WO2014046392A1 - Organic compound and electroluminescent element having same - Google Patents

Organic compound and electroluminescent element having same Download PDF

Info

Publication number
WO2014046392A1
WO2014046392A1 PCT/KR2013/007821 KR2013007821W WO2014046392A1 WO 2014046392 A1 WO2014046392 A1 WO 2014046392A1 KR 2013007821 W KR2013007821 W KR 2013007821W WO 2014046392 A1 WO2014046392 A1 WO 2014046392A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
compound
substituted
unsubstituted
formula
Prior art date
Application number
PCT/KR2013/007821
Other languages
French (fr)
Korean (ko)
Inventor
이용환
김태형
손효석
배형찬
박호철
이창준
신진용
백영미
Original Assignee
주식회사 두산
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 두산 filed Critical 주식회사 두산
Publication of WO2014046392A1 publication Critical patent/WO2014046392A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • 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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • 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
    • 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
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • 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
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
    • 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
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission

Definitions

  • the present invention relates to a novel organic compound and an organic electroluminescent device comprising the same, and more particularly to a novel organic compound having excellent hole injection ability, hole transport ability and light emission ability, and the like as a material of the organic material layer
  • the present invention relates to an organic EL device having improved characteristics such as efficiency, driving voltage, and lifetime.
  • the material used as the organic material layer may be classified into a light emitting layer material, a hole injection layer material, a hole transport layer material, an electron transport layer material, an electron injection layer material and the like according to its function.
  • the material ('light emitting layer material') forming the light emitting layer of the organic EL device may be classified into blue, green, and red light emitting material according to the light emitting color.
  • yellow and orange light emitting layer materials are also used as the light emitting layer material to realize a better natural color.
  • a host / dopant system may be used as the light emitting layer material.
  • the dopant material may 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 phosphorescent materials can theoretically improve luminous efficiency up to four times that of fluorescence, attracting attention not only on phosphorescent dopants but also on phosphorescent host materials.
  • hole transport layer material As the hole transport layer material, the hole blocking layer material, and the electron transport layer material, NPB, BCP, Alq 3 and the like represented by the following formulas are widely known, and as the light emitting layer material, anthracene derivatives have been reported as fluorescent dopant / host materials.
  • phosphorescent materials having great advantages in terms of efficiency improvement include metal complex compounds including Ir such as Firpic, Ir (ppy) 3 , and (acac) Ir (btp) 2 , which are blue, green, and red plated materials. It is used as a raw material. To date, CBP has shown excellent properties as a phosphorescent host material.
  • an object of the present invention is to provide a novel organic compound that can be used as a light emitting layer material and can improve the efficiency, life and stability of the device when used in the light emitting layer of the organic electroluminescent device.
  • an object of this invention is to provide the organic electroluminescent element containing the said novel organic compound.
  • the present invention provides a compound represented by the following formula (1):
  • Ring A is a 6-membered heterocycle containing CR 3 and N, a 6-membered ring substituted with R 3 , or a 6-membered heterocycle containing two N;
  • X 1 and X 2 are each independently selected from the group consisting of O, S, Se, N (Ar 1 ), C (Ar 2 ) (Ar 3 ) and Si (Ar 4 ) (Ar 5 ), wherein X At least one of 1 and X 2 is N (Ar 1 );
  • Y 1 to Y 4 are the same as or different from each other, and each independently N or CR 4, wherein, when there are a plurality of CR 4 , they are different from each other or the same;
  • a is 1 or 2;
  • L represents a substituted or unsubstituted C 6 to C 60 arylene group, a substituted or unsubstituted heteroarylene group having 5 to 60 nuclear atoms, a substituted or unsubstituted aryl-triyl, or a substituted or Unsubstituted heteroaryl-triyl,
  • L is a substituted or unsubstituted C 6 to C 60 arylene group, or a substituted or unsubstituted heteroarylene group having 5 to 60 nuclear atoms,
  • L is substituted or unsubstituted aryl-triyl, or substituted or unsubstituted heteroaryl-triyl;
  • B is a substituted or unsubstituted carbazole group, or a substituent represented by the following formula (3), wherein when B is plural, they are different from each other or the same;
  • Ring C is a 6-membered heterocycle containing CR 7 and N, a 6-membered ring substituted with R 7 , or a 6-membered heterocycle containing two N;
  • X 3 and X 4 are each independently selected from the group consisting of O, S, Se, N (Ar 6 ), C (Ar 7 ) (Ar 8 ) and Si (Ar 9 ) (Ar 10 ),
  • Y 5 to Y 8 are the same as or different from each other, and each independently N or CR 8, wherein, when a plurality of CR 8 plurals, they are different from or the same;
  • R 5 to R 8 and Ar 6 to Ar 10 is a single bond, connected to L of Formula 2;
  • R 1 to R 8 are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano, nitro, a substituted or unsubstituted C 1 -C 40 alkyl group, a substituted or unsubstituted C 2 -C 40 Alkenyl group, substituted or unsubstituted C 2 to C 40 alkynyl group, substituted or unsubstituted C 3 to C 40 cycloalkyl group, substituted or unsubstituted heterocycloalkyl group having 3 to 40 nuclear atoms, substituted or unsubstituted Substituted C 6 ⁇ C 60 aryl group, substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, substituted or unsubstituted C 1 ⁇ C 40 alkyloxy group, substituted or unsubstituted C 6 ⁇ C 60 aryloxy group, substituted or unsubstituted C 3 to C 40 alkyl
  • Ar 1 to Ar 10 are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C 1 to C 40 alkyl group, substituted or unsubstituted C 3 to C 40 A cycloalkyl group, a substituted or unsubstituted heterocycloalkyl group having 3 to 40 nuclear atoms, a substituted or unsubstituted C 6 -C 60 aryl group, a substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, Substituted or unsubstituted C 1 to C 40 alkyloxy group, substituted or unsubstituted C 6 to C 60 aryloxy group, substituted or unsubstituted C 3 to C 40 alkylsilyl group, substituted or unsubstituted C 6 ⁇ C 60 arylsilyl group, substituted or unsubstituted C 1 ⁇ C 40 Al
  • One or more substituents respectively introduced to the arylborone group, the arylphosphine group, the arylphosphine oxide group and the arylamine group are each independently deuterium, halogen, cyano, nitro, C 1 -C 40 alkyl group, C 3 -C 40 Cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C 6 to C 60 , heteroaryl group of 5 to 60 nuclear
  • the present invention is an organic EL device comprising an anode, a cathode, and at least one organic layer interposed between the anode and the cathode, at least one of the at least one organic layer is a compound represented by the formula (1) It provides an organic EL device which is characterized by including.
  • the organic material layer including the compound represented by Chemical Formula 1 is selected from the group consisting of a hole injection layer, a hole transport layer, and a light emitting layer, and is preferably a light emitting layer.
  • the compound represented by Chemical Formula 1 is included in the emission layer, it may be used as a host material and / or a dopant.
  • the compound represented by Formula 1 according to the present invention is excellent in heat resistance, hole injection ability, hole transporting ability, light emitting ability, etc.
  • the compound may be applied to an organic material layer, preferably a light emitting layer of an organic EL device.
  • the organic electroluminescent device includes the compound represented by Chemical Formula 1 as a hole injection layer material, a hole transport layer material, or a light emitting layer material (phosphorescent / fluorescent host, dopant) or the like, the light emitting performance, driving voltage, Since aspects such as lifespan, efficiency (light emitting efficiency, power efficiency) and the like can be greatly improved, they can be effectively applied to a full color display panel or the like.
  • novel organic compound according to the present invention is applied to an indoloindole-based basic skeleton formed by condensation of an indole-based moiety and an indole-based moiety, and a cover through a linking group (L).
  • a structure in which an indoloindole moiety in which a doze group or an indole moiety is condensed with an indole moiety is combined, is represented by Chemical Formula 1.
  • Compound represented by the formula (1) has a higher molecular weight than the conventional organic EL device material [for example, 4,4-dicarbazolybiphenyl (hereinafter referred to as 'CBP')] has a high glass transition temperature, and also excellent thermal stability, It has excellent hole injecting ability, hole transporting ability and light emitting ability. Therefore, when the organic electroluminescent device includes the compound of Formula 1, the driving voltage, efficiency, lifespan, etc. of the device may be improved.
  • the conventional organic EL device material for example, 4,4-dicarbazolybiphenyl (hereinafter referred to as 'CBP')
  • 'CBP' 4,4-dicarbazolybiphenyl
  • the compound represented by Formula 1 is an indoloindole-based moiety or carbazole group through the linking group (L) to an indoloindole-based basic skeleton formed by condensation of an indole-based moiety and an indole-based moiety By being combined, it has a wide bandgap (sky blue to red).
  • an indoloindole moiety or a carbazole group is bonded to an N position of an indole moiety in a basic skeleton condensed between an indole moiety and an indole moiety through a linking group (eg, arylene, heteroarylene, etc.).
  • the bandgap of the compound is widened and the triplet energy level is widened, thereby improving the phosphorescence property of the device and at the same time improving the electron and / or hole transport ability, the luminous efficiency, the driving voltage, and the life characteristics.
  • the electron transport ability etc. can also be improved according to the kind of substituent introduce
  • the compound of Formula 1 may optionally be used as a material of the electron transport layer by introducing an appropriate substituent.
  • the compound of Formula 1 may exhibit excellent properties as a light emitting layer material, especially a host material, compared to the conventional CBP due to the indoloindole-based skeleton.
  • the compound represented by Formula 1 has a variety of aryl groups and / or heteroaryl groups introduced into the indoloindole-based basic skeleton significantly increases the molecular weight of the compound, thereby improving the glass transition temperature, thereby resulting in higher than conventional CBP It can have a high thermal stability. Therefore, the device including the compound represented by the formula (1) of the present invention can greatly improve the durability and life characteristics.
  • the compound represented by Formula 1 has a small difference between the triplet energy level and the singlet energy level, so that the reverse energy transfer from the triplet to the singlet may occur.
  • thermally activated delayed fluorescence occurs, thereby improving external quantum efficiency of the device, and when the compound is used as a light emitting layer material, the light emission efficiency of the device may be increased.
  • the compound of the present invention When the compound of the present invention is adopted as a hole injection / transport layer of an organic EL device, a blue, green and / or red phosphorescent host material or a fluorescent dopant material, the compound can exhibit excellent efficiency and lifespan in comparison with the conventional CBP. have. Therefore, the compound according to the present invention can greatly contribute to the improvement of the performance and the life of the organic EL device.
  • ring A is a 6-membered heterocycle containing CR 3 and N, a 6-membered cycle substituted with R 3 , or two It is a 6-membered heterocycle containing N, Preferably it is a 6-membered ring substituted with R ⁇ 3> .
  • X 1 and X 2 are each independently selected from O, S, Se, N (Ar 1 ), C (Ar 2 ) (Ar 3 ) and Si (Ar 4 ) (Ar 5 ), wherein X At least one of 1 and X 2 is N (Ar 1 ).
  • Preferably both X 1 and X 2 are N (Ar 1 ), or X 1 and X 2 are each independently N (Ar 1 ) or S.
  • Y 1 to Y 4 are the same as or different from each other, and each independently N or CR 4 , and preferably Y 1 to Y 4 are all CR 4 . At this time, when there are a plurality of CR 4 , they are different from each other or the same.
  • R 1 to R 4 is a substituent represented by Chemical Formula 2.
  • a is 1 or 2.
  • L is a substituted or unsubstituted C 6 ⁇ C 60 arylene group, a substituted or unsubstituted heteroarylene group having 5 to 60 nuclear atoms, a substituted or unsubstituted aryl-triyl group (aryl-triyl group) Or a substituted or unsubstituted heteroaryl-triyl group, provided that when a is 1, L is a substituted or unsubstituted C 6 -C 60 arylene group, or a substituted or unsubstituted nucleus.
  • L is substituted or unsubstituted aryl-triyl, or substituted or unsubstituted heteroaryl-triyl to be.
  • the aryl-triyl group is a trivalent aryl group
  • the heteroaryl-triyl group is a trivalent heteroaryl group.
  • One or more substituents respectively introduced into the arylene group, heteroarylene group, aryl-triyl group, aryl-triyl group, and heteroaryl-triyl group of L are each independently deuterium, halogen, cyano, nitro, C 1 -C 40 Alkyl group of C 6 ⁇ C 60 aryl group, heteroaryl group of 5 to 60 nuclear atoms, C 1 ⁇ C 40 alkyloxy group, C 3 ⁇ C 40 alkylsilyl group, C 2 ⁇ C 40 alkyl
  • substituents are plural, they may be the same or different from each other.
  • L is bivalent or trivalent phenyl, biphenyl, naphthyl, indene, fluorenyl, carbazolyl, pyridine, pyrimidine, pyridazine, pyrazine, triazine, triazole, Selected from the group consisting of oxadiazole, thiadiazole, indole, benzimidazole, quinoline, isoquinoline, and quinoxaline, each independently of deuterium, halogen, cyano, nitro, alkyl group of C 1 to C 40 , C 6 ⁇ C 60 aryl group, nuclear atom 5 ⁇ 60 heteroaryl group, C 1 ⁇ C 40 alkyloxy group, C 3 ⁇ C 40 alkylsilyl group, C 2 ⁇ C 40 alkyl boron group It may be substituted with one or more substituents selected from the group consisting of.
  • L may be selected from the group consisting of the following substituents C1 to C76, but is not limited thereto.
  • B is a substituted or unsubstituted carbazole group, or a substituent represented by Formula 3. At this time, when B is plural, they are different from each other or the same.
  • ring C is a 6-membered heterocycle containing CR 7 and N, a 6-membered cycle substituted with R 7 , or a 6-membered ring containing two N's It is a heterocyclic ring, It is a 6 membered ring preferably substituted with R ⁇ 7> .
  • X 3 and X 4 are each independently selected from the group consisting of O, S, Se, N (Ar 6 ), C (Ar 7 ) (Ar 8 ) and Si (Ar 9 ) (Ar 10 ), At least one of X 3 and X 4 is N (Ar 6 ). Preferably both X 3 and X 4 are N (Ar 6 ), or X 3 and X 4 are each independently N (Ar 6 ) or S.
  • Y 5 to Y 8 are the same as or different from each other, and each independently N or CR 8 , and preferably Y 5 to Y 8 are all CR 8 . At this time, when there are a plurality of CR 8 , they are different from each other or the same.
  • R 5 to R 8 and Ar 5 to Ar 8 is a single bond, and is connected to L of Chemical Formula 2.
  • each of R 1 to R 8 is independently hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C 1 to C 40 alkyl group, substituted or unsubstituted C 3 to C 40 cycloalkyl group, Substituted or unsubstituted heterocycloalkyl group having 3 to 40 nuclear atoms, substituted or unsubstituted C 6 to C 60 aryl group, substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, substituted or unsubstituted A substituted C 1 to C 40 alkyloxy group, a substituted or unsubstituted C 6 to C 60 aryloxy group, a substituted or unsubstituted C 3 to C 40 alkylsilyl group, a substituted or unsubstituted C 6 to C Arylsilyl group of 60 , substituted or unsubstituted C 1 ⁇ C 40 alkyl boron group
  • R 1 to R 8 are each independently hydrogen, C 6 ⁇ C 60 aryl group (e.g., phenyl, naphthyl, bisphenyl), 5 to nuclear atoms Preference is given to a 60 heteroaryl group (eg pyridine).
  • aryl group e.g., phenyl, naphthyl, bisphenyl
  • 5 to nuclear atoms Preference is given to a 60 heteroaryl group (eg pyridine).
  • One or more substituents respectively introduced to the phosphine group, the arylphosphine oxide group, and the arylamine group are each independently deuterium, halogen, cyano, nitro, C 1 -C 40 alkyl group, C 3 -C 40 cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C 6 ⁇ C 60 aryl group, nuclear atoms aryl of from 5 to 60 heteroaryl group, C 1 ⁇ alkyloxy group of C 40 of, C 6 ⁇ C 60 aryloxy group, C 3 ⁇ C 40 alkyl silyl group, C 6 ⁇ C
  • Ar 1 to Ar 10 are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C 1 to C 40 alkyl group, substituted or unsubstituted C 3 to C 40 cycloalkyl groups, substituted or unsubstituted heterocycloalkyl groups having 3 to 40 nuclear atoms, substituted or unsubstituted C 6 -C 60 aryl groups, substituted or unsubstituted nuclear atoms having 5 to 60 heteroaryl groups , Substituted or unsubstituted C 1 ⁇ C 40 alkyloxy group, substituted or unsubstituted C 6 ⁇ C 60 aryloxy group, substituted or unsubstituted C 3 ⁇ C 40 alkylsilyl group, substituted or unsubstituted C 6 ⁇ C 60 arylsilyl group, substituted or unsubstituted C 1 ⁇ C 40 Alkyl
  • Ar 1 to Ar 10 may be each independently a substituted or unsubstituted C 6 ⁇ C 60 aryl group, or a substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms.
  • R 1 to R 8 , and Ar 1 to Ar 10 may be each independently selected from the group consisting of hydrogen, the following substituents S1 to S177, but is not limited thereto.
  • one of R 1 to R 4 , and Ar 1 to Ar 5 is a substituent represented by Formula 2, and one of R 5 to R 8 , and Ar 6 to Ar 10 is a single bond, Is connected to L.
  • the substituent represented by Chemical Formula 3 may be selected from the substituents represented by the following Chemical Formulas 3a to 3f, but is not limited thereto.
  • X 3 and X 4 are each independently selected from the group consisting of O, S, Se, N (Ar 6 ), C (Ar 7 ) (Ar 8 ) and Si (Ar 9 ) (Ar 10 );
  • R 5 to R 8 and Ar 6 to Ar 10 is a single bond and is connected to L of Formula 2;
  • R 5 to R 8 and Ar 6 to Ar 10 are as defined in Formula 1, respectively.
  • a plurality of R 7 are the same or different from each other, a plurality of R 8 is the same or different from each other.
  • Examples of the compound represented by Chemical Formula 1 according to the present invention include a compound represented by the following Chemical Formulas 4 to 9, but are not limited thereto.
  • X 1 and X 2 are each independently selected from the group consisting of O, S, Se, N (Ar 1 ), C (Ar 2 ) (Ar 3 ) and Si (Ar 4 ) (Ar 5 ), wherein X At least one of 1 and X 2 is N (Ar 1 );
  • R 1 to R 4 and Ar 1 to Ar 5 is a substituent represented by Formula 2;
  • R 1 to R 4 , and Ar 1 to Ar 5 are the same as defined in Chemical Formula 1.
  • Examples of the compound represented by Formula 1 according to the present invention include a compound represented by the following Formula 10, but is not limited thereto.
  • X 1 , Y 1 to Y 4 , Ring A, R 1 , R 2 , L, a and B are as defined in Formula 1, respectively,
  • a plurality of R 3 are the same or different from each other, a plurality of R 4 is the same or different from each other.
  • examples of the compound represented by Chemical Formula 1 include compounds represented by the following Chemical Formulas 11 to 16, but are not limited thereto.
  • X 1 , R 1 to R 4 , L, a and B are as defined in Formula 1, respectively,
  • the plurality of R 3 are the same or different from each other, the plurality of R 4 is the same or different from each other.
  • examples of the compound represented by Formula 1 according to the present invention include a compound represented by the following Formula 17, but is not limited thereto.
  • X 1 , X 3 , Y 1 to Y 8 , R 1 , R 2 , R 5 , R 6 , Ring A, Ring C, L and a are as defined in Formula 1, respectively.
  • examples of the compound represented by Chemical Formula 1 include a compound represented by the following Chemical Formulas 18 to 23, but are not limited thereto.
  • X 1 , X 3 , Y 5 to Y 8 , R 1 to R 6 , rings C, L and a are as defined in Formula 1, respectively,
  • the plurality of R 3 are the same or different from each other, the plurality of R 4 is the same or different from each other.
  • Specific examples of the compound represented by Chemical Formula 1 include a compound represented by Chemical Formula CH-1 to a compound represented by Chemical Formula CH-281, but are not limited thereto.
  • unsubstituted alkyl refers to a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain saturated hydrocarbon of 1 to 40 carbon atoms, examples of which are methyl, ethyl, propyl, isobutyl, sec -Butyl, pentyl, iso-amyl, hexyl and the like.
  • unsubstituted alkenyl refers to a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon double bond. do. Examples thereof include vinyl, allyl, isopropenyl, 2-butenyl, and the like, but are not limited thereto.
  • unsubstituted alkynyl means a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon triple bond. do. Examples thereof include ethynyl, 2-propynyl, and the like, but are not limited thereto.
  • unsubstituted cycloalkyl means a monovalent functional group obtained by removing a hydrogen atom from a monocyclic or polycyclic non-aromatic hydrocarbon (saturated cyclic hydrocarbon) having 3 to 40 carbon atoms.
  • cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.
  • unsubstituted heterocycloalkyl means a monovalent functional group obtained by removing a hydrogen atom from a non-aromatic hydrocarbon (saturated cyclic hydrocarbon) having 3 to 40 nuclear atoms, wherein at least one of the rings Carbon, preferably 1 to 3 carbons, is substituted with a hetero atom such as N, O or S.
  • a non-aromatic hydrocarbon saturated cyclic hydrocarbon having 3 to 40 nuclear atoms, wherein at least one of the rings Carbon, preferably 1 to 3 carbons, is substituted with a hetero atom such as N, O or S.
  • Non-limiting examples thereof include morpholine, piperazine and the like.
  • unsubstituted aryl means the monovalent functional group obtained by removing a hydrogen atom from a C6-C60 aromatic hydrocarbon combined with a single ring or two or more rings. Two or more rings may be attached in a simple or fused form with one another. Non-limiting examples thereof include phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthryl and the like.
  • unsubstituted heteroaryl is a monovalent functional group obtained by removing a hydrogen atom from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms, and preferably at least one carbon in the ring, preferably Preferably 1 to 3 carbons are substituted with a heteroatom such as N, O, S or Se.
  • heteroaryl is interpreted that two or more rings may be attached in a simple attached (pendant) or fused (fused) form with each other, and further includes a condensed form with an aryl group.
  • heteroaryl examples include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl; Polycyclics such as phenoxathienyl, indolinzinyl, indolyl, purinyl, quinolyl, benzothiazole, carbazolyl It is understood to include a ring and to include 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl, and the like.
  • unsubstituted alkyloxy means a monovalent functional group represented by RO-, wherein R is alkyl having 1 to 40 carbon atoms, and is linear, branched or cyclic ( It is interpreted as including a cyclic) structure.
  • alkyloxy may include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.
  • unsubstituted aryloxy means a monovalent functional group represented by R'O-, wherein R 'is aryl having 6 to 60 carbon atoms.
  • aryloxy include phenyloxy, naphthyloxy, diphenyloxy and the like.
  • unsubstituted alkylsilyl means silyl substituted with alkyl having 1 to 40 carbon atoms
  • unsubstituted arylsilyl means silyl substituted with aryl having 6 to 60 carbon atoms
  • "Unsubstituted arylamine” means an amine substituted with aryl having 6 to 60 carbon atoms.
  • unsubstituted alkyl boron means boron substituted with alkyl having 1 to 40 carbon atoms
  • unsubstituted aryl boron means boron substituted with aryl having 6 to 60 carbon atoms.
  • unsubstituted arylphosphine means phosphine substituted with aryl having 6 to 60 carbon atoms
  • unsubstituted arylphosphine oxide means phosphine substituted with aryl having 6 to 60 carbon atoms. Means oxide.
  • fused ring means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring or a combination thereof.
  • the compound represented by Formula 1 according to the present invention may be synthesized according to a general synthetic method [ Chem. Rev. , 60 : 313 (1960); J. Chem. SOC . 4482 (1955); Chem. Rev. 95: 2457 (1995) et al. Detailed synthesis procedures for the compounds of the present invention will be described in detail in the synthesis examples described below.
  • the present invention provides an organic electroluminescent device comprising a compound represented by the formula (1) (preferably a compound represented by the formula 4 to 23).
  • the organic electroluminescent device is an anode; Cathode; And one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers comprises a compound represented by Chemical Formula 1 (preferably, a compound represented by Chemical Formulas 4 to 23). It is characterized by including one or more.
  • the one or more organic material layers include a hole injection layer, a hole transport layer, and a light emitting layer, an electron transport layer, an electron injection layer, etc.
  • at least one organic material layer may include a compound represented by Chemical Formula 1.
  • at least one organic layer including the compound of Formula 1 may be a hole transport layer, a hole injection layer or a light emitting layer, more preferably a light emitting layer. If the compound of Formula 1 is included in the emission layer, the compound of Formula 1 may be used as a phosphorescent or fluorescent host material and / or dopant. As such, when the compound includes the organic electroluminescent device, the luminous efficiency, brightness, power efficiency, thermal stability, and lifetime of the device may be improved.
  • the organic EL device structure according to the present invention is not particularly limited, and a non-limiting example may be a structure in which a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are sequentially stacked.
  • at least one of the hole injection layer, the hole transport layer, and the light emitting layer may include at least one compound represented by Chemical Formula 1.
  • An electron injection layer may be positioned on the electron transport layer.
  • the organic EL device according to the present invention may not only have a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked, but an insulating layer or an adhesive layer may be inserted at an interface between an electrode and an organic material layer.
  • the organic electroluminescent device according to the present invention is formed by using other materials and methods known in the art, except that at least one layer of the organic material layer is formed to include the compound represented by the formula (1). Can be produced.
  • 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.
  • a silicon wafer, quartz or glass plate, metal plate, plastic film or sheet may be used as the substrate usable in the present invention.
  • examples of the anode 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), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO 2 : Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; Or carbon black, but is not limited thereto.
  • metals such as vanadium, chromium, copper, zinc and gold or alloys thereof.
  • Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO 2 : Sb
  • Conductive polymers such as polythiophene, poly (3-methylthiophene
  • the negative electrode material may be a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead or an alloy thereof; Multilayer structure materials such as LiF / Al or LiO 2 / Al, and the like, but are not limited thereto.
  • the hole injection layer, the hole transport layer, the electron injection layer and the electron transport layer is not particularly limited, conventional materials known in the art may be used.
  • Preparation Example The same procedure as in ⁇ Step 1> of Preparation Example 1, except that 6-bromo-1H-indole (25 g, 0.128 mol) was used instead of 5-bromo-1H-indole used in ⁇ Step 1>. The procedure was followed to obtain 6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole.
  • Step 1 of Preparation Example 4> instead of 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole used in ⁇ Step 2> of Preparation Example 1
  • Preparation Example 1 except that 7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole (22 g, 90.49 mmol) obtained in The procedure of step 2> was followed to obtain 7- (2-nitrophenyl) -1H-indole.
  • 2,4-dibromo-1-nitrobenzene (21.11 g, 75.41 mmol) was used instead of 1-bromo-2-nitrobenzene used in ⁇ Step 2> of Preparation Example 1, and 5- (4,4,5,5- tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole instead of 6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole (22 g, 90.49 mmol) was used in the same manner as in ⁇ Step 2> of Preparation Example 1 to obtain 6- (5-bromo-2-nitrophenyl) -1H-indole.
  • 6-chloro-1H-indole 25 g, 0.13 mol was used instead of 5-bromo-1H-indole used in ⁇ Step 1> of Preparation Example 18, and 6-chloro-1H-indole and bromobenzene (23.55) instead of Iodobenzene. g, 0.15 mol), except that 6-chloro-2-phenyl-1H-indole was obtained in the same manner as in ⁇ Step 1> of Preparation Example 20 18.
  • 6-chloro-2-phenyl-1H-indole (15 g, 55.12) obtained in ⁇ Step 1> of Preparation Example 19 instead of 5-bromo-2-phenyl-1H-indole used in ⁇ Step 2> of Preparation Example 18 mmol), except that 6- (2-nitrophenyl) -2-phenyl-1H-indole was obtained in the same manner as in ⁇ Step 2> of Preparation Example 18.
  • 6-chloro-1H-indole 25 g, 0.17 mol
  • bromobenzene 31.19 g, 0.20 mol
  • Pd (OAc) 2 (1.86 g, 5 mol)
  • Triphenylphosphine (2.17 g, 5 mol%)
  • K 2 CO 3 68.64 g, 0.50 mol
  • 1,4-dioxane 300 ml
  • 6-chloro-3-phenyl-1H-indole (15 g, 55.12) obtained in ⁇ Step 1> of Preparation Example 20 instead of 5-bromo-2-phenyl-1H-indole used in ⁇ Step 2> of Preparation Example 18 mmol), except that 6- (2-nitrophenyl) -3-phenyl-1H-indole was obtained in the same manner as in ⁇ Step 2> of Preparation Example 20 18.
  • a compound Inv-2 (3) was obtained by the same procedure as in Synthesis Example 1, except that Compound IC-3 (3 g, 10.63 mmol) obtained in Preparation Example 2 was used instead of Compound IC-1 used in Synthesis Example 1. 1.64 g, yield: 54%) was obtained.
  • a compound Inv-3 was prepared in the same manner as in Synthesis Example 1, except that Compound IC-6 (3 g, 10.63 mmol) obtained in Preparation Example 4 was used instead of Compound IC-1 used in Synthesis Example 1. 1.82 g, yield: 60%) was obtained.
  • a compound Inv-4 (Ind-4) was prepared in the same manner as in Synthesis Example 1, except that Compound IC-5 (3 g, 10.63 mmol) obtained in Preparation Example 3 was used instead of Compound IC-1 used in Synthesis Example 1. 1.52 g, yield: 50%) was obtained.
  • a compound Inv-4 (Ind-4) was prepared in the same manner as in Synthesis Example 1, except that Compound IC-2 (3 g, 10.63 mmol) obtained in Preparation Example 1 was used instead of Compound IC-1 used in Synthesis Example 1. 1.34 g, yield: 44%) was obtained.
  • a compound Inv-6 was prepared by the same procedure as in Synthesis Example 1, except that Compound IC-4 (3 g, 10.63 mmol) obtained in Preparation Example 2 was used instead of Compound IC-1 used in Synthesis Example 1. 1.4 g, yield: 46%).
  • a compound Inv-18 was prepared by the same procedure as in Synthesis Example 9, except that Compound IC-3 (3 g, 10.63 mmol) obtained in Preparation Example 2 was used instead of Compound IC-1 used in Synthesis Example 9. 1.76 g, yield: 47%).
  • a compound Inv-20 was prepared by the same procedure as in Synthesis Example 11, except that Compound IC-3 (3 g, 10.63 mmol) obtained in Preparation Example 2 was used instead of Compound IC-1 used in Synthesis Example 11. 1.67 g, yield: 53%) was obtained.
  • a compound Inv-23 (Ind-23) was obtained by the same procedure as in Synthesis Example 14, except that Compound IC-3 (3 g, 10.63 mmol) obtained in Preparation Example 2 was used instead of Compound IC-1 used in Synthesis Example 14. 1.73 g, yield: 57%) was obtained.
  • a compound Inv-40 was prepared in the same manner as in Synthesis Example 1, except that Compound IC-20 (3.80 g, 10.63 mmol) obtained in Preparation Example 18 was used instead of Compound IC-1 used in Synthesis Example 1. 2.62 g, yield: 71%).
  • Compound Inv-41 (Complete Example 1) was carried out in the same manner as in Synthesis Example 1, except that Compound IC-16 (4.61 g, 10.63 mmol) obtained in Preparation Example 16 was used instead of Compound IC-1 used in Synthesis Example 1. 1.77 g, yield: 41%).
