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WO2019143110A1 - Organic compound and organic electroluminescent element using same - Google Patents

Organic compound and organic electroluminescent element using same Download PDF

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Publication number
WO2019143110A1
WO2019143110A1 PCT/KR2019/000614 KR2019000614W WO2019143110A1 WO 2019143110 A1 WO2019143110 A1 WO 2019143110A1 KR 2019000614 W KR2019000614 W KR 2019000614W WO 2019143110 A1 WO2019143110 A1 WO 2019143110A1
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Prior art keywords
group
mmol
formula
aryl
bonded
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PCT/KR2019/000614
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French (fr)
Korean (ko)
Inventor
이용환
엄민식
홍진석
심재의
박정근
손효석
한송이
박우재
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주식회사 두산
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Priority claimed from KR1020180165794A external-priority patent/KR20190087281A/en
Application filed by 주식회사 두산 filed Critical 주식회사 두산
Publication of WO2019143110A1 publication Critical patent/WO2019143110A1/en

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    • 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
    • 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
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • 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]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to a novel organic compound and an organic electroluminescent device using the same. More particularly, the present invention relates to a novel compound having excellent thermal stability and light emitting ability, and a novel compound containing the same in one or more organic layers to improve characteristics such as luminous efficiency, And an organic electroluminescent device.
  • the organic electroluminescent device when a voltage is applied between two electrodes, holes are injected into the anode, and electrons are injected into the organic layer from the cathode. When the injected holes and electrons meet, an exciton is formed. When the exciton falls to the ground state, light is emitted.
  • the material used as the organic material layer may be classified into a light emitting material, a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on its function.
  • the light emitting layer forming material of the organic electroluminescent device can be classified into blue, green and red light emitting materials according to the luminescent color.
  • yellow and orange light emitting materials are also used as light emitting materials for realizing better color.
  • a host / dopant system can be used as a light emitting material.
  • the dopant material can be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt.
  • a metal complex compound containing heavy atoms such as Ir and Pt.
  • NPB, BCP, Alq 3 and the like are widely known as materials used for the hole injecting layer, the hole transporting layer, the hole blocking layer and the electron transporting layer, and the anthracene derivatives as a luminescent material have been reported as a fluorescent dopant / host material .
  • Ir as a phosphorescent material that has a great advantage in improving the efficiency aspects of the light-emitting material (ppy) 3, (acac) Ir (btp) 2
  • Ir metal complex compound is a blue, green and red host material that includes such as . So far, CBP has shown excellent properties as a phosphorescent host material.
  • Patent Document 1 Japanese Laid-Open Patent Publication No. 2001-160489
  • the present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide an organic electroluminescent device which can be applied to an organic electroluminescent device and which has excellent thermal stability, hole injection ability, hole transport ability, All aimed at providing excellent novel organic compounds.
  • Another object of the present invention is to provide an organic electroluminescent device including the above-described novel organic compound and exhibiting thermal stability, a low driving voltage and a high luminous efficiency, and having an improved lifetime.
  • the present invention provides a compound represented by the following general formula (1).
  • X 1 and X 2 are the same as or different from each other and each independently O or S,
  • Y 1 to Y 16 are the same as or different from each other, and each independently CR 8 or N, provided that when there are a plurality of CR 8 s , the plurality of R 8 s are the same as or different from each other,
  • Z 1 to Z 3 are the same or different and each independently CR 5 or N, at least one of them is N,
  • Ar 1 is selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, C 1 to C 40 alkyl, C 2 to C 40 alkenyl, C 2 to C 40 alkynyl, C 3 to C 40 cycloalkyl, A C 6 to C 60 aryl group,
  • the X 1 containing ring and the X 2 containing ring are asymmetrically bonded to each other based on the Z 1 to Z 3 containing ring,
  • n are each an integer of 0 to 3, m + n? 1,
  • a and B are the same or different from each other, and are each independently any one of substituents represented by the following formula (2) or (3);
  • X 3 is a single bond
  • Ar 2 represents a C 1 to C 40 alkyl group, a C 2 to C 40 alkenyl group, a C 2 to C 40 alkynyl group, a C 3 to C 40 cycloalkyl group, a C 6 to C 60 aryl group, 5 to 60 heteroaryl groups and C 6 to C 60 arylamine groups, or may be bonded to adjacent groups to form a condensed ring,
  • a, c, and f are each an integer of 0 to 3
  • b, d and e are each an integer of 0 to 4, wherein b + m? 4, d + n? 4,
  • R 1 to R 8 are the same or different from each other and each independently represents hydrogen, deuterium, halogen, cyano, nitro, C 1 to C 40 alkyl, C 2 to C 40 alkenyl, C 2 to C 40 An alkynyl group, a C 3 to C 40 cycloalkyl group, a heteroaryl group having 3 to 40 nuclear atoms, a C 6 to C 60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C 1 to C 40 alkyl A C 6 to C 60 aryloxy group, a C 1 to C 40 alkylsilyl group, a C 6 to C 60 arylsilyl group, a C 1 to C 40 alkylboron group, a C 6 to C 60 aryl boron group, C 6 ⁇ C 60 aryl phosphine group, C 6 ⁇ C 60 aryl phosphine oxide group, and a C 6 ⁇ , or selected from the group consisting of an
  • the present invention also provides an organic electroluminescent device comprising a cathode, a cathode, and at least one organic layer sandwiched between the anode and the cathode, wherein at least one of the one or more organic layers includes a compound represented by the general formula An electroluminescent device is provided.
  • At least one of the organic compound layers including the compound represented by Formula 1 may be selected from the group consisting of a hole injection layer, a hole transport layer, a light emission assist layer, a light emitting layer, an electron transport layer, and an electron injection layer, .
  • the compound represented by Formula 1 may be used as a phosphorescent host of the light emitting layer.
  • the compound represented by the general formula (1) of the present invention has excellent thermal stability and luminescent properties and can be used as a material of an organic material layer of an organic electroluminescent device.
  • novel compounds according to the invention are prepared by reacting a nitrogen-containing heteroaromatic ring (for example azine) with two dibenzo-based moieties (for example dibenzofuran or dibenzothiophene) non-symmetrically bonded to both sides thereof And a carbazole group, which is a kind of electron donating group (EDG) having an electron donor group, is bonded to at least one phenyl group of the two dibenzo series moieties, Is the basic skeleton.
  • a nitrogen-containing heteroaromatic ring for example azine
  • two dibenzo-based moieties for example dibenzofuran or dibenzothiophene
  • EDG electron donating group
  • the compound of Chemical Formula 1 has dibenzo-type moieties (eg, dibenzofuran (DBF), dibenzothiophene (DBT)) having both physicochemical properties with respect to holes and electrons, (Such as pyridine, pyrazine, and triazine) which is a kind of azine group, which is a large electron withdrawing group (EWG), and at least one carbazole group is connected to the dibenzo series moiety.
  • DPF dibenzofuran
  • DBT dibenzothiophene
  • EWG electron withdrawing group
  • the compound of Formula 1 is a bipolar compound, the recombination of holes and electrons is high, so that the hole injecting / transporting ability, luminous efficiency, driving voltage, lifetime characteristics, durability and the like can be improved.
  • the compound of formula (1) when used as a green phosphorescent material, not only excellent luminous efficiency characteristics but also low voltage driving ability can be obtained and lifetime can be increased, and thermal stability, high glass transition temperature characteristics and uniform morphology morphology). Since the organic EL device is also effective in inhibiting crystallization of the organic material layer, the performance and lifetime characteristics of the organic EL device including the compound can be greatly improved.
  • the planarity and stereoscopic property of the compound can be realized according to the bonding positions of two dibenzofurans or dibenzothiophene moieties bonded to azine groups.
  • the electron transporting ability is improved, and the driving and efficiency of the device to which these compounds are applied can be expected to be increased.
  • the dibenzofuran moiety or the dibenzothiophene moiety is more excellent in electron and hole stability than an aryl group, lifetime characteristics of a device to which such a compound is applied can be further improved.
  • two dibenzo-based moieties bonded to an azine group exhibit an asymmetric structure.
  • This asymmetric structure compound is easier to control the HOMO-LUMO value than a symmetric structure compound.
  • an asymmetric structural compound having a dibenzo-based moiety it is relatively easy to control the intermolecular distance as compared with a compound having a symmetric structure. That is, due to the nature of the dibenzo-based moiety capable of bonding at the 1,2,3,4-position, a structural disorder between the hydrogen of triazine and the dibenzo-based moiety occurs at the 1,4-bond, The distance will be farther away, which will also increase the T1 value.
  • At least one carbazole group in the form of a non-fused ring is introduced as an electron donor (EDG).
  • EDG electron donor
  • This carbazole group is electrochemically stable and has a deep HOMO level by conjugation with other amines EDG.
  • the carbazole group is also excellent in thermal stability and electrochemical stability, and has a high glass transition temperature (Tg) and excellent carrier transporting ability. Particularly, the electron and hole transport mobility is very excellent, and the balance of the carriers in the light emitting layer is very excellent.
  • the host material should have a triplet energy gap higher than the dopant of the host. That is, in order to effectively provide phosphorescent emission from the dopant, the lowest excitation state of the host must be higher energy than the lowest emission state of the dopant.
  • the compound represented by Formula 1 has a high triplet energy and can be used as a host material because the energy level can be controlled higher than that of the dopant.
  • the compound represented by the formula (1) can prevent the excitons generated in the light emitting layer from diffusing into the electron transporting layer or the hole transporting layer adjacent to the light emitting layer. Accordingly, the luminous efficiency of the device can be improved by increasing the number of the excitons contributing to the light emission in the light emitting layer, the durability and stability of the device can be improved, and the lifetime of the device can be efficiently increased.
  • the compound represented by the above formula (1) can improve the phosphorescence characteristics of the organic electroluminescent device and improve the electron injection / transport ability, luminous efficiency, driving voltage and lifetime characteristics. Therefore, the compound of Chemical Formula (1) according to the present invention can be used as a material of any one of a hole injection layer, a hole transporting layer, a light emitting layer, an electron transporting layer and an electron injecting layer which is an organic material layer of an organic electroluminescent device, , Green and / or red phosphorescent host material).
  • the compound represented by formula (1) of the present invention when used as a blue, green and / or red phosphorescent host material, preferably phosphorescent green n-type host and / or phosphor red host, for example, a full color display panel having a low driving voltage, a high efficiency and a long lifetime compared with the organic electroluminescent device can be manufactured, and a high efficiency and a long life can be improved.
  • the compound represented by the general formula (1) according to the present invention is a compound represented by the general formula (1), which comprises an azine group and two dibenzo-based moieties (dibenzofuran or dibenzothiophene moiety) At least one carbazole group, which is a kind of electron donor (EDG), is bonded to any one of six-membered rings (e.g., phenyl group) in the core.
  • EDG electron donor
  • X 1 and X 2 are the same as or different from each other and each independently O or S. At this time, when d is 0, dibenzofuran moiety is formed, and in case of S, dibenzothiophene moiety can be formed.
  • Y 1 to Y 16 are the same as or different from each other, and each independently CR 8 or N; In this case, when there are a plurality of CR 8 s , the plurality of R 8 s may be the same or different.
  • the remaining is CR 8 ;
  • At least one of Y 13 to Y 16 is N, the remaining is CR 8 ;
  • At least one of Y 1 to Y 4 is N, and at least one of Y 9 to Y 12 is N, the remainder is CR 8 ;
  • At least one of Y 5 to Y 8 is N, and at least one of Y 13 to Y 16 is N, the remainder is CR 8 ;
  • At least one of Y 1 to Y 4 is N, and when one of Y 13 to Y 16 is N, the remaining is CR 8 ;
  • Y 1 to Y 16 may all be CR 8 (see the following formulas 9 to 13).
  • R 8 is hydrogen, heavy hydrogen, a halogen group, a cyano group, a nitro group, an amino group, an alkynyl group of C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 ⁇ C 40 of, C 3 ⁇ C 40 cycloalkyl group, the number of nuclear atoms of 3 to 40 heterocycloalkyl group, C 6 ⁇ C 60 aryl group, nuclear atoms aryl of from 5 to 60 heteroaryl group, a C 1 ⁇ alkyloxy group of C 40, C 6 ⁇ C 60 aryloxy group, C group 1 ⁇ C 40 alkyl silyl, C 6 ⁇ C 60 aryl silyl group, a alkyl boronic of C 1 ⁇ C 40, an aryl boronic a C 6 ⁇ C 60, C 1 ⁇ C 40 phosphine groups, C 1 to C 40 phosphine oxide groups, and C 6 to C 60
  • R 8 is a hydrogen, a deuterium, a halogen, a cyano group, a nitro group, C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 ⁇ C 40 alkynyl group, C 3 ⁇ C 40 of the A cycloalkyl group, and a C 6 to C 60 aryl group.
  • Z 1 to Z 3 are the same or different and are each independently CR 5 or N, and at least one of them is N. In one preferred embodiment, from 1 to 3 of Z 1 to Z 3 may be N, for example, pyridine, pyrimidine, triazine. More preferably, all of Z 1 to Z 3 are N and triazine is electron-withdrawing.
  • Ar 1 is selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, C 1 to C 40 alkyl, C 2 to C 40 alkenyl, C 2 to C 40 alkynyl, C 3 to C 40 cycloalkyl, A C 6 to C 60 aryl group, and the like.
  • Ar 1 is preferably an aryl group of C 6 to C 60 , and may be, for example, a phenyl group, a biphenyl group, a naphthyl group, a triphenyl group, an anthryl group, a phenanthryl group and the like.
  • Ar 1 can be selected from the group of substituents represented by the following structural formulas.
  • Ar 1 may be substituted with at least one substituent group known in the art (for example, the same definition as R 6 ).
  • a and c are each an integer of 0 to 3
  • b and d are an integer of 0 to 4, respectively.
  • hydrogen means not substituted with R 1 to R 4
  • a to d are each an integer of 1 or more, one or more hydrogen atoms are substituted with R 1 to R 4 . it means.
  • R 1 to R 5 are the same or different, each independently represent hydrogen, deuterium, a halogen, a cyano group, a nitro group, C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 ⁇ C 40 of the An alkynyl group, a C 3 to C 40 cycloalkyl group, a heteroaryl group having 3 to 40 nuclear atoms, a C 6 to C 60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C 1 to C 40 alkyl A C 6 to C 60 aryloxy group, a C 1 to C 40 alkylsilyl group, a C 6 to C 60 arylsilyl group, a C 1 to C 40 alkylboron group, a C 6 to C 60 aryl boron group, C 6 ⁇ C 60 aryl phosphine group, C 6 ⁇ C 60 aryl phosphine oxide group, and a C 6
  • R 1 to R 5 each are plural, they are the same as or different from each other. Specifically, R 1 to R 5 are the same or different and each independently represents hydrogen, deuterium, halogen, cyano, nitro, C 1 to C 40 alkyl, C 2 to C 40 alkenyl, C 2 An alkynyl group of C 40 to C 40 , a cycloalkyl group of C 3 to C 40 , and an aryl group of C 6 to C 60 .
  • m and n are each an integer of 0 to 3, and m + n? 1.
  • m or n 0, it means that hydrogen is not substituted with A or B.
  • m and n are each an integer of 1 or more, it means that at least one hydrogen is substituted with A and B, respectively.
  • m and n may each be an integer of 0 to 2.
  • b + m and d + n may be an integer of 0 to 4, respectively.
  • a and B are electron donating substituents each of which serves to provide electrons.
  • EDG electron donating group
  • a and B are the same as or different from each other, and each independently may be any of the substituents represented by the above-described formulas (2) and (3).
  • e is an integer of 0 to 4
  • f is an integer of 0 to 3.
  • hydrogen means not substituted by R 6 and R 7
  • e and f are each an integer of 1 or more, at least one hydrogen is substituted with R 6 and R 7 respectively .
  • R 6 and R 7 are the same or different, each independently represent hydrogen, deuterium, a halogen, a cyano group, a nitro group, C 1 ⁇ alkenyl group of the C 40 alkyl group, C 2 ⁇ C 40 of, C 2 ⁇ C A C 3 to C 40 cycloalkyl group, a heteroaryl group having 3 to 40 nuclear atoms, a C 6 to C 60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C 1 to C 40 alkenyl group, C 6 -C 60 aryloxy groups, C 1 -C 40 alkylsilyl groups, C 6 -C 60 arylsilyl groups, C 1 -C 40 alkylboron groups, C 6 -C 60 a group of the arylboronic, C 6 ⁇ C 60 aryl phosphine group, C 6 ⁇ C 60 aryl phosphine oxide group, and a C 6 ⁇ selected from the
  • R 6 and R 7 are plural, they may be the same as or different from each other.
  • R 6 and R 7 are each independently hydrogen, deuterium, a halogen, a cyano group, a nitro group, C 1 ⁇ alkenyl group of the C 40 alkyl group, C 2 ⁇ C 40 of, C 2 ⁇ C 40 A C 3 to C 40 cycloalkyl group, and a C 6 to C 60 aryl group, or may be bonded to adjacent groups to form a condensed ring.
  • adjacent groups may be one R 6 and one R 6 , one R 6 and one Ar 2 , one R 7 and another R 7 , one R 7, and one Ar 2 .
  • Ar 2 represents a C 1 to C 40 alkyl group, a C 2 to C 40 alkenyl group, a C 2 to C 40 alkynyl group, a C 3 to C 40 cycloalkyl group, 6 ⁇ C 60 aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, and a C 6 ⁇ , or selected from the group consisting of an aryl amine of the C 60, or adjacent groups condensed in combination with (for example, R 6, R 7) A ring can be formed.
  • the Ar 2 may be selected from the group consisting of an aryl amine of the C 6 ⁇ C 60 aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, and a C 6 ⁇ C 60.
  • a and B are the same as or different from each other, and each independently can be any one selected from the group of substituents represented by the following structural formulas.
  • Ar 2 is the same as defined in formula (1). Although not specifically shown, the above-mentioned structural formula may be substituted with at least one substituent group known in the art (for example, the same definition as R 6 ).
  • Ar 1 to Ar 2 , and R 1 to R 8 are independently selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, A halogen atom, a cyano group, a nitro group, a C 2 to C 40 alkenyl group, an aryl group, an aryl group, an aryl group, an aryl group, an aryl group, an aryl group, alkynyl of C 2 ⁇ C 40, C 3 ⁇ C 40 cycloalkyl group, a number of nuclear atoms of 3 to 40 heterocycloalkyl group, C 1 ⁇ C 40 alkyl group, C 6 ⁇ aryl group of C 60, nuclear atoms 5 to 60 heteroaryl group, C 1 ⁇ C 40 alkyloxy group of, C 6 ⁇ C 60 aryloxy group,
  • the nitrogen-containing heterocycle having an EWG properties (such as, Z 1 ⁇ Z 3 containing ring) 2 dibenzo-based moiety that is bonded to (for example, X 1 hamyuhwan and X 2- containing rings) according to the positions of the carbon bonds of the asymmetric structure.
  • the bonding position of one of Y 1 to Y 4 of the X 1 containing ring connected to the Z 1 to Z 3 containing ring and the bonding position of one of Y 9 to Y 12 of the X 2 containing ring are asymmetric with each other .
  • the O rare cases (for example, Z 1 ⁇ Z 3-containing ring) is X 1 containing ring carbon position coupled to Y 1 il, X 2 containing ring carbon position which is bonded to the azine is Y 10 to the exception of Y 9 Y 12 (see Chemical Formula 4 below).
  • the carbon bond positions of two dibenzo-based moieties respectively linked to the nitrogen-containing heterocycle may be represented by any one of the following formulas (4) to (7).
  • the ring containing Z 1 to Z 3 in Formula 4 is bonded to any one of Y 10 to Y 12 (provided that the ring containing Z 1 to Z 3 is not bonded to Y 9 )
  • the ring containing Z 1 to Z 3 in Formula 5 is bonded to any one of Y 9 and Y 11 to Y 12 (provided that the ring containing Z 1 to Z 3 is not bonded to Y 10 )
  • the ring containing Z 1 to Z 3 in Formula 6 is bonded to any one of Y 9 , Y 10 and Y 12 (provided that the Z 1 to Z 3 containing ring is not bonded to Y 11 )
  • the ring containing Z 1 to Z 3 in the above formula (7) is bonded to any one of Y 9 to Y 11 (provided that the Z 1 to Z 3 containing ring is not bonded to Y 12 )
  • X 1 , X 2 , Y 1 to Y 16 , Z 1 to Z 3 , Ar 1 , m, n, A, B, a to d and R 1 to R 4 are as defined in Formula 1, respectively.
  • the compound represented by Formula 4 may be further represented by any one of Formulas 4a to 4c.
  • the compound represented by Formula 5 may be further represented by any one of Formulas 5a to 5c.
  • the compound represented by Formula 6 may be further represented by any one of Formulas 6a to 6c.
  • the compound represented by the above formula (7) may be further represented by any one of formulas (7a) to (7c).
  • dibenzo-based moieties such as dibenzofurane or dibenzothiophene moiety may be further represented by any one of the following formulas (8) to (12).
  • X 1 , X 2 , Z 1 to Z 3 , Ar 1 , n, A and B are as defined in the above formula (1).
  • each of X 1 and X 2 is independently O or S, and Z 1 to Z 3 are each independently CR 5 or N, a is N, Ar 1 is an aryl group of C 6 ⁇ C 60.
  • the carbon position of the X 1 -containing ring and the carbon position of the X 2 -containing ring bonded to the azine group (for example, the Z 1 to Z 3 -containing ring) have an asymmetric structure, and at least one of A and B is a carbazole group Lt; / RTI >
  • the compound represented by formula (1) according to the present invention may be further represented by any one of compounds 1 to 500 shown below.
  • the compounds represented by formula (1) of the present invention are not limited by the following examples.
  • alkyl means a monovalent substituent derived from a straight or branched saturated hydrocarbon having 1 to 40 carbon atoms.
  • alkyl include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl and hexyl.
  • alkenyl in the present invention means a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon double bond.
  • alkenyl include, but are not limited to, vinyl, allyl, isopropenyl, 2-butenyl, and the like.
  • alkynyl in the present invention means a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon triple bond.
  • alkynyls include, but are not limited to, ethynyl, 2-propynyl, and the like.
  • Cycloalkyl in the present invention means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms.
  • Examples of such cycloalkyls include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.
  • Aryl in the present invention means a monovalent substituent derived from a C6-C60 aromatic hydrocarbon having a single ring or a combination of two or more rings. Also, a form in which two or more rings are pendant or condensed with each other may be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, and the like.
  • Heteroaryl in the present invention means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms. Wherein at least one of the carbons, preferably one to three carbons, is replaced by a heteroatom such as N, O, S or Se.
  • a form in which two or more rings are pendant or condensed with each other may be included, and further, a condensed form with an aryl group may be included.
  • heteroaryls include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolizinyl, indolyl indolyl), purinyl, quinolyl, benzothiazole, carbazolyl, and heterocyclic rings such as 2-furanyl, N-imidazolyl, 2- , 2-pyridinyl, 2-pyrimidinyl, and the like, but are not limited thereto.
  • alkyloxy means a monovalent substituent group represented by R'O-, and R 'means alkyl having 1 to 40 carbon atoms.
  • alkyloxy may include linear, branched or cyclic structures. Examples of such alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy and pentoxy.
  • aryloxy means a monovalent substituent represented by RO-, and R means aryl having 6 to 60 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, diphenyloxy, and the like.
  • Alkylsilyl in the present invention refers to silyl substituted with alkyl having 1 to 40 carbon atoms
  • arylsilyl means silyl substituted with aryl having 6 to 60 carbon atoms.
  • alkyl boron is boron substituted with alkyl having 1 to 40 carbon atoms
  • aryl boron means boron substituted with aryl having 6 to 60 carbon atoms.
  • arylphosphine means a phosphine substituted with aryl having 6 to 60 carbon atoms
  • arylphosphine oxide group means that phosphine substituted with aryl having 6 to 60 carbon atoms includes O do.
  • condensed rings means condensed aliphatic rings, condensed aromatic rings, condensed heteroaliphatic rings, condensed heteroaromatic rings, or a combination thereof.
  • Arylamine in the present invention means an amine substituted with aryl having 6 to 60 carbon atoms.
  • the compounds represented by formula (1) of the present invention can be prepared without limitation by methods known in the art. For example, various syntheses can be carried out by referring to the synthesis process of the following examples.
  • the present invention provides an organic electroluminescent device comprising a compound represented by the above formula (1).
  • the organic electroluminescent device includes at least one anode, an anode, and at least one organic layer sandwiched between the anode and the cathode, and at least one of the one or more organic layers Include the compounds represented by the above formula (1).
  • the compounds may be used alone or in combination of two or more.
  • the at least one organic material layer may include at least one of a hole injecting layer, a hole transporting layer, a light emitting auxiliary layer, a light emitting layer, an electron transporting layer, and an electron injecting layer.
  • the organic compound layer containing the compound of Formula 1 is preferably a light emitting layer.
