 mmol), and toluene (80 mL) were tested in the same manner as in Sub 1-1 to obtain 11.8 g of a product. (Yield: 74%)
5. P-50 5. P-50 합성예Synthesis example
Figure PCTKR2020009674-appb-I000105
Figure PCTKR2020009674-appb-I000105
둥근바닥플라스크에 Sub 1-37 (10.0 g, 20.0 mmol), Sub 2-48 (13.4 g, 40.0 mmol), Pd2(dba)3 (0.6 g, 0.6 mmol), P(t-Bu)3 (0.3 g, 1.2 mmol), NaOt-Bu (3.8 g, 40.0 mmol), toluene (100 mL)을 상기 Sub 1-1과 동일한 방법으로 실험하여 생성물 11.2 g을 얻었다. (수율 : 70%)In a round bottom flask, Sub 1-37 (10.0 g, 20.0 mmol), Sub 2-48 (13.4 g, 40.0 mmol), Pd 2 (dba) 3 (0.6 g, 0.6 mmol), P(t-Bu) 3 ( 0.3 g, 1.2 mmol), NaOt-Bu (3.8 g, 40.0 mmol), and toluene (100 mL) were tested in the same manner as in Sub 1-1 to obtain 11.2 g of the product. (Yield: 70%)
6. P-57 6. P-57 합성예Synthesis example
Figure PCTKR2020009674-appb-I000106
Figure PCTKR2020009674-appb-I000106
둥근바닥플라스크에 Sub 1-42 (10.0 g, 20.6 mmol), Sub 2-55 (16.2 g, 41.2 mmol), Pd2(dba)3 (0.6 g, 0.6 mmol), P(t-Bu)3 (0.3 g, 1.2 mmol), NaOt-Bu (4.0 g, 41.2 mmol), toluene (103 mL)을 상기 Sub 1-1과 동일한 방법으로 실험하여 생성물 12.2 g을 얻었다. (수율 : 71%)In a round bottom flask, Sub 1-42 (10.0 g, 20.6 mmol), Sub 2-55 (16.2 g, 41.2 mmol), Pd 2 (dba) 3 (0.6 g, 0.6 mmol), P(t-Bu) 3 ( 0.3 g, 1.2 mmol), NaOt-Bu (4.0 g, 41.2 mmol), and toluene (103 mL) were tested in the same manner as in Sub 1-1 to obtain 12.2 g of the product. (Yield: 71%)
7. P-78 7. P-78 합성예Synthesis example
Figure PCTKR2020009674-appb-I000107
Figure PCTKR2020009674-appb-I000107
둥근바닥플라스크에 Sub 1-7 (10.0 g, 24.4 mmol), Sub 2-73 (19.2 g, 48.8 mmol), Pd2(dba)3 (0.7 g, 0.7 mmol), P(t-Bu)3 (0.3 g, 1.5 mmol), NaOt-Bu (4.7 g, 48.8 mmol), toluene (122 mL)을 상기 Sub 1-1과 동일한 방법으로 실험하여 생성물 14.2 g을 얻었다. (수율 : 76%)In a round bottom flask, Sub 1-7 (10.0 g, 24.4 mmol), Sub 2-73 (19.2 g, 48.8 mmol), Pd 2 (dba) 3 (0.7 g, 0.7 mmol), P(t-Bu) 3 ( 0.3 g, 1.5 mmol), NaOt-Bu (4.7 g, 48.8 mmol), and toluene (122 mL) were tested in the same manner as in Sub 1-1 to obtain 14.2 g of the product. (Yield: 76%)
8. P-91 8. P-91 합성예Synthesis example
Figure PCTKR2020009674-appb-I000108
Figure PCTKR2020009674-appb-I000108
둥근바닥플라스크에 Sub 1-7 (10.0 g, 24.4 mmol), Sub 2-86 (19.3 g, 48.8 mmol), Pd2(dba)3 (0.7 g, 0.7 mmol), P(t-Bu)3 (0.3 g, 1.5 mmol), NaOt-Bu (4.7 g, 48.8 mmol), toluene (122 mL)을 상기 Sub 1-1과 동일한 방법으로 실험하여 생성물 13.7 g을 얻었다. (수율 : 73%)In a round bottom flask, Sub 1-7 (10.0 g, 24.4 mmol), Sub 2-86 (19.3 g, 48.8 mmol), Pd 2 (dba) 3 (0.7 g, 0.7 mmol), P(t-Bu) 3 ( 0.3 g, 1.5 mmol), NaOt-Bu (4.7 g, 48.8 mmol), and toluene (122 mL) were tested in the same manner as in Sub 1-1 to obtain 13.7 g of the product. (Yield: 73%)
9. P-99 9. P-99 합성예Synthesis example
Figure PCTKR2020009674-appb-I000109
Figure PCTKR2020009674-appb-I000109
둥근바닥플라스크에 Sub 1-62 (10.0 g, 20.0 mmol), Sub 2-93 (13.8 g, 40.0 mmol), Pd2(dba)3 (0.6 g, 0.6 mmol), P(t-Bu)3 (0.2 g, 1.2 mmol), NaOt-Bu (3.8 g, 40.0 mmol), toluene (100 mL)을 상기 Sub 1-1과 동일한 방법으로 실험하여 생성물 12.5 g을 얻었다. (수율 : 77%)In a round bottom flask, Sub 1-62 (10.0 g, 20.0 mmol), Sub 2-93 (13.8 g, 40.0 mmol), Pd 2 (dba) 3 (0.6 g, 0.6 mmol), P(t-Bu) 3 ( 0.2 g, 1.2 mmol), NaOt-Bu (3.8 g, 40.0 mmol), and toluene (100 mL) were tested in the same manner as in Sub 1-1 to obtain 12.5 g of a product. (Yield: 77%)
한편, 상기와 같은 합성예에 따라 제조된 본 발명의 화합물 P-1 내지 P-128의 FD-MS 값은 하기 표 3과 같다.On the other hand, the FD-MS values of the compounds P-1 to P-128 of the present invention prepared according to the synthesis example as described above are shown in Table 3 below.
