WO2017188676A1 - Compound for organic electronic element, organic electronic element using same, and electronic device thereof - Google Patents

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

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WO2017188676A1
WO2017188676A1 PCT/KR2017/004320 KR2017004320W WO2017188676A1 WO 2017188676 A1 WO2017188676 A1 WO 2017188676A1 KR 2017004320 W KR2017004320 W KR 2017004320W WO 2017188676 A1 WO2017188676 A1 WO 2017188676A1
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group
compound
sub
formula
synthesis
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PCT/KR2017/004320
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French (fr)
Korean (ko)
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박정환
김원삼
문성윤
이윤석
한승훈
최승원
이정욱
김슬기
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덕산네오룩스 주식회사
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Priority claimed from KR1020170050859A external-priority patent/KR101796974B1/en
Application filed by 덕산네오룩스 주식회사 filed Critical 덕산네오룩스 주식회사
Priority to EP17789860.8A priority Critical patent/EP3326998B1/en
Priority to JP2018505670A priority patent/JP6469310B2/en
Priority to CN201780002876.1A priority patent/CN107922311B/en
Publication of WO2017188676A1 publication Critical patent/WO2017188676A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers

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.
  • organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material.
  • An organic electric element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween.
  • the organic layer is often made of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
  • the material used as the organic material layer in the organic electric element may be classified into a light emitting material and a charge transport material such as a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function.
  • Patent Documents 1 to 4 report the performance according to hetero type and arrangement, substituent type, fused position, etc. with respect to the 5-cyclic ring compound in the polycyclic ring compound.
  • Patent Document 1 US Patent 5843607
  • Patent Document 2 Japanese Patent Laid-Open No. 1999-162650
  • Patent Document 3 Korean Laid-Open Patent 2008-0085000
  • Patent Document 4 US Patent Publication 2010-0187977
  • Patent Document 5 Korean Laid-Open Patent 2011-0018340
  • Patent Document 6 Korean Laid-Open Patent 2009-0057711
  • Patent Literature 1 and Patent Literature 2 used indolocarbazole cores in which the heteroatoms in the 5-membered ring compound consist only of nitrogen (N), and report an example using an aryl group substituted or unsubstituted with N of indolocarbazole. have.
  • N nitrogen
  • Patent Literature 1 and Patent Literature 2 used indolocarbazole cores in which the heteroatoms in the 5-membered ring compound consist only of nitrogen (N), and report an example using an aryl group substituted or unsubstituted with N of indolocarbazole. have.
  • N nitrogen
  • PTL 3 and PTL 4 include pyridine, pyrimidine, triazine, etc., each containing an aryl group and N in an indolocarbazole for core having N heteroatoms in the same 5-ring ring compound as Patent Documents 1 and 2; Although substituted compounds are described, only examples of use for phosphorescent green host materials are described, and no performance is described for other heterocyclic compounds substituted in the indolocarbazole core.
  • Patent Document 5 describes nitrogen (N), oxygen (O), sulfur (S), carbon, etc. as a heteroatom in the 5-ring cyclic compound, but in the measurement data, only the examples using the same isotype heteroatoms are present. Thus, the performance characteristics of the 5-membered ring compound containing heteroatoms could not be confirmed.
  • the LUIMO and HOMO levels of the host material have a great influence on the efficiency and lifespan of the organic EL device, which can efficiently control electron and hole injection in the emission layer. This is because it is possible to prevent a decrease in efficiency and a decrease in life due to charge balance control, dopant quenching, and light emission at the hole transport layer interface in the light emitting layer.
  • the identification of energy transfer in the light emitting layer for the thermally activated delayed fluorescent (TADF) and exciplex can be easily identified by the PL lifetime (TRTP) method.
  • the time resolved transient PL (TRTP) method is a method of observing a decay time of a spectrum after a pulsed light source is irradiated to a host thin film. It is a measuring method.
  • TRTP measurement is a measurement method that can distinguish between fluorescence and phosphorescence, and energy transfer method, exciplex energy transfer method, and TADF energy transfer method within a mixed host material.
  • the present invention provides a compound incorporating Sub having excellent electron properties as a method for lowering power consumption, and at the same time, a compound capable of improving low driving voltage, high luminous efficiency, color purity, and lifetime of the device by using such a compound. It is an object of the present invention to provide an electronic device using the organic electric element.
  • the present invention provides a compound represented by the following general formula (1).
  • the present invention provides an organic electronic device using the compound represented by the formula (1) and an electronic device thereof.
  • electron transfer ability and thermal stability are improved by using a specific compound having an aromatic ring added to an existing core and introducing a sub substituent having strong ET properties as a material of an organic electric device.
  • the electron injection from the ETL facilitates the LUMO energy level, which is easy to achieve charge balance in the luminescence, thereby improving the luminous efficiency, heat resistance, lifespan, etc. of the organic electronic device, and lowering the driving voltage.
  • FIG. 1 is an exemplary view of an organic electroluminescent device according to the present invention.
  • halo or halogen as used herein is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I) unless otherwise indicated.
  • alkyl or “alkyl group” has a single bond of 1 to 60 carbon atoms, unless otherwise indicated, and is a straight chain alkyl group, branched chain alkyl group, cycloalkyl (alicyclic) group, alkyl-substituted cyclo Radicals of saturated aliphatic functional groups, including alkyl groups, cycloalkyl-substituted alkyl groups.
  • heteroalkyl group means that at least one of the carbon atoms constituting the alkyl group has been replaced with a heteroatom.
  • alkenyl group As used herein, the terms “alkenyl group”, “alkenyl group” or “alkynyl group” have a double or triple bond of 2 to 60 carbon atoms, respectively, unless otherwise stated, and include straight or branched chain groups. It is not limited to this.
  • cycloalkyl refers to alkyl forming a ring having 3 to 60 carbon atoms, without being limited thereto.
  • alkoxyl group means an alkyl group to which an oxygen radical is attached, and unless otherwise specified, has a carbon number of 1 to 60, and is limited herein. It is not.
  • alkenoxyl group means an alkenyl group to which an oxygen radical is attached, and unless otherwise stated, it is 2 to 60 It has carbon number of, It is not limited to this.
  • aryloxyl group or “aryloxy group” means an aryl group to which an oxygen radical is attached, and unless otherwise specified, has a carbon number of 6 to 60, but is not limited thereto.
  • aryl group and “arylene group” have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto.
  • an aryl group or an arylene group means an aromatic of a single ring or multiple rings, and includes an aromatic ring formed by neighboring substituents participating in a bond or a reaction.
  • the aryl group may be a phenyl group, a biphenyl group, a fluorene group, 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
  • the radical substituted with an aryl group has the carbon number described herein.
  • an arylalkoxy group means an alkoxy group substituted with an aryl group
  • an alkoxylcarbonyl group means a carbonyl group substituted with an alkoxyl group
  • an arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group.
  • the arylcarbonyl group is a carbonyl group substituted with an aryl group.
  • heteroalkyl means an alkyl including one or more heteroatoms unless otherwise indicated.
  • heteroaryl group or “heteroarylene group” means an aryl group or arylene group having 2 to 60 carbon atoms, each containing one or more heteroatoms, unless otherwise specified. It may include at least one of a single ring and multiple rings, and may be formed by combining adjacent functional groups.
  • heterocyclic group includes one or more heteroatoms, unless otherwise indicated, and has from 2 to 60 carbon atoms, and includes at least one of single and multiple rings, heteroaliphatic rings and hetero Aromatic rings. Adjacent functional groups may be formed in combination.
  • heteroatom refers to N, O, S, P or Si unless otherwise stated.
  • Heterocyclic groups may also include rings comprising SO 2 instead of carbon forming the ring.
  • a “heterocyclic group” includes the following compounds.
  • aliphatic as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms
  • aliphatic ring means 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. Saturated or unsaturated rings.
  • heterocompounds or heteroradicals other than the aforementioned heterocompounds include, but are not limited to, one or more heteroatoms.
  • carbonyl used in the present invention is represented by -COR ', wherein R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 3 to 30 carbon atoms. Cycloalkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.
  • ether as used herein is represented by -RO-R ', wherein R or R' are each independently of each other hydrogen, an alkyl group having 1 to 20 carbon atoms, It is an aryl group, a C3-C30 cycloalkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, or a combination thereof.
  • substituted in the term “substituted or unsubstituted” as used herein refers to deuterium, halogen, amino, nitrile, nitro, C 1 -C 20 alkyl, C 1 -C 20 alkoxyl group, C 1 ⁇ C 20 alkylamine group, C 1 ⁇ C 20 alkylthiophene group, C 6 ⁇ C 20 arylthiophene group, C 2 ⁇ C 20 alkenyl group, C 2 ⁇ C 20 alkynyl, C 3 ⁇ C 20 cycloalkyl group, 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 Group, germanium group, and C 2 ⁇ C 20 It is meant to be substituted with one or more substituents selected from the group consisting of,
  • the substituent R 1 when a is an integer of 0, the substituent R 1 is not present, that is, when a is 0, it means that all of the carbons forming the benzene ring are bonded to hydrogen. Omit formulas and compounds.
  • a when a is an integer of 1, one substituent R 1 is bonded to any one of carbons forming a benzene ring, and when a is an integer of 2 or 3, for example, a is 4 to 6
  • R 1 may be the same or different from each other.
  • the terms "ortho”, “meta”, “para” used in the present invention means the substitution position of all substituents
  • the ortho position is a substituent
  • the position of represents the neighboring compound, for example, in the case of benzene means 1, 2 digits
  • the meta (meta) position represents the next substitution position of the immediate substitution position and benzene is 1, 3 digits as an example
  • the para position means 1 or 4 digits when benzene is used as the next substitution position of the meta position.
  • Ortho- and meta- positions are non-linear types and para- positions are substituted by linear types. have.
  • the present invention provides a compound represented by the following general formula (1).
  • A is an aryl group of C 10 ,
  • B is selected from the group consisting of the following formulas B-1 to B-16,
  • W 1 and W 2 are each independently a single bond, S or O,
  • V is N or C
  • a is an integer from 0 to 6
  • b and c are integers from 0 to 4
  • d is an integer from 0 to 11
  • R 1 , R 2 , R 3 and R 4 are the same as or different from each other, and independently from each other hydrogen; heavy hydrogen; halogen; Cyano; Nitro group; C 6 ⁇ C 60 Aryl group; Fluorenyl group; C 2 ⁇ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C 3 ⁇ C 60 of aliphatic rings and C 6 ⁇ C 60; C 1 ⁇ C 50 Alkyl group; C 2 ⁇ C 20 Alkenyl group; Alkynyl groups of C 2 to C 20 ; C 1 -C 30 alkoxyl group; C 6 -C 30 aryloxy group; And -L'-N (R a ) (R b );
  • R 1 to R 4 is an aryl group, preferably an aryl group of C 6 aryl group, more preferably C 6 -C 18 -C 30 a.
  • R 1 to R 4 are heterocyclic groups, preferably C 2 ⁇ C 40 heterocyclic group, more preferably C 2 ⁇ C 30 heterocyclic group, more preferably C 2 ⁇ C 20 heterocyclic group Qi.
  • a, b, and c are two or more, each of them may be the same as or different from each other, and a plurality of R 1 or a plurality of R 2 or a plurality of R 3 may be bonded to each other to form a ring.
  • L ' is a single bond; C 6 ⁇ C 60 arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C 3 ⁇ C 60 of aliphatic rings and C 6 ⁇ C 60; And C 2 ⁇ C 60 Heterocyclic group; It is selected from the group consisting of, R a and R b are independently of each other C 6 ⁇ C 60 An aryl group; Fluorenyl group; Fused ring group of an aromatic ring of C 3 ⁇ C 60 of aliphatic rings and C 6 ⁇ C 60; And a C 2 ⁇ C 60 heterocyclic group including at least one heteroatom of O, N, S, Si, and P, and
  • L 1 is each independently a single bond; C 6 ⁇ C 60 arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C 3 ⁇ C 60 of aliphatic rings and C 6 ⁇ C 60; And C 2 ⁇ C 60 It is selected from the group consisting of; heterocyclic group,
  • the aryl group, fluorenyl group, arylene group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkoxy group, aryloxy group are each deuterium; halogen; A silane group unsubstituted or substituted with a C 1 -C 20 alkyl group or a C 6 -C 20 aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; -L'-N (R a ) (R b ); Import alkylthio of C 1 -C 20; An alkoxyl group of C 1 -C 20 ; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -
  • the formula (1) includes a compound, characterized in that represented by any one of the following formula (2) to (4).
  • the formula (1) includes a compound, characterized in that represented by any one of the following formula (5) to formula (7).
  • the formula structure Ar 1 including the pyrazine of formula (1) provides a compound represented by the following formula C-1 to formula C-20.
  • R 4 is the same as defined above, and d is any one of integers from 0 to 11.
  • the present invention includes a compound in which R 4 in Formula (1) is represented by any one of the following Formulas R-1 to R-10.
  • Q 1 to Q 15 are independently of each other CR g or N,
  • W 1 is S, O or NR h ,
  • W 2 to W 4 are S, O, NR h or CR i R j
  • R e is hydrogen; heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C 1 -C 20 alkyl group or a C 6 -C 20 aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C 1 -C 20; An alkoxyl group of C 1 -C 20 ; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A cycloalkyl group of C 3 -C 20 ; C 7 -C 20 arylalkyl group; And C 8
  • R f and R g are each independently hydrogen; heavy hydrogen; C 6 -C 20 aryl group; Fluorenyl group; A fused ring group of an aliphatic ring of C 3 ⁇ C 20 and an aromatic ring of C 6 ⁇ C 20 ; And a C 2 to C 20 heterocyclic group including at least one heteroatom of O, N, S, Si, and P; C 1 ⁇ C 20 Alkyl group; C 2 ⁇ C 20 Alkenyl group; Alkynyl groups of C 2 to C 20 ; C 1 ⁇ C 30 Alkoxyl group; It is selected from the group consisting of,
  • R h R i and R j are each independently of the other C 6 -C 20 aryl group; C 2 -C 20 heterocyclic group including at least one heteroatom of O, N, S, Si, and P; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkoxy group of C 1 -C 20 ; And a fluorenyl group; R i and R j may be bonded to each other to form a spiro compound together with C to which they are bonded,
  • q is an integer from 0 to 5 independently of each other
  • r is, independently from each other, an integer from 0 to 4,
  • s is an integer from 0 to 3 independently of each other,
  • R e to R j is an aryl group, preferably a C 6 -C 30 aryl group, more preferably a C 6 -C 18 aryl group
  • R e to R j is a heterocyclic group, preferably Is a C 2 ⁇ C 40 heterocyclic group, more preferably a C 2 ⁇ C 30 heterocyclic group, more preferably a C 2 ⁇ C 20 heterocyclic group.
  • the compound represented by the formula (1) includes the following compound.
  • the organic electric device 100 includes a first electrode 120, a second electrode 180, and a first electrode 120 and a second electrode formed on a substrate 110.
  • the organic material layer containing the compound represented by General formula (1) between 180 is provided.
  • the first electrode 120 may be an anode (anode)
  • the second electrode 180 may be a cathode (cathode)
  • the first electrode may be a cathode and the second electrode may be an anode.
  • the organic layer may include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, and an electron injection layer 170 on the first electrode 120 in sequence. At this time, the remaining layers except for the light emitting layer 150 may not be formed.
  • the hole blocking layer, the electron blocking layer, the light emitting auxiliary layer 151, the electron transport auxiliary layer, and the buffer layer 141 may be further included, and the electron transport layer 160 may serve as the hole blocking layer.
  • the organic electronic device according to the present invention may further include a protective layer formed on one surface of the first electrode and the second electrode opposite to the organic material layer.
  • the organic electroluminescent device may be manufactured using a PVD method.
  • a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode, and the hole injection layer 130, the hole transport layer 140, the light emitting layer 150, the electron transport layer 160 are disposed thereon.
  • the organic material layer including the electron injection layer 170 it can be prepared by depositing a material that can be used as a cathode thereon.
  • the light emitting auxiliary layer 151 may be further formed between the hole transport layer 140 and the light emitting layer 150, and an electron transport auxiliary layer may be further formed between the light emitting layer 150 and the electron transport layer 160.
  • the present invention provides an optical efficiency improvement layer formed on at least one side of the one side of the first electrode opposite to the organic material layer or one side of the second electrode opposite to the organic material layer in the organic electric device. It provides an organic electric element further comprising.
  • 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, the organic material layer according to the present invention can be formed in various ways Therefore, the scope of the present invention is not limited by the formation method.
  • the compound according to Chemical Formula (1) is included in the organic material layer, and the compound is contained in at least one layer of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, and a light emitting layer as the organic material layer, and the compound is one kind.
  • Single compounds or two or more compounds may be included as components of the mixture.
  • the present invention provides an organic electric device in which the light emitting layer is a phosphorescent light emitting layer in the organic material layer.
  • the compound of the present invention may be used as the light emitting layer 150, the hole transport layer 140 and / or the light emitting auxiliary layer 151 material, preferably as a host material of the light emitting layer 150. More preferably, it can be used as a phosphorescent red host material.
  • the organic electric element according to an embodiment of the present invention may be a top emission type, a bottom emission type or a double-sided emission type according to the material used.
  • WOLED White Organic Light Emitting Device
  • Various structures for white organic light emitting devices mainly used as backlight devices have been proposed and patented. Representatively, a side-by-side method in which R (Red), G (Green), and B (Blue) light emitting parts are mutually planarized, and a stacking method in which R, G, and B light emitting layers are stacked up and down. And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light therefrom. May also be applied to these WOLEDs.
  • CCM color conversion material
  • the present invention is a display device comprising the above-mentioned organic electric element; And a controller for driving the display device.
  • the organic electronic device provides an electronic device according to the present invention, wherein the organic electroluminescent device is at least one of an organic electroluminescent device, an organic solar cell, an organic photoconductor, an organic transistor, and a monochromatic or white illumination device.
  • the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.
  • Compounds (final products) according to the present invention is prepared by reacting in the following manner, but is not limited thereto.
  • R 4 ′ the same definition as R 4 above, meaning a substituent that is the same as or different from R 4
  • Sub 1 of Scheme 1 may be synthesized by the reaction paths of Scheme 2 and Scheme 3, but is not limited thereto.
  • Hal 1 , Hal 3 Cl, Br
  • SI-6 (30g, 85.90mmol), Pd (OAc) 2 (1.93g, 8.59mmol), 3-nitropyridine (1.07g, 8.59mmol), C 6 F 6 (128.9ml), DMI (85.9) obtained in the above synthesis ml) and tert- butyl peroxybenzoate (33.37 g, 171.81 mmol) were obtained using 22.67 g (yield: 76%) of the product using the synthesis method of MI-4.
  • Sub 1-III-1 (30 g, 80.33 mmol) obtained in the above synthesis was dissolved in toluene (843 ml) in a round bottom flask, followed by 2,3-dichloroquinoxaline (15.99 g, 80.33 mmol), Pd 2 (dba) 3 (1.1 g, 1.2 mmol), P ( t- Bu) 3 (0.81 g, 4.02 mmol) and NaO t- Bu (11.58 g, 120.49 mmol) were added and stirred at 100 ° C.
  • Triphenylphosphine (57.18g, 218.01mmol) and o -dichlorobenzene (145ml) were added to Sub 1-II-2 (47g, 72.67mmol) obtained in the above synthesis, and 28.15g ( Yield: 63%).
  • Sub 1-III-2 (28 g, 45.55 mmol) obtained in the above synthesis was prepared with 2,3-dichlorobenzo [f] quinoxaline (12.48 g, 50.10 mmol), Pd 2 (dba) 3 (1.25 g, 1.37 mmol), and P ( t- Bu) 3 (0.74 g, 3.64 mmol), NaO t -Bu (13.13 g, 136.64 mmol), toluene (228 ml) were added and the product 15.07 g (yield: 40%) was obtained using the Sub 1-1 synthesis method. Got.
  • Sub 1-III-9 (28 g, 66.11 mmol) obtained in the above synthesis was subjected to 1,4-dibromobenzene (17.16 g, 72.72 mmol), Pd 2 (dba) 3 (0.91 g, 0.99 mmol), P ( t -Bu) 3 (0.67 g, 3.31 mmol), NaO t -Bu (9.53 g, 99.17 mmol) and toluene (694 ml) were added to give 27.16 g (yield: 71%) of the product using the Sub 1-1 synthesis method.
  • Sub 1-I-3 (51.8g, 92.42mmol) obtained in the above synthesis was subjected to 1-bromo-2-nitrobenzene (18.67g, 92.42mmol), Pd (PPh 3 ) 4 (3.2g, 2.77mmol), K 2 CO 3 (38.32 g, 277.27 mmol), THF (407 ml), water (203 ml) were added and 43.13 g (yield: 84%) of product was obtained using the Sub 1-II-1 synthesis method.
  • Triphenylphosphine (60.9g, 232.19mmol) and o- dichlorobenzene (155ml) were added to Sub 1-II-3 (43g, 77.4mmol) obtained in the synthesis, and the product 31.61g ( Yield: 78%).
  • MI-4 (93g, 226.64mmol) obtained in the above synthesis was prepared with 1-bromo-2-nitrobenzene (45.78g, 226.64mmol), Pd (PPh 3 ) 4 (7.86g, 6.80mmol), K 2 CO 3 (93.97g , 679.92 mmol), THF (997 ml), water (498 ml) were added and 76.27 g (yield: 83%) of product was obtained using the Sub 1-II-1 synthesis method.
  • Sub 1-I-5 (17g, 43.12mmol) obtained in the above synthesis was subjected to 1-bromo-2-nitrobenzene (8.71g, 43.12mmol), Pd (PPh 3 ) 4 (1.49g, 1.29mmol), K 2 CO 3 (17.88 g, 129.35 mmol), THF (189 ml), water (95 ml) were added and 14.61 g (yield: 87%) of the product was obtained using the Sub 1-II-1 synthesis method.
  • Sub 1-I-6 (34g, 58.97mmol) obtained in the above synthesis was subjected to 1-bromo-2-nitrobenzene (11.91g, 58.97mmol), Pd (PPh 3 ) 4 (2.04g, 1.77mmol), K 2 CO 3 (24.45 g, 176.92 mmol), THF (259 ml), water (129 ml) were added and 27.64 g (yield: 82%) of product was obtained using the Sub 1-II-1 synthesis method.
  • Sub 1-I-7 (19.5 g, 47.52 mmol) obtained in the above synthesis was prepared with 1-bromo-2-nitrobenzene (9.6 g, 47.52 mmol), Pd (PPh 3 ) 4 (1.65 g, 1.43 mmol), and K 2 CO. 3 (19.70 g, 142.56 mmol), THF (209 ml), water (105 ml) were added and 16.38 g (yield: 85%) of product was obtained using the Sub 1-II-1 synthesis method.
  • Triphenylphosphine (31.05g, 118.38mmol) and o- dichlorobenzene (79ml) were added to Sub 1-II-7 (16g, 39.46mmol) obtained in the above synthesis, and the product was obtained using 12.08g ( Yield: 82%).
  • Sub 2 of Scheme 1 may be synthesized by the reaction path of the scheme, but is not limited thereto.
  • Compounds belonging to Sub 2 may be the following compounds, but are not limited thereto, and Table 2 shows Field Desorption-Mass Spectrometry (FD-MS) values of some compounds belonging to Sub 2.
  • FD-MS Field Desorption-Mass Spectrometry
  • An organic light emitting diode was manufactured according to a conventional method using the compound obtained through synthesis as a light emitting host material.
  • -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) film was vacuum deposited to form a hole injection layer having a thickness of 60 nm, and then 4,4-bis [ N -as a compound as a hole transport compound on the hole injection layer.
  • NPD (1-naphthyl) -N -phenylamino] biphenyl
  • BAlq (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum
  • BAlq the electron transport layer Bis (10-hydroxybenzo [h] quinolinato) beryllium
  • BeBq 2 the electron transport layer Bis (10-hydroxybenzo [h] quinolinato) beryllium
  • An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compound of the present invention shown in Table 4 was used instead of the compound 1-1 of the present invention as a host material of the emission layer.
  • An organic electroluminescent device was manufactured in the same manner as in Example 1, except that one of Comparative Compounds 1 to 4 was used instead of Compound 1-1 as a host material of the emission layer.
  • Examples 1 to 44 and Comparative Examples 1 to 4 prepared as described above were subjected to a forward bias DC voltage to organic electroluminescent devices to measure electroluminescence (EL) characteristics with a PR-650 of photoresearch.
  • EL electroluminescence
  • the T95 lifetime was measured using a life-time measuring instrument manufactured by McScience Inc. at 2500 cd / m 2 reference luminance.
  • Table 4 shows the results of device fabrication and evaluation.
  • the conjugation length becomes longer, which makes the charge transfer to the dopant easier. It can be confirmed that when the benzene ring is formed at a specific position of the core, the PL wavelength is shifted more red shift.

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Abstract

Provided are: an organic electronic element using a mixture of a compound of the present invention as a phosphorescent host material such that high light-emitting efficiency and low driving voltage of the organic electronic element can be achieved and the lifespan of the element can be greatly improved; and an electronic device thereof.

Description

유기전기소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치 Compound 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 빛 에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기전기소자는 통상 양극과 음극 및 이 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물 층은 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, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic electric element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. The organic layer is often made of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of 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.The material used as the organic material layer in the organic electric element may be classified into a light emitting material and a charge transport material such as a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function.
헤테로원자를 포함하고 있는 다환 고리화합물의 경우 물질 구조에 따른 특성의 차이가 매우 커서 유기전기소자의 재료로 다양한 층에 적용되고 있다. 특히 환의 개수 및 fused 위치, 헤테로원자의 종류와 배열에 따라 밴드 갭(HOMO, LUMO), 전기적 특성, 화학적 특성, 물성 등이 상이한 특징을 갖고 있어, 이를 이용한 다양한 유기전기소자의 층에 대한 적용 개발이 진행되어 왔다.In the case of polycyclic cyclic compounds containing heteroatoms, the difference in characteristics depending on the material structure is very large and applied to various layers as a material of an organic electric device. In particular, band gaps (HOMO, LUMO), electrical properties, chemical properties, and physical properties are different depending on the number of rings, the fused position, and the type and arrangement of heteroatoms. This has been going on.