  • the compound Inv-1 synthesized in Synthesis Example 1 was subjected to high purity sublimation purification by a commonly known method, and then a green organic EL device was manufactured according to the following procedure.
  • a glass substrate coated with ITO Indium tin oxide having a thickness of 1500 mm 3 was washed with distilled water ultrasonic waves. After washing with distilled water, ultrasonic washing with a solvent such as isopropyl alcohol, acetone, methanol, and drying was carried out. The substrate was transferred to a vacuum evaporator.
  • ITO Indium tin oxide
  • m-MTDATA, TCTA, Ir (ppy) 3 , CBP, and BCP used in device fabrication are as follows.
  • Example 1 Except for using the compounds Inv-2 to Inv-57 synthesized in Synthesis Examples 2 to 57 instead of the compound Inv-1 used as a host material in the formation of the light emitting layer in Example 1, the same as in Example 1 To an organic EL device.
  • An organic EL device was manufactured in the same manner as in Example 1, except that CBP was used instead of the compound Inv-1 used as the light emitting host material in forming the emission layer in Example 1.
  • the structure of CBP used is as follows.
  • Example 1 Sample Host Driving voltage (V) Current efficiency (cd / A) Example 1 Compound Inv-1 6.68 41.1 Example 2 Compound Inv-2 6.68 41.2 Example 3 Compound Inv-3 6.85 40.9 Example 4 Compound Inv-4 6.83 41.3 Example 5 Compound Inv-5 6.85 39.2 Example 6 Compound Inv-6 6.89 41.7 Example 7 Compound Inv-7 6.91 38.9 Example 8 Compound Inv-8 6.67 40.9 Example 9 Compound Inv-9 6.65 42.1 Example 10 Compound Inv-10 6.63 41.1 Example 11 Compound Inv-11 6.65 39.1 Example 12 Compound Inv-12 6.66 40.3 Example 13 Compound Inv-13 6.7 41.2 Example 14 Compound Inv-14 6.73 39.8 Example 15 Compound Inv-15 6.75 39.3 Example 16 Compound Inv-16 6.88 39.4 Example 17 Compound Inv-17 6.88 38.8 Example 18 Compound Inv-18 6.72 41.3 Example 19 Compound Inv-19 6.69 41.3 Example 20 Compound Inv-20 6.69 38.8 Example 21 Compound Inv
  • the green organic EL elements (the organic ELs produced in Examples 1 to 57, respectively) using the compounds (compounds Inv-1 to Inv-57) according to the present invention as the light emitting layer material (host material of the light emitting layer) It can be seen that the device exhibits excellent performance in terms of current efficiency and driving voltage compared to the conventional green organic EL device (organic EL device manufactured in Comparative Example 1) using the host material CBP.
  • a glass substrate coated with ITO Indium tin oxide
  • ITO Indium tin oxide
  • a solvent such as isopropyl alcohol, acetone, methanol, and drying was carried out.
  • the substrate was transferred to a vacuum evaporator.
  • DS-HIL Doosan Co., Ltd.
  • ⁇ -NPB N , which is a hole transport material on the hole injection layer
  • N- di (naphthalene-1-yl) -N , N- diphenylbenzidine) was vacuum deposited to a thickness of 150 kPa to form a hole transport layer.
  • m-CP (1,3-di (9H-carbazol-9-yl) benzene) was used as the host material and 6% of the compound Inv-15 synthesized in Synthesis Example 1 was doped as a dopant.
  • the light emitting layer was formed by vacuum deposition on the hole transport layer to a thickness of.
  • an electron transporting layer was formed by vacuum depositing Alq 3 , which is an electron transporting material, to a thickness of 250 kPa on the light emitting layer, and then an electron injection layer was formed by depositing LiF, which is an electron injection material, on the electron transporting layer, having a thickness of 10 kW.
  • Alq 3 which is an electron transporting material
  • LiF which is an electron injection material
  • aluminum was vacuum deposited to a thickness of 2000 kPa on the electron injection layer to form a cathode, thereby manufacturing an organic EL device.
  • ⁇ -NPB and m-CP used are as follows.
  • Example 58 Compound Inv-24, Inv-29, Inv-30, Inv-31, Inv-32, Inv-58, Inv-59, Inv-60 instead of Compound Inv-15 used as dopants in the formation of the emission layer in Example 58 Except for each use, the organic electroluminescent device was manufactured in the same manner as in Example 58.
  • Example 58 except that DS-H522 (Doosan Corporation) was used instead of m-CP used as a host material in forming the light emitting layer, and C-545T was used instead of compound Inv-15 used as a dopant material.
  • the organic electroluminescent device was manufactured in the same manner as in Example 58.
  • Example 58 Compound Inv-15 6.1 32.5
  • Example 59 Compound Inv-24 6.3 31.7
  • Example 60 Compound Inv-29 6.2 31.9
  • Example 61 Compound Inv-30 6.0 32.2
  • Example 62 Compound Inv-31 5.5 32.9
  • Example 63 Compound Inv-32 5.9 32.3
  • Example 64 Compound Inv-58 5.8 33.1
  • Example 65 Compound Inv-59 5.7 33.5
  • Example 66 Compound Inv-60 5.6 32.0 Comparative Example 2 C-545T 6.8 23.0
  • the compounds according to the present invention (Inv-15, Inv-24, Inv-29, Inv-30, Inv-31, Inv-32, Inv-58, Inv-59, Inv-60)
  • the green fluorescent organic EL device (the organic EL device manufactured in each of Examples 58 to 66) using as a light emitting layer material (the dopant of the light emitting layer) is a green fluorescent organic EL device using the conventional dopant C-545T (organic EL of Comparative Example 2). Element), it can be seen that it shows excellent performance in terms of current efficiency and driving voltage.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The present invention relates to a novel organic compound having excellent hole-injection, hole-transport, and light-emitting capabilities, and to an organic electroluminescent element containing the compound in at least one organic layer so as to improve the characteristics of light emitting efficiency, drive voltage, life span, etc.

Description

유기 화합물 및 이를 포함하는 유기 전계 발광 소자Organic compound and organic electroluminescent device comprising the same
본 발명은 신규의 유기 화합물 및 이를 포함하는 유기 전계 발광 소자에 관한 것으로, 보다 상세하게는 정공 주입능, 정공수송능 및 발광능 등이 우수한 신규의 유기 화합물 및 상기 화합물을 유기물층의 재료로서 포함하여 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 comprising the same, and more particularly to a novel organic compound having excellent hole injection ability, hole transport ability and light emission ability, and the like as a material of the organic material layer The present invention relates to an organic EL device having improved characteristics such as efficiency, driving voltage, and lifetime.
1950년대 Bernanose의 유기 박막 발광 관측을 시점으로 하여, 1965년 안트라센 단결정을 이용한 청색 전기발광으로 이어진 유기 전계 발광 (electroluminescent, EL) 소자(이하, 간단히'유기 EL 소자'로 칭함)에 대한 연구가 이어져 오다가, 1987년 탕(Tang)에 의하여 정공층과 발광층의 기능층으로 나눈 적층구조의 유기 EL 소자가 제시 되었다. 이후, 고효율, 고수명의 유기 EL 소자를 만들기 위하여, 소자 내 특징적인 유기물층을 도입하는 형태로 발전하여 왔으며, 이에 사용되는 특화된 물질의 개발로 이어져 왔다.From the observation of organic thin-film emission from Bernanose in the 1950s, the study of organic electroluminescent (EL) devices (hereinafter referred to simply as 'organic EL devices') followed by blue electroluminescence using anthracene single crystals in 1965 was followed. In 1987, Tang proposed an organic EL device having a laminated structure divided into a functional layer of a hole layer and a light emitting layer. Since then, in order to make a high efficiency, long life organic EL device, it has been developed in the form of introducing a characteristic organic material layer in the device, and has led to the development of specialized materials used therein.
유기 EL 소자의 두 전극 사이에 전압을 걸어 주면 양극에서는 정공이, 음극에서는 전자가 각각 유기물층으로 주입된다. 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 바닥상태로 떨어질 때 빛이 나게 된다. 유기물층으로 사용되는 물질은 그 기능에 따라, 발광층 물질, 정공 주입층 물질, 정공 수송층 물질, 전자 수송층 물질, 전자 주입층 물질 등으로 분류될 수 있다. When voltage is applied between two electrodes of the organic EL element, holes are injected into the organic material layer from the anode and electrons from the cathode, respectively. When the injected holes and electrons meet, excitons are formed, and when the excitons fall to the ground, they shine. The material used as the organic material layer may be classified into a light emitting layer material, a hole injection layer material, a hole transport layer material, an electron transport layer material, an electron injection layer material and the like according to its function.
유기 EL 소자의 발광층을 형성하는 재료('발광층 물질')는 발광색에 따라 청색, 녹색, 적색 발광층 물질로 구분될 수 있다. 그밖에, 보다 나은 천연색을 구현하기 위한 발광층 물질로서 노란색 및 주황색 발광층 물질도 사용된다. 또한, 색순도의 증가와 에너지 전이를 통해 발광 효율을 증가시키기 위하여, 발광층 물질로서 호스트/도펀트 계를 사용할 수 있다. 도판트 물질은 유기 물질을 사용하는 형광 도판트와 Ir, Pt 등의 중원자(heavy atoms)가 포함된 금속 착체 화합물을 사용하는 인광 도판트로 나눌 수 있다. 인광 재료의 개발은 이론적으로 형광에 비해 4배까지의 발광 효율을 향상시킬 수 있어, 인광 도판트 뿐만 아니라 인광 호스트 재료들에 대해 관심이 집중되고 있다. The material ('light emitting layer material') forming the light emitting layer of the organic EL device may be classified into blue, green, and red light emitting material according to the light emitting color. In addition, yellow and orange light emitting layer materials are also used as the light emitting layer material to realize a better natural color. In addition, in order to increase luminous efficiency through increasing color purity and energy transfer, a host / dopant system may be used as the light emitting layer material. The dopant material may 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 phosphorescent materials can theoretically improve luminous efficiency up to four times that of fluorescence, attracting attention not only on phosphorescent dopants but also on phosphorescent host materials.
정공 수송층 물질, 정공 차단층 물질, 전자 수송층 물질로는 하기 화학식으로 표시된 NPB, BCP, Alq3 등이 널리 알려져 있고, 발광층 물질로는 안트라센 유도체들이 형광 도판트/호스트 재료로서 보고되고 있다. 특히, 효율 향상 측면에서 큰 장점을 가지고 있는 인광 재료로는 Firpic, Ir(ppy)3, (acac)Ir(btp)2 등과 같은 Ir을 포함하는 금속 착체 화합물이 있는데, 이들은 청색, 녹색, 적색 도판트 재료로 사용되고 있다. 현재까지는 CBP가 인광 호스트 재료로 우수한 특성을 나타내고 있다.As the hole transport layer material, the hole blocking layer material, and the electron transport layer material, NPB, BCP, Alq 3 and the like represented by the following formulas are widely known, and as the light emitting layer material, anthracene derivatives have been reported as fluorescent dopant / host materials. In particular, phosphorescent materials having great advantages in terms of efficiency improvement include metal complex compounds including Ir such as Firpic, Ir (ppy) 3 , and (acac) Ir (btp) 2 , which are blue, green, and red plated materials. It is used as a raw material. To date, CBP has shown excellent properties as a phosphorescent host material.
Figure PCTKR2013007821-appb-I000001
Figure PCTKR2013007821-appb-I000001
Figure PCTKR2013007821-appb-I000002
Figure PCTKR2013007821-appb-I000002
그러나, 종래의 발광층 물질들은 발광 특성이 양호하였으나, 유리전이온도가 낮고 열적 안정성이 매우 좋지 않기 때문에, 유기 EL 소자에서의 수명 측면에서 만족할 만한 수준이 되지 못하는 실정이다. 따라서, 우수한 성능을 가지는 발광 물질의 개발이 요구되고 있다.However, although the light emitting characteristics of the conventional light emitting layer are good, the glass transition temperature is low and the thermal stability is not very good, so the situation is not satisfactory in terms of lifespan in the organic EL device. Therefore, there is a demand for development of a light emitting material having excellent performance.
본 발명은 전술한 문제점을 해결하기 위해, 발광층 물질로 사용될 수 있고, 유기 전계 발광 소자의 발광층에 사용시 소자의 효율, 수명 및 안정성 등을 향상시킬 수 있는 신규 유기 화합물을 제공하는 것을 목적으로 한다.In order to solve the above problems, an object of the present invention is to provide a novel organic compound that can be used as a light emitting layer material and can improve the efficiency, life and stability of the device when used in the light emitting layer of the organic electroluminescent device.
또, 본 발명은 상기 신규 유기 화합물을 포함하는 유기 전계 발광 소자를 제공하는 것을 목적으로 한다.Moreover, an object of this invention is to provide the organic electroluminescent element containing the said novel organic compound.
상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다:In order to achieve the above object, the present invention provides a compound represented by the following formula (1):
화학식 1
Figure PCTKR2013007821-appb-C000001
 Formula 1
Figure PCTKR2013007821-appb-C000001
상기 화학식 1에서,In Chemical Formula 1,
환 A는 CR3 및 N을 함유하는 6원의 헤테로환, R3로 치환된 6원의 환, 또는 2개의 N을 함유하는 6원의 헤테로환이고;Ring A is a 6-membered heterocycle containing CR 3 and N, a 6-membered ring substituted with R 3 , or a 6-membered heterocycle containing two N;
X1 및 X2는 각각 독립적으로 O, S, Se, N(Ar1), C(Ar2)(Ar3) 및 Si(Ar4)(Ar5)로 이루어진 군에서 선택되고, 이때, X1 및 X2 중에서 적어도 하나는 N(Ar1)이며;X 1 and X 2 are each independently selected from the group consisting of O, S, Se, N (Ar 1 ), C (Ar 2 ) (Ar 3 ) and Si (Ar 4 ) (Ar 5 ), wherein X At least one of 1 and X 2 is N (Ar 1 );
Y1 내지 Y4은 서로 같거나 또는 상이하며, 각각 독립적으로 N 또는 CR4이고, 이때 CR4가 복수인 경우, 이들은 서로 상이하거나 동일하고;Y 1 to Y 4 are the same as or different from each other, and each independently N or CR 4, wherein, when there are a plurality of CR 4 , they are different from each other or the same;
단, 상기 R1 내지 R4, 및 Ar1 내지 Ar5 중에서 하나는 하기 화학식 2로 표시되는 치환기이며,However, one of R 1 to R 4 , and Ar 1 to Ar 5 is a substituent represented by the following Chemical Formula 2,
화학식 2
Figure PCTKR2013007821-appb-C000002
 Formula 2
Figure PCTKR2013007821-appb-C000002
상기 화학식 2에서,In Chemical Formula 2,
a는 1 또는 2이고;a is 1 or 2;
L은 치환 또는 비치환된 C6~C60의 아릴렌기, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴렌기, 치환 또는 비치환된 아릴-트라이일(aryl-triyl), 또는 치환 또는 비치환된 헤테로아릴-트라이일(heteroaryl-triyl)이며,L represents a substituted or unsubstituted C 6 to C 60 arylene group, a substituted or unsubstituted heteroarylene group having 5 to 60 nuclear atoms, a substituted or unsubstituted aryl-triyl, or a substituted or Unsubstituted heteroaryl-triyl,
단, a가 1인 경우, L은 치환 또는 비치환된 C6~C60의 아릴렌기, 또는 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴렌기이며,Provided that when a is 1, L is a substituted or unsubstituted C 6 to C 60 arylene group, or a substituted or unsubstituted heteroarylene group having 5 to 60 nuclear atoms,
a가 2인 경우, L은 치환 또는 비치환된 아릴-트라이일(aryl-triyl), 또는 치환 또는 비치환된 헤테로아릴-트라이일(heteroaryl-triyl)이고;when a is 2, L is substituted or unsubstituted aryl-triyl, or substituted or unsubstituted heteroaryl-triyl;
B는 치환 또는 비치환된 카바졸기, 또는 하기 화학식 3으로 표시되는 치환기이며, 이때 B가 복수인 경우, 이들은 서로 상이하거나 동일하고;B is a substituted or unsubstituted carbazole group, or a substituent represented by the following formula (3), wherein when B is plural, they are different from each other or the same;
화학식 3
Figure PCTKR2013007821-appb-C000003
 Formula 3
Figure PCTKR2013007821-appb-C000003
상기 화학식 3에서, In Chemical Formula 3,
환 C는 CR7 및 N을 함유하는 6원의 헤테로환, R7로 치환된 6원의 환, 또는 2개의 N을 함유하는 6원의 헤테로환이고;Ring C is a 6-membered heterocycle containing CR 7 and N, a 6-membered ring substituted with R 7 , or a 6-membered heterocycle containing two N;
X3 및 X4는 각각 독립적으로 O, S, Se, N(Ar6), C(Ar7)(Ar8) 및 Si(Ar9)(Ar10)로 이루어진 군에서 선택되고, X 3 and X 4 are each independently selected from the group consisting of O, S, Se, N (Ar 6 ), C (Ar 7 ) (Ar 8 ) and Si (Ar 9 ) (Ar 10 ),
Y5 내지 Y8은 서로 같거나 또는 상이하며, 각각 독립적으로 N 또는 CR8이고, 이때 CR8이복수인 경우, 이들은 서로 상이하거나 동일하고;Y 5 to Y 8 are the same as or different from each other, and each independently N or CR 8, wherein, when a plurality of CR 8 plurals, they are different from or the same;
상기 R5 내지 R8 및 Ar6 내지 Ar10 중에서 하나는 단일 결합으로, 상기 화학식 2의 L에 연결되고;One of R 5 to R 8 and Ar 6 to Ar 10 is a single bond, connected to L of Formula 2;
R1 내지 R8은 서로 동일하거나 상이하며, 각각 독립적으로 수소, 중수소, 할로겐, 시아노, 니트로, 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C2~C40의 알케닐기, 치환 또는 비치환된 C2~C40의 알키닐기, 치환 또는 비치환된 C3~C40의 시클로알킬기, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로시클로알킬기, 치환 또는 비치환된 C6~C60의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기, 치환 또는 비치환된 C1~C40의 알킬옥시기, 치환 또는 비치환된 C6~C60의 아릴옥시기, 치환 또는 비치환된 C3~C40의 알킬실릴기, 치환 또는 비치환된 C6~C60의 아릴실릴기, 치환 또는 비치환된 C1~C40의 알킬보론기, 치환 또는 비치환된 C6~C60의 아릴보론기, 치환 또는 비치환된 C6~C60의 아릴포스핀기, 치환 또는 비치환된 C6~C60의 아릴포스핀옥사이드기, 및 치환 또는 비치환된 C6~C60의 아릴아민기로 구성된 군으로부터 선택되거나, 또는 인접한 기와 축합 고리를 형성하거나 또는 비형성하며;R 1 to R 8 are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano, nitro, a substituted or unsubstituted C 1 -C 40 alkyl group, a substituted or unsubstituted C 2 -C 40 Alkenyl group, substituted or unsubstituted C 2 to C 40 alkynyl group, substituted or unsubstituted C 3 to C 40 cycloalkyl group, substituted or unsubstituted heterocycloalkyl group having 3 to 40 nuclear atoms, substituted or unsubstituted Substituted C 6 ~ C 60 aryl group, substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, substituted or unsubstituted C 1 ~ C 40 alkyloxy group, substituted or unsubstituted C 6 ~ C 60 aryloxy group, substituted or unsubstituted C 3 to C 40 alkylsilyl group, substituted or unsubstituted C 6 to C 60 arylsilyl group, substituted or unsubstituted C 1 to C 40 alkylboron Groups, substituted or unsubstituted C 6 -C 60 arylborone groups, substituted or unsubstituted C 6 -C 60 arylphosphine groups, substituted or unsubstituted An arylphosphineoxide group of C 6 -C 60 and a substituted or unsubstituted C 6 -C 60 arylamine group, or form a condensed ring with an adjacent group or not form it;
Ar1 내지 Ar10은 서로 동일하거나 또는 상이하며, 각각 독립적으로 수소, 중수소, 할로겐, 시아노, 니트로, 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C3~C40의 시클로알킬기, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로시클로알킬기, 치환 또는 비치환된 C6~C60의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기, 치환 또는 비치환된 C1~C40의 알킬옥시기, 치환 또는 비치환된 C6~C60의 아릴옥시기, 치환 또는 비치환된 C3~C40의 알킬실릴기, 치환 또는 비치환된 C6~C60의 아릴실릴기, 치환 또는 비치환된 C1~C40의 알킬보론기, 치환 또는 비치환된 C6~C60의 아릴보론기, 치환 또는 비치환된 C6~C60의 아릴포스핀기, 치환 또는 비치환된 C6~C60의 아릴포스핀옥사이드기, 및 치환 또는 비치환된 C6~C60의 아릴아민기로 구성된 군으로부터 선택되며;Ar 1 to Ar 10 are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C 1 to C 40 alkyl group, substituted or unsubstituted C 3 to C 40 A cycloalkyl group, a substituted or unsubstituted heterocycloalkyl group having 3 to 40 nuclear atoms, a substituted or unsubstituted C 6 -C 60 aryl group, a substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, Substituted or unsubstituted C 1 to C 40 alkyloxy group, substituted or unsubstituted C 6 to C 60 aryloxy group, substituted or unsubstituted C 3 to C 40 alkylsilyl group, substituted or unsubstituted C 6 ~ C 60 arylsilyl group, substituted or unsubstituted C 1 ~ C 40 Alkyl boron group, substituted or unsubstituted C 6 ~ C 60 Aryl boron group, substituted or unsubstituted C 6 ~ C 60 an aryl phosphine group, a substituted or unsubstituted C 6 ~ C aryl phosphine oxide groups of 60, and a substituted or unsubstituted C 6 ~ C 60 aryl the It is selected from the group consisting of Min - gi;
상기 L의 아릴렌기, 헤테로아릴렌기, 아릴-트라이일, 헤테로아릴-트라이일; B의 카바졸기와; 상기 R1 내지 R8, 및 Ar1 내지 Ar10 의 알킬기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 아릴포스핀옥사이드기 및 아릴아민기에 각각 도입되는 하나 이상의 치환기는 각각 독립적으로 중수소, 할로겐, 시아노, 니트로, C1~C40의 알킬기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기로 이루어진 군에서 선택되고, 다만 상기 치환기가 복수인 경우, 이들은 서로 동일하거나 상이할 수 있다. The above arylene group, heteroarylene group, aryl-triyl, heteroaryl-triyl; Carbazole groups of B; An alkyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group, an alkyl boron group of R 1 to R 8 and Ar 1 to Ar 10 , One or more substituents respectively introduced to the arylborone group, the arylphosphine group, the arylphosphine oxide group and the arylamine group are each independently deuterium, halogen, cyano, nitro, C 1 -C 40 alkyl group, C 3 -C 40 Cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C 6 to C 60 , heteroaryl group of 5 to 60 nuclear atoms, alkyloxy group of C 1 to C 40 , C 6 to C 60 Aryloxy group, C 3 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 6 ~ C 60 If an aryl phosphine group, is selected from the group consisting of an aryl phosphine oxide of a C 6 ~ C 60, a plurality of just the above substituent, all of which are identical to each other Or it may be different.
또한, 본 발명은 양극, 음극, 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하는 유기 EL 소자로서, 상기 1층 이상의 유기물층 중 적어도 하나는 상기 화학식 1로 표시되는 화합물을 포함하는 것이 특징인 유기 EL 소자를 제공한다. In addition, the present invention is an organic EL device comprising an anode, a cathode, and at least one organic layer interposed between the anode and the cathode, at least one of the at least one organic layer is a compound represented by the formula (1) It provides an organic EL device which is characterized by including.
여기서, 상기 화학식 1로 표시되는 화합물을 포함하는 유기물층은 정공 주입층, 정공 수송층 및 발광층으로 이루어진 군에서 선택되며, 바람직하게는 발광층이다. 상기 화학식 1로 표시되는 화합물이 발광층에 포함될 경우, 호스트 물질 및/또는 도펀트로 사용될 수 있다.Herein, the organic material layer including the compound represented by Chemical Formula 1 is selected from the group consisting of a hole injection layer, a hole transport layer, and a light emitting layer, and is preferably a light emitting layer. When the compound represented by Chemical Formula 1 is included in the emission layer, it may be used as a host material and / or a dopant.
본 발명에 따른 화학식 1로 표시되는 화합물은 내열성, 정공 주입능, 정공 수송능, 발광능 등이 우수하기 때문에, 유기 전계 발광 소자의 유기물층, 바람직하게는 발광층에 적용될 수 있다.Since the compound represented by Formula 1 according to the present invention is excellent in heat resistance, hole injection ability, hole transporting ability, light emitting ability, etc., the compound may be applied to an organic material layer, preferably a light emitting layer of an organic EL device.
따라서, 유기 전계 발광 소자가 상기 화학식 1로 표시되는 화합물을 정공 주입층 물질, 정공 수송층 물질, 또는 발광층 물질(인광/형광 호스트, 도판트) 등으로 포함할 경우, 소자의 발광성능, 구동전압, 수명, 효율(발광효율, 전력효율) 등의 측면이 크게 향상될 수 있기 때문에, 풀 칼라 디스플레이 패널 등에 효과적으로 적용될 수 있다. Therefore, when the organic electroluminescent device includes the compound represented by Chemical Formula 1 as a hole injection layer material, a hole transport layer material, or a light emitting layer material (phosphorescent / fluorescent host, dopant) or the like, the light emitting performance, driving voltage, Since aspects such as lifespan, efficiency (light emitting efficiency, power efficiency) and the like can be greatly improved, they can be effectively applied to a full color display panel or the like.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에 따른 신규 유기 화합물은 인돌계 모이어티(indole-base moiety)와 인돌계 모이어티가 축합(fused)되어 이루어진 인돌로인돌계(indoloindole-based) 기본 골격에, 연결기(L)을 통해 카바졸기 또는 인돌계 모이어티와 인돌계 모이어티가 축합된 인돌로인돌계 모이어티가 결합된 구조로서, 상기 화학식 1로 표시되는 것을 특징으로 한다. 이러한 화학식 1로 표시되는 화합물은 종래 유기 EL 소자용 재료 [예: 4,4-dicarbazolybiphenyl (이하, 'CBP'라 함)] 보다 높은 분자량을 가져 유리전이온도가 높으며, 또한 열적 안정성이 우수하고, 정공 주입능, 정공 수송능, 발광능 등이 우수하다. 따라서, 상기 화학식 1의 화합물을 유기 전계 발광 소자가 포함할 경우, 소자의 구동전압, 효율, 수명 등이 향상될 수 있다.The novel organic compound according to the present invention is applied to an indoloindole-based basic skeleton formed by condensation of an indole-based moiety and an indole-based moiety, and a cover through a linking group (L). A structure in which an indoloindole moiety in which a doze group or an indole moiety is condensed with an indole moiety is combined, is represented by Chemical Formula 1. Compound represented by the formula (1) has a higher molecular weight than the conventional organic EL device material [for example, 4,4-dicarbazolybiphenyl (hereinafter referred to as 'CBP')] has a high glass transition temperature, and also excellent thermal stability, It has excellent hole injecting ability, hole transporting ability and light emitting ability. Therefore, when the organic electroluminescent device includes the compound of Formula 1, the driving voltage, efficiency, lifespan, etc. of the device may be improved.
상기 화학식 1로 표시되는 화합물은 인돌계 모이어티(indole-base moiety)와 인돌계 모이어티가 축합되어 이루어진 인돌로인돌계 기본 골격에, 연결기(L)을 통해 인돌로인돌계 모이어티 또는 카바졸기가 결합됨으로써, 넓은 밴드갭 (sky blue ~ red)을 갖는다. 특히, 인돌계 모이어티와 인돌계 모이오티가 축합된 기본 골격 중 인돌계 모이어티의 N 위치에 연결기(예컨대, 아릴렌, 헤테로아릴렌 등)를 통해 인돌로인돌계 모이어티 또는 카바졸기가 결합될 경우, 화합물의 밴드갭이 넓어지고, 삼중항 energy 레벨이 넓어져서, 소자의 인광 특성이 개선됨과 동시에 전자 및/또는 정공 수송 능력, 발광효율, 구동전압, 수명 특성 등이 개선될 수 있다. 또한, 인돌로인돌계 기본 골격에 도입되는 치환체의 종류에 따라 전자 수송 능력 등도 향상시킬 수 있다. 따라서, 상기 화학식 1의 화합물은 유기 전계 발광 소자의 유기물층 재료, 바람직하게는 정공 수송층 재료, 정공 주입층 재료, 발광층 재료, 바람직하게는 발광층 재료로 사용될 수 있다. 또한, 상기 화학식 1의 화합물은 선택적으로 적절한 치환체를 도입함으로써, 전자 수송층의 재료 등으로도 사용될 수 있다. 특히, 상기 화학식 1의 화합물은 인돌로인돌계 기본 골격으로 인해 종래 CBP에 비해 발광층 재료, 특히 호스트 재료로서의 우수한 특성을 발휘할 수 있다.The compound represented by Formula 1 is an indoloindole-based moiety or carbazole group through the linking group (L) to an indoloindole-based basic skeleton formed by condensation of an indole-based moiety and an indole-based moiety By being combined, it has a wide bandgap (sky blue to red). In particular, an indoloindole moiety or a carbazole group is bonded to an N position of an indole moiety in a basic skeleton condensed between an indole moiety and an indole moiety through a linking group (eg, arylene, heteroarylene, etc.). In this case, the bandgap of the compound is widened and the triplet energy level is widened, thereby improving the phosphorescence property of the device and at the same time improving the electron and / or hole transport ability, the luminous efficiency, the driving voltage, and the life characteristics. Moreover, the electron transport ability etc. can also be improved according to the kind of substituent introduce | transduced into an indoloindole base skeleton. Therefore, the compound of Formula 1 may be used as an organic material layer material, preferably a hole transport layer material, a hole injection layer material, a light emitting layer material, preferably a light emitting layer material of the organic electroluminescent device. In addition, the compound of Formula 1 may optionally be used as a material of the electron transport layer by introducing an appropriate substituent. In particular, the compound of Formula 1 may exhibit excellent properties as a light emitting layer material, especially a host material, compared to the conventional CBP due to the indoloindole-based skeleton.
또한, 상기 화학식 1로 표시되는 화합물은 인돌로인돌계 기본 골격에 다양한 아릴기 및/또는 헤테로아릴기가 도입되어 화합물의 분자량이 유의적으로 증대됨으로써, 유리전이온도가 향상되고, 이로 인해 종래 CBP 보다 높은 열적 안정성을 가질 수 있다. 따라서, 본 발명의 화학식 1로 표시되는 화합물을 포함하는 소자는 내구성 및 수명 특성을 크게 향상시킬 수 있다.In addition, the compound represented by Formula 1 has a variety of aryl groups and / or heteroaryl groups introduced into the indoloindole-based basic skeleton significantly increases the molecular weight of the compound, thereby improving the glass transition temperature, thereby resulting in higher than conventional CBP It can have a high thermal stability. Therefore, the device including the compound represented by the formula (1) of the present invention can greatly improve the durability and life characteristics.