화합물compound FD-MSFD-MS 화합물compound FD-MSFD-MS
P-1P-1 m/z=767.32(C58H41NO=767.97)m/z=767.32 (C 58 H 41 NO=767.97) P-2P-2 m/z=767.32(C58H41NO=767.97)m/z=767.32 (C 58 H 41 NO=767.97)
P-3P-3 m/z=767.32(C58H41NO=767.97)m/z=767.32 (C 58 H 41 NO=767.97) P-4P-4 m/z=691.29(C52H37NO=691.87)m/z=691.29 (C 52 H 37 NO=691.87)
P-5P-5 m/z=843.35(C64H45NO=844.07)m/z=843.35 (C 64 H 45 NO=844.07) P-6P-6 m/z=767.32(C58H41NO=767.97)m/z=767.32 (C 58 H 41 NO=767.97)
P-7P-7 m/z=741.3(C56H39NO=741.93)m/z=741.3 (C 56 H 39 NO=741.93) P-8P-8 m/z=741.3(C56H39NO=741.93)m/z=741.3 (C 56 H 39 NO=741.93)
P-9P-9 m/z=907.35(C68H45NO2=908.11)m/z=907.35 (C 68 H 45 NO 2 =908.11) P-10P-10 m/z=893.37(C68H47NO=894.13)m/z=893.37 (C 68 H 47 NO=894.13)
P-11P-11 m/z=893.37(C68H47NO=894.13)m/z=893.37 (C 68 H 47 NO=894.13) P-12P-12 m/z=883.38(C67H49NO=884.14)m/z=883.38 (C 67 H 49 NO=884.14)
P-13P-13 m/z=905.33(C68H43NO2=906.1)m/z=905.33 (C 68 H 43 NO 2 =906.1) P-14P-14 m/z=893.37(C68H47NO=894.13)m/z=893.37 (C 68 H 47 NO=894.13)
P-15P-15 m/z=797.28(C58H39NOS=798.02)m/z=797.28 (C 58 H 39 NOS=798.02) P-16P-16 m/z=1009.39(C76H51NO2=1010.25)m/z=1009.39 (C 76 H 51 NO 2 =1010.25)
P-17P-17 m/z=831.31(C62H41NO2=832.02)m/z=831.31 (C 62 H 41 NO 2 =832.02) P-18P-18 m/z=843.35(C64H45NO=844.07)m/z=843.35 (C 64 H 45 NO=844.07)
P-19P-19 m/z=933.36(C70H47NO2=934.15)m/z=933.36 (C 70 H 47 NO 2 =934.15) P-20P-20 m/z=741.3(C56H39NO=741.93)m/z=741.3 (C 56 H 39 NO=741.93)
P-21P-21 m/z=807.35(C61H45NO=808.04)m/z=807.35 (C 61 H 45 NO=808.04) P-22P-22 m/z=856.35(C64H44N2O=857.07)m/z=856.35 (C 64 H 44 N 2 O=857.07)
P-23P-23 m/z=869.34(C64H43N3O=870.07)m/z=869.34 (C 64 H 43 N 3 O=870.07) P-24P-24 m/z=691.29(C52H37NO=691.87)m/z=691.29 (C 52 H 37 NO=691.87)
P-25P-25 m/z=883.38(C67H49NO=884.14)m/z=883.38 (C 67 H 49 NO=884.14) P-26P-26 m/z=890.33(C67H42N2O=891.09)m/z=890.33 (C 67 H 42 N 2 O=891.09)
P-27P-27 m/z=769.31(C56H39N3O=769.95)m/z=769.31 (C 56 H 39 N 3 O=769.95) P-28P-28 m/z=843.35(C64H45NO=844.07)m/z=843.35 (C 64 H 45 NO=844.07)
P-29P-29 m/z=833.31(C62H43NS=834.09)m/z=833.31 (C 62 H 43 NS=834.09) P-30P-30 m/z=783.3(C58H41NS=784.03)m/z=783.3 (C 58 H 41 NS=784.03)
P-31P-31 m/z=783.3(C58H41NS=784.03)m/z=783.3 (C 58 H 41 NS=784.03) P-32P-32 m/z=783.3(C58H41NS=784.03)m/z=783.3 (C 58 H 41 NS=784.03)
P-33P-33 m/z=911.33(C66H45N3S=912.17)m/z=911.33 (C 66 H 45 N 3 S=912.17) P-34P-34 m/z=911.33(C66H45N3S=912.17)m/z=911.33 (C 66 H 45 N 3 S=912.17)
P-35P-35 m/z=909.34(C68H47NS=910.19)m/z=909.34 (C 68 H 47 NS=910.19) P-36P-36 m/z=757.28(C56H39NS=758)m/z=757.28 (C 56 H 39 NS=758)
P-37P-37 m/z=998.37(C74H50N2S=999.29)m/z=998.37 (C 74 H 50 N 2 S=999.29) P-38P-38 m/z=807.3(C60H41NS=808.06)m/z=807.3 (C 60 H 41 NS=808.06)
P-39P-39 m/z=1014.38(C73H50N4S=1015.29)m/z=1014.38 (C 73 H 50 N 4 S=1015.29) P-40P-40 m/z=847.29(C62H41NOS=848.08)m/z=847.29 (C 62 H 41 NOS=848.08)
P-41P-41 m/z=831.3(C62H41NS=832.08)m/z=831.3 (C 62 H 41 NS=832.08) P-42P-42 m/z=872.32(C64H44N2S=873.13)m/z=872.32 (C 64 H 44 N 2 S=873.13)
P-43P-43 m/z=859.33(C64H45NS=860.13)m/z=859.33 (C 64 H 45 NS=860.13) P-44P-44 m/z=1087.33(C80H49NS2=1088.4)m/z=1087.33 (C 80 H 49 NS 2 =1088.4)
P-45P-45 m/z=935.36(C70H49NS=936.23)m/z=935.36 (C 70 H 49 NS=936.23) P-46P-46 m/z=1023.39(C77H53NS=1024.34)m/z=1023.39 (C 77 H 53 NS=1024.34)
P-47P-47 m/z=845.28(C62H39NOS=846.06)m/z=845.28 (C 62 H 39 NOS=846.06) P-48P-48 m/z=909.34(C68H47NS=910.19)m/z=909.34 (C 68 H 47 NS=910.19)
P-49P-49 m/z=997.37(C75H51NS=998.3)m/z=997.37 (C 75 H 51 NS=998.3) P-50P-50 m/z=797.28(C58H39NOS=798.02)m/z=797.28 (C 58 H 39 NOS=798.02)
P-51P-51 m/z=757.28(C56H39NS=758)m/z=757.28 (C 56 H 39 NS=758) P-52P-52 m/z=783.3(C58H41NS=784.03)m/z=783.3 (C 58 H 41 NS=784.03)
P-53P-53 m/z=826.3(C59H42N2OS=827.06)m/z=826.3 (C 59 H 42 N 2 OS=827.06) P-54P-54 m/z=835.3(C60H41N3S=836.07)m/z=835.3 (C 60 H 41 N 3 S=836.07)
P-55P-55 m/z=784.29(C57H40N2S=785.02)m/z=784.29 (C 57 H 40 N 2 S=785.02) P-56P-56 m/z=965.31(C70H47NS2=966.27)m/z=965.31 (C 70 H 47 NS 2 =966.27)
P-57P-57 m/z=842.37(C64H46N2=843.09)m/z=842.37 (C 64 H 46 N 2 =843.09) P-58P-58 m/z=918.4(C70H50N2=919.18)m/z=918.4 (C 70 H 50 N 2 =919.18)
P-59P-59 m/z=842.37(C64H46N2=843.09)m/z=842.37 (C 64 H 46 N 2 =843.09) P-60P-60 m/z=766.33(C58H42N2=766.99)m/z=766.33 (C 58 H 42 N 2 =766.99)
P-61P-61 m/z=968.41(C74H52N2=969.24)m/z=968.41 (C 74 H 52 N 2 =969.24) P-62P-62 m/z=766.33(C58H42N2=766.99)m/z=766.33 (C 58 H 42 N 2 =766.99)
P-63P-63 m/z=866.37(C66H46N2=867.11)m/z=866.37 (C 66 H 46 N 2 =867.11) P-64P-64 m/z=816.35(C62H44N2=817.05)m/z=816.35 (C 62 H 44 N 2 =817.05)
P-65P-65 m/z=932.38(C70H48N2O=933.17)m/z=932.38 (C 70 H 48 N 2 O=933.17) P-66P-66 m/z=866.37(C66H46N2=867.11)m/z=866.37 (C 66 H 46 N 2 =867.11)
P-67P-67 m/z=980.41(C75H52N2=981.26)m/z=980.41 (C 75 H 52 N 2 =981.26) P-68P-68 m/z=892.38(C68H48N2=893.15)m/z=892.38 (C 68 H 48 N 2 =893.15)
P-69P-69 m/z=882.4(C67H50N2=883.15)m/z=882.4 (C 67 H 50 N 2 =883.15) P-70P-70 m/z=1073.45(C79H55N5=1074.34)m/z=1073.45 (C 79 H 55 N 5 =1074.34)
P-71P-71 m/z=931.39(C70H49N3=932.18)m/z=931.39 (C 70 H 49 N 3 =932.18) P-72P-72 m/z=918.4(C70H50N2=919.18)m/z=918.4 (C 70 H 50 N 2 =919.18)
P-73P-73 m/z=932.38(C70H48N2O=933.17)m/z=932.38 (C 70 H 48 N 2 O=933.17) P-74P-74 m/z=931.39(C70H49N3=932.18)m/z=931.39 (C 70 H 49 N 3 =932.18)
P-75P-75 m/z=918.4(C70H50N2=919.18)m/z=918.4 (C 70 H 50 N 2 =919.18) P-76P-76 m/z=944.39(C70H48N4=945.18)m/z=944.39 (C 70 H 48 N 4 =945.18)
P-77P-77 m/z=816.35(C62H44N2=817.05)m/z=816.35 (C 62 H 44 N 2 =817.05) P-78P-78 m/z=766.33(C58H42N2=766.99)m/z=766.33 (C 58 H 42 N 2 =766.99)
P-79P-79 m/z=766.33(C58H42N2=766.99)m/z=766.33 (C 58 H 42 N 2 =766.99) P-80P-80 m/z=766.33(C58H42N2=766.99)m/z=766.33 (C 58 H 42 N 2 =766.99)
P-81P-81 m/z=766.33(C58H42N2=766.99)m/z=766.33 (C 58 H 42 N 2 =766.99) P-82P-82 m/z=766.33(C58H42N2=766.99)m/z=766.33 (C 58 H 42 N 2 =766.99)