그 대표적인 예로 하기 특허문헌 1 내지 특허문헌4에서는 다환 고리화합물 중 5환 고리 화합물에 대해 헤테로 종류 및 배열, 치환기 종류, fused 위치 등에 따른 성능을 보고하고 있다. As a representative example, the following Patent Documents 1 to 4 report the performance according to hetero type and arrangement, substituent type, fused position, etc. with respect to the 5-cyclic ring compound in the polycyclic ring compound.
[특허문헌 1] : 미국 등록특허 5843607[Patent Document 1]: US Patent 5843607
[특허문헌 2] : 일본 공개특허 1999-162650[Patent Document 2]: Japanese Patent Laid-Open No. 1999-162650
[특허문헌 3] : 한국 공개특허 2008-0085000[Patent Document 3]: Korean Laid-Open Patent 2008-0085000
[특허문헌 4] : 미국 공개특허 2010-0187977[Patent Document 4]: US Patent Publication 2010-0187977
[특허문헌 5] : 한국 공개특허 2011-0018340[Patent Document 5]: Korean Laid-Open Patent 2011-0018340
[특허문헌 6] : 한국 공개특허 2009-0057711 [Patent Document 6]: Korean Laid-Open Patent 2009-0057711
특허문헌 1 및 특허문헌 2는 5환 고리 화합물 내 헤테로원자가 질소(N)로만 구성된 인돌로카바졸 코어를 사용하였으며, 인돌로카바졸의 N에 치환 또는 비치환된 아릴기를 사용한 실시예를 보고 하고 있다. 하지만 상기 선행발명 1의 경우 치환기로 알킬기, 아미노기, 알콕시기 등이 치환 또는 비치환된 단순 아릴기만 존재하여 다환 고리화합물의 치환기 효과에 대해 서 입증하기에는 매우 부족하였으며, 정공 수송 재료로서의 사용만 기재되어 있고, 인광 호스트 재료로서의 사용은 기재되어 있지 않았다. Patent Literature 1 and Patent Literature 2 used indolocarbazole cores in which the heteroatoms in the 5-membered ring compound consist only of nitrogen (N), and report an example using an aryl group substituted or unsubstituted with N of indolocarbazole. have. However, in the case of the preceding invention 1, there was only a simple aryl group in which an alkyl group, an amino group, an alkoxy group, etc. were substituted or unsubstituted as a substituent, and thus it was very insufficient to prove the substituent effect of the polycyclic cyclic compound. And use as a phosphorescent host material is not described.
특허문헌 3 및 특허문헌 4는 상기 특허문헌 1 및 특허문헌 2와 동일한 5환 고리 화합물 내 헤테로원자가 N인 인돌로카바졸 포 코어에 각각 아릴기와 N을 함하는 피리딘, 피리미딘, 트리아진 등이 치환된 화합물을 기재하고 있지만, 인광 그린 호스트 물질에 대한 사용 예만 기재되어 있으며, 인돌로카바졸 코어에 치환되는 다른 헤테로고리 화합물에 대한 성능에 대해서는 기재되어 있지 않았다. PTL 3 and PTL 4 include pyridine, pyrimidine, triazine, etc., each containing an aryl group and N in an indolocarbazole for core having N heteroatoms in the same 5-ring ring compound as Patent Documents 1 and 2; Although substituted compounds are described, only examples of use for phosphorescent green host materials are described, and no performance is described for other heterocyclic compounds substituted in the indolocarbazole core.
특허문헌 5는 5환 고리화합물 내 헤테로원자를 질소(N), 산소(O), 황(S), 탄소 등이 기재되어 있으나, 성능 측정 데이터에는 모두 서로 동일한 동형 헤테로원자를 사용한 실시예만 존재하여, 이형 헤테로원자를 포함하는 5환 고리 화합물의 성능적 특성을 확인할 수 없었다. Patent Document 5 describes nitrogen (N), oxygen (O), sulfur (S), carbon, etc. as a heteroatom in the 5-ring cyclic compound, but in the measurement data, only the examples using the same isotype heteroatoms are present. Thus, the performance characteristics of the 5-membered ring compound containing heteroatoms could not be confirmed.
따라서 상기 특허문헌에서는 동형 헤테로원자를 포함하는 5환 고리화합물이 갖는 낮은 전하 캐리어 이동도 및 낮은 산화 안정성에 대한 해결방안이 기재되어있지 않았다. Therefore, the above patent document does not describe a solution for low charge carrier mobility and low oxidative stability of the 5-ring cyclic compound including isotype heteroatoms.
5환 고리 화합물 분자가 일반적으로 적층될 때, 인접한 π-전자가 많아짐에 따라 강한 전기적 상호작용을 갖게 되는데, 이는 전하 캐리어 이동도와 밀접한 연관이 있으며, 특히 N-N type인 동형의 5환 고리화합물은 분자가 적층될 때, 분자간의 배열순서가 edge-to-face 형태를 갖게 되는 반면, 헤테로원자가 서로 다른 이형의 5환 고리화합물은 분자의 패킹구조가 역방향으로 마주보는 파이-적층구조(antiparallelcofacial π-stacking structure)를 가져 분자간의 배열 순서가 face-to-face 형태를 갖게 된다. 이 적층구조의 원인인 비대칭으로 배치된 헤테로원자 N에 치환되는 치환기의 입체효과로 인하여 상대적으로 높은 캐리어 이동도 및 높은 산화안정성을 야기시킨다고 보고 되었다. (Org. Lett. 2008, 10, 1199) When five-membered cyclic compound molecules are generally stacked, they have strong electrical interactions with more adjacent π-electrons, which are closely related to charge carrier mobility, especially in the NN-type homocyclic cyclic compound. When the molecules are stacked, the order of intermolecular molecules has an edge-to-face shape, whereas heterocyclic heterocyclic compounds having different heteroatoms have a pi-stacking structure in which molecular packing structures face each other in reverse directions. structure) has the face-to-face arrangement order between molecules. Asymmetrically arranged heteroatoms N which are responsible for this lamination structure It has been reported that the steric effect of substituted substituents causes relatively high carrier mobility and high oxidative stability. ( Org . Lett . 2008, 10 , 1199)
특허문헌 6에서는 7환 이상의 다양한 다환 고리 화합물에 대하여 형광 호스트 물질로 사용한 예가 보고 되었다. In patent document 6, the example used as a fluorescent host material with respect to various polycyclic ring compounds of 7 or more rings was reported.
상기 내용과 같이 다환 고리화합물에 대한 fused 위치 및 고리 개수, 헤테로원자의 배열, 종류에 따른 특성 변화에 대해서는 아직도 개발이 충분히 이루어지지 않은 상태이다. As described above, development of the fused position, the number of rings, the arrangement of heteroatoms, and the characteristics of the polycyclic cyclic compound have not been sufficiently developed.
특히 인광 발광 도펀트 재료를 이용하는 인광형 유기전기소자에 있어서 호스트 물질의 LUIMO, 및 HOMO level 은 유기전기소자의 효울 및 수명에 매우 큰 영향을 주는 요인으로서 이는 발광층 내 전자 및 정공 주입을 효율적으로 조절 가능하냐에 따라 발광층 내 charge balance 조절, 도펀트 퀜칭(quenching) 및 정공 수송층 계면에서의 발광으로 인한 효율 저하 및 수명 저하를 방지할 수 있기 때문이다.In particular, in the phosphorescent organic EL device using the phosphorescent dopant material, the LUIMO and HOMO levels of the host material have a great influence on the efficiency and lifespan of the organic EL device, which can efficiently control electron and hole injection in the emission layer. This is because it is possible to prevent a decrease in efficiency and a decrease in life due to charge balance control, dopant quenching, and light emission at the hole transport layer interface in the light emitting layer.
형광 및 인광 발광용 호스트 물질의 경우 최근들어 TADF(Thermal activatied delayed fluorescent) , Exciplex 등을 이용한 유기전기소자의 효율 증가 및 수명 증가 등을 연구하고 있으며, 특히 호스트 물질에서 도펀트 물질로의 에너지 전달 방법 규명에 많은 연구가 진행되고 있다. In the case of fluorescent and phosphorescent light emitting materials, researches on increasing efficiency and lifespan of organic electric devices using thermally activated delayed fluorescent (TADF) and Exciplex have been recently conducted. Especially, the method of transferring energy from the host material to the dopant material has been investigated. There is a lot of research going on.
TADF (Thermal activatied delayed fluorescent), exciplex에 대한 발광층 내 에너지 전달 규명은 여러가지 방법들이 있지만, PL lifetime (TRTP) 측정법으로 손쉽게 확인할 수 있다. The identification of energy transfer in the light emitting layer for the thermally activated delayed fluorescent (TADF) and exciplex can be easily identified by the PL lifetime (TRTP) method.
TRTP (Time resolved transient PL) 측정법은 펄스 광원을 호스트 박막에 조사한 후, 시간에 따른 스펙트럼의 감소(Decay time)를 관찰하는 방식으로서 에너지 전달 및 발광 지연시간 관찰을 통해 에너지 전달 방식을 규명할 수 있는 측정방법이다. 상기 TRTP 측정은 형광과 인광의 구분 및 mixed 호스트 물질 내에서의 에너지 전달방식, exciplex 에너지 전달방식, TADF 에너지 전달 방식 등을 구분해 줄 수 있는 측정법이다. The time resolved transient PL (TRTP) method is a method of observing a decay time of a spectrum after a pulsed light source is irradiated to a host thin film. It is a measuring method. The TRTP measurement is a measurement method that can distinguish between fluorescence and phosphorescence, and energy transfer method, exciplex energy transfer method, and TADF energy transfer method within a mixed host material.
이처럼 호스트 물질로부터 도펀트 물질로 에너지가 전달되는 방식에 따라 효율 및 수명에 영향을 주는 다양한 요인들이 존재하며, 물질에 따라 에너지 전달 방식이 상이하여, 아직까지 안정되고 효율적인 유기전기소자용 호스트 재료의 개발이 충분히 이루어지지 않은 상태이다. 따라서 새로운 재료의 개발이 계속 요구되고 있으며, 특히 발광층의 호스트 물질에 대한 개발이 절실히 요구되고 있다. As such, there are various factors that affect efficiency and lifespan depending on the way energy is transferred from the host material to the dopant material, and the energy transfer method differs depending on the material. This is not enough. Therefore, the development of new materials is continuously required, and in particular, the development of the host material of the light emitting layer is urgently required.
현재 OLED 소자의 경우 소비 전력을 낮추며, 색순도를 높이는 방향으로 개발되고 있다. 본 발명은 소비 전력을 낮추기 위한 방법으로 electron 특성이 우수한 Sub를 도입한 화합물을 제공함과 동시에, 이러한 화합물을 이용하여 소자의 낮은 구동전압, 높은 발광 효율, 색순도 및 수명을 향상시킬 수 있는 화합물, 이를 이용한 유기전기소자 그 전자장치를 제공하는 것을 목적으로 한다.OLED devices are currently being developed to lower power consumption and to increase color purity. The present invention provides a compound incorporating Sub having excellent electron properties as a method for lowering power consumption, and at the same time, a compound capable of improving low driving voltage, high luminous efficiency, color purity, and lifetime of the device by using such a compound. It is an object of the present invention to provide an electronic device using the organic electric element.
본 발명은 하기 화학식 (1)로 표시되는 화합물을 제공한다. The present invention provides a compound represented by the following general formula (1).
화학식 (1) Formula (1)
Figure PCTKR2017004320-appb-I000001
Figure PCTKR2017004320-appb-I000001
또한, 본 발명은 상기 화학식 (1)로 표시되는 화합물을 이용한 유기전기소자 및 그 전자장치를 제공한다.In addition, the present invention provides an organic electronic device using the compound represented by the formula (1) and an electronic device thereof.
본 발명에 따르면, 기존 코어에 방향족 고리를 추가Fused 하고 ET 특성이 강한 sub 치환기의 도입한 특정 화합물을 유기전기소자의 재료로 이용함으로써, 전자 수송 능력(electron transfer ability) 및 열적 안정성이 향상되고, ETL로부터 electron injection이 용이하게 되어 발광증 내 전하균형을 이루기에 용이한 LUMO 에너지 레벨을 가져 유기전기소자의 발광 효율, 내열성, 수명 등을 향상시킬 수 있고 구동 전압을 낮출 수 있다.According to the present invention, electron transfer ability and thermal stability are improved by using a specific compound having an aromatic ring added to an existing core and introducing a sub substituent having strong ET properties as a material of an organic electric device. The electron injection from the ETL facilitates the LUMO energy level, which is easy to achieve charge balance in the luminescence, thereby improving the luminous efficiency, heat resistance, lifespan, etc. of the organic electronic device, and lowering the driving voltage.
도 1은 본 발명에 따른 유기전기발광소자의 예시도이다. 1 is an exemplary view of an organic electroluminescent device according to the present invention.
100 : 유기전기소자 110 : 기판100: organic electric element 110: substrate
120 : 제 1전극(양극) 130 : 정공주입층120: first electrode (anode) 130: hole injection layer
140 : 정공수송층 141 : 버퍼층140: hole transport layer 141: buffer layer
150 : 발광층 151 : 발광보조층150 light emitting layer 151 light emitting auxiliary layer
160 : 전자수송층 170 : 전자주입층160: electron transport layer 170: electron injection layer
180 : 제 2전극(음극)180: second electrode (cathode)
도 2는 비교화합물 1 내지 4 및 본 발명 화합물 1-1의 PL 결과를 나타낸다.2 shows PL results of Comparative Compounds 1 to 4 and Compound 1-1 of the present invention.
도 3은 화합물 1-1의 1H NMR 결과를 나타낸다.3 shows the 1H NMR results of compound 1-1.
도 4는 화합물 1-1의 13C NMR 결과를 나타낸다.4 shows the 13C NMR results of compound 1-1.
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, with reference to the embodiment of the present invention will be described in detail. In describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the 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 구성요소와 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 component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are only to distinguish the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It should be understood that the 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 otherwise indicated, the meanings of the following terms are as follows:
본 명세서에서 사용된 용어 "할로" 또는 "할로겐"은 다른 설명이 없는 한 불소(F), 브롬(Br), 염소(Cl) 또는 요오드(I)이다.The term "halo" or "halogen" as used herein is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I) unless otherwise indicated.
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 indicated, and is a straight chain alkyl group, branched chain alkyl group, cycloalkyl (alicyclic) group, alkyl-substituted cyclo Radicals of saturated aliphatic functional groups, including alkyl groups, cycloalkyl-substituted alkyl groups.
본 발명에 사용된 용어 "할로알킬기" 또는 "할로겐알킬기"는 다른 설명이 없는 한 할로겐으로 치환된 알킬기를 의미한다. As used herein, the term "haloalkyl group" or "halogenalkyl group" means an alkyl group substituted with halogen unless otherwise specified.
본 발명에 사용된 용어 "헤테로알킬기"는 알킬기를 구성하는 탄소원자 중 하나 이상이 헤테로원자로 대체된 것을 의미한다.The term "heteroalkyl group" as used herein means that at least one of the carbon atoms constituting the alkyl group has been replaced with a heteroatom.
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.As used herein, the terms "alkenyl group", "alkenyl group" or "alkynyl group" have a double or triple bond of 2 to 60 carbon atoms, respectively, unless otherwise stated, and include straight or branched chain groups. It is 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 herein, unless otherwise stated, refers to alkyl forming a ring having 3 to 60 carbon atoms, without being 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.As used herein, the term "alkoxyl group", "alkoxy group", or "alkyloxy group" means an alkyl group to which an oxygen radical is attached, and unless otherwise specified, has a carbon number of 1 to 60, and is limited herein. It is not.
본 발명에 사용된 용어 "알켄옥실기", "알켄옥시기", "알켄일옥실기", 또는 "알켄일옥시기"는 산소 라디칼이 부착된 알켄일기를 의미하며, 다른 설명이 없는 한 2 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다.As used herein, the term "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" means an alkenyl group to which an oxygen radical is attached, and unless otherwise stated, it is 2 to 60 It has carbon number of, It is not limited to this.
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.As used herein, the term "aryloxyl group" or "aryloxy group" means an aryl group to which an oxygen radical is attached, and unless otherwise specified, has a carbon number of 6 to 60, but 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.As used herein, the terms "aryl group" and "arylene group" have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto. In the present invention, an aryl group or an arylene group means an aromatic of a single ring or multiple rings, and includes an aromatic ring formed by neighboring substituents participating in a bond or a reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, 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 the radical substituted with an aryl group has the carbon number 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.Also, when prefixes are named consecutively, it means that the substituents are listed in the order described first. For example, an arylalkoxy group means an alkoxy group substituted with an aryl group, an alkoxylcarbonyl group means a carbonyl group substituted with an alkoxyl group, and an arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group. Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.
본 명세서에서 사용된 용어 "헤테로알킬"은 다른 설명이 없는 한 하나 이상의 헤테로원자를 포함하는 알킬을 의미한다. 본 발명에 사용된 용어 "헤테로아릴기" 또는 "헤테로아릴렌기"는 다른 설명이 없는 한 각각 하나 이상의 헤테로원자를 포함하는 탄소수 2 내지 60의 아릴기 또는 아릴렌기를 의미하며, 여기에 제한되는 것은 아니며, 단일 고리 및 다중 고리 중 적어도 하나를 포함하며, 이웃한 작용기기가 결합하여 형성될 수도 있다.As used herein, the term “heteroalkyl” means an alkyl including one or more heteroatoms unless otherwise indicated. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or arylene group having 2 to 60 carbon atoms, each containing one or more heteroatoms, unless otherwise specified. It may include at least one of a single ring and multiple rings, and may be formed by combining adjacent functional groups.
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.As used herein, the term “heterocyclic group” includes one or more heteroatoms, unless otherwise indicated, and has from 2 to 60 carbon atoms, and includes at least one of single and multiple rings, heteroaliphatic rings and hetero Aromatic rings. Adjacent functional groups may be formed in combination.
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 stated.
또한 "헤테로고리기"는 고리를 형성하는 탄소 대신 SO2를 포함하는 고리도 포함할 수 있다. 예컨대, "헤테로고리기"는 다음 화합물을 포함한다. "Heterocyclic groups" may also include rings comprising SO 2 instead of carbon forming the ring. For example, a "heterocyclic group" includes the following compounds.
Figure PCTKR2017004320-appb-I000002
Figure PCTKR2017004320-appb-I000002
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 stated, the term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms, and the "aliphatic ring" means 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 stated, the term "ring" as used herein 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. Saturated or unsaturated rings.
전술한 헤테로화합물 이외의 그 밖의 다른 헤테로화합물 또는 헤테로라디칼은 하나 이상의 헤테로원자를 포함하며, 여기에 제한되는 것은 아니다.Other heterocompounds or heteroradicals other than the aforementioned heterocompounds include, but are not limited to, one or more heteroatoms.
다른 설명이 없는 한, 본 발명에 사용된 용어 "카르보닐"이란 -COR'로 표시되는 것이며, 여기서 R'은 수소, 탄소수 1 내지 20 의 알킬기, 탄소수 6 내지 30 의 아릴기, 탄소수 3 내지 30의 사이클로알킬기, 탄소수 2 내지 20의 알켄일기, 탄소수 2 내지 20의 알킨일기, 또는 이들의 조합인 것이다.Unless otherwise stated, the term "carbonyl" used in the present invention is represented by -COR ', wherein R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 3 to 30 carbon atoms. Cycloalkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.
다른 설명이 없는 한, 본 발명에 사용된 용어 "에테르"란 -R-O-R'로 표시되는 것이며, 여기서 R 또는 R'은 각각 서로 독립적으로 수소, 탄소수 1 내지 20의 알킬기, 탄소수 6 내지 30의 아릴기, 탄소수 3 내지 30의 사이클로알킬기, 탄소수 2 내지 20의 알켄일기, 탄소수 2 내지 20의 알킨일기, 또는 이들의 조합인 것이다.Unless otherwise specified, the term "ether" as used herein is represented by -RO-R ', wherein R or R' are each independently of each other hydrogen, an alkyl group having 1 to 20 carbon atoms, It is an aryl group, a C3-C30 cycloalkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, or a combination thereof.
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.Also, unless expressly stated, the term "substituted" in the term "substituted or unsubstituted" as used herein refers to deuterium, halogen, amino, nitrile, nitro, C 1 -C 20 alkyl, C 1 -C 20 alkoxyl group, C 1 ~ C 20 alkylamine group, C 1 ~ C 20 alkylthiophene group, C 6 ~ C 20 arylthiophene group, C 2 ~ C 20 alkenyl group, C 2 ~ C 20 alkynyl, C 3 ~ C 20 cycloalkyl group, 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 Group, germanium group, and C 2 ~ C 20 It is meant to be substituted with one or more substituents selected from the group consisting of, but 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 otherwise specified, the formulas used in the present invention apply in the same manner as the substituent definitions by the exponential definition of the following formula.
Figure PCTKR2017004320-appb-I000003
Figure PCTKR2017004320-appb-I000003
여기서, a가 0의 정수인 경우 치환기 R1은 부존재하는 것을 의미하는데, 즉 a가 0인 경우는 벤젠 고리를 형성하는 탄소에 모두 수소가 결합된 것을 의미하며, 이때 탄소에 결합된 수소의 표시를 생략하고 화학식이나 화합물을 기재 할 수 있다. 또한, a가 1의 정수인 경우 하나의 치환기 R1은 벤젠 고리를 형성하는 탄소 중 어느 하나의 탄소에 결합하며, a가 2 또는 3의 정수인 경우 예컨대 아래와 같이 결합할 수 있고, a가 4 내지 6의 정수인 경우에도 이와 유사한 방식으로 벤젠고리의 탄소에 결합하며, a가 2 이상의 정수인 경우 R1은 서로 같거나 상이할 수 있다. Herein, when a is an integer of 0, the substituent R 1 is not present, that is, when a is 0, it means that all of the carbons forming the benzene ring are bonded to hydrogen. Omit formulas and compounds. In addition, when a is an integer of 1, one substituent R 1 is bonded to any one of carbons forming a benzene ring, and when a is an integer of 2 or 3, for example, a is 4 to 6 In the same manner in the case of the integer of the bond to the carbon of the benzene ring, when a is an integer of 2 or more, R 1 may be the same or different from each other.
Figure PCTKR2017004320-appb-I000004
Figure PCTKR2017004320-appb-I000004
또한 명시적인 설명이 없는 한, 본 발명에서 사용된 용어 "오소(ortho)", "메타(meta)", "파라(para)"는 모든 치환기의 치환 위치를 뜻하며, 오소(ortho) 위치란 치환기의 위치가 바로 이웃하는 화합물을 나타내고, 일예로 벤젠일 경우 1, 2 자리를 뜻하고, 메타(meta) 위치란 바로 이웃 치환위치의 다음 치환위치를 나타내며 벤젠을 예시로 했을 때 1, 3자리를 뜻하며, 파라(para) 위치란 메타(meta) 위치의 다음 치환위치로써 벤젠을 예시로 했을 때 1, 4자리를 뜻한다. 보다 상세한 치환위치 예에 대한 설명은 하기와 같고, 오소-(ortho-), 메타-(meta-)위치는 non-linear한 type, 파라-(para-)위치는 linear한 type으로 치환됨을 확인할 수 있다. Also, unless stated otherwise, the terms "ortho", "meta", "para" used in the present invention means the substitution position of all substituents, the ortho position is a substituent The position of represents the neighboring compound, for example, in the case of benzene means 1, 2 digits, and the meta (meta) position represents the next substitution position of the immediate substitution position and benzene is 1, 3 digits as an example The para position means 1 or 4 digits when benzene is used as the next substitution position of the meta position. A more detailed description of the substitution positions is as follows. Ortho- and meta- positions are non-linear types and para- positions are substituted by linear types. have.
[ortho-위치의 예시][example of ortho-position]
Figure PCTKR2017004320-appb-I000005
Figure PCTKR2017004320-appb-I000005
[meta-위치의 예시][example of meta-location]
Figure PCTKR2017004320-appb-I000006
Figure PCTKR2017004320-appb-I000006
[meta-위치의 예시][example of meta-location]
Figure PCTKR2017004320-appb-I000007
Figure PCTKR2017004320-appb-I000007
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 element including the same will be described.
본 발명은 하기 화학식 (1)로 표시되는 화합물을 제공한다. The present invention provides a compound represented by the following general formula (1).
화학식 (1)Formula (1)
Figure PCTKR2017004320-appb-I000008
Figure PCTKR2017004320-appb-I000008
{상기 화학식 (1)에서,{In the above formula (1),
1) A는 C10의 아릴기이며,1) A is an aryl group of C 10 ,
2) B는 하기 화학식 B-1 내지 B-16로 이루어진 군에서 선택되고,2) B is selected from the group consisting of the following formulas B-1 to B-16,
B-1 B-2 B-3 B-4 B-5 B-1 B-2 B-3 B-4 B-5
Figure PCTKR2017004320-appb-I000009
Figure PCTKR2017004320-appb-I000009
B-6 B7 B-8 B-9 B-10B-6 B7 B-8 B-9 B-10
Figure PCTKR2017004320-appb-I000010
Figure PCTKR2017004320-appb-I000010
B-11 B-12 B-13 B-14 B-15 B-16B-11 B-12 B-13 B-14 B-15 B-16
Figure PCTKR2017004320-appb-I000011
Figure PCTKR2017004320-appb-I000011
상기 화학식 B-1 내지 B-16에서 "*" 는 2개의 N을 포함하는 pyrazine고리와 결합하여 융합고리를 형성하는 결합 부분을 나타내고,In Formulas B-1 to B-16, "*" represents a binding moiety that combines with a pyrazine ring containing two N to form a fused ring,
3) W1 및 W2는 각각 독립적으로 단일결합, S 또는 O이고,3) W 1 and W 2 are each independently a single bond, S or O,
4) V는 N 또는 C이고,4) V is N or C,
5) X는 O 또는 S이고,5) X is O or S,
6) a는 0 내지 6의 정수이고, b 및 c는 0 내지 4의 정수이고, d는 0 내지 11의 정수이며,6) a is an integer from 0 to 6, b and c are integers from 0 to 4, d is an integer from 0 to 11,
7) R1, R2, R3 및 R4는 서로 동일하거나 상이하며, 서로 독립적으로 수소; 중수소; 할로겐; 시아노; 나이트로기; 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~C50의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕실기; C6~C30의 아릴옥시기; 및 -L'-N(Ra)(Rb);로 이루어진 군에서 선택되며,7) R 1 , R 2 , R 3 and R 4 are the same as or different from each other, and independently from each other hydrogen; heavy hydrogen; halogen; Cyano; Nitro group; C 6 ~ C 60 Aryl group; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; C 1 ~ C 50 Alkyl group; C 2 ~ C 20 Alkenyl group; Alkynyl groups of C 2 to C 20 ; C 1 -C 30 alkoxyl group; C 6 -C 30 aryloxy group; And -L'-N (R a ) (R b );
R1 내지 R4가　아릴기인 경우, 바람직하게는 C6-C30의 아릴기, 더욱 바람직하게는 C6-C18의 아릴기이다. R1 내지 R4가 헤테로고리기인 경우, 바람직하게는 C2~C40의 헤테로고리기, 더욱 바람직하게는 C2~C30의 헤테로고리기, 더욱 바람직하게는 C2~C20의 헤테로고리기이다.When R 1 to R 4 is an aryl group, preferably an aryl group of C 6 aryl group, more preferably C 6 -C 18 -C 30 a. When R 1 to R 4 are heterocyclic groups, preferably C 2 ~ C 40 heterocyclic group, more preferably C 2 ~ C 30 heterocyclic group, more preferably C 2 ~ C 20 heterocyclic group Qi.