  • the light emitting layer of the organic electroluminescence device of the present invention may include a host material (preferably, a phosphorescent host material).
  • the light emitting layer of the organic electroluminescent device of the present invention may contain a compound other than the compound of Formula 1 as a host.
  • the structure of the organic electroluminescent device of the present invention is not particularly limited, and examples thereof include a substrate, an anode, a hole injecting layer, a hole transporting layer, a light emitting auxiliary layer, a light emitting layer, an electron transporting layer, an electron injecting layer and a cathode sequentially stacked Structure. At least one of the hole injecting layer, the hole transporting layer, the light-emitting auxiliary layer, the light emitting layer, the electron transporting layer, and the electron injecting layer may include the compound represented by Formula 1, ≪ / RTI > compounds. Further, the structure of the organic electroluminescent device of the present invention may be a structure in which an insulating layer or an adhesive layer is inserted into the interface between the electrode and the organic layer.
  • the organic electroluminescent device of the present invention can be manufactured by forming an organic material layer and an electrode by materials and methods known in the art, except that at least one of the organic material layers includes the compound represented by the above formula have.
  • the organic material layer may be formed by a vacuum deposition method or a solution coating method.
  • the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.
  • the substrate used in the fabrication of the organic electroluminescent device of the present invention is not particularly limited, but silicon wafer, quartz, glass plate, metal plate, plastic film and sheet can be used.
  • the positive electrode material examples include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of a metal and an oxide such as ZnO: Al or SnO2: Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole or polyaniline; And carbon black, but are not limited thereto.
  • Examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead or alloys thereof; And multi-layer structure materials such as LiF / Al or LiO2 / Al, but are not limited thereto.
  • the hole injecting layer, the hole transporting layer, the electron injecting layer and the electron transporting layer are not particularly limited, and ordinary materials known in the art can be used.
  • NBS (11.1 g, 62.1 mmol) was added to 150 mL of a methylene chloride mixture with 2 ', 4'-dichloro- [1,1'-biphenyl] -2-ol (13.5 g, 56.5 mmol) and Diisopropylamine ) was slowly added thereto and stirred at 40 ° C for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride and sodium thiosulfate aqueous solution, and the mixture was filtered with MgSO 4 . After removing the solvent of the filtered organic layer, 3-bromo-2 ', 4'-dichloro- [1,1'-biphenyl] -2-ol (13.5 g, yield 75%) .
  • the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO 4 . After removing the solvent of the filtered organic layer, the desired compound C2 (8.5 g, yield 85%) was obtained by column chromatography.
  • NBS (13.6 g, 76.4 mmol) was added to 200 mL of a methylene chloride mixture of 2 ', 6'-dichloro- [1,1'-biphenyl] -2-ol (16.6 g, 69.4 mmol) and Diisopropylamine ) was slowly added thereto and stirred at 40 ° C for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride and sodium thiosulfate aqueous solution, and the mixture was filtered with MgSO 4 . After removing the solvent of the filtered organic layer, 3-bromo-2 ', 6'-dichloro- [1,1'-biphenyl] -2-ol (17.0 g, yield 77%) .
  • Tri-tert-butylphosphine (0.9 mL, 3.7 mmol) was added and the mixture was stirred at 110 ° C for 8 hours. After completion of the reaction, the product was extracted, and the solvent was removed. The solid was dissolved in toluene to remove silica, and then the desired product, 9- (8-chlorodibenzo [b, d] furan- carbazole (11.51 g, yield 51%).
  • 2,3,4-trichloropyridine (100.0 g, 548.1 mmol) and 2-methoxyphenyl boronic acid (87.5 g, 141.7 mmol) are placed in a 2-neck flask at room temperature.
  • Pd (PPh 3) 4 (19.0 g, 16.4mmol) and KF (47.8 g, 822.2 mmol) is added.
  • the mixture is stirred at 100 ° C for 5 hours. After completion of the reaction, the solution is subjected to silica filtration.
  • 3,4-dichloro-2- (2-methoxyphenyl) pyridine (40.0 g, 157.4 mmol) is dissolved in 400 ml of methylene chloride and placed in a 2-neck flask. Keep the condition at 0 °C in an ice bath. Of BBr 3 (22.7 ml, 236.1 mmol ) was slowly added. After completion of the reaction, 400 ml of distilled water at 0 ° C is slowly added. The reaction is extracted with methylene chloride and silica filtered. After removal of the solvent, a white solid compound, 2- (3,4-dichloropyridin-2-yl) phenol (31.4 g, yield 83%) was obtained.
  • a glass substrate coated with ITO Indium Tin Oxide
  • ITO Indium Tin Oxide
  • the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, dried and transferred to a UV OZONE cleaner (Power Sonic 405, Hoshin Tech), the substrate was cleaned using UV for 5 minutes, The substrate was transferred.
  • a solvent such as isopropyl alcohol, acetone, or methanol
  • a green organic electroluminescent device was fabricated in the same manner as in Example 1, except that CBP was used instead of the compound 119 as a luminescent host material in forming the light emitting layer.
  • a green organic electroluminescent device was fabricated in the same manner as in Example 1, except that Compound I was used instead of Compound 119 as a luminescent host material in forming the light emitting layer.
  • a green organic electroluminescent device was fabricated in the same manner as in Example 1, except that Compound II was used instead of Compound 119 as a luminescent host material in forming the light emitting layer.
  • the driving voltage, current efficiency and emission peak at the current density of 10 mA / cm 2 were measured for each of the green organic electroluminescent devices manufactured in Examples 1 to 21 and Comparative Examples 1 to 3, Respectively.
  • Example 1 119 4.62 516 55.5 Example 2 239 4.55 516 62.1 Example 3 219 5.46 516 42.1 Example 4 59 5.33 516 43.0 Example 5 99 4.95 516 51.2 Example 6 240 5.01 516 53.1 Example 7 118 4.88 516 48.2 Example 8 117 4.58 516 40.2 Example 9 254 5.11 516 55.5 Example 10 284 4.76 516 42.1 Example 11 304 4.54 516 58.0 Example 12 360 4.99 516 52.7 Example 13 386 5.01 516 55.5 Example 14 259 4.21 516 56.3 Example 15 266 5.46 516 49.6 Example 16 290 4.87 516 47.2 Example 17 289 5.21 516 53.1 Example 18 409 4.77 516 52.1 Example 19 407 4.56 516 53.3 Example 20 415 4.99 516 47.7 Example 21 481 4.89 516 56.6 Comparative Example 1 CBP 6.93 516 38.2 Comparative Example 2
  • the green organic electroluminescent devices of Examples 1 to 21, in which the compound according to the present invention was applied to the light emitting layer were compared with the green organic electroluminescent devices of Comparative Examples 1 to 3 in which CBP, It was found that the current efficiency and the driving voltage were superior to those of the electroluminescent device.

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Abstract

The present invention relates to a novel organic compound and an organic electroluminescent element using same and, more specifically, to a novel compound having excellent luminous performance and to an organic electroluminescent element having improved characteristics, such as high luminous efficiency, a low driving voltage, and a long lifespan, by containing the novel compound in one or more organic material layers.

Description

유기 화합물 및 이를 이용한 유기 전계 발광 소자Organic compounds and organic electroluminescent devices using the same
본 발명은 신규한 유기 화합물 및 이를 이용한 유기 전계 발광 소자에 관한 것으로, 보다 상세하게는 열안정성과 발광능이 우수한 신규 화합물 및 이를 하나 이상의 유기물층에 포함함으로써 발광효율, 구동 전압, 수명 등의 특성이 향상된 유기 전계 발광 소자에 관한 것이다.The present invention relates to a novel organic compound and an organic electroluminescent device using the same. More particularly, the present invention relates to a novel compound having excellent thermal stability and light emitting ability, and a novel compound containing the same in one or more organic layers to improve characteristics such as luminous efficiency, And an organic electroluminescent device.
1950년대 Bernanose의 유기 박막 발광 관측을 시점으로 1965년 안트라센 단결정을 이용한 청색 전기발광으로 이어진 유기 전계 발광(electroluminescent) 소자에 대한 연구는 1987년 탕(Tang)에 의하여 정공층과 발광층의 기능층으로 나눈 적층구조의 유기 전계 발광 소자가 제시되었다. 이후 고효율, 고수명의 유기 전계 발광 소자를 만들기 위하여, 소자 내 각각의 특징적인 유기물 층을 도입하는 형태로 발전하여 왔으며, 이에 사용되는 특화된 물질의 개발로 이어졌다. A study on organic electroluminescent devices that resulted in blue electroluminescence using anthracene single crystals in 1965 based on observation of organic thin film emission of Bernanose in the 1950s was conducted by Tang in 1987 divided by the functional layer of the hole layer and the light emitting layer An organic electroluminescent device having a laminated structure has been proposed. Since then, in order to make high efficiency and high number of organic electroluminescent devices, each organic material layer has been developed into a form of introducing a characteristic organic material layer in the device, leading to the development of specialized materials used therefor.
유기 전계 발광 소자는 두 전극 사이에 전압을 걸어 주면 양극에서는 정공이 주입되고, 음극에서는 전자가 유기물층으로 주입된다. 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 바닥상태로 떨어질 때 빛이 나게 된다. 이때 유기물층으로 사용되는 물질은 그 기능에 따라, 발광 물질, 정공 주입 물질, 정공 수송 물질, 전자 수송 물질, 전자 주입 물질 등으로 분류될 수 있다. In the organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected into the anode, and electrons are injected into the organic layer from the cathode. When the injected holes and electrons meet, an exciton is formed. When the exciton falls to the ground state, light is emitted. The material used as the organic material layer may be classified into a light emitting material, a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on its function.
유기 전계 발광 소자의 발광층 형성재료는 발광색에 따라 청색, 녹색, 적색 발광 재료로 구분될 수 있다. 그밖에, 보다 나은 천연색을 구현하기 위한 발광재료로 노란색 및 주황색 발광재료도 사용된다. 또한, 색순도의 증가와 에너지 전이를 통한 발광 효율을 증가시키기 위하여, 발광 재료로서 호스트/도펀트 계를 사용할 수 있다. The light emitting layer forming material of the organic electroluminescent device can be classified into blue, green and red light emitting materials according to the luminescent color. In addition, yellow and orange light emitting materials are also used as light emitting materials for realizing better color. Further, in order to increase the color purity and increase the luminous efficiency through energy transfer, a host / dopant system can be used as a light emitting material.
도판트 물질은 유기 물질을 사용하는 형광 도판트와 Ir, Pt 등의 중원자(heavy atoms)가 포함된 금속 착체 화합물을 사용하는 인광 도판트로 나눌 수 있다. 이러한 인광 재료의 개발은 이론적으로 형광에 비해 4배까지의 발광 효율을 향상시킬 수 있어 인광 도판트 뿐만 아니라 인광 호스트 재료들에 대해 관심이 집중되고 있다. The dopant material can be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. The development of such a phosphorescent material can theoretically improve the luminous efficiency up to 4 times as compared with that of fluorescence, and attention is focused on phosphorescent host materials as well as phosphorescent dopants.
현재까지 정공 주입층, 정공 수송층, 정공 차단층, 전자 수송층에 사용되는 물질로는 NPB, BCP, Alq3 등이 널리 알려져 있고, 발광 물질로는 안트라센 유도체들이 형광 도판트/호스트 재료로서 보고되고 있다. 특히 발광재료 중 효율 향상 측면에서 큰 장점을 가지고 있는 인광 재료로서는 Firpic, Ir(ppy)3, (acac)Ir(btp)2 등과 같은 Ir을 포함하는 금속 착체 화합물이 청색, 녹색, 적색 도판트 재료로 사용되고 있다. 현재까지는 CBP가 인광 호스트 재료로 우수한 특성을 나타내고 있다. NPB, BCP, Alq 3 and the like are widely known as materials used for the hole injecting layer, the hole transporting layer, the hole blocking layer and the electron transporting layer, and the anthracene derivatives as a luminescent material have been reported as a fluorescent dopant / host material . In particular Firpic, Ir as a phosphorescent material that has a great advantage in improving the efficiency aspects of the light-emitting material (ppy) 3, (acac) Ir (btp) 2 Ir metal complex compound is a blue, green and red host material that includes such as . So far, CBP has shown excellent properties as a phosphorescent host material.
그러나 종래 발광 물질들은 발광 특성 측면에서 유리한 면이 있으나, 유리전이온도가 낮고 열적 안정성이 매우 좋지 않기 때문에, 유기 전계 발광 소자에서의 수명 측면에서 만족할만한 수준이 되지 못하고 있다. 따라서, 우수한 성능을 가지는 발광 물질의 개발이 요구되고 있다.However, conventional luminescent materials are advantageous in terms of luminescence properties, but they are not satisfactory in terms of lifetime in an organic electroluminescent device because the glass transition temperature is low and the thermal stability is not very good. Therefore, development of a luminescent material having excellent performance is required.
[선행기술문헌][Prior Art Literature]
[특허문헌][Patent Literature]
(특허문헌 1) 일본공개특허공보 제2001-160489호(Patent Document 1) Japanese Laid-Open Patent Publication No. 2001-160489
본 발명은 전술한 문제점을 해결하기 위해 안출된 것으로서, 보다 구체적으로 유기 전계 발광 소자에 적용할 수 있으며, 열안정성과 정공 주입능, 정공 수송능, 발광능, 전자 수송능, 전자 주입능 등이 모두 우수한 신규 유기 화합물을 제공하는 것을 목적으로 한다. SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide an organic electroluminescent device which can be applied to an organic electroluminescent device and which has excellent thermal stability, hole injection ability, hole transport ability, All aimed at providing excellent novel organic compounds.
또한, 본 발명은 전술한 신규 유기 화합물을 포함하여 열적 안정성, 낮은 구동전압과 높은 발광효율을 나타내며, 수명이 향상되는 유기 전계 발광 소자를 제공하는 것을 또 다른 목적으로 한다.Another object of the present invention is to provide an organic electroluminescent device including the above-described novel organic compound and exhibiting thermal stability, a low driving voltage and a high luminous efficiency, and having an improved lifetime.
상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1 로 표시되는 화합물을 제공한다.In order to achieve the above object, the present invention provides a compound represented by the following general formula (1).
Figure PCTKR2019000614-appb-C000001
Figure PCTKR2019000614-appb-C000001
상기 화학식 1에서,In Formula 1,
X1 및 X2는 서로 동일하거나 상이하며, 각각 독립적으로 O 또는 S이고,X 1 and X 2 are the same as or different from each other and each independently O or S,
Y1 내지 Y16은 서로 동일하거나 상이하며, 각각 독립적으로 CR8 또는 N이고, 이때 CR8이 복수 개인 경우 복수의 R8은 서로 동일하거나 또는 상이하며, Y 1 to Y 16 are the same as or different from each other, and each independently CR 8 or N, provided that when there are a plurality of CR 8 s , the plurality of R 8 s are the same as or different from each other,
Z1 내지 Z3는 서로 동일하거나 상이하며, 각각 독립적으로 CR5 또는 N이고, 이들 중 적어도 하나는 N이고,Z 1 to Z 3 are the same or different and each independently CR 5 or N, at least one of them is N,
Ar1은 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기 및 C6~C60의 아릴기로 이루어진 군에서 선택되고,Ar 1 is selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, C 1 to C 40 alkyl, C 2 to C 40 alkenyl, C 2 to C 40 alkynyl, C 3 to C 40 cycloalkyl, A C 6 to C 60 aryl group,
다만, Z1 내지 Z3 함유 환을 기준으로 상기 X1 함유 환과 상기 X2 함유 환은 서로 비대칭적으로 결합되며,Provided that the X 1 containing ring and the X 2 containing ring are asymmetrically bonded to each other based on the Z 1 to Z 3 containing ring,
m 및 n은 각각 0 내지 3의 정수이며, m+n ≥ 1이고,m and n are each an integer of 0 to 3, m + n? 1,
A 및 B는 서로 동일하거나 상이하며, 각각 독립적으로 하기 화학식 2 또는 화학식 3으로 표시되는 치환체 중 어느 하나이며;A and B are the same or different from each other, and are each independently any one of substituents represented by the following formula (2) or (3);
[화학식 2](2)
Figure PCTKR2019000614-appb-I000001
Figure PCTKR2019000614-appb-I000001
[화학식 3](3)
Figure PCTKR2019000614-appb-I000002
Figure PCTKR2019000614-appb-I000002
상기 화학식 2 또는 3에서,In the general formula (2) or (3)
*은 상기 화학식 1에 결합되는 부위를 의미하고,* Represents a moiety bonded to Formula 1,
X3는 단일결합이고,X 3 is a single bond,
Ar2 는 C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 혹은 인접한 기와 결합하여 축합 고리를 형성할 수 있고,Ar 2 represents a C 1 to C 40 alkyl group, a C 2 to C 40 alkenyl group, a C 2 to C 40 alkynyl group, a C 3 to C 40 cycloalkyl group, a C 6 to C 60 aryl group, 5 to 60 heteroaryl groups and C 6 to C 60 arylamine groups, or may be bonded to adjacent groups to form a condensed ring,
a, c 및 f는 각각 0 내지 3의 정수이고,a, c, and f are each an integer of 0 to 3,
b, d 및 e는 각각 0 내지 4의 정수이며, 이때 b+m≤4, d+n≤4이고,b, d and e are each an integer of 0 to 4, wherein b + m? 4, d + n? 4,
R1 내지 R8은 서로 동일하거나 상이하며, 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 혹은 인접한 기와 결합하여 축합 고리를 형성할 수 있고, 이때 상기 R1 내지 R7이 각각 복수인 경우, 이들은 서로 동일하거나 상이하고,R 1 to R 8 are the same or different from each other and each independently represents hydrogen, deuterium, halogen, cyano, nitro, C 1 to C 40 alkyl, C 2 to C 40 alkenyl, C 2 to C 40 An alkynyl group, a C 3 to C 40 cycloalkyl group, a heteroaryl group having 3 to 40 nuclear atoms, a C 6 to C 60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C 1 to C 40 alkyl A C 6 to C 60 aryloxy group, a C 1 to C 40 alkylsilyl group, a C 6 to C 60 arylsilyl group, a C 1 to C 40 alkylboron group, a C 6 to C 60 aryl boron group, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~, or selected from the group consisting of an aryl amine of the C 60 of, or adjacent groups combine to form a condensed ring And when R 1 to R 7 are each plural, they may be the same or different from each other,
상기 Ar1 내지 Ar2, 및 R1 내지 R8의 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 아릴포스핀옥사이드기 및 아릴아민기는 각각 독립적으로 중수소, 할로겐, 시아노기, 니트로기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C1~C40의 알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환될 수 있으며, 이때 상기 치환기가 복수인 경우, 이들은 서로 동일하거나 상이할 수 있다.Alkyl group of said Ar 1 to Ar 2, and R 1 to R 8, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl A halogen atom, a cyano group, a nitro group, a C 2 to C 40 alkenyl group, a C 2 to C 40 alkenyl group, an aryloxy group, an aryloxy group, A cycloalkyl group having 3 to 40 carbon atoms, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C 1 to C 40 alkyl group, a C 6 to C 60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms A C 1 to C 40 alkyloxy group, a C 6 to C 60 aryloxy group, a C 1 to C 40 alkylsilyl group, a C 6 to C 60 arylsilyl group, a C 1 to C 40 alkyl boron group, C 6 ~ C 60 aryl group of boron, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~ selected from the group consisting of an arylamine C in 60 If the first plural number, and wherein said substituent is substituted by at least one substituent, these may be the same or different from each other.
또한, 본 발명은 양극, 음극 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하고, 상기 1층 이상의 유기물층 중 적어도 하나는 상기 화학식 1로 표시되는 화합물을 포함하는 것인 유기 전계 발광 소자를 제공한다. The present invention also provides an organic electroluminescent device comprising a cathode, a cathode, and at least one organic layer sandwiched between the anode and the cathode, wherein at least one of the one or more organic layers includes a compound represented by the general formula An electroluminescent device is provided.
여기서, 상기 화학식 1로 표시되는 화합물을 포함하는 유기물층 중 적어도 하나는 정공 주입층, 정공 수송층, 발광 보조층, 발광층, 전자 수송층 및 전자 주입층으로 이루어진 군에서 선택될 수 있으며, 발광층인 것이 바람직하다. 이때, 상기 화학식 1로 표시되는 화합물은 발광층의 인광 호스트로 사용될 수 있다.At least one of the organic compound layers including the compound represented by Formula 1 may be selected from the group consisting of a hole injection layer, a hole transport layer, a light emission assist layer, a light emitting layer, an electron transport layer, and an electron injection layer, . At this time, the compound represented by Formula 1 may be used as a phosphorescent host of the light emitting layer.
본 발명의 화학식 1로 표시되는 화합물은 열적 안정성 및 발광 특성이 우수하기 때문에 유기 전계 발광 소자의 유기물층의 재료로 사용될 수 있다.The compound represented by the general formula (1) of the present invention has excellent thermal stability and luminescent properties and can be used as a material of an organic material layer of an organic electroluminescent device.
특히, 본 발명의 화학식 1로 표시되는 화합물을 인광 호스트 재료로 사용할 경우, 종래의 호스트 재료에 비해 낮은 구동전압, 높은 효율 및 긴 수명을 갖는 유기 전계 발광 소자를 제조할 수 있고, 나아가 성능 및 수명이 향상된 풀 칼라 디스플레이 패널도 제조할 수 있다.In particular, when the compound represented by Formula 1 of the present invention is used as a phosphorescent host material, an organic electroluminescent device having a lower driving voltage, higher efficiency, and longer lifetime than conventional host materials can be manufactured. Further, This improved full color display panel can also be manufactured.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
<유기 화합물><Organic compounds>
본 발명에 따른 신규 화합물은, 함질소 헤테로방향족환(예, azine)과, 이의 양측에 비(非)대칭적으로 결합된 2개의 디벤조계 모이어티(예, 디벤조퓨란 또는 디벤조티오펜)를 포함하는 코어(core)를 가지며, 상기 2개의 디벤조계 모이어티 중 적어도 하나의 페닐기에, 전자공여성을 갖는 전자주게기(electron donating group, EDG)의 일종인 카바졸(carbazole)기가 연결되는 구조를 기본 골격으로 한다. The novel compounds according to the invention are prepared by reacting a nitrogen-containing heteroaromatic ring (for example azine) with two dibenzo-based moieties (for example dibenzofuran or dibenzothiophene) non-symmetrically bonded to both sides thereof And a carbazole group, which is a kind of electron donating group (EDG) having an electron donor group, is bonded to at least one phenyl group of the two dibenzo series moieties, Is the basic skeleton.
구체적으로, 상기 화학식 1의 화합물은 정공(hole)과 전자(electron)에 대한 양쪽성의 물리화학적 성질을 가진 디벤조계 모이어티[예, dibenzofuran (DBF), dibenzothiophene (DBT)]와, 전자흡수성이 큰 전자끌게기(EWG)인 아진기의 일종인 함질소 헤테로방향족환(예, pyridine, pyrazine, triazine)을 포함하며, 상기 디벤조계 모이어티에 적어도 하나의 카바졸기가 연결된다. 이러한 화학식 1의 화합물은 양극성(bipolar) 화합물이기 때문에, 정공과 전자의 재결합이 높아 정공 주입/수송 능력, 발광 효율, 구동 전압, 수명 특성, 내구성 등을 향상시킬 수 있다. 특히, 상기 화학식 1의 화합물을 그린 인광재료로서 적용할 경우, 우수한 발광효율 특성을 가질 뿐만 아니라 저전압 구동이 가능하여 수명 상승 효과를 나타낼 수 있으며, 열적 안정성, 높은 유리전이온도 특성 및 균일한 모폴로지(morphology)를 가져 소자 특성이 우수하다. 그리고 유기물층의 결정화 억제에도 효과가 있으므로, 상기 화합물을 포함하는 유기 전계 발광 소자의 성능 및 수명 특성이 크게 향상될 수 있다. Specifically, the compound of Chemical Formula 1 has dibenzo-type moieties (eg, dibenzofuran (DBF), dibenzothiophene (DBT)) having both physicochemical properties with respect to holes and electrons, (Such as pyridine, pyrazine, and triazine) which is a kind of azine group, which is a large electron withdrawing group (EWG), and at least one carbazole group is connected to the dibenzo series moiety. Since the compound of Formula 1 is a bipolar compound, the recombination of holes and electrons is high, so that the hole injecting / transporting ability, luminous efficiency, driving voltage, lifetime characteristics, durability and the like can be improved. In particular, when the compound of formula (1) is used as a green phosphorescent material, not only excellent luminous efficiency characteristics but also low voltage driving ability can be obtained and lifetime can be increased, and thermal stability, high glass transition temperature characteristics and uniform morphology morphology). Since the organic EL device is also effective in inhibiting crystallization of the organic material layer, the performance and lifetime characteristics of the organic EL device including the compound can be greatly improved.