P-83P-83 m/z=845.35(C61H43N5=846.05)m/z=845.35 (C 61 H 43 N 5 =846.05) P-84P-84 m/z=982.39(C74H50N2O=983.23)m/z=982.39 (C 74 H 50 N 2 O=983.23)
P-85P-85 m/z=717.34(C55H43N=717.96)m/z=717.34 (C 55 H 43 N=717.96) P-86P-86 m/z=767.36(C59H45N=768.02)m/z=767.36 (C 59 H 45 N=768.02)
P-87P-87 m/z=793.37(C61H47N=794.05)m/z=793.37 (C 61 H 47 N=794.05) P-88P-88 m/z=717.34(C55H43N=717.96)m/z=717.34 (C 55 H 43 N=717.96)
P-89P-89 m/z=869.4(C67H51N=870.15)m/z=869.4 (C 67 H 51 N=870.15) P-90P-90 m/z=793.37(C61H47N=794.05)m/z=793.37 (C 61 H 47 N=794.05)
P-91P-91 m/z=793.37(C61H47N=794.05)m/z=793.37 (C 61 H 47 N=794.05) P-92P-92 m/z=817.37(C63H47N=818.08)m/z=817.37 (C 63 H 47 N=818.08)
P-93P-93 m/z=869.4(C67H51N=870.15)m/z=869.4 (C 67 H 51 N=870.15) P-94P-94 m/z=843.39(C65H49N=844.11)m/z=843.39 (C 65 H 49 N=844.11)
P-95P-95 m/z=843.39(C65H49N=844.11)m/z=843.39 (C 65 H 49 N=844.11) P-96P-96 m/z=959.41(C73H53NO=960.23)m/z=959.41 (C 73 H 53 NO=960.23)
P-97P-97 m/z=1055.41(C81H53NO=1056.32)m/z=1055.41 (C 81 H 53 NO=1056.32) P-98P-98 m/z=997.44(C75H55N3=998.29)m/z=997.44 (C 75 H 55 N 3 =998.29)
P-99P-99 m/z=807.35(C61H45NO=808.04)m/z=807.35 (C 61 H 45 NO=808.04) P-100P-100 m/z=882.4(C67H50N2=883.15)m/z=882.4 (C 67 H 50 N 2 =883.15)
P-101P-101 m/z=857.37(C65H47NO=858.1)m/z=857.37 (C 65 H 47 NO=858.1) P-102P-102 m/z=793.37(C61H47N=794.05)m/z=793.37 (C 61 H 47 N=794.05)
P-103P-103 m/z=793.37(C61H47N=794.05)m/z=793.37 (C 61 H 47 N=794.05) P-104P-104 m/z=767.36(C59H45N=768.02)m/z=767.36 (C 59 H 45 N=768.02)
P-105P-105 m/z=833.4(C64H51N=834.12)m/z=833.4 (C 64 H 51 N=834.12) P-106P-106 m/z=884.39(C65H48N4=885.13)m/z=884.39 (C 65 H 48 N 4 =885.13)
P-107P-107 m/z=839.36(C65H45N=840.08)m/z=839.36 (C 65 H 45 N=840.08) P-108P-108 m/z=717.34(C55H43N=717.96)m/z=717.34 (C 55 H 43 N=717.96)
P-109P-109 m/z=909.43(C70H55N=910.22)m/z=909.43 (C 70 H 55 N=910.22) P-110P-110 m/z=795.36(C59H45N3=796.03)m/z=795.36 (C 59 H 45 N 3 =796.03)
P-111P-111 m/z=793.37(C61H47N=794.05)m/z=793.37 (C 61 H 47 N=794.05) P-112P-112 m/z=869.4(C67H51N=870.15)m/z=869.4 (C 67 H 51 N=870.15)
P-113P-113 m/z=961.34(C71H47NOS=962.22)m/z=961.34 (C 71 H 47 NOS=962.22) P-114P-114 m/z=961.34(C71H47NOS=962.22)m/z=961.34 (C 71 H 47 NOS=962.22)
P-115P-115 m/z=1095.46(C83H57N3=1096.39)m/z=1095.46 (C 83 H 57 N 3 =1096.39) P-116P-116 m/z=1122.49(C86H62N2=1123.46)m/z=1122.49 (C 86 H 62 N 2 =1123.46)
P-117P-117 m/z=709.28(C52H36FNO=709.86)m/z=709.28 (C 52 H 36 FNO=709.86) P-118P-118 m/z=825.34(C61H47NS=826.11)m/z=825.34 (C 61 H 47 NS=826.11)
P-119P-119 m/z=856.38(C65H48N2=857.11)m/z=856.38 (C 65 H 48 N 2 =857.11) P-120P-120 m/z=743.36(C57H45N=743.99)m/z=743.36 (C 57 H 45 N=743.99)
P-121P-121 m/z=873.36(C65H47NO2=874.1)m/z=873.36 (C 65 H 47 NO 2 =874.1) P-122P-122 m/z=732.26(C53H36N2S=732.95)m/z=732.26 (C 53 H 36 N 2 S=732.95)
P-123P-123 m/z=771.37(C58H37D5N2=772.02)m/z=771.37 (C 58 H 37 D 5 N 2 =772.02) P-124P-124 m/z=722.37(C55H38D5N=722.99)m/z=722.37 (C 55 H 38 D 5 N=722.99)
P-125P-125 m/z=767.32(C58H41NO=767.97)m/z=767.32 (C 58 H 41 NO=767.97) P-126P-126 m/z=767.32(C58H41NO=767.97)m/z=767.32 (C 58 H 41 NO=767.97)
P-127P-127 m/z=767.32(C58H41NO=767.97)m/z=767.32 (C 58 H 41 NO=767.97) P-128P-128 m/z=767.32(C58H41NO=767.97)m/z=767.32 (C 58 H 41 NO=767.97)
유기전기소자의 제조평가Manufacturing evaluation of organic electric devices
[[ 실시예Example 1] One] 녹색유기전기발광소자Green organic electroluminescent device ( ( 발광보조층Light-emitting auxiliary layer ))
본 발명의 화합물을 발광보조층 물질로 사용하여 통상적인 방법에 따라 유기전기발광소자를 제작하였다. 먼저, 유리 기판에 형성된 ITO층(양극) 위에 우선 홀 주입층으로서 N1-(naphthalen-2-yl)-N4,N4-bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N1-phenylbenzene-1,4-diamine (2-TNATA로 약기함) 막을 진공증착하여 60 nm 두께로 형성하였다. 이어서, 이 막 상에 정공수송 화합물로서 4,4-비스[N-(1-나프틸)-N-페닐아미노]비페닐 (이하 -NPD로 약기함)를 60 nm 두께로 진공증착하여 홀 수송층을 형성하였다. 이어서, 발광보조층 재료로서 본 발명의 화합물 P-1을 20 nm의 두께로 진공증착하여 발광보조층을 형성하였다. 발광보조층을 형성한 후, 발광보조층 상부에 호스트로서는 CBP[4,4'-N,N'-dicarbazole-biphenyl], 도판트로서는 Ir(ppy)3 [tris(2-phenylpyridine)-iridium]을 95:5 중량으로 도핑함으로써 상기 발광보조층 위에 30 nm 두께의 발광층을 증착하였다. 홀 저지층으로 (1,1’-비스페닐)-4-올레이토)비스(2-메틸-8-퀴놀린올레이토)알루미늄(이하 BAlq로 약기함)을 10 nm 두께로 진공증착하고, 전자수송층으로 트리스(8-퀴놀리놀)알루미늄(이하 Alq3로 약칭함)을 40 nm 두께로 성막하였다. 이후, 전자주입층으로 할로젠화 알칼리 금속인 LiF를 0.2 nm 두께로 증착하고, 이어서 Al을 150 nm의 두께로 증착하여 음극으로 사용함으로써 유기전계 발광소자를 제조하였다.An organic electroluminescent device was manufactured according to a conventional method by using the compound of the present invention as a light emitting auxiliary layer material. First, N1-(naphthalen-2-yl)-N4,N4-bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N1 as a hole injection layer on the ITO layer (anode) formed on the glass substrate. A -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) film was vacuum-deposited to form a thickness of 60 nm. Subsequently, 4,4-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (hereinafter abbreviated as -NPD) as a hole transport compound was vacuum-deposited to a thickness of 60 nm on the film to form a hole transport layer. Formed. Subsequently, the compound P-1 of the present invention was vacuum-deposited to a thickness of 20 nm as a material for the auxiliary layer to form an auxiliary layer. After forming the light-emitting auxiliary layer, CBP[4,4'-N,N'-dicarbazole-biphenyl] as a host and Ir(ppy)3 [tris(2-phenylpyridine)-iridium] as a dopant on the light-emitting auxiliary layer By doping with 95:5 weight, a light emitting layer having a thickness of 30 nm was deposited on the light emitting auxiliary layer. As a hole blocking layer, (1,1'-bisphenyl)-4-oleato)bis(2-methyl-8-quinolinoleato)aluminum (hereinafter abbreviated as BAlq) was vacuum deposited to a thickness of 10 nm, and the electron transport layer As a result, tris(8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was deposited to a thickness of 40 nm. Thereafter, as an electron injection layer, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm and used as a cathode, thereby manufacturing an organic light emitting diode.