또한 상기 a, b 및 c가 2 이상인 경우 각각 복수로서 서로 동일하거나 상이하며 복수의 R1끼리 혹은 복수의 R2끼리 혹은 복수의 R3끼리 서로 결합하여 고리를 형성할 수 있다.In addition, when a, b, and c are two or more, each of them may be the same as or different from each other, and a plurality of R 1 or a plurality of R 2 or a plurality of R 3 may be bonded to each other to form a ring.
8) L'은 단일결합; C6~C60의 아릴렌기; 플루오렌일렌기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 C2~C60의 헤테로고리기;로 이루어진 군에서 선택되며, 상기 Ra 및 Rb은 서로 독립적으로 C6~C60의 아릴기; 플루오렌일기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기;로 이루어진 군에서 선택되며,8) L 'is a single bond; C 6 ~ C 60 arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; And C 2 ~ C 60 Heterocyclic group; It is selected from the group consisting of, R a and R b are independently of each other C 6 ~ C 60 An aryl group; Fluorenyl group; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; And a C 2 ~ C 60 heterocyclic group including at least one heteroatom of O, N, S, Si, and P, and
9) L1은 각각 독립적으로 단일결합; C6~C60의 아릴렌기; 플루오렌일렌기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 C2~C60의 헤테로고리기;로 이루어진 군에서 선택되고,9) L 1 is each independently a single bond; C 6 ~ C 60 arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; And C 2 ~ C 60 It is selected from the group consisting of; heterocyclic group,
여기서, 상기 아릴기, 플루오렌닐기, 아릴렌기, 헤테로고리기, 융합고리기, 알킬기, 알켄일기, 알콕시기, 아릴옥시기는 각각 중수소; 할로겐; C1-C20의 알킬기 또는 C6-C20의 아릴기로 치환 또는 비치환된 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; -L'-N(Ra)(Rb); 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 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 더욱 치환될 수 있으며, 또한 이들 치환기들은 서로 결합하여 고리를 형성할 수도 있으며, 여기서 '고리'란 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 불포화 고리를 포함한다.}Here, the aryl group, fluorenyl group, arylene group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkoxy group, aryloxy group are each deuterium; halogen; A silane group unsubstituted or substituted with a C 1 -C 20 alkyl group or a C 6 -C 20 aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; -L'-N (R a ) (R b ); Import alkylthio of C 1 -C 20; An alkoxyl group of C 1 -C 20 ; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group; A cycloalkyl group of C 3 -C 20 ; It may be further substituted with one or more substituents selected from the group consisting of C 7 -C 20 arylalkyl group and C 8 -C 20 arylalkenyl group, and these substituents may also be bonded to each other to form a 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, and includes a saturated or unsaturated ring.}
본 발명에서, 상기 화학식 (1)은 하기 화학식 2 내지 화학식 4 중 어느 하나로 표시되는 것을 특징으로 하는 화합물을 포함한다.In the present invention, the formula (1) includes a compound, characterized in that represented by any one of the following formula (2) to (4).
<화학식 2> <화학식 3> <화학식 4><Formula 2> <Formula 3> <Formula 4>
Figure PCTKR2017004320-appb-I000012
Figure PCTKR2017004320-appb-I000012
(상기 화학식 2 내지 화학식 4에서, X, L1, Ar1, R1, R2, R3, a, b, c는 상기에서 정의한 바와 동일하다)(In Formulas 2 to 4, X, L 1 , Ar 1 , R 1 , R 2 , R 3 , a, b, c are the same as defined above).
또한 본 발명에서 상기 화학식 (1)은 하기 화학식 5 내지 화학식 7 중 어느 하나로 표시되는 것을 특징으로 하는 화합물을 포함한다.In the present invention, the formula (1) includes a compound, characterized in that represented by any one of the following formula (5) to formula (7).
<화학식 5> <화학식 6> <화학식 7> <Formula 5> <Formula 6> <Formula 7>
Figure PCTKR2017004320-appb-I000013
Figure PCTKR2017004320-appb-I000013
(상기 화학식 5 내지 화학식 7에서, X, L1, Ar1, R1, R2, R3, R4, a, b, c, d, B는 상기에서 정의한 바와 동일하다)(In Formula 5 to Formula 7, X, L 1 , Ar 1 , R 1 , R 2 , R 3 , R 4 , a, b, c, d, B are the same as defined above)
본 발명의 일 실시예에서, 상기 화학식 (1)의 상기 pyrazine을 포함한 화학식 구조 Ar1은 하기 화학식 C-1 내지 화학식 C-20 로 표시되는 화합물을 제공한다.In one embodiment of the present invention, the formula structure Ar 1 including the pyrazine of formula (1) provides a compound represented by the following formula C-1 to formula C-20.
C-1 C-2 C-3 C-4 C-5 C-6C-1 C-2 C-3 C-4 C-5 C-6
Figure PCTKR2017004320-appb-I000014
Figure PCTKR2017004320-appb-I000014
C-7 C-8 C-9 C-10 C-11 C-12 C-13 C-14  C-7 C-8 C-9 C-10 C-11 C-12 C-13 C-14
Figure PCTKR2017004320-appb-I000015
Figure PCTKR2017004320-appb-I000015
C-15 C-16 C-17 C-18 C-19 C-20  C-15 C-16 C-17 C-18 C-19 C-20
Figure PCTKR2017004320-appb-I000016
Figure PCTKR2017004320-appb-I000016
C-21 C-22C-21 C-22
Figure PCTKR2017004320-appb-I000017
Figure PCTKR2017004320-appb-I000017
(상기 화학식 C-1 내지 C-22에서, R4는 상기에서 정의한 바와 동일하고, d는 0 내지 11의 정수 중 어느 하나이다.)(In the above formulas C-1 to C-22, R 4 is the same as defined above, and d is any one of integers from 0 to 11.)
본 발명은 상기 화학식 (1)에서 R4가 하기 화학식 R-1 내지 R-10 중 어느 하나로 표시되는 화합물을 포함한다.The present invention includes a compound in which R 4 in Formula (1) is represented by any one of the following Formulas R-1 to R-10.
<R-1> <R-2> <R-3> <R-4> <R-5><R-1> <R-2> <R-3> <R-4> <R-5>
Figure PCTKR2017004320-appb-I000018
Figure PCTKR2017004320-appb-I000018
<R-6> <R-7> <R-8> <R-9> <R-10><R-6> <R-7> <R-8> <R-9> <R-10>
Figure PCTKR2017004320-appb-I000019
Figure PCTKR2017004320-appb-I000019
(상기 화학식 R-1 내지 R-10에서,(In the above formula R-1 to R-10,
1) Q1 내지 Q15는 서로 독립적으로 CRg 또는 N이고,1) Q 1 to Q 15 are independently of each other CR g or N,
2) W1은 S, O 또는 NRh이고, 2) W 1 is S, O or NR h ,
3) W2 내지 W4는 S, O, NRh 또는 CRiRj 3) W 2 to W 4 are S, O, NR h or CR i R j
4) Re는 수소; 중수소; 할로겐; C1-C20의 알킬기 또는 C6-C20의 아릴기로 치환 또는 비치환된 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; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C20의 헤테로고리기; C3-C20의 시클로알킬기; C7-C20의 아릴알킬기; 및 C8-C20의 아릴알켄일기로 이루어진 군에서 선택되거나, 또는 이웃한 기끼리 서로 결합하여 고리를 형성할 수 있으며,4) R e is hydrogen; heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C 1 -C 20 alkyl group or a C 6 -C 20 aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C 1 -C 20; An alkoxyl group of C 1 -C 20 ; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A cycloalkyl group of C 3 -C 20 ; C 7 -C 20 arylalkyl group; And C 8 -C 20 It is selected from the group consisting of an aryl alkenyl group, or adjacent groups may combine with each other to form a ring,
5) Rf 및 Rg는 서로 독립적으로 수소; 중수소; C6~C20의 아릴기; 플루오렌일기; C3~C20의 지방족고리와 C6~C20의 방향족고리의 융합고리기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C20의 헤테로고리기; C1~C20의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕실기;로 구성된 군에서 선택되고,5) R f and R g are each independently hydrogen; heavy hydrogen; C 6 -C 20 aryl group; Fluorenyl group; A fused ring group of an aliphatic ring of C 3 ~ C 20 and an aromatic ring of C 6 ~ C 20 ; And a C 2 to C 20 heterocyclic group including at least one heteroatom of O, N, S, Si, and P; C 1 ~ C 20 Alkyl group; C 2 ~ C 20 Alkenyl group; Alkynyl groups of C 2 to C 20 ; C 1 ~ C 30 Alkoxyl group; It is selected from the group consisting of,
6) Rh Ri 및 Rj는 서로 독립적으로 C6-C20의 아릴기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2-C20의 헤테로고리기; C1-C20의 알킬기; C2-C20의 알켄일기; C1-C20의 알콕시기; 및 플루오렌일기;로 구성된 군에서 선택되고, Ri 및 Rj는 서로 결합하여 이들이 결합된 C와 함께 스파이로(spiro) 화합물을 형성할 수 있고,6) R h R i and R j are each independently of the other C 6 -C 20 aryl group; C 2 -C 20 heterocyclic group including at least one heteroatom of O, N, S, Si, and P; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkoxy group of C 1 -C 20 ; And a fluorenyl group; R i and R j may be bonded to each other to form a spiro compound together with C to which they are bonded,
7) q는 서로 독립적으로 0 내지 5의 정수이고,7) q is an integer from 0 to 5 independently of each other,
8) r는 서로 독립적으로 0 내지 4의 정수이고,8) r is, independently from each other, an integer from 0 to 4,
9) s는 서로 독립적으로 0 내지 3의 정수이고,9) s is an integer from 0 to 3 independently of each other,
q,r 및 s가 각각이 2 이상의 정수인 경우, Re는 서로 동일하거나 상이하며,when q, r and s are each an integer of 2 or more, R e is the same as or different from each other,
*은 결합부분을 나타낸다.* Represents a coupling part.
상기 Re 내지 Rj가 아릴기인 경우, 바람직하게는 C6-C30의 아릴기, 더욱 바람직하게는 C6-C18의 아릴기이고, Re 내지 Rj가 헤테로고리기인 경우, 바람직하게는 C2~C40의 헤테로고리기, 더욱 바람직하게는 C2~C30의 헤테로고리기, 더욱 바람직하게는 C2~C20의 헤테로고리기이다.)When R e to R j is an aryl group, preferably a C 6 -C 30 aryl group, more preferably a C 6 -C 18 aryl group, when R e to R j is a heterocyclic group, preferably Is a C 2 ~ C 40 heterocyclic group, more preferably a C 2 ~ C 30 heterocyclic group, more preferably a C 2 ~ C 20 heterocyclic group.)
구체적으로 본 발명은 상기 화학식 (1)로 표시되는 화합물이 하기 화합물을 포함한다.Specifically, in the present invention, the compound represented by the formula (1) includes the following compound.
Figure PCTKR2017004320-appb-I000020
Figure PCTKR2017004320-appb-I000020
Figure PCTKR2017004320-appb-I000021
Figure PCTKR2017004320-appb-I000021
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Figure PCTKR2017004320-appb-I000023
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Figure PCTKR2017004320-appb-I000024
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Figure PCTKR2017004320-appb-I000025
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Figure PCTKR2017004320-appb-I000026
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Figure PCTKR2017004320-appb-I000027
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Figure PCTKR2017004320-appb-I000028
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Figure PCTKR2017004320-appb-I000029
Figure PCTKR2017004320-appb-I000029
Figure PCTKR2017004320-appb-I000030
Figure PCTKR2017004320-appb-I000030
Figure PCTKR2017004320-appb-I000031
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Figure PCTKR2017004320-appb-I000032
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Figure PCTKR2017004320-appb-I000033
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Figure PCTKR2017004320-appb-I000035
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Figure PCTKR2017004320-appb-I000036
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Figure PCTKR2017004320-appb-I000037
Figure PCTKR2017004320-appb-I000037
Figure PCTKR2017004320-appb-I000038
Figure PCTKR2017004320-appb-I000038
Figure PCTKR2017004320-appb-I000039
Figure PCTKR2017004320-appb-I000039
Figure PCTKR2017004320-appb-I000040
Figure PCTKR2017004320-appb-I000040
Figure PCTKR2017004320-appb-I000041
Figure PCTKR2017004320-appb-I000041
Figure PCTKR2017004320-appb-I000042
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Figure PCTKR2017004320-appb-I000048
Figure PCTKR2017004320-appb-I000048
Figure PCTKR2017004320-appb-I000049
Figure PCTKR2017004320-appb-I000049
Figure PCTKR2017004320-appb-I000050
Figure PCTKR2017004320-appb-I000050
Figure PCTKR2017004320-appb-I000051
Figure PCTKR2017004320-appb-I000051
Figure PCTKR2017004320-appb-I000052
Figure PCTKR2017004320-appb-I000052
Figure PCTKR2017004320-appb-I000053
Figure PCTKR2017004320-appb-I000053
도 1을 참조하여 설명하면, 본 발명에 따른 유기전기소자(100)는 기판(110) 상에 형성된 제 1전극(120), 제 2전극(180) 및 제 1전극(120)과 제 2전극(180) 사이에 화학식 (1)로 표시되는 화합물을 포함하는 유기물층을 구비한다. 이때, 제 1전극(120)은 애노드(양극)이고, 제 2전극(180)은 캐소드(음극)일 수 있으며, 인버트형의 경우에는 제 1전극이 캐소드이고 제 2전극이 애노드일 수 있다.Referring to FIG. 1, the organic electric device 100 according to the present invention includes a first electrode 120, a second electrode 180, and a first electrode 120 and a second electrode formed on a substrate 110. The organic material layer containing the compound represented by General formula (1) between 180 is provided. In this case, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (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(120) 상에 순차적으로 정공주입층(130), 정공수송층(140), 발광층(150), 전자수송층(160) 및 전자주입층(170)을 포함할 수 있다. 이때, 발광층(150)을 제외한 나머지 층들이 형성되지 않을 수 있다. 정공저지층, 전자저지층, 발광보조층(151), 전자수송보조층, 버퍼층(141) 등을 더 포함할 수도 있고, 전자수송층(160) 등이 정공저지층의 역할을 할 수도 있을 것이다.The organic layer may include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, and an electron injection layer 170 on the first electrode 120 in sequence. At this time, the remaining layers except for the light emitting layer 150 may not be formed. The hole blocking layer, the electron blocking layer, the light emitting auxiliary layer 151, the electron transport auxiliary layer, and the buffer layer 141 may be further included, and the electron transport layer 160 may serve as the hole blocking layer.
또한, 미도시하였지만 본 발명에 따른 유기전기소자는 제 1전극과 제 2전극중 적어도 일면 중 상기 유기물층과 반대되는 일면에 형성된 보호층을 더 포함할 수 있다.In addition, although not shown, the organic electronic device according to the present invention may further include a protective layer formed on one surface of the first electrode and the second electrode opposite to the organic material layer.
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.Meanwhile, even in the same core, band gaps, electrical characteristics, and interface characteristics may vary depending on which substituents are bonded at which positions. Therefore, the selection of cores and the combination of sub-substituents bound thereto are also very significant. Importantly, long life and high efficiency can be achieved at the same time when an optimal combination of energy level and T1 value and intrinsic properties (mobility, interfacial properties, etc.) of each organic material layer is achieved.
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(130), 정공수송층(140), 발광층(150), 전자수송층(160) 및 전자주입층(170)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 PVD method. For example, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode, and the hole injection layer 130, the hole transport layer 140, the light emitting layer 150, the electron transport layer 160 are disposed thereon. After forming the organic material layer including the electron injection layer 170, it can be prepared by depositing a material that can be used as a cathode thereon.
또한, 정공수송층(140)과 발광층(150) 사이에 발광보조층(151)을, 발광층(150)과 전자수송층(160) 사이에 전자수송보조층을 추가로 더 형성할 수 있다.In addition, the light emitting auxiliary layer 151 may be further formed between the hole transport layer 140 and the light emitting layer 150, and an electron transport auxiliary layer may be further formed between the light emitting layer 150 and the electron transport layer 160.
이에 따라, 본 발명은 상기 유기전기소자에서 상기 제 1전극의 일측면 중 상기 유기물층과 반대되는 일측 또는 상기 제 2전극의 일측면 중 상기 유기물층과 반대되는 일측 중 적어도 하나에 형성되는 광효율개선층을 더 포함하는 유기전기소자를 제공한다.Accordingly, the present invention provides an optical efficiency improvement layer formed on at least one side of the one side of the first electrode opposite to the organic material layer or one side of the second electrode opposite to the organic material layer in the organic electric device. It provides an organic electric element further comprising.
또한 본 발명에서 상기 유기물층은 스핀코팅 공정, 노즐 프린팅 공정, 잉크젯 프린팅 공정, 슬롯코팅 공정, 딥코팅 공정 및 롤투롤 공정 중 어느 하나에 의해 형성되고, 본 발명에 따른 유기물층은 다양한 방법으로 형성될 수 있으므로, 그 형성방법에 의해 본 발명의 권리범위가 제한되는 것은 아니다.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, the organic material layer according to the present invention can be formed in various ways Therefore, the scope of the present invention is not limited by the formation method.
본 발명에서 상기 화학식 (1)에 따른 화합물은 상기 유기물층에 포함되고, 상기 유기물층으로서 정공주입층, 정공수송층, 발광보조층 및 발광층 중 적어도 하나의 층에 상기 화합물이 함유되며, 상기 화합물은 1종 단독 화합물 또는 2종 이상의 화합물을 혼합물의 성분으로서 포함함 될 수 있다. In the present invention, the compound according to Chemical Formula (1) is included in the organic material layer, and the compound is contained in at least one layer of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, and a light emitting layer as the organic material layer, and the compound is one kind. Single compounds or two or more compounds may be included as components of the mixture.
또 다른 구체적인 예로서, 본 발명은 상기 유기물층에서 상기 발광층이 인광 발광층인 유기전기소자를 제공한다. 예컨대, 본 발명의 화합물은 발광층(150), 정공수송층(140) 및/또는 발광보조층(151) 재료로 사용될 수 있으며, 바람직하게는 발광층(150)의 호스트 재료로 사용될 수 있다. 더 바람직하게는 인광 레드 호스트 재료로 사용될 수 있다.As another specific example, the present invention provides an organic electric device in which the light emitting layer is a phosphorescent light emitting layer in the organic material layer. For example, the compound of the present invention may be used as the light emitting layer 150, the hole transport layer 140 and / or the light emitting auxiliary layer 151 material, preferably as a host material of the light emitting layer 150. More preferably, it can be used as a phosphorescent red host material.
본 발명의 일 실시예에 따른 유기전기소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic electric element according to an embodiment of the present invention may be a top emission type, a bottom emission type or a double-sided emission type according to the material used.
WOLED(White Organic Light Emitting Device)는 고해상도 실현이 용이하고 공정성이 우수한 한편, 기존의 LCD의 칼라필터 기술을 이용하여 제조될 수 있는 이점이 있다. 주로 백라이트 장치로 사용되는 백색 유기발광소자에 대한 다양한 구조들이 제안되고 특허화되고 있다. 대표적으로, R(Red), G(Green), B(Blue) 발광부들을 상호평면적으로 병렬배치(side-by-side) 방식, R, G, B 발광층이 상하로 적층되는 적층(stacking) 방식이 있고, 청색(B) 유기발광층에 의한 전계발광과 이로부터의 광을 이용하여 무기형광체의 자발광(photo-luminescence)을 이용하는 색변환물질(color conversion material, CCM) 방식 등이 있는데, 본 발명은 이러한 WOLED에도 적용될 수 있을 것이다. WOLED (White Organic Light Emitting Device) has the advantage that can be manufactured using the color filter technology of the existing LCD while being easy to realize high resolution and excellent processability. Various structures for white organic light emitting devices mainly used as backlight devices have been proposed and patented. Representatively, a side-by-side method in which R (Red), G (Green), and B (Blue) light emitting parts are mutually planarized, and a stacking method in which R, G, and B light emitting layers are stacked up and down. And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light therefrom. May also be applied to these WOLEDs.
또한 본 발명은 상기한 유기전기소자를 포함하는 디스플레이장치 ; 및 상기 디스플레이장치를 구동하는 제어부;를 포함하는 전자장치를 제공한다. In another aspect, the present invention is a display device comprising the above-mentioned organic electric element; 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 organic electronic device provides an electronic device according to the present invention, wherein the organic electroluminescent device is at least one of an organic electroluminescent device, an organic solar cell, an organic photoconductor, an organic transistor, and a monochromatic or white illumination 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 a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.
이하에서, 본 발명의 상기 화학식 (1),(2)로 표시되는 화합물의 합성예 및 본 발명의 유기전기소자의 제조예에 관하여 실시예를 들어 구체적으로 설명하지만, 본 발명의 하기 실시예로 한정되는 것은 아니다.Hereinafter, the synthesis examples of the compounds represented by the general formulas (1) and (2) of the present invention and the production examples of the organic electric device of the present invention will be described in detail with reference to Examples, but the following Examples of the present invention. It is not limited.
[[ 합성예Synthesis Example ]]
본 발명에 따른 화합물(final products)은 하기와 같은 방법으로 반응하여 제조되며, 이에 한정되는 것은 아니다. Compounds (final products) according to the present invention is prepared by reacting in the following manner, but is not limited thereto.
<반응식 1><Scheme 1>
Figure PCTKR2017004320-appb-I000054
Figure PCTKR2017004320-appb-I000054
또는or
Figure PCTKR2017004320-appb-I000055
Figure PCTKR2017004320-appb-I000055
Hal1= Cl, Br Hal 1 = Cl, Br
R4' = 상기 R4의 정의와 동일하고, R4와 동일하거나 상이한 치환기를 뜻함R 4 ′ = the same definition as R 4 above, meaning a substituent that is the same as or different from R 4
I. Sub 1의 합성I. Synthesis of Sub 1
상기 반응식 1의 Sub 1은 하기 반응식 2 및 반응식 3의 반응경로에 의해 합성될 수 있으나, 이에 한정되는 것은 아니다.Sub 1 of Scheme 1 may be synthesized by the reaction paths of Scheme 2 and Scheme 3, but is not limited thereto.
반응식 2Scheme 2
Figure PCTKR2017004320-appb-I000056
Figure PCTKR2017004320-appb-I000056
Figure PCTKR2017004320-appb-I000057
Figure PCTKR2017004320-appb-I000057
반응식 3Scheme 3
Figure PCTKR2017004320-appb-I000058
Figure PCTKR2017004320-appb-I000058
Hal2= I, BrHal 2 = I, Br
Hal1, Hal3= Cl, BrHal 1 , Hal 3 = Cl, Br
상기 반응식 1에서, (
Figure PCTKR2017004320-appb-I000059
)의 반응물의 경우는 하기와 같이 4개의 문헌을 참조하여 합성하였다.In Scheme 1, (
Figure PCTKR2017004320-appb-I000059
In the case of the reaction product), it was synthesized with reference to four documents as follows.
1) 주식회사 두산이 출원한 한국 등록특허 제 10-1488560호 (2015.02.03 일자 등록공고)에 개시된 합성방법을 사용하였다. (반응식 A 참조)1) The synthesis method disclosed in Korean Patent Registration No. 10-1488560 filed by Doosan Corporation (registered date of 2015.02.03) was used. (See Scheme A)
<반응식 A>Scheme A
Figure PCTKR2017004320-appb-I000060
Figure PCTKR2017004320-appb-I000060
2) BASF가 출원한 국제 공개특허 PCT-EP2015-068240 호 (최우선출원일 2014.08.08)에 개시된 합성방법을 사용하였다. <반응식 B 참조>2) The synthesis method disclosed in International Publication No. PCT-EP2015-068240 filed by BASF (first application date 2014.08.08) was used. See Scheme B.
<반응식 B> Scheme B
Figure PCTKR2017004320-appb-I000061
Figure PCTKR2017004320-appb-I000061
3) Soochow University가 출원한 중국 공개특허 제 2016-10316704 호 (출원일 2016.05.13)에 개시된 합성방법을 사용하였다. <반응식 C 참조>3) The synthesis method disclosed in Chinese Unexamined Patent Application No. 2016-10316704 filed on May 13, 2016, filed by Soochow University, was used. See Scheme C.
<반응식 C>Scheme C
Figure PCTKR2017004320-appb-I000062
Figure PCTKR2017004320-appb-I000062
4) 엘지디스플레이 주식회사가 출원한 한국 공개특허 제 2015-0130953 호 (최우선출원일 2014.12.05)에 개시된 합성방법을 사용하였다. <화합물 6의 합성 참조>4) The synthesis method disclosed in Korean Unexamined Patent Application No. 2015-0130953 filed by LG Display Co., Ltd. (first application date 2014.12.05) was used. See Synthesis of Compound 6
Sub 1에 속하는 구체적 화합물의 합성예는 다음과 같다.Synthesis examples of specific compounds belonging to Sub 1 are as follows.