또한 본 발명에서는 아진기에 결합되는 2개의 디벤조퓨란 또는 디벤조티오펜 모이어티의 결합 위치에 따라, 화합물의 평면성 및 입체성이 구현될 수 있다. 이로 인해 전자의 전달 능력이 향상되어 이러한 화합물이 적용된 소자의 구동 및 효율 증가 효과를 기대할 수 있다. 더욱이, 상기 디벤조퓨란 모이어티 또는 디벤조티오펜 모이어티는 아릴기에 비해 전자 및 정공 안정성이 뛰어나므로, 이러한 화합물이 적용된 소자의 수명 특성을 보다 향상시킬 수 있다. 특히, 본 발명에서는 아진기에 결합되는 2개의 디벤조계 모이어티가 비대칭 구조(Asymmetry)를 나타내는데, 이러한 비대칭 구조의 화합물은 대칭 구조 화합물에 비해 HOMO-LUMO 값 조절이 용이하다. 일례로, 디벤조계 모이어티를 갖는 비대칭 구조 화합물의 경우, 대칭 구조를 갖는 화합물에 비해 분자간 거리의 조절이 상대적으로 용이하다. 즉, 1,2,3,4 번 위치에 결합이 가능한 디벤조계 모이어티의 특성상 1,4번 결합에서의 트리아진의 수소와 디벤조계 모이어티 간의 구조적 장애(Steric hindrance)가 발생하여 분자간 거리가 멀어지게 되며, 이로 인해 T1 값 또한 높아지게 된다. 전술한 특성을 이용할 경우 화학 구조의 비대칭성(Asymmetry)을 통해 유기물층 재료의 HOMO-LUMO 및 T1, S1 값의 튜닝이 가능하다.In the present invention, the planarity and stereoscopic property of the compound can be realized according to the bonding positions of two dibenzofurans or dibenzothiophene moieties bonded to azine groups. As a result, the electron transporting ability is improved, and the driving and efficiency of the device to which these compounds are applied can be expected to be increased. Furthermore, since the dibenzofuran moiety or the dibenzothiophene moiety is more excellent in electron and hole stability than an aryl group, lifetime characteristics of a device to which such a compound is applied can be further improved. In particular, in the present invention, two dibenzo-based moieties bonded to an azine group exhibit an asymmetric structure. This asymmetric structure compound is easier to control the HOMO-LUMO value than a symmetric structure compound. For example, in the case of an asymmetric structural compound having a dibenzo-based moiety, it is relatively easy to control the intermolecular distance as compared with a compound having a symmetric structure. That is, due to the nature of the dibenzo-based moiety capable of bonding at the 1,2,3,4-position, a structural disorder between the hydrogen of triazine and the dibenzo-based moiety occurs at the 1,4-bond, The distance will be farther away, which will also increase the T1 value. By using the above-mentioned characteristics, it is possible to adjust the HOMO-LUMO and T1 and S1 values of the organic material layer through the asymmetry of the chemical structure.
아울러, 본 발명에서는 전자주게기(EDG)로서 비(非)융합환 형태의 카바졸기가 적어도 하나 이상 도입된다. 이러한 카바졸기는 다른 아민류 EDG에 비해 conjugation을 이루어 전기화학적으로 안정하며 deep HOMO level을 가진다. 또한 카바졸기는 열적 안정성과 전기화학적 안정성이 매우 우수하고, 높은 유리전이온도(Tg)와 우수한 캐리어 수송 능력을 갖는다. 특히 전자 및 정공 수송 이동성이 매우 우수하여, 발광층 내에서의 캐리어들의 밸런스가 매우 우수한 특성들을 나타낼 수 있다.In the present invention, at least one carbazole group in the form of a non-fused ring is introduced as an electron donor (EDG). This carbazole group is electrochemically stable and has a deep HOMO level by conjugation with other amines EDG. The carbazole group is also excellent in thermal stability and electrochemical stability, and has a high glass transition temperature (Tg) and excellent carrier transporting ability. Particularly, the electron and hole transport mobility is very excellent, and the balance of the carriers in the light emitting layer is very excellent.
한편 유기 전계 발광 소자의 인광 발광층에서, 호스트 물질은 호스트의 삼중항 에너지 갭이 도펀트보다 높아야 한다. 즉, 도펀트로부터 효과적으로 인광 발광을 제공하기 위해서는 호스트의 가장 낮은 여기 상태가 도펀트의 가장 낮은 방출 상태보다 에너지가 더 높아야 한다. 상기 화학식 1로 표시되는 화합물은 높은 삼중항 에너지를 가지며, 에너지 준위가 도펀트에 비해 높게 조절될 수 있어 호스트 물질로 사용될 수 있다. 이러한 화학식 1로 표시되는 화합물은 발광층에서 생성된 엑시톤이 발광층에 인접하는 전자 수송층 또는 정공 수송층으로 확산되는 것을 방지할 수 있다. 이로 인해, 발광층 내 발광에 기여하는 엑시톤의 수가 증가됨으로써 소자의 발광 효율이 개선될 수 있고, 소자의 내구성 및 안정성이 향상되어 소자의 수명 또한 효율적으로 증가될 수 있다.On the other hand, in the phosphorescent light emitting layer of the organic electroluminescent device, the host material should have a triplet energy gap higher than the dopant of the host. That is, in order to effectively provide phosphorescent emission from the dopant, the lowest excitation state of the host must be higher energy than the lowest emission state of the dopant. The compound represented by Formula 1 has a high triplet energy and can be used as a host material because the energy level can be controlled higher than that of the dopant. The compound represented by the formula (1) can prevent the excitons generated in the light emitting layer from diffusing into the electron transporting layer or the hole transporting layer adjacent to the light emitting layer. Accordingly, the luminous efficiency of the device can be improved by increasing the number of the excitons contributing to the light emission in the light emitting layer, the durability and stability of the device can be improved, and the lifetime of the device can be efficiently increased.
전술한 사항들로 인해, 상기 화학식 1 로 표시되는 화합물은 유기 전계 발광 소자의 인광 특성을 향상시킴과 동시에, 전자 주입/수송 능력, 발광 효율, 구동 전압, 수명 특성 등을 향상시킬 수 있다. 따라서, 본 발명에 따른 화학식 1의 화합물은 유기 전계 발광 소자의 유기물층인 정공 주입층, 정공 수송층, 발광층, 전자 수송층 및 전자 주입층 중 어느 하나의 재료로 사용될 수 있으며, 바람직하게는 발광층 재료(청색, 녹색 및/또는 적색의 인광 호스트 재료)로 사용될 수 있다. 특히, 본 발명의 화학식 1로 표시되는 화합물을 청색, 녹색 및/또는 적색의 인광 호스트 재료, 바람직하게는 인광 그린 n-type 호스트 및/또는 인광 레드 호스트로 사용시, 종래의 발광 호스트 재료(예를 들어, CBP)에 비해 낮은 구동전압, 높은 효율 및 장수명을 갖는 유기 전계 발광 소자를 제조할 수 있고, 나아가 고효율 및 장수명 특성이 향상된 풀 칼라 디스플레이 패널도 제조할 수 있다.Due to the above-mentioned matters, the compound represented by the above formula (1) can improve the phosphorescence characteristics of the organic electroluminescent device and improve the electron injection / transport ability, luminous efficiency, driving voltage and lifetime characteristics. Therefore, the compound of Chemical Formula (1) according to the present invention can be used as a material of any one of a hole injection layer, a hole transporting layer, a light emitting layer, an electron transporting layer and an electron injecting layer which is an organic material layer of an organic electroluminescent device, , Green and / or red phosphorescent host material). In particular, when the compound represented by formula (1) of the present invention is used as a blue, green and / or red phosphorescent host material, preferably phosphorescent green n-type host and / or phosphor red host, For example, a full color display panel having a low driving voltage, a high efficiency and a long lifetime compared with the organic electroluminescent device can be manufactured, and a high efficiency and a long life can be improved.
구체적으로, 본 발명에 따른 화학식 1로 표시되는 화합물은, 아진기와 이의 양측에 비(非)대칭적으로 연결된 2개의 디벤조계 모이어티(디벤조퓨란 또는 디벤조티오펜 모이어티)를 포함하는 코어(core)로 가지며, 상기 코어 내 어느 하나의 6원 고리(예, 페닐기)에 전자주게기(EDG)의 일종인 카바졸기가 적어도 하나 이상 결합된다. Specifically, the compound represented by the general formula (1) according to the present invention is a compound represented by the general formula (1), which comprises an azine group and two dibenzo-based moieties (dibenzofuran or dibenzothiophene moiety) At least one carbazole group, which is a kind of electron donor (EDG), is bonded to any one of six-membered rings (e.g., phenyl group) in the core.
상기 화학식 1로 표시되는 화합물에서, X1 및 X2는 서로 동일하거나 상이하며, 각각 독립적으로 O 또는 S이다. 이때, O일 경우에는 디벤조퓨란 모이어티를 형성하며, S일 경우에는 디벤조티오펜 모이어티를 형성할 수 있다.In the compound represented by the general formula (1), X 1 and X 2 are the same as or different from each other and each independently O or S. At this time, when d is 0, dibenzofuran moiety is formed, and in case of S, dibenzothiophene moiety can be formed.
Y1 내지 Y16은 서로 동일하거나 상이하며, 각각 독립적으로 CR8 또는 N이다. 이때 CR8이 복수 개인 경우 복수의 R8은 서로 동일하거나 또는 상이할 수 있다. 예를 들면, Y1 내지 Y4 중 하나 이상이 N일 경우, 나머지는 CR8이고; Y13 내지 Y16 중 하나 이상이 N일 경우, 나머지는 CR8이고; Y1 내지 Y4 중 하나 이상이 N이며, Y9 내지 Y12 중 하나 이상이 N일 경우, 나머지는 CR8이고; Y5 내지 Y8 중 하나 이상이 N이며, Y13 내지 Y16 중 하나 이상이 N일 경우, 나머지는 CR8이고; Y1 내지 Y4 중 하나 이상이 N이며, Y13 내지 Y16 중 하나가 N일 경우, 나머지는 CR8이고; Y1 내지 Y16가 모두 CR8일 수 있다(하기 화학식 9 내지 13 참조). Y 1 to Y 16 are the same as or different from each other, and each independently CR 8 or N; In this case, when there are a plurality of CR 8 s , the plurality of R 8 s may be the same or different. For example, when at least one of Y 1 to Y 4 is N, the remaining is CR 8 ; When at least one of Y 13 to Y 16 is N, the remaining is CR 8 ; At least one of Y 1 to Y 4 is N, and at least one of Y 9 to Y 12 is N, the remainder is CR 8 ; At least one of Y 5 to Y 8 is N, and at least one of Y 13 to Y 16 is N, the remainder is CR 8 ; At least one of Y 1 to Y 4 is N, and when one of Y 13 to Y 16 is N, the remaining is CR 8 ; Y 1 to Y 16 may all be CR 8 (see the following formulas 9 to 13).
여기서, R8은 수소, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택될 수 있다. 구체적으로, R8은 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 및 C6~C60의 아릴기로 이루어진 군에서 선택되는 것이 바람직하다.Wherein, R 8 is hydrogen, heavy hydrogen, a halogen group, a cyano group, a nitro group, an amino group, an alkynyl group of C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 of, C 3 ~ C 40 cycloalkyl group, the number of nuclear atoms of 3 to 40 heterocycloalkyl group, C 6 ~ C 60 aryl group, nuclear atoms aryl of from 5 to 60 heteroaryl group, a C 1 ~ alkyloxy group of C 40, C 6 ~ C 60 aryloxy group, C group 1 ~ C 40 alkyl silyl, C 6 ~ C 60 aryl silyl group, a alkyl boronic of C 1 ~ C 40, an aryl boronic a C 6 ~ C 60, C 1 ~ C 40 phosphine groups, C 1 to C 40 phosphine oxide groups, and C 6 to C 60 arylamine groups. Specifically, R 8 is a hydrogen, a deuterium, a halogen, a cyano group, a nitro group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 of the A cycloalkyl group, and a C 6 to C 60 aryl group.
Z1 내지 Z3는 서로 동일하거나 상이하며, 각각 독립적으로 CR5 또는 N이고, 이들 중 적어도 하나는 N이다. 바람직한 일 실시예를 들면, Z1 내지 Z3는 중 1~3개가 N일 수 있으며, 예를 들면, 피리딘, 피리미딘, 트리아진일 수 있다. 보다 바람직하게는Z1 내지 Z3가 모두 N으로, 전자 끄는 특성이 큰 트리아진이다.Z 1 to Z 3 are the same or different and are each independently CR 5 or N, and at least one of them is N. In one preferred embodiment, from 1 to 3 of Z 1 to Z 3 may be N, for example, pyridine, pyrimidine, triazine. More preferably, all of Z 1 to Z 3 are N and triazine is electron-withdrawing.
Ar1은 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기 및 C6~C60의 아릴기로 이루어진 군에서 선택될 수 있다. 구체적으로, Ar1은 C6~C60의 아릴기인 것이 바람직하며, 예컨대 페닐기, 비페닐기, 나프틸기, 트리페닐기, 안트릴기, 페난트릴기 등일 수 있다.Ar 1 is selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, C 1 to C 40 alkyl, C 2 to C 40 alkenyl, C 2 to C 40 alkynyl, C 3 to C 40 cycloalkyl, A C 6 to C 60 aryl group, and the like. Specifically, Ar 1 is preferably an aryl group of C 6 to C 60 , and may be, for example, a phenyl group, a biphenyl group, a naphthyl group, a triphenyl group, an anthryl group, a phenanthryl group and the like.
본 발명의 일 구체예를 들면, Ar1는 하기 구조식으로 표시된 치환체 군에서 선택될 수 있다.In one embodiment of the present invention, Ar 1 can be selected from the group of substituents represented by the following structural formulas.
Figure PCTKR2019000614-appb-I000003
Figure PCTKR2019000614-appb-I000003
이때 전술한 구조식에 표시되지 않았으나, 상기 Ar1은 당 분야에 공지된 치환기(예컨대, R6의 정의부와 동일)가 적어도 하나 이상 치환될 수 있다.At this time, although not shown in the above-mentioned structural formula, Ar 1 may be substituted with at least one substituent group known in the art (for example, the same definition as R 6 ).
a 및 c는 각각 0 내지 3의 정수이고, b 및 d는 각각 0 내지 4의 정수이다. 이때, a 내지 d가 0일 경우에는 수소가 각각 R1 내지 R4로 치환되지 않은 것을 의미하고, a 내지 d가 각각 1 이상의 정수일 경우에는 하나 이상의 수소가 각각 R1 내지 R4로 치환되는 것을 의미한다.a and c are each an integer of 0 to 3, and b and d are an integer of 0 to 4, respectively. When a to d are 0, hydrogen means not substituted with R 1 to R 4 , and when a to d are each an integer of 1 or more, one or more hydrogen atoms are substituted with R 1 to R 4 . it means.
R1 내지 R5는 서로 동일하거나 상이하며, 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 혹은 인접한 기와 결합하여 축합 고리를 형성할 수 있다. 이때 R1 내지 R5가 각각 복수인 경우, 이들은 서로 동일하거나 상이하다. 구체적으로, 상기 R1 내지 R5는 서로 동일하거나 상이하며, 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기 및 C6~C60의 아릴기로 이루어진 군에서 선택되는 것이 바람직하다.R 1 to R 5 are the same or different, each independently represent hydrogen, deuterium, a halogen, a cyano group, a nitro group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 of the An alkynyl group, a C 3 to C 40 cycloalkyl group, a heteroaryl group having 3 to 40 nuclear atoms, a C 6 to C 60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C 1 to C 40 alkyl A C 6 to C 60 aryloxy group, a C 1 to C 40 alkylsilyl group, a C 6 to C 60 arylsilyl group, a C 1 to C 40 alkylboron group, a C 6 to C 60 aryl boron group, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~, or selected from the group consisting of an aryl amine of the C 60 of, or adjacent groups combine to form a condensed ring . Here, when R 1 to R 5 each are plural, they are the same as or different from each other. Specifically, R 1 to R 5 are the same or different and each independently represents hydrogen, deuterium, halogen, cyano, nitro, C 1 to C 40 alkyl, C 2 to C 40 alkenyl, C 2 An alkynyl group of C 40 to C 40 , a cycloalkyl group of C 3 to C 40 , and an aryl group of C 6 to C 60 .
m 및 n은 각각 0 내지 3의 정수이며, m+n≥1이다. 이때, m 또는 n이 0일 경우에는 수소가 A 또는 B로 치환되지 않은 것을 의미하고, m 및 n이 각각 1 이상의 정수일 경우에는 하나 이상의 수소가 각각 A 및 B로 치환되는 것을 의미한다. 바람직하게는, m 및 n은 각각 0 내지 2의 정수일 수 있다. 예를 들면, m=1, n=0; m=0, n=1; m=1, n=1; m=2, n=0; m=0, n=2일 수 있다. 더욱 바람직하게는, m=1, n=0 또는 m=1, n=1일 수 있다. 즉, 후술되는 A와 B 는 적어도 하나 이상 존재할 수 있다. m and n are each an integer of 0 to 3, and m + n? 1. When m or n is 0, it means that hydrogen is not substituted with A or B. When m and n are each an integer of 1 or more, it means that at least one hydrogen is substituted with A and B, respectively. Preferably, m and n may each be an integer of 0 to 2. For example, m = 1, n = 0; m = 0, n = 1; m = 1, n = 1; m = 2, n = 0; m = 0, n = 2. More preferably, m = 1, n = 0 or m = 1 and n = 1. That is, at least one of A and B described later may exist.
또한 상기 b+m, d+n은 각각 0 내지 4의 정수일 수 있다. 바람직하게는, b+m=1일 경우, d+n=0 또는 d+n=1일 수 있다.And b + m and d + n may be an integer of 0 to 4, respectively. Preferably, when b + m = 1, d + n = 0 or d + n = 1.
본 발명의 화학식 1에서, A 및 B는 각각 전자를 제공하는 역할을 하는 전자공여성 치환체이다. 본 발명에서는, 전자주게기(electron donating group, EDG)의 일종으로서, 카바졸기가 적어도 하나 이상 도입될 수 있다. 구체적으로, A 및 B는 서로 동일하거나 상이하며, 각각 독립적으로 상기 화학식 2 또는 화학식 3으로 표시되는 치환체 중 어느 하나일 수 있다. In the formula (1) of the present invention, A and B are electron donating substituents each of which serves to provide electrons. In the present invention, as a kind of electron donating group (EDG), at least one carbazole group may be introduced. Specifically, A and B are the same as or different from each other, and each independently may be any of the substituents represented by the above-described formulas (2) and (3).
상기 화학식 2 및 3으로 표시되는 치환체에서, X3는 단일결합이다. In the substituents represented by the above formulas (2) and (3), X 3 is a single bond.
e는 0 내지 4의 정수이고, f는 0 내지 3의 정수이다. 이때, e 및 f가 각각 0일 경우에는 수소가 각각 R6 및 R7으로 치환되지 않은 것을 의미하고, e 및f 가 각각 1 이상의 정수일 경우에는 하나 이상의 수소가 각각 R6 및 R7으로 치환되는 것을 의미한다.e is an integer of 0 to 4, and f is an integer of 0 to 3. When e and f are each 0, hydrogen means not substituted by R 6 and R 7 , and when e and f are each an integer of 1 or more, at least one hydrogen is substituted with R 6 and R 7 respectively .
여기서, R6 및 R7는 서로 동일하거나 상이하며, 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 혹은 인접한 기와 결합하여 축합 고리를 형성할 수 있다. 이때 R6 및 R7이 복수인 경우, 이들은 서로 동일하거나 상이할 수 있다. 바람직한 일 실시예를 들면, R6 및 R7는 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기 및 C6~C60의 아릴기로 이루어진 군에서 선택되거나, 혹은 인접한 기와 결합하여 축합 고리를 형성할 수 있다. 이때, 인접한 기로는 하나의 R6와 다른 하나의 R6, 하나의 R6와 하나의 Ar2, 하나의 R7과 다른 하나의 R7, 하나의 R7과 하나의 Ar2일 수 있다.Wherein, R 6 and R 7 are the same or different, each independently represent hydrogen, deuterium, a halogen, a cyano group, a nitro group, C 1 ~ alkenyl group of the C 40 alkyl group, C 2 ~ C 40 of, C 2 ~ C A C 3 to C 40 cycloalkyl group, a heteroaryl group having 3 to 40 nuclear atoms, a C 6 to C 60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C 1 to C 40 alkenyl group, C 6 -C 60 aryloxy groups, C 1 -C 40 alkylsilyl groups, C 6 -C 60 arylsilyl groups, C 1 -C 40 alkylboron groups, C 6 -C 60 a group of the arylboronic, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~ selected from the group consisting of an aryl amine of the C 60 or, or in adjacent groups combine a condensed ring . When R 6 and R 7 are plural, they may be the same as or different from each other. , For one preferred embodiment, R 6 and R 7 are each independently hydrogen, deuterium, a halogen, a cyano group, a nitro group, C 1 ~ alkenyl group of the C 40 alkyl group, C 2 ~ C 40 of, C 2 ~ C 40 A C 3 to C 40 cycloalkyl group, and a C 6 to C 60 aryl group, or may be bonded to adjacent groups to form a condensed ring. At this time, adjacent groups may be one R 6 and one R 6 , one R 6 and one Ar 2 , one R 7 and another R 7 , one R 7, and one Ar 2 .
상기 화학식 2 또는 3으로 표시되는 치환체에서, Ar2는 C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 혹은 인접한 기(예, R6, R7)와 결합하여 축합 고리를 형성할 수 있다. 구체적으로, 상기 Ar2는 C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되는 것이 바람직하다.In the substituent represented by the general formula (2) or (3), Ar 2 represents a C 1 to C 40 alkyl group, a C 2 to C 40 alkenyl group, a C 2 to C 40 alkynyl group, a C 3 to C 40 cycloalkyl group, 6 ~ C 60 aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, and a C 6 ~, or selected from the group consisting of an aryl amine of the C 60, or adjacent groups condensed in combination with (for example, R 6, R 7) A ring can be formed. Specifically, the Ar 2 may be selected from the group consisting of an aryl amine of the C 6 ~ C 60 aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, and a C 6 ~ C 60.
본 발명의 일 구체예를 들면, A 및 B는 서로 동일하거나 또는 상이하며, 각각 독립적으로 하기 구조식으로 표시되는 치환체 군 중에서 선택된 어느 하나일 수 있다.In an embodiment of the present invention, A and B are the same as or different from each other, and each independently can be any one selected from the group of substituents represented by the following structural formulas.
Figure PCTKR2019000614-appb-I000004
Figure PCTKR2019000614-appb-I000004
상기 화학식에서,In the above formulas,
*은 상기 화학식 1에 결합되는 부위를 의미하고,* Represents a moiety bonded to Formula 1,
상기 Ar2는 화학식 1에서 정의한 바와 같다. 또한 구체적으로 표시되지 않았으나, 전술한 구조식은 당 분야에 공지된 치환기(예컨대, R6의 정의부와 동일)가 적어도 하나 이상 치환될 수 있다. Ar 2 is the same as defined in formula (1). Although not specifically shown, the above-mentioned structural formula may be substituted with at least one substituent group known in the art (for example, the same definition as R 6 ).
전술한 화학식 1에서, Ar1 내지 Ar2, 및 R1 내지 R8의 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 아릴포스핀옥사이드기 및 아릴아민기는 각각 독립적으로 중수소, 할로겐, 시아노기, 니트로기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C1~C40의 알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환될 수 있으며, 이때 상기 치환기가 복수인 경우, 이들은 서로 동일하거나 상이할 수 있다.In the above-described formula (1), Ar 1 to Ar 2 , and R 1 to R 8 are independently selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, A halogen atom, a cyano group, a nitro group, a C 2 to C 40 alkenyl group, an aryl group, an aryl group, an aryl group, an aryl group, an aryl group, alkynyl of C 2 ~ C 40, C 3 ~ C 40 cycloalkyl group, a number of nuclear atoms of 3 to 40 heterocycloalkyl group, C 1 ~ C 40 alkyl group, C 6 ~ aryl group of C 60, nuclear atoms 5 to 60 heteroaryl group, C 1 ~ C 40 alkyloxy group of, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C aryl silyl group of 60, C 1 ~ C 40 alkyl group of boron, C 6 ~ C 60 aryl group of boron, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~ C 60 aryl amine of achieving the If true, and it may be substituted with one or more substituent species selected from the group, wherein the substituent of the plurality, they may be the same or different from each other.