게다가, 상기 화학식 1로 표시되는 화합물은 삼중항 에너지레벨과 일중항 에너지 레벨의 차이가 적어, 삼중항에서 일중항으로의 역에너지 이동이 일어날 수 있다. 이로 인해 열활성화 지연 형광(thermally activated delayed fluorescence)이 일어나 소자의 외부 양자 효율이 향상되기 때문에, 상기 화합물을 발광층 재료로 사용할 경우, 소자의 발광 효율이 상승될 수 있다.In addition, the compound represented by Formula 1 has a small difference between the triplet energy level and the singlet energy level, so that the reverse energy transfer from the triplet to the singlet may occur. As a result, thermally activated delayed fluorescence occurs, thereby improving external quantum efficiency of the device, and when the compound is used as a light emitting layer material, the light emission efficiency of the device may be increased.
이와 같은 본 발명의 화합물을 유기 EL 소자의 정공 주입/수송층, 청색, 녹색 및/또는 적색의 인광 호스트 재료 또는 형광 도펀트 재료로 채택할 경우, 종래 CBP 대비 효율 및 수명 면에서 월등히 우수한 효과를 발휘할 수 있다. 따라서, 본 발명에 따른 화합물은 유기 EL 소자의 성능 개선 및 수명 향상에 크게 기여할 수 있다.When the compound of the present invention is adopted as a hole injection / transport layer of an organic EL device, a blue, green and / or red phosphorescent host material or a fluorescent dopant material, the compound can exhibit excellent efficiency and lifespan in comparison with the conventional CBP. have. Therefore, the compound according to the present invention can greatly contribute to the improvement of the performance and the life of the organic EL device.
본 발명에 따른 화학식 1로 표시되는 화합물에서, 환 A는 CR3 및 N을 함유하는 6원(menbered)의 헤테로환(heterocycle), R3로 치환된 6원의 환(cycle), 또는 2개의 N을 함유하는 6원의 헤테로환이고, 바람직하게는 R3로 치환된 6원의 환이다.In the compound represented by the formula (1) according to the present invention, ring A is a 6-membered heterocycle containing CR 3 and N, a 6-membered cycle substituted with R 3 , or two It is a 6-membered heterocycle containing N, Preferably it is a 6-membered ring substituted with R <3> .
상기 X1 및 X2는 각각 독립적으로 O, S, Se, N(Ar1), C(Ar2)(Ar3) 및 Si(Ar4)(Ar5)로 이루어진 군에서 선택되고, 이때 X1 및 X2 중에서 적어도 하나는 N(Ar1)이다. 바람직하게는 X1 및 X2가 모두 N(Ar1)이거나, 또는 X1 및 X2이 각각 독립적으로 N(Ar1) 또는 S이다.X 1 and X 2 are each independently selected from O, S, Se, N (Ar 1 ), C (Ar 2 ) (Ar 3 ) and Si (Ar 4 ) (Ar 5 ), wherein X At least one of 1 and X 2 is N (Ar 1 ). Preferably both X 1 and X 2 are N (Ar 1 ), or X 1 and X 2 are each independently N (Ar 1 ) or S.
또, 상기 Y1 내지 Y4는 서로 동일하거나 또는 상이하며, 각각 독립적으로 N 또는 CR4이고, 바람직하게는 Y1 내지 Y4가 모두 CR4이다. 이때, CR4가 복수인 경우, 이들은 서로 상이하거나 동일하다.In addition, Y 1 to Y 4 are the same as or different from each other, and each independently N or CR 4 , and preferably Y 1 to Y 4 are all CR 4 . At this time, when there are a plurality of CR 4 , they are different from each other or the same.
다만, 상기 R1 내지 R4, 및 Ar1 내지 Ar5 중에서 하나는 상기 화학식 2로 표시되는 치환기이다.However, one of R 1 to R 4 , and Ar 1 to Ar 5 is a substituent represented by Chemical Formula 2.
상기 화학식 2에서, a는 1 또는 2이다.In Formula 2, a is 1 or 2.
또, 상기 L은 치환 또는 비치환된 C6~C60의 아릴렌기, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴렌기, 치환 또는 비치환된 아릴-트라이일기(aryl-triyl group), 또는 치환 또는 비치환된 헤테로아릴-트라이일기(heteroaryl-triyl group)이며, 단 a가 1인 경우, L은 치환 또는 비치환된 C6~C60의 아릴렌기, 또는 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴렌기이고, a가 2인 경우, L은 치환 또는 비치환된 아릴-트라이일(aryl-triyl), 또는 치환 또는 비치환된 헤테로아릴-트라이일(heteroaryl-triyl)이다. 여기서, 아릴-트라이일기(aryl-triyl group)는 3가의 아릴기(trivalent aryl group)이며, 헤테로아릴-트라이일기(heteroaryl-triyl group)는 3가의 헤테로아릴기이다.In addition, L is a substituted or unsubstituted C 6 ~ C 60 arylene group, a substituted or unsubstituted heteroarylene group having 5 to 60 nuclear atoms, a substituted or unsubstituted aryl-triyl group (aryl-triyl group) Or a substituted or unsubstituted heteroaryl-triyl group, provided that when a is 1, L is a substituted or unsubstituted C 6 -C 60 arylene group, or a substituted or unsubstituted nucleus. When a heteroarylene group having 5 to 60 atoms and a is 2, L is substituted or unsubstituted aryl-triyl, or substituted or unsubstituted heteroaryl-triyl to be. Here, the aryl-triyl group is a trivalent aryl group, and the heteroaryl-triyl group is a trivalent heteroaryl group.
상기 L의 아릴렌기, 헤테로아릴렌기, 아릴-트라이일기, 아릴-트라이일기, 헤테로아릴-트라이일기에 각각 도입되는 하나 이상의 치환기는 각각 독립적으로 중수소, 할로겐, 시아노, 니트로, C1~C40의 알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C3~C40의 알킬실릴기, C2~C40의 알킬보론기로 이루어진 군에서 선택되고, 다만 상기 치환기가 복수인 경우, 이들은 서로 동일하거나 상이할 수 있다.One or more substituents respectively introduced into the arylene group, heteroarylene group, aryl-triyl group, aryl-triyl group, and heteroaryl-triyl group of L are each independently deuterium, halogen, cyano, nitro, C 1 -C 40 Alkyl group of C 6 ~ C 60 aryl group, heteroaryl group of 5 to 60 nuclear atoms, C 1 ~ C 40 alkyloxy group, C 3 ~ C 40 alkylsilyl group, C 2 ~ C 40 alkyl When selected from the group consisting of boron groups, provided that the substituents are plural, they may be the same or different from each other.
바람직하게는 L은 2가(bivalent) 또는 3가(trivalent)의 페닐, 바이페닐, 나프틸, 인덴, 플루오레닐, 카바졸릴, 피리딘, 피리미딘, 피리다진, 피라진, 트리아진, 트라이졸, 옥사다이아졸, 싸이아다이아졸, 인돌, 벤즈이미다졸, 퀴놀린, 이소퀴놀린, 및 퀴녹살린으로 이루어진 군에서 선택되며, 이들은 각각 독립적으로 중수소, 할로겐, 시아노, 니트로, C1~C40의 알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C3~C40의 알킬실릴기, C2~C40의 알킬보론기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있다.Preferably L is bivalent or trivalent phenyl, biphenyl, naphthyl, indene, fluorenyl, carbazolyl, pyridine, pyrimidine, pyridazine, pyrazine, triazine, triazole, Selected from the group consisting of oxadiazole, thiadiazole, indole, benzimidazole, quinoline, isoquinoline, and quinoxaline, each independently of deuterium, halogen, cyano, nitro, alkyl group of C 1 to C 40 , C 6 ~ C 60 aryl group, nuclear atom 5 ~ 60 heteroaryl group, C 1 ~ C 40 alkyloxy group, C 3 ~ C 40 alkylsilyl group, C 2 ~ C 40 alkyl boron group It may be substituted with one or more substituents selected from the group consisting of.
보다 바람직하게는 상기 L이 하기 치환기 C1 내지 C76으로 이루어진 군에서 선택될 수 있으나, 이에 한정되지 않는다.More preferably, L may be selected from the group consisting of the following substituents C1 to C76, but is not limited thereto.
Figure PCTKR2013007821-appb-I000003
Figure PCTKR2013007821-appb-I000003
Figure PCTKR2013007821-appb-I000004
Figure PCTKR2013007821-appb-I000004
Figure PCTKR2013007821-appb-I000005
Figure PCTKR2013007821-appb-I000005
상기 화학식 2에서, B는 치환 또는 비치환된 카바졸기, 또는 상기 화학식 3으로 표시되는 치환기이다. 이때, B가 복수인 경우, 이들은 서로 상이하거나 동일하다.In Formula 2, B is a substituted or unsubstituted carbazole group, or a substituent represented by Formula 3. At this time, when B is plural, they are different from each other or the same.
상기 화학식 3에서, 환 C는 CR7 및 N을 함유하는 6원(menbered)의 헤테로환(heterocycle), R7로 치환된 6원의 환(cycle), 또는 2개의 N을 함유하는 6원의 헤테로환이고, 바람직하게는 R7로 치환된 6원의 환이다.In Formula 3, ring C is a 6-membered heterocycle containing CR 7 and N, a 6-membered cycle substituted with R 7 , or a 6-membered ring containing two N's It is a heterocyclic ring, It is a 6 membered ring preferably substituted with R <7> .
또, 상기 X3 및 X4는 각각 독립적으로 O, S, Se, N(Ar6), C(Ar7)(Ar8) 및 Si(Ar9)(Ar10)으로 이루어진 군에서 선택되고, 이때 X3 및 X4 중에서 적어도 하나는 N(Ar6)이다. 바람직하게는 X3 및 X4가 모두 N(Ar6)이거나, 또는 X3 및 X4가 각각 독립적으로 N(Ar6) 또는 S이다.In addition, X 3 and X 4 are each independently selected from the group consisting of O, S, Se, N (Ar 6 ), C (Ar 7 ) (Ar 8 ) and Si (Ar 9 ) (Ar 10 ), At least one of X 3 and X 4 is N (Ar 6 ). Preferably both X 3 and X 4 are N (Ar 6 ), or X 3 and X 4 are each independently N (Ar 6 ) or S.
또, 상기 Y5 내지 Y8은 서로 동일하거나 또는 상이하며, 각각 독립적으로 N 또는 CR8이고, 바람직하게는 Y5 내지 Y8이 모두 CR8이다. 이때, CR8가 복수인 경우, 이들은 서로 상이하거나 동일하다.In addition, Y 5 to Y 8 are the same as or different from each other, and each independently N or CR 8 , and preferably Y 5 to Y 8 are all CR 8 . At this time, when there are a plurality of CR 8 , they are different from each other or the same.
단, 상기 R5 내지 R8, 및 Ar5 내지 Ar8 중에서 하나는 단일 결합으로, 상기 화학식 2의 L에 연결된다.However, one of R 5 to R 8 , and Ar 5 to Ar 8 is a single bond, and is connected to L of Chemical Formula 2.
또, 상기 R1 내지 R8은 각각 독립적으로 수소, 중수소, 할로겐, 시아노, 니트로, 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C3~C40의 시클로알킬기, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로시클로알킬기, 치환 또는 비치환된 C6~C60의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기, 치환 또는 비치환된 C1~C40의 알킬옥시기, 치환 또는 비치환된 C6~C60의 아릴옥시기, 치환 또는 비치환된 C3~C40의 알킬실릴기, 치환 또는 비치환된 C6~C60의 아릴실릴기, 치환 또는 비치환된 C1~C40의 알킬보론기, 치환 또는 비치환된 C6~C60의 아릴보론기, 치환 또는 비치환된 C6~C60의 아릴포스핀기, 치환 또는 비치환된 C6~C60의 아릴포스핀옥사이드기 및 치환 또는 비치환된 C6~C60의 아릴아민기로 구성된 군으로부터 선택될 수 있다. 다만, 넓은 band-gap과 열안정성을 고려했을 때, R1 내지 R8은 각각 독립적으로 수소, C6~C60의 아릴기(예: 페닐, 나프틸, 비스페닐), 핵원자수 5 내지 60의 헤테로아릴기(예: 피리딘)인 것이 바람직하다.In addition, each of R 1 to R 8 is independently hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C 1 to C 40 alkyl group, substituted or unsubstituted C 3 to C 40 cycloalkyl group, Substituted or unsubstituted heterocycloalkyl group having 3 to 40 nuclear atoms, substituted or unsubstituted C 6 to C 60 aryl group, substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, substituted or unsubstituted A substituted C 1 to C 40 alkyloxy group, a substituted or unsubstituted C 6 to C 60 aryloxy group, a substituted or unsubstituted C 3 to C 40 alkylsilyl group, a substituted or unsubstituted C 6 to C Arylsilyl group of 60 , substituted or unsubstituted C 1 ~ C 40 alkyl boron group, substituted or unsubstituted C 6 ~ C 60 aryl boron group, substituted or unsubstituted C 6 ~ C 60 arylphosphine group , Substituted or unsubstituted C 6 ~ C 60 arylphosphine oxide group and substituted or unsubstituted C 6 ~ C 60 arylamine group Can be selected. However, considering the wide band-gap and thermal stability, R 1 to R 8 are each independently hydrogen, C 6 ~ C 60 aryl group (e.g., phenyl, naphthyl, bisphenyl), 5 to nuclear atoms Preference is given to a 60 heteroaryl group (eg pyridine).
이때, 상기 R1 내지 R8의 알킬기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 아릴포스핀옥사이드기, 아릴아민기에 각각 도입되는 하나 이상의 치환기는 각각 독립적으로 중수소, 할로겐, 시아노, 니트로, C1~C40의 알킬기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, 및 C6~C60의 아릴포스핀옥사이드기로 이루어진 군에서 선택되고, 다만 상기 치환기기 복수인 경우, 이들은 서로 동일하거나 상이할 수 있다. At this time, the alkyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkyl boron group, aryl boron group, aryl of the R 1 to R 8 One or more substituents respectively introduced to the phosphine group, the arylphosphine oxide group, and the arylamine group are each independently deuterium, halogen, cyano, nitro, C 1 -C 40 alkyl group, C 3 -C 40 cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C 6 ~ C 60 aryl group, nuclear atoms aryl of from 5 to 60 heteroaryl group, C 1 ~ alkyloxy group of C 40 of, C 6 ~ C 60 aryloxy group, C 3 ~ C 40 alkyl silyl group, C 6 ~ C aryl silyl group of 60, C 1 ~ C 40 group of an alkyl boron, C 6 ~ aryl of C 60 boron group, C 6 ~ C 60 aryl phosphine group, and C 6 ~ C 60 It is selected from the group consisting of an aryl phosphine oxide group, but in the case of a plurality of the substituents, they may be the same or different from each other Can be.
또, Ar1 내지 Ar10은 서로 동일하거나 상이하며, 각각 독립적으로 수소, 중수소, 할로겐, 시아노, 니트로, 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C3~C40의 시클로알킬기, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로시클로알킬기, 치환 또는 비치환된 C6~C60의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기, 치환 또는 비치환된 C1~C40의 알킬옥시기, 치환 또는 비치환된 C6~C60의 아릴옥시기, 치환 또는 비치환된 C3~C40의 알킬실릴기, 치환 또는 비치환된 C6~C60의 아릴실릴기, 치환 또는 비치환된 C1~C40의 알킬보론기, 치환 또는 비치환된 C6~C60의 아릴보론기, 치환 또는 비치환된 C6~C60의 아릴포스핀기, 치환 또는 비치환된 C6~C60의 아릴포스핀옥사이드기, 및 치환 또는 비치환된 C6~C60의 아릴아민기로 구성된 군으로부터 선택될 수 있다.Ar 1 to Ar 10 are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C 1 to C 40 alkyl group, substituted or unsubstituted C 3 to C 40 cycloalkyl groups, substituted or unsubstituted heterocycloalkyl groups having 3 to 40 nuclear atoms, substituted or unsubstituted C 6 -C 60 aryl groups, substituted or unsubstituted nuclear atoms having 5 to 60 heteroaryl groups , Substituted or unsubstituted C 1 ~ C 40 alkyloxy group, substituted or unsubstituted C 6 ~ C 60 aryloxy group, substituted or unsubstituted C 3 ~ C 40 alkylsilyl group, substituted or unsubstituted C 6 ~ C 60 arylsilyl group, substituted or unsubstituted C 1 ~ C 40 Alkyl boron group, substituted or unsubstituted C 6 ~ C 60 Aryl boron group, substituted or unsubstituted C 6 ~ C 60 of the aryl phosphine group, a substituted or unsubstituted C 6 ~ C 60 aryl phosphine oxide group, and a substituted or unsubstituted C 6 ~ C 60 aryl ah Groups may be selected from the group consisting of.
바람직하게는 Ar1 내지 Ar10은 각각 독립적으로 치환 또는 비치환된 C6~C60의 아릴기, 또는 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기일 수 있다.Preferably Ar 1 to Ar 10 may be each independently a substituted or unsubstituted C 6 ~ C 60 aryl group, or a substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms.
상기 Ar1 내지 Ar10의 알킬기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 아릴포스핀옥사이드기, 아릴아민기에 각각 도입되는 하나 이상의 치환기는 각각 독립적으로 중수소, 할로겐, 시아노, 니트로, C1~C40의 알킬기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, 및 C6~C60의 아릴포스핀옥사이드기로 이루어진 군에서 선택되고, 다만 상기 치환기기 복수인 경우, 이들은 서로 동일하거나 상이할 수 있다. The alkyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkyl boron group, aryl boron group, aryl phosphine group of Ar 1 to Ar 10 , aryl phosphine oxide groups, one or more substituents each of which introduces the aryl amine is each independently selected from deuterium, halogen, cyano, nitro, C cycloalkyl group of 1 ~ C 40 alkyl group, C 3 ~ C 40 of nuclear atoms 3 A heterocycloalkyl group of 40 to 40, an aryl group of C 6 to C 60 , a heteroaryl group of 5 to 60 nuclear atoms, an alkyloxy group of C 1 to C 40 , an aryloxy group of C 6 to C 60 , C 3 to C 40 alkyl silyl group, C 6 ~ C 60 aryl silyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 6 ~ C 60 aryl phosphine group, and C 6 It is selected from the group consisting of aryl phosphine oxide group of ~ C 60 , but in the case of a plurality of the substituents, they may be the same or different from each other have.
본 발명에 따른 화합물에서, 상기 R1 내지 R8, 및 Ar1 내지 Ar10은 각각 독립적으로 수소, 하기 치환기 S1 내지 S177으로 이루어진 군에서 선택될 수 있는데, 이에 한정되는 것은 아니다. 다만, R1 내지 R4, 및 Ar1 내지 Ar5 중에서 하나는 상기 화학식 2로 표시되는 치환기이고, 또 R5 내지 R8, 및 Ar6 내지 Ar10 중에서 하나는 단일 결합으로, 상기 화학식 2의 L에 연결된다.In the compound according to the present invention, R 1 to R 8 , and Ar 1 to Ar 10 may be each independently selected from the group consisting of hydrogen, the following substituents S1 to S177, but is not limited thereto. However, one of R 1 to R 4 , and Ar 1 to Ar 5 is a substituent represented by Formula 2, and one of R 5 to R 8 , and Ar 6 to Ar 10 is a single bond, Is connected to L.
Figure PCTKR2013007821-appb-I000006
Figure PCTKR2013007821-appb-I000006
Figure PCTKR2013007821-appb-I000007
Figure PCTKR2013007821-appb-I000007
Figure PCTKR2013007821-appb-I000008
Figure PCTKR2013007821-appb-I000008
Figure PCTKR2013007821-appb-I000009
Figure PCTKR2013007821-appb-I000009
Figure PCTKR2013007821-appb-I000010
Figure PCTKR2013007821-appb-I000010
Figure PCTKR2013007821-appb-I000011
Figure PCTKR2013007821-appb-I000011
본 발명에 따른 화합물에서, 상기 화학식 3으로 표시되는 치환기는 하기 화학식 3a 내지 3f로 표시되는 치환기 중에서 선택될 수 있는데, 이에 한정되는 것은 아니다.In the compound according to the present invention, the substituent represented by Chemical Formula 3 may be selected from the substituents represented by the following Chemical Formulas 3a to 3f, but is not limited thereto.
[화학식 3a][Formula 3a]
Figure PCTKR2013007821-appb-I000012
Figure PCTKR2013007821-appb-I000012
[화학식 3b][Formula 3b]
Figure PCTKR2013007821-appb-I000013
Figure PCTKR2013007821-appb-I000013
[화학식 3c][Formula 3c]
Figure PCTKR2013007821-appb-I000014
;
Figure PCTKR2013007821-appb-I000014
;
[화학식 3d][Formula 3d]
Figure PCTKR2013007821-appb-I000015
;
Figure PCTKR2013007821-appb-I000015
;
[화학식 3e][Formula 3e]
Figure PCTKR2013007821-appb-I000016
;
Figure PCTKR2013007821-appb-I000016
;
[화학식 3f][Formula 3f]
Figure PCTKR2013007821-appb-I000017
Figure PCTKR2013007821-appb-I000017
상기 화학식 3a 내지 3f에서,In Chemical Formulas 3a to 3f,
X3 및 X4는 각각 독립적으로 O, S, Se, N(Ar6), C(Ar7)(Ar8) 및 Si(Ar9)(Ar10)로 이루어진 군에서 선택되고;X 3 and X 4 are each independently selected from the group consisting of O, S, Se, N (Ar 6 ), C (Ar 7 ) (Ar 8 ) and Si (Ar 9 ) (Ar 10 );
다만, R5 내지 R8 및 Ar6 내지 Ar10 중에서 하나는 단일 결합으로, 상기 화학식 2의 L에 연결되며;Provided that one of R 5 to R 8 and Ar 6 to Ar 10 is a single bond and is connected to L of Formula 2;
R5 내지 R8 및 Ar6 내지 Ar10은 각각 화학식 1에 정의된 바와 같고,R 5 to R 8 and Ar 6 to Ar 10 are as defined in Formula 1, respectively,
이때, 복수의 R7은 서로 동일하거나 상이하며, 복수의 R8은 서로 동일하거나 상이하다.In this case, a plurality of R 7 are the same or different from each other, a plurality of R 8 is the same or different from each other.
본 발명에 따른 화학식 1로 표시되는 화합물의 예로는 하기 화학식 4 내지 9로 표시되는 화합물 등이 있는데, 이에 한정되지 않는다.Examples of the compound represented by Chemical Formula 1 according to the present invention include a compound represented by the following Chemical Formulas 4 to 9, but are not limited thereto.
화학식 4
Figure PCTKR2013007821-appb-C000004
 Formula 4
Figure PCTKR2013007821-appb-C000004
화학식 5
Figure PCTKR2013007821-appb-C000005
 Formula 5
Figure PCTKR2013007821-appb-C000005
화학식 6
Figure PCTKR2013007821-appb-C000006
 Formula 6
Figure PCTKR2013007821-appb-C000006
화학식 7
Figure PCTKR2013007821-appb-C000007
 Formula 7
Figure PCTKR2013007821-appb-C000007
화학식 8
Figure PCTKR2013007821-appb-C000008
 Formula 8
Figure PCTKR2013007821-appb-C000008
화학식 9
Figure PCTKR2013007821-appb-C000009
 Formula 9
Figure PCTKR2013007821-appb-C000009
상기 화학식 4 내지 9에서, In Chemical Formulas 4 to 9,
X1 및 X2는 각각 독립적으로 O, S, Se, N(Ar1), C(Ar2)(Ar3) 및 Si(Ar4)(Ar5)로 이루어진 군에서 선택되고, 이때, X1 및 X2 중에서 적어도 하나는 N(Ar1)이며;X 1 and X 2 are each independently selected from the group consisting of O, S, Se, N (Ar 1 ), C (Ar 2 ) (Ar 3 ) and Si (Ar 4 ) (Ar 5 ), wherein X At least one of 1 and X 2 is N (Ar 1 );
단, 상기 R1 내지 R4, 및 Ar1 내지 Ar5 중에서 하나는 상기 화학식 2로 표시되는 치환기이며;Provided that one of R 1 to R 4 and Ar 1 to Ar 5 is a substituent represented by Formula 2;
상기 R1 내지 R4, 및 Ar1 내지 Ar5는 각각 화학식 1에서 정의된 바와 같다.R 1 to R 4 , and Ar 1 to Ar 5 are the same as defined in Chemical Formula 1.
본 발명에 따른 화학식 1로 표시되는 화합물의 예로는 하기 화학식 10으로 표시되는 화합물 등이 있는데, 이에 한정되지 않는다.Examples of the compound represented by Formula 1 according to the present invention include a compound represented by the following Formula 10, but is not limited thereto.
화학식 10
Figure PCTKR2013007821-appb-C000010
 Formula 10
Figure PCTKR2013007821-appb-C000010
상기 화학식 10에서,In Chemical Formula 10,
X1, Y1 내지 Y4, 환 A, R1, R2, L, a 및 B는 각각 화학식 1에 정의된 바와 같고,X 1 , Y 1 to Y 4 , Ring A, R 1 , R 2 , L, a and B are as defined in Formula 1, respectively,
이때, 복수의 R3는 서로 동일하거나 상이하며, 복수의 R4는 서로 동일하거나 상이하다.At this time, a plurality of R 3 are the same or different from each other, a plurality of R 4 is the same or different from each other.
또, 상기 화학식 1로 표시되는 화합물의 예로는 하기 화학식 11 내지 16으로 표시되는 화합물 등이 있는데, 이에 한정되지 않는다.In addition, examples of the compound represented by Chemical Formula 1 include compounds represented by the following Chemical Formulas 11 to 16, but are not limited thereto.
화학식 11
Figure PCTKR2013007821-appb-C000011
 Formula 11
Figure PCTKR2013007821-appb-C000011
화학식 12
Figure PCTKR2013007821-appb-C000012
 Formula 12
Figure PCTKR2013007821-appb-C000012
화학식 13
Figure PCTKR2013007821-appb-C000013
 Formula 13
Figure PCTKR2013007821-appb-C000013
화학식 14 Formula 14
화학식 15
Figure PCTKR2013007821-appb-C000015
 Formula 15
Figure PCTKR2013007821-appb-C000015
화학식 16
Figure PCTKR2013007821-appb-C000016
 Formula 16
Figure PCTKR2013007821-appb-C000016
상기 화학식 11 내지 16에서, In Chemical Formulas 11 to 16,
X1, R1 내지 R4, L, a 및 B는 각각 화학식 1에 정의된 바와 같고,X 1 , R 1 to R 4 , L, a and B are as defined in Formula 1, respectively,
이때, 복수의 R3는 서로 동일하거나 상이하며, 복수의 R4는 서로 동일하거나 상이하다.In this case, the plurality of R 3 are the same or different from each other, the plurality of R 4 is the same or different from each other.
또, 본 발명에 따른 화학식 1로 표시되는 화합물의 예로는 하기 화학식 17로 표시되는 화합물 등이 있는데, 이에 한정되지 않는다.In addition, examples of the compound represented by Formula 1 according to the present invention include a compound represented by the following Formula 17, but is not limited thereto.
화학식 17
Figure PCTKR2013007821-appb-C000017
 Formula 17
Figure PCTKR2013007821-appb-C000017
상기 화학식 17에서,In Chemical Formula 17,
X1, X3, Y1 내지 Y8, R1, R2, R5, R6, 환 A, 환 C, L 및 a는 각각 화학식 1에 정의된 바와 같다.X 1 , X 3 , Y 1 to Y 8 , R 1 , R 2 , R 5 , R 6 , Ring A, Ring C, L and a are as defined in Formula 1, respectively.
또, 상기 화학식 1로 표시되는 화합물의 예로는 하기 화학식 18 내지 23으로 표시되는 화합물 등이 있는데, 이에 한정되지 않는다.In addition, examples of the compound represented by Chemical Formula 1 include a compound represented by the following Chemical Formulas 18 to 23, but are not limited thereto.
화학식 18
Figure PCTKR2013007821-appb-C000018
 Formula 18
Figure PCTKR2013007821-appb-C000018
화학식 19
Figure PCTKR2013007821-appb-C000019
 Formula 19
Figure PCTKR2013007821-appb-C000019
화학식 20
Figure PCTKR2013007821-appb-C000020
 Formula 20
Figure PCTKR2013007821-appb-C000020
화학식 21
Figure PCTKR2013007821-appb-C000021
 Formula 21
Figure PCTKR2013007821-appb-C000021
화학식 22
Figure PCTKR2013007821-appb-C000022
 Formula 22
Figure PCTKR2013007821-appb-C000022
화학식 23
Figure PCTKR2013007821-appb-C000023
 Formula 23
Figure PCTKR2013007821-appb-C000023
상기 화학식 18 내지 23에서,In Chemical Formulas 18 to 23,
X1, X3, Y5 내지 Y8, R1 내지 R6, 환 C, L 및 a는 각각 화학식 1에 정의된 바와 같고,X 1 , X 3 , Y 5 to Y 8 , R 1 to R 6 , rings C, L and a are as defined in Formula 1, respectively,
이때, 복수의 R3는 서로 동일하거나 상이하며, 복수의 R4는 서로 동일하거나 상이하다.In this case, the plurality of R 3 are the same or different from each other, the plurality of R 4 is the same or different from each other.
상기 화학식 1로 표시되는 화합물의 구체적인 예로는 하기 화학식 CH-1로 표시되는 화합물 내지 화학식 CH-281로 표시되는 화합물 등이 있는데, 이에 한정되지 않는다. Specific examples of the compound represented by Chemical Formula 1 include a compound represented by Chemical Formula CH-1 to a compound represented by Chemical Formula CH-281, but are not limited thereto.
Figure PCTKR2013007821-appb-I000018
Figure PCTKR2013007821-appb-I000018
Figure PCTKR2013007821-appb-I000019
Figure PCTKR2013007821-appb-I000019
Figure PCTKR2013007821-appb-I000020
Figure PCTKR2013007821-appb-I000020
Figure PCTKR2013007821-appb-I000021
Figure PCTKR2013007821-appb-I000021
Figure PCTKR2013007821-appb-I000022
Figure PCTKR2013007821-appb-I000022
Figure PCTKR2013007821-appb-I000023
Figure PCTKR2013007821-appb-I000023
Figure PCTKR2013007821-appb-I000024
Figure PCTKR2013007821-appb-I000024
Figure PCTKR2013007821-appb-I000025
Figure PCTKR2013007821-appb-I000025
Figure PCTKR2013007821-appb-I000026
Figure PCTKR2013007821-appb-I000026
Figure PCTKR2013007821-appb-I000027
Figure PCTKR2013007821-appb-I000027
Figure PCTKR2013007821-appb-I000028
Figure PCTKR2013007821-appb-I000028
Figure PCTKR2013007821-appb-I000029
Figure PCTKR2013007821-appb-I000029
Figure PCTKR2013007821-appb-I000030
Figure PCTKR2013007821-appb-I000030
Figure PCTKR2013007821-appb-I000031
Figure PCTKR2013007821-appb-I000031
Figure PCTKR2013007821-appb-I000032
Figure PCTKR2013007821-appb-I000032
Figure PCTKR2013007821-appb-I000033
Figure PCTKR2013007821-appb-I000033
Figure PCTKR2013007821-appb-I000034
Figure PCTKR2013007821-appb-I000034
Figure PCTKR2013007821-appb-I000035
Figure PCTKR2013007821-appb-I000035
Figure PCTKR2013007821-appb-I000036
Figure PCTKR2013007821-appb-I000036
Figure PCTKR2013007821-appb-I000037
Figure PCTKR2013007821-appb-I000037
Figure PCTKR2013007821-appb-I000038
Figure PCTKR2013007821-appb-I000038
Figure PCTKR2013007821-appb-I000039
Figure PCTKR2013007821-appb-I000039
Figure PCTKR2013007821-appb-I000040
Figure PCTKR2013007821-appb-I000040
Figure PCTKR2013007821-appb-I000041
Figure PCTKR2013007821-appb-I000041
Figure PCTKR2013007821-appb-I000042
Figure PCTKR2013007821-appb-I000042
본 발명에서 사용된 "비치환된 알킬"은 탄소수 1 내지 40의 직쇄 또는 측쇄의 포화 탄화수소로부터 수소 원자를 제거하여 얻어지는 1가의 작용기를 의미하며, 이의 예로는 메틸, 에틸, 프로필, 이소부틸, sec-부틸, 펜틸, iso-아밀, 헥실 등을 포함한다. As used herein, "unsubstituted alkyl" refers to a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain saturated hydrocarbon of 1 to 40 carbon atoms, examples of which are methyl, ethyl, propyl, isobutyl, sec -Butyl, pentyl, iso-amyl, hexyl and the like.