1. M-I-1 합성예1. Synthesis Example of M-I-1
Figure PCTKR2017004320-appb-I000063
Figure PCTKR2017004320-appb-I000063
1) S-I-1 합성1) S-I-1 Synthesis
(4-bromonaphthalen-1-yl)boronic acid (28g, 111.6mmol)을 둥근바닥플라스크에 THF (491ml)로 녹인 후에, 2-iodo-1-(methylsulfinyl)naphthalene (35.28g, 111.6mmol), Pd(PPh3)4 (1.93g, 1.67mmol), NaOH (6.70g, 167.40mmol), 물 (246ml)을 첨가하고 80 ℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 30g (수율: 68%)을 얻었다.After dissolving (4-bromonaphthalen-1-yl) boronic acid (28g, 111.6mmol) in THF (491ml) in a round bottom flask, 2-iodo-1- (methylsulfinyl) naphthalene (35.28g, 111.6mmol), Pd ( PPh 3 ) 4 (1.93 g, 1.67 mmol), NaOH (6.70 g, 167.40 mmol) and water (246 ml) were added and stirred at 80 ° C. After completion of the reaction, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain a product 30g (yield: 68%).
2) M-I-1 합성2) M-I-1 Synthesis
상기 합성에서 얻어진 S-I-1 (30g, 75.89mmol)를 둥근바닥플라스크에 triflic acid (100.7ml, 1138.35mmol)와 함께 넣고 상온에서 24시간 동안 교반한 뒤, pyridine 수용액 (1329ml, pyridine : H2O = 1 : 5)을 천천히 적가하고 30분 동안 환류 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 21.8g (수율: 79%)를 얻었다.SI-1 (30g, 75.89mmol) obtained in the above synthesis was added to triflic acid (100.7ml, 1138.35mmol) in a round bottom flask and stirred at room temperature for 24 hours, followed by aqueous pyridine solution (1329ml, pyridine: H 2 O = 1: 5) was slowly added dropwise and stirred at reflux for 30 minutes. After completion of the reaction, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to give 21.8 g (yield: 79%) of the product.
2) M-I-2 합성2) M-I-2 Synthesis
Figure PCTKR2017004320-appb-I000064
Figure PCTKR2017004320-appb-I000064
1) S-I-2 합성1) S-I-2 Synthesis
(4-bromonaphthalen-1-yl)boronic acid (29g, 115.59mmol), THF (509ml), 2-iodo-3-(methylsulfinyl)naphthalene (36.54g, 115.59mmol), Pd(PPh3)4 (2g, 1.73mmol), NaOH (6.94g, 173.38mmol), 물 (254ml)을 상기 S-I-1의 합성방법을 사용하여 생성물 30.16g (수율: 66%)을 얻었다.(4-bromonaphthalen-1-yl) boronic acid (29g, 115.59mmol), THF (509ml), 2-iodo-3- (methylsulfinyl) naphthalene (36.54g, 115.59mmol), Pd (PPh 3 ) 4 (2g, 1.73 mmol), NaOH (6.94 g, 173.38 mmol) and water (254 ml) were obtained using 30.16 g (yield: 66%) of the product using the synthesis method of SI-1.
2) M-I-2 합성2) M-I-2 Synthesis
상기 합성에서 얻어진 S-I-2 (30g, 75.89mmol), triflic acid (100.7ml, 1138.35mmol), pyridine 수용액 (1329.6ml, pyridine : H2O = 1 : 5)을 상기 M-I-1의 합성방법을 사용하여 생성물 20.1g (수율: 73%)를 얻었다.SI-2 (30g, 75.89mmol), triflic acid (100.7ml, 1138.35mmol), pyridine aqueous solution (1329.6ml, pyridine: H 2 O = 1: 5) obtained in the above synthesis using the method of synthesis of MI-1 This gave 20.1 g (yield: 73%) of product.
3) M-I-3 합성3) M-I-3 Synthesis
Figure PCTKR2017004320-appb-I000065
Figure PCTKR2017004320-appb-I000065
1) S-I-3 합성1) S-I-3 Synthesis
(4-bromonaphthalen-1-yl)boronic acid (31g, 123.56mmol), THF (543ml), 1-iodo-2-(methylsulfinyl)naphthalene (31g, 123.56mmol), Pd(PPh3)4 (2.14g, 1.85mmol), NaOH (7.41g, 185.34mmol), 물 (272ml)을 상기 S-I-1의 합성방법을 사용하여 생성물 30.77g (수율: 63%)을 얻었다.(4-bromonaphthalen-1-yl) boronic acid (31g, 123.56mmol), THF (543ml), 1-iodo-2- (methylsulfinyl) naphthalene (31g, 123.56mmol), Pd (PPh 3 ) 4 (2.14g, 1.85 mmol), NaOH (7.41 g, 185.34 mmol) and water (272 ml) were obtained using the synthesis method of SI-1 to obtain 30.77 g (yield: 63%) of the product.
2) M-I-3 합성2) M-I-3 Synthesis
상기 합성에서 얻어진 S-I-3 (30g, 75.89mmol), triflic acid (100.7ml, 1138.35mmol), pyridine 수용액 (1329.6ml, pyridine : H2O = 1 : 5)을 상기 M-I-1의 합성방법을 사용하여 생성물 20.7g (수율: 75%)를 얻었다.SI-3 (30g, 75.89mmol), triflic acid (100.7ml, 1138.35mmol), pyridine aqueous solution (1329.6ml, pyridine: H 2 O = 1: 5) obtained in the above synthesis using the method of synthesis of MI-1 This gave 20.7 g (yield: 75%) of product.
4) M-I-4 합성4) M-I-4 Synthesis
Figure PCTKR2017004320-appb-I000066
Figure PCTKR2017004320-appb-I000066
1) S-I-4 합성1) S-I-4 Synthesis
(4-bromonaphthalen-1-yl)boronic acid (34g, 135.52mmol), THF (596ml), 3-iodonaphthalen-2-ol (36.60g, 135.52mmol), Pd(PPh3)4 (2.35g, 2.03mmol), NaOH (8.13g, 203.28mmol), 물 (298ml)을 상기 S-I-1의 합성방법을 사용하여 생성물 30.29g (수율: 64%)을 얻었다.(4-bromonaphthalen-1-yl) boronic acid (34g, 135.52mmol), THF (596ml), 3-iodonaphthalen-2-ol (36.60g, 135.52mmol), Pd (PPh 3 ) 4 (2.35g, 2.03mmol ), NaOH (8.13 g, 203.28 mmol) and water (298 ml) were obtained using 30.29 g (yield: 64%) of the product using the above synthesis method of SI-1.
2) M-I-4 합성2) M-I-4 Synthesis
출발물질인 S-I-4 (30g, 85.90mmol)를 둥근바닥플라스크에 Pd(OAc)2 (1.93g, 8.59mmol), 3-nitropyridine (1.07g, 8.59mmol)과 함께 넣고 C6F6 (128.9ml), DMI (85.9ml)로 녹인 후, tert-butyl peroxybenzoate (33.37g, 171.81mmol)를 첨가하고 90℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 21.18g (수율: 71%)를 얻었다.Starting material SI-4 (30g, 85.90mmol) was added to Pd (OAc) 2 (1.93g, 8.59mmol), 3-nitropyridine (1.07g, 8.59mmol) in a round bottom flask and C 6 F 6 (128.9ml) ), And then dissolved in DMI (85.9ml), tert- butyl peroxybenzoate (33.37g, 171.81mmol) was added and stirred at 90 ℃. After completion of the reaction, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain 21.18 g (yield: 71%) of the product.
5) M-I-5 합성 5) M-I-5 Synthesis
Figure PCTKR2017004320-appb-I000067
Figure PCTKR2017004320-appb-I000067
1) S-I-5 합성1) S-I-5 Synthesis
(4-bromonaphthalen-1-yl)boronic acid (35g, 139.50mmol), THF (614ml), 2-iodonaphthalen-1-ol (37.68g, 139.50mmol), Pd(PPh3)4 (2.42g, 2.09mmol), NaOH (8.37g, 209.26mmol), 물 (307ml)을 상기 S-I-1의 합성방법을 사용하여 생성물 30.21g (수율: 62%)을 얻었다.(4-bromonaphthalen-1-yl) boronic acid (35g, 139.50mmol), THF (614ml), 2-iodonaphthalen-1-ol (37.68g, 139.50mmol), Pd (PPh 3 ) 4 (2.42g, 2.09mmol ), NaOH (8.37 g, 209.26 mmol) and water (307 ml) were obtained using 30.21 g (yield: 62%) of the product using the synthesis method of SI-1.
2) M-I-5 합성2) M-I-5 Synthesis
상기 합성에서 얻어진 S-I-5 (30g, 85.90mmol), Pd(OAc)2 (1.93g, 8.59mmol), 3-nitropyridine (1.07g, 8.59mmol), C6F6 (128.9ml), DMI (85.9ml), tert-butyl peroxybenzoate (33.37g, 171.81mmol)를 상기 M-I-4의 합성방법을 사용하여 생성물 22.07g (수율: 74%)를 얻었다.SI-5 (30 g, 85.90 mmol), Pd (OAc) 2 (1.93 g, 8.59 mmol) obtained in the above synthesis, 3-nitropyridine (1.07 g, 8.59 mmol), C 6 F 6 (128.9 ml), DMI (85.9 ml) and tert- butyl peroxybenzoate (33.37g, 171.81mmol) were obtained using the synthesis method of MI-4 to obtain 22.07g (yield: 74%) of the product.
6) M-I-6 합성6) M-I-6 Synthesis
Figure PCTKR2017004320-appb-I000068
Figure PCTKR2017004320-appb-I000068
1) S-I-6 합성1) S-I-6 Synthesis
(4-bromonaphthalen-1-yl)boronic acid (35g, 139.50mmol), THF (614ml), 1-iodonaphthalen-2-ol (37.68g, 139.50mmol), Pd(PPh3)4 (2.42g, 2.09mmol), NaOH (8.37g, 209.26mmol), 물 (307ml)을 상기 S-I-1의 합성방법을 사용하여 생성물 31.67g (수율: 65%)을 얻었다.(4-bromonaphthalen-1-yl) boronic acid (35g, 139.50mmol), THF (614ml), 1-iodonaphthalen-2-ol (37.68g, 139.50mmol), Pd (PPh 3 ) 4 (2.42g, 2.09mmol ), NaOH (8.37 g, 209.26 mmol) and water (307 ml) were obtained using 31.67 g (yield: 65%) of the product using the synthesis method of SI-1.
2) M-I-6 합성2) M-I-6 Synthesis
상기 합성에서 얻어진 S-I-6 (30g, 85.90mmol), Pd(OAc)2 (1.93g, 8.59mmol), 3-nitropyridine (1.07g, 8.59mmol), C6F6 (128.9ml), DMI (85.9ml), tert-butyl peroxybenzoate (33.37g, 171.81mmol)를 상기 M-I-4의 합성방법을 사용하여 생성물 22.67g (수율: 76%)를 얻었다.SI-6 (30g, 85.90mmol), Pd (OAc) 2 (1.93g, 8.59mmol), 3-nitropyridine (1.07g, 8.59mmol), C 6 F 6 (128.9ml), DMI (85.9) obtained in the above synthesis ml) and tert- butyl peroxybenzoate (33.37 g, 171.81 mmol) were obtained using 22.67 g (yield: 76%) of the product using the synthesis method of MI-4.
1. Sub 1-1 합성예1.Sub 1-1 Synthesis Example
Figure PCTKR2017004320-appb-I000069
Figure PCTKR2017004320-appb-I000069
Figure PCTKR2017004320-appb-I000070
Figure PCTKR2017004320-appb-I000070
(1) Sub 1-I-1 합성 ( 1) Sub 1-I-1 Synthesis
출발물질인 M-I-1 (70g, 192.69mmol)를 둥근바닥플라스크에 DMF (1214ml)로 녹인 후에, Bis(pinacolato)diboron (53.83g, 211.96mmol), Pd(dppf)Cl2 (4.23g, 5.78mmol), KOAc (56.73g, 578.08mmol)를 첨가하고 90℃에서 교반하였다. 반응이 완료되면 증류를 통해 DMF를 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 64.05g (수율: 81%)를 얻었다.After starting MI-1 (70g, 192.69mmol) was dissolved in DMF (1214ml) in a round bottom flask, Bis (pinacolato) diboron (53.83g, 211.96mmol), Pd (dppf) Cl 2 (4.23g, 5.78mmol), KOAc (56.73 g, 578.08 mmol) was added and stirred at 90 ° C. After the reaction was completed, DMF was removed by distillation and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 , concentrated, and the resulting compound was purified by silicagel column and recrystallized to give 64.05 g (yield: 81%) of the product.
(2) Sub 1-II-1 합성(2) Sub 1-II-1 Synthesis
상기 합성에서 얻어진 Sub 1-I-1 (63.2g, 154.02mmol)를 둥근바닥플라스크에 THF (216ml)로 녹인 후에, 1-bromo-2-nitrobenzene (34.22g, 169.42mmol), Pd(PPh3)4 (4.23g, 4.62mmol), K2CO3 (44.40g, 462.06mmol), 물 (108ml)을 첨가하고 80°C에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 45.59g (수율: 73%)을 얻었다.Sub 1-I-1 (63.2 g, 154.02 mmol) obtained in the above synthesis was dissolved in THF (216 ml) in a round bottom flask, followed by 1-bromo-2-nitrobenzene (34.22 g, 169.42 mmol) and Pd (PPh 3 ). 4 (4.23 g, 4.62 mmol), K 2 CO 3 (44.40 g, 462.06 mmol), water (108 ml) were added and stirred at 80 ° C. After the reaction was completed, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to give the product 45.59g (yield: 73%).
(3) Sub 1-III-1 합성(3) Sub 1-III-1 Synthesis
상기 합성에서 얻어진 Sub 1-II-1 (45.50, 112.22mmol)를 둥근바닥플라스크에 o-dichlorobenzene (224ml)으로 녹인 후에, triphenylphosphine (88.30g, 336.65mmol)을 첨가하고 200℃에서 교반하였다. 반응이 완료되면 증류를 통해 o-dichlorobenzene을 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축 한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 31.85g (수율: 76%)를 얻었다.Sub 1-II-1 (45.50, 112.22mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene (224ml) in a round bottom flask, triphenylphosphine (88.30g, 336.65mmol) was added and stirred at 200 ° C. After the reaction was completed, o -dichlorobenzene was removed by distillation and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 , concentrated and the resulting compound was silicagel column and recrystallized to give 31.85g (yield: 76%) of the product.
(4) Sub 1-1 합성(4) Sub 1-1 synthesis
상기 합성에서 얻어진 Sub 1-III-1 (30g, 80.33mmol)을 둥근바닥플라스크에 toluene (843ml)으로 녹인 후에, 2,3-dichloroquinoxaline (15.99g, 80.33mmol), Pd2(dba)3 (1.1g, 1.2mmol)을, P(t-Bu)3 (0.81g, 4.02mmol)을, NaOt-Bu (11.58g, 120.49mmol)을 을 첨가하고 100℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 17.65g (수율: 41%)를 얻었다.Sub 1-III-1 (30 g, 80.33 mmol) obtained in the above synthesis was dissolved in toluene (843 ml) in a round bottom flask, followed by 2,3-dichloroquinoxaline (15.99 g, 80.33 mmol), Pd 2 (dba) 3 (1.1 g, 1.2 mmol), P ( t- Bu) 3 (0.81 g, 4.02 mmol) and NaO t- Bu (11.58 g, 120.49 mmol) were added and stirred at 100 ° C. After completion of the reaction, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain 17.65 g (yield: 41%) of the product.
2. Sub 1-4 합성예2. Sub 1-4 Synthesis Example
Figure PCTKR2017004320-appb-I000071
Figure PCTKR2017004320-appb-I000071
Figure PCTKR2017004320-appb-I000072
Figure PCTKR2017004320-appb-I000072
(1) Sub 1-II-2 합성(1) Sub 1-II-2 Synthesis
상기 합성에서 얻어진 Sub 1-I-1 (41g, 99.92mmol)에 2-(3-bromo-4-nitrophenyl)-9-phenyl-9H-carbazole (44.29g, 99.92mmol), Pd(PPh3)4 (3.46g, 3.00mmol), K2CO3 (41.43g, 299.75mmol), THF (440ml), 물 (220ml)을 첨가하고 상기 Sub 1-II-1 합성법을 사용하여 생성물 47.82g (수율: 74%)을 얻었다.Sub 1-I-1 (41 g, 99.92 mmol) obtained in the above synthesis of 2- (3-bromo-4-nitrophenyl) -9-phenyl-9H-carbazole (44.29 g, 99.92 mmol), Pd (PPh 3 ) 4 (3.46 g, 3.00 mmol), K 2 CO 3 (41.43 g, 299.75 mmol), THF (440 ml), water (220 ml) were added and the product 47.82 g (yield: 74) using the Sub 1-II-1 synthesis method %) Was obtained.
(2) Sub 1-III-2 합성(2) Sub 1-III-2 Synthesis
상기 합성에서 얻어진 Sub 1-II-2 (47g, 72.67mmol)에 triphenylphosphine (57.18g, 218.01mmol), o-dichlorobenzene (145ml)을 첨가하고 상기 Sub 1-III-1 합성법을 사용하여 생성물 28.15g (수율: 63%)를 얻었다.Triphenylphosphine (57.18g, 218.01mmol) and o -dichlorobenzene (145ml) were added to Sub 1-II-2 (47g, 72.67mmol) obtained in the above synthesis, and 28.15g ( Yield: 63%).
(3) Sub 1-4 합성(3) Sub 1-4 synthesis
상기 합성에서 얻어진 Sub 1-III-2 (28g, 45.55mmol)에 2,3-dichlorobenzo[f]quinoxaline (12.48g, 50.10mmol), Pd2(dba)3 (1.25g, 1.37mmol), P(t-Bu)3 (0.74g, 3.64mmol), NaOt-Bu (13.13g, 136.64mmol), toluene (228ml)을 첨가하고 상기 Sub 1-1 합성법을 사용하여 생성물 15.07g (수율: 40%)를 얻었다.Sub 1-III-2 (28 g, 45.55 mmol) obtained in the above synthesis was prepared with 2,3-dichlorobenzo [f] quinoxaline (12.48 g, 50.10 mmol), Pd 2 (dba) 3 (1.25 g, 1.37 mmol), and P ( t- Bu) 3 (0.74 g, 3.64 mmol), NaO t -Bu (13.13 g, 136.64 mmol), toluene (228 ml) were added and the product 15.07 g (yield: 40%) was obtained using the Sub 1-1 synthesis method. Got.
3. Sub 1-10 합성예3. Synthesis Example of Sub 1-10
Figure PCTKR2017004320-appb-I000073
Figure PCTKR2017004320-appb-I000073
Figure PCTKR2017004320-appb-I000074
Figure PCTKR2017004320-appb-I000074
(1) Sub 1-IV-1 합성(1) Sub 1-IV-1 Synthesis
상기 합성에서 얻어진 Sub 1-III-9 (28g, 66.11mmol)에 1,4-dibromobenzene (17.16g, 72.72mmol), Pd2(dba)3 (0.91g, 0.99mmol), P(t-Bu)3 (0.67g, 3.31mmol), NaOt-Bu (9.53g, 99.17mmol), toluene (694ml)을 첨가하고 상기 Sub 1-1 합성법을 사용하여 생성물 27.16g (수율: 71%)를 얻었다.Sub 1-III-9 (28 g, 66.11 mmol) obtained in the above synthesis was subjected to 1,4-dibromobenzene (17.16 g, 72.72 mmol), Pd 2 (dba) 3 (0.91 g, 0.99 mmol), P ( t -Bu) 3 (0.67 g, 3.31 mmol), NaO t -Bu (9.53 g, 99.17 mmol) and toluene (694 ml) were added to give 27.16 g (yield: 71%) of the product using the Sub 1-1 synthesis method.
(2) Sub 1-V-1 합성(2) Sub 1-V-1 synthesis
상기 합성에서 얻어진 Sub 1-IV-1 (27.16g, 46.95mmol)을 둥근바닥플라스크에 DMF (235ml)로 녹인 후에, Bis(pinacolato)diboron (13.11g, 51.64mmol), Pd(dppf)Cl2 (1.03g, 1.41mmol), KOAc (13.82g, 140.84mmol)를 첨가하고 120℃에서 교반하였다. 반응이 완료되면 증류를 통해 DMF를 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 22.03g (수율: 75%)를 얻었다.Sub 1-IV-1 (27.16 g, 46.95 mmol) obtained in the above synthesis was dissolved in DMF (235 ml) in a round bottom flask, followed by Bis (pinacolato) diboron (13.11 g, 51.64 mmol), Pd (dppf) Cl 2 (1.03g, 1.41mmol), KOAc (13.82 g, 140.84 mmol) was added and stirred at 120 ° C. After the reaction was completed, DMF was removed by distillation and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 , concentrated and the resulting compound was silicagel column and recrystallized to give 22.03g (yield: 75%) of the product.
(3) Sub 1-10 합성(3) Sub 1-10 synthesis
상기 합성에서 얻어진 Sub 1-V-1 (22.03g, 35.21mmol)에 2,3-dichlorobenzo[4,5]thieno[2,3-b]pyrazine (8.98g, 35.21mmol), Pd(PPh3)4 (0.61g, 0.53mmol), K2CO3 (7.30g, 52.82mmol), THF (155ml), 물 (77.47ml)을 첨가하고 상기 Sub 1-II-1 합성법을 사용하여 생성물 9.61g (수율: 38%)을 얻었다.2,3-dichlorobenzo [4,5] thieno [2,3-b] pyrazine (8.98g, 35.21mmol), Pd (PPh 3 ) in Sub 1-V-1 (22.03g, 35.21mmol) obtained in the above synthesis 4 (0.61 g, 0.53 mmol), K 2 CO 3 (7.30 g, 52.82 mmol), THF (155 ml), water (77.47 ml) were added and 9.61 g (yield) of the product using the above Sub 1-II-1 synthesis. : 38%).
4. Sub 1-24 합성예4. Sub 1-24 Synthesis Example
Figure PCTKR2017004320-appb-I000075
Figure PCTKR2017004320-appb-I000075
Figure PCTKR2017004320-appb-I000076
Figure PCTKR2017004320-appb-I000076
Figure PCTKR2017004320-appb-I000077
Figure PCTKR2017004320-appb-I000077
1) S-I-7 합성1) S-I-7 Synthesis
(4-bromo-6-(dibenzo[b,d]furan-2-yl)naphthalen-1-yl)boronic acid (100g, 239.77mmol), THF (1055ml), 2-iodonaphthalen-1-ol (64.75g, 239.77mmol), Pd(PPh3)4 (4.16g, 3.60mmol), NaOH (14.39g, 359.65mmol), 물 (527ml)을 상기 S-I-1의 합성방법을 사용하여 생성물 86.51g (수율: 70%)을 얻었다.(4-bromo-6- (dibenzo [b, d] furan-2-yl) naphthalen-1-yl) boronic acid (100g, 239.77mmol), THF (1055ml), 2-iodonaphthalen-1-ol (64.75g , 239.77 mmol), Pd (PPh 3 ) 4 (4.16 g, 3.60 mmol), NaOH (14.39 g, 359.65 mmol), water (527 ml) were obtained using the synthesis method of the above SI-1 86.51 g (yield: 70 %) Was obtained.
2) M-I-7 합성2) M-I-7 Synthesis
출발물질인 S-I-7 (86g, 166.86mmol)를 둥근바닥플라스크에 Pd(OAc)2 (3.75g, 16.69mmol), 3-nitropyridine (2.07g, 16.69mmol)과 함께 넣고 C6F6 (250ml), DMI (167ml)로 녹인 후, tert-butyl peroxybenzoate (64.82g, 333.71mmol)를 첨가하고 90℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 62.53g (수율: 73%)를 얻었다.Starting material SI-7 (86g, 166.86mmol) was added to Pd (OAc) 2 (3.75g, 16.69mmol) and 3-nitropyridine (2.07g, 16.69mmol) in a round bottom flask with C 6 F 6 (250ml) After dissolving with DMI (167ml), tert- butyl peroxybenzoate (64.82g, 333.71mmol) was added and stirred at 90 ° C. After the reaction was completed, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to give 62.53g (yield: 73%) of the product.
3) Sub 1-I-3 합성3) Sub 1-I-3 Synthesis
상기 합성에서 얻어진 M-I-7 (62.50g, 121.74mmol), DMF (609ml), Bis(pinacolato)diboron (34.01g, 133.91mmol), Pd(dppf)Cl2 (2.67g, 3.65mmol), KOAc (35.84g, 365.22mmol)를 상기 Sub 1-V-1 합성방법을 사용하여 생성물 51.86g (수율: 76%)를 얻었다.MI-7 (62.50 g, 121.74 mmol), DMF (609 mL), Bis (pinacolato) diboron (34.01 g, 133.91 mmol), Pd (dppf) Cl 2 obtained in the above synthesis (2.67g, 3.65mmol), KOAc (35.84 g, 365.22 mmol) was obtained using 51.86 g (yield: 76%) of the product using the Sub 1-V-1 synthesis method.
4) Sub 1-II-3 합성4) Sub 1-II-3 Synthesis
상기 합성에서 얻어진 Sub 1-I-3 (51.8g, 92.42mmol)에 1-bromo-2-nitrobenzene (18.67g, 92.42mmol), Pd(PPh3)4 (3.2g, 2.77mmol), K2CO3 (38.32g, 277.27mmol), THF (407ml), 물 (203ml)을 첨가하고 상기 Sub 1-II-1 합성법을 사용하여 생성물 43.13g (수율: 84%)을 얻었다.Sub 1-I-3 (51.8g, 92.42mmol) obtained in the above synthesis was subjected to 1-bromo-2-nitrobenzene (18.67g, 92.42mmol), Pd (PPh 3 ) 4 (3.2g, 2.77mmol), K 2 CO 3 (38.32 g, 277.27 mmol), THF (407 ml), water (203 ml) were added and 43.13 g (yield: 84%) of product was obtained using the Sub 1-II-1 synthesis method.
5) Sub 1-III-3 합성5) Sub 1-III-3 Synthesis
상기 합성에서 얻어진 Sub 1-II-3 (43g, 77.4mmol)에 triphenylphosphine (60.9g, 232.19mmol), o-dichlorobenzene (155ml)을 첨가하고 상기 Sub 1-III-1 합성법을 사용하여 생성물 31.61g (수율: 78%)를 얻었다.Triphenylphosphine (60.9g, 232.19mmol) and o- dichlorobenzene (155ml) were added to Sub 1-II-3 (43g, 77.4mmol) obtained in the synthesis, and the product 31.61g ( Yield: 78%).