[[ 실시예Example 2] 내지 [ 2] to [ 실시예Example 30] 30]
발광보조층 물질로 본 발명의 화합물 P-1 대신 하기 표 4에 기재된 본 발명의 화합물을 사용한 점을 제외하고는 실시예 1과 동일한 방법으로 유기전기발광소자를 제작하였다.An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compound of the present invention described in Table 4 was used instead of the compound P-1 of the present invention as the light emitting auxiliary layer material.
[[ 비교예Comparative example 1] One]
발광보조층을 형성하지 않은 것을 제외하고는 상기 실시예 1과 동일한 방법으로 유기전기발광소자를 제작하였다.An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the light emission auxiliary layer was not formed.
[[ 비교예Comparative example 2] 내지 [ 2] to [ 비교예Comparative example 5] 5]
발광보조층 물질로 비교화합물 A 내지 비교화합물 D를 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 유기전기발광소자를 제작하였다.An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound A to Comparative Compound D were used as the light emitting auxiliary layer material.
[비교화합물 A] [비교화합물 B] [비교화합물 C] [비교화합물 D][Comparative compound A] [Comparative compound B] [Comparative compound C] [Comparative compound D]
Figure PCTKR2020009674-appb-I000110
Figure PCTKR2020009674-appb-I000110
이와 같이 제조된 실시예 및 비교예 유기전기발광소자들에 순바이어스 직류전압을 가하여 포토리서치(photoresearch)사의 PR-650으로 전기발광(EL) 특성을 측정하였으며, 그 측정 결과 5000 cd/m2 기준 휘도에서 맥사이언스사에서 제조된 수명 측정 장비를 통해 T95 수명을 측정하였다. 하기 표 4는 소자제작 및 평가한 결과를 나타낸다.The electroluminescence (EL) characteristics were measured with a PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared as described above, and the measurement result was based on 5000 cd/m 2 In the luminance, the T95 life was measured using a life measurement equipment manufactured by McScience. Table 4 below shows the results of device fabrication and evaluation.
화합물compound 구동전압Driving voltage 전류(mA/cm2)Current (mA/cm 2 ) 휘도(cd/m2)Luminance (cd/m 2 ) 효율(cd/A)Efficiency (cd/A) T(95)T(95)
비교예(1)Comparative Example (1) -- 6.0 6.0 21.6 21.6 5000.0 5000.0 23.2 23.2 57.4 57.4
비교예(2)Comparative Example (2) 비교화합물 AComparative compound A 5.7 5.7 12.5 12.5 5000.0 5000.0 40.1 40.1 73.6 73.6
비교예(3)Comparative Example (3) 비교화합물 BComparative compound B 5.8 5.8 12.0 12.0 5000.0 5000.0 41.8 41.8 80.3 80.3
비교예(4)Comparative Example (4) 비교화합물 CComparative compound C 5.9 5.9 12.8 12.8 5000.0 5000.0 39.0 39.0 66.1 66.1
비교예(5)Comparative Example (5) 비교화합물 DComparative compound D 5.6 5.6 11.0 11.0 5000.0 5000.0 45.5 45.5 88.8 88.8
실시예(1)Example (1) P-1P-1 5.2 5.2 8.1 8.1 5000.0 5000.0 61.4 61.4 104.8 104.8
실시예(2)Example (2) P-2P-2 5.2 5.2 8.1 8.1 5000.0 5000.0 61.6 61.6 105.0 105.0
실시예(3)Example (3) P-3P-3 5.3 5.3 8.7 8.7 5000.0 5000.0 57.8 57.8 103.7 103.7
실시예(4)Example (4) P-4P-4 5.3 5.3 8.9 8.9 5000.0 5000.0 56.2 56.2 102.6 102.6
실시예(5)Example (5) P-5P-5 5.3 5.3 8.9 8.9 5000.0 5000.0 56.0 56.0 104.1 104.1
실시예(6)Example (6) P-6P-6 5.1 5.1 8.2 8.2 5000.0 5000.0 61.1 61.1 104.9 104.9
실시예(7)Example (7) P-17P-17 5.4 5.4 8.6 8.6 5000.0 5000.0 58.3 58.3 103.1 103.1
실시예(8)Example (8) P-24P-24 5.3 5.3 9.4 9.4 5000.0 5000.0 53.3 53.3 101.0 101.0
실시예(9)Example (9) P-28P-28 5.4 5.4 9.2 9.2 5000.0 5000.0 54.2 54.2 102.9 102.9
실시예(10)Example (10) P-30P-30 5.2 5.2 8.5 8.5 5000.0 5000.0 58.9 58.9 104.0 104.0
실시예(11)Example (11) P-35P-35 5.3 5.3 8.9 8.9 5000.0 5000.0 56.1 56.1 103.1 103.1
실시예(12)Example (12) P-37P-37 5.4 5.4 9.1 9.1 5000.0 5000.0 55.2 55.2 102.1 102.1
실시예(13)Example (13) P-41P-41 5.1 5.1 9.0 9.0 5000.0 5000.0 55.6 55.6 102.6 102.6
실시예(14)Example (14) P-47P-47 5.1 5.1 9.1 9.1 5000.0 5000.0 55.1 55.1 102.3 102.3
실시예(15)Example (15) P-50P-50 5.4 5.4 9.3 9.3 5000.0 5000.0 53.7 53.7 100.4 100.4
실시예(16)Example (16) P-52P-52 5.1 5.1 9.2 9.2 5000.0 5000.0 54.5 54.5 100.3 100.3
실시예(17)Example (17) P-56P-56 5.2 5.2 9.4 9.4 5000.0 5000.0 53.4 53.4 101.1 101.1
실시예(18)Example (18) P-57P-57 5.3 5.3 8.7 8.7 5000.0 5000.0 57.5 57.5 103.1 103.1
실시예(19)Example (19) P-59P-59 5.3 5.3 8.8 8.8 5000.0 5000.0 56.8 56.8 102.8 102.8
실시예(20)Example (20) P-60P-60 5.3 5.3 9.0 9.0 5000.0 5000.0 55.6 55.6 102.1 102.1
실시예(21)Example (21) P-65P-65 5.4 5.4 9.1 9.1 5000.0 5000.0 54.8 54.8 101.7 101.7
실시예(22)Example (22) P-77P-77 5.5 5.5 9.4 9.4 5000.0 5000.0 53.2 53.2 101.4 101.4
실시예(23)Example (23) P-78P-78 5.5 5.5 9.2 9.2 5000.0 5000.0 54.1 54.1 100.0 100.0
실시예(24)Example (24) P-87P-87 5.3 5.3 9.2 9.2 5000.0 5000.0 54.3 54.3 100.5 100.5
실시예(25)Example (25) P-91P-91 5.4 5.4 9.3 9.3 5000.0 5000.0 53.5 53.5 100.7 100.7
실시예(26)Example (26) P-99P-99 5.3 5.3 9.4 9.4 5000.0 5000.0 53.0 53.0 100.6 100.6
실시예(27)Example (27) P-103P-103 5.3 5.3 9.0 9.0 5000.0 5000.0 55.5 55.5 102.1 102.1
실시예(28)Example (28) P-108P-108 5.3 5.3 8.8 8.8 5000.0 5000.0 56.7 56.7 102.4 102.4
실시예(29)Example (29) P-125P-125 5.2 5.2 8.5 8.5 5000.0 5000.0 58.5 58.5 104.1 104.1
실시예(30)Example (30) P-126P-126 5.3 5.3 8.8 8.8 5000.0 5000.0 57.1 57.1 103.4 103.4
상기 표 4의 결과로부터 알 수 있듯이, 본 발명의 유기전기발광소자용 재료를 발광보조층 재료로 사용하여 녹색유기전기발광소자를 제작한 경우, 발광보조층을 형성하지 않거나 본 발명의 화합물과 기본 골격이 유사한 비교화합물 A 내지 비교화합물 D를 사용한 비교예보다 유기전기발광소자의 발광 효율 및 수명을 개선시킬 수 있다.As can be seen from the results of 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, the light emitting auxiliary layer is not formed or the compound of the present invention is It is possible to improve the luminous efficiency and lifespan of the organic electroluminescent device compared to Comparative Examples using Comparative Compound A to Comparative Compound D having a similar skeleton.