한편 본 발명에 따라 화학식 1로 표시되는 화합물은, EWG 특성을 갖는 함질소 헤테로환(예, Z1~Z3 함유 환)에 결합되는 2개의 디벤조계 모이어티(예, X1 함유환 및 X2 함유환)의 탄소 결합위치에 따라 서로 비대칭적인(Asymmetric) 구조를 이루게 된다. 구체적으로, Z1 내지 Z3 함유 환에 연결되는 상기 X1 함유 환의 Y1~Y4 중 하나의 결합위치와, 상기 X2 함유 환의 Y9~Y12 중 하나의 결합위치가 서로 비대칭 구조를 나타낸다. 일례로, 아진기(예, Z1~Z3 함유 환)에 결합되는 X1 함유 환의 탄소위치가 Y1 일 경우, 상기 아진기에 결합되는 X2 함유 환의 탄소위치는 Y9을 제외한 Y10 내지 Y12 중 어느 하나일 수 있다(하기 화학식 4 참조). 이와 같이 함질소 헤테로환에 각각 연결되는 2개의 디벤조계 모이어티의 탄소 결합위치를 보다 구체화하면, 하기 화학식 4 내지 7 중 어느 하나로 표시될 수 있다.In accordance with the present invention compound represented by the formula (1), the nitrogen-containing heterocycle having an EWG properties (such as, Z 1 ~ Z 3 containing ring) 2 dibenzo-based moiety that is bonded to (for example, X 1 hamyuhwan and X 2- containing rings) according to the positions of the carbon bonds of the asymmetric structure. Specifically, the bonding position of one of Y 1 to Y 4 of the X 1 containing ring connected to the Z 1 to Z 3 containing ring and the bonding position of one of Y 9 to Y 12 of the X 2 containing ring are asymmetric with each other . In one example, the O rare cases (for example, Z 1 ~ Z 3-containing ring) is X 1 containing ring carbon position coupled to Y 1 il, X 2 containing ring carbon position which is bonded to the azine is Y 10 to the exception of Y 9 Y 12 (see Chemical Formula 4 below). The carbon bond positions of two dibenzo-based moieties respectively linked to the nitrogen-containing heterocycle may be represented by any one of the following formulas (4) to (7).
[화학식 4] [Chemical Formula 4]
Figure PCTKR2019000614-appb-I000005
Figure PCTKR2019000614-appb-I000005
[화학식 5] [Chemical Formula 5]
Figure PCTKR2019000614-appb-I000006
Figure PCTKR2019000614-appb-I000006
[화학식 6] [Chemical Formula 6]
Figure PCTKR2019000614-appb-I000007
Figure PCTKR2019000614-appb-I000007
[화학식 7] (7)
Figure PCTKR2019000614-appb-I000008
Figure PCTKR2019000614-appb-I000008
상기 화학식 4 내지 7에서, In the above formulas 4 to 7,
상기 화학식 4의 Z1 내지 Z3 함유환은 Y10 내지 Y12 중 어느 하나와 결합되며(단, Z1 내지 Z3 함유환이 Y9과 결합되는 것은 제외됨), The ring containing Z 1 to Z 3 in Formula 4 is bonded to any one of Y 10 to Y 12 (provided that the ring containing Z 1 to Z 3 is not bonded to Y 9 )
상기 화학식 5의 Z1 내지 Z3 함유환은 Y9, Y11 내지 Y12 중 어느 하나와 결합되며(단, Z1 내지 Z3 함유환이 Y10과 결합되는 것은 제외됨), The ring containing Z 1 to Z 3 in Formula 5 is bonded to any one of Y 9 and Y 11 to Y 12 (provided that the ring containing Z 1 to Z 3 is not bonded to Y 10 )
상기 화학식 6의 Z1 내지 Z3 함유환은 Y9, Y10 및 Y12 중 어느 하나와 결합되며(단, Z1 내지 Z3 함유환이 Y11과 결합되는 것은 제외됨), The ring containing Z 1 to Z 3 in Formula 6 is bonded to any one of Y 9 , Y 10 and Y 12 (provided that the Z 1 to Z 3 containing ring is not bonded to Y 11 )
상기 화학식 7의 Z1 내지 Z3 함유환은 Y9 내지 Y11 중 어느 하나와 결합되며(단, Z1 내지 Z3 함유환이 Y12와 결합되는 것은 제외됨), The ring containing Z 1 to Z 3 in the above formula (7) is bonded to any one of Y 9 to Y 11 (provided that the Z 1 to Z 3 containing ring is not bonded to Y 12 )
X1, X2, Y1 내지 Y16, Z1 내지 Z3, Ar1, m, n, A, B, a 내지 d, R1 내지 R4는 각각 상기 화학식 1에서 정의한 바와 같다.X 1 , X 2 , Y 1 to Y 16 , Z 1 to Z 3 , Ar 1 , m, n, A, B, a to d and R 1 to R 4 are as defined in Formula 1, respectively.
본 발명의 일 구체예를 들면, 상기 화학식 4로 표시되는 화합물은 각각 화학식 4a 내지 화학식 4c 중 어느 하나로 보다 구체화될 수 있다. In one embodiment of the present invention, the compound represented by Formula 4 may be further represented by any one of Formulas 4a to 4c.
[화학식 4a][Chemical Formula 4a]
Figure PCTKR2019000614-appb-I000009
Figure PCTKR2019000614-appb-I000009
[화학식 4b](4b)
Figure PCTKR2019000614-appb-I000010
Figure PCTKR2019000614-appb-I000010
[화학식 4c][Chemical Formula 4c]
Figure PCTKR2019000614-appb-I000011
Figure PCTKR2019000614-appb-I000011
본 발명의 다른 일 구체예를 들면, 상기 화학식 5로 표시되는 화합물은 각각 화학식 5a 내지 화학식 5c 중 어느 하나로 보다 구체화될 수 있다. In another embodiment of the present invention, the compound represented by Formula 5 may be further represented by any one of Formulas 5a to 5c.
[화학식 5a][Chemical Formula 5a]
Figure PCTKR2019000614-appb-I000012
Figure PCTKR2019000614-appb-I000012
[화학식 5b][Chemical Formula 5b]
Figure PCTKR2019000614-appb-I000013
Figure PCTKR2019000614-appb-I000013
[화학식 5c][Chemical Formula 5c]
Figure PCTKR2019000614-appb-I000014
Figure PCTKR2019000614-appb-I000014
본 발명의 또 다른 일 구체예를 들면, 상기 화학식 6으로 표시되는 화합물은 각각 화학식 6a 내지 화학식 6c 중 어느 하나로 보다 구체화될 수 있다.In another embodiment of the present invention, the compound represented by Formula 6 may be further represented by any one of Formulas 6a to 6c.
[화학식 6a][Chemical Formula 6a]
Figure PCTKR2019000614-appb-I000015
Figure PCTKR2019000614-appb-I000015
[화학식 6b][Formula 6b]
Figure PCTKR2019000614-appb-I000016
Figure PCTKR2019000614-appb-I000016
[화학식 6c][Chemical Formula 6c]
Figure PCTKR2019000614-appb-I000017
Figure PCTKR2019000614-appb-I000017
본 발명의 또 다른 일 구체예를 들면, 상기 화학식 7로 표시되는 화합물은 각각 화학식 7a 내지 화학식 7c 중 어느 하나로 보다 구체화될 수 있다.In another embodiment of the present invention, the compound represented by the above formula (7) may be further represented by any one of formulas (7a) to (7c).
[화학식 7a][Formula 7a]
Figure PCTKR2019000614-appb-I000018
Figure PCTKR2019000614-appb-I000018
[화학식 7b][Formula 7b]
Figure PCTKR2019000614-appb-I000019
Figure PCTKR2019000614-appb-I000019
[화학식 7c][Formula 7c]
Figure PCTKR2019000614-appb-I000020
Figure PCTKR2019000614-appb-I000020
또한 상기 화학식 1로 표시되는 화합물에서, 디벤조계 모이어티, 일례로 디벤조퓨란 또는 디벤조티오펜 모이어티를 보다 구체화하면, 하기 화학식 8 내지 12 중 어느 하나로 표시될 수 있다.In the compound represented by Formula 1, dibenzo-based moieties such as dibenzofurane or dibenzothiophene moiety may be further represented by any one of the following formulas (8) to (12).
[화학식 8][Chemical Formula 8]
Figure PCTKR2019000614-appb-I000021
Figure PCTKR2019000614-appb-I000021
[화학식 9][Chemical Formula 9]
Figure PCTKR2019000614-appb-I000022
Figure PCTKR2019000614-appb-I000022
[화학식 10][Chemical formula 10]
Figure PCTKR2019000614-appb-I000023
Figure PCTKR2019000614-appb-I000023
[화학식 11](11)
Figure PCTKR2019000614-appb-I000024
Figure PCTKR2019000614-appb-I000024
[화학식 12][Chemical Formula 12]
Figure PCTKR2019000614-appb-I000025
Figure PCTKR2019000614-appb-I000025
상기 화학식 8 내지 12에서, In Formulas 8 to 12,
X1, X2, Z1 내지 Z3, Ar1, n, A, B는 각각 상기 화학식 1에서 정의한 바와 같다.X 1 , X 2 , Z 1 to Z 3 , Ar 1 , n, A and B are as defined in the above formula (1).
상기 화학식 8 및 화학식 12 중 어느 하나로 표시되는 화합물의 보다 구체적인 일례를 들면, X1 및 X2는 각각 독립적으로 O 또는 S이고, Z1 내지 Z3는 각각 독립적으로 CR5 또는 N이되, 이들 모두가 N이며, Ar1은 C6~C60의 아릴기이다. More specifically, each of X 1 and X 2 is independently O or S, and Z 1 to Z 3 are each independently CR 5 or N, a is N, Ar 1 is an aryl group of C 6 ~ C 60.
또한 상기 아진기(예, Z1~Z3 함유 환)에 결합되는 X1 함유 환의 탄소 위치와 X2 함유 환의 탄소 위치는 서로 비대칭 구조를 이루게 되며, 상기 A와 B 중 적어도 하나는, 카바졸기일 수 있다.The carbon position of the X 1 -containing ring and the carbon position of the X 2 -containing ring bonded to the azine group (for example, the Z 1 to Z 3 -containing ring) have an asymmetric structure, and at least one of A and B is a carbazole group Lt; / RTI &gt;
이상에서 설명한 본 발명에 따른 화학식 1로 표시되는 화합물은 하기 예시되는 화합물 1 내지 500 중 어느 하나로 표시되는 화합물로 보다 구체화될 수 있다. 그러나, 본 발명의 화학식 1로 표시되는 화합물이 하기 예시된 것들에 의해 한정되는 것은 아니다.The compound represented by formula (1) according to the present invention may be further represented by any one of compounds 1 to 500 shown below. However, the compounds represented by formula (1) of the present invention are not limited by the following examples.
Figure PCTKR2019000614-appb-I000026
Figure PCTKR2019000614-appb-I000026
Figure PCTKR2019000614-appb-I000027
Figure PCTKR2019000614-appb-I000027
Figure PCTKR2019000614-appb-I000028
Figure PCTKR2019000614-appb-I000028
Figure PCTKR2019000614-appb-I000029
Figure PCTKR2019000614-appb-I000029
Figure PCTKR2019000614-appb-I000030
Figure PCTKR2019000614-appb-I000030
Figure PCTKR2019000614-appb-I000031
Figure PCTKR2019000614-appb-I000031
Figure PCTKR2019000614-appb-I000032
Figure PCTKR2019000614-appb-I000032
Figure PCTKR2019000614-appb-I000033
Figure PCTKR2019000614-appb-I000033
Figure PCTKR2019000614-appb-I000034
Figure PCTKR2019000614-appb-I000034
Figure PCTKR2019000614-appb-I000035
Figure PCTKR2019000614-appb-I000035
Figure PCTKR2019000614-appb-I000036
Figure PCTKR2019000614-appb-I000036
Figure PCTKR2019000614-appb-I000037
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Figure PCTKR2019000614-appb-I000038
Figure PCTKR2019000614-appb-I000038
Figure PCTKR2019000614-appb-I000039
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Figure PCTKR2019000614-appb-I000040
Figure PCTKR2019000614-appb-I000040
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Figure PCTKR2019000614-appb-I000042
본 발명에서 "알킬"은 탄소수 1 내지 40개의 직쇄 또는 측쇄의 포화 탄화수소에서 유래되는 1가의 치환기를 의미한다. 이러한 알킬의 예로는 메틸, 에틸, 프로필, 이소부틸, sec-부틸, 펜틸, iso-아밀, 헥실 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, "alkyl" means a monovalent substituent derived from a straight or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples of such alkyl include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl and hexyl.
본 발명에서 "알케닐(alkenyl)"은 탄소-탄소 이중 결합을 1개 이상 가진 탄소수 2 내지 40개의 직쇄 또는 측쇄의 불포화 탄화수소에서 유래되는 1가의 치환기를 의미한다. 이러한 알케닐의 예로는 비닐(vinyl), 알릴(allyl), 이소프로펜일(isopropenyl), 2-부텐일(2-butenyl) 등을 들 수 있으나, 이에 한정되지는 않는다."Alkenyl" in the present invention means a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon double bond. Examples of such alkenyl include, but are not limited to, vinyl, allyl, isopropenyl, 2-butenyl, and the like.
본 발명에서 "알키닐(alkynyl)"은 탄소-탄소 삼중 결합을 1개 이상 가진 탄소수 2 내지 40개의 직쇄 또는 측쇄의 불포화 탄화수소에서 유래되는 1가의 치환기를 의미한다. 이러한 알키닐의 예로는 에티닐(ethynyl), 2-프로파닐(2-propynyl) 등을 들 수 있으나, 이에 한정되지는 않는다.The term "alkynyl" in the present invention means a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon triple bond. Examples of such alkynyls include, but are not limited to, ethynyl, 2-propynyl, and the like.
본 발명에서 "시클로알킬"은 탄소수 3 내지 40개의 모노사이클릭 또는 폴리사이클릭 비-방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 이러한 사이클로알킬의 예로는 사이클로프로필, 사이클로펜틸, 사이클로헥실, 노르보닐(norbornyl), 아다만틴(adamantine) 등을 들 수 있으나, 이에 한정되지는 않는다."Cycloalkyl" in the present invention means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyls include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.
본 발명에서 "헤테로시클로알킬"은 핵원자수 3 내지 40개의 비-방향족 탄화수소로부터 유래된 1가의 치환기를 의미하며, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, S 또는 Se와 같은 헤테로 원자로 치환된다. 이러한 헤테로시클로알킬의 예로는 모르폴린, 피페라진 등을 들 수 있으나, 이에 한정되지는 않는다."Heterocycloalkyl" in the present invention means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, wherein at least one carbon of the ring, preferably 1 to 3 carbons, Or &lt; RTI ID = 0.0 &gt; Se. &Lt; / RTI &gt; Examples of such heterocycloalkyl include, but are not limited to, morpholine, piperazine, and the like.
본 발명에서 "아릴"은 단독 고리 또는 2 이상의 고리가 조합된 탄소수 6 내지 60개의 방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 또한, 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된 형태도 포함될 수 있다. 이러한 아릴의 예로는 페닐, 나프틸, 페난트릴, 안트릴 등을 들 수 있으나, 이에 한정되지는 않는다."Aryl" in the present invention means a monovalent substituent derived from a C6-C60 aromatic hydrocarbon having a single ring or a combination of two or more rings. Also, a form in which two or more rings are pendant or condensed with each other may be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, and the like.
본 발명에서 "헤테로아릴"은 핵원자수 5 내지 60개의 모노헤테로사이클릭 또는 폴리헤테로사이클릭 방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 이때, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, S 또는 Se와 같은 헤테로원자로 치환된다. 또한, 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된 형태도 포함될 수 있고, 나아가 아릴기와의 축합된 형태도 포함될 수 있다. 이러한 헤테로아릴의 예로는 피리딜, 피라지닐, 피리미디닐, 피리다지닐, 트리아지닐과 같은 6-원 모노사이클릭 고리, 페녹사티에닐(phenoxathienyl), 인돌리지닐(indolizinyl), 인돌릴(indolyl), 퓨리닐(purinyl), 퀴놀릴(quinolyl), 벤조티아졸(benzothiazole), 카바졸릴(carbazolyl)과 같은 폴리사이클릭 고리 및 2-퓨라닐, N-이미다졸릴, 2-이속사졸릴, 2-피리디닐, 2-피리미디닐 등을 들 수 있으나, 이에 한정되지는 않는다."Heteroaryl" in the present invention means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms. Wherein at least one of the carbons, preferably one to three carbons, is replaced by a heteroatom such as N, O, S or Se. In addition, a form in which two or more rings are pendant or condensed with each other may be included, and further, a condensed form with an aryl group may be included. Examples of such heteroaryls include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolizinyl, indolyl indolyl), purinyl, quinolyl, benzothiazole, carbazolyl, and heterocyclic rings such as 2-furanyl, N-imidazolyl, 2- , 2-pyridinyl, 2-pyrimidinyl, and the like, but are not limited thereto.
본 발명에서 "알킬옥시"는 R'O-로 표시되는 1가의 치환기로, 상기 R'는 탄소수 1 내지 40개의 알킬을 의미한다. 이러한 알킬옥시는 직쇄(linear), 측쇄(branched) 또는 사이클릭(cyclic) 구조를 포함할 수 있다. 이러한 알킬옥시의 예로는 메톡시, 에톡시, n-프로폭시, 1-프로폭시, t-부톡시, n-부톡시, 펜톡시 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, "alkyloxy" means a monovalent substituent group represented by R'O-, and R 'means alkyl having 1 to 40 carbon atoms. Such alkyloxy may include linear, branched or cyclic structures. Examples of such alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy and pentoxy.
본 발명에서 "아릴옥시"는 RO-로 표시되는 1가의 치환기로, 상기 R은 탄소수 6 내지 60개의 아릴을 의미한다. 이러한 아릴옥시의 예로는 페닐옥시, 나프틸옥시, 디페닐옥시 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, "aryloxy" means a monovalent substituent represented by RO-, and R means aryl having 6 to 60 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, diphenyloxy, and the like.
본 발명에서 "알킬실릴"은 탄소수 1 내지 40개의 알킬로 치환된 실릴이고, "아릴실릴"은 탄소수 6 내지 60개의 아릴로 치환된 실릴을 의미한다."Alkylsilyl" in the present invention refers to silyl substituted with alkyl having 1 to 40 carbon atoms, and "arylsilyl" means silyl substituted with aryl having 6 to 60 carbon atoms.
본 발명에서 "알킬보론"은 탄소수 1 내지 40개의 알킬로 치환된 보론이고, "아릴보론"은 탄소수 6 내지 60개의 아릴로 치환된 보론을 의미한다.In the present invention, "alkyl boron" is boron substituted with alkyl having 1 to 40 carbon atoms, and "aryl boron" means boron substituted with aryl having 6 to 60 carbon atoms.
본 발명에서 "아릴포스핀"은 탄소수 6 내지 60개의 아릴로 치환된 포스핀을 의미하고, "아릴포스핀옥사이드기"는 탄소수 6 내지 60개의 아릴로 치환된 포스핀이 O를 포함하는 것을 의미한다.In the present invention, "arylphosphine" means a phosphine substituted with aryl having 6 to 60 carbon atoms, and "arylphosphine oxide group" means that phosphine substituted with aryl having 6 to 60 carbon atoms includes O do.
본 발명에서 "축합 고리"는 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리, 축합 헤테로방향족 고리 또는 이들의 조합된 형태를 의미한다.In the present invention, the term "condensed rings" means condensed aliphatic rings, condensed aromatic rings, condensed heteroaliphatic rings, condensed heteroaromatic rings, or a combination thereof.
본 발명에서 "아릴아민"은 탄소수 6 내지 60개의 아릴로 치환된 아민을 의미한다."Arylamine" in the present invention means an amine substituted with aryl having 6 to 60 carbon atoms.
이와 같은 본 발명의 화학식 1로 표시되는 화합물은 당 분야에 공지된 방법에 따라 제한 없이 제조될 수 있다. 일례로, 하기 실시예의 합성과정을 참고하여 다양하게 합성할 수 있다.The compounds represented by formula (1) of the present invention can be prepared without limitation by methods known in the art. For example, various syntheses can be carried out by referring to the synthesis process of the following examples.
<유기 전계 발광 소자>&Lt; Organic electroluminescent device &
본 발명은 상기 화학식 1로 표시되는 화합물을 포함하는 유기 전계 발광 소자를 제공한다.The present invention provides an organic electroluminescent device comprising a compound represented by the above formula (1).
보다 구체적으로, 본 발명에 따른 유기 전계 발광 소자는 양극(anode), 음극(cathode) 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하며, 상기 1층 이상의 유기물층 중 적어도 하나는 상기 화학식 1로 표시되는 화합물을 포함한다. 이때, 상기 화합물은 단독으로 사용되거나, 또는 2 이상이 혼합되어 사용될 수 있다.More specifically, the organic electroluminescent device according to the present invention includes at least one anode, an anode, and at least one organic layer sandwiched between the anode and the cathode, and at least one of the one or more organic layers Include the compounds represented by the above formula (1). At this time, the compounds may be used alone or in combination of two or more.
상기 1층 이상의 유기물층은 정공 주입층, 정공 수송층, 발광 보조층, 발광층, 전자 수송층 및 전자 주입층 중 어느 하나 이상일 수 있고, 이 중에서 적어도 하나의 유기물층은 상기 화학식 1로 표시되는 화합물을 포함할 수 있다. 구체적으로, 상기 화학식 1의 화합물을 포함하는 유기물층은 발광층인 것이 바람직하다.The at least one organic material layer may include at least one of a hole injecting layer, a hole transporting layer, a light emitting auxiliary layer, a light emitting layer, an electron transporting layer, and an electron injecting layer. have. Specifically, the organic compound layer containing the compound of Formula 1 is preferably a light emitting layer.
본 발명의 유기 전계 발광 소자의 발광층은 호스트 재료(바람직하게는, 인광 호스트 재료)를 포함할 수 있다. 또한, 본 발명의 유기 전계 발광 소자의 발광층은 상기 화학식 1의 화합물 이외의 화합물을 호스트로 포함할 수 있다.The light emitting layer of the organic electroluminescence device of the present invention may include a host material (preferably, a phosphorescent host material). The light emitting layer of the organic electroluminescent device of the present invention may contain a compound other than the compound of Formula 1 as a host.
이러한 본 발명의 유기 전계 발광 소자의 구조는 특별히 한정되지 않으나, 비제한적인 예로 기판, 양극, 정공 주입층, 정공 수송층, 발광 보조층, 발광층, 전자 수송층, 전자 주입층 및 음극이 순차적으로 적층된 구조일 수 있다. 이때, 상기 정공 주입층, 정공 수송층, 발광 보조층, 발광층, 전자 수송층 및 전자 주입층 중 하나 이상은 상기 화학식 1로 표시되는 화합물을 포함할 수 있고, 바람직하게는 발광층이 상기 화학식 1로 표시되는 화합물을 포함할 수 있다. 또한, 본 발명의 유기 전계 발광 소자의 구조는 전극과 유기물층 계면에 절연층 또는 접착층이 삽입된 구조일 수 있다.The structure of the organic electroluminescent device of the present invention is not particularly limited, and examples thereof include a substrate, an anode, a hole injecting layer, a hole transporting layer, a light emitting auxiliary layer, a light emitting layer, an electron transporting layer, an electron injecting layer and a cathode sequentially stacked Structure. At least one of the hole injecting layer, the hole transporting layer, the light-emitting auxiliary layer, the light emitting layer, the electron transporting layer, and the electron injecting layer may include the compound represented by Formula 1, &Lt; / RTI &gt; compounds. Further, the structure of the organic electroluminescent device of the present invention may be a structure in which an insulating layer or an adhesive layer is inserted into the interface between the electrode and the organic layer.
한편, 본 발명의 유기 전계 발광 소자는 상기 유기물층 중 1층 이상이 상기 화학식 1로 표시되는 화합물을 포함하는 것을 제외하고는, 당업계에 공지된 재료 및 방법으로 유기물층 및 전극을 형성하여 제조할 수 있다.Meanwhile, the organic electroluminescent device of the present invention can be manufactured by forming an organic material layer and an electrode by materials and methods known in the art, except that at least one of the organic material layers includes the compound represented by the above formula have.
상기 유기물층은 진공 증착법이나 용액 도포법에 의하여 형성될 수 있다. 상기 용액 도포법의 예로는 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯 프린팅 또는 열 전사법 등이 있으나, 이에 한정되지는 않는다.The organic material layer may be formed by a vacuum deposition method or a solution coating method. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.
본 발명의 유기 전계 발광 소자 제조시 사용되는 기판은 특별히 한정되지 않으나, 실리콘 웨이퍼, 석영, 유리판, 금속판, 플라스틱 필름 및 시트 등을 사용할 수 있다.The substrate used in the fabrication of the organic electroluminescent device of the present invention is not particularly limited, but silicon wafer, quartz, glass plate, metal plate, plastic film and sheet can be used.
또한, 양극 물질로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연산화물, 인듐산화물, 인듐 주석 산화물(ITO), 인듐 아연 산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SnO2:Sb와 같은 금속과 산화물의 조합; 폴리티오펜, 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDT), 폴리피롤 또는 폴리아닐린과 같은 전도성 고분자; 및 카본블랙 등을 들 수 있으나, 이에 한정되지는 않는다.Examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of a metal and an oxide such as ZnO: Al or SnO2: Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole or polyaniline; And carbon black, but are not limited thereto.