6) Sub 1-24 합성6) Sub 1-24 Synthesis
상기 합성에서 얻어진 Sub 1-III-3 (31.61g, 60.37mmol)에 2,3-dichlorobenzofuro[2,3-b]pyrazine (15.88g, 66.41mmol), Pd2(dba)3 (1.66g, 1.81mmol), P(t-Bu)3 (0.98g, 4.83mmol), NaOt-Bu (17.41g, 181.11mmol), toluene (302ml)을 첨가하고 상기 Sub 1-1 합성법을 사용하여 생성물 18.41g (수율: 42%)를 얻었다.Sub 1-III-3 (31.61g, 60.37mmol) obtained from the above synthesis in 2,3-dichlorobenzofuro [2,3-b] pyrazine (15.88g, 66.41mmol), Pd 2 (dba) 3 (1.66g, 1.81 mmol), P ( t -Bu) 3 (0.98 g, 4.83 mmol), NaO t -Bu (17.41 g, 181.11 mmol), toluene (302 ml) were added and the product 18.41 g ( Yield: 42%).
5. Sub 1-41 합성예5. Sub 1-41 Synthesis Example
Figure PCTKR2017004320-appb-I000078
Figure PCTKR2017004320-appb-I000078
Figure PCTKR2017004320-appb-I000079
Figure PCTKR2017004320-appb-I000079
Figure PCTKR2017004320-appb-I000080
Figure PCTKR2017004320-appb-I000080
1) Sub 1-I-41) Sub 1-I-4
상기 합성에서 얻어진 M-I-2 (105g, 289.04mmol), DMF (1445ml), Bis(pinacolato)diboron (80.74g, 317.95mmol), Pd(dppf)Cl2 (6.34g, 8.67mmol), KOAc (85.10g, 867.12mmol)를 상기 Sub 1-V-1 합성방법을 사용하여 생성물 93.70g (수율: 79%)를 얻었다.MI-2 (105g, 289.04mmol), DMF (1445ml), Bis (pinacolato) diboron (80.74g, 317.95mmol), Pd (dppf) Cl 2 obtained in the above synthesis (6.34g, 8.67mmol), KOAc (85.10 g, 867.12 mmol) was obtained using the Sub 1-V-1 synthesis method to obtain 93.70 g (yield: 79%) of the product.
2) Sub 1-II-4 합성2) Sub 1-II-4 Synthesis
상기 합성에서 얻어진 M-I-4 (93g, 226.64mmol)에 1-bromo-2-nitrobenzene (45.78g, 226.64mmol), Pd(PPh3)4 (7.86g, 6.80mmol), K2CO3 (93.97g, 679.92mmol), THF (997ml), 물 (498ml)을 첨가하고 상기 Sub 1-II-1 합성법을 사용하여 생성물 76.27g (수율: 83%)을 얻었다.MI-4 (93g, 226.64mmol) obtained in the above synthesis was prepared with 1-bromo-2-nitrobenzene (45.78g, 226.64mmol), Pd (PPh 3 ) 4 (7.86g, 6.80mmol), K 2 CO 3 (93.97g , 679.92 mmol), THF (997 ml), water (498 ml) were added and 76.27 g (yield: 83%) of product was obtained using the Sub 1-II-1 synthesis method.
3) Sub 1-III-4 합성3) Sub 1-III-4 Synthesis
상기 합성에서 얻어진 Sub 1-II-4 (76g, 187.44mmol)에 triphenylphosphine (147.49g, 562.31mmol), o-dichlorobenzene (375ml)을 첨가하고 상기 Sub 1-III-1 합성법을 사용하여 생성물 53.20g (수율: 76%)를 얻었다.Triphenylphosphine (147.49g, 562.31mmol) and o- dichlorobenzene (375ml) were added to Sub 1-II-4 (76g, 187.44mmol) obtained in the above synthesis, and the product 53.20g ( Yield: 76%).
4) Sub 1-IV-2 합성4) Sub 1-IV-2 Synthesis
상기 합성에서 얻어진 Sub 1-III-4 (53g, 141.91mmol)에 1,3-dibromodibenzo[b,d]thiophene (48.54g, 141.91mmol), Pd2(dba)3 (1.95g, 2.13mmol), P(t-Bu)3 (1.44g, 7.10mmol), NaOt-Bu (20.46g, 212.87mmol), toluene (1490ml)을 첨가하고 상기 Sub 1-1 합성법을 사용하여 생성물 32.42g (수율: 36%)를 얻었다.Sub 1-III-4 (53g, 141.91mmol) obtained in the above synthesis with 1,3-dibromodibenzo [b, d] thiophene (48.54g, 141.91mmol), Pd 2 (dba) 3 (1.95g, 2.13mmol), P ( t -Bu) 3 (1.44g, 7.10mmol), NaO t -Bu (20.46g, 212.87mmol), toluene (1490ml) were added and 32.42g product using the Sub 1-1 synthesis method (yield: 36 %) Was obtained.
5) Sub 1-V-2 합성5) Sub 1-V-2 Synthesis
상기 합성에서 얻어진 Sub 1-IV-2 (32g, 50.42mmol), DMF (252ml), Bis(pinacolato)diboron (14.09g, 55.47mmol), Pd(dppf)Cl2 (1.11g, 1.51mmol), KOAc (14.85g, 151.27mmol)를 상기 Sub 1-V-1 합성방법을 사용하여 생성물 25.09g (수율: 73%)를 얻었다.Sub 1-IV-2 (32 g, 50.42 mmol), DMF (252 ml), Bis (pinacolato) diboron (14.09 g, 55.47 mmol), Pd (dppf) Cl 2 obtained in the above synthesis (1.11g, 1.51mmol), KOAc (14.85 g, 151.27 mmol) was obtained 25.09 g (yield: 73%) of the product using the Sub 1-V-1 synthesis method.
6) Sub 1-41 합성6) Sub 1-41 Synthesis
상기 합성에서 얻어진 Sub 1-V-2 (25g, 36.67mmol)에 2,3-dichlorobenzofuro[2,3-b]pyrazine (8.77g, 36.67mmol), Pd(PPh3)4 (0.64g, 0.55mmol), K2CO3 (7.60g, 55.01mmol), THF (161ml), 물 (80ml)을 첨가하고 상기 Sub 1-II-1 합성법을 사용하여 생성물 11.40g (수율: 41%)을 얻었다.2,3-dichlorobenzofuro [2,3-b] pyrazine (8.77g, 36.67mmol), Pd (PPh 3 ) 4 (0.64g, 0.55mmol) in Sub 1-V-2 (25g, 36.67mmol) obtained in the above synthesis ), K 2 CO 3 (7.60 g, 55.01 mmol), THF (161 ml), water (80 ml) were added and the product 11.40 g (yield: 41%) was obtained using the Sub 1-II-1 synthesis method.
6. Sub 1-18 합성예6. Sub 1-18 Synthesis Example
Figure PCTKR2017004320-appb-I000081
Figure PCTKR2017004320-appb-I000081
Figure PCTKR2017004320-appb-I000082
Figure PCTKR2017004320-appb-I000082
1) Sub 1-I-51) Sub 1-I-5
상기 합성에서 얻어진 M-I-5 (19g, 54.72mmol), DMF (274ml), Bis(pinacolato)diboron (15.29g, 60.19mmol), Pd(dppf)Cl2 (1.20g, 1.64mmol), KOAc (16.11g, 164.17mmol)를 상기 Sub 1-V-1 합성방법을 사용하여 생성물 17.91g (수율: 83%)를 얻었다.MI-5 (19 g, 54.72 mmol), DMF (274 ml), Bis (pinacolato) diboron (15.29 g, 60.19 mmol), Pd (dppf) Cl 2 obtained in the above synthesis (1.20g, 1.64mmol), KOAc (16.11 g, 164.17 mmol) was obtained using the Sub 1-V-1 synthesis method to obtain 17.91 g (yield: 83%) of product.
2) Sub 1-II-5 합성2) Sub 1-II-5 Synthesis
상기 합성에서 얻어진 Sub 1-I-5 (17g, 43.12mmol)에 1-bromo-2-nitrobenzene (8.71g, 43.12mmol), Pd(PPh3)4 (1.49g, 1.29mmol), K2CO3 (17.88g, 129.35mmol), THF (189ml), 물 (95ml)을 첨가하고 상기 Sub 1-II-1 합성법을 사용하여 생성물 14.61g (수율: 87%)을 얻었다.Sub 1-I-5 (17g, 43.12mmol) obtained in the above synthesis was subjected to 1-bromo-2-nitrobenzene (8.71g, 43.12mmol), Pd (PPh 3 ) 4 (1.49g, 1.29mmol), K 2 CO 3 (17.88 g, 129.35 mmol), THF (189 ml), water (95 ml) were added and 14.61 g (yield: 87%) of the product was obtained using the Sub 1-II-1 synthesis method.
3) Sub 1-III-5 합성3) Sub 1-III-5 Synthesis
상기 합성에서 얻어진 Sub 1-II-5 (14.5g, 37.24mmol)에 triphenylphosphine (29.30g, 111.71mmol), o-dichlorobenzene (74ml)을 첨가하고 상기 Sub 1-III-1 합성법을 사용하여 생성물 10.65g (수율: 80%)를 얻었다.To the Sub 1-II-5 (14.5g, 37.24mmol) obtained in the above synthesis, triphenylphosphine (29.30g, 111.71mmol) and o- dichlorobenzene (74ml) were added and the product 10.65g using the Sub 1-III-1 synthesis method. (Yield 80%) was obtained.
4) Sub 1-18 합성4) Sub 1-18 Synthesis
상기 합성에서 얻어진 Sub 1-III-5 (10.5g, 29.38mmol)에 2,3-dichloroquinoxaline (5.85g, 29.38mmol), Pd2(dba)3 (0.40g, 0.44mmol), P(t-Bu)3 (0.30g, 1.47mmol), NaOt-Bu (4.23g, 44.07mmol), toluene (308ml)을 첨가하고 상기 Sub 1-1 합성법을 사용하여 생성물 11g (수율: 72%)를 얻었다.Sub 1-III-5 (10.5g, 29.38mmol) obtained in the above synthesis, 2,3-dichloroquinoxaline (5.85g, 29.38mmol), Pd 2 (dba) 3 (0.40g, 0.44mmol), P ( t -Bu ) 3 (0.30 g, 1.47 mmol), NaO t -Bu (4.23 g, 44.07 mmol) and toluene (308 ml) were added and the product 11 g (yield: 72%) was obtained using the Sub 1-1 synthesis method.
7. Sub 1-44 합성예7.Sub 1-44 Synthesis Example
Figure PCTKR2017004320-appb-I000083
Figure PCTKR2017004320-appb-I000083
Figure PCTKR2017004320-appb-I000084
Figure PCTKR2017004320-appb-I000084
Figure PCTKR2017004320-appb-I000085
Figure PCTKR2017004320-appb-I000085
1) S-I-8 합성1) S-I-8 Synthesis
(4-chloronaphthalen-1-yl)boronic acid (31.07g, 150.5mmol), THF (662ml), 3-bromo-6-(dibenzo[b,d]thiophen-3-yl)naphthalen-2-ol (61g, 150.5mmol), Pd(PPh3)4 (2.61g, 2.26mmol), NaOH (9.03g, 225.75mmol), 물 (331ml)을 상기 S-I-1의 합성방법을 사용하여 생성물 51.31g (수율: 70%)을 얻었다.(4-chloronaphthalen-1-yl) boronic acid (31.07g, 150.5mmol), THF (662ml), 3-bromo-6- (dibenzo [b, d] thiophen-3-yl) naphthalen-2-ol (61g , 150.5 mmol), Pd (PPh 3 ) 4 (2.61 g, 2.26 mmol), NaOH (9.03 g, 225.75 mmol), water (331 ml) were obtained using the synthesis method of SI-1 above. 51.31 g (yield: 70 %) Was obtained.
2) M-I-8 합성2) M-I-8 Synthesis
S-I-8 (51g, 104.72mmol), Pd(OAc)2 (2.35g, 10.47mmol), 3-nitropyridine (1.30g, 10.47mmol)과 함께 넣고 C6F6 (157.1ml), DMI (104ml)로 녹인 후, tert-butyl peroxybenzoate (40.68g, 209.44mmol)를 상기 M-I-8의 합성방법을 사용하여 생성물 36.57g (수율: 72%)를 얻었다.Add with SI-8 (51g, 104.72mmol), Pd (OAc) 2 (2.35g, 10.47mmol), 3-nitropyridine (1.30g, 10.47mmol) and with C 6 F 6 (157.1ml), DMI (104ml) After dissolving, tert- butyl peroxybenzoate (40.68 g, 209.44 mmol) was obtained by 36.57 g (yield: 72%) of the product using the synthesis method of MI-8.
3) Sub 1-I-63) Sub 1-I-6
상기 합성에서 얻어진 M-I-8 (36g, 74.23mmol), DMF (371ml), Bis(pinacolato)diboron (20.73g, 81.65mmol), Pd(dppf)Cl2 (1.63g, 2.23mmol), KOAc (21.85g, 222.68mmol)를 상기 Sub 1-V-1 합성방법을 사용하여 생성물 34.23g (수율: 80%)를 얻었다.MI-8 (36 g, 74.23 mmol), DMF (371 ml), Bis (pinacolato) diboron (20.73 g, 81.65 mmol), Pd (dppf) Cl 2 obtained in the above synthesis (1.63g, 2.23mmol), KOAc (21.85 g, 222.68 mmol) was obtained using the Sub 1-V-1 synthesis method to obtain 34.23 g (yield: 80%) of the product.
4) Sub 1-II-6 합성4) Sub 1-II-6 Synthesis
상기 합성에서 얻어진 Sub 1-I-6 (34g, 58.97mmol)에 1-bromo-2-nitrobenzene (11.91g, 58.97mmol), Pd(PPh3)4 (2.04g, 1.77mmol), K2CO3 (24.45g, 176.92mmol), THF (259ml), 물 (129ml)을 첨가하고 상기 Sub 1-II-1 합성법을 사용하여 생성물 27.64g (수율: 82%)을 얻었다.Sub 1-I-6 (34g, 58.97mmol) obtained in the above synthesis was subjected to 1-bromo-2-nitrobenzene (11.91g, 58.97mmol), Pd (PPh 3 ) 4 (2.04g, 1.77mmol), K 2 CO 3 (24.45 g, 176.92 mmol), THF (259 ml), water (129 ml) were added and 27.64 g (yield: 82%) of product was obtained using the Sub 1-II-1 synthesis method.
5) Sub 1-III-6 합성5) Sub 1-III-6 Synthesis
상기 합성에서 얻어진 Sub 1-II-6 (27.5g, 48.11mmol)에 triphenylphosphine (37.85g, 144.32mmol), o-dichlorobenzene (96ml)을 첨가하고 상기 Sub 1-III-1 합성법을 사용하여 생성물 20.25g (수율: 78%)를 얻었다.Triphenylphosphine (37.85g, 144.32mmol) and o- dichlorobenzene (96ml) were added to Sub 1-II-6 (27.5g, 48.11mmol) obtained in the above synthesis, and 20.25g of the product was obtained using the Sub 1-III-1 synthesis method. (Yield 78%) was obtained.
6) Sub 1-44 합성6) Sub 1-44 Synthesis
상기 합성에서 얻어진 Sub 1-III-6 (20g, 37.06mmol)에 2,3-dichlorobenzo[f]quinoxaline (9.23g, 37.06mmol), Pd2(dba)3 (0.51g, 0.56mmol), P(t-Bu)3 (0.37g, 1.85mmol), NaOt-Bu (5.34g, 55.59mmol), toluene (389ml)을 첨가하고 상기 Sub 1-1 합성법을 사용하여 생성물 11.15g (수율: 40%)를 얻었다.2,3-dichlorobenzo [f] quinoxaline (9.23g, 37.06mmol), Pd 2 (dba) 3 (0.51g, 0.56mmol), and P (Sub-1-III-6 (20g, 37.06mmol) obtained in the above synthesis t- Bu) 3 (0.37 g, 1.85 mmol), NaO t -Bu (5.34 g, 55.59 mmol), toluene (389 ml) were added and the product 11.15 g (yield: 40%) was obtained using the Sub 1-1 synthesis method. Got.
8. Sub 1-52 합성예8. Sub 1-52 Synthesis Example
Figure PCTKR2017004320-appb-I000086
Figure PCTKR2017004320-appb-I000086
Figure PCTKR2017004320-appb-I000087
Figure PCTKR2017004320-appb-I000087
1) Sub 1-I-71) Sub 1-I-7
상기 합성에서 얻어진 M-I-3 (22g, 60.56mmol), DMF (302ml), Bis(pinacolato)diboron (16.92g, 66.62mmol), Pd(dppf)Cl2 (1.33g, 1.82mmol), KOAc (17.83g, 181.68mmol)를 상기 Sub 1-V-1 합성방법을 사용하여 생성물 20.38g (수율: 82%)를 얻었다.MI-3 (22g, 60.56mmol), DMF (302ml), Bis (pinacolato) diboron (16.92g, 66.62mmol), Pd (dppf) Cl 2 obtained in the above synthesis (1.33g, 1.82mmol), KOAc (17.83 g, 181.68 mmol) was obtained using 20.38 g (yield: 82%) of the product using the Sub 1-V-1 synthesis method.
2) Sub 1-II-7 합성2) Sub 1-II-7 Synthesis
상기 합성에서 얻어진 Sub 1-I-7 (19.5g, 47.52mmol)에 1-bromo-2-nitrobenzene (9.6g, 47.52mmol), Pd(PPh3)4 (1.65g, 1.43mmol), K2CO3 (19.70g, 142.56mmol), THF (209ml), 물 (105ml)을 첨가하고 상기 Sub 1-II-1 합성법을 사용하여 생성물 16.38g (수율: 85%)을 얻었다.Sub 1-I-7 (19.5 g, 47.52 mmol) obtained in the above synthesis was prepared with 1-bromo-2-nitrobenzene (9.6 g, 47.52 mmol), Pd (PPh 3 ) 4 (1.65 g, 1.43 mmol), and K 2 CO. 3 (19.70 g, 142.56 mmol), THF (209 ml), water (105 ml) were added and 16.38 g (yield: 85%) of product was obtained using the Sub 1-II-1 synthesis method.
3) Sub 1-III-7 합성3) Sub 1-III-7 Synthesis
상기 합성에서 얻어진 Sub 1-II-7 (16g, 39.46mmol)에 triphenylphosphine (31.05g, 118.38mmol), o-dichlorobenzene (79ml)을 첨가하고 상기 Sub 1-III-1 합성법을 사용하여 생성물 12.08g (수율: 82%)를 얻었다.Triphenylphosphine (31.05g, 118.38mmol) and o- dichlorobenzene (79ml) were added to Sub 1-II-7 (16g, 39.46mmol) obtained in the above synthesis, and the product was obtained using 12.08g ( Yield: 82%).
4) Sub 1-52 합성4) Sub 1-52 Synthesis
상기 합성에서 얻어진 Sub 1-III-7 (12g, 32.13mmol)에 2,3-dichloroquinoxaline (6.40g, 32.13mmol), Pd2(dba)3 (0.44g, 0.48mmol), P(t-Bu)3 (0.33g, 1.61mmol), NaOt-Bu (4.63g, 48.20mmol), toluene (337ml)을 첨가하고 상기 Sub 1-1 합성법을 사용하여 생성물 11.71g (수율: 68%)를 얻었다.Sub 1-III-7 (12g, 32.13mmol) obtained in the above synthesis, 2,3-dichloroquinoxaline (6.40g, 32.13mmol), Pd 2 (dba) 3 (0.44g, 0.48mmol), P ( t -Bu) 3 (0.33 g, 1.61 mmol), NaO t -Bu (4.63 g, 48.20 mmol) and toluene (337 ml) were added and the product 11.71 g (yield: 68%) was obtained using the Sub 1-1 synthesis method.
9. Sub 1-64 합성예9.Sub 1-64 Synthesis Example
Figure PCTKR2017004320-appb-I000088
Figure PCTKR2017004320-appb-I000088
Figure PCTKR2017004320-appb-I000089
Figure PCTKR2017004320-appb-I000089
1) Sub 1-IV-3 합성1) Sub 1-IV-3 Synthesis
상기 합성에서 얻어진 Sub 1-III-7 (39g, 104.43mmol)에 3-bromo-7-iododibenzo[b,d]furan (38.95g, 104.43mmol), Pd2(dba)3 (1.43g, 1.57mmol), P(t-Bu)3 (1.06g, 5.22mmol), NaOt-Bu (15.05g, 156.64mmol), toluene (1096ml)을 첨가하고 상기 Sub 1-1 합성법을 사용하여 생성물 38.76g (수율: 60%)를 얻었다.Sub 1-III-7 (39g, 104.43mmol) obtained in the above synthesis of 3-bromo-7-iododibenzo [b, d] furan (38.95g, 104.43mmol), Pd 2 (dba) 3 (1.43g, 1.57mmol) ), P ( t -Bu) 3 (1.06 g, 5.22 mmol), NaO t -Bu (15.05 g, 156.64 mmol), toluene (1096 ml) were added and 38.76 g (yield) was obtained using the Sub 1-1 synthesis method. : 60%).
2) Sub 1-V-3 합성2) Sub 1-V-3 Synthesis
상기 합성에서 얻어진 Sub 1-IV-3 (38.5g, 62.24mmol), DMF (311ml), Bis(pinacolato)diboron (17.39g, 68.47mmol), Pd(dppf)Cl2 (1.37g, 1.87mmol), KOAc (18.33g, 186.73mmol)를 상기 Sub 1-V-1 합성방법을 사용하여 생성물 31.49g (수율: 76%)를 얻었다.Sub 1-IV-3 (38.5g, 62.24mmol), DMF (311ml), Bis (pinacolato) diboron (17.39g, 68.47mmol), Pd (dppf) Cl 2 obtained in the above synthesis (1.37g, 1.87mmol), KOAc (18.33 g, 186.73 mmol) was obtained 31.49 g (yield: 76%) of the product using the Sub 1-V-1 synthesis method.
3) Sub 1-64 합성3) Sub 1-64 Synthesis
상기 합성에서 얻어진 Sub 1-V-3 (31g, 46.57mmol)에 2,3-dichlorobenzofuro[2,3-b]pyrazine (11.13g, 46.57mmol), Pd(PPh3)4 (0.81g, 0.70mmol), K2CO3 (9.66g, 69.86mmol), THF (205ml), 물 (102ml)을 첨가하고 상기 Sub 1-II-1 합성법을 사용하여 생성물 11.06g (수율: 32%)을 얻었다.Sub 1-V-3 (31g, 46.57mmol) obtained in the above synthesis in 2,3-dichlorobenzofuro [2,3-b] pyrazine (11.13g, 46.57mmol), Pd (PPh 3 ) 4 (0.81g, 0.70mmol) ), K 2 CO 3 (9.66 g, 69.86 mmol), THF (205 ml), water (102 ml) were added and the product 11.06 g (yield: 32%) was obtained using the Sub 1-II-1 synthesis method.
10. Sub 1- 합성예10.Sub 1- Synthesis Example
Figure PCTKR2017004320-appb-I000090
Figure PCTKR2017004320-appb-I000090
Figure PCTKR2017004320-appb-I000091
Figure PCTKR2017004320-appb-I000091
1) Sub 1-I-81) Sub 1-I-8
상기 합성에서 얻어진 M-I-6 (20g, 57.60mmol), DMF (288ml), Bis(pinacolato)diboron (16.09g, 63.36mmol), Pd(dppf)Cl2 (1.26g, 1.73mmol), KOAc (16.96g, 172.81mmol)를 상기 Sub 1-V-1 합성방법을 사용하여 생성물 17.94g (수율: 79%)를 얻었다.MI-6 (20g, 57.60mmol), DMF (288ml), Bis (pinacolato) diboron (16.09g, 63.36mmol), Pd (dppf) Cl 2 obtained in the above synthesis (1.26g, 1.73mmol), KOAc (16.96 g, 172.81 mmol) was obtained using the Sub 1-V-1 synthesis method to obtain 17.94 g (yield: 79%) of the product.
2) Sub 1-II-8 합성2) Sub 1-II-8 Synthesis
상기 합성에서 얻어진 Sub 1-I-8 (17g, 43.12mmol)에 3-bromo-4-nitro-1,1'-biphenyl (11.99g, 43.12mmol), Pd(PPh3)4 (1.49g, 1.29mmol), K2CO3 (17.88g, 129.35mmol), THF (189ml), 물 (94ml)을 첨가하고 상기 Sub 1-II-1 합성법을 사용하여 생성물 15.45g (수율: 77%)을 얻었다.Sub 1-I-8 (17g, 43.12mmol) obtained in the above synthesis 3-bromo-4-nitro-1,1'-biphenyl (11.99g, 43.12mmol), Pd (PPh 3 ) 4 (1.49g, 1.29 mmol), K 2 CO 3 (17.88 g, 129.35 mmol), THF (189 ml), water (94 ml) were added to give 15.45 g (yield: 77%) of the product using the Sub 1-II-1 synthesis.
2) Sub 1-III-8 합성2) Sub 1-III-8 Synthesis
상기 합성에서 얻어진 Sub 1-II-8 (15g, 32.22mmol)에 triphenylphosphine (25.36g, 96.67mmol), o-dichlorobenzene (64ml)을 첨가하고 상기 Sub 1-III-1 합성법을 사용하여 생성물 11.73g (수율: 84%)를 얻었다.To the Sub 1-II-8 (15g, 32.22mmol) obtained in the above synthesis, triphenylphosphine (25.36g, 96.67mmol) and o- dichlorobenzene (64ml) were added and the product 11.73g ( Yield: 84%).
3) Sub 1-70 합성3) Sub 1-70 Synthesis
상기 합성에서 얻어진 Sub 1-III-8 (11g, 25.37mmol)에 2,3-dichlorodibenzo[f,h]quinoxaline (7.59g, 25.37mmol), Pd2(dba)3 (0.35g, 0.38mmol), P(t-Bu)3 (0.26g, 1.27mmol), NaOt-Bu (3.66g, 38.06mmol), toluene (266ml)을 첨가하고 상기 Sub 1-1 합성법을 사용하여 생성물 11.13g (수율: 63%)를 얻었다.2,3-dichlorodibenzo [f, h] quinoxaline (7.59 g, 25.37 mmol), Pd 2 (dba) 3 (0.35 g, 0.38 mmol), in Sub 1-III-8 (11 g, 25.37 mmol) obtained in the above synthesis; P ( t- Bu) 3 (0.26 g, 1.27 mmol), NaO t -Bu (3.66 g, 38.06 mmol), toluene (266 ml) were added and the product 11.13 g (yield: 63) was obtained using the Sub 1-1 synthesis method. %) Was obtained.