다시 말해, 발광보조층이 형성되지 않은 비교예 1보다는 비교화합물 A 내지 비교화합물 D 중 하나를 사용하여 발광보조층을 사용한 비교예 2 내지 비교예 5의 경우 소자의 구동전압, 효율, 수명이 개선되었으며, 비교예 2 내지 비교예 5 중 하나를 발광보조층으로 사용한 경우보다 본 발명의 화합물을 발광보조층 재료로 사용한 경우, 유기전기 발광소자의 구동전압이 낮아지고, 발광효율 및 수명이 향상되었다.In other words, in the case of Comparative Examples 2 to 5 using one of Comparative Compound A to Comparative Compound D and using one of Comparative Compound A to Comparative Example 5, rather than Comparative Example 1 in which the auxiliary layer was not formed, the driving voltage, efficiency, and lifetime of the device were improved When the compound of the present invention was used as a light emitting auxiliary layer material than when one of Comparative Examples 2 to 5 was used as a light emitting auxiliary layer, the driving voltage of the organic electroluminescent device was lowered, and luminous efficiency and lifespan were improved. .
비교화합물 A 내지 비교화합물 C는 다이페닐플루오렌의 페닐에 아미노기가 치환되어 있다는 점에서 본 발명의 화합물과 유사하지만, 본 발명의 화합물은 아미노기의 치환기 중 적어도 하나가 플루오렌모이어티를 포함하는 축합 다환고리가 치환되어 있다는 점에서 상이하다.Comparative compounds A to C are similar to the compounds of the present invention in that an amino group is substituted with the phenyl of diphenylfluorene, but the compounds of the present invention are condensed in which at least one of the substituents of the amino group contains a fluorene moiety. It differs in that the polycyclic ring is substituted.
본 발명의 화합물과 비교화합물 A를 비교하면, 단순 플루오렌이 치환된 비교화합물 A 보다 플루오렌 모이어에 벤조퓨란, 벤조싸이오펜, 인돌, 인덴이 축합된 구조가 치환된 본 발명의 화합물이 구동, 효율, 수명 면에서 현저하게 향상되었는데, 이는 플루오렌 모이어티에 상기 벤조퓨란, 벤조싸이오펜 등의 구조가 더 축합될 경우 분자의 planarity가 증가하여 Hole Mobility가 향상되고, 이로 인해 Hole이 호스트로 보다 빠르게 주입되어 발광보조층과 호스트 사이의 계면발광이 줄고, 호스트 내에서 주로 발광이 이루어지기 때문에 Charge balance가 향상되어 구동 및 효율, 수명이 향상되는 것으로 판단된다.When comparing the compound of the present invention with the comparative compound A, the compound of the present invention in which the structure in which benzofuran, benzothiophene, indole, and indene is condensed in a fluorene moiety is substituted rather than a simple fluorene-substituted comparative compound A, The efficiency and lifespan have been remarkably improved.This is because when the structures such as benzofuran and benzothiophene are further condensed with the fluorene moiety, the planarity of the molecule increases and the hole mobility is improved. By injection, the interfacial light emission between the light emitting auxiliary layer and the host is reduced, and since light is mainly emitted in the host, the charge balance is improved and driving, efficiency, and lifespan are improved.
본 발명의 화합물과 비교화합물 B를 비교하면, 비교화합물 B는 본 발명의 화합물과 유사하지만 본 발명의 화합물에 추가적으로 치환된 아미노기가 더 치환되어 있다. 따라서, 본 발명의 화합물보다 더 큰 분자량을 가지게 되고, 이로 인해 Tg 값이 증가하여 너무 높은 증착온도를 필요로 하게 되고 그 과정에서 소자 수명 및 효율에 영향을 주는 것으로 판단된다.Comparing the compound of the present invention and the comparative compound B, the comparative compound B is similar to the compound of the present invention, but the amino group further substituted with the compound of the present invention is further substituted. Therefore, it has a higher molecular weight than the compound of the present invention, and thus, the Tg value increases, requiring too high a deposition temperature, and it is determined that the device life and efficiency are affected in the process.
한편, 비교화합물 C 및 비교화합물 D와 본 발명의 화합물 P-86을 가우시안(Gaussian) 프로그램의 DFT method (B3LYP/6-31g(D))를 이용하여 측정한 데이터는 하기 표 5와 같다.Meanwhile, the data measured using the DFT method (B3LYP/6-31g(D)) of the Gaussian program of Comparative Compound C and Comparative Compound D and Compound P-86 of the present invention are shown in Table 5 below.
　 LUMO (eV)LUMO (eV)
비교화합물 CComparative compound C -1.685-1.685
비교화합물 DComparative compound D -1.132-1.132
P-125P-125 -1.063-1.063
본 발명의 화합물과 비교화합물 C, 비교화합물 D를 비교하면, 비교화합물 C는 아미노기에 비스나프토벤조퓨란이 치환되어 있고, 비교화합물 D는 아미노기가 치환된 위치가 다이페닐플루오렌의 페닐이 아닌 플루오렌쪽에 치환이 되어있다는 점에서 차이가 있다. 상기 표 5에서 볼 수 있듯이 비교화합물 C와 비교화합물 D의 경우 본 발명의 화합물보다 LUMO level이 더 낮은 것을 확인할 수 있는데, 이로 인해 비교화합물 C 및 비교화합물 D는 본 발명의 화합물보다 발광층으로부터 넘어오는 전자를 효과적으로 저지할 수 없기 때문에 소자 결과에서도 현저한 차이를 보이는 것으로 판단된다.Comparing the compound of the present invention with Comparative Compound C and Comparative Compound D, Comparative Compound C has an amino group substituted with bisnaphthobenzofuran, and Comparative Compound D has an amino group substituted at the position where the amino group is substituted is not phenyl of diphenylfluorene. There is a difference in that there is a substitution on the fluorene side. As can be seen in Table 5, it can be seen that the LUMO level of Comparative Compound C and Comparative Compound D is lower than that of the compound of the present invention. Accordingly, Comparative Compound C and Comparative Compound D Since the electrons cannot be effectively blocked, it is judged that there is a significant difference in the device results.
이러한 결과는 비교화합물 A 내지 비교화합물 D와 본 발명의 화합물같이 분자가 구성되는 기본골격이 유사한 화합물일지라도, 치환기의 치환 위치 및 치환기의 종류에 따라 Hole 특성, 광효율 특성, 에너지 레벨(HOMO, LUMO), 정공 주입 및 이동도 특성, 정공과 전자의 Charge balance 등과 같은 화합물의 특성이 달라질 수 있으며, 이로 인해 소자의 결과가 예측하기 어려울 만큼 현저하게 도출될 수 있음을 시사하고 있다.These results indicate that even if the compound of the compound of the present invention is similar to the basic structure of the molecule, such as Comparative Compound A to Comparative Compound D and the compound of the present invention, hole characteristics, light efficiency characteristics, and energy levels (HOMO, LUMO) depend on the substitution position of the substituent and the type of the substituent. , Hole injection and mobility characteristics, and the characteristics of the compound, such as the charge balance between holes and electrons, may vary, suggesting that the result of the device may be remarkably derived so that it is difficult to predict.
이상의 설명은 본 발명을 예시적으로 설명한 것에 불과한 것으로, 본 발명에 속하는 기술분야에서 통상의 지식을 가지는 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 변형이 가능할 것이다. 따라서, 본 명세서에 개시된 실시예들은 본 발명을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시예에 의하여 본 발명의 사상과 범위가 한정되는 것은 아니다. 본 발명의 보호범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 모든 기술은 본 발명의 권리범위에 포함하는 것으로 해석되어야 할 것이다.The above description is only illustrative of the present invention, and those of ordinary skill in the art to which the present invention pertains will be able to make various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in the present specification are not intended to limit the present invention, but to explain the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The scope of protection of the present invention should be interpreted by the claims below, and all technologies within the scope equivalent thereto should be construed as being included in the scope of the present invention.