또, 본 발명에서 "비치환된 알케닐(alkenyl)"은 탄소-탄소 이중 결합을 1개 이상 가진, 탄소수 2 내지 40의 직쇄 또는 측쇄의 불포화 탄화수소로부터 수소 원자를 제거하여 얻어지는 1가의 작용기를 의미한다. 이의 예로는 비닐(vinyl), 알릴(allyl), 이소프로펜일(isopropenyl), 2-부텐일(2-butenyl) 등이 있으며, 이에 한정되는 것은 아니다.In the present invention, "unsubstituted alkenyl" refers to a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon double bond. do. Examples thereof include vinyl, allyl, isopropenyl, 2-butenyl, and the like, but are not limited thereto.
또, 본 발명에서 "비치환된 알키닐(alkynyl)"은 탄소-탄소 삼중 결합을 1개 이상 가진, 탄소수 2 내지 40의 직쇄 또는 측쇄의 불포화 탄화수소로부터 수소 원자를 제거하여 얻어지는 1가의 작용기를 의미한다. 이의 예로는 에타인일(ethynyl), 2-프로파인일(2-propynyl) 등이 있는데, 이에 제한되는 것은 아니다.In addition, in the present invention, "unsubstituted alkynyl" means a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon triple bond. do. Examples thereof include ethynyl, 2-propynyl, and the like, but are not limited thereto.
또, 본 발명에서 "비치환된 시클로알킬"은 탄소수 3 내지 40의 모노사이클릭 또는 폴리사이클릭 비-방향족 탄화수소(포화 고리형 탄화수소)로부터 수소 원자를 제거하여 얻어지는 1가의 작용기를 의미한다. 이러한 시클로알킬의 예로는 시클로프로필, 시클로펜틸, 시클로헥실, 놀보닐(norbornyl), 아다만틴(adamantine)등이 있는데, 이에 한정되지 않는다.In the present invention, "unsubstituted cycloalkyl" means a monovalent functional group obtained by removing a hydrogen atom from a monocyclic or polycyclic non-aromatic hydrocarbon (saturated cyclic hydrocarbon) having 3 to 40 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.
또, 본 발명에서 "비치환된 헤테로시클로알킬"은 핵원자수 3 내지 40의 비-방향족 탄화수소(포화 고리형 탄화수소)로부터 수소 원자를 제거하여 얻어지는 1가의 작용기를 의미하며, 이때 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O 또는 S와 같은 헤테로 원자로 치환된다. 이의 비-제한적인 예로는 모르폴린, 피페라진 등이 있다.In addition, in the present invention, "unsubstituted heterocycloalkyl" means a monovalent functional group obtained by removing a hydrogen atom from a non-aromatic hydrocarbon (saturated cyclic hydrocarbon) having 3 to 40 nuclear atoms, wherein at least one of the rings Carbon, preferably 1 to 3 carbons, is substituted with a hetero atom such as N, O or S. Non-limiting examples thereof include morpholine, piperazine and the like.
또, 본 발명에서 "비치환된 아릴"은 단독 고리 혹은 2 이상의 고리가 조합된, 탄소수 6 내지 60의 방향족 탄화수소로부터 수소 원자를 제거하여 얻어지는 1가의 작용기를 의미한다. 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된(fused) 형태로 부착될 수 있다. 이의 비제한적인 예로는 페닐, 비페닐, 터페닐(terphenyl), 나프틸, 페난트릴, 안트릴 등이 있다.In addition, in this invention, "unsubstituted aryl" means the monovalent functional group obtained by removing a hydrogen atom from a C6-C60 aromatic hydrocarbon combined with a single ring or two or more rings. Two or more rings may be attached in a simple or fused form with one another. Non-limiting examples thereof include phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthryl and the like.
또, 본 발명에서 "비치환된 헤테로아릴"은 핵원자수 5 내지 60의 모노헤테로사이클릭 또는 폴리헤테로사이클릭 방향족 탄화수소로부터 수소 원자를 제거하여 얻어지는 1가의 작용기로서, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, S 또는 Se와 같은 헤테로원자로 치환된다. 이때, 헤테로아릴은 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된(fused) 형태로 부착될 수 있고, 나아가 아릴기와의 축합된 형태도 포함하는 것으로 해석한다. 이러한 헤테로아릴의 비제한적인 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 고리를 포함하고, 2-퓨라닐, N-이미다졸릴, 2-이속사졸릴, 2-피리디닐, 2-피리미디닐 등도 포함하는 것으로 해석한다.In the present invention, "unsubstituted heteroaryl" is a monovalent functional group obtained by removing a hydrogen atom from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms, and preferably at least one carbon in the ring, preferably Preferably 1 to 3 carbons are substituted with a heteroatom such as N, O, S or Se. At this time, heteroaryl is interpreted that two or more rings may be attached in a simple attached (pendant) or fused (fused) form with each other, and further includes a condensed form with an aryl group. Non-limiting examples of such heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl; Polycyclics such as phenoxathienyl, indolinzinyl, indolyl, purinyl, quinolyl, benzothiazole, carbazolyl It is understood to include a ring and to include 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl, and the like.
또, 본 발명에서 "비치환된 알킬옥시"는 RO-로 표시되는 1가의 작용기를 의미하며, 이때 상기 R은 탄소수 1 내지 40개의 알킬로서, 직쇄(linear), 측쇄(branched) 또는 사이클릭(cyclic) 구조를 포함하는 것으로 해석한다. 이러한 알킬옥시의 예로는 메톡시, 에톡시, n-프로폭시, 1-프로폭시, t-부톡시, n-부톡시, 펜톡시 등이 포함될 수 있으며 이에 한정되지는 않는다. In addition, in the present invention, "unsubstituted alkyloxy" means a monovalent functional group represented by RO-, wherein R is alkyl having 1 to 40 carbon atoms, and is linear, branched or cyclic ( It is interpreted as including a cyclic) structure. Examples of such alkyloxy may include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.
또, 본 발명에서 "비치환된 아릴옥시"는 R'O-로 표시되는 1가의 작용기를 의미하며, 이때 상기 R'는 탄소수 6 내지 60의 아릴이다. 아릴옥시의 비제한적인 예로는 페닐옥시, 나프틸옥시, 디페닐옥시 등이 있다.In the present invention, "unsubstituted aryloxy" means a monovalent functional group represented by R'O-, wherein R 'is aryl having 6 to 60 carbon atoms. Non-limiting examples of aryloxy include phenyloxy, naphthyloxy, diphenyloxy and the like.
또, 본 발명에서 "비치환된 알킬실릴"은 탄소수 1 내지 40의 알킬로 치환된 실릴을 의미하며, "비치환된 아릴실릴"은 탄소수 6 내지 60의 아릴로 치환된 실릴을 의미하고, "비치환된 아릴아민"은 탄소수 6 내지 60의 아릴로 치환된 아민을 의미한다.In addition, in the present invention, "unsubstituted alkylsilyl" means silyl substituted with alkyl having 1 to 40 carbon atoms, "unsubstituted arylsilyl" means silyl substituted with aryl having 6 to 60 carbon atoms, " "Unsubstituted arylamine" means an amine substituted with aryl having 6 to 60 carbon atoms.
또, 본 발명에서 "비치환된 알킬보론"는 탄소수 1 내지 40의 알킬로 치환된 보론을 의미하며, "비치환된 아릴보론"은 탄소수 6 내지 60의 아릴로 치환된 보론을 의미한다.In addition, in the present invention, "unsubstituted alkyl boron" means boron substituted with alkyl having 1 to 40 carbon atoms, "unsubstituted aryl boron" means boron substituted with aryl having 6 to 60 carbon atoms.
또한, 본 발명에서 "비치환된 아릴포스핀"은 탄소수 6 내지 60의 아릴로 치환된 포스핀을 의미하고, "비치환된 아릴포스핀옥사이드"는 탄소수 6 내지 60의 아릴로 치환된 포스핀옥사이드를 의미한다.Also, in the present invention, "unsubstituted arylphosphine" means phosphine substituted with aryl having 6 to 60 carbon atoms, and "unsubstituted arylphosphine oxide" means phosphine substituted with aryl having 6 to 60 carbon atoms. Means oxide.
또한, 본 발명에서 "축합(fused) 고리"는 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리, 축합 헤테로방향족 고리 또는 이들의 조합된 형태를 의미한다.In the present invention, "fused ring" means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring or a combination thereof.
본 발명에 따른 화학식 1로 표시되는 화합물은 일반적인 합성방법에 따라 합성될 수 있다 [Chem. Rev., 60:313 (1960); J. Chem. SOC. 4482 (1955); Chem. Rev. 95: 2457 (1995) 등 참조]. 본 발명의 화합물에 대한 상세한 합성 과정은 후술하는 합성예에서 구체적으로 기술하도록 한다.The compound represented by Formula 1 according to the present invention may be synthesized according to a general synthetic method [ Chem. Rev. , 60 : 313 (1960); J. Chem. SOC . 4482 (1955); Chem. Rev. 95: 2457 (1995) et al. Detailed synthesis procedures for the compounds of the present invention will be described in detail in the synthesis examples described below.
한편, 본 발명은 전술한 화학식 1로 표시되는 화합물(바람직하게는 화학식 4 내지 23으로 표시되는 화합물)을 포함하는 유기 전계 발광 소자를 제공한다.On the other hand, the present invention provides an organic electroluminescent device comprising a compound represented by the formula (1) (preferably a compound represented by the formula 4 to 23).
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 화합물(바람직하게는 화학식 4 내지 23으로 표시되는 화합물)을 1종 이상 포함하는 것을 특징으로 한다.Specifically, the organic electroluminescent device according to the present invention is an anode; Cathode; And one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers comprises a compound represented by Chemical Formula 1 (preferably, a compound represented by Chemical Formulas 4 to 23). It is characterized by including one or more.
상기 1층 이상의 유기물층으로는 정공주입층, 정공수송층, 및 발광층, 전자수송층, 전자주입층 등이 있는데, 이 중에서 적어도 하나의 유기물층이 상기 화학식 1로 표시되는 화합물을 포함할 수 있다. 바람직하게는 상기 화학식 1의 화합물을 포함하는 1층 이상의 유기물층은 정공 수송층, 정공 주입층 또는 발광층일 수 있으며, 보다 바람직하게는 발광층일 수 있다. 만약, 상기 화학식 1의 화합물이 발광층에 포함될 경우, 상기 화학식 1의 화합물은 인광 또는 형광 호스트 물질 및/또는 도펀트로 사용될 수 있다. 이와 같이 상기 화합물을 유기 전계 발광 소자가 포함할 경우, 소자의 발광효율, 휘도, 전력효율, 열적 안정성 및 수명이 향상될 수 있다. The one or more organic material layers include a hole injection layer, a hole transport layer, and a light emitting layer, an electron transport layer, an electron injection layer, etc. Among these, at least one organic material layer may include a compound represented by Chemical Formula 1. Preferably, at least one organic layer including the compound of Formula 1 may be a hole transport layer, a hole injection layer or a light emitting layer, more preferably a light emitting layer. If the compound of Formula 1 is included in the emission layer, the compound of Formula 1 may be used as a phosphorescent or fluorescent host material and / or dopant. As such, when the compound includes the organic electroluminescent device, the luminous efficiency, brightness, power efficiency, thermal stability, and lifetime of the device may be improved.
본 발명에 따른 유기 EL 소자 구조는 특별히 한정되지 않으며, 비제한적인 예로는 기판, 양극, 정공 주입층, 정공 수송층, 발광층, 전자 수송층 및 음극이 순차적으로 적층된 구조일 수 있다. 이때, 정공 주입층, 정공 수송층 및 발광층 중 하나 이상은 상기 화학식 1로 표시되는 화합물을 1종 이상 포함할 수 있다. 상기 전자 수송층 위에는 전자 주입층이 위치할 수도 있다.The organic EL device structure according to the present invention is not particularly limited, and a non-limiting example may be a structure in which a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are sequentially stacked. In this case, at least one of the hole injection layer, the hole transport layer, and the light emitting layer may include at least one compound represented by Chemical Formula 1. An electron injection layer may be positioned on the electron transport layer.
또한, 본 발명에 따른 유기 EL 소자는 전술한 바와 같이 양극, 1층 이상의 유기물층 및 음극이 순차적으로 적층된 구조뿐만 아니라, 전극과 유기물층 계면에 절연층 또는 접착층이 삽입될 수 있다. In addition, as described above, the organic EL device according to the present invention may not only have a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked, but an insulating layer or an adhesive layer may be inserted at an interface between an electrode and an organic material layer.
본 발명에 따른 유기 전계 발광 소자는 상기 유기물층 중 1층 이상이 상기 화학식 1로 표시되는 화합물을 포함하도록 형성하는 것을 제외하고는, 당 기술 분야에 알려져 있는 재료 및 방법을 이용하여 다른 유기물층 및 전극을 형성하여 제조될 수 있다.The organic electroluminescent device according to the present invention is formed by using other materials and methods known in the art, except that at least one layer of the organic material layer is formed to include the compound represented by the formula (1). Can be produced.
상기 유기물층은 진공증착법이나 용액 도포법에 의하여 형성될 수 있다. 상기 용액 도포법의 예로는 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯 프린팅 또는 열 전사법 등이 있으나, 이들에만 한정되지 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 발명에서 사용 가능한 기판으로는 실리콘 웨이퍼, 석영 또는 유리판, 금속판, 플라스틱 필름이나 시트 등이 사용될 수 있다. As the substrate usable in the present invention, a silicon wafer, quartz or glass plate, metal plate, plastic film or sheet may be used.
또, 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 및 폴리아닐린과 같은 전도성 고분자; 또는 카본블랙 등이 있으나, 이들에만 한정되는 것은 아니다. In addition, examples of the anode 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), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO 2 : Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; Or carbon black, but is not limited thereto.
또, 음극 물질로는 마그네슘, 칼슘, 나트륨, 칼륨, 타이타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석, 또는 납과 같은 금속 또는 이들의 합금; LiF/Al 또는 LiO2/Al과 같은 다층 구조 물질 등이 있으나, 이들에만 한정되는 것은 아니다. The negative electrode material may be a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead or an alloy thereof; Multilayer structure materials such as LiF / Al or LiO 2 / Al, and the like, but are not limited thereto.
또한, 정공 주입층, 정공 수송층, 전자 주입층 및 전자 수송층은 특별히 한정되는 것은 아니며, 당업계에 알려진 통상의 물질이 사용될 수 있다. In addition, the hole injection layer, the hole transport layer, the electron injection layer and the electron transport layer is not particularly limited, conventional materials known in the art may 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 merely to illustrate the present invention and the present invention is not limited by the following examples.
[준비예 1] 화합물 IC-1의 합성Preparation Example 1 Synthesis of Compound IC-1
<단계 1> 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole의 합성<Step 1> Synthesis of 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole
Figure PCTKR2013007821-appb-I000043
Figure PCTKR2013007821-appb-I000043
질소 기류 하에서 5-bromo-1H-indole (25 g, 0.128 mol), 4,4,4',4',5,5, 5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (48.58 g, 0.191 mol), Pd(dppf)Cl2 (5.2 g, 5 mol), KOAc (37.55 g, 0.383 mol) 및 1,4-dioxane (500 ml)를 혼합한 후, 130℃에서 12시간 동안 교반하였다.5-bromo-1H-indole (25 g, 0.128 mol), 4,4,4 ', 4', 5,5, 5 ', 5'-octamethyl-2,2'-bi (1,3) under nitrogen stream , 2-dioxaborolane) (48.58 g, 0.191 mol), Pd (dppf) Cl 2 (5.2 g, 5 mol), KOAc (37.55 g, 0.383 mol) and 1,4-dioxane (500 ml) Stir at 130 ° C. for 12 h.
반응이 종결된 후, 에틸아세테이트로 추출한 다음 MgSO4로 수분을 제거하고, 컬럼크로마토그래피 (Hexane: ethyl acetate(EA) = 10:1 (v/v))로 정제하여 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole (22.32 g, 수율 72%)을 얻었다. After the reaction was completed, the resultant was extracted with ethyl acetate, followed by removing moisture with MgSO 4 , and purified by column chromatography (Hexane: ethyl acetate (EA) = 10: 1 (v / v)) to obtain 5- (4,4, 5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole (22.32 g, yield 72%) was obtained.
1H-NMR: δ 1.24 (s, 12H), 6.45 (d, 1H), 7.27 (d, 1H), 7.42 (d, 1H), 7.52 (d, 1H), 7.95 (s, 1H), 8.21 (s, 1H) 1 H-NMR: δ 1.24 (s, 12H), 6.45 (d, 1H), 7.27 (d, 1H), 7.42 (d, 1H), 7.52 (d, 1H), 7.95 (s, 1H), 8.21 ( s, 1 H)
<단계 2> 5-(2-nitrophenyl)-1H-indole의 합성<Step 2> Synthesis of 5- (2-nitrophenyl) -1H-indole
Figure PCTKR2013007821-appb-I000044
Figure PCTKR2013007821-appb-I000044
질소 기류 하에서 1-bromo-2-nitrobenzene (15.23 g, 75.41 mmol)과 상기 준비예 1의 <단계 1>에서 얻은 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole (22 g, 90.49 mmol)를, NaOH (9.05 g, 226.24 mmol) 및 THF/H2O (400 ml/200 ml)와 혼합한 다음, 40 ℃에서 Pd(PPh3)4(4.36 g, 5 mol%)를 넣은 후, 80 ℃에서 12시간 동안 교반하였다. 1-bromo-2-nitrobenzene (15.23 g, 75.41 mmol) under nitrogen stream and 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- obtained in <Step 1> of Preparation Example 1 2-yl) -1H-indole (22 g, 90.49 mmol) was mixed with NaOH (9.05 g, 226.24 mmol) and THF / H 2 O (400 ml / 200 ml), followed by Pd (PPh 3 ) 4 (4.36 g, 5 mol%) was added thereto, followed by stirring at 80 ° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출한 다음, MgSO4를 넣고 여과하여 유기층을 얻었다. 얻어진 유기층에서 용매를 제거한 후, 컬럼 크로마토그래피 (Hexane:EA = 3:1 (v/v))로 정제하여 5-(2-nitrophenyl)-1H-indole (11.32 g, 수율 63%)을 얻었다. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered to obtain an organic layer. After the solvent was removed from the obtained organic layer, the residue was purified by column chromatography (Hexane: EA = 3: 1 (v / v)) to obtain 5- (2-nitrophenyl) -1H-indole (11.32 g, 63% yield).
1H-NMR: δ 6.47 (d, 1H), 7.25 (d, 1H), 7.44 (d, 1H), 7.53 (d, 1H), 7.65 (t, 1H), 7.86 (t, 1H), 7.95 (s, 1H), 8.00 (d, 1H), 8.09 (t, 1H), 8.20 (s, 1H) 1 H-NMR: δ 6.47 (d, 1H), 7.25 (d, 1H), 7.44 (d, 1H), 7.53 (d, 1H), 7.65 (t, 1H), 7.86 (t, 1H), 7.95 ( s, 1H), 8.00 (d, 1H), 8.09 (t, 1H), 8.20 (s, 1H)
<단계 3> 5-(2-nitrophenyl)-1-phenyl-1H-indole의 합성<Step 3> Synthesis of 5- (2-nitrophenyl) -1-phenyl-1H-indole
Figure PCTKR2013007821-appb-I000045
Figure PCTKR2013007821-appb-I000045
질소 기류 하에서 상기 준비예 1의 <단계 2>에서 얻은 5-(2-nitrophenyl)-1H-indole (11 g, 46.17 mmol)를, iodobenzene (14.13 g, 69.26 mmol), Cu powder (0.29 g, 4.62 mmol), K2CO3 (6.38 g, 46.17 mmol), Na2SO4 (6.56 g, 46.17 mmol), 및 nitrobenzene (200 ml)와 혼합한 후, 190 ℃에서 12시간 동안 교반하였다. 5- (2-nitrophenyl) -1H-indole (11 g, 46.17 mmol) obtained in <Step 2> of Preparation Example 1 under nitrogen stream, iodobenzene (14.13 g, 69.26 mmol), Cu powder (0.29 g, 4.62 mmol), K 2 CO 3 (6.38 g, 46.17 mmol), Na 2 SO 4 (6.56 g, 46.17 mmol), and nitrobenzene (200 ml) were mixed and stirred at 190 ° C. for 12 hours.
반응 종결 후 nitrobenzene을 제거하고 메틸렌클로라이드로 유기층을 분리하여 MgSO4를 사용하여 물을 제거하였다. 물이 제거된 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:MC = 3:1 (v/v))로 정제하여 5-(2-nitrophenyl)-1-phenyl-1H-indole (10.30 g, 수율 71%)을 얻었다. After completion of the reaction, nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed using MgSO 4 . The solvent was removed from the organic layer, which was freed of water, and then purified by column chromatography (Hexane: MC = 3: 1 (v / v)) to give 5- (2-nitrophenyl) -1-phenyl-1H-indole (10.30 g, yield). 71%).
1H-NMR: δ 6.48 (d, 1H), 7.26 (d, 1H), 7.45 (m, 3H), 7.55 (m, 4H), 7.63 (t, 1H), 7.84 (t, 1H), 7.93 (s, 1H), 8.01 (d, 1H), 8.11 (t, 1H) 1 H-NMR: δ 6.48 (d, 1H), 7.26 (d, 1H), 7.45 (m, 3H), 7.55 (m, 4H), 7.63 (t, 1H), 7.84 (t, 1H), 7.93 ( s, 1H), 8.01 (d, 1H), 8.11 (t, 1H)
<단계 4> 화합물 IC-1 및 IC-2의 합성 Step 4 Synthesis of Compounds IC-1 and IC-2
Figure PCTKR2013007821-appb-I000046
Figure PCTKR2013007821-appb-I000046
질소 기류 하에서 상기 <단계 3>에서 얻은 5-(2-nitrophenyl)-1-phenyl-1H-indole (5 g, 15.91 mmol), triphenylphosphine (10.43 g, 39.77 mmol) 및 1,2-dichlorobenzene (50 ml)를 혼합하고 12시간 동안 교반하였다.5- (2-nitrophenyl) -1-phenyl-1H-indole (5 g, 15.91 mmol), triphenylphosphine (10.43 g, 39.77 mmol) and 1,2-dichlorobenzene (50 ml) obtained in <Step 3> under a nitrogen stream. ) Was mixed and stirred for 12 hours.
반응 종료 후 1,2-dichlorobenzene를 제거한 다음, 디클로로메탄으로 추출하였다. 얻어진 유기층에 대해 MgSO4로 물을 제거한 다음, 컬럼크로마토그래피 (Hexane:MC=3:1 (v/v))로 정제하여 화합물 IC-1 (2.38 g, 수율 53%) 및 화합물 IC-2 (1.30 g, 수율 29%)를 얻었다.After the reaction was completed, 1,2-dichlorobenzene was removed and extracted with dichloromethane. The obtained organic layer was removed with MgSO 4 , and then purified by column chromatography (Hexane: MC = 3: 1 (v / v)) to give Compound IC-1 (2.38 g, Yield 53%) and Compound IC-2 ( 1.30 g, yield 29%) was obtained.
화합물 IC-1의 1H-NMR: δ 6.99 (d, 1H), 7.12 (t, 1H), 7.27 (t, 1H), 7.32 (d, 1H), 7.41 (t, 1H), 7.50 (d, 1H), 7.60 (m, 5H), 7.85 (d, 1H), 8.02 (d, 1H), 10.59 (s, 1H) 1 H-NMR of compound IC-1: δ 6.99 (d, 1H), 7.12 (t, 1H), 7.27 (t, 1H), 7.32 (d, 1H), 7.41 (t, 1H), 7.50 (d, 1H), 7.60 (m, 5H), 7.85 (d, 1H), 8.02 (d, 1H), 10.59 (s, 1H)
화합물 IC-2의 1H-NMR: δ 6.98 (d, 1H), 7.13 (t, 1H), 7.26 (t, 1H), 7.33 (d, 1H), 7.42 (t, 1H), 7.51 (s, 1H), 7.61 (m, 5H), 7.84 (d, 1H), 8.03 (s, 1H), 10.58 (s, 1H) 1 H-NMR of compound IC-2: δ 6.98 (d, 1H), 7.13 (t, 1H), 7.26 (t, 1H), 7.33 (d, 1H), 7.42 (t, 1H), 7.51 (s, 1H), 7.61 (m, 5H), 7.84 (d, 1H), 8.03 (s, 1H), 10.58 (s, 1H)
[준비예 2] 화합물 IC-3 및 IC-4의 합성Preparation Example 2 Synthesis of Compounds IC-3 and IC-4
<단계 1> 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole의 합성Step 1 Synthesis of 6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole
Figure PCTKR2013007821-appb-I000047
Figure PCTKR2013007821-appb-I000047
준비예 <단계 1>에서 사용된 5-bromo-1H-indole 대신 6-bromo-1H-indole (25 g, 0.128 mol)를 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 1>과 동일한 과정을 수행하여 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole을 얻었다.Preparation Example The same procedure as in <Step 1> of Preparation Example 1, except that 6-bromo-1H-indole (25 g, 0.128 mol) was used instead of 5-bromo-1H-indole used in <Step 1>. The procedure was followed to obtain 6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole.
1H-NMR: δ 1.25 (s, 12H), 6.52 (d, 1H), 7.16 (d, 1H), 7.21 (d, 1H), 7.49 (d, 1H), 7.53 (s, 1H), 8.15 (s, 1H) 1 H-NMR: δ 1.25 (s, 12H), 6.52 (d, 1H), 7.16 (d, 1H), 7.21 (d, 1H), 7.49 (d, 1H), 7.53 (s, 1H), 8.15 ( s, 1 H)
<단계 2> 6-(2-nitrophenyl)-1H-indole의 합성Step 2 Synthesis of 6- (2-nitrophenyl) -1H-indole
Figure PCTKR2013007821-appb-I000048
Figure PCTKR2013007821-appb-I000048
준비예 1의 <단계 2>에서 사용된 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole 대신 상기 준비예 2의 <단계 1>에서 얻은 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole (22 g, 90.49 mmol)를 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 2>과 동일한 과정을 수행하여 6-(2-nitrophenyl)-1H-indole을 얻었다.<Step 1 of Preparation Example 2> instead of 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole used in <Step 2> of Preparation Example 1 Preparation Example 1, except that 6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole (22 g, 90.49 mmol) obtained in 6- (2-nitrophenyl) -1H-indole was obtained by the same process as in <Step 2>.
1H-NMR: δ 6.57 (d, 1H), 7.07 (d, 1H), 7.24 (d, 1H), 7.35 (s, 1H), 7.43 (t, 1H), 7.50 (d, 1H), 7.58 (t, 1H), 7.66 (d, 1H), 7.78 (d, 1H), 8.19 (s, 1H) 1 H-NMR: δ 6.57 (d, 1H), 7.07 (d, 1H), 7.24 (d, 1H), 7.35 (s, 1H), 7.43 (t, 1H), 7.50 (d, 1H), 7.58 ( t, 1H), 7.66 (d, 1H), 7.78 (d, 1H), 8.19 (s, 1H)
<단계 3> 6-(2-nitrophenyl)-1-phenyl-1H-indole의 합성<Step 3> Synthesis of 6- (2-nitrophenyl) -1-phenyl-1H-indole
Figure PCTKR2013007821-appb-I000049
Figure PCTKR2013007821-appb-I000049
준비예 1의 <단계 3>에서 사용된 5-(2-nitrophenyl)-1H-indole 대신 상기 준비예 2의 <단계 2>에서 얻은 6-(2-nitrophenyl)-1H-indole (11 g, 46.17 mmol)를 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 3>과 동일한 과정을 수행하여 6-(2-nitrophenyl)-1-phenyl-1H-indole을 얻었다.6- (2-nitrophenyl) -1H-indole (11 g, 46.17) obtained in <Step 2> of Preparation Example 2 instead of 5- (2-nitrophenyl) -1H-indole used in <Step 3> of Preparation Example 1 Except for using mmol), 6- (2-nitrophenyl) -1-phenyl-1H-indole was obtained by the same process as <Step 3> of Preparation Example 1.
1H-NMR: δ 6.81 (d, 1H), 7.12 (t, 1H), 7.22 (t, 1H), 7.35 (s, 1H), 7.43 (d, 1H), 7.51 (m, 3H), 7.56 (m, 2H), 7.62 (m, 2H), 7.85 (d, 1H), 8.02 (d, 1H) 1 H-NMR: δ 6.81 (d, 1H), 7.12 (t, 1H), 7.22 (t, 1H), 7.35 (s, 1H), 7.43 (d, 1H), 7.51 (m, 3H), 7.56 ( m, 2H), 7.62 (m, 2H), 7.85 (d, 1H), 8.02 (d, 1H)
<단계 4> 화합물 IC-3 및 IC-4의 합성Step 4 Synthesis of Compounds IC-3 and IC-4
Figure PCTKR2013007821-appb-I000050
Figure PCTKR2013007821-appb-I000050
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 준비예 3의 <단계 3>에서 얻은 6-(2-nitrophenyl)-1-phenyl-1H-indole(5 g, 15.91 mmol)를 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 4>과 동일한 과정을 수행하여 화합물 IC-3 및 IC-4를 얻었다.6- (2-nitrophenyl) -1-phenyl-1H obtained in <Step 3> of Preparation Example 3 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 Except that -indole (5 g, 15.91 mmol) was used, the same procedure as in <Step 4> of Preparation Example 1 was performed to obtain compounds IC-3 and IC-4.