또한, 음극 물질로는 마그네슘, 칼슘, 나트륨, 칼륨, 타이타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석, 또는 납과 같은 금속 또는 이들의 합금; 및 LiF/Al 또는 LiO2/Al과 같은 다층 구조 물질 등을 들 수 있으나, 이에 한정되지는 않는다.Examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead or alloys thereof; And multi-layer structure materials such as LiF / Al or LiO2 / Al, but are not limited thereto.
또한, 정공 주입층, 정공 수송층, 전자 주입층 및 전자 수송층은 특별히 한정되는 것은 아니며, 당 업계에 알려진 통상의 물질을 사용할 수 있다.The hole injecting layer, the hole transporting layer, the electron injecting layer and the electron transporting layer are not particularly limited, and ordinary materials known in the art can be used.
이하, 본 발명을 실시예를 통하여 상세히 설명하면 다음과 같다. 단, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.
[준비예 1] C1 의 합성 [Preparation Example 1] Synthesis of C1
<단계 1> 3-(6-bromodibenzo[b,d]furan-1-yl)-9-phenyl-9H-carbazole 의 합성Synthesis of 3- (6-bromodibenzo [b, d] furan-1-yl) -9-phenyl-9H-carbazole
Figure PCTKR2019000614-appb-I000043
Figure PCTKR2019000614-appb-I000043
4,6-dibromodibenzo[b,d]furan (40.0 g, 122.7 mmol)와 (9-phenyl-9H-carbazol-3-yl)boronic acid (35.2 g, 122.7 mmol) 및 Pd(PPh3)4 (2.8 g, 2.5 mmol), K2CO3 (40.7 g, 294.5 mmol)를 toluene 300 ml과 H2O 150 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성물을 추출하고, 용매 제거 후 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물인 3-(6-bromodibenzo[b,d]furan-1-yl)-9-phenyl-9H-carbazole (44.9 g, 수율 75 %)을 얻었다.4,6-dibromodibenzo [b, d] furan (40.0 g, 122.7 mmol) and (9-phenyl-9H-carbazol -3-yl) boronic acid (35.2 g, 122.7 mmol) and Pd (PPh 3) 4 (2.8 g, 2.5 mmol) and K 2 CO 3 (40.7 g, 294.5 mmol) were added to toluene (300 ml) and H 2 O (150 ml), and the mixture was stirred at 110 ° C for 8 hours. After the completion of the reaction, the product was extracted and the solvent was removed. The solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the target compound, 3- (6-bromodibenzo [b, d] furan- carbazole (44.9 g, yield 75%).
<단계 2> C1 의 합성<Step 2> Synthesis of C1
Figure PCTKR2019000614-appb-I000044
Figure PCTKR2019000614-appb-I000044
3-(6-bromodibenzo[b,d]furan-1-yl)-9-phenyl-9H-carbazole (16.8 g, 34.3 mmol)와 Pd(dppf)Cl2 (0.5 g, 0.7 mmol), potassium acetate (5.1 g, 51.5 mmol) 및 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (11.3 g, 44.6 mmol)을 1,4-Dioxane 150 ml에 넣고 110℃에서 5시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C1 (15.8 g, 수율 86 %)을 얻었다.A solution of Pd (dppf) Cl 2 (0.5 g, 0.7 mmol), potassium acetate (16.8 g, 34.3 mmol) and 3- (6-bromodibenzo [b, d] furan- 5.1 g, 51.5 mmol) and 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane (11.3 g, 44.6 mmol ) Was added to 150 ml of 1,4-dioxane and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO 4 . After removing the solvent of the filtered organic layer, C1 (15.8 g, yield 86%) was obtained by column chromatography.
[준비예 2] C2 의 합성[Preparation Example 2] Synthesis of C2
<단계 1> 2,4-dichloro-2'-methoxy-1,1'-biphenyl의 합성<Step 1> Synthesis of 2,4-dichloro-2'-methoxy-1,1'-biphenyl
Figure PCTKR2019000614-appb-I000045
Figure PCTKR2019000614-appb-I000045
2-methoxyphenyl boronic acid (18.5 g, 121.7 mmol)와 1-bromo-2,4-dichlorobenzene (25.0 g, 110.7 mmol), Pd(PPh3)4 (6.4 g, 5.5 mmol) 및 KOH (11.1 g, 276.7 mmol)를 DME 300 ml와 H2O 150 ml에 넣고 85℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 2,4-dichloro-2'-methoxy-1,1'-biphenyl (23.5 g, 수율 84 %)을 얻었다.2-methoxyphenyl boronic acid (18.5 g , 121.7 mmol) and 1-bromo-2,4-dichlorobenzene ( 25.0 g, 110.7 mmol), Pd (PPh 3) 4 (6.4 g, 5.5 mmol) and KOH (11.1 g, 276.7 mmol) were added to DME (300 ml) and H 2 O (150 ml), and the mixture was stirred at 85 ° C for 12 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO 4 . After removing the solvent of the filtered organic layer, 2,4-dichloro-2'-methoxy-1,1'-biphenyl (23.5 g, yield 84%) was obtained by column chromatography.
<단계 2> 2',4'-dichloro-[1,1'-biphenyl]-2-ol 의 합성<Step 2> Synthesis of 2 ', 4'-dichloro- [1,1'-biphenyl] -2-ol
Figure PCTKR2019000614-appb-I000046
Figure PCTKR2019000614-appb-I000046
2,4-dichloro-2'-methoxy-1,1'-biphenyl (17.0 g, 67.2 mmol)과 pyridine hydrochloride (38.8 g, 335.8 mmol)를 혼합하고 190℃에서 12시간 동안 교반하였다. 반응 종결 후 증류수와 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 2',4'-dichloro-[1,1'-biphenyl]-2-ol (12.8 g, 수율 80 %)을 얻었다.2,4-dichloro-2'-methoxy-1,1'-biphenyl (17.0 g, 67.2 mmol) and pyridine hydrochloride (38.8 g, 335.8 mmol) were mixed and stirred at 190 ° C for 12 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and methylene chloride, and the mixture was filtered with MgSO 4 . After removal of the solvent of the filtered organic layer, 2'-, 4'-dichloro- [1,1'-biphenyl] -2-ol (12.8 g, yield 80%) was obtained by column chromatography.
<단계 3> 3-bromo-2',4'-dichloro-[1,1'-biphenyl]-2-ol 의 합성<Step 3> Synthesis of 3-bromo-2 ', 4'-dichloro- [1,1'-biphenyl] -2-ol
Figure PCTKR2019000614-appb-I000047
Figure PCTKR2019000614-appb-I000047
2',4'-dichloro-[1,1'-biphenyl]-2-ol (13.5 g, 56.5 mmol)과 Diisopropylamine (1.2 mL, 8.5 mmol)을 메틸렌클로라이드 혼합물 150 ml에 NBS (11.1 g, 62.1 mmol)을 천천히 넣고 40℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드와 Sodium thiosulfate 수용액으로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 3-bromo-2',4'-dichloro-[1,1'-biphenyl]-2-ol (13.5 g, 수율 75 %)을 얻었다.NBS (11.1 g, 62.1 mmol) was added to 150 mL of a methylene chloride mixture with 2 ', 4'-dichloro- [1,1'-biphenyl] -2-ol (13.5 g, 56.5 mmol) and Diisopropylamine ) Was slowly added thereto and stirred at 40 ° C for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride and sodium thiosulfate aqueous solution, and the mixture was filtered with MgSO 4 . After removing the solvent of the filtered organic layer, 3-bromo-2 ', 4'-dichloro- [1,1'-biphenyl] -2-ol (13.5 g, yield 75%) .
<단계 4> 6-bromo-3-chlorodibenzo[b,d]furan 의 합성<Step 4> Synthesis of 6-bromo-3-chlorodibenzo [b, d] furan
Figure PCTKR2019000614-appb-I000048
Figure PCTKR2019000614-appb-I000048
3-bromo-2',4'-dichloro-[1,1'-biphenyl]-2-ol (18.0 g, 56.6 mmol)와 sodium hydrosulfite (1.8 g, 5.7 mmol), KOH (12.7 g, 226.4 mmol) 및 tetrabutylammonium bromide (2.0 g, 11.3 mmol)를 DMF 200 ml에 넣고 155℃에서 5시간 동안 교반하였다. 반응 종결 후 증류수를 넣고, 생성된 고체를 필터한다. 메틸렌클로라이드로 추출하고 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 6-bromo-3-chlorodibenzo[b,d]furan (14.2 g, 수율 89 %)을 얻었다.Sodium hydrosulfite (1.8 g, 5.7 mmol) and KOH (12.7 g, 226.4 mmol) were added to a solution of 3-bromo- And tetrabutylammonium bromide (2.0 g, 11.3 mmol) were added to DMF (200 ml), and the mixture was stirred at 155 ° C for 5 hours. After completion of the reaction, distilled water is added, and the resulting solid is filtered. After extraction with methylene chloride, the solvent was removed and the desired compound, 6-bromo-3-chlorodibenzo [b, d] furan (14.2 g, yield 89%) was obtained by column chromatography.
<단계 5> 3-(7-chlorodibenzo[b,d]furan-4-yl)-9-phenyl-9H-carbazole 의 합성<Step 5> Synthesis of 3- (7-chlorodibenzo [b, d] furan-4-yl) -9-phenyl-9H-
Figure PCTKR2019000614-appb-I000049
Figure PCTKR2019000614-appb-I000049
(9-phenyl-9H-carbazol-3-yl)boronic acid (12.9 g, 44.9 mmol)와 6-bromo-3-chlorodibenzo[b,d]furan (11.5 g, 40.9 mmol) 및 Pd(PPh3)4 (1.4 g, 1.2 mmol), K2CO3 (13.6 g, 98.0 mmol)를 toluene 150 ml과 H2O 75 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성된 고체는 필터하였다. 필터된 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물인 3-(7-chlorodibenzo[b,d]furan-4-yl)-9-phenyl-9H-carbazole (13.8 g, 수율 76 %)을 얻었다.3-chlorodibenzo [b, d] furan (11.5 g, 40.9 mmol) and Pd (PPh 3 ) 4 (9.9 g, 44.9 mmol) (1.4 g, 1.2 mmol) and K 2 CO 3 (13.6 g, 98.0 mmol) were added to toluene (150 ml) and H 2 O (75 ml), and the mixture was stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The obtained solid was dissolved in toluene, filtered through a silica filter, and recrystallized to obtain 13.8 g (yield: 76%) of 3- (7-chlorodibenzo [b, d] furan- &Lt; / RTI &gt;
<단계 6> C2 의 합성<Step 6> Synthesis of C2
Figure PCTKR2019000614-appb-I000050
Figure PCTKR2019000614-appb-I000050
3-(7-chlorodibenzo[b,d]furan-4-yl)-9-phenyl-9H-carbazole (8.3 g, 18.7 mmol)와 Pd(dppf)Cl2 (0.6 g, 0.8 mmol), potassium acetate (3.7 g, 37.5 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (6.2 g, 24.4 mmol) 및 X-Phos (1.8 g, 3.8 mmol)을 1,4-Dioxane 80 ml에 넣고 110℃에서 5시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C2 (8.5 g, 수율 85 %)을 얻었다.A solution of Pd (dppf) Cl 2 (0.6 g, 0.8 mmol), potassium acetate (8.3 g, 18.7 mmol) and 3- (7-chlorodibenzo [b, d] furan- 3.7 g, 37.5 mmol), 4,4,4 ', 4', 5,5,5,5-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (6.2 g, 24.4 mmol ) And X-Phos (1.8 g, 3.8 mmol) were added to 80 ml of 1,4-dioxane and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO 4 . After removing the solvent of the filtered organic layer, the desired compound C2 (8.5 g, yield 85%) was obtained by column chromatography.
[준비예 3] C3 의 합성[Preparation Example 3] Synthesis of C3
<단계 1> 2,6-dichloro-2'-methoxy-1,1'-biphenyl의 합성<Step 1> Synthesis of 2,6-dichloro-2'-methoxy-1,1'-biphenyl
Figure PCTKR2019000614-appb-I000051
Figure PCTKR2019000614-appb-I000051
2-methoxyphenyl boronic acid (18.5 g, 121.7 mmol)와 1-bromo-2,4-dichlorobenzene (25.0 g, 110.7 mmol), Pd(PPh3)4 (6.4 g, 5.5 mmol) 및 KOH (11.1 g, 276.7 mmol)를 DME 300 ml와 H2O 150 ml에 넣고 85℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 2,6-dichloro-2'-methoxy-1,1'-biphenyl (24.6 g, 수율 88 %)을 얻었다.2-methoxyphenyl boronic acid (18.5 g , 121.7 mmol) and 1-bromo-2,4-dichlorobenzene ( 25.0 g, 110.7 mmol), Pd (PPh 3) 4 (6.4 g, 5.5 mmol) and KOH (11.1 g, 276.7 mmol) were added to DME (300 ml) and H 2 O (150 ml), and the mixture was stirred at 85 ° C for 12 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO 4 . After removing the solvent of the filtered organic layer, 2,6-dichloro-2'-methoxy-1,1'-biphenyl (24.6 g, yield 88%) was obtained by column chromatography.
<단계 2> 2',6'-dichloro-[1,1'-biphenyl]-2-ol 의 합성<Step 2> Synthesis of 2 ', 6'-dichloro- [1,1'-biphenyl] -2-ol
Figure PCTKR2019000614-appb-I000052
Figure PCTKR2019000614-appb-I000052
2,6-dichloro-2'-methoxy-1,1'-biphenyl (22.5 g, 88.9 mmol)과 pyridine hydrochloride (41.1 g, 355.56 mmol)를 혼합하고 190℃에서 12시간 동안 교반하였다. 반응 종결 후 증류수와 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 2',6'-dichloro-[1,1'-biphenyl]-2-ol (17.4 g, 수율 82 %)을 얻었다.2,6-dichloro-2'-methoxy-1,1'-biphenyl (22.5 g, 88.9 mmol) and pyridine hydrochloride (41.1 g, 355.56 mmol) were mixed and stirred at 190 ° C for 12 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and methylene chloride, and the mixture was filtered with MgSO 4 . After removing the solvent of the filtered organic layer, 2'-, 6'-dichloro- [1,1'-biphenyl] -2-ol (17.4 g, yield 82%) was obtained by column chromatography.
<단계 3> 3-bromo-2',6'-dichloro-[1,1'-biphenyl]-2-ol 의 합성<Step 3> Synthesis of 3-bromo-2 ', 6'-dichloro- [1,1'-biphenyl] -2-ol
Figure PCTKR2019000614-appb-I000053
Figure PCTKR2019000614-appb-I000053
2',6'-dichloro-[1,1'-biphenyl]-2-ol (16.6 g, 69.4 mmol)과 Diisopropylamine (1.5 mL, 10.4 mmol)을 메틸렌클로라이드 혼합물 200 ml에 NBS (13.6 g, 76.4 mmol)을 천천히 넣고 40℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드와 Sodium thiosulfate 수용액으로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 3-bromo-2',6'-dichloro-[1,1'-biphenyl]-2-ol (17.0 g, 수율 77 %)을 얻었다.NBS (13.6 g, 76.4 mmol) was added to 200 mL of a methylene chloride mixture of 2 ', 6'-dichloro- [1,1'-biphenyl] -2-ol (16.6 g, 69.4 mmol) and Diisopropylamine ) Was slowly added thereto and stirred at 40 ° C for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride and sodium thiosulfate aqueous solution, and the mixture was filtered with MgSO 4 . After removing the solvent of the filtered organic layer, 3-bromo-2 ', 6'-dichloro- [1,1'-biphenyl] -2-ol (17.0 g, yield 77%) .
<단계 4> 6-bromo-1-chlorodibenzo[b,d]furan 의 합성<Step 4> Synthesis of 6-bromo-1-chlorodibenzo [b, d] furan
Figure PCTKR2019000614-appb-I000054
Figure PCTKR2019000614-appb-I000054
3-bromo-2',6'-dichloro-[1,1'-biphenyl]-2-ol (33.0 g, 103.8 mmol)와 sodium hydrosulfite (3.3 g, 10.4 mmol), KOH (23.3 g, 415.1 mmol) 및 tetrabutylammonium bromide (3.6 g, 20.8 mmol)를 DMF 200 ml에 넣고 155℃에서 5시간 동안 교반하였다. 반응 종결 후 증류수를 넣고, 생성된 고체를 필터한다. 메틸렌클로라이드로 추출하고 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 6-bromo-1-chlorodibenzo[b,d]furan (24.8 g, 수율 85 %)을 얻었다.Sodium hydrosulfite (3.3 g, 10.4 mmol) and KOH (23.3 g, 415.1 mmol) were added to a solution of 3-bromo- And tetrabutylammonium bromide (3.6 g, 20.8 mmol) were added to DMF (200 ml), and the mixture was stirred at 155 ° C for 5 hours. After completion of the reaction, distilled water is added, and the resulting solid is filtered. After extraction with methylene chloride, the solvent was removed and the desired compound, 6-bromo-1-chlorodibenzo [b, d] furan (24.8 g, yield 85%) was obtained by column chromatography.
<단계 5> 3-(9-chlorodibenzo[b,d]furan-4-yl)-9-phenyl-9H-carbazole 의 합성<Step 5> Synthesis of 3- (9-chlorodibenzo [b, d] furan-4-yl) -9-phenyl-9H-carbazole
Figure PCTKR2019000614-appb-I000055
Figure PCTKR2019000614-appb-I000055
(9-phenyl-9H-carbazol-3-yl)boronic acid (14.6 g, 50.8 mmol)와 6-bromo-1-chlorodibenzo[b,d]furan (13.0 g, 46.8 mmol) 및 Pd(PPh3)4 (1.6 g, 1.4 mmol), K2CO3 (15.3 g, 110.8 mmol)를 toluene 150 ml과 H2O 75 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성된 고체는 필터하였다. 필터된 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물인 3-(9-chlorodibenzo[b,d]furan-4-yl)-9-phenyl-9H-carbazole (15.2 g, 수율 74 %)을 얻었다.B, d] furan (13.0 g, 46.8 mmol) and Pd (PPh 3 ) 4 (14.8 g, 50.8 mmol) (1.6 g, 1.4 mmol) and K 2 CO 3 (15.3 g, 110.8 mmol) were added to toluene (150 ml) and H 2 O (75 ml), and the mixture was stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The obtained solid was dissolved in toluene, filtered through silica, and recrystallized to obtain 15.2 g (yield: 74%) of 3- (9-chlorodibenzo [b, d] furan- &Lt; / RTI &gt;
<단계 6> C3 의 합성<Step 6> Synthesis of C3
Figure PCTKR2019000614-appb-I000056
Figure PCTKR2019000614-appb-I000056
3-(9-chlorodibenzo[b,d]furan-4-yl)-9-phenyl-9H-carbazole (15.1 g, 34.0 mmol)와 Pd(dppf)Cl2 (1.0 g, 1.36 mmol), potassium acetate (6.7 g, 68.0 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (11.2 g, 44.2 mmol) 및 X-Phos (3.2 g, 6.8 mmol)을 1,4-Dioxane 80 ml에 넣고 110℃에서 5시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C3 (14.6 g, 수율 80 %)을 얻었다.Pd (dppf) Cl 2 (1.0 g, 1.36 mmol) and potassium acetate (15.1 g, 34.0 mmol) were added to a solution of 3- (9-chlorodibenzo [b, d] furan- 6.7 g, 68.0 mmol), 4,4,4 ', 4,5,5,5,5-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (11.2 g, 44.2 mmol ) And X-Phos (3.2 g, 6.8 mmol) were added to 80 ml of 1,4-dioxane and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO 4 . After removing the solvent of the filtered organic layer, C3 (14.6 g, yield 80%) of the target compound C3 was obtained by column chromatography.
[준비예 4] C4 의 합성[Preparation Example 4] Synthesis of C4
<단계 1> 4-(6-bromodibenzo[b,d]furan-4-yl)-9-phenyl-9H-carbazole 의 합성Synthesis of 4- (6-bromodibenzo [b, d] furan-4-yl) -9-phenyl-9H-carbazole
Figure PCTKR2019000614-appb-I000057
Figure PCTKR2019000614-appb-I000057
4,6-dibromodibenzo[b,d]furan (40.0 g, 122.7 mmol)와 (9-phenyl-9H-carbazol-3-yl)boronic acid (35.2 g, 122.7 mmol) 및 Pd(PPh3)4 (2.8 g, 2.5 mmol), K2CO3 (40.7 g, 294.5 mmol)를 toluene 300 ml과 H2O 150 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성물을 추출하고, 용매 제거 후 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물인 4-(6-bromodibenzo[b,d]furan-4-yl)-9-phenyl-9H-carbazole (38.4 g, 수율 64 %)을 얻었다.4,6-dibromodibenzo [b, d] furan (40.0 g, 122.7 mmol) and (9-phenyl-9H-carbazol -3-yl) boronic acid (35.2 g, 122.7 mmol) and Pd (PPh 3) 4 (2.8 g, 2.5 mmol) and K 2 CO 3 (40.7 g, 294.5 mmol) were added to toluene (300 ml) and H 2 O (150 ml), and the mixture was stirred at 110 ° C for 8 hours. After the completion of the reaction, the product was extracted and the solvent was removed. The solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the target compound, 4- (6-bromodibenzo [b, d] furan- carbazole (38.4 g, yield 64%).
<단계 2> C4 의 합성<Step 2> Synthesis of C4
Figure PCTKR2019000614-appb-I000058
Figure PCTKR2019000614-appb-I000058
4-(6-bromodibenzo[b,d]furan-4-yl)-9-phenyl-9H-carbazole (20.0 g, 41.0 mmol)와 Pd(dppf)Cl2 (0.6 g, 0.8 mmol), potassium acetate (6.0 g, 61.4 mmol) 및 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (13.5 g, 53.2 mmol)을 1,4-Dioxane 150 ml에 넣고 110℃에서 5시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C4 (18.2 g, 수율 83 %)을 얻었다.Pd (dppf) Cl 2 (0.6 g, 0.8 mmol), potassium acetate (20.0 g, 41.0 mmol) and 4- 6.0 g, 61.4 mmol) and 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) ) Was added to 150 ml of 1,4-dioxane and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO 4 . After removing the solvent of the filtered organic layer, C4 (18.2 g, yield 83%) of the desired compound was obtained by column chromatography.
[준비예 5] C5 의 합성[Preparation Example 5] Synthesis of C5
<단계 1> 2-(6-bromodibenzo[b,d]furan-4-yl)-9-phenyl-9H-carbazole 의 합성Synthesis of 2- (6-bromodibenzo [b, d] furan-4-yl) -9-phenyl-9H-carbazole
Figure PCTKR2019000614-appb-I000059
Figure PCTKR2019000614-appb-I000059
4,6-dibromodibenzo[b,d]furan (40.0 g, 122.7 mmol)와 (9-phenyl-9H-carbazol-3-yl)boronic acid (35.2 g, 122.7 mmol) 및 Pd(PPh3)4 (2.8 g, 2.5 mmol), K2CO3 (40.7 g, 294.5 mmol)를 toluene 300 ml과 H2O 150 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성물을 추출하고, 용매 제거 후 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물인 2-(6-bromodibenzo[b,d]furan-4-yl)-9-phenyl-9H-carbazole (50.3 g, 수율 84 %)을 얻었다.4,6-dibromodibenzo [b, d] furan (40.0 g, 122.7 mmol) and (9-phenyl-9H-carbazol -3-yl) boronic acid (35.2 g, 122.7 mmol) and Pd (PPh 3) 4 (2.8 g, 2.5 mmol) and K 2 CO 3 (40.7 g, 294.5 mmol) were added to toluene (300 ml) and H 2 O (150 ml), and the mixture was stirred at 110 ° C for 8 hours. After the completion of the reaction, the product was extracted and the solvent was removed, and the solid was dissolved in toluene to remove the solvent. The residue was recrystallized to obtain 2- (6-bromodibenzo [b, d] furan- carbazole (50.3 g, yield 84%).
<단계 2> C5 의 합성<Step 2> Synthesis of C5
Figure PCTKR2019000614-appb-I000060
Figure PCTKR2019000614-appb-I000060
2-(6-bromodibenzo[b,d]furan-4-yl)-9-phenyl-9H-carbazole (20.0 g, 41.0 mmol)와 Pd(dppf)Cl2 (0.6 g, 0.8 mmol), potassium acetate (6.0 g, 61.4 mmol) 및 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (13.5 g, 53.2 mmol)을 1,4-Dioxane 150 ml에 넣고 110℃에서 5시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C5 (18.6 g, 수율 85 %)을 얻었다.Pd (dppf) Cl 2 (0.6 g, 0.8 mmol) and potassium acetate (20.0 g, 41.0 mmol) were added to a solution of 2- (6-bromodibenzo [b, d] furan- 6.0 g, 61.4 mmol) and 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) ) Was added to 150 ml of 1,4-dioxane and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO 4 . After removing the solvent of the filtered organic layer, C5 (18.6 g, yield 85%) was obtained by column chromatography.