Claims (17)

  1. 하기 화학식 1로 표시되는 화합물Compound represented by the following formula (1)
    화학식 1 화학식 2Formula 1 Formula 2
    Figure PCTKR2020009674-appb-I000111
    Figure PCTKR2020009674-appb-I000111
    {상기 화학식 1 및 화학식 2에서,{In Formula 1 and Formula 2,
    1) R1, R2, R3, R4, R5, R6 및 R7은 서로 독립적으로 수소; 중수소; 할로겐; C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C60의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕실기; 및 C6~C30의 아릴옥시기;로 이루어진 군에서 선택되며,1) R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently hydrogen; heavy hydrogen; halogen; C 6 ~ C 60 aryl group; Fluorenyl group; O, N, S, Si, and C 2 ~ C 60 heterocyclic group containing at least one heteroatom of P; A fused ring group of an aliphatic ring of C 3 to C 60 and an aromatic ring of C 6 to C 60 ; C 1 ~ C 60 alkyl group; C 2 ~ C 20 alkenyl group; Alkynyl group of C 2 ~ C 20 ; An alkoxyl group of C 1 to C 30 ; And C 6 ~ C 30 aryloxy group; is selected from the group consisting of,
    또한 상기 a, b, c, d, e, f 및 g가 서로 독립적으로 2 이상인 경우 각각 복수로서 서로 동일하거나 상이하며, 복수의 R1끼리 혹은 복수의 R2끼리 혹은 복수의 R3끼리 혹은 복수의 R4끼리 혹은 복수의 R5끼리 혹은 복수의 R6끼리 혹은 복수의 R7끼리 서로 결합하여 고리를 형성할 수 있고,In addition, the a, b, c, d, e, f and g are the same or different, a plurality of each or more independently 2 to each other, a plurality of R 1 each other or a plurality of R 2 to each other or a plurality of R 3 to each other or a plurality Of R 4 or a plurality of R 5 or a plurality of R 6 or a plurality of R 7 may be bonded to each other to form a ring,
    2) L1, L2 및 L3는 서로 독립적으로 단일결합; C6-C60의 아릴렌기; 플루오렌일기; C2~C60의 헤테로고리기; 및 C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기;로 이루어진 군에서 선택되며, R4와 L1은 서로 결합하여 고리를 형성할 수 있고,2) L 1 , L 2 and L 3 are each independently a single bond; C 6 -C 60 arylene group; Fluorenyl group; C 2 ~ C 60 heterocyclic group; And a fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; and R 4 and L 1 may be bonded to each other to form a ring,
    3) Ar1은 C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; 및 C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기;로 이루어진 군에서 선택되며,3) Ar1 is a C 6 ~ C 60 aryl group; Fluorenyl group; O, N, S, Si, and C 2 -C 60 heterocyclic group containing at least one heteroatom of P; And a fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ;
    4) A는 상기 화학식 2로 표시되며, 상기 화학식 2의 R5, R6 및 R7 중 적어도 어느 하나는 L3과 결합하고, 단, L3이 단일결합일 경우 상기 화학식 1의 N과 결합하며, R5, R6 및 R7은 서로 독립적으로 L3과 고리를 형성할 수 있고,4) A is N and the combination of Formula 1, if is represented by the general formula (2), the general formula (2) in R 5, R 6 and R 7 at least one of which is a single bond in combination with L 3, with the proviso, L 3 il And, R 5 , R 6 and R 7 may independently form a ring with L 3 ,
    5) R' 및 R”은 서로 독립적으로 C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; 및 C1~C60의 알킬기;로 이루어진 군에서 선택되며, R' 및 R”은 서로 결합하여 스파이로 고리를 형성할 수 있고,5) R'and R” are each independently a C 6 ~C 60 aryl group; Fluorenyl group; O, N, S, Si, and C 2 ~ C 60 heterocyclic group containing at least one heteroatom of P; And C 1 ~ C 60 Alkyl group; is selected from the group consisting of, R'and R" may be bonded to each other to form a ring with a spy,
    6) X는 NRa, O, S 또는 CRbRc이며,6) X is NR a , O, S or CR b R c ,
    상기 Ra, Rb 및 Rc는 서로 독립적으로 C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; 및 C1~C60의 알킬기;로 이루어진 군에서 선택되고,R a , R b and R c are each independently a C 6 ~ C 60 aryl group; Fluorenyl group; O, N, S, Si, and C 2 ~ C 60 heterocyclic group containing at least one heteroatom of P; And C 1 ~ C 60 alkyl group; is selected from the group consisting of,
    7) a는 0 내지 5의 정수이며, b, c, d, e 및 g는 서로 독립적으로 0 내지 4의 정수이고, f는 0 내지 2의 정수이며,7) a is an integer of 0 to 5, b, c, d, e and g are independently an integer of 0 to 4, and f is an integer of 0 to 2,
    여기서, 상기 아릴기, 플루오렌일기, 아릴렌기, 헤테로고리기, 플루오렌일렌기, 융합고리기, 알킬기, 알켄일기, 알콕실기 및 아릴옥시기는 각각 중수소; 할로겐; 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; C1-C20의 알킬싸이오기; C1-C20의 알콕실기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 중수소로 치환된 C6-C20의 아릴기; 플루오렌일기; C2-C20의 헤테로고리기; C3-C20의 시클로알킬기; C7-C20의 아릴알킬기 및 C8-C20의 아릴알켄일기;로 이루어진 군에서 선택된 하나 이상의 치환기로 더욱 치환될 수 있으며, 또한 이들 치환기들은 서로 결합하여 고리를 형성할 수도 있으며, 여기서 '고리'란 C3-C60의 지방족고리 또는 C6-C60의 방향족고리 또는 C2-C60의 헤테로고리 또는 이들의 조합으로 이루어진 융합 고리를 말하며, 포화 또는 불포화 고리를 포함하고,Here, the aryl group, fluorenyl group, arylene group, heterocyclic group, fluorenylene group, fused ring group, alkyl group, alkenyl group, alkoxyl group and aryloxy group are each deuterium; halogen; Silane group; Siloxane group; Boron group; Germanium group; Cyano group; Nitro group; C 1 -C 20 alkylthio group; An alkoxyl group of C 1 -C 20 ; A C 1 -C 20 alkyl group; An alkenyl group of C 2 -C 20 ; Alkynyl group of C 2 -C 20 ; C 6 -C 20 aryl group; A C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group; A C 3 -C 20 cycloalkyl group; C 7 -C 20 arylalkyl group and C 8 -C 20 arylalkenyl group; may be further substituted with one or more substituents selected from the group consisting of, and these substituents may be bonded to each other to form a ring, wherein ' The term'ring' refers to a fused ring consisting of a C 3 -C 60 aliphatic ring or a C 6 -C 60 aromatic ring or a C 2 -C 60 hetero ring or a combination thereof, and includes a saturated or unsaturated ring,
    단, 하기 화학식 11로 표시되는 화합물은 제외하며,However, except for the compound represented by the following formula (11),
    화학식 11Formula 11
    Figure PCTKR2020009674-appb-I000112
    Figure PCTKR2020009674-appb-I000112
    상기 화학식 11에서,In Formula 11,
    1) R1 내지 R4, L1, L2, Ar1, a, b, c 및 d는 상기 화학식 1에서의 정의와 동일하고,1) R 1 to R 4 , L 1 , L 2 , Ar1, a, b, c and d are the same as defined in Formula 1,