화합물 IC-3의 1H-NMR: δ 6.80 (d, 1H), 7.11 (t, 1H), 7.23 (t, 1H), 7.42 (d, 1H), 7.50 (m, 3H), 7.57 (m, 2H), 7.63 (m, 2H), 7.86 (d, 1H), 8.03 (d, 1H), 9.81 (s, 1H) 1 H-NMR of compound IC-3: δ 6.80 (d, 1H), 7.11 (t, 1H), 7.23 (t, 1H), 7.42 (d, 1H), 7.50 (m, 3H), 7.57 (m, 2H), 7.63 (m, 2H), 7.86 (d, 1H), 8.03 (d, 1H), 9.81 (s, 1H)
화합물 IC-4의 1H-NMR: δ 6.81 (d, 1H), 7.12 (t, 1H), 7.22 (t, 1H), 7.43 (s, 1H), 7.51 (m, 3H), 7.58 (m, 2H), 7.64 (m, 2H), 7.85 (d, 1H), 8.02 (s, 1H), 9.82 (s, 1H) 1 H-NMR of compound IC-4: δ 6.81 (d, 1H), 7.12 (t, 1H), 7.22 (t, 1H), 7.43 (s, 1H), 7.51 (m, 3H), 7.58 (m, 2H), 7.64 (m, 2H), 7.85 (d, 1H), 8.02 (s, 1H), 9.82 (s, 1H)
[준비예 3] 화합물 IC-5의 합성Preparation Example 3 Synthesis of Compound IC-5
<단계 1> 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole의 합성<Step 1> Synthesis of 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole
Figure PCTKR2013007821-appb-I000051
Figure PCTKR2013007821-appb-I000051
준비예 1의 <단계 1>에서 사용된 5-bromo-1H-indole 대신 4-bromo-1H-indole (25 g, 0.128 mol)를 사용하는 것을 제외하고는 상기 준비예 1의 <단계 1>과 동일한 과정을 수행하여 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole을 얻었다.<Step 1> of Preparation Example 1, except that 4-bromo-1H-indole (25 g, 0.128 mol) instead of 5-bromo-1H-indole used in <Step 1> of Preparation Example 1 The same procedure was followed to obtain 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole.
1H NMR: δ 1.26 (s, 12H), 6.43 (d, 1H), 7.26 (t, 1H), 7.48 (d, 1H), 7.74 (d, 1H), 7.85 (d, 1H), 8.23 (s, 1H) 1 H NMR: δ 1.26 (s, 12H), 6.43 (d, 1H), 7.26 (t, 1H), 7.48 (d, 1H), 7.74 (d, 1H), 7.85 (d, 1H), 8.23 (s , 1H)
<단계 2> 4-(2-nitrophenyl)-1H-indole의 합성<Step 2> Synthesis of 4- (2-nitrophenyl) -1H-indole
Figure PCTKR2013007821-appb-I000052
Figure PCTKR2013007821-appb-I000052
준비예 1의 <단계 2>에서 사용된 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole 대신 상기 준비예 3의 <단계 1>에서 얻은 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole (22 g, 90.49 mmol)을 사용하는 것을 제외하고는 상기 준비예 1의 <단계 2>와 동일한 과정을 수행하여 4-(2-nitrophenyl)-1H-indole을 얻었다.<Step 1 of Preparation Example 3> instead of 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole used in <Step 2> of Preparation Example 1 Preparation Example 1, except that 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole (22 g, 90.49 mmol) obtained in The same procedure as in <Step 2> was performed to obtain 4- (2-nitrophenyl) -1H-indole.
1H NMR: δ 6.45 (d, 1H), 7.27 (t, 1H), 7.50 (d, 1H), 7.66 (t, 1H), 7.75 (d, 1H), 7.89 (m, 2H), 7.99 (d, 1H), 8.04 (d, 1H), 8.24 (s, 1H) 1 H NMR: δ 6.45 (d, 1H), 7.27 (t, 1H), 7.50 (d, 1H), 7.66 (t, 1H), 7.75 (d, 1H), 7.89 (m, 2H), 7.99 (d , 1H), 8.04 (d, 1H), 8.24 (s, 1H)
<단계 3> 4-(2-nitrophenyl)-1-phenyl-1H-indole의 합성<Step 3> Synthesis of 4- (2-nitrophenyl) -1-phenyl-1H-indole
Figure PCTKR2013007821-appb-I000053
Figure PCTKR2013007821-appb-I000053
준비예 1의 <단계 3>에서 사용된 5-(2-nitrophenyl)-1H-indole 대신 상기 준비예 3의 <단계 2>에서 얻은 4-(2-nitrophenyl)-1H-indole (11 g, 46.17 mmol)을 사용하는 것을 제외하고는 준비예 1의 <단계 3>과 동일한 과정을 수행하여 4-(2-nitrophenyl)-1-phenyl-1H-indole을 얻었다.4- (2-nitrophenyl) -1H-indole (11 g, 46.17) obtained in <Step 2> of Preparation Example 3 instead of 5- (2-nitrophenyl) -1H-indole used in <Step 3> of Preparation Example 1 A 4- (2-nitrophenyl) -1-phenyl-1H-indole was obtained in the same manner as in <Step 3> of Preparation Example 1, except that mmol) was used.
1H NMR: δ 6.47 (d, 1H), 7.28 (t, 1H), 7.47 (m, 2H), 7.52 (m, 2H), 7.60 (m, 2H), 7.67 (t, 1H), 7.75 (d, 1H), 7.89 (m, 2H), 8.00 (d, 1H), 8.06 (d, 1H) 1 H NMR: δ 6.47 (d, 1H), 7.28 (t, 1H), 7.47 (m, 2H), 7.52 (m, 2H), 7.60 (m, 2H), 7.67 (t, 1H), 7.75 (d , 1H), 7.89 (m, 2H), 8.00 (d, 1H), 8.06 (d, 1H)
<단계 4> 화합물 IC-5의 합성Step 4 Synthesis of Compound IC-5
Figure PCTKR2013007821-appb-I000054
Figure PCTKR2013007821-appb-I000054
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 3의 <단계 3>에서 얻은 4-(2-nitrophenyl)-1-phenyl-1H-indole (5 g, 15.91 mmol)을 사용하는 것을 제외하고는 준비예 1의 <단계 4>와 동일한 과정을 수행하여 화합물 IC-5을 얻었다.4- (2-nitrophenyl) -1-phenyl- obtained in <Step 3> of Preparation Example 3 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 Except for using 1H-indole (5 g, 15.91 mmol) was carried out the same procedure as in <step 4> of Preparation Example 1 to obtain a compound IC-5.
1H NMR: δ 6.49 (d, 1H), 7.29 (t, 1H), 7.46 (m, 2H), 7.54 (m, 2H), 7.61 (d, 1H), 7.69 (t, 1H), 7.74 (d, 1H), 7.88 (m, 2H), 8.01 (d, 1H), 8.04 (d, 1H), 8.23 (s, 1H) 1 H NMR: δ 6.49 (d, 1H), 7.29 (t, 1H), 7.46 (m, 2H), 7.54 (m, 2H), 7.61 (d, 1H), 7.69 (t, 1H), 7.74 (d , 1H), 7.88 (m, 2H), 8.01 (d, 1H), 8.04 (d, 1H), 8.23 (s, 1H)
[준비예 4] IC-6의 합성Preparation Example 4 Synthesis of IC-6
<단계 1> 7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole의 합성<Step 1> Synthesis of 7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole
Figure PCTKR2013007821-appb-I000055
Figure PCTKR2013007821-appb-I000055
준비예 1의 <단계 1>에서 사용된 5-bromo-1H-indole 대신 7-bromo-1H-indole (25 g, 0.128 mol)를 사용하는 것을 제외하고는, 준비예 1의 <단계 1>과 동일한 과정을 수행하여 7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole을 얻었다.<Step 1> of Preparation Example 1 except that 7-bromo-1H-indole (25 g, 0.128 mol) was used instead of 5-bromo-1H-indole used in <Step 1> of Preparation Example 1 The same procedure was followed to obtain 7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole.
1H NMR: δ 1.25 (s, 12H), 6.43 (d, 1H), 7.25 (d, 1H), 7.45 (t, 1H), 7.56 (d, 1H), 7.71 (d, 1H), 8.22 (s, 1H) 1 H NMR: δ 1.25 (s, 12H), 6.43 (d, 1H), 7.25 (d, 1H), 7.45 (t, 1H), 7.56 (d, 1H), 7.71 (d, 1H), 8.22 (s , 1H)
<단계 2> 7-(2-nitrophenyl)-1H-indole의 합성Step 2 Synthesis of 7- (2-nitrophenyl) -1H-indole
Figure PCTKR2013007821-appb-I000056
Figure PCTKR2013007821-appb-I000056
준비예 1의 <단계 2>에서 사용된 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole 대신 상기 준비예 4의 <단계 1>에서 얻은 7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole (22 g, 90.49 mmol)을 사용하는 것을 제외하고는 준비예 1의 <단계 2>와 동일한 과정을 수행하여 7-(2-nitrophenyl)-1H-indole을 얻었다.<Step 1 of Preparation Example 4> instead of 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole used in <Step 2> of Preparation Example 1 Preparation Example 1 except that 7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole (22 g, 90.49 mmol) obtained in The procedure of step 2> was followed to obtain 7- (2-nitrophenyl) -1H-indole.
1H NMR: δ 6.42 (d, 1H), 7.24 (d, 1H), 7.43 (t, 1H), 7.55 (d, 1H), 7.70 (m, 2H), 7.88 (t, 1H), 8.01 (d, 1H), 8.11 (d, 1H), 8.23 (s, 1H) 1 H NMR: δ 6.42 (d, 1H), 7.24 (d, 1H), 7.43 (t, 1H), 7.55 (d, 1H), 7.70 (m, 2H), 7.88 (t, 1H), 8.01 (d , 1H), 8.11 (d, 1H), 8.23 (s, 1H)
<단계 3> 7-(2-nitrophenyl)-1-phenyl-1H-indole의 합성<Step 3> Synthesis of 7- (2-nitrophenyl) -1-phenyl-1H-indole
Figure PCTKR2013007821-appb-I000057
Figure PCTKR2013007821-appb-I000057
준비예 1의 <단계 3>에서 사용된 5-(2-nitrophenyl)-1H-indole 대신 상기 준비예 4의 <단계 2>에서 얻은 7-(2-nitrophenyl)-1H-indole (11 g, 46.17 mmol)을 사용하는 것을 제외하고는 준비예 1의 <단계 3>과 동일한 과정을 수행하여 7-(2-nitrophenyl)-1-phenyl-1H-indole을 얻었다.7- (2-nitrophenyl) -1H-indole (11 g, 46.17) obtained in <Step 2> of Preparation Example 4 instead of 5- (2-nitrophenyl) -1H-indole used in <Step 3> of Preparation Example 1 Except for using mmol), 7- (2-nitrophenyl) -1-phenyl-1H-indole was obtained by the same process as <Step 3> of Preparation Example 1.
1H NMR: δ 6.43 (d, 1H), 7.26 (d, 1H), 7.44 (m, 3H), 7.56 (m, 4H), 7.71 (m, 2H), 7.89 (t, 1H), 8.02 (d, 1H), 8.10 (d, 1H) 1 H NMR: δ 6.43 (d, 1H), 7.26 (d, 1H), 7.44 (m, 3H), 7.56 (m, 4H), 7.71 (m, 2H), 7.89 (t, 1H), 8.02 (d , 1H), 8.10 (d, 1H)
<단계 4> 화합물 IC-6의 합성Step 4 Synthesis of Compound IC-6
Figure PCTKR2013007821-appb-I000058
Figure PCTKR2013007821-appb-I000058
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 4의 <단계 3>에서 얻은 7-(2-nitrophenyl)-1-phenyl-1H-indole (5 g, 15.91 mmol)을 사용하는 것을 제외하고는 준비예 1의 <단계 4>와 동일한 과정을 수행하여 화합물 IC-6을 얻었다.Instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1, 7- (2-nitrophenyl) -1-phenyl- obtained in <Step 3> of Preparation Example 4 Except for using 1H-indole (5 g, 15.91 mmol) was carried out in the same manner as in <Step 4> of Preparation Example 1 to obtain a compound IC-6.
1H NMR: δ 6.45 (d, 1H), 7.24 (d, 1H), 7.45 (m, 3H), 7.57 (m, 3H), 7.63 (d, 1H), 7.70 (d, 1H), 7.88 (t, 1H), 8.00 (d, 1H), 8.09 (d, 1H), 8.22 (s, 1H) 1 H NMR: δ 6.45 (d, 1H), 7.24 (d, 1H), 7.45 (m, 3H), 7.57 (m, 3H), 7.63 (d, 1H), 7.70 (d, 1H), 7.88 (t , 1H), 8.00 (d, 1H), 8.09 (d, 1H), 8.22 (s, 1H)
[준비예 5] 화합물 IC-7의 합성Preparation Example 5 Synthesis of Compound IC-7
<단계 1> 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole의 합성<Step 1> Synthesis of 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole
준비예 1의 <단계 1>과 동일하게 수행하여 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole을 합성하였다.In the same manner as in <Step 1> of Preparation Example 1, 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole was synthesized.
<단계 2> 5-(5-bromo-2-nitrophenyl)-1H-indole의 합성<Step 2> Synthesis of 5- (5-bromo-2-nitrophenyl) -1H-indole
Figure PCTKR2013007821-appb-I000059
Figure PCTKR2013007821-appb-I000059
준비예 1의 <단계 2>에서 사용된 1-bromo-2-nitrobenzene 대신 2,4-dibromo-1-nitrobenzene (21.04 g, 75.41 mmol)을 사용하는 것을 제외하고는, 준비예 1의 <단계 2>와 동일한 과정을 수행하여 5-(5-bromo-2-nitrophenyl)-1H-indole을 얻었다.<Step 2 of Preparation Example 1, except that 2,4-dibromo-1-nitrobenzene (21.04 g, 75.41 mmol) was used instead of 1-bromo-2-nitrobenzene used in <Step 2> of Preparation Example 1 > And the same process as in the 5- (5-bromo-2-nitrophenyl) -1H-indole was obtained.
1H NMR: δ 6.45 (d, 1H), 7.26 (d, 1H), 7.45 (d, 1H), 7.55 (d, 1H), 7.64 (d, 1H), 7.85 (d, 1H), 7.96 (s, 1H), 8.13 (s, 1H), 8.21 (s, 1H) 1 H NMR: δ 6.45 (d, 1H), 7.26 (d, 1H), 7.45 (d, 1H), 7.55 (d, 1H), 7.64 (d, 1H), 7.85 (d, 1H), 7.96 (s , 1H), 8.13 (s, 1H), 8.21 (s, 1H)
<단계 3> 5-(5-bromo-2-nitrophenyl)-1-phenyl-1H-indole의 합성<Step 3> Synthesis of 5- (5-bromo-2-nitrophenyl) -1-phenyl-1H-indole
Figure PCTKR2013007821-appb-I000060
Figure PCTKR2013007821-appb-I000060
준비예 1의 <단계 3>에서 사용된 5-(2-nitrophenyl)-1H-indole 대신 상기 준비예 5의 <단계 2>에서 얻은 5-(5-bromo-2-nitrophenyl)-1H-indole (14.59 g, 46.17 mmol)을 사용하는 것을 제외하고는, 준비예 1의 <단계 3>과 동일한 과정을 수행하여 5-(5-bromo-2-nitrophenyl)-1-phenyl-1H-indole을 얻었다.Instead of 5- (2-nitrophenyl) -1H-indole used in <Step 3> of Preparation Example 1, 5- (5-bromo-2-nitrophenyl) -1H-indole ( 14.59 g, 46.17 mmol) was used in the same manner as in <Step 3> of Preparation Example 1 to obtain 5- (5-bromo-2-nitrophenyl) -1-phenyl-1H-indole.
1H NMR: δ 6.44 (d, 1H), 7.25 (d, 1H), 7.46 (m, 3H), 7.56 (m, 4H), 7.65 (d, 1H), 7.86 (d, 1H), 7.95 (s, 1H), 8.11 (s, 1H) 1 H NMR: δ 6.44 (d, 1H), 7.25 (d, 1H), 7.46 (m, 3H), 7.56 (m, 4H), 7.65 (d, 1H), 7.86 (d, 1H), 7.95 (s , 1H), 8.11 (s, 1H)
<단계 4> 화합물 IC-7의 합성Step 4 Synthesis of Compound IC-7
Figure PCTKR2013007821-appb-I000061
Figure PCTKR2013007821-appb-I000061
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 5의 <단계 3>에서 얻은 5-(5-bromo-2-nitrophenyl)-1-phenyl-1H-indole (6.24 g, 15.91 mmol)을 사용하는 것을 제외하고는, 준비예 1의 <단계 4>와 동일한 과정을 수행하여 화합물 IC-7을 얻었다.5- (5-bromo-2-nitrophenyl)-obtained in <Step 3> of Preparation Example 5 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 Except for using 1-phenyl-1H-indole (6.24 g, 15.91 mmol), Compound IC-7 was obtained by the same procedure as <Step 4> of Preparation Example 1.
1H-NMR: δ 6.45 (d, 1H), 7.26 (d, 1H), 7.38 (m, 2H), 7.45 (d, 1H), 7.51 (d, 1H), 7.57 (m, 3H), 7.64 (d, 1H), 7.85 (d, 1H), 8.10 (s, 1H), 8.23 (s, 1H) 1 H-NMR: δ 6.45 (d, 1H), 7.26 (d, 1H), 7.38 (m, 2H), 7.45 (d, 1H), 7.51 (d, 1H), 7.57 (m, 3H), 7.64 ( d, 1H), 7.85 (d, 1H), 8.10 (s, 1H), 8.23 (s, 1H)
[준비예 6] 화합물 IC-8의 합성Preparation Example 6 Synthesis of Compound IC-8
<단계 1> 6-(5-bromo-2-nitrophenyl)-1H-indole의 합성<Step 1> Synthesis of 6- (5-bromo-2-nitrophenyl) -1H-indole
Figure PCTKR2013007821-appb-I000062
Figure PCTKR2013007821-appb-I000062
준비예 1의 <단계 2>에서 사용된 1-bromo-2-nitrobenzene 대신 2,4-dibromo-1-nitrobenzene (21.11 g, 75.41 mmol)을 사용하고, 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole 대신 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole (22 g, 90.49 mmol)을 사용하는 것을 제외하고는, 준비예 1의 <단계 2>와 동일한 과정을 수행하여 6-(5-bromo-2-nitrophenyl)-1H-indole을 얻었다.2,4-dibromo-1-nitrobenzene (21.11 g, 75.41 mmol) was used instead of 1-bromo-2-nitrobenzene used in <Step 2> of Preparation Example 1, and 5- (4,4,5,5- tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole instead of 6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole (22 g, 90.49 mmol) was used in the same manner as in <Step 2> of Preparation Example 1 to obtain 6- (5-bromo-2-nitrophenyl) -1H-indole.
1H NMR: δ 6.51 (d, 1H), 7.31 (d, 1H), 7.50 (d, 1H), 7.60 (d, 1H), 7.69 (d, 1H), 7.90 (d, 1H), 8.01 (s, 1H), 8.14 (s, 1H), 8.25 (s, 1H) 1 H NMR: δ 6.51 (d, 1H), 7.31 (d, 1H), 7.50 (d, 1H), 7.60 (d, 1H), 7.69 (d, 1H), 7.90 (d, 1H), 8.01 (s , 1H), 8.14 (s, 1H), 8.25 (s, 1H)
<단계 2> 6-(5-bromo-2-nitrophenyl)-1-phenyl-1H-indole의 합성<Step 2> Synthesis of 6- (5-bromo-2-nitrophenyl) -1-phenyl-1H-indole
Figure PCTKR2013007821-appb-I000063
Figure PCTKR2013007821-appb-I000063
준비예 1의 <단계 3>에서 사용된 5-(2-nitrophenyl)-1H-indole 대신 상기 준비예 6의 <단계 1>에서 얻은 6-(5-bromo-2-nitrophenyl)-1H-indole (14.59 g, 46.17 mmol)을 사용하는 것을 제외하고는 준비예 1의 <단계 3>과 동일한 과정을 수행하여 6-(5-bromo-2-nitrophenyl)-1-phenyl-1H-indole을 얻었다.Instead of 5- (2-nitrophenyl) -1H-indole used in <Step 3> of Preparation Example 1, 6- (5-bromo-2-nitrophenyl) -1H-indole ( 14.59 g, 46.17 mmol) was obtained in the same manner as in <Step 3> of Preparation Example 1, to obtain 6- (5-bromo-2-nitrophenyl) -1-phenyl-1H-indole.
1H NMR: δ 6.49 (d, 1H), 7.30 (d, 1H), 7.51 (m, 3H), 7.61 (m, 4H), 7.70 (d, 1H), 7.91 (d, 1H), 8.00 (s, 1H), 8.16 (s, 1H) 1 H NMR: δ 6.49 (d, 1H), 7.30 (d, 1H), 7.51 (m, 3H), 7.61 (m, 4H), 7.70 (d, 1H), 7.91 (d, 1H), 8.00 (s , 1H), 8.16 (s, 1H)
<단계 3> 화합물 IC-8의 합성Step 3 Synthesis of Compound IC-8
Figure PCTKR2013007821-appb-I000064
Figure PCTKR2013007821-appb-I000064
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 6의 <단계 2>에서 얻은 6-(5-bromo-2-nitrophenyl)-1-phenyl-1H-indole (6.23 g, 15.91 mmol)을 사용하는 것을 제외하고는, 준비예 1의 <단계 4>와 동일한 과정을 수행하여 화합물 IC-8을 얻었다.6- (5-bromo-2-nitrophenyl)-obtained in <Step 2> of Preparation Example 6 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 Except for using 1-phenyl-1H-indole (6.23 g, 15.91 mmol), the compound IC-8 was obtained by the same procedure as <Step 4> of Preparation Example 1.
1H-NMR: δ 6.47 (d, 1H), 7.28 (d, 1H), 7.40 (m, 2H), 7.47 (d, 1H), 7.53 (d, 1H), 7.59 (m, 3H), 7.66 (d, 1H), 7.87 (d, 1H), 8.12 (s, 1H), 8.25 (s, 1H) 1 H-NMR: δ 6.47 (d, 1H), 7.28 (d, 1H), 7.40 (m, 2H), 7.47 (d, 1H), 7.53 (d, 1H), 7.59 (m, 3H), 7.66 ( d, 1H), 7.87 (d, 1H), 8.12 (s, 1H), 8.25 (s, 1H)
[준비예 7] 화합물 IC-9의 합성Preparation Example 7 Synthesis of Compound IC-9
<단계 1> 5-(2-nitrophenyl)-1-o-tolyl-1H-indole의 합성<Step 1> Synthesis of 5- (2-nitrophenyl) -1-o-tolyl-1H-indole
Figure PCTKR2013007821-appb-I000065
Figure PCTKR2013007821-appb-I000065
준비예 1의 <단계 3>에서 사용된 Iodobenzene 대신 1-bromo-2-methylbenzene (11.77 g, 69.26 mmol)을 사용하는 것을 제외하고는, 준비예 1의 <단계 3>과 동일한 과정을 수행하여 5-(2-nitrophenyl)-1-o-tolyl-1H-indole을 얻었다.Except for using 1-bromo-2-methylbenzene (11.77 g, 69.26 mmol) instead of Iodobenzene used in <step 3> of Preparation Example 1 was carried out in the same manner as in <Step 3> of Preparation Example 1 -(2-nitrophenyl) -1-o-tolyl-1H-indole was obtained.
1H-NMR: δ 1.92 (s, 3H), 6.47 (d, 1H), 7.25 (d, 1H), 7.46 (m, 3H), 7.56 (m, 3H), 7.64 (t, 1H), 7.85 (t, 1H), 7.94 (s, 1H), 8.00 (d, 1H), 8.12 (t, 1H) 1 H-NMR: δ 1.92 (s, 3H), 6.47 (d, 1H), 7.25 (d, 1H), 7.46 (m, 3H), 7.56 (m, 3H), 7.64 (t, 1H), 7.85 ( t, 1H), 7.94 (s, 1H), 8.00 (d, 1H), 8.12 (t, 1H)
<단계 2> 화합물 IC-9 의 합성<Step 2> Synthesis of Compound IC-9
Figure PCTKR2013007821-appb-I000066
Figure PCTKR2013007821-appb-I000066
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 7의 <단계 1>에서 얻은 5-(2-nitrophenyl)-1-o-tolyl-1H-indole (5.22 g, 15.91 mmol)을 사용하는 것을 제외하고는, 준비예 1의 <단계 4>와 동일한 과정을 수행하여 화합물 IC-9를 얻었다.5- (2-nitrophenyl) -1-o- obtained in <Step 1> of Preparation Example 7 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 Except for using tolyl-1H-indole (5.22 g, 15.91 mmol), the compound IC-9 was obtained by the same procedure as <Step 4> of Preparation Example 1.
1H-NMR: δ 1.93 (s, 3H), 6.98 (d, 1H), 7.11 (t, 1H), 7.28 (t, 1H), 7.31 (d, 1H), 7.42 (t, 1H), 7.51 (d, 1H), 7.61 (m, 4H), 7.86 (d, 1H), 8.01 (d, 1H), 10.58 (s, 1H) 1 H-NMR: δ 1.93 (s, 3H), 6.98 (d, 1H), 7.11 (t, 1H), 7.28 (t, 1H), 7.31 (d, 1H), 7.42 (t, 1H), 7.51 ( d, 1H), 7.61 (m, 4H), 7.86 (d, 1H), 8.01 (d, 1H), 10.58 (s, 1H)
[준비예 8] 화합물 IC-10의 합성Preparation Example 8 Synthesis of Compound IC-10
<단계 1> 1-(biphenyl-4-yl)-5-(2-nitrophenyl)-1H-indole의 합성<Step 1> Synthesis of 1- (biphenyl-4-yl) -5- (2-nitrophenyl) -1H-indole
Figure PCTKR2013007821-appb-I000067
Figure PCTKR2013007821-appb-I000067
준비예 1의 <단계 3>에서 사용된 Iodobenzene 대신 4-bromobiphenyl (16.07 g, 69.26 mmol)을 사용하는 것을 제외하고는, 준비예 1의 <단계 3>과 동일한 과정을 수행하여 1-(biphenyl-4-yl)-5-(2-nitrophenyl)-1H-indole을 얻었다.Except for using 4-bromobiphenyl (16.07 g, 69.26 mmol) instead of Iodobenzene used in <step 3> of Preparation Example 1 was carried out the same process as <step 3> of Preparation Example 1 1- (biphenyl- 4-yl) -5- (2-nitrophenyl) -1H-indole was obtained.
1H-NMR: δ 6.73 (d, 1H), 7.18 (d, 1H), 7.39 (m, 2H), 7.47 (m, 3H), 7.54 (d, 1H), 7.59 (m, 3H), 7.64 (m, 4H), 7.75 (d, 2H), 7.82 (d, 1H) 1 H-NMR: δ 6.73 (d, 1H), 7.18 (d, 1H), 7.39 (m, 2H), 7.47 (m, 3H), 7.54 (d, 1H), 7.59 (m, 3H), 7.64 ( m, 4H), 7.75 (d, 2H), 7.82 (d, 1H)
<단계 2> 화합물 IC-10의 합성Step 2 Synthesis of Compound IC-10
Figure PCTKR2013007821-appb-I000068
Figure PCTKR2013007821-appb-I000068
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 8의 <단계 1>에서 얻은 1-(biphenyl-4-yl)-5-(2-nitrophenyl)-1H-indole (6.20 g, 15.91 mmol)을 사용하는 것을 제외하고는, 준비예 1의 <단계 4>와 동일한 과정을 수행하여 화합물 IC-10를 얻었다.1- (biphenyl-4-yl) -5- obtained in <Step 1> of Preparation Example 8 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 Except for using (2-nitrophenyl) -1H-indole (6.20 g, 15.91 mmol), Compound IC-10 was obtained by the same procedure as <Step 4> of Preparation Example 1.
1H-NMR: δ 6.75 (d, 1H), 7.20 (d, 1H), 7.42 (m, 2H), 7.51 (m, 3H), 7.56 (d, 1H), 7.62 (m, 3H), 7.68 (m, 3H), 7.76 (d, 2H), 7.85 (d, 1H), 10.45 (s, 1H) 1 H-NMR: δ 6.75 (d, 1H), 7.20 (d, 1H), 7.42 (m, 2H), 7.51 (m, 3H), 7.56 (d, 1H), 7.62 (m, 3H), 7.68 ( m, 3H), 7.76 (d, 2H), 7.85 (d, 1H), 10.45 (s, 1H)
[준비예 9] 화합물 IC-11의 합성Preparation Example 9 Synthesis of Compound IC-11
<단계 1> 화합물 IC-11-1의 합성Step 1 Synthesis of Compound IC-11-1
Figure PCTKR2013007821-appb-I000069
Figure PCTKR2013007821-appb-I000069
준비예 1의 <단계 3>에서 사용된 Iodobenzene 대신 1-bromo-3,5-diphenyl benzene (21.33 g, 69.26 mmol)을 사용하는 것을 제외하고는, 준비예 1의 <단계 3>과 동일한 과정을 수행하여 화합물 IC-11-1을 얻었다.The same procedure as in <Step 3> of Preparation Example 1 was performed except that 1-bromo-3,5-diphenyl benzene (21.33 g, 69.26 mmol) was used instead of Iodobenzene used in <Step 3> of Preparation Example 1. This was carried out to obtain compound IC-11-1.
1H-NMR: δ 6.98 (d, 1H), 7.11 (t, 1H), 7.24 (t, 1H), 7.38 (t, 2H), 7.46 (m, 6H), 7.58 (d, 1H), 7.81 (d, 4H), 7.87 (m, 4H), 7.93 (d, 1H), 7.99 (d, 1H) 1 H-NMR: δ 6.98 (d, 1H), 7.11 (t, 1H), 7.24 (t, 1H), 7.38 (t, 2H), 7.46 (m, 6H), 7.58 (d, 1H), 7.81 ( d, 4H), 7.87 (m, 4H), 7.93 (d, 1H), 7.99 (d, 1H)
<단계 2> 화합물 IC-11의 합성Step 2 Synthesis of Compound IC-11
Figure PCTKR2013007821-appb-I000070
Figure PCTKR2013007821-appb-I000070
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 9의 <단계 1>에서 얻은 화합물 IC-11-1 (7.41 g, 15.91 mmol)을 사용하는 것을 제외하고는, 준비예 1의 <단계 4>와 동일한 과정을 수행하여 화합물 IC-11를 얻었다.Compound IC-11-1 obtained in <Step 1> of Preparation Example 9 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 (7.41 g, 15.91 mmol Except for using), the same procedure as in <Step 4> of Preparation Example 1 to obtain a compound IC-11.
1H-NMR: δ 6.97 (d, 1H), 7.10 (t, 1H), 7.23 (t, 1H), 7.37 (t, 2H), 7.45 (m, 6H), 7.58 (d, 1H), 7.80 (d, 4H), 7.86 (m, 3H), 7.92 (d, 1H), 7.98 (d, 1H), 10.60 (s, 1H) 1 H-NMR: δ 6.97 (d, 1H), 7.10 (t, 1H), 7.23 (t, 1H), 7.37 (t, 2H), 7.45 (m, 6H), 7.58 (d, 1H), 7.80 ( d, 4H), 7.86 (m, 3H), 7.92 (d, 1H), 7.98 (d, 1H), 10.60 (s, 1H)
[준비예 10] 화합물 IC-12의 합성Preparation Example 10 Synthesis of Compound IC-12
<단계 1> 5-(2-nitrophenyl)-1-(2-(trifluoromethyl)phenyl)-1H-indole의 합성<Step 1> Synthesis of 5- (2-nitrophenyl) -1- (2- (trifluoromethyl) phenyl) -1H-indole
Figure PCTKR2013007821-appb-I000071
Figure PCTKR2013007821-appb-I000071
준비예 1의 <단계 3>에서 사용된 Iodobenzene 대신 1-bromo-2-(trifluoromethyl)benzene (15.58 g, 69.26 mmol)을 사용하는 것을 제외하고는 준비예 1의 <단계 3>과 동일한 과정을 수행하여 5-(2-nitrophenyl)-1-(2-(trifluoromethyl)phenyl)-1H-indole을 얻었다.The same procedure as in <Step 3> of Preparation Example 1 was performed except that 1-bromo-2- (trifluoromethyl) benzene (15.58 g, 69.26 mmol) was used instead of Iodobenzene used in <Step 3> of Preparation Example 1. 5- (2-nitrophenyl) -1- (2- (trifluoromethyl) phenyl) -1H-indole was obtained.