Sub 1의 예시Example of Sub 1
Figure PCTKR2017004320-appb-I000092
Figure PCTKR2017004320-appb-I000092
Figure PCTKR2017004320-appb-I000093
Figure PCTKR2017004320-appb-I000093
Figure PCTKR2017004320-appb-I000094
Figure PCTKR2017004320-appb-I000094
Figure PCTKR2017004320-appb-I000095
Figure PCTKR2017004320-appb-I000095
Figure PCTKR2017004320-appb-I000096
Figure PCTKR2017004320-appb-I000096
Figure PCTKR2017004320-appb-I000097
Figure PCTKR2017004320-appb-I000097
Figure PCTKR2017004320-appb-I000098
Figure PCTKR2017004320-appb-I000098
Figure PCTKR2017004320-appb-I000099
Figure PCTKR2017004320-appb-I000099
Figure PCTKR2017004320-appb-I000100
Figure PCTKR2017004320-appb-I000100
Figure PCTKR2017004320-appb-I000101
Figure PCTKR2017004320-appb-I000101
Figure PCTKR2017004320-appb-I000102
Figure PCTKR2017004320-appb-I000102
Figure PCTKR2017004320-appb-I000103
Figure PCTKR2017004320-appb-I000103
Figure PCTKR2017004320-appb-I000104
Figure PCTKR2017004320-appb-I000104
Figure PCTKR2017004320-appb-I000105
Figure PCTKR2017004320-appb-I000105
Figure PCTKR2017004320-appb-I000106
Figure PCTKR2017004320-appb-I000106
Figure PCTKR2017004320-appb-I000107
Figure PCTKR2017004320-appb-I000107
화합물compound FD-MSFD-MS 화합물compound FD-MSFD-MS
Sub 1-1Sub 1-1 m/z=541.05(C32H16ClN3S2=542.07)m / z = 541.05 (C 32 H 16 ClN 3 S 2 = 542.07) Sub 1-4Sub 1-4 m/z=782.14(C50H27ClN4S2=783.36)m / z = 782.14 (C 50 H 27 ClN 4 S 2 = 783.36)
Sub 1-10Sub 1-10 m/z=717.11(C46H24ClN3S2=718.29)m / z = 717.11 (C 46 H 24 ClN 3 S 2 = 718.29) Sub 1-18Sub 1-18 m/z=519.11(C34H18ClN3O=519.99)m / z = 519.11 (C 34 H 18 ClN 3 O = 519.99)
Sub 1-24Sub 1-24 m/z=725.15(C48H24ClN3O3=726.19)m / z = 725.15 (C 48 H 24 ClN 3 O 3 = 726.19) Sub 1-41Sub 1-41 m/z=757.10(C48H24ClN3OS2=758.31)m / z = 757.10 (C 48 H 24 ClN 3 OS 2 = 758.31)
Sub 1-44Sub 1-44 m/z=751.15(C50H26ClN3OS=752.29)m / z = 751.15 (C 50 H 26 ClN 3 OS = 752.29) Sub 1-52Sub 1-52 m/z=535.09(C34H18ClN3S=536.05)m / z = 535.09 (C 34 H 18 ClN 3 S = 536.05)
Sub 1-64Sub 1-64 m/z=741.13(C48H24ClN3O2S=742.25)m / z = 741.13 (C 48 H 24 ClN 3 O 2 S = 742.25) Sub 1-70Sub 1-70 m/z=695.18(C48H26ClN3O=696.21)m / z = 695.18 (C 48 H 26 ClN 3 O = 696.21)
II. Sub 2의 합성II. Synthesis of Sub 2
상기 반응식 1의 Sub 2는 반응식의 반응경로에 의해 합성될 수 있으나, 이에 한정되는 것은 아니다.Sub 2 of Scheme 1 may be synthesized by the reaction path of the scheme, but is not limited thereto.
Figure PCTKR2017004320-appb-I000108
Figure PCTKR2017004320-appb-I000108
Sub 2에 속하는 구체적 화합물의 합성예는 다음과 같다.Synthesis examples of specific compounds belonging to Sub 2 are as follows.
1. Sub 2-1 합성예1.Sub 2-1 Synthesis Example
<반응식 24>Scheme 24
Figure PCTKR2017004320-appb-I000109
Figure PCTKR2017004320-appb-I000109
출발물질인 bromobenzene (29.16 g, 185.72 mmol)를 둥근바닥플라스크에 DMF (930ml)로 녹인 후에, Bis(pinacolato)diboron (51.88 g, 204.29 mmol), Pd(dppf)Cl2 (4.55 g, 5.57 mmol), KOAc (54.68 g, 557.16 mmol)를 첨가하고 90℃에서 교반하였다. 반응이 완료되면 증류를 통해 DMF를 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 31.84 g (수율: 84%)를 얻었다.After starting bromobenzene (29.16 g, 185.72 mmol) was dissolved in DMF (930 ml) in a round bottom flask, Bis (pinacolato) diboron (51.88 g, 204.29 mmol) and Pd (dppf) Cl 2 (4.55 g, 5.57 mmol) , KOAc (54.68 g, 557.16 mmol) was added and stirred at 90 ° C. After the reaction was completed, DMF was removed by distillation and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 , concentrated and the resulting compound was silicagel column and recrystallized to give 31.84 g (yield: 84%) of the product.
2. Sub 2-3 합성예2. Sub 2-3 Synthesis Example
<반응식 25>Scheme 25
Figure PCTKR2017004320-appb-I000110
Figure PCTKR2017004320-appb-I000110
출발물질인 2-bromonaphthalene (21.53 g, 103.97 mmol)에 Bis(pinacolato)diboron (29.04 g, 114.37 mmol), Pd(dppf)Cl2 (2.55 g, 3.12 mmol), KOAc (30.61 g, 311.92 mmol), DMF (520ml)를 첨가하고 상기 Sub 2-1 합성법을 사용하여 생성물 21.14 g (수율: 80%)를 얻었다.Bis (pinacolato) diboron (29.04 g, 114.37 mmol) and Pd (dppf) Cl 2 in 2-bromonaphthalene (21.53 g, 103.97 mmol) as starting materials (2.55 g, 3.12 mmol), KOAc (30.61 g, 311.92 mmol), DMF (520 ml) were added to give 21.14 g (yield: 80%) of the product using the Sub 2-1 synthesis method.
3. Sub 2-5 합성예3. Synthesis Example of Sub 2-5
<반응식 26>Scheme 26
Figure PCTKR2017004320-appb-I000111
Figure PCTKR2017004320-appb-I000111
출발물질인 3-bromo-1,1'-biphenyl (16.24 g, 69.67 mmol)에 Bis(pinacolato)diboron (19.46 g, 76.63 mmol), Pd(dppf)Cl2 (1.71 g, 2.09 mmol), KOAc (20.51 g, 209.00 mmol), DMF (350ml)를 첨가하고 상기 Sub 2-1 합성법을 사용하여 생성물 15.81 g (수율: 81%)를 얻었다.Bis (pinacolato) diboron (19.46 g, 76.63 mmol), Pd (dppf) Cl 2 in 3-bromo-1,1'-biphenyl (16.24 g, 69.67 mmol) (1.71 g, 2.09 mmol), KOAc (20.51 g, 209.00 mmol), DMF (350 ml) were added and 15.81 g (yield: 81%) of the product was obtained using the Sub 2-1 synthesis method.
4. Sub 2-12 합성예4. Sub 2-12 Synthesis Example
<반응식 27>Scheme 27
Figure PCTKR2017004320-appb-I000112
Figure PCTKR2017004320-appb-I000112
출발물질인 1-bromobenzene-2,3,4,5,6-d5 (10.85 g, 66.96 mmol)에 Bis(pinacolato)diboron (18.70 g, 73.65 mmol), Pd(dppf)Cl2 (1.64 g, 2.01 mmol), KOAc (19.71 g, 200.88 mmol), DMF (335ml)를 첨가하고 상기 Sub 2-1 합성법을 사용하여 생성물 10.22 g (수율: 73%)를 얻었다.Bis (pinacolato) diboron (18.70 g, 73.65 mmol), Pd (dppf) Cl 2 in 1-bromobenzene-2,3,4,5,6-d5 (10.85 g, 66.96 mmol) (1.64 g, 2.01 mmol), KOAc (19.71 g, 200.88 mmol), DMF (335 ml) were added and the product 10.22 g (yield: 73%) was obtained using the Sub 2-1 synthesis method.
5. Sub 2-21 합성예5. Sub 2-21 Synthesis Example
<반응식 28>Scheme 28
Figure PCTKR2017004320-appb-I000113
Figure PCTKR2017004320-appb-I000113
출발물질인 4-bromodibenzo[b,d]thiophene (14.23 g, 54.08 mmol)에 Bis(pinacolato)diboron (15.11 g, 59.48 mmol), Pd(dppf)Cl2 (1.32 g, 1.62 mmol), KOAc (15.92 g, 162.23 mmol), DMF (270ml)를 첨가하고 상기 Sub 2-1 합성법을 사용하여 생성물 13.76 g (수율: 82%)를 얻었다.Bis (pinacolato) diboron (15.11 g, 59.48 mmol) and Pd (dppf) Cl 2 in 4-bromodibenzo [b, d] thiophene (14.23 g, 54.08 mmol) (1.32 g, 1.62 mmol), KOAc (15.92 g, 162.23 mmol), DMF (270 ml) were added and 13.76 g (yield: 82%) of product was obtained using the Sub 2-1 synthesis method.
6. Sub 2-28 합성예6.Sub 2-28 Synthesis Example
<반응식 29>Scheme 29
Figure PCTKR2017004320-appb-I000114
Figure PCTKR2017004320-appb-I000114
출발물질인 2-bromodibenzo[b,d]furan (16.35 g, 66.17 mmol)에 Bis(pinacolato)diboron (18.48 g, 72.79 mmol), Pd(dppf)Cl2 (1.62 g, 1.99 mmol), KOAc (19.48 g, 198.51 mmol), DMF (330ml)를 첨가하고 상기 Sub 2-1 합성법을 사용하여 생성물 16.74 g (수율: 86%)를 얻었다.Bis (pinacolato) diboron (18.48 g, 72.79 mmol), Pd (dppf) Cl 2 in 2-bromodibenzo [b, d] furan (16.35 g, 66.17 mmol) (1.62 g, 1.99 mmol), KOAc (19.48 g, 198.51 mmol), DMF (330 ml) were added and the product 16.74 g (yield: 86%) was obtained using the Sub 2-1 synthesis method.
7. Sub 2-32 합성예7.Sub 2-32 Synthesis Example
<반응식 30>Scheme 30
Figure PCTKR2017004320-appb-I000115
Figure PCTKR2017004320-appb-I000115
출발물질인 3-bromo-9-phenyl-9H-carbazole (12.17 g, 37.77 mmol)에 Bis(pinacolato)diboron (10.55 g, 41.55 mmol), Pd(dppf)Cl2 (0.93 g, 1.13 mmol), KOAc (11.12 g, 113.31 mmol), DMF (190ml)를 첨가하고 상기 Sub 2-1 합성법을 사용하여 생성물 10.46 g (수율: 75%)를 얻었다.Bis (pinacolato) diboron (10.55 g, 41.55 mmol), Pd (dppf) Cl 2 in 3-bromo-9-phenyl-9H-carbazole (12.17 g, 37.77 mmol) (0.93 g, 1.13 mmol), KOAc (11.12 g, 113.31 mmol), DMF (190 ml) were added and the product 10.46 g (yield: 75%) was obtained using the Sub 2-1 synthesis method.
8. Sub 2-27 합성예8. Sub 2-27 Synthesis Example
<반응식 31>Scheme 31
Figure PCTKR2017004320-appb-I000116
Figure PCTKR2017004320-appb-I000116
출발물질인 1-bromodibenzo[b,d]furan (16.78 g, 67.91 mmol)에 Bis(pinacolato)diboron (18.97 g, 74.70 mmol), Pd(dppf)Cl2 (1.66 g, 2.04 mmol), KOAc (19.99 g, 203.73 mmol), DMF (340ml)를 첨가하고 상기 Sub 2-1 합성법을 사용하여 생성물 15.98 g (수율: 80%)를 얻었다.Bis (pinacolato) diboron (18.97 g, 74.70 mmol) and Pd (dppf) Cl 2 in 1-bromodibenzo [b, d] furan (16.78 g, 67.91 mmol) (1.66 g, 2.04 mmol), KOAc (19.99 g, 203.73 mmol), DMF (340 ml) was added to give 15.98 g (yield: 80%) of the product using the Sub 2-1 synthesis method.
9. Sub 2-36 합성예9. Sub 2-36 Synthesis Example
<반응식 32>Scheme 32
Figure PCTKR2017004320-appb-I000117
Figure PCTKR2017004320-appb-I000117
출발물질인 1-bromothianthrene (13.31 g, 45.09 mmol)에 Bis(pinacolato)diboron (12.59 g, 49.60 mmol), Pd(dppf)Cl2 (1.10 g, 1.35 mmol), KOAc (13.27 g, 135.26 mmol), DMF (225ml)를 첨가하고 상기 Sub 2-1 합성법을 사용하여 생성물 10.34 g (수율: 67%)를 얻었다.Bis (pinacolato) diboron (12.59 g, 49.60 mmol), Pd (dppf) Cl 2 in 1-bromothianthrene (13.31 g, 45.09 mmol) (1.10 g, 1.35 mmol), KOAc (13.27 g, 135.26 mmol), DMF (225 ml) were added and the product 10.34 g (yield: 67%) was obtained using the Sub 2-1 synthesis method.
Sub 2에 속하는 화합물은 아래와 같은 화합물일 수 있으나, 이에 한정되는 것은 아니며, 표 2는 Sub 2에 속하는 일부 화합물의 FD-MS(Field Desorption-Mass Spectrometry) 값을 나타낸 것이다.Compounds belonging to Sub 2 may be the following compounds, but are not limited thereto, and Table 2 shows Field Desorption-Mass Spectrometry (FD-MS) values of some compounds belonging to Sub 2.
Figure PCTKR2017004320-appb-I000118
Figure PCTKR2017004320-appb-I000118
Figure PCTKR2017004320-appb-I000119
Figure PCTKR2017004320-appb-I000119
Figure PCTKR2017004320-appb-I000120
Figure PCTKR2017004320-appb-I000120
Figure PCTKR2017004320-appb-I000121
Figure PCTKR2017004320-appb-I000121
화합물compound FD-MSFD-MS 화합물compound FD-MSFD-MS
Sub 2-1Sub 2-1 m/z=204.13(C12H17BO2=204.08)m / z = 204.13 (C 12 H 17 BO 2 = 204.08) Sub 2-3Sub 2-3 m/z=254.15(C16H19BO2= 254.14)m / z = 254.15 (C 16 H 19 BO 2 = 254.14)
Sub 2-5Sub 2-5 m/z=280.16(C18H21BO2=280.17)m / z = 280.16 (C 18 H 21 BO 2 = 280.17) Sub 2-12Sub 2-12 m/z=209.16(C12H12D5BO2=209.11)m / z = 209.16 (C 12 H 12 D 5 BO 2 = 209.11)
Sub 2-21Sub 2-21 m/z=310.12(C18H19BO2S=310.22)m / z = 310.12 (C 18 H 19 BO 2 S = 310.22) Sub 2-28Sub 2-28 m/z=294.14(C18H19BO3=294.16)m / z = 294.14 (C 18 H 19 BO 3 = 294.16)
Sub 2-32Sub 2-32 m/z=369.19(C24H24BNO2=369.27)m / z = 369.19 (C 24 H 24 BNO 2 = 369.27) Sub 2-27Sub 2-27 m/z=294.14(C18H19BO3=294.16)m / z = 294.14 (C 18 H 19 BO 3 = 294.16)
Sub 2-36Sub 2-36 m/z=342.09(C18H19BO2S2=342.28)m / z = 342.09 (C 18 H 19 BO 2 S 2 = 342.28)
III. Product 합성III. Product Synthesis
Sub 1 (1 당량)을 둥근바닥플라스크에 THF로 녹인 후에, Sub 2 (1 당량), Pd(PPh3)4 (0.04 당량), NaOH (3 당량), 물을 첨가하고 70℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 화합물을 silicagel column 및 재결정하여 최종 생성물(final product)를 얻었다.Sub 1 (1 equiv) was dissolved in THF in a round bottom flask, then Sub 2 (1 equiv), Pd (PPh 3 ) 4 (0.04 equiv), NaOH (3 equiv), water were added and stirred at 70 ° C. After completion of the reaction, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain a final product.
1-1 합성예1-1 Synthesis Example
Figure PCTKR2017004320-appb-I000122
Figure PCTKR2017004320-appb-I000122
Sub 1-1 (9g, 16.79mmol)을 둥근바닥플라스크에 THF(74ml)로 녹인 후에, Sub 2-1 (3.43g, 16.79mmol), Pd(PPh3)4 (0.78g, 0.67mmol), NaOH (2.01g, 50.37mmol), 물(37ml)을 첨가하고 70℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 7.47g를 얻었다. (수율: 77%)Sub 1-1 (9g, 16.79mmol) was dissolved in THF (74ml) in a round bottom flask, then Sub 2-1 (3.43g, 16.79mmol), Pd (PPh 3 ) 4 (0.78g, 0.67mmol), NaOH (2.01 g, 50.37 mmol) and water (37 ml) were added and stirred at 70 ° C. After the reaction was completed, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was silicagel column and recrystallized to obtain the product 7.47g. (Yield 77%)
1-14 합성예1-14 Synthesis Example
Figure PCTKR2017004320-appb-I000123
Figure PCTKR2017004320-appb-I000123
Sub 1-4 (9g, 10.88mmol), THF(48ml), Sub 2-1 (2.22g, 10.88mmol), Pd(PPh3)4 (0.5g, 0.44mmol), NaOH (1.31g, 32.63mmol), 물(24ml)을 상기 1-1 합성방법을 사용하여 생성물 6.71g를 얻었다. (수율: 71%)Sub 1-4 (9g, 10.88mmol), THF (48ml), Sub 2-1 (2.22g, 10.88mmol), Pd (PPh 3 ) 4 (0.5g, 0.44mmol), NaOH (1.31g, 32.63mmol) , Water (24 ml) was obtained using 6.1 g of the product using the synthesis method 1-1 above. (Yield 71%)
1-30 합성예1-30 Synthesis Example
Figure PCTKR2017004320-appb-I000124
Figure PCTKR2017004320-appb-I000124
Sub 1-10 (11g, 15.31mmol), THF(67ml), Sub 2-18 (3.4g, 15.31mmol), Pd(PPh3)4 (0.71g, 0.61mmol), NaOH (1.84g, 45.94mmol), 물(34ml)을 상기 1-1 합성방법을 사용하여 생성물 7.51g를 얻었다. (수율: 63%)Sub 1-10 (11g, 15.31mmol), THF (67ml), Sub 2-18 (3.4g, 15.31mmol), Pd (PPh 3 ) 4 (0.71g, 0.61mmol), NaOH (1.84g, 45.94mmol) , Water (34 ml) was obtained using the synthesis method 1-1 to 7.51g of the product. (Yield 63%)
1-44 합성예1-44 Synthesis Example
Figure PCTKR2017004320-appb-I000125
Figure PCTKR2017004320-appb-I000125
Sub 1-1 (11g, 20.52mmol), THF(90ml), Sub 2-16 (4.21g, 20.52mmol), Pd(PPh3)4 (0.95g, 0.82mmol), NaOH (2.46g, 61.56mmol), 물(45ml)을 상기 1-1 합성방법을 사용하여 생성물 7.72g를 얻었다. (수율: 65%)Sub 1-1 (11g, 20.52mmol), THF (90ml), Sub 2-16 (4.21g, 20.52mmol), Pd (PPh 3 ) 4 (0.95g, 0.82mmol), NaOH (2.46g, 61.56mmol) , Water (45ml) was obtained using the synthesis method 1-1 to 7.72g. (Yield 65%)
1-45 합성예1-45 Synthesis Example
Figure PCTKR2017004320-appb-I000126
Figure PCTKR2017004320-appb-I000126
Sub 1-1 (11g, 20.52mmol), THF(90ml), Sub 2-34 (8.65g, 20.52mmol), Pd(PPh3)4 (0.95g, 0.82mmol), NaOH (2.46g, 61.56mmol), 물(45ml)을 상기 1-1 합성방법을 사용하여 생성물 9.95g를 얻었다. (수율: 61%)Sub 1-1 (11g, 20.52mmol), THF (90ml), Sub 2-34 (8.65g, 20.52mmol), Pd (PPh 3 ) 4 (0.95g, 0.82mmol), NaOH (2.46g, 61.56mmol) , Water (45ml) was obtained using the method of synthesis 1-1 to 9.95g. (Yield 61%)
2-7 합성예2-7 Synthesis Example
Figure PCTKR2017004320-appb-I000127
Figure PCTKR2017004320-appb-I000127
Sub 1-24 (11g, 15.15mmol), THF(66ml), Sub 2-20 (3.47g, 15.15mmol), Pd(PPh3)4 (0.7g, 0.61mmol), NaOH (1.82g, 45.44mmol), 물(33ml)을 상기 1-1 합성방법을 사용하여 생성물 7.69g를 얻었다. (수율: 64%)Sub 1-24 (11g, 15.15mmol), THF (66ml), Sub 2-20 (3.47g, 15.15mmol), Pd (PPh 3 ) 4 (0.7g, 0.61mmol), NaOH (1.82g, 45.44mmol) , Water (33ml) was obtained using the synthesis method 1-1 to 7.69g. (Yield 64%)
2-9 합성예2-9 Synthesis Example
Figure PCTKR2017004320-appb-I000128
Figure PCTKR2017004320-appb-I000128
Sub 1-25 (11g, 19.64mmol), THF(86ml), Sub 2-13 (5.6g, 19.64mmol), Pd(PPh3)4 (0.91g, 0.79mmol), NaOH (2.36g, 58.93mmol), 물(43ml)을 상기 1-1 합성방법을 사용하여 생성물 9.92g를 얻었다. (수율: 74%)Sub 1-25 (11 g, 19.64 mmol), THF (86 ml), Sub 2-13 (5.6 g, 19.64 mmol), Pd (PPh 3 ) 4 (0.91 g, 0.79 mmol), NaOH (2.36 g, 58.93 mmol) , Water (43 ml) was obtained using 9.1 g of the product using the synthesis method 1-1. (Yield 74%)
3-16 합성예3-16 Synthesis Example
Figure PCTKR2017004320-appb-I000129
Figure PCTKR2017004320-appb-I000129
Sub 1-29 (11g, 18.77mmol), THF(82ml), Sub 2-29 (5.54g, 18.77mmol), Pd(PPh3)4 (0.87g, 0.75mmol), NaOH (2.25g, 56.30mmol), 물(41ml)을 상기 1-1 합성방법을 사용하여 생성물 8.5g를 얻었다. (수율: 63%)Sub 1-29 (11g, 18.77mmol), THF (82ml), Sub 2-29 (5.54g, 18.77mmol), Pd (PPh 3 ) 4 (0.87g, 0.75mmol), NaOH (2.25g, 56.30mmol) , Water (41 ml) was obtained using the synthesis method 1-1 to 8.5g. (Yield 63%)
4-3 합성예4-3 Synthesis Example
Figure PCTKR2017004320-appb-I000130
Figure PCTKR2017004320-appb-I000130
Sub 1-44 (11g, 14.62mmol), THF(64ml), Sub 2-22 (4.54g, 14.62mmol), Pd(PPh3)4 (0.68g, 0.58mmol), NaOH (1.75g, 43.87mmol), 물(32ml)을 상기 1-1 합성방법을 사용하여 생성물 8.03g를 얻었다. (수율: 61%)Sub 1-44 (11 g, 14.62 mmol), THF (64 ml), Sub 2-22 (4.54 g, 14.62 mmol), Pd (PPh 3 ) 4 (0.68 g, 0.58 mmol), NaOH (1.75 g, 43.87 mmol) , Water (32 ml) was obtained using 8.01 g of the product using the synthesis method 1-1. (Yield 61%)
5-9 합성예5-9 Synthesis Example
Figure PCTKR2017004320-appb-I000131
Figure PCTKR2017004320-appb-I000131
Sub 1-52 (11g, 20.52mmol), THF(90ml), Sub 2-32 (7.58g, 20.52mmol), Pd(PPh3)4 (0.95g, 0.82mmol), NaOH (2.46g, 61.56mmol), 물(45ml)을 상기 1-1 합성방법을 사용하여 생성물 10.98g를 얻었다. (수율: 72%)Sub 1-52 (11g, 20.52mmol), THF (90ml), Sub 2-32 (7.58g, 20.52mmol), Pd (PPh 3 ) 4 (0.95g, 0.82mmol), NaOH (2.46g, 61.56mmol) , Water (45ml) was obtained by the above synthesis method 1-1 to 10.98g. (Yield 72%)
5-25 합성예5-25 Synthesis Example
Figure PCTKR2017004320-appb-I000132
Figure PCTKR2017004320-appb-I000132
Sub 1-57 (11g, 14.32mmol), THF(63ml), Sub 2-1 (2.92g, 14.32mmol), Pd(PPh3)4 (0.66g, 0.57mmol), NaOH (1.72g, 42.95mmol), 물(31ml)을 상기 1-1 합성방법을 사용하여 생성물 8.35g를 얻었다. (수율: 72%)Sub 1-57 (11g, 14.32mmol), THF (63ml), Sub 2-1 (2.92g, 14.32mmol), Pd (PPh 3 ) 4 (0.66g, 0.57mmol), NaOH (1.72g, 42.95mmol) , Water (31 ml) was obtained using the synthesis method 1-1 to 8.35 g of the product. (Yield 72%)
5-41 합성예5-41 Synthesis Example
Figure PCTKR2017004320-appb-I000133
Figure PCTKR2017004320-appb-I000133
Sub 1-64 (11g, 14.82mmol), THF(65ml), Sub 2-1 (3.02g, 14.82mmol), Pd(PPh3)4 (0.69g, 0.59mmol), NaOH (1.78g, 44.46mmol), 물(32ml)을 상기 1-1 합성방법을 사용하여 생성물 8.83g를 얻었다. (수율: 76%)Sub 1-64 (11g, 14.82mmol), THF (65ml), Sub 2-1 (3.02g, 14.82mmol), Pd (PPh 3 ) 4 (0.69g, 0.59mmol), NaOH (1.78g, 44.46mmol) , Water (32 ml) was obtained by the above 1-1 synthesis method to obtain 8.83 g of the product. (Yield 76%)
6-15 합성예6-15 Synthesis Example
Figure PCTKR2017004320-appb-I000134
Figure PCTKR2017004320-appb-I000134
Sub 1-78 (11g, 21.15mmol), THF(93ml), Sub 2-1 (4.32g, 21.15mmol), Pd(PPh3)4 (0.98g, 0.85mmol), NaOH (2.54g, 63.46mmol), 물(46ml)을 상기 1-1 합성방법을 사용하여 생성물 9.27g를 얻었다. (수율: 78%)Sub 1-78 (11 g, 21.15 mmol), THF (93 ml), Sub 2-1 (4.32 g, 21.15 mmol), Pd (PPh 3 ) 4 (0.98 g, 0.85 mmol), NaOH (2.54 g, 63.46 mmol) , Water (46 ml) was obtained using 9.1 g of the product using the 1-1 synthesis method. (Yield 78%)