    2) R11, R12 및 R13은 서로 독립적으로 수소; 중수소; 할로겐; C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C60의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕실기; 및 C6~C30의 아릴옥시기;로 이루어진 군에서 선택되며, 또한 상기 x, y 및 z가 2 이상인 경우 각각 복수로서 서로 동일하거나 상이하며, 복수의 R11끼리 혹은 복수의 R12끼리 혹은 복수의 R13끼리 서로 결합하여 고리를 형성할 수 있고,2) R 11 , R 12 and R 13 are each independently hydrogen; heavy hydrogen; halogen; C 6 ~ C 60 aryl group; Fluorenyl group; O, N, S, Si, and C 2 ~ C 60 heterocyclic group containing at least one heteroatom of P; A fused ring group of an aliphatic ring of C 3 to C 60 and an aromatic ring of C 6 to C 60 ; C 1 ~ C 60 alkyl group; C 2 ~ C 20 alkenyl group; Alkynyl group of C 2 ~ C 20 ; An alkoxyl group of C 1 to C 30 ; And C 6 ~ C 30 aryloxy group; is selected from the group consisting of, and when x, y and z are 2 or more, each is the same as or different from each other as a plurality, and a plurality of R 11 or a plurality of R 12 or A plurality of R 13 can be bonded to each other to form a ring,
    3) R14 및 R15는 상기 화학식 2에서 정의된 R' 및 R”와 동일하며,3) R 14 and R 15 are the same as R'and R” defined in Formula 2,
    4) x는 0 내지 3의 정수이며, y는 0 내지 2의 정수이고, z는 0 내지 4의 정수이다.}4) x is an integer from 0 to 3, y is an integer from 0 to 2, and z is an integer from 0 to 4.}
  2. 제1항에 있어서, 상기 화학식 1이 하기 화학식 1-1 또는 화학식 1-2로 표시되는 화합물The compound of claim 1, wherein the formula 1 is represented by the following formula 1-1 or 1-2
    화학식 1-1 화학식 1-2Formula 1-1 Formula 1-2
    Figure PCTKR2020009674-appb-I000113
    Figure PCTKR2020009674-appb-I000114
    Figure PCTKR2020009674-appb-I000113
    Figure PCTKR2020009674-appb-I000114
    {상기 화학식 1-1 및 화학식 1-2에서,{In Formula 1-1 and Formula 1-2,
    1) R1, R2, R3, R4, R5, R6, R7, L1, L2, L3, R', R”, Ar1, X, a, b, c, d, e, f 및 g는 청구항 1에 정의된 바와 동일하고1) R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , L 1 , L 2 , L 3 , R', R”, Ar1, X, a, b, c, d, e, f and g are the same as defined in claim 1, and
    2) R15 및 R17은 서로 독립적으로 수소; 중수소; C1-C60의 알콕실기; C1-C60의 알킬기; C2-C60의 알켄일기; C2-C60의 알킨일기; C6-C60의 아릴기; 중수소로 치환된 C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 시클로알킬기; C7-C60의 아릴알킬기; 및 C8-C60의 아릴알켄일기;로 이루어진 군에서 선택되며, 복수의 R15끼리 혹은 복수의 R17끼리 서로 결합하여 고리를 형성할 수 있고,2) R 15 and R 17 are each independently hydrogen; heavy hydrogen; An alkoxyl group of C 1 -C 60 ; A C 1 -C 60 alkyl group; An alkenyl group of C 2 -C 60 ; Alkynyl group of C 2 -C 60 ; C 6 -C 60 aryl group; A C 6 -C 60 aryl group substituted with deuterium; Fluorenyl group; O, N, S, Si, and C 2 -C 60 heterocyclic group containing at least one heteroatom of P; A C 3 -C 60 cycloalkyl group; C 7 -C 60 arylalkyl group; And C 8 -C 60 arylalkenyl group; selected from the group consisting of, a plurality of R 15 to each other or a plurality of R 17 to each other can form a ring,
    3) e' 및 g'은 서로 독립적으로 0 내지 3의 정수이다.}3) e'and g'are each independently an integer of 0 to 3.}
  3. 제1항에 있어서, 상기 화학식 1이 하기 화학식 1-3, 화학식 1-4 또는 화학식 1-5로 표시되는 화합물The compound of claim 1, wherein the formula 1 is represented by the following formulas 1-3, 1-4, or 1-5
    화학식 1-3 화학식 1-4Formula 1-3 Formula 1-4
    Figure PCTKR2020009674-appb-I000115
    Figure PCTKR2020009674-appb-I000115
    화학식 1-5Formula 1-5
    Figure PCTKR2020009674-appb-I000116
    Figure PCTKR2020009674-appb-I000116
    {상기 화학식 1-3 내지 화학식 1-5에서,{In Formulas 1-3 to 1-5,
    R1 내지 R4, L1 내지 L3, Ar1, A, a, b, c 및 d는 상기 청구항 1에서 정의한 바와 동일하다.}R 1 to R 4 , L 1 to L 3 , Ar1, A, a, b, c and d are the same as defined in claim 1.}
  4. 제1항에 있어서, 상기 화학식 2가 하기 화학식 2-1 내지 화학식 2-4 중 어느 하나로 표시되는 화합물The compound of claim 1, wherein Formula 2 is represented by any one of Formulas 2-1 to 2-4 below.
    화학식 2-1 화학식 2-2Formula 2-1 Formula 2-2
    Figure PCTKR2020009674-appb-I000117
    Figure PCTKR2020009674-appb-I000117
    화학식 2-3 화학식 2-4Formula 2-3 Formula 2-4
    Figure PCTKR2020009674-appb-I000118
    Figure PCTKR2020009674-appb-I000118
    {상기 화학식 2-1 내지 화학식 2-4에서,{In Formula 2-1 to Formula 2-4,
    R5, R6, R7, R', R”, Ra, Rb, Rc, e, f 및 g는 상기 청구항 1에서 정의한 바와 동일하다.}R 5 , R 6 , R 7 , R', R”, R a , R b , R c , e, f and g are the same as defined in claim 1 above.}
  5. 제1항에 있어서, 상기 화학식 2가 하기 화학식 2-5 내지 화학식 2-10 중 어느 하나로 표시되는 화합물The compound of claim 1, wherein Formula 2 is represented by any one of Formulas 2-5 to 2-10 below.
    화학식 2-5 화학식 2-6Formula 2-5 Formula 2-6
    Figure PCTKR2020009674-appb-I000119
    Figure PCTKR2020009674-appb-I000119
    화학식 2-7 화학식 2-8Chemical Formula 2-7 Chemical Formula 2-8
    Figure PCTKR2020009674-appb-I000120
    Figure PCTKR2020009674-appb-I000120
    화학식 2-9 화학식 2-10Chemical Formula 2-9 Chemical Formula 2-10
    Figure PCTKR2020009674-appb-I000121
    Figure PCTKR2020009674-appb-I000121
    {상기 화학식 2-5 내지 화학식 2-10에서,{In Formula 2-5 to Formula 2-10,
    R5, R6, R7, X, R', R”, e, f 및 g는 상기 청구항 1에서 정의한 바와 동일하다.}R 5 , R 6 , R 7 , X, R', R”, e, f and g are the same as defined in claim 1.}
  6. 제1항에 있어서, 상기 화학식 1이 하기 화학식 1-6 내지 화학식 1-11 중 어느 하나로 표시되는 화합물The compound of claim 1, wherein the formula 1 is represented by any one of the following formulas 1-6 to 1-11
    화학식 1-6 화학식 1-7Formula 1-6 Formula 1-7
    Figure PCTKR2020009674-appb-I000122
    Figure PCTKR2020009674-appb-I000122
    화학식 1-8 화학식 1-9Chemical Formula 1-8 Chemical Formula 1-9
    Figure PCTKR2020009674-appb-I000123
    Figure PCTKR2020009674-appb-I000123
    화학식 1-10 화학식 1-11Formula 1-10 Formula 1-11
    Figure PCTKR2020009674-appb-I000124
    Figure PCTKR2020009674-appb-I000124
    {상기 화학식 1-6 내지 화학식 1-11에서,{In Formula 1-6 to Formula 1-11,
    1) R1 내지 R7, L1 내지 L3, R', R”, Ar1, X, a, b, c, d, e, f 및 g는 상기 청구항 1에서 정의한 바와 동일하며,1) R 1 to R 7 , L 1 to L 3 , R', R”, Ar1, X, a, b, c, d, e, f and g are the same as defined in claim 1,
    2) R15, R17, e' 및 g'은 상기 청구항 2에서 정의한 바와 동일하다.}2) R 15 , R 17 , e'and g'are the same as defined in claim 2.}
  7. 제1항에 있어서, 상기 R1, R2, R3, R4, R5, R6 및 R7은 서로 독립적으로 수소; 중수소; C6~C25의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C30의 헤테로고리기; C3~C30의 지방족고리와 C6~C30의 방향족고리의 융합고리기; 및 C1~C20의 알킬기; 로 이루어진 군에서 선택되며, 상기 a, b, c, d, e, f 및 g가 2 이상인 경우 각각 복수로서 서로 동일하거나 상이며, 복수의 R1끼리 혹은 복수의 R2끼리 혹은 복수의 R3끼리 혹은 복수의 R4끼리 혹은 복수의 R5끼리 혹은 복수의 R6끼리 혹은 복수의 R7끼리 서로 결합하여 고리를 형성할 수 있는 것을 특징으로 하는 화합물The method of claim 1, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently hydrogen; heavy hydrogen; C 6 ~ C 25 aryl group; Fluorenyl group; O, N, S, Si, and C 2 ~ C 30 heterocyclic group containing at least one heteroatom of P; A fused ring group of an aliphatic ring of C 3 to C 30 and an aromatic ring of C 6 to C 30 ; And a C 1 to C 20 alkyl group; Is selected from the group consisting of, wherein a, b, c, d, e, f and g are two cases is the same or onto one another as a plurality of each or more, a plurality of R 1 each other or a plurality of R 2 to each other or a plurality of R 3 A compound characterized in that a ring can be formed by bonding to each other or between a plurality of R 4 or a plurality of R 5 or a plurality of R 6 or a plurality of R 7 to each other