1H-NMR: δ 6.48 (d, 1H), 7.26 (d, 1H), 7.47 (m, 3H), 7.57 (m, 3H), 7.63 (t, 1H), 7.84 (t, 1H), 7.95 (s, 1H), 8.01 (d, 1H), 8.13 (t, 1H) 1 H-NMR: δ 6.48 (d, 1H), 7.26 (d, 1H), 7.47 (m, 3H), 7.57 (m, 3H), 7.63 (t, 1H), 7.84 (t, 1H), 7.95 ( s, 1H), 8.01 (d, 1H), 8.13 (t, 1H)
<단계 2> 화합물 IC-12의 합성Step 2 Synthesis of Compound IC-12
Figure PCTKR2013007821-appb-I000072
Figure PCTKR2013007821-appb-I000072
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 10의 <단계 1>에서 얻은 5-(2-nitrophenyl)-1-(2-(trifluoromethyl)phenyl)-1H-indole (6.23 g, 15.91 mmol)을 사용하는 것을 제외하고는, 준비예 1의 <단계 4>와 동일한 과정을 수행하여 화합물 IC-12를 얻었다.5- (2-nitrophenyl) -1- (2 obtained in <Step 1> of Preparation Example 10 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 Compound IC-12 was obtained by the same procedure as <Step 4> of Preparation Example 1, except that-(trifluoromethyl) phenyl) -1H-indole (6.23 g, 15.91 mmol) was used.
1H-NMR: δ 6.97 (d, 1H), 7.12 (t, 1H), 7.29 (t, 1H), 7.32 (d, 1H), 7.41 (t, 1H), 7.52 (d, 1H), 7.60 (m, 4H), 7.85 (d, 1H), 8.01 (d, 1H), 10.57 (s, 1H) 1 H-NMR: δ 6.97 (d, 1H), 7.12 (t, 1H), 7.29 (t, 1H), 7.32 (d, 1H), 7.41 (t, 1H), 7.52 (d, 1H), 7.60 ( m, 4H), 7.85 (d, 1H), 8.01 (d, 1H), 10.57 (s, 1H)
[준비예 11] 화합물 IC-13의 합성Preparation Example 11 Synthesis of Compound IC-13
<단계 1> 1-(biphenyl-3-yl)-5-(2-nitrophenyl)-1H-indole의 합성<Step 1> Synthesis of 1- (biphenyl-3-yl) -5- (2-nitrophenyl) -1H-indole
Figure PCTKR2013007821-appb-I000073
Figure PCTKR2013007821-appb-I000073
준비예 1의 <단계 3>에서 사용된 Iodobenzene 대신 3-bromobiphenyl (16.07 g, 69.26 mmol)을 사용하는 것을 제외하고는, 준비예 1의 <단계 3>과 동일한 과정을 수행하여 5-(2-nitrophenyl)-1-(2-(trifluoromethyl)phenyl)-1H-indole을 얻었다.Except for using 3-bromobiphenyl (16.07 g, 69.26 mmol) instead of Iodobenzene used in <step 3> of Preparation Example 1, 5- (2- nitrophenyl) -1- (2- (trifluoromethyl) phenyl) -1H-indole was obtained.
1H-NMR: δ 6.75 (d, 1H), 7.19 (d, 1H), 7.38 (m, 2H), 7.48 (m, 3H), 7.52 (d, 1H), 7.58 (m, 3H), 7.65 (m, 4H), 7.76 (m, 2H), 7.85 (d, 1H) 1 H-NMR: δ 6.75 (d, 1H), 7.19 (d, 1H), 7.38 (m, 2H), 7.48 (m, 3H), 7.52 (d, 1H), 7.58 (m, 3H), 7.65 ( m, 4H), 7.76 (m, 2H), 7.85 (d, 1H)
<단계 2> 화합물 IC-13의 합성Step 2 Synthesis of Compound IC-13
Figure PCTKR2013007821-appb-I000074
Figure PCTKR2013007821-appb-I000074
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 11의 <단계 1>에서 얻은 1-(biphenyl-3-yl)-5-(2-nitrophenyl)-1H-indole (6.20 g, 15.91 mmol)을 사용하는 것을 제외하고는 준비예 1의 <단계 4>와 동일한 과정을 수행하여 화합물 IC-13를 얻었다.1- (biphenyl-3-yl) -5- obtained in <Step 1> of Preparation Example 11 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 Compound IC-13 was obtained by the same procedure as <Step 4> of Preparation Example 1, except that (2-nitrophenyl) -1H-indole (6.20 g, 15.91 mmol) was used.
1H-NMR: δ 6.74 (d, 1H), 7.21 (d, 1H), 7.41 (m, 2H), 7.52 (m, 3H), 7.56 (d, 1H), 7.61 (m, 3H), 7.69 (m, 3H), 7.77 (m, 2H), 7.86 (d, 1H), 10.44 (s, 1H) 1 H-NMR: δ 6.74 (d, 1H), 7.21 (d, 1H), 7.41 (m, 2H), 7.52 (m, 3H), 7.56 (d, 1H), 7.61 (m, 3H), 7.69 ( m, 3H), 7.77 (m, 2H), 7.86 (d, 1H), 10.44 (s, 1H)
[준비예 12] 화합물 IC-14의 합성Preparation 12 Synthesis of Compound IC-14
<단계 1> 1-(biphenyl-3-yl)-6-(2-nitrophenyl)-1H-indole의 합성<Step 1> Synthesis of 1- (biphenyl-3-yl) -6- (2-nitrophenyl) -1H-indole
Figure PCTKR2013007821-appb-I000075
Figure PCTKR2013007821-appb-I000075
준비예 1의 <단계 3>에서 사용된 5-(2-nitrophenyl)-1H-indole과 iodobenzene 대신 6-(2-nitrophenyl)-1H-indole과 3-bromobiphenyl (11 g, 46.17 mmol)를 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 3>과 동일한 과정을 수행하여 1-(biphenyl-3-yl)-6-(2-nitrophenyl)-1H-indole을 얻었다.6- (2-nitrophenyl) -1H-indole and 3-bromobiphenyl (11 g, 46.17 mmol) were used instead of 5- (2-nitrophenyl) -1H-indole and iodobenzene used in <Step 3> of Preparation Example 1. Except that, 1- (biphenyl-3-yl) -6- (2-nitrophenyl) -1H-indole was obtained by the same process as <Step 3> of Preparation Example 1.
1H-NMR: δ 6.76 (d, 1H), 7.18 (d, 1H), 7.37 (m, 2H), 7.47 (m, 3H), 7.51 (d, 1H), 7.57 (m, 3H), 7.64 (m, 4H), 7.75 (m, 2H), 7.86 (d, 1H) 1 H-NMR: δ 6.76 (d, 1H), 7.18 (d, 1H), 7.37 (m, 2H), 7.47 (m, 3H), 7.51 (d, 1H), 7.57 (m, 3H), 7.64 ( m, 4H), 7.75 (m, 2H), 7.86 (d, 1H)
<단계 2> 화합물 IC-14의 합성Step 2 Synthesis of Compound IC-14
Figure PCTKR2013007821-appb-I000076
Figure PCTKR2013007821-appb-I000076
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 12의 <단계 1>에서 얻은 1-(biphenyl-3-yl)-6-(2-nitrophenyl)-1H-indole (6.20 g, 15.91 mmol)을 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 4>과 동일한 과정을 수행하여 화합물 IC-14을 얻었다.1- (biphenyl-3-yl) -6- obtained in <Step 1> of Preparation Example 12 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 Except for using (2-nitrophenyl) -1H-indole (6.20 g, 15.91 mmol), Compound IC-14 was obtained by the same process as <Step 4> of Preparation Example 1.
1H-NMR: δ 6.75 (d, 1H), 7.20 (d, 1H), 7.40 (m, 2H), 7.51 (m, 3H), 7.57 (d, 1H), 7.62 (m, 3H), 7.70 (m, 3H), 7.76 (m, 2H), 7.85 (d, 1H), 10.43 (s, 1H) 1 H-NMR: δ 6.75 (d, 1H), 7.20 (d, 1H), 7.40 (m, 2H), 7.51 (m, 3H), 7.57 (d, 1H), 7.62 (m, 3H), 7.70 ( m, 3H), 7.76 (m, 2H), 7.85 (d, 1H), 10.43 (s, 1H)
[준비예 13] 화합물 IC-15의 합성Preparation Example 13 Synthesis of Compound IC-15
<단계 1> 1-(biphenyl-4-yl)-6-(2-nitrophenyl)-1H-indole의 합성<Step 1> Synthesis of 1- (biphenyl-4-yl) -6- (2-nitrophenyl) -1H-indole
Figure PCTKR2013007821-appb-I000077
Figure PCTKR2013007821-appb-I000077
준비예 1의 <단계 3>에서 사용된 5-(2-nitrophenyl)-1H-indole과 iodobenzene 대신 6-(2-nitrophenyl)-1H-indole과 4-bromobiphenyl(11 g, 46.17 mmol)을 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 3>과 동일한 과정을 수행하여 1-(biphenyl-4-yl)-6-(2-nitrophenyl)-1H-indole을 얻었다.6- (2-nitrophenyl) -1H-indole and 4-bromobiphenyl (11 g, 46.17 mmol) were used instead of 5- (2-nitrophenyl) -1H-indole and iodobenzene used in <Step 3> of Preparation Example 1. Except that, 1- (biphenyl-4-yl) -6- (2-nitrophenyl) -1H-indole was obtained by the same process as <Step 3> of Preparation Example 1.
1H-NMR: δ 6.74 (d, 1H), 7.19 (d, 1H), 7.40 (m, 2H), 7.46 (m, 3H), 7.55 (d, 1H), 7.58 (m, 3H), 7.63 (m, 4H), 7.75 (d, 2H), 7.83 (d, 1H) 1 H-NMR: δ 6.74 (d, 1H), 7.19 (d, 1H), 7.40 (m, 2H), 7.46 (m, 3H), 7.55 (d, 1H), 7.58 (m, 3H), 7.63 ( m, 4H), 7.75 (d, 2H), 7.83 (d, 1H)
<단계 2> 화합물 IC-15의 합성Step 2 Synthesis of Compound IC-15
Figure PCTKR2013007821-appb-I000078
Figure PCTKR2013007821-appb-I000078
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 13의 <단계 1>에서 얻은 1-(biphenyl-4-yl)-6-(2-nitrophenyl)-1H-indole (6.20 g, 15.91 mmol)을 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 4>과 동일한 과정을 수행하여 화합물 화합물 IC-15을 얻었다.1- (biphenyl-4-yl) -6- obtained in <Step 1> of Preparation Example 13 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 Except for using (2-nitrophenyl) -1H-indole (6.20 g, 15.91 mmol), was prepared in the same manner as in <Step 4> of Preparation Example 1 to obtain a compound compound IC-15.
1H-NMR: δ 6.74 (d, 1H), 7.19 (d, 1H), 7.43 (m, 2H), 7.52 (m, 3H), 7.57 (d, 1H), 7.63 (m, 3H), 7.69 (m, 3H), 7.75 (d, 2H), 7.86 (d, 1H), 10.46 (s, 1H) 1 H-NMR: δ 6.74 (d, 1H), 7.19 (d, 1H), 7.43 (m, 2H), 7.52 (m, 3H), 7.57 (d, 1H), 7.63 (m, 3H), 7.69 ( m, 3H), 7.75 (d, 2H), 7.86 (d, 1H), 10.46 (s, 1H)
[준비예 14] 화합물 IC-16의 합성Preparation 14 Synthesis of Compound IC-16
<단계 1> 화합물 IC-16-1의 합성Step 1 Synthesis of Compound IC-16-1
Figure PCTKR2013007821-appb-I000079
Figure PCTKR2013007821-appb-I000079
준비예 1의 <단계 3>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 6-(2-nitrophenyl)-1H-indole (11 g, 46.17 mmol)을 사용하고, iodobenzene 대신 1-bromo-3,5-diphenyl benzene (14.13 g, 69.26 mmol)을 사용하는 것을 제외하고는, 준비예 1의 <단계 3>과 동일한 과정을 수행하여 화합물-16-1을 얻었다.6- (2-nitrophenyl) -1H-indole (11 g, 46.17 mmol) was used instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 3> of Preparation Example 1, iodobenzene Instead of using 1-bromo-3,5-diphenyl benzene (14.13 g, 69.26 mmol) instead, the same process as in <Step 3> of Preparation Example 1 to obtain a compound-16-1.
1H-NMR: δ 6.98 (d, 1H), 7.11 (t, 1H), 7.24 (t, 1H), 7.38 (m, 2H), 7.45 (m, 6H), 7.57 (d, 1H), 7.80 (d, 4H), 7.86 (m, 4H), 7.92 (d, 1H), 7.98 (d, 1H) 1 H-NMR: δ 6.98 (d, 1H), 7.11 (t, 1H), 7.24 (t, 1H), 7.38 (m, 2H), 7.45 (m, 6H), 7.57 (d, 1H), 7.80 ( d, 4H), 7.86 (m, 4H), 7.92 (d, 1H), 7.98 (d, 1H)
<단계 2> 화합물 IC-16의 합성Step 2 Synthesis of Compound IC-16
Figure PCTKR2013007821-appb-I000080
Figure PCTKR2013007821-appb-I000080
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 14의 <단계 1>에서 얻은 IC-16-1 (7.41 g, 15.91 mmol)을 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 4>과 동일한 과정을 수행하여 화합물 IC-16을 얻었다.IC-16-1 obtained in <Step 1> of Preparation Example 14 (7.41 g, 15.91 mmol) instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 Except for using, the same procedure as in <Step 4> of Preparation Example 1 to obtain a compound IC-16.
1H-NMR: δ 6.97 (d, 1H), 7.10 (t, 1H), 7.23 (t, 1H), 7.37 (t, 2H), 7.45 (m, 6H), 7.58 (d, 1H), 7.80 (d, 4H), 7.86 (m, 3H), 7.92 (d, 1H), 7.98 (d, 1H), 10.59 (s, 1H) 1 H-NMR: δ 6.97 (d, 1H), 7.10 (t, 1H), 7.23 (t, 1H), 7.37 (t, 2H), 7.45 (m, 6H), 7.58 (d, 1H), 7.80 ( d, 4H), 7.86 (m, 3H), 7.92 (d, 1H), 7.98 (d, 1H), 10.59 (s, 1H)
[준비예 15] 화합물 IC-17의 합성Preparation 15 Synthesis of Compound IC-17
<단계 1> 6-(2-nitrophenyl)-1-(3-(trifluoromethyl)phenyl)-1H-indole의 합성<Step 1> Synthesis of 6- (2-nitrophenyl) -1- (3- (trifluoromethyl) phenyl) -1H-indole
Figure PCTKR2013007821-appb-I000081
Figure PCTKR2013007821-appb-I000081
준비예 1의 <단계 3>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole과 iodobenzene 대신 6-(2-nitrophenyl)-1H-indole과 1-bromo-3-(trifluoromethyl)benzene (11 g, 46.17 mmol)을 사용하는 것을 제외하고는, 준비예 1의 <단계 3>과 동일한 과정을 수행하여 6-(2-nitrophenyl)-1-(3-(trifluoromethyl)phenyl)-1H-indole을 얻었다.6- (2-nitrophenyl) -1H-indole and 1-bromo-3- (trifluoromethyl) instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole and iodobenzene used in <Step 3> of Preparation Example 1 Except for using benzene (11 g, 46.17 mmol), 6- (2-nitrophenyl) -1- (3- (trifluoromethyl) phenyl) -1H was carried out in the same manner as in <Step 3> of Preparation Example 1. got -indole
1H-NMR: δ 6.80 (d, 1H), 7.11 (t, 1H), 7.21 (t, 1H), 7.36 (s, 1H), 7.42 (s, 1H), 7.50 (m, 2H), 7.55 (m, 2H), 7.63 (m, 2H), 7.86 (d, 1H), 8.01 (d, 1H) 1 H-NMR: δ 6.80 (d, 1H), 7.11 (t, 1H), 7.21 (t, 1H), 7.36 (s, 1H), 7.42 (s, 1H), 7.50 (m, 2H), 7.55 ( m, 2H), 7.63 (m, 2H), 7.86 (d, 1H), 8.01 (d, 1H)
<단계 2> 화합물 IC-17의 합성Step 2 Synthesis of Compound IC-17
Figure PCTKR2013007821-appb-I000082
Figure PCTKR2013007821-appb-I000082
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 15의 <단계 1>에서 얻은 6-(2-nitrophenyl)-1-(3-(trifluoromethyl)phenyl)-1H-indole (6.07 g, 15.91 mmol)을 사용하는 것을 제외하고는 상기 준비예 1의 <단계 4>과 동일한 과정을 수행하여 화합물 IC-17을 얻었다.6- (2-nitrophenyl) -1- (3 obtained in <Step 1> of Preparation Example 15 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 Compound IC-17 was obtained by the same procedure as <Step 4> of Preparation Example 1, except that-(trifluoromethyl) phenyl) -1H-indole (6.07 g, 15.91 mmol) was used.
1H-NMR: δ 6.81 (d, 1H), 7.12 (t, 1H), 7.24 (t, 1H), 7.43 (d, 1H), 7.51 (m, 2H), 7.58 (m, 2H), 7.64 (m, 2H), 7.85 (d, 1H), 8.02 (d, 1H), 9.82 (s, 1H) 1 H-NMR: δ 6.81 (d, 1H), 7.12 (t, 1H), 7.24 (t, 1H), 7.43 (d, 1H), 7.51 (m, 2H), 7.58 (m, 2H), 7.64 ( m, 2H), 7.85 (d, 1H), 8.02 (d, 1H), 9.82 (s, 1H)
[준비예 16] 화합물 IC-18의 합성Preparation 16 Synthesis of Compound IC-18
<단계 1> 3-(5-(2-nitrophenyl)-1H-indol-1-yl)-9-phenyl-9H-carbazole의 합성<Step 1> Synthesis of 3- (5- (2-nitrophenyl) -1H-indol-1-yl) -9-phenyl-9H-carbazole
Figure PCTKR2013007821-appb-I000083
Figure PCTKR2013007821-appb-I000083
준비예 1의 <단계 3>에서 사용된 5-(2-nitrophenyl)-1H-indole과 Iodobenzene 대신 6-(2-nitrophenyl)-1H-indole (11 g, 46.17 mmol)과 3-bromo-9-phenyl-9H-carbazole (22.30 g, 69.26 mmol)을 사용하는 것을 제외하고는, 준비예 1의 <단계 3>과 동일한 과정을 수행하여 3-(5-(2-nitrophenyl)-1H-indol-1-yl)-9-phenyl-9H-carbazole을 얻었다.6- (2-nitrophenyl) -1H-indole (11 g, 46.17 mmol) and 3-bromo-9- instead of 5- (2-nitrophenyl) -1H-indole and Iodobenzene used in <Step 3> of Preparation Example 1 Except for using phenyl-9H-carbazole (22.30 g, 69.26 mmol), was subjected to the same process as in <Step 3> of Preparation Example 1 to 3- (5- (2-nitrophenyl) -1H-indol-1 -yl) -9-phenyl-9H-carbazole was obtained.
GC-Mass (이론치: 479.16 g/mol, 측정치: 479 g/mol)GC-Mass (Theoretical value: 479.16 g / mol, Measured value: 479 g / mol)
<단계 2> 화합물 IC-18의 합성Step 2 Synthesis of Compound IC-18
Figure PCTKR2013007821-appb-I000084
Figure PCTKR2013007821-appb-I000084
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 16의 <단계 1>에서 얻은 3-(5-(2-nitrophenyl)-1H-indol-1-yl)-9-phenyl-9H-carbazole (7.62 g, 15.91 mmol)을 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 4>과 동일한 과정을 수행하여 화합물 IC-18을 얻었다.3- (5- (2-nitrophenyl) -1H obtained in <Step 1> of Preparation Example 16 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 Compound IC-18 was prepared by the same procedure as in <Step 4> of Preparation Example 1, except that -indol-1-yl) -9-phenyl-9H-carbazole (7.62 g, 15.91 mmol) was used. Got it.
GC-Mass (이론치: 447.17 g/mol, 측정치: 447 g/mol)GC-Mass (Theoretical value: 447.17 g / mol, Measured value: 447 g / mol)
[준비예 17] 화합물 IC-19의 합성Preparation 17 Synthesis of Compound IC-19
<단계 1> 9-(4,6-diphenyl-1,3,5-triazin-2-yl)-3-(5-(2-nitrophenyl)-1H-indol-1-yl)-9H-carbazole의 합성<Step 1> of 9- (4,6-diphenyl-1,3,5-triazin-2-yl) -3- (5- (2-nitrophenyl) -1H-indol-1-yl) -9H-carbazole synthesis
Figure PCTKR2013007821-appb-I000085
Figure PCTKR2013007821-appb-I000085
준비예 1의 <단계 3>에서 사용된 5-(2-nitrophenyl)-1H-indole 대신 6-(2-nitrophenyl)-1H-indole (11 g, 46.17 mmol)을 사용하고, Iodobenzene 대신 3-bromo-9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9H-carbazole (33.03 g, 69.26 mmol)을 사용하는 것을 제외하고는, 준비예 1의 <단계 3>과 동일한 과정을 수행하여 9-(4,6-diphenyl-1,3,5-triazin-2-yl)-3-(5-(2-nitrophenyl)-1H-indol-1-yl)-9H-carbazole을 얻었다.6- (2-nitrophenyl) -1H-indole (11 g, 46.17 mmol) was used instead of 5- (2-nitrophenyl) -1H-indole used in <Step 3> of Preparation Example 1, and 3-bromo instead of Iodobenzene <Step 3> of Preparation Example 1, except that -9- (4,6-diphenyl-1,3,5-triazin-2-yl) -9H-carbazole (33.03 g, 69.26 mmol) was used. 9- (4,6-diphenyl-1,3,5-triazin-2-yl) -3- (5- (2-nitrophenyl) -1H-indol-1-yl) -9H-carbazole Got.
GC-Mass (이론치: 634.21 g/mol, 측정치: 634 g/mol)GC-Mass (Theoretical value: 634.21 g / mol, Measured value: 634 g / mol)
<단계 2> 3-(9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9H-carbazol-3-yl)-3,10-dihydropyrrolo[3,2-a]carbazole의 합성<Step 2> 3- (9- (4,6-diphenyl-1,3,5-triazin-2-yl) -9H-carbazol-3-yl) -3,10-dihydropyrrolo [3,2-a] Synthesis of carbazole
Figure PCTKR2013007821-appb-I000086
Figure PCTKR2013007821-appb-I000086
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 17의 <단계 1>에서 얻은 9-(4,6-diphenyl-1,3,5-triazin-2-yl)-3-(5-(2-nitrophenyl)-1H-indol-1-yl)-9H-carbazole (10.09 g, 15.91 mmol)을 사용하는 것을 제외하고는 상기 준비예 1의 <단계 4>과 동일한 과정을 수행하여 화합물 IC-19을 얻었다.9- (4,6-diphenyl-1,3 obtained in <Step 1> of Preparation Example 17 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 Preparation Example, except that, 5-triazin-2-yl) -3- (5- (2-nitrophenyl) -1H-indol-1-yl) -9H-carbazole (10.09 g, 15.91 mmol) was used Compound IC-19 was obtained by the same procedure as <Step 4> of 1.
GC-Mass (이론치: 602.22 g/mol, 측정치: 602 g/mol)GC-Mass (Theoretical value: 602.22 g / mol, Measured value: 602 g / mol)
[준비예 18] 화합물 IC-20의 합성Preparation 18 Synthesis of Compound IC-20
<단계 1> 5-bromo-2-phenyl-1H-indole의 합성<Step 1> Synthesis of 5-bromo-2-phenyl-1H-indole
Figure PCTKR2013007821-appb-I000087
Figure PCTKR2013007821-appb-I000087
질소 기류 하에서 5-bromo-1H-indole (25 g, 0.13 mol), Iodobenzene (31.22 g, 0.15 mol), Pd(OAc)2 (1.43 g, 5 mol%), Triphenylphosphine (1.67 g, 5 mol%), KOAc (37.55 g, 0.38 mol) 및 H2O (300 ml)를 혼합한 다음, 110 ℃에서 24시간 동안 교반하였다.5-bromo-1H-indole (25 g, 0.13 mol), Iodobenzene (31.22 g, 0.15 mol), Pd (OAc) 2 (1.43 g, 5 mol%), Triphenylphosphine (1.67 g, 5 mol%) under nitrogen stream , KOAc (37.55 g, 0.38 mol) and H 2 O (300 ml) were mixed and then stirred at 110 ° C. for 24 hours.
반응이 종결된 후 에틸아세테이트로 추출한 다음, MgSO4로 수분을 제거하고, 컬럼크로마토그래피 (Hexane:EA = 10:1 (v/v))로 정제하여 5-bromo-2-phenyl-1H-indole (16.66 g, 수율 48%)을 얻었다. After the reaction was completed, the resultant was extracted with ethyl acetate, followed by removing water with MgSO 4 , and purified by column chromatography (Hexane: EA = 10: 1 (v / v)) to obtain 5-bromo-2-phenyl-1H-indole. (16.66 g, yield 48%) was obtained.
1H-NMR: δ 6.89 (dd, 1H), 7.20 (dd, 1H), 7.34 (m, 1H), 7.36 (d, 1H), 7.47 (t, 2H), 7.71 (d, 1H), 7.86 (dd, 2H), 11.74 (s, 1H) 1 H-NMR: δ 6.89 (dd, 1H), 7.20 (dd, 1H), 7.34 (m, 1H), 7.36 (d, 1H), 7.47 (t, 2H), 7.71 (d, 1H), 7.86 ( dd, 2H), 11.74 (s, 1H)
<단계 2> 5-(2-nitrophenyl)-2-phenyl-1H-indole의 합성<Step 2> Synthesis of 5- (2-nitrophenyl) -2-phenyl-1H-indole
Figure PCTKR2013007821-appb-I000088
Figure PCTKR2013007821-appb-I000088
질소 기류 하에서 2-nitrophenylboronic acid (11.04 g, 66.14 mmol)과 상기 준비예 18의 <단계 1>에서 얻은 5-bromo-2-phenyl-1H-indole (15 g, 55.12 mmol), NaOH (6.61 g, 165.36 mmol) 및 THF/H2O(200 ml/100 ml)를 혼합한 다음, 40℃에서 Pd(PPh3)4(3.18 g, 5 mol)를 넣은 후, 80 ℃에서 12시간 동안 교반하였다. 2-nitrophenylboronic acid (11.04 g, 66.14 mmol) under nitrogen stream, 5-bromo-2-phenyl-1H-indole (15 g, 55.12 mmol) obtained in <Step 1> of Preparation Example 18, NaOH (6.61 g, 165.36 mmol) and THF / H 2 O (200 ml / 100 ml) were mixed, and then Pd (PPh 3 ) 4 (3.18 g, 5 mol) was added at 40 ° C., followed by stirring at 80 ° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출한 다음, MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:EA = 5:1 (v/v))로 정제하여 5-(2-nitrophenyl)-2-phenyl-1H-indole (10.74 g, 수율 62%)을 얻었다. After completion of the reaction was extracted with methylene chloride, MgSO 4 was added and filtered. The solvent was removed from the obtained organic layer, and then purified by column chromatography (Hexane: EA = 5: 1 (v / v)) to give 5- (2-nitrophenyl) -2-phenyl-1H-indole (10.74 g, yield 62%). Got.
1H-NMR: δ 6.88 (dd, 1H), 7.21 (d, 1H), 7.32 (m, 1H), 7.34 (d, 1H), 7.46 (m, 3H), 7.64 (m, 2H), 7.77 (d, 2H), 8.02 (d, 2H), 11.73 (s, 1H) 1 H-NMR: δ 6.88 (dd, 1H), 7.21 (d, 1H), 7.32 (m, 1H), 7.34 (d, 1H), 7.46 (m, 3H), 7.64 (m, 2H), 7.77 ( d, 2H), 8.02 (d, 2H), 11.73 (s, 1H)
<단계 3> 5-(2-nitrophenyl)-1,2-diphenyl-1H-indole의 합성<Step 3> Synthesis of 5- (2-nitrophenyl) -1,2-diphenyl-1H-indole
Figure PCTKR2013007821-appb-I000089
Figure PCTKR2013007821-appb-I000089
준비예 1의 <단계 3>에서 사용된 5-(2-nitrophenyl)-1H-indole 대신 상기 준비예 18의 <단계 2>에서 얻은 5-(2-nitrophenyl)-2-phenyl-1H-indole (10.74 g, 34.20 mmol)을 사용하는 것을 제외하고는, 준비예 1의 <단계 3>과 동일한 과정을 수행하여 5-(2-nitrophenyl)-1,2-diphenyl-1H-indole을 얻었다.Instead of 5- (2-nitrophenyl) -1H-indole used in <Step 3> of Preparation Example 1, 5- (2-nitrophenyl) -2-phenyl-1H-indole ( 10.74 g, 34.20 mmol) was used in the same manner as in <Step 3> of Preparation Example 1 to obtain 5- (2-nitrophenyl) -1,2-diphenyl-1H-indole.
GC-Mass (이론치: 390.14 g/mol, 측정치: 390 g/mol)GC-Mass (Theoretical value: 390.14 g / mol, Measured value: 390 g / mol)
<단계 4> 화합물 IC-20의 합성Step 4 Synthesis of Compound IC-20
Figure PCTKR2013007821-appb-I000090
Figure PCTKR2013007821-appb-I000090
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 18의 <단계 3>에서 얻은 5-(2-nitrophenyl)-1,2-diphenyl-1H-indole (9.34 g, 23.94 mmol)을 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 4>과 동일한 과정을 수행하여 화합물 IC-20을 얻었다.5- (2-nitrophenyl) -1,2- obtained in <Step 3> of Preparation Example 18 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 Except for using diphenyl-1H-indole (9.34 g, 23.94 mmol), Compound IC-20 was obtained by the same process as <Step 4> of Preparation Example 1.
GC-Mass (이론치: 358.15 g/mol, 측정치: 358 g/mol)GC-Mass (Theoretical value: 358.15 g / mol, Measured value: 358 g / mol)
[준비예 19] 화합물 IC-21의 합성Preparation Example 19 Synthesis of Compound IC-21
<단계 1> 6-chloro-2-phenyl-1H-indole의 합성<Step 1> Synthesis of 6-chloro-2-phenyl-1H-indole
Figure PCTKR2013007821-appb-I000091
Figure PCTKR2013007821-appb-I000091
준비예 18의 <단계 1>에서 사용된 5-bromo-1H-indole 대신 6-chloro-1H-indole (25 g, 0.13 mol)을 사용하고, Iodobenzene 대신 6-chloro-1H-indole과 bromobenzene (23.55 g, 0.15 mol)을 사용하는 것을 제외하고는, 상기 준비예 20 18의 <단계 1>과 동일한 과정을 수행하여 6-chloro-2-phenyl-1H-indole을 얻었다.6-chloro-1H-indole (25 g, 0.13 mol) was used instead of 5-bromo-1H-indole used in <Step 1> of Preparation Example 18, and 6-chloro-1H-indole and bromobenzene (23.55) instead of Iodobenzene. g, 0.15 mol), except that 6-chloro-2-phenyl-1H-indole was obtained in the same manner as in <Step 1> of Preparation Example 20 18.