[준비예 6] C6 의 합성[Preparation Example 6] Synthesis of C6
<단계 1> 1-(6-bromodibenzo[b,d]furan-4-yl)-9-phenyl-9H-carbazole 의 합성Synthesis of 1- (6-bromodibenzo [b, d] furan-4-yl) -9-phenyl-9H-carbazole
Figure PCTKR2019000614-appb-I000061
Figure PCTKR2019000614-appb-I000061
4,6-dibromodibenzo[b,d]furan (40.0 g, 122.7 mmol)와 (9-phenyl-9H-carbazol-3-yl)boronic acid (35.2 g, 122.7 mmol) 및 Pd(PPh3)4 (2.8 g, 2.5 mmol), K2CO3 (40.7 g, 294.5 mmol)를 toluene 300 ml과 H2O 150 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성물을 추출하고, 용매 제거 후 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물인 1-(6-bromodibenzo[b,d]furan-4-yl)-9-phenyl-9H-carbazole (34.8 g, 수율 58 %)을 얻었다.4,6-dibromodibenzo [b, d] furan (40.0 g, 122.7 mmol) and (9-phenyl-9H-carbazol -3-yl) boronic acid (35.2 g, 122.7 mmol) and Pd (PPh 3) 4 (2.8 g, 2.5 mmol) and K 2 CO 3 (40.7 g, 294.5 mmol) were added to toluene (300 ml) and H 2 O (150 ml), and the mixture was stirred at 110 ° C for 8 hours. After the completion of the reaction, the product was extracted and the solvent was removed, and the solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound, 1- (6-bromodibenzo [b, d] furan- carbazole (34.8 g, yield 58%).
<단계 2> C6 의 합성<Step 2> Synthesis of C6
Figure PCTKR2019000614-appb-I000062
Figure PCTKR2019000614-appb-I000062
1-(6-bromodibenzo[b,d]furan-4-yl)-9-phenyl-9H-carbazole (20.0 g, 41.0 mmol)와 Pd(dppf)Cl2 (0.6 g, 0.8 mmol), potassium acetate (6.0 g, 61.4 mmol) 및 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (13.5 g, 53.2 mmol)을 1,4-Dioxane 150 ml에 넣고 110℃에서 5시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C6 (17.8 g, 수율 81 %)을 얻었다.Pd (dppf) Cl 2 (0.6 g, 0.8 mmol), potassium acetate (20.0 g, 41.0 mmol) and 1- 6.0 g, 61.4 mmol) and 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) ) Was added to 150 ml of 1,4-dioxane and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO 4 . After removing the solvent of the filtered organic layer, the desired compound C6 (17.8 g, yield 81%) was obtained by column chromatography.
[준비예 7] C7 의 합성[Preparation Example 7] Synthesis of C7
<단계 1> 9-(8-chlorodibenzo[b,d]furan-4-yl)-9H-carbazole의 합성<Step 1> Synthesis of 9- (8-chlorodibenzo [b, d] furan-4-yl) -9H-carbazole
Figure PCTKR2019000614-appb-I000063
Figure PCTKR2019000614-appb-I000063
9H-carbazole (10.3 g, 61.4 mmol)와 6-bromo-2-chlorodibenzo[b,d]furan (17.3 g, 61.4 mmol) 및 Pd2(dba)3 (1.7 g, 1.8 mmol), sodium tert-butoxide (8.8 g, 92.0 mmol)와 toluene 150 ml을 넣고, Tri-tert-butylphosphine (0.9 mL, 3.7 mmol)를 첨가한 후 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성물을 추출하고, 용매 제거 후 고체를 toluene에 녹여 silica 필터를 한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 9-(8-chlorodibenzo[b,d]furan-4-yl)-9H-carbazole (11.51 g, 수율 51 %)을 얻었다.6-bromo-2-chlorodibenzo [b, d] furan (17.3 g, 61.4 mmol) and Pd 2 (dba) 3 (1.7 g, 1.8 mmol), sodium tert-butoxide (8.8 g, 92.0 mmol) and toluene (150 mL) were added. Tri-tert-butylphosphine (0.9 mL, 3.7 mmol) was added and the mixture was stirred at 110 ° C for 8 hours. After completion of the reaction, the product was extracted, and the solvent was removed. The solid was dissolved in toluene to remove silica, and then the desired product, 9- (8-chlorodibenzo [b, d] furan- carbazole (11.51 g, yield 51%).
<단계 2> C7 의 합성<Step 2> Synthesis of C7
Figure PCTKR2019000614-appb-I000064
Figure PCTKR2019000614-appb-I000064
9-(8-chlorodibenzo[b,d]furan-4-yl)-9H-carbazole (6.9 g, 18.7 mmol)와 Pd(dppf)Cl2 (0.6 g, 0.8 mmol), potassium acetate (3.7 g, 37.5 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (6.2 g, 24.4 mmol) 및 X-Phos (1.8 g, 3.8 mmol)을 1,4-Dioxane 80 ml에 넣고 110℃에서 5시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C7 (7.3 g, 수율 85 %)을 얻었다.Potassium acetate (3.7 g, 37.5 mmol) and Pd (dppf) Cl 2 (0.6 g, 0.8 mmol) and 9- (8-chlorodibenzo [b, d] furan- mmol), 4,4,4 ', 4,5,5,5,5-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (6.2 g, 24.4 mmol) Phos (1.8 g, 3.8 mmol) was added to 80 ml of 1,4-dioxane and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO 4 . After removing the solvent of the filtered organic layer, C7 (7.3 g, yield 85%) was obtained by column chromatography.
[준비예 8] C8 의 합성[Preparation Example 8] Synthesis of C8
<단계 1> 9-(7-bromodibenzo[b,d]furan-3-yl)-9H-carbazole의 합성<Step 1> Synthesis of 9- (7-bromodibenzo [b, d] furan-3-yl) -9H-carbazole
Figure PCTKR2019000614-appb-I000065
Figure PCTKR2019000614-appb-I000065
9H-carbazole (10.3 g, 61.4 mmol)와 3,7-dibromodibenzo[b,d]furan (20.0 g, 61.4 mmol) 및 Pd2(dba)3 (1.7 g, 1.8 mmol), sodium tert-butoxide (8.8 g, 92.0 mmol)와 toluene 150 ml을 넣고, Tri-tert-butylphosphine (0.9 mL, 3.7 mmol)를 첨가한 후 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성물을 추출하고, 용매 제거 후 고체를 toluene에 녹여 silica 필터를 한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 9-(7-bromodibenzo[b,d]furan-3-yl)-9H-carbazole (13.16 g, 수율 52 %)을 얻었다.(10.0 g, 61.4 mmol), 3,7-dibromodibenzo [b, d] furan (20.0 g, 61.4 mmol) and Pd 2 (dba) 3 (1.7 g, 1.8 mmol), sodium tert- g, 92.0 mmol) and toluene (150 mL) were added. Tri-tert-butylphosphine (0.9 mL, 3.7 mmol) was added and the mixture was stirred at 110 ° C for 8 hours. After completion of the reaction, the product was extracted and the solvent was removed, and the solid was dissolved in toluene to remove the silica filter. The desired compound, 9- (7-bromodibenzo [b, d] furan- carbazole (13.16 g, yield 52%).
<단계 2> C8 의 합성<Step 2> Synthesis of C8
Figure PCTKR2019000614-appb-I000066
Figure PCTKR2019000614-appb-I000066
9-(7-bromodibenzo[b,d]furan-3-yl)-9H-carbazole (8.2 g, 19.8 mmol)와 Pd(dppf)Cl2 (0.3 g, 0.4 mmol), potassium acetate (2.9 g, 29.7 mmol) 및 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (6.5 g, 25.8 mmol)을 1,4-Dioxane 60 ml에 넣고 110℃에서 5시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C8 (7.3 g, 수율 80 %)을 얻었다.Potassium acetate (2.9 g, 29.7 mmol) and Pd (dppf) Cl 2 (0.3 g, 0.4 mmol) and 9- (7-bromodibenzo [b, d] furan- mmol) and 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (6.5 g, 25.8 mmol) 4-Dioxane (60 ml), and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO 4 . After removing the solvent of the filtered organic layer, C8 (7.3 g, yield 80%) was obtained by column chromatography.
[준비예 9] C9 의 합성[Preparation Example 9] Synthesis of C9
<단계 1> 3-(8-bromodibenzo[b,d]furan-3-yl)-9-phenyl-9H-carbazole의 합성Synthesis of 3- (8-bromodibenzo [b, d] furan-3-yl) -9-phenyl-9H-carbazole
Figure PCTKR2019000614-appb-I000067
Figure PCTKR2019000614-appb-I000067
(9-phenyl-9H-carbazol-3-yl)boronic acid (17.6 g, 61.4 mmol)와 2-bromo-7-iododibenzo[b,d]furan (22.9 g, 61.4 mmol) 및 Pd(PPh3)4 (1.4 g, 1.2 mmol), K2CO3 (20.4 g, 147.2 mmol)를 toluene 150 ml과 H2O 75 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성물을 추출하고, 용매 제거 후 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물인 3-(8-bromodibenzo[b,d]furan-3-yl)-9-phenyl-9H-carbazole (22.2 g, 수율 74 %)을 얻었다.(9-phenyl-9H-carbazol -3-yl) boronic acid (17.6 g, 61.4 mmol) and 2-bromo-7-iododibenzo [ b, d] furan (22.9 g, 61.4 mmol) and Pd (PPh 3) 4 (1.4 g, 1.2 mmol) and K 2 CO 3 (20.4 g, 147.2 mmol) were added to toluene (150 ml) and H 2 O (75 ml), and the mixture was stirred at 110 ° C for 8 hours. (8-bromodibenzo [b, d] furan-3-yl) -9-phenyl-9H-quinolinone was obtained by removing the solvent and then dissolving the solid in toluene, carbazole (22.2 g, yield 74%).
<단계 2> C9 의 합성<Step 2> Synthesis of C9
Figure PCTKR2019000614-appb-I000068
Figure PCTKR2019000614-appb-I000068
3-(8-bromodibenzo[b,d]furan-3-yl)-9-phenyl-9H-carbazole (9.4 g, 19.2 mmol)와 Pd(dppf)Cl2 (0.3 g, 0.4 mmol), potassium acetate (2.8 g, 28.8 mmol) 및 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (6.3 g, 25.0 mmol)을 1,4-Dioxane 60 ml에 넣고 110℃에서 5시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C9 (7.8 g, 수율 76 %)을 얻었다.(Dppf) Cl 2 (0.3 g, 0.4 mmol), potassium acetate (9.4 g, 19.2 mmol) and 3- (8-bromodibenzo [b, d] furan- 2.8 g, 28.8 mmol) and 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane ) Was added to 1,4-dioxane (60 ml), and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO 4 . After removing the solvent of the filtered organic layer, C9 (7.8 g, yield 76%) was obtained by column chromatography.
[준비예 10] C10 의 합성[Preparation Example 10] Synthesis of C10
<단계 1> 1-(7-chlorodibenzo[b,d]furan-1-yl)-9-phenyl-9H-carbazole의 합성<Step 1> Synthesis of 1- (7-chlorodibenzo [b, d] furan-1-yl) -9-phenyl-9H-carbazole
Figure PCTKR2019000614-appb-I000069
Figure PCTKR2019000614-appb-I000069
(9-phenyl-9H-carbazol-1-yl)boronic acid (17.6 g, 61.4 mmol)와 1-bromo-7-chlorodibenzo[b,d]furan (17.3 g, 61.4 mmol) 및 Pd(PPh3)4 (1.4 g, 1.2 mmol), K2CO3 (20.4 g, 147.2 mmol)를 toluene 150 ml과 H2O 75 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성물을 추출하고, 용매 제거 후 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물인 1-(7-chlorodibenzo[b,d]furan-1-yl)-9-phenyl-9H-carbazole (19.9 g, 수율 73 %)을 얻었다.(9-phenyl-9H-carbazol -1-yl) boronic acid (17.6 g, 61.4 mmol) and 1-bromo-7-chlorodibenzo [ b, d] furan (17.3 g, 61.4 mmol) and Pd (PPh 3) 4 (1.4 g, 1.2 mmol) and K 2 CO 3 (20.4 g, 147.2 mmol) were added to toluene (150 ml) and H 2 O (75 ml), and the mixture was stirred at 110 ° C for 8 hours. (7-chlorodibenzo [b, d] furan-1-yl) -9-phenyl-9H-quinolinecarboxylic acid was obtained by removing the solvent, dissolving the solid in toluene, carbazole (19.9 g, yield 73%).
<단계 2> C10 의 합성<Step 2> Synthesis of C10
Figure PCTKR2019000614-appb-I000070
Figure PCTKR2019000614-appb-I000070
1-(7-chlorodibenzo[b,d]furan-1-yl)-9-phenyl-9H-carbazole (8.3 g, 18.7 mmol)와 Pd(dppf)Cl2 (0.6 g, 0.8 mmol), potassium acetate (3.7 g, 37.5 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (6.2 g, 24.4 mmol) 및 X-Phos (1.8 g, 3.8 mmol)을 1,4-Dioxane 80 ml에 넣고 110℃에서 5시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C12 (6.8 g, 수율 68 %)을 얻었다.A solution of Pd (dppf) Cl 2 (0.6 g, 0.8 mmol), potassium acetate (8.3 g, 18.7 mmol) and 1- (7-chlorodibenzo [b, d] furan- 3.7 g, 37.5 mmol), 4,4,4 ', 4', 5,5,5,5-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (6.2 g, 24.4 mmol ) And X-Phos (1.8 g, 3.8 mmol) were added to 80 ml of 1,4-dioxane and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO 4 . After removing the solvent of the filtered organic layer, C12 (6.8 g, yield 68%) was obtained by column chromatography.
[준비예 11] C11 의 합성[Preparation Example 11] Synthesis of C11
<단계 1> 9-(8-chlorodibenzo[b,d]furan-2-yl)-9H-carbazole의 합성Synthesis of 9- (8-chlorodibenzo [b, d] furan-2-yl) -9H-carbazole
Figure PCTKR2019000614-appb-I000071
Figure PCTKR2019000614-appb-I000071
9H-carbazole (10.3 g, 61.4 mmol)와 2-bromo-8-chlorodibenzo[b,d]furan (17.3 g, 61.4 mmol) 및 Pd2(dba)3 (1.7 g, 1.8 mmol), sodium tert-butoxide (8.8 g, 92.0 mmol)와 toluene 150 ml을 넣고, Tri-tert-butylphosphine (0.9 mL, 3.7 mmol)를 첨가한 후 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성물을 추출하고, 용매 제거 후 고체를 toluene에 녹여 silica 필터를 한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 9-(8-chlorodibenzo[b,d]furan-2-yl)-9H-carbazole (12.0 g, 수율 53 %)을 얻었다.8-chlorodibenzo [b, d] furan (17.3 g, 61.4 mmol) and Pd 2 (dba) 3 (1.7 g, 1.8 mmol), sodium tert-butoxide (8.8 g, 92.0 mmol) and toluene (150 mL) were added. Tri-tert-butylphosphine (0.9 mL, 3.7 mmol) was added and the mixture was stirred at 110 ° C for 8 hours. After the completion of the reaction, the product was extracted and the solvent was removed. The solid was dissolved in toluene, filtered through silica, and then purified by column chromatography to obtain the target compound, 9- (8-chlorodibenzo [b, d] furan- carbazole (12.0 g, yield 53%).
<단계 2> C11 의 합성<Step 2> Synthesis of C11
Figure PCTKR2019000614-appb-I000072
Figure PCTKR2019000614-appb-I000072
9-(8-chlorodibenzo[b,d]furan-2-yl)-9H-carbazole (6.9 g, 18.7 mmol)와 Pd(dppf)Cl2 (0.6 g, 0.8 mmol), potassium acetate (3.7 g, 37.5 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (6.2 g, 24.4 mmol) 및 X-Phos (1.8 g, 3.8 mmol)을 1,4-Dioxane 80 ml에 넣고 110℃에서 5시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C11 (6.0 g, 수율 70 %)을 얻었다.Potassium acetate (3.7 g, 37.5 mmol) and Pd (dppf) Cl 2 (0.6 g, 0.8 mmol) and 9- (8-chlorodibenzo [b, d] furan- mmol), 4,4,4 ', 4,5,5,5,5-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (6.2 g, 24.4 mmol) Phos (1.8 g, 3.8 mmol) was added to 80 ml of 1,4-dioxane and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO 4 . After removing the solvent of the filtered organic layer, C11 (6.0 g, yield 70%) as a target compound was obtained by column chromatography.
[준비예 12] C12 의 합성[Preparation Example 12] Synthesis of C12
<단계 1> 4-(8-chlorodibenzo[b,d]furan-1-yl)-9-phenyl-9H-carbazole의 합성Synthesis of 4- (8-chlorodibenzo [b, d] furan-1-yl) -9-phenyl-9H-carbazole
Figure PCTKR2019000614-appb-I000073
Figure PCTKR2019000614-appb-I000073
(9-phenyl-9H-carbazol-4-yl)boronic acid (17.6 g, 61.4 mmol)와 1-bromo-8-chlorodibenzo[b,d]furan (17.3 g, 61.4 mmol) 및 Pd(PPh3)4 (1.4 g, 1.2 mmol), K2CO3 (20.4 g, 147.2 mmol)를 toluene 150 ml과 H2O 75 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성물을 추출하고, 용매 제거 후 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물인 4-(8-chlorodibenzo[b,d]furan-1-yl)-9-phenyl-9H-carbazole (19.6 g, 수율 72 %)을 얻었다.(9-phenyl-9H-carbazol -4-yl) boronic acid (17.6 g, 61.4 mmol) and 1-bromo-8-chlorodibenzo [ b, d] furan (17.3 g, 61.4 mmol) and Pd (PPh 3) 4 (1.4 g, 1.2 mmol) and K 2 CO 3 (20.4 g, 147.2 mmol) were added to toluene (150 ml) and H 2 O (75 ml), and the mixture was stirred at 110 ° C for 8 hours. (8-chlorodibenzo [b, d] furan-1-yl) -9-phenyl-9H-quinolinecarboxylic acid was obtained by removing the solvent from the reaction mixture, carbazole (19.6 g, yield 72%).
<단계 2> C12 의 합성<Step 2> Synthesis of C12
Figure PCTKR2019000614-appb-I000074
Figure PCTKR2019000614-appb-I000074
4-(8-chlorodibenzo[b,d]furan-1-yl)-9-phenyl-9H-carbazole (8.3 g, 18.7 mmol)와 Pd(dppf)Cl2 (0.6 g, 0.8 mmol), potassium acetate (3.7 g, 37.5 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (6.2 g, 24.4 mmol) 및 X-Phos (1.8 g, 3.8 mmol)을 1,4-Dioxane 80 ml에 넣고 110℃에서 5시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C12 (6.9 g, 수율 69 %)을 얻었다.Pd (dppf) Cl 2 (0.6 g, 0.8 mmol), potassium acetate (8.3 g, 18.7 mmol) and 4- (8-chlorodibenzo [b, d] furan- 3.7 g, 37.5 mmol), 4,4,4 ', 4', 5,5,5,5-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (6.2 g, 24.4 mmol ) And X-Phos (1.8 g, 3.8 mmol) were added to 80 ml of 1,4-dioxane and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO 4 . After removing the solvent of the filtered organic layer, C12 (6.9 g, yield 69%) was obtained by column chromatography.
[준비예 13] C13 의 합성[Preparation Example 13] Synthesis of C13
<단계 1> 3,4-dichloro-2-(2-methoxyphenyl)pyridine 의 합성<Step 1> Synthesis of 3,4-dichloro-2- (2-methoxyphenyl) pyridine
Figure PCTKR2019000614-appb-I000075
Figure PCTKR2019000614-appb-I000075
상온에서 2,3,4-trichloropyridine (100.0 g, 548.1 mmol), 2-methoxyphenyl boronic acid (87.5 g, 141.7 mmol)을 2-neck flask 에 넣는다. Pd(PPh3)4 (19.0 g, 16.4mmol)과 KF (47.8 g, 822.2 mmol)을 첨가한다. Toluene 1100 ml 첨가 후 100 ℃ 에서 5시간 교반한다. 반응 종결 후 용액을 실리카 필터 한다. 용매 제거 후 컬럼크로마토그래피(MC:Hexane=1:1)로 정제 후 연녹색의 고체 화합물 3,4-dichloro-2-(2-methoxyphenyl)pyridine (124.0 g, 수율 89 %)을 얻었다.2,3,4-trichloropyridine (100.0 g, 548.1 mmol) and 2-methoxyphenyl boronic acid (87.5 g, 141.7 mmol) are placed in a 2-neck flask at room temperature. Of Pd (PPh 3) 4 (19.0 g, 16.4mmol) and KF (47.8 g, 822.2 mmol) is added. After adding 1100 ml of toluene, the mixture is stirred at 100 ° C for 5 hours. After completion of the reaction, the solution is subjected to silica filtration. After removal of the solvent, the solid compound 3,4-dichloro-2- (2-methoxyphenyl) pyridine (124.0 g, yield 89%) was obtained as a pale green solid after purification by column chromatography (MC: Hexane = 1: 1).
<단계 2> 2-(3,4-dichloropyridin-2-yl)phenol 의 합성<Step 2> Synthesis of 2- (3,4-dichloropyridin-2-yl) phenol
Figure PCTKR2019000614-appb-I000076
Figure PCTKR2019000614-appb-I000076
3,4-dichloro-2-(2-methoxyphenyl)pyridine (40.0 g, 157.4 mmol)을 메틸렌클로라이드 400 ml 에 녹여 2-neck flask에 넣는다. Ice bath에서 0 ℃ 조건을 유지한다. BBr3 (22.7 ml, 236.1 mmol)을 천천히 첨가한다. 반응 종료 후 0 ℃ 의 증류수 400 ml를 천천히 첨가한다. 반응물을 메틸렌클로라이드로 추출하고 실리카 필터 한다. 용매 제거 후 흰색 고체 화합물 2-(3,4-dichloropyridin-2-yl)phenol (31.4g, 수율 83 %)을 얻었다.3,4-dichloro-2- (2-methoxyphenyl) pyridine (40.0 g, 157.4 mmol) is dissolved in 400 ml of methylene chloride and placed in a 2-neck flask. Keep the condition at 0 ℃ in an ice bath. Of BBr 3 (22.7 ml, 236.1 mmol ) was slowly added. After completion of the reaction, 400 ml of distilled water at 0 ° C is slowly added. The reaction is extracted with methylene chloride and silica filtered. After removal of the solvent, a white solid compound, 2- (3,4-dichloropyridin-2-yl) phenol (31.4 g, yield 83%) was obtained.
<단계 3> 4-chlorobenzofuro[3,2-b]pyridine 의 합성<Step 3> Synthesis of 4-chlorobenzofuro [3,2-b] pyridine
Figure PCTKR2019000614-appb-I000077
Figure PCTKR2019000614-appb-I000077
2-(3,4-dichloropyridin-2-yl)phenol (23.0 g, 95.8 mmol)과 KOH (21.5 g, 383.2 mmol) sodium hydrosulfite (3.1 g, 9.6 mmol)을 2-neck flask에 넣는다. DMF 180 ml 첨가 후 tetrabutylammonium bromide (3.3 g, 19.2 mmol)을 넣는다. 155 ℃ 조건에서 2시간 교반한다. 반응 종료 후 증류수 400 ml를 천천히 첨가한다. 반응물을 메틸렌클로라이드로 추출하고 실리카 필터 한다. 용매 제거 후 흰색 고체 4-chlorobenzofuro[3,2-b]pyridine (13.8 g, 수율 71 %)을 얻었다.2-neck flask is charged with 23.0 g (95.8 mmol) of 2- (3,4-dichloropyridin-2-yl) phenol and 3.1 g of sodium hydrosulfite (21.5 g, 383.2 mmol) in KOH. Add 180 ml of DMF and add tetrabutylammonium bromide (3.3 g, 19.2 mmol). Stir 2 hours at 155 &lt; 0 &gt; C. After completion of the reaction, 400 ml of distilled water is slowly added. The reaction is extracted with methylene chloride and silica filtered. After removal of the solvent, white solid 4-chlorobenzofuro [3,2-b] pyridine (13.8 g, yield 71%) was obtained.