화합물compound FD-MSFD-MS 화합물compound FD-MSFD-MS
1-11-1 m/z=577.16(C40H23N3S=577.71)m / z = 577.16 (C 40 H 23 N 3 S = 577.71) 1-21-2 m/z=627.18(C44H25N3S=627.77)m / z = 627.18 (C 44 H 25 N 3 S = 627.77)
1-41-4 m/z=868.27(C62H36N4S=869.06)m / z = 868.27 (C 62 H 36 N 4 S = 869.06) 1-61-6 m/z=683.15(C26H25N3S2=683.85) m / z = 683.15 (C 26 H 25 N 3 S 2 = 683.85)
1-81-8 m/z=627.18(C44H25N3S=627.77)m / z = 627.18 (C 44 H 25 N 3 S = 627.77) 1-141-14 m/z=868.27(C62H36N4S=869.06) m / z = 868.27 (C 62 H 36 N 4 S = 869.06)
1-161-16 m/z=633.13(C42H23N3S2=633.79)m / z = 633.13 (C 42 H 23 N 3 S 2 = 633.79) 1-261-26 m/z=683.15(C26H25N3S2=683.85)m / z = 683.15 (C 26 H 25 N 3 S 2 = 683.85)
1-301-30 m/z=777.17(C52H28FN3S2=777.94)m / z = 777.17 (C 52 H 28 FN 3 S 2 = 777.94) 1-341-34 m/z=667.17(C46H25N3OS=667.79)m / z = 667.17 (C 46 H 25 N 3 OS = 667.79)
1-391-39 m/z=693.19(C48H27N3-OS=693.82)m / z = 693.19 (C 48 H 27 N 3 -OS = 693.82) 1-441-44 m/z=578.16(C39H22N4S=578.69)m / z = 578.16 (C 39 H 22 N 4 S = 578.69)
1-451-45 m/z=794.23(C54H30N6S=794.94)m / z = 794.23 (C 54 H 30 N 6 S = 794.94) 2-12-1 m/z=561.18(C40H23N3O=561.64)m / z = 561.18 (C 40 H 23 N 3 O = 561.64)
2-42-4 m/z=707.17(C48H25N3-O2S=707.81)m / z = 707.17 (C 48 H 25 N 3 -O 2 S = 707.81) 2-52-5 m/z=743.20(C52H29N3-OS=743.88)m / z = 743.20 (C 52 H 29 N 3 -OS = 743.88)
2-72-7 m/z=792.22(C55H28N4-O3=792.85)m / z = 792.22 (C 55 H 28 N 4 -O 3 = 792.85) 2-92-9 m/z=682.24(C48H22D5N3O2=682.79)m / z = 682.24 (C 48 H 22 D 5 N 3 O 2 = 682.79)
3-13-1 m/z=577.16(C40H23N3S=577.71)m / z = 577.16 (C 40 H 23 N 3 S = 577.71) 3-23-2 m/z=627.18(C44H25N3S=627.77)m / z = 627.18 (C 44 H 25 N 3 S = 627.77)
3-43-4 m/z=653.19(C46H27N3S=653.80)m / z = 653.19 (C 46 H 27 N 3 S = 653.80) 3-153-15 m/z=733.16(C50H27N3S2=733.91) m / z = 733.16 (C 50 H 27 N 3 S 2 = 733.91)
3-163-16 m/z=718.18(C49H26N4OS=718.83) m / z = 718.18 (C 49 H 26 N 4 OS = 718.83) 3-193-19 m/z=683.15(C26H25N3S2=683.85)m / z = 683.15 (C 26 H 25 N 3 S 2 = 683.85)
3-363-36 m/z=693.19(C48H27N3-OS=693.82)m / z = 693.19 (C 48 H 27 N 3 -OS = 693.82) 3-443-44 m/z=717.19(C50H27N3-OS=717.85)m / z = 717.19 (C 50 H 27 N 3 -OS = 717.85)
3-453-45 m/z=799.18(C54H29N3-OS2=799.97)m / z = 799.18 (C 54 H 29 N 3 -OS 2 = 799.97) 4-14-1 m/z=561.18(C40H23N3O=561.64)m / z = 561.18 (C 40 H 23 N 3 O = 561.64)
4-24-2 m/z=687.23(C50H29N3O=687.80)m / z = 687.23 (C 50 H 29 N 3 O = 687.80) 4-34-3 m/z=899.21(C62H33N3OS2=900.09) m / z = 899.21 (C 62 H 33 N 3 OS 2 = 900.09)
4-94-9 m/z=677.21(C48H27N3O2=677.76)m / z = 677.21 (C 48 H 27 N 3 O 2 = 677.76) 5-15-1 m/z=577.16(C40H23N3S=577.71)m / z = 577.16 (C 40 H 23 N 3 S = 577.71)
5-25-2 m/z=627.18(C44H25N3S=627.77)m / z = 627.18 (C 44 H 25 N 3 S = 627.77) 5-75-7 m/z=632.21(C44H20D5N3S=632.80)m / z = 632.21 (C 44 H 20 D 5 N 3 S = 632.80)
5-85-8 m/z=677.19(C48H27N3S=677.83)m / z = 677.19 (C 48 H 27 N 3 S = 677.83) 5-95-9 m/z=742.22(C52H30N4S=742.90)m / z = 742.22 (C 52 H 30 N 4 S = 742.90)
5-115-11 m/z=818.25(C58H34N4S=819.00)m / z = 818.25 (C 58 H 34 N 4 S = 819.00) 5-245-24 m/z=723.14(C48H25N3OS2=723.87)m / z = 723.14 (C 48 H 25 N 3 OS 2 = 723.87)
5-255-25 m/z=809.20(C56H31N3S2=810.01)m / z = 809.20 (C 56 H 31 N 3 S 2 = 810.01) 5-265-26 m/z=709.16(C48H27N3S2=709.89)m / z = 709.16 (C 48 H 27 N 3 S 2 = 709.89)
5-315-31 m/z=683.15(C26H25N3S2=683.85)m / z = 683.15 (C 26 H 25 N 3 S 2 = 683.85) 5-415-41 m/z=783.20(C54H279N3O2S=783.91)m / z = 783.20 (C 54 H 279 N 3 O 2 S = 783.91)
5-425-42 m/z=617.16(C42H23N3OS=617.73)m / z = 617.16 (C 42 H 23 N 3 OS = 617.73) 5-445-44 m/z=733.22(C51H31N3OS=733.89)m / z = 733.22 (C 51 H 31 N 3 OS = 733.89)
6-16-1 m/z=611.20(C44H25N3O=611.70)m / z = 611.20 (C 44 H 25 N 3 O = 611.70) 6-26-2 m/z=651.19(C46H25N3O2=651.73)m / z = 651.19 (C 46 H 25 N 3 O 2 = 651.73)
6-36-3 m/z=743.20(C52H29N3OS=743.88)m / z = 743.20 (C 52 H 29 N 3 OS = 743.88) 6-56-5 m/z=713.25(C52H31N3O=713.84)m / z = 713.25 (C 52 H 31 N 3 O = 713.84)
6-76-7 m/z=737.25(C54H31N3O=737.86)m / z = 737.25 (C 54 H 31 N 3 O = 737.86) 6-126-12 m/z=918.30(C66H38N4O2=919.06) m / z = 918.30 (C 66 H 38 N 4 O 2 = 919.06)
6-156-15 m/z=561.18(C40H23N3O=561.64)m / z = 561.18 (C 40 H 23 N 3 O = 561.64)
한편, 상기에서는 화학식 (1)로 표시되는 본 발명의 예시적 합성예를 설명하였지만, 이들은 모두 Buchwald-Hartwig cross coupling 반응, Miyaura boration 반응, Suzuki cross-coupling 반응, Intramolecular acid-induced cyclization 반응 (J. mater. Chem . 1999, 9, 2095.), Pd(II)-catalyzed oxidative cyclization 반응 (Org. Lett . 2011, 13, 5504), Grignard 반응, Cyclic Dehydration 반응 및 PPh3-mediated reductive cyclization 반응 (J. Org . Chem. 2005, 70, 5014.) 등에 기초한 것으로 구체적 합성예에 명시된 치환기 이외에 화학식 (1)에 정의된 다른 치환기 (R1, R2, R3, R4, L1, L2, Ar1 등의 치환기)가 결합되더라도 상기 반응이 진행된다는 것을 당업자라면 쉽게 이해할 수 있을 것이다.On the other hand, in the above described exemplary synthetic examples of the present invention represented by the formula (1), these are all Buchwald-Hartwig cross coupling reaction, Miyaura boration reaction, Suzuki cross-coupling reaction, Intramolecular acid-induced cyclization reaction ( J. mater. Chem . 1999, 9 , 2095.), Pd (II) -catalyzed oxidative cyclization reaction ( Org. Lett . 2011, 13 , 5504), Grignard reaction, Cyclic Dehydration reaction and PPh 3 -mediated reductive cyclization reaction ( J. Org. Chem. 2005, 70, 5014.) or the like in addition to the substituents specifically set forth in the Preparation example the other substituents (R 1, as defined in the formula (1) based on R 2, R 3, R 4 , L 1, L 2, Ar One It will be readily understood by those skilled in the art that the reaction proceeds even when the substituents, such as the like) are attached.
유기전기소자의 제조평가Manufacturing Evaluation of Organic Electrical Device
[실시예 1] 적색유기전기발광소자 (인광호스트)Example 1 Red organic electroluminescent device (phosphorescent host)
합성을 통해 얻은 화합물을 발광층의 발광 호스트 물질로 사용하여 통상적인 방법에 따라 유기전계발광소자를 제작하였다. 먼저, 유리 기판에 형성된 ITO층(양극) 상에 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 두께의 정공주입층을 형성한 후, 정공주입층 위에 정공수송화합물로서 화합물로서 4,4-비스[N-(1-나프틸)-N-페닐아미노]비페닐(이하NPD로 약기함)를 60 nm 두께로 진공증착하여 정공수송층을 형성하였다. 정공 수송층 상부에 호스트로서는 상기 발명 화합물 1-1을 사용하였으며, 도판트 물질로 (piq)2Ir(acac)[bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate]를 95:5 중량비로 도핑하여 30nm 두께로 발광층을 증착하였다. 이어서 정공저지층으로 (1,1'-비스페닐)-4-올레이토)비스(2-메틸-8-퀴놀린올레이토)알루미늄(이하 BAlq로 약기함) 을 5nm 두께로 진공증착하고, 전자수송층으로 Bis(10-hydroxybenzo[h]quinolinato)beryllium (이하, “BeBq2”로 약기함)를 40 nm 두께로 성막하였다. 이후, 전자주입층으로 할로젠화 알칼리 금속인 LiF를 0.2 nm 두께로 증착하고, 이어서 Al을 150 nm의 두께로 증착하여 음극으로 사용함으로서 유기전계발광소자를 제조하였다.An organic light emitting diode was manufactured according to a conventional method using the compound obtained through synthesis as a light emitting host material. First, N 1- (naphthalen-2-yl) -N 4 , N 4 -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N 1 on the ITO layer (anode) formed on the glass substrate. -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) film was vacuum deposited to form a hole injection layer having a thickness of 60 nm, and then 4,4-bis [ N -as a compound as a hole transport compound on the hole injection layer. (1-naphthyl) -N -phenylamino] biphenyl (abbreviated as NPD) was vacuum deposited to a thickness of 60 nm to form a hole transport layer. Compound 1-1 of the present invention was used as a host on the hole transport layer, and the dopant was doped with (piq) 2 Ir (acac) [bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate] at a 95: 5 weight ratio. A light emitting layer was deposited to a thickness of 30 nm. Subsequently, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) was vacuum deposited to a thickness of 5 nm as a hole blocking layer, and the electron transport layer Bis (10-hydroxybenzo [h] quinolinato) beryllium (hereinafter abbreviated as “BeBq 2 ”) was formed to a thickness of 40 nm. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then, Al was deposited to a thickness of 150 nm to use an organic light emitting diode.
[[ 실시예Example 2] 내지 [ 2] to [ 실시예Example 44]  44] 레드유기전기발광소자Red organic electroluminescent device
발광층의 호스트 물질로 본 발명의 실시예에 따른 화합물 1-1 대신 하기 표 4에 기재된 본 발명의 화합물을 사용한 점을 제외하고는 상기 실시예 1과 동일한 방법으로 유기전기발광소자를 제조하였다.An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compound of the present invention shown in Table 4 was used instead of the compound 1-1 of the present invention as a host material of the emission layer.
[[ 비교예Comparative example 1] 내지 [ 1] to [ 비교예Comparative example 4] 4]
발광층의 호스트 물질로 본 발명의 실시예에 따른 화합물 1-1 대신 비교화합물 1 내지 비교화합물 4 중 하나를 사용한 점을 제외하고는 상기 실시예 1과 동일한 방법으로 유기전기발광소자를 제조하였다.An organic electroluminescent device was manufactured in the same manner as in Example 1, except that one of Comparative Compounds 1 to 4 was used instead of Compound 1-1 as a host material of the emission layer.
비교화합물 1 비교화합물 2 비교화합물 3 비교화합물 4Comparative Compound 1 Comparative Compound 2 Comparative Compound 3 Comparative Compound 4
Figure PCTKR2017004320-appb-I000135
Figure PCTKR2017004320-appb-I000135
이와 같이 제조된 실시예 1 내지 44, 비교예 1 내지 비교예 4는 유기전기발광소자들에 순바이어스 직류전압을 가하여 포토리서치(photoresearch)사의 PR-650으로 전기발광(EL) 특성을 측정하였으며, 그 측정결과 2500cd/m2 기준 휘도에서 맥사이언스사에서 제조된 수명 측정 장비를 통해 T95 수명을 측정하였다. 하기 표 4는 소자제작 및 평가한 결과를 나타낸다.Examples 1 to 44 and Comparative Examples 1 to 4 prepared as described above were subjected to a forward bias DC voltage to organic electroluminescent devices to measure electroluminescence (EL) characteristics with a PR-650 of photoresearch. As a result of the measurement, the T95 lifetime was measured using a life-time measuring instrument manufactured by McScience Inc. at 2500 cd / m 2 reference luminance. Table 4 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) CIECIE
XX YY
비교예(1)Comparative Example (1) 비교화합물 1 Comparative Compound 1 6.1 6.1 26.9 26.9 2500 2500 10.310.3 112.1 112.1 0.65 0.65 0.320.32
비교예(2)Comparative Example (2) 비교화합물 2Comparative Compound 2 6.0 6.0 24.0 24.0 2500 2500 13.813.8 110.8 110.8 0.660.66 0.330.33
비교예(3)Comparative Example (3) 비교화합물 3Comparative Compound 3 5.8 5.8 22.9 22.9 2500 2500 11.411.4 108.3 108.3 0.650.65 0.330.33
비교예(4)Comparative Example (4) 비교화합물 4Comparative Compound 4 5.6 5.6 18.5 18.5 2500 2500 18.218.2 119.7 119.7 0.660.66 0.320.32
실시예(1)Example (1) 화합물 1-1Compound 1-1 5.2 5.2 14.6 14.6 2500 2500 26.126.1 162.7 162.7 0.680.68 0.330.33
실시예(2)Example (2) 화합물 1-2Compound 1-2 5.2 5.2 14.5 14.5 2500 2500 26.226.2 163.1 163.1 0.680.68 0.330.33
실시예(3)Example (3) 화합물 1-4Compound 1-4 5.2 5.2 14.2 14.2 2500 2500 26.626.6 162.2 162.2 0.680.68 0.330.33
실시예(4)Example (4) 화합물 1-6Compound 1-6 5.2 5.2 14.4 14.4 2500 2500 26.326.3 160.2 160.2 0.680.68 0.320.32
실시예(5)Example (5) 화합물 1-8Compound 1-8 5.2 5.2 14.1 14.1 2500 2500 26.726.7 158.1 158.1 0.680.68 0.330.33
실시예(6)Example (6) 화합물 1-16Compound 1-16 5.1 5.1 14.1 14.1 2500 2500 26.726.7 158.4 158.4 0.680.68 0.330.33
실시예(7)Example (7) 화합물 1-26Compound 1-26 5.1 5.1 14.0 14.0 2500 2500 26.926.9 159.0 159.0 0.680.68 0.330.33
실시예(8)Example (8) 화합물 1-34Compound 1-34 5.2 5.2 13.2 13.2 2500 2500 28.028.0 158.8 158.8 0.680.68 0.320.32
실시예(9)Example (9) 화합물 1-39Compound 1-39 5.2 5.2 13.6 13.6 2500 2500 27.427.4 158.4 158.4 0.680.68 0.320.32
실시예(10)Example (10) 화합물 1-44Compound 1-44 5.2 5.2 14.2 14.2 2500 2500 26.626.6 158.2 158.2 0.680.68 0.330.33
실시예(11)Example (11) 화합물 5-1Compound 5-1 5.2 5.2 13.9 13.9 2500 2500 27.027.0 157.7 157.7 0.680.68 0.320.32
실시예(12)Example (12) 화합물 5-2Compound 5-2 5.2 5.2 14.1 14.1 2500 2500 26.726.7 156.5 156.5 0.680.68 0.320.32
실시예(13)Example (13) 화합물 5-7Compound 5-7 5.2 5.2 14.4 14.4 2500 2500 26.326.3 156.3 156.3 0.680.68 0.320.32
실시예(14)Example (14) 화합물 5-8Compound 5-8 5.2 5.2 14.2 14.2 2500 2500 26.626.6 154.1 154.1 0.680.68 0.330.33
실시예(15)Example (15) 화합물 5-9Compound 5-9 5.2 5.2 13.8 13.8 2500 2500 27.127.1 153.4 153.4 0.680.68 0.330.33
실시예(16)Example (16) 화합물 5-11Compound 5-11 5.2 5.2 14.5 14.5 2500 2500 26.226.2 152.8 152.8 0.680.68 0.330.33
실시예(17)Example (17) 화합물 5-24Compound 5-24 5.1 5.1 14.7 14.7 2500 2500 26.026.0 152.7 152.7 0.680.68 0.330.33
실시예(18)Example (18) 화합물 5-26Compound 5-26 5.1 5.1 14.4 14.4 2500 2500 26.426.4 151.9 151.9 0.680.68 0.330.33
실시예(19)Example (19) 화합물 5-31Compound 5-31 5.1 5.1 14.2 14.2 2500 2500 26.726.7 151.5 151.5 0.680.68 0.330.33
실시예(20)Example (20) 화합물 5-42Compound 5-42 5.2 5.2 13.7 13.7 2500 2500 27.327.3 151.4 151.4 0.680.68 0.330.33
실시예(21)Example (21) 화합물 5-44Compound 5-44 5.2 5.2 14.0 14.0 2500 2500 26.826.8 149.2 149.2 0.680.68 0.330.33
실시예(22)Example (22) 화합물 3-1Compound 3-1 5.3 5.3 14.2 14.2 2500 2500 26.626.6 153.0 153.0 0.680.68 0.330.33
실시예(23)Example (23) 화합물 3-2Compound 3-2 5.3 5.3 14.6 14.6 2500 2500 26.126.1 150.8 150.8 0.680.68 0.330.33
실시예(24)Example (24) 화합물 3-4Compound 3-4 5.3 5.3 14.4 14.4 2500 2500 26.426.4 151.4 151.4 0.680.68 0.330.33
실시예(25)Example (25) 화합물 3-15Compound 3-15 5.3 5.3 14.5 14.5 2500 2500 26.326.3 149.5 149.5 0.680.68 0.320.32
실시예(26)Example (26) 화합물 3-19Compound 3-19 5.2 5.2 14.2 14.2 2500 2500 26.626.6 143.8 143.8 0.680.68 0.320.32
실시예(27)Example (27) 화합물 3-36Compound 3-36 5.3 5.3 14.0 14.0 2500 2500 26.926.9 144.2 144.2 0.680.68 0.320.32
실시예(28)Example (28) 화합물 3-44Compound 3-44 5.3 5.3 14.1 14.1 2500 2500 26.726.7 139.2 139.2 0.680.68 0.330.33
실시예(29)Example (29) 화합물 3-45Compound 3-45 5.3 5.3 14.0 14.0 2500 2500 26.926.9 141.7 141.7 0.680.68 0.330.33
실시예(30)Example (30) 화합물 2-1Compound 2-1 5.3 5.3 14.6 14.6 2500 2500 26.126.1 145.9 145.9 0.680.68 0.330.33
실시예(31)Example (31) 화합물 2-4Compound 2-4 5.2 5.2 14.4 14.4 2500 2500 26.426.4 140.2 140.2 0.680.68 0.320.32
실시예(32)Example (32) 화합물 2-5Compound 2-5 5.2 5.2 14.3 14.3 2500 2500 26.526.5 139.4 139.4 0.680.68 0.330.33
실시예(33)Example (33) 화합물 2-9Compound 2-9 5.3 5.3 14.0 14.0 2500 2500 26.926.9 139.9 139.9 0.680.68 0.330.33
실시예(34)Example (34) 화합물 6-1Compound 6-1 5.4 5.4 14.5 14.5 2500 2500 26.226.2 138.8 138.8 0.680.68 0.330.33
실시예(35)Example (35) 화합물 6-2Compound 6-2 5.4 5.4 14.5 14.5 2500 2500 26.326.3 133.1 133.1 0.680.68 0.320.32
실시예(36)Example (36) 화합물 6-3Compound 6-3 5.4 5.4 14.6 14.6 2500 2500 26.126.1 134.2 134.2 0.680.68 0.320.32
실시예(37)Example (37) 화합물 6-5Compound 6-5 5.4 5.4 14.4 14.4 2500 2500 26.426.4 131.6 131.6 0.680.68 0.330.33
실시예(38)Example (38) 화합물 6-7Compound 6-7 5.3 5.3 14.7 14.7 2500 2500 26.026.0 135.3 135.3 0.680.68 0.330.33
실시예(39)Example (39) 화합물 6-9Compound 6-9 5.2 5.2 14.8 14.8 2500 2500 25.925.9 133.5 133.5 0.680.68 0.330.33
실시예(40)Example (40) 화합물 6-12Compound 6-12 5.4 5.4 14.5 14.5 2500 2500 26.326.3 131.4 131.4 0.680.68 0.320.32
실시예(41)Example (41) 화합물 6-15Compound 6-15 5.6 5.6 15.0 15.0 2500 2500 25.725.7 129.2 129.2 0.680.68 0.330.33
실시예(42)Example (42) 화합물 4-1Compound 4-1 5.5 5.5 15.5 15.5 2500 2500 25.125.1 133.1 133.1 0.680.68 0.330.33
실시예(43)Example (43) 화합물 4-2Compound 4-2 5.5 5.5 16.4 16.4 2500 2500 24.224.2 130.5 130.5 0.680.68 0.330.33
실시예(44)Example (44) 화합물 4-9Compound 4-9 5.5 5.5 14.8 14.8 2500 2500 25.925.9 130.2 130.2 0.680.68 0.320.32
상기 표 4의 측정 결과에서 알 수 있듯이, 본 발명의 일 실시예에 따른 화합물을 발광층의 인광 적색 호스트 재료로 사용한 실시예 1 내지 실시예 44의 경우 비교예 1 내지 비교예 4에 비하여 구동전압, 발광효율, 수명 및 색순도가 현저히 개선된 것을 확인할 수 있었다.As can be seen from the measurement results of Table 4, in the case of Examples 1 to 44 using the compound according to one embodiment of the present invention as a phosphorescent red host material of the light emitting layer, the driving voltage, compared to Comparative Examples 1 to 4, It was confirmed that the luminous efficiency, lifetime and color purity were significantly improved.
현재 본 발명자들은 소비전력을 낮추고, 효율 및 색순도를 높이고자 하는 연구를 진행하고 있는 바, 전자 이동 특성이 우수한 sub 치환기가 필요한 상황이다. 이에 따라 기존 인광 레드 호스트로 사용되는 fused pyrimidine type의 치환기 보다 전자 이동 특성이 우수한 fused pyrazine type 치환기를 도입하고자 하였으며, 실제로 비교화합물 4와 같은 형태의 특정 치환기(fused pyrazine type)의 도입으로 전자 이동 특성이 우수하여 효율이 상승하고 구동전압이 당겨지는 결과를 나타내는 것을 확인할 수 있었다.Currently, the inventors of the present invention are researching to lower power consumption and increase efficiency and color purity, and thus a situation is required for a sub substituent having excellent electron transfer characteristics. Accordingly, we tried to introduce a fused pyrazine type substituent which has better electron transfer characteristics than the fused pyrimidine type substituent used as a phosphorescent red host. In fact, electron transfer characteristics were introduced by introducing a specific substituent (fused pyrazine type) like Comparative Compound 4. It was confirmed that this resulted in excellent efficiency and a result of pulling the driving voltage.
Figure PCTKR2017004320-appb-I000136
Figure PCTKR2017004320-appb-I000136
비교예 1~3과 비교예 4를 비교하여 보면 sub 치환기로 퀴녹살린(fused pyrazine)을 갖는 비교예 4의 경우가 N의 치환 위치가 상이한 sub 치환기로 fused pyrimidine이 결합된 비교화합물 1~3보다 효율이 상승하고 구동전압이 현저히 개선되는 것을 확인 할 수 있었다. 이는 동일코어이긴 하나, 특정치환기가 결합됨으로써 에너지 밴드갭이 달라지고, 높은 electron mobility를 야기하는 것으로 설명할 수 있다.Comparing Comparative Examples 1 to 3 with Comparative Example 4, Comparative Example 4 having quinoxaline (fused pyrazine) as a sub substituent was compared to Comparative Compounds 1 to 3 where fused pyrimidine was bonded to a sub substituent having a different substitution position of N. It was confirmed that the efficiency is increased and the driving voltage is significantly improved. Although this is the same core, it can be explained that the specific band is combined, the energy band gap is changed, causing high electron mobility.