  8. 제1항에 있어서, 상기 화학식 1 및 화학식 2의 상기 R1, R2, R3, R4, R5, R6 및 R7은 서로 독립적으로, 복수의 R1끼리 혹은 복수의 R2끼리 혹은 복수의 R3끼리 혹은 복수의 R4끼리 혹은 복수의 R5끼리 혹은 복수의 R6끼리 혹은 복수의 R7끼리 서로 결합하여 고리를 형성하는 경우, 벤젠, 나프틸, 벤조퓨란, 벤조싸이오펜, 인돌 또는 인덴 고리를 형성하는 것을 특징으로 하는 화합물The method of claim 1, wherein the formula (1) and the of formula 2 R 1, R 2, R 3, R 4, R 5, R 6 and R 7, independently of each other, a plurality of R 1 together with each other or a plurality of R 2 Or, when a plurality of R 3 or a plurality of R 4 or a plurality of R 5 or a plurality of R 6 or R 7 are bonded to each other to form a ring, benzene, naphthyl, benzofuran, benzothiophene , A compound characterized in that it forms an indole or indene ring
  9. 제1항에 있어서, 상기 화학식 1로 나타내는 화합물이 하기 화합물 P-1 내지 P-128 중 어느 하나인 것을 특징으로 하는 화합물The compound according to claim 1, wherein the compound represented by Formula 1 is any one of the following compounds P-1 to P-128
    Figure PCTKR2020009674-appb-I000125
    Figure PCTKR2020009674-appb-I000125
    Figure PCTKR2020009674-appb-I000126
    Figure PCTKR2020009674-appb-I000126
    Figure PCTKR2020009674-appb-I000127
    Figure PCTKR2020009674-appb-I000127
    Figure PCTKR2020009674-appb-I000128
    Figure PCTKR2020009674-appb-I000128
    Figure PCTKR2020009674-appb-I000129
    Figure PCTKR2020009674-appb-I000129
    Figure PCTKR2020009674-appb-I000130
    Figure PCTKR2020009674-appb-I000130
    Figure PCTKR2020009674-appb-I000131
    Figure PCTKR2020009674-appb-I000131
    Figure PCTKR2020009674-appb-I000132
    Figure PCTKR2020009674-appb-I000132
    Figure PCTKR2020009674-appb-I000133
    Figure PCTKR2020009674-appb-I000133
    Figure PCTKR2020009674-appb-I000134
    Figure PCTKR2020009674-appb-I000134
    Figure PCTKR2020009674-appb-I000135
    Figure PCTKR2020009674-appb-I000135
    Figure PCTKR2020009674-appb-I000136
    Figure PCTKR2020009674-appb-I000136
    Figure PCTKR2020009674-appb-I000137
    Figure PCTKR2020009674-appb-I000137
    Figure PCTKR2020009674-appb-I000138
    Figure PCTKR2020009674-appb-I000138
    Figure PCTKR2020009674-appb-I000139
    Figure PCTKR2020009674-appb-I000139
    Figure PCTKR2020009674-appb-I000140
    Figure PCTKR2020009674-appb-I000140
    Figure PCTKR2020009674-appb-I000141
    Figure PCTKR2020009674-appb-I000141
    Figure PCTKR2020009674-appb-I000142
    Figure PCTKR2020009674-appb-I000142
    Figure PCTKR2020009674-appb-I000143
    Figure PCTKR2020009674-appb-I000143
    Figure PCTKR2020009674-appb-I000144
    Figure PCTKR2020009674-appb-I000144
    Figure PCTKR2020009674-appb-I000145
    Figure PCTKR2020009674-appb-I000145
    Figure PCTKR2020009674-appb-I000146
    Figure PCTKR2020009674-appb-I000146
    Figure PCTKR2020009674-appb-I000147
    Figure PCTKR2020009674-appb-I000147
    Figure PCTKR2020009674-appb-I000148
    Figure PCTKR2020009674-appb-I000148
    Figure PCTKR2020009674-appb-I000149
    Figure PCTKR2020009674-appb-I000149
    Figure PCTKR2020009674-appb-I000150
    Figure PCTKR2020009674-appb-I000150
    Figure PCTKR2020009674-appb-I000151
    Figure PCTKR2020009674-appb-I000151
    Figure PCTKR2020009674-appb-I000152
    Figure PCTKR2020009674-appb-I000152
    Figure PCTKR2020009674-appb-I000153
    Figure PCTKR2020009674-appb-I000153
    Figure PCTKR2020009674-appb-I000154
    Figure PCTKR2020009674-appb-I000154
    Figure PCTKR2020009674-appb-I000155
    Figure PCTKR2020009674-appb-I000155
    Figure PCTKR2020009674-appb-I000156
    Figure PCTKR2020009674-appb-I000156
  10. 양극, 음극 및 상기 양극과 음극 사이에 형성된 유기물층을 포함하는 유기전기소자에 있어서, 상기 유기물층은 제1항의 화학식 1로 표시되는 단독화합물 또는 2 이상의 화합물을 포함하는 것을 특징으로 하는 유기전기소자. An organic electric device comprising an anode, a cathode, and an organic material layer formed between the anode and the cathode, wherein the organic material layer comprises a single compound represented by Formula 1 of claim 1 or two or more compounds.
  11. 제10항에 있어서, 상기 유기물층은 정공주입층, 정공수송층, 발광보조층, 발광층, 전자수송보조층, 전자수송층 및 전자주입층 중 적어도 하나를 포함하는 것을 특징으로 하는 유기전기소자The organic electric device of claim 10, wherein the organic material layer comprises at least one of a hole injection layer, a hole transport layer, a light emission auxiliary layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer.
  12. 제10항에 있어서, 상기 유기물층은 발광보조층인 것을 특징으로 하는 유기전기소자The organic electric device of claim 10, wherein the organic material layer is a light emission auxiliary layer.
  13. 제10항에 있어서, 상기 제 1전극과 제 2전극의 일면 중 상기 유기물층과 반대되는 적어도 일면에 형성되는 광효율 개선층을 더 포함하는 유기전기소자The organic electric device of claim 10, further comprising a light efficiency improvement layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer.
  14. 제10항에 있어서, 상기 유기물층은 상기 양극 상에 순차적으로 형성된 정공수송층, 발광층 및 전자수송층을 포함하는 스택을 둘 이상 포함하는 것을 특징으로 하는 유기전기소자The organic electric device of claim 10, wherein the organic material layer comprises at least two stacks including a hole transport layer, a light emitting layer, and an electron transport layer sequentially formed on the anode.
  15. 제10항에 있어서, 상기 유기물층은 상기 둘 이상의 스택사이에 형성된 전하생성층을 더 포함하는 것을 특징으로 하는 유기전기소자The organic electric device of claim 10, wherein the organic material layer further comprises a charge generation layer formed between the two or more stacks.
  16. 제10항의 유기전기소자를 포함하는 디스플레이장치; 및 상기 디스플레이장치를 구동하는 제어부;를 포함하는 전자장치A display device including the organic electric device of claim 10; And a control unit for driving the display device.
  17. 제15항에 있어서, 상기 유기전기소자는 유기전기발광소자(OLED), 유기태양전지, 유기감광체(OPC), 유기트랜지스터(유기 TFT), 및 단색 또는 백색 조명용 소자 중 적어도 하나인 것을 특징으로 하는 전자장치The method of claim 15, wherein the organic electric device is at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a single or white lighting device. Electronic device
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