<단계 4> (4-chlorobenzofuro[3,2-b]pyridin-6-yl)boronic acid 의 합성<Step 4> Synthesis of (4-chlorobenzofuro [3,2-b] pyridin-6-yl) boronic acid
Figure PCTKR2019000614-appb-I000078
Figure PCTKR2019000614-appb-I000078
4-chlorobenzofuro[3,2-b]pyridine (30.0 g, 147.3 mmol)과 THF 300 ml 첨가 후 -78 ℃ 에서 n-butyllithium (70.7 ml, 176.8 mmol)을 넣는다. 2시간 후 -78 ℃ 에서 Triisopropyl borate (70.7 ml, 176.8 mmol)를 넣은 후 2시간이 지나고 HCl 을 첨가한다. 반응물을 메틸렌클로라이드로 추출하고 용매 제거 후 흰색 고체 (4-chlorobenzofuro[3,2-b]pyridin-6-yl)boronic acid (26.7 g, 수율 66 %)을 얻었다.4-chlorobenzofuro [3,2-b] pyridine (30.0 g, 147.3 mmol) and THF (300 ml) were added and n-butyllithium (70.7 ml, 176.8 mmol) was added at -78 ° C. After 2 hours, add triisopropyl borate (70.7 ml, 176.8 mmol) at -78 ° C and add HCl for 2 hours. The reaction mixture was extracted with methylene chloride and the solvent was removed to obtain 26.7 g (yield 66%) of 4-chlorobenzofuro [3,2-b] pyridin-6-yl) boronic acid.
<단계 5> 4-chloro-6-(9-phenyl-9H-carbazol-3-yl)benzofuro[3,2-b]pyridine 의 합성Step 5 Synthesis of 4-chloro-6- (9-phenyl-9H-carbazol-3-yl) benzofuro [3,2-b]
Figure PCTKR2019000614-appb-I000079
Figure PCTKR2019000614-appb-I000079
(4-chlorobenzofuro[3,2-b]pyridin-6-yl)boronic acid (13.4 g, 48.9 mmol)와 3-bromo-9-phenyl-9H-carbazole (15.0 g, 46.6 mmol) 및 Pd(PPh3)4 (1.6 g, 1.4 mmol), K2CO3 (15.4 g, 111.7 mmol)를 toluene 150 ml과 H2O 75 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성된 고체는 필터하였다. 필터된 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물인 4-chloro-6-(9-phenyl-9H-carbazol-3-yl)benzofuro[3,2-b]pyridine (17.0 g, 수율 82 %)을 얻었다.9-phenyl-9H-carbazole (15.0 g, 46.6 mmol) and Pd (PPh 3 ) were added to a solution of 4-chlorobenzofuro [3,2- b] pyridin- ) 4 (1.6 g, 1.4 mmol) and K 2 CO 3 (15.4 g, 111.7 mmol) were added to toluene (150 ml) and H 2 O (75 ml), and the mixture was stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the target compound, 4-chloro-6- (9-phenyl-9H-carbazol-3-yl) benzofuro [3,2- 82%).
<단계 6> C13의 합성<Step 6> Synthesis of C13
Figure PCTKR2019000614-appb-I000080
Figure PCTKR2019000614-appb-I000080
4-chloro-6-(9-phenyl-9H-carbazol-3-yl)benzofuro[3,2-b]pyridine (15.0 g, 33.7 mmol)와 Pd(dppf)Cl2 (1.0 g, 1.3 mmol), potassium acetate (6.6 g, 67.4 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (10.3 g, 40.5 mmol) 및 X-Phos (3.2 g, 6.7 mmol)을 1,4-Dioxane 250 ml에 넣고 110℃에서 5시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C13 (15.9 g, 수율 88 %)을 얻었다.3-yl) benzofuro [3,2-b] pyridine (15.0 g, 33.7 mmol) and Pd (dppf) Cl 2 (1.0 g, 1.3 mmol) potassium acetate (6.6 g, 67.4 mmol), 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) , 40.5 mmol) and X-Phos (3.2 g, 6.7 mmol) were placed in 250 ml of 1,4-dioxane and stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO 4 . After removing the solvent of the filtered organic layer, C13 (15.9 g, yield 88%) of the target compound was obtained by column chromatography.
[합성예 1] 119 의 합성[Synthesis Example 1] Synthesis of 119
Figure PCTKR2019000614-appb-I000081
Figure PCTKR2019000614-appb-I000081
C1 (6.0 g, 11.2 mmol)와 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6-phenyl-1,3,5-triazine (4.0 g, 11.2 mmol) 및 Pd(PPh3)4 (0.3 g, 0.2 mmol), K2CO3 (3.7 g, 26.9 mmol)를 toluene 30 ml과 H2O 15 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성된 고체는 필터하였다. 필터된 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물 119 (7.0 g, 수율 85 %)을 얻었다.Cl (6.0 g, 11.2 mmol) and 2-chloro-4- (dibenzo [b, d] furan-1-yl) -6-phenyl-1,3,5-triazine (4.0 g, 11.2 mmol) PPh 3 ) 4 (0.3 g, 0.2 mmol) and K 2 CO 3 (3.7 g, 26.9 mmol) were added to toluene 30 ml and H 2 O 15 ml and stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 119 (7.0 g, yield 85%).
[LCMS] : 731[LCMS]: 731
[합성예 2] 239 의 합성[Synthesis Example 2] Synthesis of 239
Figure PCTKR2019000614-appb-I000082
Figure PCTKR2019000614-appb-I000082
C1 (6.0 g, 11.2 mmol)와 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (4.0 g, 11.2 mmol) 및 Pd(PPh3)4 (0.3 g, 0.2 mmol), K2CO3 (3.7 g, 26.9 mmol)를 toluene 30 ml과 H2O 15 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성된 고체는 필터하였다. 필터된 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물 239 (6.9 g, 수율 84 %)을 얻었다.Cl (6.0 g, 11.2 mmol) and 2-chloro-4- (dibenzo [b, d] furan-3-yl) -6- PPh 3 ) 4 (0.3 g, 0.2 mmol) and K 2 CO 3 (3.7 g, 26.9 mmol) were added to toluene 30 ml and H 2 O 15 ml and stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 239 (6.9 g, yield 84%).
[LCMS] : 731[LCMS]: 731
[합성예 3] 219 의 합성[Synthesis Example 3] Synthesis of 219
Figure PCTKR2019000614-appb-I000083
Figure PCTKR2019000614-appb-I000083
C2 (6.0 g, 11.2 mmol)와 2-chloro-4-(dibenzo[b,d]furan-4-yl)-6-phenyl-1,3,5-triazine (4.0 g, 11.2 mmol) 및 Pd(PPh3)4 (0.3 g, 0.2 mmol), K2CO3 (3.7 g, 26.9 mmol)를 toluene 30 ml과 H2O 15 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성된 고체는 필터하였다. 필터된 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물 219 (7.0 g, 수율 85 %)을 얻었다.Dibenzo [b, d] furan-4-yl) -6-phenyl-1,3,5-triazine (4.0 g, 11.2 mmol) and Pd PPh 3 ) 4 (0.3 g, 0.2 mmol) and K 2 CO 3 (3.7 g, 26.9 mmol) were added to toluene 30 ml and H 2 O 15 ml and stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the target compound 219 (7.0 g, yield 85%).
[LCMS] : 731[LCMS]: 731
[합성예 4] 59 의 합성[Synthesis Example 4] Synthesis of 59
Figure PCTKR2019000614-appb-I000084
Figure PCTKR2019000614-appb-I000084
C3 (6.0 g, 11.2 mmol)와 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (4.0 g, 11.2 mmol) 및 Pd(PPh3)4 (0.3 g, 0.2 mmol), K2CO3 (3.7 g, 26.9 mmol)를 toluene 30 ml과 H2O 15 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성된 고체는 필터하였다. 필터된 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물 59 (6.4 g, 수율 78 %)을 얻었다.3-yl) -6-phenyl-1,3,5-triazine (4.0 g, 11.2 mmol) and Pd (2-chloro-4- PPh 3 ) 4 (0.3 g, 0.2 mmol) and K 2 CO 3 (3.7 g, 26.9 mmol) were added to toluene 30 ml and H 2 O 15 ml and stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 59 (6.4 g, yield 78%).
[LCMS] : 731[LCMS]: 731
[합성예 5] 99 의 합성[Synthesis Example 5] Synthesis of 99
Figure PCTKR2019000614-appb-I000085
Figure PCTKR2019000614-appb-I000085
C3 (6.0 g, 11.2 mmol)와 2-chloro-4-(dibenzo[b,d]furan-4-yl)-6-phenyl-1,3,5-triazine (4.0 g, 11.2 mmol) 및 Pd(PPh3)4 (0.3 g, 0.2 mmol), K2CO3 (3.7 g, 26.9 mmol)를 toluene 30 ml과 H2O 15 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성된 고체는 필터하였다. 필터된 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물인 99 (6.0 g, 수율 73 %)을 얻었다.4-yl) -6-phenyl-1,3,5-triazine (4.0 g, 11.2 mmol) and Pd (2-chloro-4- PPh 3 ) 4 (0.3 g, 0.2 mmol) and K 2 CO 3 (3.7 g, 26.9 mmol) were added to toluene 30 ml and H 2 O 15 ml and stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the target compound, 99 (6.0 g, yield 73%).
[LCMS] : 731[LCMS]: 731
[합성예 6] 240 의 합성[Synthesis Example 6] Synthesis of 240
Figure PCTKR2019000614-appb-I000086
Figure PCTKR2019000614-appb-I000086
C4 (6.0 g, 11.2 mmol)와 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (4.0 g, 11.2 mmol) 및 Pd(PPh3)4 (0.3 g, 0.2 mmol), K2CO3 (3.7 g, 26.9 mmol)를 toluene 30 ml과 H2O 15 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성된 고체는 필터하였다. 필터된 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물 240 (6.7 g, 수율 82 %)을 얻었다.Dibenzo [b, d] furan-3-yl) -6-phenyl-1,3,5-triazine (4.0 g, 11.2 mmol) and Pd PPh 3 ) 4 (0.3 g, 0.2 mmol) and K 2 CO 3 (3.7 g, 26.9 mmol) were added to toluene 30 ml and H 2 O 15 ml and stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 240 (6.7 g, yield 82%).
[LCMS] : 731[LCMS]: 731
[합성예 7] 118 의 합성[Synthesis Example 7] Synthesis of 118
Figure PCTKR2019000614-appb-I000087
Figure PCTKR2019000614-appb-I000087
C5 (6.0 g, 11.2 mmol)와 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6-phenyl-1,3,5-triazine (4.0 g, 11.2 mmol) 및 Pd(PPh3)4 (0.3 g, 0.2 mmol), K2CO3 (3.7 g, 26.9 mmol)를 toluene 30 ml과 H2O 15 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성된 고체는 필터하였다. 필터된 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물 118 (6.9 g, 수율 84 %)을 얻었다.C5 (6.0 g, 11.2 mmol) and 2-chloro-4- (dibenzo [b, d] furan-1- yl) -6- PPh 3 ) 4 (0.3 g, 0.2 mmol) and K 2 CO 3 (3.7 g, 26.9 mmol) were added to toluene 30 ml and H 2 O 15 ml and stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 118 (6.9 g, yield 84%).
[LCMS] : 731[LCMS]: 731
[합성예 8] 117 의 합성[Synthesis Example 8] Synthesis of 117
Figure PCTKR2019000614-appb-I000088
Figure PCTKR2019000614-appb-I000088
C6 (6.0 g, 11.2 mmol)와 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6-phenyl-1,3,5-triazine (4.0 g, 11.2 mmol) 및 Pd(PPh3)4 (0.3 g, 0.2 mmol), K2CO3 (3.7 g, 26.9 mmol)를 toluene 30 ml과 H2O 15 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성된 고체는 필터하였다. 필터된 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물 117 (6.5 g, 수율 79 %)을 얻었다.(6.0 g, 11.2 mmol) and 2-chloro-4- (dibenzo [b, d] furan-1- yl) -6- PPh 3 ) 4 (0.3 g, 0.2 mmol) and K 2 CO 3 (3.7 g, 26.9 mmol) were added to toluene 30 ml and H 2 O 15 ml and stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 117 (6.5 g, yield 79%).
[LCMS] : 731[LCMS]: 731
[합성예 9] 254 의 합성[Synthesis Example 9] Synthesis of 254
Figure PCTKR2019000614-appb-I000089
Figure PCTKR2019000614-appb-I000089
C1 (6.0 g, 11.2 mmol)와 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-(dibenzo[b,d]furan-1-yl)-1,3,5-triazine (4.9 g, 11.2 mmol) 및 Pd(PPh3)4 (0.3 g, 0.2 mmol), K2CO3 (3.7 g, 26.9 mmol)를 toluene 30 ml과 H2O 15 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성된 고체는 필터하였다. 필터된 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물 254 (7.2 g, 수율 80 %)을 얻었다.Dibenzo [b, d] furan-1-yl) -1,3-dihydro- 30 ml of toluene and 15 ml of H 2 O were added to a solution of 5-triazine (4.9 g, 11.2 mmol), Pd (PPh 3 ) 4 (0.3 g, 0.2 mmol) and K 2 CO 3 Lt; / RTI &gt; for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 254 (7.2 g, yield 80%).
[LCMS] : 807[LCMS]: 807
[합성예 10] 284 의 합성[Synthesis Example 10] Synthesis of 284
Figure PCTKR2019000614-appb-I000090
Figure PCTKR2019000614-appb-I000090
C3 (6.0 g, 11.2 mmol)와 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-(dibenzo[b,d]furan-4-yl)-1,3,5-triazine (4.9 g, 11.2 mmol) 및 Pd(PPh3)4 (0.3 g, 0.2 mmol), K2CO3 (3.7 g, 26.9 mmol)를 toluene 30 ml과 H2O 15 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성된 고체는 필터하였다. 필터된 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물 284 (6.1 g, 수율 67 %)을 얻었다.4-yl) -4-chloro-6- (dibenzo [b, d] furan- 30 ml of toluene and 15 ml of H 2 O were added to a solution of 5-triazine (4.9 g, 11.2 mmol), Pd (PPh 3 ) 4 (0.3 g, 0.2 mmol) and K 2 CO 3 Lt; / RTI &gt; for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 284 (6.1 g, yield 67%).
[LCMS] : 807[LCMS]: 807
[합성예 11] 304 의 합성[Synthesis Example 11] Synthesis of 304
Figure PCTKR2019000614-appb-I000091
Figure PCTKR2019000614-appb-I000091
C7 (5.1 g, 11.2 mmol)와 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6-(naphthalen-1-yl)-1,3,5-triazine (4.6 g, 11.2 mmol) 및 Pd(PPh3)4 (0.3 g, 0.2 mmol), K2CO3 (3.7 g, 26.9 mmol)를 toluene 30 ml과 H2O 15 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성된 고체는 필터하였다. 필터된 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물 304 (6.6 g, 수율 84 %)을 얻었다.C7 (5.1 g, 11.2 mmol) and 2-chloro-4- (dibenzo [b, d] furan-1-yl) -6- (naphthalen- 11.2 mmol), Pd (PPh 3 ) 4 (0.3 g, 0.2 mmol) and K 2 CO 3 (3.7 g, 26.9 mmol) were added to toluene 30 ml and H 2 O 15 ml and stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 304 (6.6 g, yield 84%).
[LCMS] : 705[LCMS]: 705
[합성예 12] 360 의 합성[Synthesis Example 12] Synthesis of 360
Figure PCTKR2019000614-appb-I000092
Figure PCTKR2019000614-appb-I000092
C1 (6.0 g, 11.2 mmol)와 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-(naphthalen-2-yl)-1,3,5-triazine (4.9 g, 11.2 mmol) 및 Pd(PPh3)4 (0.3 g, 0.2 mmol), K2CO3 (3.7 g, 26.9 mmol)를 toluene 30 ml과 H2O 15 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성된 고체는 필터하였다. 필터된 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물 360 (7.3 g, 수율 83 %)을 얻었다.Cl (6.0 g, 11.2 mmol) and 2-chloro-4- (dibenzo [b, d] furan-3-yl) -6- (naphthalen- 11.2 mmol), Pd (PPh 3 ) 4 (0.3 g, 0.2 mmol) and K 2 CO 3 (3.7 g, 26.9 mmol) were added to toluene 30 ml and H 2 O 15 ml and stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the title compound 360 (7.3 g, yield 83%).
[LCMS] : 781[LCMS]: 781
[합성예 13] 386 의 합성[Synthesis Example 13] Synthesis of 386
Figure PCTKR2019000614-appb-I000093
Figure PCTKR2019000614-appb-I000093
C8 (5.1 g, 11.2 mmol)와 2-([1,1':3',1''-terphenyl]-5'-yl)-4-chloro-6-(dibenzo[b,d]furan-4-yl)-1,3,5-triazine (5.7 g, 11.2 mmol) 및 Pd(PPh3)4 (0.3 g, 0.2 mmol), K2CO3 (3.7 g, 26.9 mmol)를 toluene 60 ml과 H2O 15 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성된 고체는 필터하였다. 필터된 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물 386 (6.4 g, 수율 71 %)을 얻었다.C8 (5.1 g, 11.2 mmol) and 2 - ([1,1 ': 3', 1 "-terphenyl] -5'-yl) -4-chloro-6- (dibenzo [b, -yl) -1,3,5-triazine (5.7 g , 11.2 mmol) and Pd (PPh 3) 4 (0.3 g, 0.2 mmol), K 2 CO 3 (3.7 g, 26.9 mmol) to toluene and 60 ml H 2 O 15 ml and the mixture was stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 386 (6.4 g, yield 71%).
[LCMS] : 807[LCMS]: 807
[합성예 14] 259 의 합성[Synthesis Example 14] Synthesis of 259
Figure PCTKR2019000614-appb-I000094
Figure PCTKR2019000614-appb-I000094
C9 (6.0 g, 11.2 mmol)와 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-(dibenzo[b,d]furan-3-yl)-1,3,5-triazine (4.9 g, 11.2 mmol) 및 Pd(PPh3)4 (0.3 g, 0.2 mmol), K2CO3 (3.7 g, 26.9 mmol)를 toluene 60 ml과 H2O 15 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성된 고체는 필터하였다. 필터된 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물 259 (6.3 g, 수율 70 %)을 얻었다.Dibenzo [b, d] furan-3-yl) - 1, 3, 60 ml of toluene and 15 ml of H 2 O were added to a solution of 5-triazine (4.9 g, 11.2 mmol), Pd (PPh 3 ) 4 (0.3 g, 0.2 mmol) and K 2 CO 3 Lt; / RTI &gt; for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the target compound 259 (6.3 g, yield 70%).
[LCMS] : 807[LCMS]: 807
[합성예 15] 266 의 합성[Synthesis Example 15] 266 Synthesis
Figure PCTKR2019000614-appb-I000095
Figure PCTKR2019000614-appb-I000095
C10 (6.0 g, 11.2 mmol)와 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-(dibenzo[b,d]furan-4-yl)-1,3,5-triazine 및 Pd(PPh3)4 (0.3 g, 0.2 mmol), K2CO3 (3.7 g, 26.9 mmol)를 toluene 60 ml과 H2O 15 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성된 고체는 필터하였다. 필터된 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물 266 (6.2 g, 수율 69 %)을 얻었다.D] benzo [b, d] furan-4-yl) -1,3- 5-triazine, Pd (PPh 3 ) 4 (0.3 g, 0.2 mmol) and K 2 CO 3 (3.7 g, 26.9 mmol) were added to toluene 60 ml and H 2 O 15 ml and stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 266 (6.2 g, yield 69%).
[LCMS] : 807[LCMS]: 807
[합성예 16] 290 의 합성[Synthesis Example 16] Synthesis of 290
Figure PCTKR2019000614-appb-I000096
Figure PCTKR2019000614-appb-I000096
C11 (5.1 g, 11.2 mmol)와 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-(dibenzo[b,d]furan-3-yl)-1,3,5-triazine (4.9 g, 11.2 mmol) 및 Pd(PPh3)4 (0.3 g, 0.2 mmol), K2CO3 (3.7 g, 26.9 mmol)를 toluene 60 ml과 H2O 15 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성된 고체는 필터하였다. 필터된 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물 290 (5.6 g, 수율 68 %)을 얻었다.(5.1 g, 11.2 mmol) and 2 - ([1,1'-biphenyl] -4-yl) -4-chloro-6- (dibenzo [b, d] furan- 60 ml of toluene and 15 ml of H 2 O were added to a solution of 5-triazine (4.9 g, 11.2 mmol), Pd (PPh 3 ) 4 (0.3 g, 0.2 mmol) and K 2 CO 3 Lt; / RTI &gt; for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 290 (5.6 g, yield 68%).
[LCMS] : 731[LCMS]: 731
[합성예 17] 289 의 합성[Synthesis Example 17] Synthesis of 289
Figure PCTKR2019000614-appb-I000097
Figure PCTKR2019000614-appb-I000097
C12 (6.0 g, 11.2 mmol)와 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-(dibenzo[b,d]furan-3-yl)-1,3,5-triazine (4.9 g, 11.2 mmol) 및 Pd(PPh3)4 (0.3 g, 0.2 mmol), K2CO3 (3.7 g, 26.9 mmol)를 toluene 60 ml과 H2O 15 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 생성된 고체는 필터하였다. 필터된 고체를 toluene에 녹여 silica 필터를 한 후 재결정하여 목적 화합물 289 (6.0 g, 수율 67 %)을 얻었다.4-yl) -4-chloro-6- (dibenzo [b, d] furan-3-yl) 60 ml of toluene and 15 ml of H 2 O were added to a solution of 5-triazine (4.9 g, 11.2 mmol), Pd (PPh 3 ) 4 (0.3 g, 0.2 mmol) and K 2 CO 3 Lt; / RTI &gt; for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 289 (6.0 g, yield 67%).
[LCMS] : 807[LCMS]: 807
[합성예 18] 409 의 합성[Synthesis Example 18] Synthesis of 409
Figure PCTKR2019000614-appb-I000098
Figure PCTKR2019000614-appb-I000098
C7 (4.6 g, 10 mmol)와 2,4-dichloro-6-phenyl-1,3,5-triazine (2.3 g, 10 mmol) 및 Pd(PPh3)4 (0.3 g, 0.2 mmol), K2CO3 (3.7 g, 26.9 mmol)를 toluene 60 ml과 H2O 15 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 추출한 다음 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거하고 컬럼크로마토그래피를 이용하여 고체를 얻었다. 여기에 C8 (4.6 g, 10 mmol) 을 첨가 후 Pd(PPh3)4 (0.3 g, 0.2 mmol), K2CO3 (3.7 g, 26.9 mmol)를 toluene 60 ml과 H2O 15 ml에 넣고 110℃에서 8시간 동안 교반하였다. 위와 동일한 방법으로 정제하여 목적 화합물 409 (5.3 g, 수율 65 %)을 얻었다.C7 (4.6 g, 10 mmol) and 2,4-dichloro-6-phenyl- 1,3,5-triazine (2.3 g, 10 mmol) and Pd (PPh 3) 4 (0.3 g, 0.2 mmol), K 2 CO 3 (3.7 g, 26.9 mmol) was added to toluene (60 ml) and H 2 O (15 ml), and the mixture was stirred at 110 ° C for 8 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and then MgSO 4 was added thereto. The solvent was removed from the obtained organic layer, and a solid was obtained by column chromatography. Then this was added to C8 (4.6 g, 10 mmol) to Pd (PPh 3) 4 (0.3 g, 0.2 mmol), K 2 CO 3 (3.7 g, 26.9 mmol) put in 15 ml toluene 60 ml and H 2 O And the mixture was stirred at 110 DEG C for 8 hours. The target compound 409 (5.3 g, yield 65%) was obtained by purification in the same manner as above.
[LCMS] : 820[LCMS]: 820
[합성예 19] 407 의 합성[Synthesis Example 19] Synthesis of 407
Figure PCTKR2019000614-appb-I000099
C9 (5.3 g, 10 mmol)와 2,4-dichloro-6-phenyl-1,3,5-triazine (2.3 g, 10 mmol) 및 Pd(PPh3)4 (0.3 g, 0.2 mmol), K2CO3 (3.7 g, 26.9 mmol)를 toluene 60 ml과 H2O 15 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 추출한 다음 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거하고 컬럼크로마토그래피를 이용하여 고체를 얻었다. 여기에 C10 (5.3 g, 10 mmol) 을 첨가 후 Pd(PPh3)4 (0.3 g, 0.2 mmol), K2CO3 (3.7 g, 26.9 mmol)를 toluene 60 ml과 H2O 15 ml에 넣고 110℃에서 8시간 동안 교반하였다. 위와 동일한 방법으로 정제하여 목적 화합물 407 (6.2 g, 수율 64 %)을 얻었다.
Figure PCTKR2019000614-appb-I000099
C9 (5.3 g, 10 mmol) and 2,4-dichloro-6-phenyl- 1,3,5-triazine (2.3 g, 10 mmol) and Pd (PPh 3) 4 (0.3 g, 0.2 mmol), K 2 CO 3 (3.7 g, 26.9 mmol) was added to toluene (60 ml) and H 2 O (15 ml), and the mixture was stirred at 110 ° C for 8 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and then MgSO 4 was added thereto. The solvent was removed from the obtained organic layer, and a solid was obtained by column chromatography. Here the C10 was added to (5.3 g, 10 mmol) Pd (PPh 3) 4 (0.3 g, 0.2 mmol), K 2 CO 3 (3.7 g, 26.9 mmol) put in 15 ml toluene 60 ml and H 2 O And the mixture was stirred at 110 DEG C for 8 hours. The target compound 407 (6.2 g, yield 64%) was obtained by purification in the same manner as above.