1H-NMR: δ 6.92 (d, 1H), 7.02 (dd, 1H), 7.33 (t, 1H), 7.41 (s, 1H), 7.47 (t, 2H), 7.54 (d, 1H), 7.85 (d, 2H), 11.68 (s, 1H) 1 H-NMR: δ 6.92 (d, 1H), 7.02 (dd, 1H), 7.33 (t, 1H), 7.41 (s, 1H), 7.47 (t, 2H), 7.54 (d, 1H), 7.85 ( d, 2H), 11.68 (s, 1H)
<단계 2> 6-(2-nitrophenyl)-2-phenyl-1H-indole의 합성<Step 2> Synthesis of 6- (2-nitrophenyl) -2-phenyl-1H-indole
Figure PCTKR2013007821-appb-I000092
Figure PCTKR2013007821-appb-I000092
준비예 18의 <단계 2>에서 사용된 5-bromo-2-phenyl-1H-indole 대신 상기 준비예 19의 <단계 1>에서 얻은 6-chloro-2-phenyl-1H-indole (15 g, 55.12 mmol)을 사용하는 것을 제외하고는, 상기 준비예 18의 <단계 2>와 동일한 과정을 수행하여 6-(2-nitrophenyl)-2-phenyl-1H-indole을 얻었다.6-chloro-2-phenyl-1H-indole (15 g, 55.12) obtained in <Step 1> of Preparation Example 19 instead of 5-bromo-2-phenyl-1H-indole used in <Step 2> of Preparation Example 18 mmol), except that 6- (2-nitrophenyl) -2-phenyl-1H-indole was obtained in the same manner as in <Step 2> of Preparation Example 18.
1H-NMR: δ 6.91 (d, 1H), 7.03 (d, 1H), 7.31 (t, 1H), 7.42 (s, 1H), 7.48 (m, 3H), 7.53 (d, 1H), 7.76 (m, 3H), 8.01 (d, 2H), 11.66 (s, 1H) 1 H-NMR: δ 6.91 (d, 1H), 7.03 (d, 1H), 7.31 (t, 1H), 7.42 (s, 1H), 7.48 (m, 3H), 7.53 (d, 1H), 7.76 ( m, 3H), 8.01 (d, 2H), 11.66 (s, 1H)
<단계 3> 6-(2-nitrophenyl)-1,2-diphenyl-1H-indole의 합성Step 3 Synthesis of 6- (2-nitrophenyl) -1,2-diphenyl-1H-indole
Figure PCTKR2013007821-appb-I000093
Figure PCTKR2013007821-appb-I000093
준비예 1의 <단계 3>에서 사용된 5-(2-nitrophenyl)-1H-indole 대신 상기 준비예 19의 <단계 2>에서 얻은 6-(2-nitrophenyl)-2-phenyl-1H-indole (10.74 g, 34.20 mmol)을 사용하는 것을 제외하고는, 준비예 1의 <단계 3>과 동일한 과정을 수행하여 6-(2-nitrophenyl)-1,2-diphenyl-1H-indole을 얻었다.6- (2-nitrophenyl) -2-phenyl-1H-indole obtained in <Step 2> of Preparation Example 19 instead of 5- (2-nitrophenyl) -1H-indole used in <Step 3> of Preparation Example 1 10.74 g, 34.20 mmol) was used in the same manner as in <Step 3> of Preparation Example 1 to obtain 6- (2-nitrophenyl) -1,2-diphenyl-1H-indole.
GC-Mass (이론치: 390.14 g/mol, 측정치: 390 g/mol)GC-Mass (Theoretical value: 390.14 g / mol, Measured value: 390 g / mol)
<단계 4> 6-(2-nitrophenyl)-1,2-diphenyl-1H-indole의 합성Step 4 Synthesis of 6- (2-nitrophenyl) -1,2-diphenyl-1H-indole
Figure PCTKR2013007821-appb-I000094
Figure PCTKR2013007821-appb-I000094
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 19의 <단계 3>에서 얻은 6-(2-nitrophenyl)-1,2-diphenyl-1H-indole (9.34 g, 23.94 mmol)을 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 4>과 동일한 과정을 수행하여 화합물 IC-21을 얻었다.6- (2-nitrophenyl) -1,2- obtained in <Step 3> of Preparation Example 19 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 Except for using diphenyl-1H-indole (9.34 g, 23.94 mmol), Compound IC-21 was obtained by the same procedure as <Step 4> of Preparation Example 1 above.
GC-Mass (이론치: 358.15 g/mol, 측정치: 358 g/mol)GC-Mass (Theoretical value: 358.15 g / mol, Measured value: 358 g / mol)
[준비예 20] 화합물 IC-22의 합성Preparation Example 20 Synthesis of Compound IC-22
<단계 1> 6-chloro-3-phenyl-1H-indole의 합성<Step 1> Synthesis of 6-chloro-3-phenyl-1H-indole
Figure PCTKR2013007821-appb-I000095
Figure PCTKR2013007821-appb-I000095
질소 기류 하에서 6-chloro-1H-indole (25 g, 0.17 mol), bromobenzene (31.19 g, 0.20 mol), Pd(OAc)2 (1.86 g, 5 mol), Triphenylphosphine (2.17 g, 5 mol%), K2CO3 (68.64 g, 0.50 mol) 및 1,4-dioxane (300 ml)를 혼합한 다음, 130 ℃에서 18시간 동안 교반하였다.6-chloro-1H-indole (25 g, 0.17 mol), bromobenzene (31.19 g, 0.20 mol), Pd (OAc) 2 (1.86 g, 5 mol), Triphenylphosphine (2.17 g, 5 mol%), under nitrogen stream K 2 CO 3 (68.64 g, 0.50 mol) and 1,4-dioxane (300 ml) were mixed and then stirred at 130 ° C. for 18 hours.
반응이 종결된 후 에틸아세테이트로 추출한 다음, MgSO4로 수분을 제거하고, 컬럼크로마토그래피 (Hexane:EA = 10:1 (v/v))로 정제하여 6-chloro-3-phenyl-1H-indole (24.5 g, 수율 65%)을 얻었다. After completion of the reaction, the mixture was extracted with ethyl acetate, followed by removing water with MgSO 4 , and purified by column chromatography (Hexane: EA = 10: 1 (v / v)) to obtain 6-chloro-3-phenyl-1H-indole. (24.5 g, yield 65%) was obtained.
1H-NMR: δ 7.10 (dd, 1H), 7.25 (m, 1H), 7.43 (t, 2H), 7.49 (d, 1H), 7.67 (dd, 2H), 7.73 (d, 1H), 7.85 (d, 1H), 11.49 (s, 1H) 1 H-NMR: δ 7.10 (dd, 1H), 7.25 (m, 1H), 7.43 (t, 2H), 7.49 (d, 1H), 7.67 (dd, 2H), 7.73 (d, 1H), 7.85 ( d, 1 H), 11.49 (s, 1 H)
<단계 2> 6-(2-nitrophenyl)-3-phenyl-1H-indole의 합성<Step 2> Synthesis of 6- (2-nitrophenyl) -3-phenyl-1H-indole
Figure PCTKR2013007821-appb-I000096
Figure PCTKR2013007821-appb-I000096
준비예 18의 <단계 2>에서 사용된 5-bromo-2-phenyl-1H-indole 대신 상기 준비예 20의 <단계 1>에서 얻은 6-chloro-3-phenyl-1H-indole (15 g, 55.12 mmol)을 사용하는 것을 제외하고는, 상기 준비예 20 18의 <단계 2>와 동일한 과정을 수행하여 6-(2-nitrophenyl)-3-phenyl-1H-indole을 얻었다.6-chloro-3-phenyl-1H-indole (15 g, 55.12) obtained in <Step 1> of Preparation Example 20 instead of 5-bromo-2-phenyl-1H-indole used in <Step 2> of Preparation Example 18 mmol), except that 6- (2-nitrophenyl) -3-phenyl-1H-indole was obtained in the same manner as in <Step 2> of Preparation Example 20 18.
1H-NMR: δ 7.11 (d, 1H), 7.26 (m, 1H), 7.44 (t, 2H), 7.48 (m, 2H), 7.55 (m, 3H), 7.61 (d, 1H), 7.73 (d, 1H), 8.00 (d, 2H), 11.48 (s, 1H) 1 H-NMR: δ 7.11 (d, 1H), 7.26 (m, 1H), 7.44 (t, 2H), 7.48 (m, 2H), 7.55 (m, 3H), 7.61 (d, 1H), 7.73 ( d, 1H), 8.00 (d, 2H), 11.48 (s, 1H)
<단계 3> 6-(2-nitrophenyl)-1,3-diphenyl-1H-indole의 합성<Step 3> Synthesis of 6- (2-nitrophenyl) -1,3-diphenyl-1H-indole
Figure PCTKR2013007821-appb-I000097
Figure PCTKR2013007821-appb-I000097
준비예 1의 <단계 3>에서 사용된 5-(2-nitrophenyl)-1H-indole 대신 상기 준비예 20의 <단계 2>에서 얻은 6-(2-nitrophenyl)-3-phenyl-1H-indole (12.11 g, 38.58 mmol)을 사용하는 것을 제외하고는, 준비예 1의 <단계 3>과 동일한 과정을 수행하여 6-(2-nitrophenyl)-1,3-diphenyl-1H-indole을 얻었다.6- (2-nitrophenyl) -3-phenyl-1H-indole obtained in <Step 2> of Preparation Example 20 instead of 5- (2-nitrophenyl) -1H-indole used in <Step 3> of Preparation Example 1 12.11 g, 38.58 mmol) was used in the same manner as in <Step 3> of Preparation Example 1 to obtain 6- (2-nitrophenyl) -1,3-diphenyl-1H-indole.
GC-Mass (이론치: 390.14 g/mol, 측정치: 390 g/mol)GC-Mass (Theoretical value: 390.14 g / mol, Measured value: 390 g / mol)
<단계 4> 6-(2-nitrophenyl)-1,3-diphenyl-1H-indole의 합성Step 4 Synthesis of 6- (2-nitrophenyl) -1,3-diphenyl-1H-indole
Figure PCTKR2013007821-appb-I000098
Figure PCTKR2013007821-appb-I000098
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 20의 <단계 3>에서 얻은 6-(2-nitrophenyl)-1,3-diphenyl-1H-indole (10.53 g, 27.00 mmol)을 사용하는 것을 제외하고는 상기 준비예 1의 <단계 4>과 동일한 과정을 수행하여 화합물 IC-22을 얻었다.6- (2-nitrophenyl) -1,3- obtained in <Step 3> of Preparation Example 20 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 Compound IC-22 was obtained by the same procedure as <Step 4> of Preparation Example 1, except that diphenyl-1H-indole (10.53 g, 27.00 mmol) was used.
GC-Mass (이론치: 358.15 g/mol, 측정치: 358 g/mol)GC-Mass (Theoretical value: 358.15 g / mol, Measured value: 358 g / mol)
[준비예 21] 화합물 IC-23의 합성Preparation Example 21 Synthesis of Compound IC-23
<단계 1> 5-bromo-2,3-diphenyl-1H-indole의 합성<Step 1> Synthesis of 5-bromo-2,3-diphenyl-1H-indole
Figure PCTKR2013007821-appb-I000099
Figure PCTKR2013007821-appb-I000099
준비예 20의 <단계 1>에서 사용된 6-chloro-1H-indole 대신 5-bromo-2-phenyl-1H-indole (46.24 g, 0.17 mol)을 사용하는 것을 제외하고는, 상기 준비예 20의 <단계 1>과 동일한 과정을 수행하여 5-bromo-2,3-diphenyl-1H-indole을 얻었다.Preparation Example 20, except that 5-bromo-2-phenyl-1H-indole (46.24 g, 0.17 mol) instead of 6-chloro-1H-indole used in <Step 1> of Preparation Example 20 5-bromo-2,3-diphenyl-1H-indole was obtained in the same manner as in <Step 1>.
1H-NMR: δ 7.23 (d, 1H), 7.31 (t, 2H), 7.43 (m, 6H), 7.67 (d, 1H), 7.71 (d, 1H), 7.84 (d, 2H), 11.34 (s, 1H) 1 H-NMR: δ 7.23 (d, 1H), 7.31 (t, 2H), 7.43 (m, 6H), 7.67 (d, 1H), 7.71 (d, 1H), 7.84 (d, 2H), 11.34 ( s, 1 H)
<단계 2> 5-(2-nitrophenyl)-2,3-diphenyl-1H-indole의 합성<Step 2> Synthesis of 5- (2-nitrophenyl) -2,3-diphenyl-1H-indole
Figure PCTKR2013007821-appb-I000100
Figure PCTKR2013007821-appb-I000100
준비예 18의 <단계 2>에서 사용된 5-bromo-2-phenyl-1H-indole 대신 상기 준비예 21의 <단계 1>에서 얻은 5-bromo-2,3-diphenyl-1H-indole (35.40 g, 0.102 mol)을 사용하는 것을 제외하고는, 상기 준비예 18의 <단계 2>와 동일한 과정을 수행하여 5-(2-nitrophenyl)-2,3-diphenyl-1H-indole을 얻었다.5-bromo-2,3-diphenyl-1H-indole (35.40 g) obtained in <Step 1> of Preparation Example 21 instead of 5-bromo-2-phenyl-1H-indole used in <Step 2> of Preparation Example 18 , Except that 0.102 mol) was used, to obtain 5- (2-nitrophenyl) -2,3-diphenyl-1H-indole by following the same procedure as in <Step 2> of Preparation Example 18.
GC-Mass (이론치: 390.14 g/mol, 측정치: 390 g/mol)GC-Mass (Theoretical value: 390.14 g / mol, Measured value: 390 g / mol)
<단계 3> 5-(2-nitrophenyl)-2,3-diphenyl-1H-indole의 합성<Step 3> Synthesis of 5- (2-nitrophenyl) -2,3-diphenyl-1H-indole
Figure PCTKR2013007821-appb-I000101
Figure PCTKR2013007821-appb-I000101
준비예 1의 <단계 3>에서 사용된 5-(2-nitrophenyl)-1H-indole 대신 상기 준비예 21의 <단계 2>에서 얻은 5-(2-nitrophenyl)-2,3-diphenyl-1H-indole (27.84 g, 71.40 mmol)을 사용하는 것을 제외하고는, 준비예 1의 <단계 3>과 동일한 과정을 수행하여 5-(2-nitrophenyl)-1,2,3-triphenyl-1H-indole을 얻었다.5- (2-nitrophenyl) -2,3-diphenyl-1H- obtained in <Step 2> of Preparation Example 21 instead of 5- (2-nitrophenyl) -1H-indole used in <Step 3> of Preparation Example 1 A 5- (2-nitrophenyl) -1,2,3-triphenyl-1H-indole was prepared in the same manner as in <Step 3> of Preparation Example 1, except that indole (27.84 g, 71.40 mmol) was used. Got it.
GC-Mass (이론치: 466.17 g/mol, 측정치: 466 g/mol)GC-Mass (Theoretical value: 466.17 g / mol, Measured value: 466 g / mol)
<단계 4> 화합물 IC-23의 합성Step 4 Synthesis of Compound IC-23
Figure PCTKR2013007821-appb-I000102
Figure PCTKR2013007821-appb-I000102
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 21의 <단계 3>에서 얻은 5-(2-nitrophenyl)-1,2,3-triphenyl-1H-indole (19.96 g, 42.84 mmol)을 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 4>과 동일한 과정을 수행하여 화합물 IC-23을 얻었다.5- (2-nitrophenyl) -1,2, obtained in <Step 3> of Preparation Example 21 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 Except for using 3-triphenyl-1H-indole (19.96 g, 42.84 mmol), Compound IC-23 was obtained by the same procedure as <Step 4> of Preparation Example 1 above.
GC-Mass (이론치: 434.18 g/mol, 측정치: 434 g/mol)GC-Mass (Theoretical value: 434.18 g / mol, Measured value: 434 g / mol)
[준비예 22] 화합물 IC-24의 합성Preparation 22 Synthesis of Compound IC-24
<단계 1> 6-chloro-2,3-diphenyl-1H-indole의 합성<Step 1> Synthesis of 6-chloro-2,3-diphenyl-1H-indole
Figure PCTKR2013007821-appb-I000103
Figure PCTKR2013007821-appb-I000103
준비예 20의 <단계 1>에서 사용된 6-chloro-1H-indole 대신 6-chloro-2-phenyl-1H-indole(34.05 g, 0.15 mmol)을 사용하는 것을 제외하고는, 상기 준비예 20의 <단계 1>과 동일한 과정을 수행하여 6-chloro-2,3-diphenyl-1H-indole을 얻었다.Preparation Example 20, except that 6-chloro-2-phenyl-1H-indole (34.05 g, 0.15 mmol) instead of 6-chloro-1H-indole used in <Step 1> of Preparation Example 20 6-chloro-2,3-diphenyl-1H-indole was obtained in the same manner as in <Step 1>.
1H-NMR: δ 7.18 (d, 1H), 7.29 (t, 2H), 7.50 (m, 6H), 7.62 (d, 1H), 7.75 (d, 1H), 7.89 (d, 2H), 11.35 (s, 1H) 1 H-NMR: δ 7.18 (d, 1H), 7.29 (t, 2H), 7.50 (m, 6H), 7.62 (d, 1H), 7.75 (d, 1H), 7.89 (d, 2H), 11.35 ( s, 1 H)
<단계 2> 6-(2-nitrophenyl)-2,3-diphenyl-1H-indole의 합성<Step 2> Synthesis of 6- (2-nitrophenyl) -2,3-diphenyl-1H-indole
Figure PCTKR2013007821-appb-I000104
Figure PCTKR2013007821-appb-I000104
준비예 18의 <단계 2>에서 사용된 5-bromo-2-phenyl-1H-indole 대신 상기 준비예 22의 <단계 1>에서 얻은 6-chloro-2,3-diphenyl-1H-indole(27.27 g, 0.05 mol)을 사용하는 것을 제외하고는, 상기 준비예 18의 <단계 2>와 동일한 과정을 수행하여 6-(2-nitrophenyl)-2,3-diphenyl-1H-indole을 얻었다.6-chloro-2,3-diphenyl-1H-indole (27.27 g) obtained in <Step 1> of Preparation Example 22 instead of 5-bromo-2-phenyl-1H-indole used in <Step 2> of Preparation Example 18 , 0.05 mol) was used, and the same procedure as in <Step 2> of Preparation Example 18 was performed, to obtain 6- (2-nitrophenyl) -2,3-diphenyl-1H-indole.
GC-Mass (이론치: 390.14 g/mol, 측정치: 390 g/mol)GC-Mass (Theoretical value: 390.14 g / mol, Measured value: 390 g / mol)
<단계 3> 6-(2-nitrophenyl)-1,2,3-triphenyl-1H-indole의 합성<Step 3> Synthesis of 6- (2-nitrophenyl) -1,2,3-triphenyl-1H-indole
Figure PCTKR2013007821-appb-I000105
Figure PCTKR2013007821-appb-I000105
준비예 1의 <단계 3>에서 사용된 5-(2-nitrophenyl)-1H-indole 대신 상기 준비예 22의 <단계 2>에서 얻은 6-(2-nitrophenyl)-2,3-diphenyl-1H-indole (11.70 g, 30.00 mmol)을 사용하는 것을 제외하고는, 준비예 1의 <단계 3>과 동일한 과정을 수행하여 6-(2-nitrophenyl)-1,2,3-triphenyl-1H-indole을 얻었다.6- (2-nitrophenyl) -2,3-diphenyl-1H- obtained in <Step 2> of Preparation Example 22 instead of 5- (2-nitrophenyl) -1H-indole used in <Step 3> of Preparation Example 1 Except for using indole (11.70 g, 30.00 mmol), 6- (2-nitrophenyl) -1,2,3-triphenyl-1H-indole was prepared in the same manner as in <Step 3> of Preparation Example 1. Got it.
GC-Mass (이론치: 466.17 g/mol, 측정치: 466 g/mol)GC-Mass (Theoretical value: 466.17 g / mol, Measured value: 466 g / mol)
<단계 4> 화합물 IC-24의 합성Step 4 Synthesis of Compound IC-24
Figure PCTKR2013007821-appb-I000106
Figure PCTKR2013007821-appb-I000106
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 22의 <단계 3>에서 얻은 6-(2-nitrophenyl)-1,2,3-triphenyl-1H-indole (9.78 g, 21.00 mmol)을 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 4>과 동일한 과정을 수행하여 화합물 IC-24을 얻었다.6- (2-nitrophenyl) -1,2, obtained in <Step 3> of Preparation Example 22 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 Except for using 3-triphenyl-1H-indole (9.78 g, 21.00 mmol), and a compound IC-24 was obtained in the same manner as in <Step 4> of Preparation Example 1.
GC-Mass (이론치: 434.18 g/mol, 측정치: 434 g/mol)GC-Mass (Theoretical value: 434.18 g / mol, Measured value: 434 g / mol)
[준비예 23] 화합물 IC-25의 합성Preparation 23 Synthesis of Compound IC-25
<단계 1> 1-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-6-(2-nitrophenyl)-1H-indole의 합성<Step 1> Synthesis of 1- (3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -6- (2-nitrophenyl) -1H-indole
Figure PCTKR2013007821-appb-I000107
Figure PCTKR2013007821-appb-I000107
질소 기류 하에서 6-(2-nitrophenyl)-1H-indole (10 g, 41.97 mmol), 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (17.32 g, 50.37 mmol), Pd(OAc)2 (0.47 g, 5 mol%), NaO(t-bu) (8.07 g, 83.95 mmol), P(t-bu)3 (0.85 g, 4.19 mmol) 및 Toluene (100 ml)을 혼합한 다음, 110 ℃에서 12시간 동안 교반하였다.6- (2-nitrophenyl) -1H-indole (10 g, 41.97 mmol), 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (17.32 g, 50.37 mmol) under nitrogen stream , Pd (OAc) 2 (0.47 g, 5 mol%), NaO (t-bu) (8.07 g, 83.95 mmol), P (t-bu) 3 (0.85 g, 4.19 mmol) and Toluene (100 ml) After mixing, the mixture was stirred at 110 ° C. for 12 hours.
반응이 종결된 후 에틸아세테이트로 추출한 다음, MgSO4로 수분을 제거하고, 컬럼크로마토그래피 (Hexane:EA = 3:1 (v/v))로 정제하여 1-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-6-(2-nitrophenyl)-1H-indole (15.8 g, 수율 69%)을 얻었다. After completion of the reaction, the mixture was extracted with ethyl acetate, followed by water removal with MgSO 4 , and purified by column chromatography (Hexane: EA = 3: 1 (v / v)) to obtain 1- (3- (4,6-diphenyl). -1,3,5-triazin-2-yl) phenyl) -6- (2-nitrophenyl) -1H-indole (15.8 g, yield 69%) was obtained.
GC-Mass (이론치: 545.19 g/mol, 측정치: 545 g/mol)GC-Mass (Theoretical value: 545.19 g / mol, Measured value: 545 g / mol)
<단계 2> 화합물 IC-25의 합성Step 2 Synthesis of Compound IC-25
Figure PCTKR2013007821-appb-I000108
Figure PCTKR2013007821-appb-I000108
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 23의 <단계 1>에서 얻은 1-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-6-(2-nitrophenyl)-1H-indole (15.8 g, 29.00 mmol)을 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 4>과 동일한 과정을 수행하여 화합물 IC-25을 얻었다.1- (3- (4,6-diphenyl-) obtained in <Step 1> of Preparation Example 23 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 <Step 4> of Preparation Example 1, except that 1,3,5-triazin-2-yl) phenyl) -6- (2-nitrophenyl) -1H-indole (15.8 g, 29.00 mmol) was used. Compound IC-25 was obtained by performing the same procedure as in the following.
GC-Mass (이론치: 513.20 g/mol, 측정치: 513 g/mol)GC-Mass (Theoretical value: 513.20 g / mol, Measured value: 513 g / mol)
[준비예 24] 화합물 IC-26의 합성Preparation 24 Synthesis of Compound IC-26
<단계 1> 1-(3-(4,6-diphenylpyrimidin-2-yl)phenyl)-6-(2-nitrophenyl)-1H-indole의 합성<Step 1> Synthesis of 1- (3- (4,6-diphenylpyrimidin-2-yl) phenyl) -6- (2-nitrophenyl) -1H-indole
Figure PCTKR2013007821-appb-I000109
Figure PCTKR2013007821-appb-I000109
준비예 23의 <단계 1>에서 사용된 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine 대신 2-(3-chloro phenyl)-4,6-diphenylpyrimidine (17.27 g, 50.37 mmol)을 사용하는 것을 제외하고는, 상기 준비예 25 23의 <단계 1>과 동일한 과정을 수행하여 1-(3-(4,6-diphenylpyrimidin-2-yl)phenyl)-6-(2-nitrophenyl)-1H-indole을 얻었다.2- (3-chlorophenyl) -4,6-diphenylpyrimidine (17.27 g) instead of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine used in <Step 1> of Preparation Example 23 , 50.37 mmol) was subjected to the same process as in <Step 1> of Preparation Example 25-23, 1- (3- (4,6-diphenylpyrimidin-2-yl) phenyl) -6- ( 2-nitrophenyl) -1H-indole was obtained.
GC-Mass (이론치: 544.19 g/mol, 측정치: 544 g/mol)GC-Mass (Theoretical value: 544.19 g / mol, Measured value: 544 g / mol)
<단계 2> 화합물 IC-26의 합성Step 2 Synthesis of Compound IC-26
Figure PCTKR2013007821-appb-I000110
Figure PCTKR2013007821-appb-I000110
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 24의 <단계 1>에서 얻은 1-(3-(4,6-diphenylpyrimidin-2-yl)phenyl)-6-(2-nitrophenyl)-1H-indole (15.7 g, 29.00 mmol)을 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 4>과 동일한 과정을 수행하여 화합물 IC-26을 얻었다.1- (3- (4,6-diphenylpyrimidin-) obtained in <Step 1> of Preparation Example 24 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 Compound IC was carried out in the same manner as in <Step 4> of Preparation Example 1, except that 2-yl) phenyl) -6- (2-nitrophenyl) -1H-indole (15.7 g, 29.00 mmol) was used. Got -26.
GC-Mass (이론치: 512.20 g/mol, 측정치: 512 g/mol)GC-Mass (Theoretical value: 512.20 g / mol, Measured value: 512 g / mol)
[준비예 25] 화합물 IC-27의 합성Preparation 25 Synthesis of Compound IC-27
<단계 1> 1-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-5-(2-nitrophenyl)-1H-indole의 합성<Step 1> Synthesis of 1- (3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -5- (2-nitrophenyl) -1H-indole
Figure PCTKR2013007821-appb-I000111
Figure PCTKR2013007821-appb-I000111
준비예 23의 <단계 1>에서 사용된 6-(2-nitrophenyl)-1H-indole 대신 5-(2-nitrophenyl)-1H-indole (10 g, 41.97 mmol)을 사용하는 것을 제외하고는, 상기 준비예 23의 <단계 1>과 동일한 과정을 수행하여 11-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-5-(2-nitro phenyl)-1H-indole을 얻었다.Except for using 5- (2-nitrophenyl) -1H-indole (10 g, 41.97 mmol) instead of 6- (2-nitrophenyl) -1H-indole used in <Step 1> of Preparation Example 23, 11- (3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -5- (2-nitro phenyl)-by following the same procedure as in <Step 1> of Preparation Example 23 1H-indole was obtained.
GC-Mass (이론치: 545.19 g/mol, 측정치: 545 g/mol)GC-Mass (Theoretical value: 545.19 g / mol, Measured value: 545 g / mol)
<단계 2> 화합물 IC-27의 합성Step 2 Synthesis of Compound IC-27
Figure PCTKR2013007821-appb-I000112
Figure PCTKR2013007821-appb-I000112
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 25의 <단계 1>에서 얻은 11-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-5-(2-nitro phenyl)-1H-indole (15.8 g, 29.00 mmol)을 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 4>과 동일한 과정을 수행하여 화합물 IC-27을 얻었다.11- (3- (4,6-diphenyl-) obtained in <Step 1> of Preparation Example 25 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 <Step 4 of Preparation Example 1, except that 1,3,5-triazin-2-yl) phenyl) -5- (2-nitro phenyl) -1H-indole (15.8 g, 29.00 mmol) was used. Compound IC-27 was obtained by following the same procedure as>.
GC-Mass (이론치: 513.20 g/mol, 측정치: 513 g/mol)GC-Mass (Theoretical value: 513.20 g / mol, Measured value: 513 g / mol)
[준비예 26] 화합물 IC-28의 합성Preparation 26 Synthesis of Compound IC-28
<단계 1> 1-(3-(4,6-diphenylpyrimidin-2-yl)phenyl)-5-(2-nitrophenyl)-1H-indole의 합성<Step 1> Synthesis of 1- (3- (4,6-diphenylpyrimidin-2-yl) phenyl) -5- (2-nitrophenyl) -1H-indole
Figure PCTKR2013007821-appb-I000113
Figure PCTKR2013007821-appb-I000113
준비예 23의 <단계 1>에서 사용된 6-(2-nitrophenyl)-1H-indole 대신 5-(2-nitrophenyl)-1H-indole (10 g, 41.97 mmol)을 사용하고, 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine 대신 2-(3-chloro phenyl)-4,6-diphenylpyrimidine (17.27 g, 50.37 mmol)을 사용하는 것을 제외하고는, 상기 준비예 23의 <단계 1>과 동일한 과정을 수행하여 1-(3-(4,6-diphenylpyrimidin-2-yl)phenyl)-5-(2-nitrophenyl)-1H-indole을 얻었다.5- (2-nitrophenyl) -1H-indole (10 g, 41.97 mmol) was used instead of 6- (2-nitrophenyl) -1H-indole used in <Step 1> of Preparation Example 23, and 2- (3- Preparation Example 23, except that 2- (3-chlorophenyl) -4,6-diphenylpyrimidine (17.27 g, 50.37 mmol) was used instead of chlorophenyl) -4,6-diphenyl-1,3,5-triazine. 1- (3- (4,6-diphenylpyrimidin-2-yl) phenyl) -5- (2-nitrophenyl) -1H-indole was obtained by the same process as in <Step 1>.
GC-Mass (이론치: 544.19 g/mol, 측정치: 544 g/mol)GC-Mass (Theoretical value: 544.19 g / mol, Measured value: 544 g / mol)
<단계 2> 화합물 IC-28의 합성Step 2 Synthesis of Compound IC-28
Figure PCTKR2013007821-appb-I000114
Figure PCTKR2013007821-appb-I000114
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 26의 <단계 1>에서 얻은 1-(3-(4,6-diphenylpyrimidin-2-yl)phenyl)-5-(2-nitrophenyl)-1H-indole (15.7 g, 29.00 mmol)을 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 4>과 동일한 과정을 수행하여 화합물 IC-28을 얻었다.1- (3- (4,6-diphenylpyrimidin-) obtained in <Step 1> of Preparation Example 26 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 Compound IC was carried out in the same manner as in <Step 4> of Preparation Example 1, except that 2-yl) phenyl) -5- (2-nitrophenyl) -1H-indole (15.7 g, 29.00 mmol) was used. Got -28.