즉, sub 치환기로 fused pyrimidine이 아닌 fused pyrazine을 도입한 본 발명화합물의 경우, LUMO Level이 낮아짐에 따라 ETL로부터 발광층으로 electron injection이 용이해져, 발광층 내에 전하 균형을 향상시키기 때문에 구동 전압과 수명이 개선되는 것으로 판단된다.That is, in the case of the compound of the present invention in which fused pyrazine instead of fused pyrimidine is used as a sub substituent, as the LUMO level decreases, electron injection from the ETL to the light emitting layer is facilitated, thereby improving charge balance in the light emitting layer, thereby improving driving voltage and lifetime. It seems to be.
또한 6환 헤테로고리 core의 특정 위치에 벤젠이 하나 더 fused됨에 따라 conjugation 길이가 길어져 dopant로의 전하이동이 용이해지기 때문에 효율면에서 우수한 결과를 나타내는 것으로 판단된다. 이는 코어의 특정 위치에 벤젠고리가 형성될 경우 PL 파장이 보다 red shift 되는 것으로 확인할 수 있는데, (비교화합물 4, 발명화합물 1-1의 PL data 비교: 527nm에서 555 nm로 장파장화됨)In addition, as the benzene is further fused to a specific position of the 6-membered heterocyclic core, the conjugation length becomes longer, which makes the charge transfer to the dopant easier. It can be confirmed that when the benzene ring is formed at a specific position of the core, the PL wavelength is shifted more red shift.
호스트의 파장을 장파장화 시킴으로써 도펀트로의 전하 이동이 용이해져 효율 및 색순도가 향상되는 것을 확인할 수 있다.It can be seen that by increasing the wavelength of the host, charge transfer to the dopant is facilitated, thereby improving efficiency and color purity.
결과적으로 fused pyrazine type 치환기의 효과(높은 전하 캐리어 이동도, 구동전압을 향상) 및 코어의 특정 위치에 추가적인 벤젠고리가 더 형성됨에(7환) 따라 호스트에서 도판트로의 전하 이동이 원활해 질 수 있도록 가장 적절한 HOMO/LUMO, T1 값 및 에너지 밴드갭을 갖게 되어 소자 전체의 성능이 향상된 것으로 사료된다.As a result, the effect of fused pyrazine type substituents (higher charge carrier mobility, improved driving voltage) and additional benzene rings are formed at certain positions in the core (7 rings), which facilitates charge transfer from the host to the dopant. The most appropriate HOMO / LUMO, T1 value and energy bandgap are considered to improve the overall device performance.
<비교화합물 1 내지 4 및 본 발명 화합물 1-1의 PL data><PL data of Comparative Compounds 1 to 4 and Compound 1-1 of the present invention>
　 비교화합물 1Comparative Compound 1 비교화합물 2Comparative Compound 2 비교화합물 3Comparative Compound 3 비교화합물 4Comparative Compound 4 발명 화합물 1-1Invention Compound 1-1
PL (nm)PL (nm) 515515 497497 507507 527527 555555
도 4 참조 See Figure 4
이상의 설명은 본 발명을 예시적으로 설명한 것에 불과한 것으로, 본 발명이 속하는 기술분야에서 통상의 지식을 가지는 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 변형이 가능할 것이다. 따라서, 본 명세서에 개시된 실시 예들은 본 발명을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시 예에 의하여 본 발명의 사상과 범위가 한정되는 것은 아니다. The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains may various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention but to describe the present invention, and the spirit and scope of the present invention are not limited thereto.
본 발명의 보호범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술은 본 발명의 권리범위에 포함하는 것으로 해석되어야 할 것이다.The protection scope of the present invention should be interpreted by the following claims, and all the technologies within the equivalent scope should be interpreted as being included in the scope of the present invention.

Claims (12)

  1. 하기 화학식 (1)로 표시되는 화합물 Compound represented by the following formula (1)
    화학식 (1)Formula (1)
    Figure PCTKR2017004320-appb-I000137
    Figure PCTKR2017004320-appb-I000137
    {상기 화학식 (1)에서,{In the above formula (1),
    1) A는 C10의 아릴기이며,1) A is an aryl group of C 10 ,
    2) B는 하기 화학식 B-1 내지 B-16로 이루어진 군에서 선택되고,2) B is selected from the group consisting of the following formulas B-1 to B-16,
    B-1 B-2 B-3 B-4 B-5 B-1 B-2 B-3 B-4 B-5
    Figure PCTKR2017004320-appb-I000138
    Figure PCTKR2017004320-appb-I000138
    B-6 B7 B-8 B-9 B-10B-6 B7 B-8 B-9 B-10
    Figure PCTKR2017004320-appb-I000139
    Figure PCTKR2017004320-appb-I000139
    B-11 B-12 B-13 B-14 B-15 B-16B-11 B-12 B-13 B-14 B-15 B-16
    Figure PCTKR2017004320-appb-I000140
    Figure PCTKR2017004320-appb-I000140
    상기 화학식 B-1 내지 B-16에서 "*" 는 2개의 N을 포함하는 pyrazine고리와 결합하여 융합고리를 형성하는 결합 부분을 나타내고,In Formulas B-1 to B-16, "*" represents a binding moiety that combines with a pyrazine ring containing two N to form a fused ring,
    3) W1 및 W2는 각각 독립적으로 단일결합, S 또는 O이고,3) W 1 and W 2 are each independently a single bond, S or O,
    4) V는 N 또는 C이고,4) V is N or C,
    5) X는 O 또는 S이고,5) X is O or S,
    6) a는 0 내지 6의 정수이고, b 및 c는 0 내지 4의 정수이고, d는 0 내지 11의 정수이며,6) a is an integer from 0 to 6, b and c are integers from 0 to 4, d is an integer from 0 to 11,
    7) R1, R2, R3 및 R4는 서로 동일하거나 상이하며, 서로 독립적으로 수소; 중수소; 할로겐; 시아노; 나이트로기; 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~C50의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕실기; C6~C30의 아릴옥시기; 및 -L'-N(Ra)(Rb);로 이루어진 군에서 선택되며,7) R 1 , R 2 , R 3 and R 4 are the same as or different from each other, and independently from each other hydrogen; heavy hydrogen; halogen; Cyano; Nitro group; C 6 ~ C 60 Aryl group; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; C 1 ~ C 50 Alkyl group; C 2 ~ C 20 Alkenyl group; Alkynyl groups of C 2 to C 20 ; C 1 -C 30 alkoxyl group; C 6 -C 30 aryloxy group; And -L'-N (R a ) (R b );
    또는 상기 a, b 및 c가 2 이상인 경우 각각 복수로서 서로 동일하거나 상이하며 복수의 R1끼리 혹은 복수의 R2끼리 혹은 복수의 R3끼리 서로 결합하여 고리를 형성할 수 있으며,Or when a, b, and c are two or more, each of which is the same as or different from each other, and a plurality of R 1 or a plurality of R 2 or a plurality of R 3 may be bonded to each other to form a ring.
    8) L'은 단일결합; C6~C60의 아릴렌기; 플루오렌일렌기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 C2~C60의 헤테로고리기;로 이루어진 군에서 선택되며, 상기 Ra 및 Rb은 서로 독립적으로 C6~C60의 아릴기; 플루오렌일기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기;로 이루어진 군에서 선택되며,8) L 'is a single bond; C 6 ~ C 60 arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; And C 2 ~ C 60 Heterocyclic group; It is selected from the group consisting of, R a and R b are independently of each other C 6 ~ C 60 An aryl group; Fluorenyl group; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; And a C 2 ~ C 60 heterocyclic group including at least one heteroatom of O, N, S, Si, and P, and
    9) L1은 각각 독립적으로 단일결합; C6~C60의 아릴렌기; 플루오렌일렌기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 C2~C60의 헤테로고리기;로 이루어진 군에서 선택되고,9) L 1 is each independently a single bond; C 6 ~ C 60 arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; And C 2 ~ C 60 It is selected from the group consisting of; heterocyclic group,
    여기서, 상기 아릴기, 플루오렌닐기, 아릴렌기, 헤테로고리기, 융합고리기, 알킬기, 알켄일기, 알콕시기, 아릴옥시기는 각각 중수소; 할로겐; C1-C20의 알킬기 또는 C6-C20의 아릴기로 치환 또는 비치환된 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; -L'-N(Ra)(Rb); 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 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 더욱 치환 될 수 있으며, 또한 이들 치환기들은 서로 결합하여 고리를 형성할 수도 있으며, 여기서 '고리'란 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 불포화 고리를 포함한다.}Here, the aryl group, fluorenyl group, arylene group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkoxy group, aryloxy group are each deuterium; halogen; A silane group unsubstituted or substituted with a C 1 -C 20 alkyl group or a C 6 -C 20 aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; -L'-N (R a ) (R b ); Import alkylthio of C 1 -C 20; An alkoxyl group of C 1 -C 20 ; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group; A cycloalkyl group of C 3 -C 20 ; It may be further substituted with one or more substituents selected from the group consisting of C 7 -C 20 arylalkyl group and C 8 -C 20 arylalkenyl group, and these substituents may be bonded to each other to form a 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, and includes a saturated or unsaturated ring.}
  2. 제 1항에 있어서,The method of claim 1,
    상기 화학식 (1)은 하기 화학식 2 내지 화학식 4 중 어느 하나로 표시되는 것을 특징으로 하는 화합물.Formula (1) is a compound, characterized in that represented by any one of the following formula (2).
    <화학식 2> <화학식 3> <화학식 4><Formula 2> <Formula 3> <Formula 4>
    Figure PCTKR2017004320-appb-I000141
    Figure PCTKR2017004320-appb-I000141
    (상기 화학식 2 내지 화학식 4에서,(In Formula 2 to Formula 4,
    X, L1, Ar1, R1, R2, R3, a, b, c는 상기 청구항 1에서 정의한 바와 동일하다)X, L 1 , Ar 1 , R 1 , R 2 , R 3 , a, b, c are the same as defined in claim 1 above)
  3. 제 1항에 있어서,The method of claim 1,
    상기 화학식 (1)은 하기 화학식 5 내지 화학식 7 중 어느 하나로 표시되는 것을 특징으로 하는 화합물.Formula (1) is a compound, characterized in that represented by any one of the following formula (5).
    <화학식 5> <화학식 6> <화학식 7> <Formula 5> <Formula 6> <Formula 7>
    Figure PCTKR2017004320-appb-I000142
    Figure PCTKR2017004320-appb-I000142
    (상기 화학식 5 내지 화학식 7에서,(In Formula 5 to Formula 7,
    X, L1, Ar1, R1, R2, R3, R4, a, b, c, d, B는 상기 청구항 1에서 정의한 바와 동일하다)X, L 1 , Ar 1 , R 1 , R 2 , R 3 , R 4 , a, b, c, d, B are the same as defined in claim 1 above)
  4. 제 1항에 있어서, 상기 화학식 (1)에서 상기 pyrazine을 포함한 화학식 구조 Ar1은 하기 화학식 C-1 내지 화학식 C-20 중 어느 하나인 것을 특징으로 하는 화합물.The compound of claim 1, wherein the formula Ar 1 including the pyrazine in formula (1) is any one of the following formulas C-1 to C-20.
    C-1 C-2 C-3 C-4 C-5 C-6C-1 C-2 C-3 C-4 C-5 C-6
    Figure PCTKR2017004320-appb-I000143
    Figure PCTKR2017004320-appb-I000143
    C-7 C-8 C-9 C-10 C-11 C-12 C-13 C-14  C-7 C-8 C-9 C-10 C-11 C-12 C-13 C-14
    Figure PCTKR2017004320-appb-I000144
    Figure PCTKR2017004320-appb-I000144
    C-15 C-16 C-17 C-18 C-19 C-20   C-15 C-16 C-17 C-18 C-19 C-20
    Figure PCTKR2017004320-appb-I000145
    Figure PCTKR2017004320-appb-I000145
    C-21 C-22C-21 C-22
    Figure PCTKR2017004320-appb-I000146
    Figure PCTKR2017004320-appb-I000146
    (상기 화학식 C-1 내지 C-22에서, R4는 청구항 1에서 정의한 바와 동일하고, d는 0 내지 11의 정수 중 어느 하나이다.)(In the formulas C-1 to C-22, R 4 is the same as defined in claim 1, and d is any one of integers from 0 to 11.)
  5. 제 1항에 있어서,The method of claim 1,
    상기 화학식 (1)에서 R4는 하기 화학식 R-1 내지 R-10 중 어느 하나로 표시되는 것을 특징으로 하는 화합물.R 4 in the formula (1) is a compound, characterized in that represented by any one of the following formula R-1 to R-10.
    <R-1> <R-2> <R-3> <R-4> <R-5><R-1> <R-2> <R-3> <R-4> <R-5>
    Figure PCTKR2017004320-appb-I000147
    Figure PCTKR2017004320-appb-I000147
    <R-6> <R-7> <R-8> <R-9> <R-10><R-6> <R-7> <R-8> <R-9> <R-10>
    Figure PCTKR2017004320-appb-I000148
    Figure PCTKR2017004320-appb-I000148
    (상기 화학식 R-1 내지 R-10에서,(In the above formula R-1 to R-10,
    1) Q1 내지 Q15는 서로 독립적으로 CRg 또는 N이고,1) Q 1 to Q 15 are independently of each other CR g or N,
    2) W1은 S, O 또는 NRh이고, 2) W 1 is S, O or NR h ,
    3) W2 내지 W4는 S, O, NRh 또는 CRiRj 3) W 2 to W 4 are S, O, NR h or CR i R j
    4) Re는 수소; 중수소; 할로겐; C1-C20의 알킬기 또는 C6-C20의 아릴기로 치환 또는 비치환된 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; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C20의 헤테로고리기; C3-C20의 시클로알킬기; C7-C20의 아릴알킬기; 및 C8-C20의 아릴알켄일기로 이루어진 군에서 선택되거나, 또는 이웃한 기끼리 서로 결합하여 고리를 형성할 수 있으며,4) R e is hydrogen; heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C 1 -C 20 alkyl group or a C 6 -C 20 aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C 1 -C 20; An alkoxyl group of C 1 -C 20 ; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A cycloalkyl group of C 3 -C 20 ; C 7 -C 20 arylalkyl group; And C 8 -C 20 It is selected from the group consisting of an aryl alkenyl group, or adjacent groups may combine with each other to form a ring,
    5) Rf 및 Rg는 서로 독립적으로 수소; 중수소; C6~C20의 아릴기; 플루오렌일기; C3~C20의 지방족고리와 C6~C20의 방향족고리의 융합고리기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C20의 헤테로고리기; C1~C20의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕실기;로 구성된 군에서 선택되고,5) R f and R g are each independently hydrogen; heavy hydrogen; C 6 -C 20 aryl group; Fluorenyl group; A fused ring group of an aliphatic ring of C 3 ~ C 20 and an aromatic ring of C 6 ~ C 20 ; And a C 2 to C 20 heterocyclic group including at least one heteroatom of O, N, S, Si, and P; C 1 ~ C 20 Alkyl group; C 2 ~ C 20 Alkenyl group; Alkynyl groups of C 2 to C 20 ; C 1 ~ C 30 Alkoxyl group; It is selected from the group consisting of,
    6) Rh Ri 및 Rj는 서로 독립적으로 C6-C20의 아릴기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2-C20의 헤테로고리기; C1-C20의 알킬기; C2-C20의 알켄일기; C1-C20의 알콕시기; 및 플루오렌일기;로 구성된 군에서 선택되고, Ri 및 Rj는 서로 결합하여 이들이 결합된 C와 함께 스파이로(spiro) 화합물을 형성할 수 있고,6) R h R i and R j are each independently of the other C 6 -C 20 aryl group; C 2 -C 20 heterocyclic group including at least one heteroatom of O, N, S, Si, and P; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkoxy group of C 1 -C 20 ; And a fluorenyl group; R i and R j may be bonded to each other to form a spiro compound together with C to which they are bonded,
    7) q는 서로 독립적으로 0 내지 5의 정수이고,7) q is an integer from 0 to 5 independently of each other,
    8) r는 서로 독립적으로 0 내지 4의 정수이고,8) r is, independently from each other, an integer from 0 to 4,
    9) s는 서로 독립적으로 0 내지 3의 정수이고,9) s is an integer from 0 to 3 independently of each other,
    q,r 및 s가 각각이 2 이상의 정수인 경우, Re는 서로 동일하거나 상이하며,when q, r and s are each an integer of 2 or more, R e is the same as or different from each other,
    *은 결합부분을 나타낸다.)* Indicates a coupling part.)
  6. 제 1항에 있어서,The method of claim 1,
    하기 화합물 중 하나인 것을 특징으로 하는 화합물. Compound which is one of the following compounds.
    Figure PCTKR2017004320-appb-I000149
    Figure PCTKR2017004320-appb-I000149
    Figure PCTKR2017004320-appb-I000150
    Figure PCTKR2017004320-appb-I000150
    Figure PCTKR2017004320-appb-I000151
    Figure PCTKR2017004320-appb-I000151
    Figure PCTKR2017004320-appb-I000152
    Figure PCTKR2017004320-appb-I000152
    Figure PCTKR2017004320-appb-I000153
    Figure PCTKR2017004320-appb-I000153
    Figure PCTKR2017004320-appb-I000154
    Figure PCTKR2017004320-appb-I000154
    Figure PCTKR2017004320-appb-I000155
    Figure PCTKR2017004320-appb-I000155
    Figure PCTKR2017004320-appb-I000156
    Figure PCTKR2017004320-appb-I000156
    Figure PCTKR2017004320-appb-I000157
    Figure PCTKR2017004320-appb-I000157
    Figure PCTKR2017004320-appb-I000158
    Figure PCTKR2017004320-appb-I000158
    Figure PCTKR2017004320-appb-I000159
    Figure PCTKR2017004320-appb-I000159
    Figure PCTKR2017004320-appb-I000160
    Figure PCTKR2017004320-appb-I000160
    Figure PCTKR2017004320-appb-I000161
    Figure PCTKR2017004320-appb-I000161
    Figure PCTKR2017004320-appb-I000162
    Figure PCTKR2017004320-appb-I000162
    Figure PCTKR2017004320-appb-I000163
    Figure PCTKR2017004320-appb-I000163
    Figure PCTKR2017004320-appb-I000164
    Figure PCTKR2017004320-appb-I000164
    Figure PCTKR2017004320-appb-I000165
    Figure PCTKR2017004320-appb-I000165
    Figure PCTKR2017004320-appb-I000166
    Figure PCTKR2017004320-appb-I000166
    Figure PCTKR2017004320-appb-I000167
    Figure PCTKR2017004320-appb-I000167
    Figure PCTKR2017004320-appb-I000168
    Figure PCTKR2017004320-appb-I000168
    Figure PCTKR2017004320-appb-I000169
    Figure PCTKR2017004320-appb-I000169
    Figure PCTKR2017004320-appb-I000170
    Figure PCTKR2017004320-appb-I000170
    Figure PCTKR2017004320-appb-I000171
    Figure PCTKR2017004320-appb-I000171
    Figure PCTKR2017004320-appb-I000172
    Figure PCTKR2017004320-appb-I000172
    Figure PCTKR2017004320-appb-I000173
    Figure PCTKR2017004320-appb-I000173
    Figure PCTKR2017004320-appb-I000174
    Figure PCTKR2017004320-appb-I000174
    Figure PCTKR2017004320-appb-I000175
    Figure PCTKR2017004320-appb-I000175
    Figure PCTKR2017004320-appb-I000176
    Figure PCTKR2017004320-appb-I000176
    Figure PCTKR2017004320-appb-I000177
    Figure PCTKR2017004320-appb-I000177
    Figure PCTKR2017004320-appb-I000178
    Figure PCTKR2017004320-appb-I000178
    Figure PCTKR2017004320-appb-I000179
    Figure PCTKR2017004320-appb-I000179
    Figure PCTKR2017004320-appb-I000180
    Figure PCTKR2017004320-appb-I000180
    Figure PCTKR2017004320-appb-I000181
    Figure PCTKR2017004320-appb-I000181
    Figure PCTKR2017004320-appb-I000182
    Figure PCTKR2017004320-appb-I000182
  7. 제 1전극; 제 2전극; 및 상기 제 1전극과 제 2전극 사이에 위치하는 유기물층;을 포함하는 유기전기소자에 있어서,A first electrode; Second electrode; And an organic material layer positioned between the first electrode and the second electrode.
    상기 유기물층은 제 1항 내지 제 6항 중 어느 한 항의 화합물을 포함하는 것을 특징으로 하는 유기전기소자.The organic material layer is an organic electroluminescent device comprising the compound of any one of claims 1 to 6.
  8. 제 7항에 있어서, The method of claim 7, wherein
    상기 유기물층의 정공주입층, 정공수송층, 발광보조층, 전자수송보조층, 전자수송층 및 발광층 중 적어도 하나의 층에 상기 화합물이 함유되며, 상기 화합물은 1종 단독 화합물 또는 2종 이상의 화합물을 혼합물의 성분으로서 포함하는 것을 특징으로 하는 유기전기소자.The compound is contained in at least one of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, an electron transport auxiliary layer, an electron transport layer and a light emitting layer of the organic material layer, the compound is a single compound or two or more compounds of the mixture An organic electric device comprising as a component.
  9. 제 7항에 있어서,The method of claim 7, wherein
    상기 화합물은 상기 발광층의 인광호스트 재료로 사용되는 것을 특징으로 하는 유기전기소자.And the compound is used as a phosphorescent host material of the light emitting layer.
  10. 제 7항에 있어서,The method of claim 7, wherein
    상기 유기물층은 스핀코팅 공정, 노즐 프린팅 공정, 잉크젯 프린팅 공정, 슬롯코팅 공정, 딥코팅 공정 또는 롤투롤 공정에 의해 형성되는 것을 특징으로 하는 유기전기소자.The organic material layer is formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process.
  11. 제 7항의 유기전기소자를 포함하는 디스플레이장치; 및 상기 디스플레이장치를 구동하는 제어부를 포함하는 전자장치.A display device comprising the organic electronic device of claim 7; And a controller for driving the display device.
  12. 제 11항에 있어서,The method of claim 11,
    상기 유기전기소자는 유기전기발광소자, 유기태양전지, 유기감광체, 유기트랜지스터, 및 단색 또는 백색 조명용 소자 중 하나인 것을 특징으로 하는 전자장치.The organic electronic device is an electronic device, characterized in that one of the organic electroluminescent device, an organic solar cell, an organic photosensitive member, an organic transistor, and a single color or white illumination device.
PCT/KR2017/004320 2016-04-26 2017-04-24 Compound for organic electronic element, organic electronic element using same, and electronic device thereof WO2017188676A1 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190031673A1 (en) * 2017-07-27 2019-01-31 Semiconductor Energy Laboratory Co., Ltd. Organic Compound, Light-Emitting Element, Light-Emitting Device, Electronic Device, and Lighting Device
KR20200007195A (en) * 2018-07-12 2020-01-22 엘티소재주식회사 Heterocyclic compound and organic light emitting device comprising same
US10797247B2 (en) 2014-07-24 2020-10-06 Duk San Neolux Co., Ltd. Compound for organic electric element, organic electric element comprising the same and electronic device thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130083817A (en) * 2012-01-13 2013-07-23 덕산하이메탈(주) Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof
KR20150032447A (en) * 2013-09-16 2015-03-26 롬엔드하스전자재료코리아유한회사 Novel organic electroluminescent compounds and organic electroluminescent device comprising the same
KR20150135109A (en) * 2014-05-23 2015-12-02 롬엔드하스전자재료코리아유한회사 An organic electroluminescent compound and an organic electroluminescent device comprising the same
KR20150141147A (en) * 2014-06-09 2015-12-17 롬엔드하스전자재료코리아유한회사 An organic electroluminescent compound and an organic electroluminescent device comprising the same
KR20160022784A (en) * 2014-08-20 2016-03-02 롬엔드하스전자재료코리아유한회사 Multi-component host material and an organic electroluminescence device comprising the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130083817A (en) * 2012-01-13 2013-07-23 덕산하이메탈(주) Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof
KR20150032447A (en) * 2013-09-16 2015-03-26 롬엔드하스전자재료코리아유한회사 Novel organic electroluminescent compounds and organic electroluminescent device comprising the same
KR20150135109A (en) * 2014-05-23 2015-12-02 롬엔드하스전자재료코리아유한회사 An organic electroluminescent compound and an organic electroluminescent device comprising the same
KR20150141147A (en) * 2014-06-09 2015-12-17 롬엔드하스전자재료코리아유한회사 An organic electroluminescent compound and an organic electroluminescent device comprising the same
KR20160022784A (en) * 2014-08-20 2016-03-02 롬엔드하스전자재료코리아유한회사 Multi-component host material and an organic electroluminescence device comprising the same

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10797247B2 (en) 2014-07-24 2020-10-06 Duk San Neolux Co., Ltd. Compound for organic electric element, organic electric element comprising the same and electronic device thereof
US20190031673A1 (en) * 2017-07-27 2019-01-31 Semiconductor Energy Laboratory Co., Ltd. Organic Compound, Light-Emitting Element, Light-Emitting Device, Electronic Device, and Lighting Device
KR20190013567A (en) * 2017-07-27 2019-02-11 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Organic compound, light-emitting element, light-emitting device, electronic device, and lighting device
KR102072705B1 (en) 2017-07-27 2020-02-03 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Organic compound, light-emitting element, light-emitting device, electronic device, and lighting device
JP2022125052A (en) * 2017-07-27 2022-08-26 株式会社半導体エネルギー研究所 Light-emitting element
JP7377315B2 (en) 2017-07-27 2023-11-09 株式会社半導体エネルギー研究所 Light emitting devices, mixed materials and materials for light emitting devices
KR20200007195A (en) * 2018-07-12 2020-01-22 엘티소재주식회사 Heterocyclic compound and organic light emitting device comprising same
KR102169327B1 (en) 2018-07-12 2020-10-23 엘티소재주식회사 Heterocyclic compound and organic light emitting device comprising same

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