[LCMS] : 972[LCMS]: 972
[합성예 20] 415 의 합성[Synthesis Example 20] Synthesis of 415
Figure PCTKR2019000614-appb-I000100
Figure PCTKR2019000614-appb-I000100
C1 (5.3 g, 10 mmol)와 2,4-dichloro-6-phenyl-1,3,5-triazine (2.3 g, 10 mmol) 및 Pd(PPh3)4 (0.3 g, 0.2 mmol), K2CO3 (3.7 g, 26.9 mmol)를 toluene 60 ml과 H2O 15 ml에 넣고 110℃에서 8시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 추출한 다음 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거하고 컬럼크로마토그래피를 이용하여 고체를 얻었다. 여기에 C12 (5.3 g, 10 mmol) 을 첨가 후 Pd(PPh3)4 (0.3 g, 0.2 mmol), K2CO3 (3.7 g, 26.9 mmol)를 toluene 60 ml과 H2O 15 ml에 넣고 110℃에서 8시간 동안 교반하였다. 위와 동일한 방법으로 정제하여 목적 화합물 415 (6.1 g, 수율 63 %)을 얻었다.C1 (5.3 g, 10 mmol) and 2,4-dichloro-6-phenyl- 1,3,5-triazine (2.3 g, 10 mmol) and Pd (PPh 3) 4 (0.3 g, 0.2 mmol), K 2 CO 3 (3.7 g, 26.9 mmol) was added to toluene (60 ml) and H 2 O (15 ml), and the mixture was stirred at 110 ° C for 8 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and then MgSO 4 was added thereto. The solvent was removed from the obtained organic layer, and a solid was obtained by column chromatography. Here the C12 was added to (5.3 g, 10 mmol) Pd (PPh 3) 4 (0.3 g, 0.2 mmol), K 2 CO 3 (3.7 g, 26.9 mmol) put in 15 ml toluene 60 ml and H 2 O And the mixture was stirred at 110 DEG C for 8 hours. The target compound 415 (6.1 g, yield 63%) was obtained by purification in the same manner as above.
[LCMS] : 972 [LCMS]: 972
[합성예 21] 481 의 합성[Synthesis Example 21] Synthesis of 481
Figure PCTKR2019000614-appb-I000101
Figure PCTKR2019000614-appb-I000101
C13 (5.36 g, 10 mmol), 2-chloro-4-(dibenzo[b,d]thiophen-3-yl)-6-phenyl-1,3,5-triazine (3.73 g, 10 mmol), Pd(PPh3)4 (0.34 g, 0.3 mmol), K2CO3 (2.76 g, 20 mmol)를 Toluene 100 ml/H2O 25 ml에 넣고 100℃에서 8시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터 된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 481 (4.63 g, 수율 62 %)을 얻었다.C13 (5.36 g, 10 mmol), 2-chloro-4- (dibenzo [b, d] thiophen-3- yl) -6- PPh 3 ) 4 (0.34 g, 0.3 mmol) and K 2 CO 3 (2.76 g, 20 mmol) were added to 25 ml of toluene 100 ml / H 2 O and the mixture was stirred at 100 ° C for 8 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO 4 . After removing the solvent of the filtered organic layer, 481 (4.63 g, yield 62%) of the target compound was obtained by column chromatography.
[LCMS] : 747[LCMS]: 747
[실시예 1 내지 21] 녹색 유기 전계 발광 소자의 제작[Examples 1 to 21] Fabrication of green organic electroluminescent device
상기 합성예 1 내지 21에서 합성된 화합물을 통상적으로 알려진 방법으로 고순도 승화정제를 한 후 아래의 과정에 따라 녹색 유기 전계 발광 소자를 제작하였다.The compounds synthesized in Synthesis Examples 1 to 21 were subjected to high purity sublimation purification by a conventionally known method, and then a green organic electroluminescent device was fabricated according to the following procedure.
먼저, ITO (Indium tin oxide)가 1500Å 두께로 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후 UV OZONE 세정기 (Power sonic 405, 화신테크)로 이송시킨 다음 UV를 이용하여 상기 기판을 5분간 세정하고 진공 증착기로 기판을 이송하였다.First, a glass substrate coated with ITO (Indium Tin Oxide) with a thickness of 1500 Å was washed with distilled water ultrasonic waves. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, dried and transferred to a UV OZONE cleaner (Power Sonic 405, Hoshin Tech), the substrate was cleaned using UV for 5 minutes, The substrate was transferred.
이렇게 준비된 ITO 투명 전극 위에 m-MTDATA (60 nm)/TCTA (80 nm)/ 90%의 상기 합성예 화합물 + 10%의 Ir(ppy)3 (30 nm)/BCP (10 nm)/Alq3 (30 nm)/LiF (1 nm)/Al (200 nm) 순으로 적층하여 유기 전계 발광 소자를 제작하였다.(60 nm) / TCTA (80 nm) / 90% of the above exemplified compound + 10% of Ir (ppy) 3 (30 nm) / BCP (10 nm) / Alq 3 30 nm) / LiF (1 nm) / Al (200 nm) were stacked in this order to fabricate an organic electroluminescent device.
[비교예 1] 녹색 유기 전계 발광 소자의 제작[Comparative Example 1] Production of green organic electroluminescent device
발광층 형성시 발광 호스트 물질로서 화합물 119 대신 CBP를 사용한 것을 제외하고는, 상기 실시예 1과 동일한 과정으로 녹색 유기 전계 발광 소자를 제작하였다.A green organic electroluminescent device was fabricated in the same manner as in Example 1, except that CBP was used instead of the compound 119 as a luminescent host material in forming the light emitting layer.
[비교예 2] 녹색 유기 전계 발광 소자의 제작[Comparative Example 2] Production of green organic electroluminescent device
발광층 형성시 발광 호스트 물질로서 화합물 119 대신 화합물 Ⅰ을 사용한 것을 제외하고는, 상기 실시예 1과 동일한 과정으로 녹색 유기 전계 발광 소자를 제작하였다.A green organic electroluminescent device was fabricated in the same manner as in Example 1, except that Compound I was used instead of Compound 119 as a luminescent host material in forming the light emitting layer.
[비교예 3] 녹색 유기 전계 발광 소자의 제작[Comparative Example 3] Production of green organic electroluminescent device
발광층 형성시 발광 호스트 물질로서 화합물 119 대신 화합물 Ⅱ를 사용한 것을 제외하고는, 상기 실시예 1과 동일한 과정으로 녹색 유기 전계 발광 소자를 제작하였다.A green organic electroluminescent device was fabricated in the same manner as in Example 1, except that Compound II was used instead of Compound 119 as a luminescent host material in forming the light emitting layer.
참고로, 실시예 1 내지 21, 및 비교예 1 내지 3에서 사용된 m-MTDATA, TCTA, Ir(ppy)3, CBP, BCP, 화합물 Ⅰ 및 화합물 Ⅱ의 구조는 각각 하기와 같다.The structures of m-MTDATA, TCTA, Ir (ppy) 3 , CBP, BCP, Compound I and Compound II used in Examples 1 to 21 and Comparative Examples 1 to 3 are as follows.
Figure PCTKR2019000614-appb-I000102
Figure PCTKR2019000614-appb-I000102
Figure PCTKR2019000614-appb-I000103
Figure PCTKR2019000614-appb-I000103
Figure PCTKR2019000614-appb-I000104
Figure PCTKR2019000614-appb-I000104
[평가예 1] [Evaluation Example 1]
실시예 1 내지 21, 비교예 1 내지 3에서 제작한 각각의 녹색 유기 전계 발광 소자에 대하여 전류밀도 10 mA/㎠에서의 구동전압, 전류효율 및 발광피크를 측정하고, 그 결과를 하기 표 1에 나타내었다.The driving voltage, current efficiency and emission peak at the current density of 10 mA / cm 2 were measured for each of the green organic electroluminescent devices manufactured in Examples 1 to 21 and Comparative Examples 1 to 3, Respectively.
샘플Sample 호스트Host 구동전압(V)The driving voltage (V) 발광피크(nm)Emission peak (nm) 전류효율(cd/A)Current efficiency (cd / A)
실시예 1Example 1 119119 4.624.62 516516 55.555.5
실시예 2Example 2 239239 4.554.55 516516 62.162.1
실시예 3Example 3 219219 5.465.46 516516 42.142.1
실시예 4Example 4 5959 5.335.33 516516 43.043.0
실시예 5Example 5 9999 4.954.95 516516 51.251.2
실시예 6Example 6 240240 5.015.01 516516 53.153.1
실시예 7Example 7 118118 4.884.88 516516 48.248.2
실시예 8Example 8 117117 4.584.58 516516 40.240.2
실시예 9Example 9 254254 5.115.11 516516 55.555.5
실시예 10Example 10 284284 4.764.76 516516 42.142.1
실시예 11Example 11 304304 4.544.54 516516 58.058.0
실시예 12Example 12 360360 4.994.99 516516 52.752.7
실시예 13Example 13 386386 5.015.01 516516 55.555.5
실시예 14Example 14 259259 4.214.21 516516 56.356.3
실시예 15Example 15 266266 5.465.46 516516 49.649.6
실시예 16Example 16 290290 4.874.87 516516 47.247.2
실시예 17Example 17 289289 5.215.21 516516 53.153.1
실시예 18Example 18 409409 4.774.77 516516 52.152.1
실시예 19Example 19 407407 4.564.56 516516 53.353.3
실시예 20Example 20 415415 4.994.99 516516 47.747.7
실시예 21Example 21 481481 4.894.89 516516 56.656.6
비교예 1Comparative Example 1 CBPCBP 6.936.93 516516 38.238.2
비교예 2Comparative Example 2 화합물 ⅠCompound I 5.675.67 516516 42.142.1
비교예 3Comparative Example 3 화합물 ⅡCompound II 5.555.55 516516 41.241.2
상기 표 1에 나타낸 바와 같이, 본 발명에 따른 화합물을 발광층에 적용한 실시예 1 내지 21의 녹색 유기전계 발광소자는, 종래 CBP, 화합물 Ⅰ 및 화합물 Ⅱ를 발광층에 적용한 비교예 1 내지 3의 녹색 유기전계 발광소자에 비해 전류효율 및 구동전압 면에서 보다 우수한 성능을 나타내는 것을 알 수 있었다. As shown in Table 1, the green organic electroluminescent devices of Examples 1 to 21, in which the compound according to the present invention was applied to the light emitting layer, were compared with the green organic electroluminescent devices of Comparative Examples 1 to 3 in which CBP, It was found that the current efficiency and the driving voltage were superior to those of the electroluminescent device.

Claims (10)

  1. 하기 화학식 1로 표시되는 화합물:A compound represented by the following formula (1):
    [화학식 1][Chemical Formula 1]
    Figure PCTKR2019000614-appb-I000105
    Figure PCTKR2019000614-appb-I000105
    상기 화학식 1에서,In Formula 1,
    X1 및 X2는 서로 동일하거나 상이하며, 각각 독립적으로 O 또는 S이고,X 1 and X 2 are the same as or different from each other and each independently O or S,
    Y1 내지 Y16은 서로 동일하거나 상이하며, 각각 독립적으로 CR8 또는 N이고, 이때 CR8이 복수 개인 경우 복수의 R8은 서로 동일하거나 또는 상이하며, Y 1 to Y 16 are the same as or different from each other, and each independently CR 8 or N, provided that when there are a plurality of CR 8 s , the plurality of R 8 s are the same as or different from each other,
    Z1 내지 Z3는 서로 동일하거나 상이하며, 각각 독립적으로 CR5 또는 N이고, 이들 중 적어도 하나는 N이고,Z 1 to Z 3 are the same or different and each independently CR 5 or N, at least one of them is N,
    Ar1은 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기 및 C6~C60의 아릴기로 이루어진 군에서 선택되고,Ar 1 is selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, C 1 to C 40 alkyl, C 2 to C 40 alkenyl, C 2 to C 40 alkynyl, C 3 to C 40 cycloalkyl, A C 6 to C 60 aryl group,
    다만, Z1 내지 Z3 함유 환을 기준으로 상기 X1 함유 환과 상기 X2 함유 환은 서로 비대칭적으로 결합되며,Provided that the X 1 containing ring and the X 2 containing ring are asymmetrically bonded to each other based on the Z 1 to Z 3 containing ring,
    m 및 n은 각각 0 내지 3의 정수이며, m+n ≥ 1이고,m and n are each an integer of 0 to 3, m + n? 1,
    A 및 B는 서로 동일하거나 상이하며, 각각 독립적으로 하기 화학식 2 또는 화학식 3으로 표시되는 치환체 중 어느 하나이며;A and B are the same or different from each other, and are each independently any one of substituents represented by the following formula (2) or (3);
    [화학식 2](2)
    Figure PCTKR2019000614-appb-I000106
    Figure PCTKR2019000614-appb-I000106
    [화학식 3](3)
    Figure PCTKR2019000614-appb-I000107
    Figure PCTKR2019000614-appb-I000107
    상기 화학식 2 또는 3에서,In the general formula (2) or (3)
    *은 상기 화학식 1에 결합되는 부위를 의미하고,* Represents a moiety bonded to Formula 1,
    X3는 단일결합이고,X 3 is a single bond,
    Ar2 는 C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 혹은 인접한 기와 결합하여 축합 고리를 형성할 수 있고,Ar 2 represents a C 1 to C 40 alkyl group, a C 2 to C 40 alkenyl group, a C 2 to C 40 alkynyl group, a C 3 to C 40 cycloalkyl group, a C 6 to C 60 aryl group, 5 to 60 heteroaryl groups and C 6 to C 60 arylamine groups, or may be bonded to adjacent groups to form a condensed ring,
    a, c 및 f는 각각 0 내지 3의 정수이고,a, c, and f are each an integer of 0 to 3,
    b, d 및 e는 각각 0 내지 4의 정수이며, 이때 b+m≤4, d+n≤4이고,b, d and e are each an integer of 0 to 4, wherein b + m? 4, d + n? 4,
    R1 내지 R8은 서로 동일하거나 상이하며, 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 혹은 인접한 기와 결합하여 축합 고리를 형성할 수 있고, 이때 상기 R1 내지 R7이 각각 복수인 경우, 이들은 서로 동일하거나 상이하고,R 1 to R 8 are the same or different from each other and each independently represents hydrogen, deuterium, halogen, cyano, nitro, C 1 to C 40 alkyl, C 2 to C 40 alkenyl, C 2 to C 40 An alkynyl group, a C 3 to C 40 cycloalkyl group, a heteroaryl group having 3 to 40 nuclear atoms, a C 6 to C 60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C 1 to C 40 alkyl A C 6 to C 60 aryloxy group, a C 1 to C 40 alkylsilyl group, a C 6 to C 60 arylsilyl group, a C 1 to C 40 alkylboron group, a C 6 to C 60 aryl boron group, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~, or selected from the group consisting of an aryl amine of the C 60 of, or adjacent groups combine to form a condensed ring And when R 1 to R 7 are each plural, they may be the same or different from each other,
    상기 Ar1 내지 Ar2, 및 R1 내지 R8의 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 아릴포스핀옥사이드기 및 아릴아민기는 각각 독립적으로 중수소, 할로겐, 시아노기, 니트로기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C1~C40의 알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환될 수 있으며, 이때 상기 치환기가 복수인 경우, 이들은 서로 동일하거나 상이할 수 있다.Alkyl group of said Ar 1 to Ar 2, and R 1 to R 8, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl A halogen atom, a cyano group, a nitro group, a C 2 to C 40 alkenyl group, a C 2 to C 40 alkenyl group, an aryloxy group, an aryloxy group, A cycloalkyl group having 3 to 40 carbon atoms, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C 1 to C 40 alkyl group, a C 6 to C 60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms A C 1 to C 40 alkyloxy group, a C 6 to C 60 aryloxy group, a C 1 to C 40 alkylsilyl group, a C 6 to C 60 arylsilyl group, a C 1 to C 40 alkyl boron group, C 6 ~ C 60 aryl group of boron, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~ selected from the group consisting of an arylamine C in 60 If the first plural number, and wherein said substituent is substituted by at least one substituent, these may be the same or different from each other.
  2. 제1항에 있어서,The method according to claim 1,
    상기 화학식 1로 표시되는 화합물은 하기 화학식 4 내지 화학식 7 중 어느 하나로 표시되는 화합물:The compound represented by the formula (1) is represented by any one of the following formulas (4) to (7)
    [화학식 4] [Chemical Formula 4]
    Figure PCTKR2019000614-appb-I000108
    Figure PCTKR2019000614-appb-I000108
    [화학식 5] [Chemical Formula 5]
    Figure PCTKR2019000614-appb-I000109
    Figure PCTKR2019000614-appb-I000109
    [화학식 6] [Chemical Formula 6]
    Figure PCTKR2019000614-appb-I000110
    Figure PCTKR2019000614-appb-I000110
    [화학식 7] (7)
    Figure PCTKR2019000614-appb-I000111
    Figure PCTKR2019000614-appb-I000111
    상기 화학식 4 내지 7에서, In the above formulas 4 to 7,
    상기 화학식 4의 Z1 내지 Z3 함유환은 Y10 내지 Y12 중 어느 하나와 결합되며(단, Z1 내지 Z3 함유환이 Y9과 결합되는 것은 제외됨), The ring containing Z 1 to Z 3 in Formula 4 is bonded to any one of Y 10 to Y 12 (provided that the ring containing Z 1 to Z 3 is not bonded to Y 9 )
    상기 화학식 5의 Z1 내지 Z3 함유환은 Y9, Y11 내지 Y12 중 어느 하나와 결합되며(단, Z1 내지 Z3 함유환이 Y10과 결합되는 것은 제외됨), The ring containing Z 1 to Z 3 in Formula 5 is bonded to any one of Y 9 and Y 11 to Y 12 (provided that the ring containing Z 1 to Z 3 is not bonded to Y 10 )
    상기 화학식 6의 Z1 내지 Z3 함유환은 Y9, Y10 및 Y12 중 어느 하나와 결합되며(단, Z1 내지 Z3 함유환이 Y11과 결합되는 것은 제외됨), The ring containing Z 1 to Z 3 in Formula 6 is bonded to any one of Y 9 , Y 10 and Y 12 (provided that the Z 1 to Z 3 containing ring is not bonded to Y 11 )
    상기 화학식 7의 Z1 내지 Z3 함유환은 Y9 내지 Y11 중 어느 하나와 결합되며(단, Z1 내지 Z3 함유환이 Y12와 결합되는 것은 제외됨), The ring containing Z 1 to Z 3 in the above formula (7) is bonded to any one of Y 9 to Y 11 (provided that the Z 1 to Z 3 containing ring is not bonded to Y 12 )
    X1, X2, Y1 내지 Y16, Z1 내지 Z3, Ar1, m, n, A, B, a 내지 d, R1 내지 R4는 각각 제1항에서 정의한 바와 같다.X 1 , X 2 , Y 1 to Y 16 , Z 1 to Z 3 , Ar 1 , m, n, A, B, a to d and R 1 to R 4 are as defined in claim 1, respectively.
  3. 제1항에 있어서,The method according to claim 1,
    상기 화학식 1로 표시되는 화합물은 하기 화학식 8 내지 12 중 어느 하나로 표시되는 화합물.The compound represented by the formula (1) is represented by any one of the following formulas (8) to (12).
    [화학식 8][Chemical Formula 8]
    Figure PCTKR2019000614-appb-I000112
    Figure PCTKR2019000614-appb-I000112
    [화학식 9][Chemical Formula 9]
    Figure PCTKR2019000614-appb-I000113
    Figure PCTKR2019000614-appb-I000113
    [화학식 10][Chemical formula 10]
    Figure PCTKR2019000614-appb-I000114
    Figure PCTKR2019000614-appb-I000114
    [화학식 11](11)
    Figure PCTKR2019000614-appb-I000115
    Figure PCTKR2019000614-appb-I000115
    [화학식 12][Chemical Formula 12]
    Figure PCTKR2019000614-appb-I000116
    Figure PCTKR2019000614-appb-I000116
    상기 화학식 8 내지 12에서,In Formulas 8 to 12,
    X1, X2, Z1 내지 Z3, Ar1, n, A, B는 각각 제1항에서 정의한 바와 같다.X 1 , X 2 , Z 1 to Z 3 , Ar 1 , n, A and B are as defined in claim 1, respectively.
  4. 제1항에 있어서,The method according to claim 1,
    상기 Z1 내지 Z3는 모두 N인 화합물.Wherein Z 1 to Z 3 are all N.
  5. 제1항에 있어서,The method according to claim 1,
    상기 A 및 B는 서로 동일하거나 상이하며, 각각 독립적으로 하기 구조식으로 표시되는 치환체 군에서 선택되는 어느 하나인 화합물.Wherein A and B are the same or different from each other, and each independently selected from the group consisting of substituents represented by the following structural formulas.
    Figure PCTKR2019000614-appb-I000117
    Figure PCTKR2019000614-appb-I000117
    상기 화학식에서,In the above formulas,
    *은 상기 화학식 1에 결합되는 부위를 의미하고,* Represents a moiety bonded to Formula 1,
    Ar2는 제1항에서 정의한 바와 같다.Ar &lt; 2 &gt; is as defined in claim 1.
  6. 제1항에 있어서,The method according to claim 1,
    상기 Ar1은 하기 구조식으로 표시된 치환체 군에서 선택되는 어느 하나인 화합물.Wherein Ar &lt; 1 &gt; is any one selected from the substituent groups represented by the following structural formulas.
    Figure PCTKR2019000614-appb-I000118
    Figure PCTKR2019000614-appb-I000118
  7. 제1항에 있어서,The method according to claim 1,
    상기 R1 내지 R5 및 R8는 서로 동일하거나 상이하며, 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기 및 C6~C60의 아릴기로 이루어진 군에서 선택되고,R 1 to R 5 and R 8 are the same or different and each independently represents hydrogen, deuterium, halogen, cyano, nitro, C 1 to C 40 alkyl, C 2 to C 40 alkenyl, C 2 An alkynyl group of C 40 to C 40 , a cycloalkyl group of C 3 to C 40 , and an aryl group of C 6 to C 60 ,
    상기 R6 및 R7은 서로 동일하거나 상이하며, 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, C6~C60의 아릴기 및 핵원자수 5 내지 60의 헤테로아릴기로 이루어진 군에서 선택되거나, 혹은 인접한 기와 결합하여 축합 고리를 형성하는 화합물.Wherein R 6 and R 7 are the same or different, each independently represent hydrogen, deuterium, a halogen, a cyano group, a nitro group, C 1 ~ alkenyl group of the C 40 alkyl group, C 2 ~ C 40 of, C 2 ~ C 40 A cycloalkyl group having 3 to 40 carbon atoms, an aryl group having 6 to 60 carbon atoms and a heteroaryl group having 5 to 60 nuclear atoms, or is bonded to an adjacent group to form a condensed ring.
  8. 양극, 음극 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하고,An organic electroluminescent device comprising a cathode, a cathode, and at least one organic layer interposed between the anode and the cathode,
    상기 1층 이상의 유기물층 중 적어도 하나는 제1항 내지 제7항 중 어느 한 항에 기재된 화합물을 포함하는 것인 유기 전계 발광 소자.Wherein at least one of the one or more organic layers includes a compound according to any one of claims 1 to 7.
  9. 제8항에 있어서,9. The method of claim 8,
    상기 화합물을 포함하는 유기물층은 정공 주입층, 정공 수송층, 발광 보조층, 발광층, 전자 수송층 및 전자 주입층으로 이루어진 군에서 선택되는 것인 유기 전계 발광 소자.Wherein the organic compound layer containing the compound is selected from the group consisting of a hole injecting layer, a hole transporting layer, a light emitting auxiliary layer, a light emitting layer, an electron transporting layer, and an electron injecting layer.
  10. 제9항에 있어서,10. The method of claim 9,
    상기 화합물을 포함하는 유기물층은 인광 발광층인 유기 전계 발광 소자.Wherein the organic compound layer containing the compound is a phosphorescent light-emitting layer.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008072596A1 (en) * 2006-12-13 2008-06-19 Konica Minolta Holdings, Inc. Organic electroluminescent device, display and illuminating device
WO2013069242A1 (en) * 2011-11-07 2013-05-16 出光興産株式会社 Material for organic electroluminescent elements, and organic electroluminescent element using same
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Publication number Priority date Publication date Assignee Title
WO2008072596A1 (en) * 2006-12-13 2008-06-19 Konica Minolta Holdings, Inc. Organic electroluminescent device, display and illuminating device
WO2013069242A1 (en) * 2011-11-07 2013-05-16 出光興産株式会社 Material for organic electroluminescent elements, and organic electroluminescent element using same
KR20160028524A (en) * 2014-05-05 2016-03-11 메르크 파텐트 게엠베하 Materials for organic light emitting devices
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