GC-Mass (이론치: 512.20 g/mol, 측정치: 512 g/mol)GC-Mass (Theoretical value: 512.20 g / mol, Measured value: 512 g / mol)
[준비예 27] 화합물 IC-29의 합성Preparation 27 Synthesis of Compound IC-29
<단계 1> 9-phenyl-9H-carbazol-2-amine의 합성Step 1 Synthesis of 9-phenyl-9H-carbazol-2-amine
Figure PCTKR2013007821-appb-I000115
Figure PCTKR2013007821-appb-I000115
질소 기류 하에서 9.66 g (30.0 mmol)의 2-bromo-9-phenyl-9H-carbazole을 Toluene 100 ml 에 녹인 후, 여기에 28 % aqueous ammonia 10.2 ml (150 mmol)과 Cu 0.10 g (5 mol%)를 넣고, 110 ℃에서 12시간 동안 교반하였다. 9.66 g (30.0 mmol) of 2-bromo-9-phenyl-9H-carbazole was dissolved in 100 ml of Toluene under nitrogen stream, followed by 10.2 ml (150 mmol) of 28% aqueous ammonia and 0.10 g (5 mol%) of Cu. Was added and stirred at 110 ° C. for 12 h.
반응 종결 후 메틸렌클로라이드로 추출한 다음, MgSO4를 넣고 필터링하였다. 필터링된 유기층에서 용매를 제거한 다음, 컬럼크로마토그래피를 이용하여 9-phenyl-9H-carbazol-2-amine 6.5 g (yield: 83%)을 얻었다.After completion of the reaction was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, 6.5 g (yield: 83%) of 9-phenyl-9H-carbazol-2-amine was obtained using column chromatography.
1H-NMR: δ 6.51 (s, 2H), 6.72 (m, 2H), 7.53 (m, 2H), 7.55 (m, 5H), 7.98 (d, 1H), 8.05 (d, 1H), 8.62 (d, 1H) 1 H-NMR: δ 6.51 (s, 2H), 6.72 (m, 2H), 7.53 (m, 2H), 7.55 (m, 5H), 7.98 (d, 1H), 8.05 (d, 1H), 8.62 ( d, 1H)
<단계 2> 화합물 IC-29의 합성Step 2 Synthesis of Compound IC-29
Figure PCTKR2013007821-appb-I000116
Figure PCTKR2013007821-appb-I000116
질소 기류 하에서 5.16 g (20.0 mmol)의 9-phenyl-9H-carbazol-2-amine을 H2O/dioxane (10 ml/90 ml)에 녹인 후, 여기에 triethanolammonium chloride 0.372 g (2 mmol) 과 RuCln`H2O 0.052 g (0.2 mmol)과 PPh3 0.158 g (0.6 mmol), SnCl2`2H2O 0.452 g (2 mmol)을 넣은 다음, 180 ℃에서 20시간 동안 교반하였다. Under nitrogen stream, 5.16 g (20.0 mmol) of 9-phenyl-9H-carbazol-2-amine was dissolved in H 2 O / dioxane (10 ml / 90 ml), followed by 0.372 g (2 mmol) of triethanolammonium chloride and RuCln into the `H 2 O 0.052 g (0.2 mmol) and PPh 3 0.158 g (0.6 mmol) , SnCl 2` 2H 2 O 0.452 g (2 mmol) and stirred at 180 ℃ for 20 hours.
반응 종결 후 aqueous 5% HCl에 반응물을 붓고, 메틸렌클로라이드로 추출한 다음, MgSO4를 넣고 필터링하였다. 필터링된 유기층에서 용매를 제거한 후, 컬럼크로마토그래피를 이용하여 화합물 IC-29 2.8 g (yield: 54%)을 얻었다.After the completion of the reaction, the reaction was poured into aqueous 5% HCl, extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, using a column chromatography to give the compound IC-29 2.8 g (yield: 54%).
1H-NMR: δ 6.48 (d, 1H), 7.35 (m, 4H), 7.58 (m, 5H), 7.98 (d, 1H), 8.15 (d, 1H), 8.59 (d, 1H), 10.12 (s, 1H) 1 H-NMR: δ 6.48 (d, 1H), 7.35 (m, 4H), 7.58 (m, 5H), 7.98 (d, 1H), 8.15 (d, 1H), 8.59 (d, 1H), 10.12 ( s, 1 H)
[준비예 28] 화합물 IC-30의 합성Preparation Example 28 Synthesis of Compound IC-30
<단계 1> 9-phenyl-9H-carbazol-1-amine의 합성Step 1 Synthesis of 9-phenyl-9H-carbazol-1-amine
Figure PCTKR2013007821-appb-I000117
Figure PCTKR2013007821-appb-I000117
준비예 27의 <단계 1>에서 사용된 2-bromo-9-phenyl-9H-carbazole 대신 1-bromo-9-phenyl-9H-carbazole 9.66 g (30.0 mmol)을 사용하는 것을 제외하고는, 준비예 27의 <단계 1>과 동일한 과정을 수행하여 9-phenyl-9H-carbazol-1-amine6.2 g (yield: 80%)을 얻었다.Preparation Example 27, except that 9.66 g (30.0 mmol) of 1-bromo-9-phenyl-9H-carbazole was used instead of 2-bromo-9-phenyl-9H-carbazole used in <Step 1> of Preparation Example 27. The same procedure as in <Step 1> of 27 was performed to obtain 6.2 g (yield: 80%) of 9-phenyl-9H-carbazol-1-amine.
1H-NMR: δ 6.37 (s, 2H), 6.82 (d, 1H), 7.15 (t, 1H), 7.36 (m, 2H), 7.62 (m, 5H), 8.02 (d, 1H), 8.63 (d, 1H) 1 H-NMR: δ 6.37 (s, 2H), 6.82 (d, 1H), 7.15 (t, 1H), 7.36 (m, 2H), 7.62 (m, 5H), 8.02 (d, 1H), 8.63 ( d, 1H)
<단계 2> 화합물 IC-30의 합성Step 2 Synthesis of Compound IC-30
Figure PCTKR2013007821-appb-I000118
Figure PCTKR2013007821-appb-I000118
준비예 27의 <단계 2>에서 사용된 9-phenyl-9H-carbazol-2-amine 대신 준비예 28의 <단계 1>에서 얻은 9-phenyl-9H-carbazol-1-amine 5.16 g (20.0 mmol)을 사용하는 것을 제외하고는, 준비예 27의 <단계 2>와 동일한 과정을 수행하여 화합물 IC-30 2.4 g (yield: 42%)을 얻었다.5.16 g (20.0 mmol) of 9-phenyl-9H-carbazol-1-amine obtained in <Step 1> of Preparation Example 28 instead of 9-phenyl-9H-carbazol-2-amine used in <Step 2> of Preparation Example 27 Except for using, the same procedure as in <Step 2> of Preparation Example 27 was carried out to obtain 2.4 g (yield: 42%) of compound IC-30.
1H-NMR: δ 6.52 (d, 1H), 7.41 (m, 3H), 7.58 (m, 5H), 8.01 (d, 1H), 8.18 (d, 1H), 8.62 (d, 1H), 10.22 (s, 1H) 1 H-NMR: δ 6.52 (d, 1H), 7.41 (m, 3H), 7.58 (m, 5H), 8.01 (d, 1H), 8.18 (d, 1H), 8.62 (d, 1H), 10.22 ( s, 1 H)
[준비예 29] 화합물 IC-31의 합성Preparation Example 29 Synthesis of Compound IC-31
<단계 1> 1-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-6-(2-nitrophenyl)-1H-indole의 합성<Step 1> Synthesis of 1- (3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -6- (2-nitrophenyl) -1H-indole
Figure PCTKR2013007821-appb-I000119
Figure PCTKR2013007821-appb-I000119
질소 기류 하에서 6-(2-nitrophenyl)-1H-indole (10 g, 41.97 mmol), 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (17.32 g, 50.37 mmol), Pd(OAc)2 (0.47 g, 5 mol%), NaO(t-bu) (8.07 g, 83.95 mmol), P(t-bu)3 (0.85 g, 4.19 mmol) 및 Toluene (100 ml)을 혼합한 다음, 110 ℃에서 12시간 동안 교반하였다.6- (2-nitrophenyl) -1H-indole (10 g, 41.97 mmol), 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (17.32 g, 50.37 mmol) under nitrogen stream , Pd (OAc) 2 (0.47 g, 5 mol%), NaO (t-bu) (8.07 g, 83.95 mmol), P (t-bu) 3 (0.85 g, 4.19 mmol) and Toluene (100 ml) After mixing, the mixture was stirred at 110 ° C. for 12 hours.
반응이 종결된 후 에틸아세테이트로 추출한 다음, MgSO4로 수분을 제거하고, 컬럼크로마토그래피 (Hexane:EA = 3:1 (v/v))로 정제하여 1-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-6-(2-nitrophenyl)-1H-indole (15.8 g, 수율 69%)을 얻었다. After completion of the reaction, the mixture was extracted with ethyl acetate, followed by water removal with MgSO 4 , and purified by column chromatography (Hexane: EA = 3: 1 (v / v)) to obtain 1- (3- (4,6-diphenyl). -1,3,5-triazin-2-yl) phenyl) -6- (2-nitrophenyl) -1H-indole (15.8 g, yield 69%) was obtained.
GC-Mass (이론치: 545.19 g/mol, 측정치: 545 g/mol)GC-Mass (Theoretical value: 545.19 g / mol, Measured value: 545 g / mol)
<단계 2> 화합물 IC-31의 합성Step 2 Synthesis of Compound IC-31
Figure PCTKR2013007821-appb-I000120
Figure PCTKR2013007821-appb-I000120
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 29의 <단계 1>에서 얻은 1-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-6-(2-nitrophenyl)-1H-indole(15.8 g, 29.00 mmol)을 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 4>과 동일한 과정을 수행하여 화합물 IC-31을 얻었다.1- (3- (4,6-diphenyl-) obtained in <Step 1> of Preparation Example 29 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 <Step 4> of Preparation Example 1, except that 1,3,5-triazin-2-yl) phenyl) -6- (2-nitrophenyl) -1H-indole (15.8 g, 29.00 mmol) was used. Compound IC-31 was obtained by the same procedure as the above.
GC-Mass (이론치: 513.20 g/mol, 측정치: 513 g/mol)GC-Mass (Theoretical value: 513.20 g / mol, Measured value: 513 g / mol)
[준비예 30] 화합물 IC-32의 합성 Preparation Example 30 Synthesis of Compound IC-32
<단계 1> 1-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-5-(2-nitrophenyl)-1H-indole의 합성<Step 1> Synthesis of 1- (3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -5- (2-nitrophenyl) -1H-indole
Figure PCTKR2013007821-appb-I000121
Figure PCTKR2013007821-appb-I000121
준비예 29의 <단계 1>에서 사용된 6-(2-nitrophenyl)-1H-indole 대신 5-(2-nitrophenyl)-1H-indole (10 g, 41.97 mmol)을 사용하는 것을 제외하고는, 상기 준비예 29의 <단계 1>과 동일한 과정을 수행하여 11-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-5-(2-nitro phenyl)-1H-indole을 얻었다.Except for using 5- (2-nitrophenyl) -1H-indole (10 g, 41.97 mmol) instead of 6- (2-nitrophenyl) -1H-indole used in <Step 1> of Preparation Example 29, 11- (3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -5- (2-nitro phenyl)-by following the same procedure as in <Step 1> of Preparation Example 29 1H-indole was obtained.
GC-Mass (이론치: 545.19 g/mol, 측정치: 545 g/mol)GC-Mass (Theoretical value: 545.19 g / mol, Measured value: 545 g / mol)
<단계 2> 화합물 IC-32 합성Step 2 Synthesis of Compound IC-32
Figure PCTKR2013007821-appb-I000122
Figure PCTKR2013007821-appb-I000122
준비예 1의 <단계 4>에서 사용된 5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 준비예 30의 <단계 1>에서 얻은 11-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-5-(2-nitro phenyl)-1H-indole (15.8 g, 29.00 mmol)을 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 4>과 동일한 과정을 수행하여 화합물 IC-32을 얻었다.11- (3- (4,6-diphenyl-) obtained in <Step 1> of Preparation Example 30 instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole used in <Step 4> of Preparation Example 1 <Step 4 of Preparation Example 1, except that 1,3,5-triazin-2-yl) phenyl) -5- (2-nitro phenyl) -1H-indole (15.8 g, 29.00 mmol) was used. Compound IC-32 was obtained by following the same procedure as>.
GC-Mass (이론치: 513.20 g/mol, 측정치: 513 g/mol)GC-Mass (Theoretical value: 513.20 g / mol, Measured value: 513 g / mol)
[합성예 1] 화합물 Inv-1의 합성Synthesis Example 1 Synthesis of Compound Inv-1
Figure PCTKR2013007821-appb-I000123
Figure PCTKR2013007821-appb-I000123
질소 기류 하에서 준비예 1에서 얻은 화합물 IC-1 (3 g, 10.63 mmol), 4,4'-dibromo-1,1'-biphenyl (1.33 g, 4.25 mmol), Cu powder (0.07 g, 1.06 mmol), K2CO3 (1.47 g, 10.63 mmol), Na2SO4 (1.51 g, 10.63 mmol), nitrobenzene (100 ml)를 혼합한 다음, 210 ℃에서 24시간 동안 교반하였다. Compound IC-1 (3 g, 10.63 mmol), 4,4'-dibromo-1,1'-biphenyl (1.33 g, 4.25 mmol), Cu powder (0.07 g, 1.06 mmol) obtained in Preparation Example 1 under a nitrogen stream. , K 2 CO 3 (1.47 g, 10.63 mmol), Na 2 SO 4 (1.51 g, 10.63 mmol), and nitrobenzene (100 ml) were mixed and then stirred at 210 ° C. for 24 hours.
반응 종결 후 nitrobenzene을 제거한 다음, 메틸렌클로라이드로 유기층을 분리하고, MgSO4를 사용하여 분리된 유기층에서 물을 제거하였다. 물이 제거된 유기층에서 용매를 제거한 다음, 컬럼 크로마토그래피 (Hexane:MC = 1:1 (v/v))로 정제하여 화합물 Inv-1 (2g, 수율: 66 %)을 얻었다. After completion of the reaction, nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed from the separated organic layer using MgSO 4 . The solvent was removed from the organic layer to which water was removed, and then purified by column chromatography (Hexane: MC = 1: 1 (v / v)) to give the compound Inv-1 (2g, yield: 66%).
GC-Mass (이론치: 714.85 g/mol, 측정치: 715 g/mol)GC-Mass (Theoretical value: 714.85 g / mol, Measured value: 715 g / mol)
[합성예 2] 화합물 Inv-2의 합성Synthesis Example 2 Synthesis of Compound Inv-2
Figure PCTKR2013007821-appb-I000124
Figure PCTKR2013007821-appb-I000124
합성예 1에서 사용된 화합물 IC-1 대신 준비예 2에서 얻은 화합물 IC-3 (3 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-2 (1.64 g, 수율: 54 %)를 얻었다.A compound Inv-2 (3) was obtained by the same procedure as in Synthesis Example 1, except that Compound IC-3 (3 g, 10.63 mmol) obtained in Preparation Example 2 was used instead of Compound IC-1 used in Synthesis Example 1. 1.64 g, yield: 54%) was obtained.
GC-Mass (이론치: 714.85 g/mol, 측정치: 715 g/mol)GC-Mass (Theoretical value: 714.85 g / mol, Measured value: 715 g / mol)
[합성예 3] 화합물 Inv-3의 합성Synthesis Example 3 Synthesis of Compound Inv-3
Figure PCTKR2013007821-appb-I000125
Figure PCTKR2013007821-appb-I000125
합성예 1에서 사용된 화합물 IC-1 대신 준비예 4에서 얻은 화합물 IC-6 (3 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-3 (1.82 g, 수율: 60 %)를 얻었다.A compound Inv-3 was prepared in the same manner as in Synthesis Example 1, except that Compound IC-6 (3 g, 10.63 mmol) obtained in Preparation Example 4 was used instead of Compound IC-1 used in Synthesis Example 1. 1.82 g, yield: 60%) was obtained.
GC-Mass (이론치: 714.85 g/mol, 측정치: 715 g/mol)GC-Mass (Theoretical value: 714.85 g / mol, Measured value: 715 g / mol)
[합성예 4] 화합물 Inv-4의 합성Synthesis Example 4 Synthesis of Compound Inv-4
Figure PCTKR2013007821-appb-I000126
Figure PCTKR2013007821-appb-I000126
합성예 1에서 사용된 화합물 IC-1 대신 준비예 3에서 얻은 화합물 IC-5(3 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-4 (1.52 g, 수율: 50 %)를 얻었다.A compound Inv-4 (Ind-4) was prepared in the same manner as in Synthesis Example 1, except that Compound IC-5 (3 g, 10.63 mmol) obtained in Preparation Example 3 was used instead of Compound IC-1 used in Synthesis Example 1. 1.52 g, yield: 50%) was obtained.
GC-Mass (이론치: 714.85 g/mol, 측정치: 715 g/mol)GC-Mass (Theoretical value: 714.85 g / mol, Measured value: 715 g / mol)
[합성예 5] 화합물 Inv-5의 합성Synthesis Example 5 Synthesis of Compound Inv-5
Figure PCTKR2013007821-appb-I000127
Figure PCTKR2013007821-appb-I000127
합성예 1에서 사용된 화합물 IC-1 대신 준비예 1에서 얻은 화합물 IC-2 (3 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-4 (1.34 g, 수율: 44 %)를 얻었다.A compound Inv-4 (Ind-4) was prepared in the same manner as in Synthesis Example 1, except that Compound IC-2 (3 g, 10.63 mmol) obtained in Preparation Example 1 was used instead of Compound IC-1 used in Synthesis Example 1. 1.34 g, yield: 44%) was obtained.
GC-Mass (이론치: 714.85 g/mol, 측정치: 715 g/mol)GC-Mass (Theoretical value: 714.85 g / mol, Measured value: 715 g / mol)
[합성예 6] 화합물 Inv-6의 합성Synthesis Example 6 Synthesis of Compound Inv-6
Figure PCTKR2013007821-appb-I000128
Figure PCTKR2013007821-appb-I000128
합성예 1에서 사용된 화합물 IC-1 대신 준비예 2에서 얻은 화합물 IC-4 (3 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-6 (1.4 g, 수율: 46 %)를 얻었다.A compound Inv-6 was prepared by the same procedure as in Synthesis Example 1, except that Compound IC-4 (3 g, 10.63 mmol) obtained in Preparation Example 2 was used instead of Compound IC-1 used in Synthesis Example 1. 1.4 g, yield: 46%).
GC-Mass (이론치: 714.85 g/mol, 측정치: 715 g/mol)GC-Mass (Theoretical value: 714.85 g / mol, Measured value: 715 g / mol)
[합성예 7] 화합물 Inv-7의 합성Synthesis Example 7 Synthesis of Compound Inv-7
Figure PCTKR2013007821-appb-I000129
Figure PCTKR2013007821-appb-I000129
합성예 1에서 사용된 4,4'-dibromo-1,1'-biphenyl 대신 2,7-dibromo-9-phenyl-9H-carbazole (1.70 g, 4.25 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-7 (1.67 g, 수율: 53 %)를 얻었다.Except for using 2,7-dibromo-9-phenyl-9H-carbazole (1.70 g, 4.25 mmol) instead of 4,4'-dibromo-1,1'-biphenyl used in Synthesis Example 1, the synthesis The same procedure as in Example 1 was carried out to obtain compound Inv-7 (1.67 g, yield: 53%).
GC-Mass (이론치: 803.95 g/mol, 측정치: 803 g/mol)GC-Mass (Theoretical value: 803.95 g / mol, Measured value: 803 g / mol)
[합성예 8] 화합물 Inv-8의 합성Synthesis Example 8 Synthesis of Compound Inv-8
Figure PCTKR2013007821-appb-I000130
Figure PCTKR2013007821-appb-I000130
합성예 1에서 사용된 4,4'-dibromo-1,1'-biphenyl 대신 2,7-dibromo-9,9-dimethyl-9H-fluorene (1.50 g, 4.25 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-8 (1.47 g, 수율: 46 %)를 얻었다.Except for using 2,7-dibromo-9,9-dimethyl-9H-fluorene (1.50 g, 4.25 mmol) instead of 4,4'-dibromo-1,1'-biphenyl used in Synthesis Example 1, Compound Inv-8 (1.47 g, yield: 46%) was obtained by the same process as in Synthesis Example 1.
GC-Mass (이론치: 754.92 g/mol, 측정치: 754 g/mol)GC-Mass (Theoretical value: 754.92 g / mol, Measured value: 754 g / mol)
[합성예 9] 화합물 Inv-9의 합성Synthesis Example 9 Synthesis of Compound Inv-9
Figure PCTKR2013007821-appb-I000131
Figure PCTKR2013007821-appb-I000131
합성예 1에서 사용된 4,4'-dibromo-1,1'-biphenyl 대신 2,7-dibromo-9,9-diphenyl-9H-fluorene (2.02 g, 4.25 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-9 (1.83 g, 수율: 49 %)를 얻었다.Except for using 2,7-dibromo-9,9-diphenyl-9H-fluorene (2.02 g, 4.25 mmol) instead of 4,4'-dibromo-1,1'-biphenyl used in Synthesis Example 1, Compound Inv-9 (1.83 g, yield: 49%) was obtained by the same process as in Synthesis Example 1.
GC-Mass (이론치: 879.06 g/mol, 측정치: 879 g/mol)GC-Mass (Theoretical value: 879.06 g / mol, Measured value: 879 g / mol)
[합성예 10] 화합물 Inv-10의 합성Synthesis Example 10 Synthesis of Compound Inv-10
Figure PCTKR2013007821-appb-I000132
Figure PCTKR2013007821-appb-I000132
합성예 1에서 사용된 4,4'-dibromo-1,1'-biphenyl 대신 2,7-dibromo-9,9'-spirobi[fluorene] (2.01 g, 4.25 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-10 (1.75 g, 수율: 47 %)를 얻었다.Except for using 2,7-dibromo-9,9'-spirobi [fluorene] (2.01 g, 4.25 mmol) instead of 4,4'-dibromo-1,1'-biphenyl used in Synthesis Example 1, Compound Inv-10 (1.75 g, yield: 47%) was obtained by the same process as in Synthesis Example 1.
GC-Mass (이론치: 877.04 g/mol, 측정치: 877 g/mol)GC-Mass (Theoretical value: 877.04 g / mol, Measured value: 877 g / mol)
[합성예 11] 화합물 Inv-11의 합성Synthesis Example 11 Synthesis of Compound Inv-11
Figure PCTKR2013007821-appb-I000133
Figure PCTKR2013007821-appb-I000133
합성예 1에서 사용된 4,4'-dibromo-1,1'-biphenyl 대신 4,4'-dibromo-2,2'-dimethyl-1,1'-biphenyl (1.44 g, 4.25 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-11 (1.74 g, 수율: 55 %)를 얻었다.4,4'-dibromo-2,2'-dimethyl-1,1'-biphenyl (1.44 g, 4.25 mmol) instead of 4,4'-dibromo-1,1'-biphenyl used in Synthesis Example 1 Except that, the same procedure as in Synthesis Example 1 was carried out to obtain compound Inv-11 (1.74 g, yield: 55%).
GC-Mass (이론치: 742.91 g/mol, 측정치: 742 g/mol)GC-Mass (Theoretical value: 742.91 g / mol, Measured value: 742 g / mol)
[합성예 12] 화합물 Inv-12의 합성Synthesis Example 12 Synthesis of Compound Inv-12
Figure PCTKR2013007821-appb-I000134
Figure PCTKR2013007821-appb-I000134
합성예 1에서 사용된 4,4'-dibromo-1,1'-biphenyl 대신 3,3'-dibromo-1,1'-biphenyl (1.33 g, 4.25 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-12 (1.85 g, 수율: 61 %)를 얻었다.Except for using 3,3'-dibromo-1,1'-biphenyl (1.33 g, 4.25 mmol) instead of 4,4'-dibromo-1,1'-biphenyl used in Synthesis Example 1, the synthesis The same procedure as in Example 1 was carried out to obtain compound Inv-12 (1.85 g, yield: 61%).
GC-Mass (이론치: 714.85 g/mol, 측정치: 714 g/mol)GC-Mass (Theoretical value: 714.85 g / mol, Measured value: 714 g / mol)
[합성예 13] 화합물 Inv-13의 합성Synthesis Example 13 Synthesis of Compound Inv-13
Figure PCTKR2013007821-appb-I000135
Figure PCTKR2013007821-appb-I000135
합성예 1에서 사용된 4,4'-dibromo-1,1'-biphenyl 대신 1,3-dibromobenzene (1.00 g, 4.25 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-13 (1.90 g, 수율: 70 %)를 얻었다.The same procedure as in Synthesis Example 1 was performed except that 1,3-dibromobenzene (1.00 g, 4.25 mmol) was used instead of 4,4'-dibromo-1,1'-biphenyl used in Synthesis Example 1. Compound Inv-13 (1.90 g, yield: 70%) was obtained.
GC-Mass (이론치: 638.76 g/mol, 측정치: 638 g/mol)GC-Mass (Theoretical value: 638.76 g / mol, Measured value: 638 g / mol)
[합성예 14] 화합물 Inv-14의 합성Synthesis Example 14 Synthesis of Compound Inv-14
합성예 1에서 사용된 4,4'-dibromo-1,1'-biphenyl 대신 3,5-dibromo-1,1'-biphenyl (1.33 g, 4.25 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-14 (1.76 g, 수율: 58 %)를 얻었다.Synthesis Example 3,5-dibromo-1,1'-biphenyl (1.33 g, 4.25 mmol) was used instead of 4,4'-dibromo-1,1'-biphenyl used in Synthesis Example 1. Compound Inv-14 (1.76 g, yield: 58%) was obtained in the same manner as 1.
GC-Mass (이론치: 714.85 g/mol, 측정치: 714 g/mol)GC-Mass (Theoretical value: 714.85 g / mol, Measured value: 714 g / mol)
[합성예 15] 화합물 Inv-15의 합성Synthesis Example 15 Synthesis of Compound Inv-15
Figure PCTKR2013007821-appb-I000137
Figure PCTKR2013007821-appb-I000137
합성예 1에서 사용된 4,4'-dibromo-1,1'-biphenyl 대신 2,4-dibromo-6-phenyl-1,3,5-triazine (1.34 g, 4.25 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-15 (1.34 g, 수율: 44 %)를 얻었다.Except for using 2,4-dibromo-6-phenyl-1,3,5-triazine (1.34 g, 4.25 mmol) instead of 4,4'-dibromo-1,1'-biphenyl used in Synthesis Example 1 Was carried out in the same manner as in Synthesis Example 1 to obtain compound Inv-15 (1.34 g, yield: 44%).
GC-Mass (이론치: 717.82 g/mol, 측정치: 717 g/mol)GC-Mass (Theoretical value: 717.82 g / mol, Measured value: 717 g / mol)
[합성예 16] 화합물 Inv-16의 합성Synthesis Example 16 Synthesis of Compound Inv-16
Figure PCTKR2013007821-appb-I000138
Figure PCTKR2013007821-appb-I000138
합성예 7에서 사용된 화합물 IC-1 대신 준비예 2에서 얻은 화합물 IC-3 (3 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 7과 동일한 과정을 수행하여 화합물 Inv-16 (1.74 g, 수율: 51 %)를 얻었다.Compound Inv-16 (3) was carried out in the same manner as in Synthesis Example 7, except that Compound IC-3 (3 g, 10.63 mmol) obtained in Preparation Example 2 was used instead of Compound IC-1 used in Synthesis Example 7. 1.74 g, yield: 51%) was obtained.
GC-Mass (이론치: 803.95 g/mol, 측정치: 803 g/mol)GC-Mass (Theoretical value: 803.95 g / mol, Measured value: 803 g / mol)
[합성예 17] 화합물 Inv-17의 합성Synthesis Example 17 Synthesis of Compound Inv-17
Figure PCTKR2013007821-appb-I000139
Figure PCTKR2013007821-appb-I000139
합성예 8에서 사용된 화합물 IC-1 대신 준비예 2에서 얻은 화합물 IC-3 (3 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 8과 동일한 과정을 수행하여 화합물 Inv-17 (1.76 g, 수율: 55 %)를 얻었다.Compound Inv-17 (Compound Inv-17 (Compound 3-1) (3 g, 10.63 mmol) obtained in Preparation Example 2 was used instead of compound IC-1 used in Synthesis Example 8 by the same procedure as in Synthesis Example 8. 1.76 g, yield: 55%) was obtained.
GC-Mass (이론치: 754.92 g/mol, 측정치: 754 g/mol)GC-Mass (Theoretical value: 754.92 g / mol, Measured value: 754 g / mol)
[합성예 18] 화합물 Inv-18의 합성Synthesis Example 18 Synthesis of Compound Inv-18
Figure PCTKR2013007821-appb-I000140
Figure PCTKR2013007821-appb-I000140
합성예 9에서 사용된 화합물 IC-1 대신 준비예 2에서 얻은 화합물 IC-3(3 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 9와 동일한 과정을 수행하여 화합물 Inv-18 (1.76 g, 수율: 47 %)를 얻었다.A compound Inv-18 was prepared by the same procedure as in Synthesis Example 9, except that Compound IC-3 (3 g, 10.63 mmol) obtained in Preparation Example 2 was used instead of Compound IC-1 used in Synthesis Example 9. 1.76 g, yield: 47%).
GC-Mass (이론치: 879.06 g/mol, 측정치: 879 g/mol)GC-Mass (Theoretical value: 879.06 g / mol, Measured value: 879 g / mol)
[합성예 19] 화합물 Inv-19의 합성Synthesis Example 19 Synthesis of Compound Inv-19
Figure PCTKR2013007821-appb-I000141
Figure PCTKR2013007821-appb-I000141
합성예 10에서 사용된 화합물 IC-1 대신 준비예 2에서 얻은 화합물 IC-3 (3 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 10과 동일한 과정을 수행하여 화합물 Inv-19 (1.94 g, 수율: 52 %)를 얻었다.Except for using the compound IC-3 (3 g, 10.63 mmol) obtained in Preparation Example 2 instead of the compound IC-1 used in Synthesis Example 10, the compound Inv-19 ( 1.94 g, yield: 52%) was obtained.
GC-Mass (이론치: 877.04 g/mol, 측정치: 877 g/mol)GC-Mass (Theoretical value: 877.04 g / mol, Measured value: 877 g / mol)
[합성예 20] 화합물 Inv-20의 합성Synthesis Example 20 Synthesis of Compound Inv-20
Figure PCTKR2013007821-appb-I000142
Figure PCTKR2013007821-appb-I000142
합성예 11에서 사용된 화합물 IC-1 대신 준비예 2에서 얻은 화합물 IC-3 (3 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 11과 동일한 과정을 수행하여 화합물 Inv-20 (1.67 g, 수율: 53 %)를 얻었다.A compound Inv-20 was prepared by the same procedure as in Synthesis Example 11, except that Compound IC-3 (3 g, 10.63 mmol) obtained in Preparation Example 2 was used instead of Compound IC-1 used in Synthesis Example 11. 1.67 g, yield: 53%) was obtained.
GC-Mass (이론치: 742.91 g/mol, 측정치: 742 g/mol)GC-Mass (Theoretical value: 742.91 g / mol, Measured value: 742 g / mol)
[합성예 21] 화합물 Inv-21의 합성Synthesis Example 21 Synthesis of Compound Inv-21
Figure PCTKR2013007821-appb-I000143
Figure PCTKR2013007821-appb-I000143
합성예 12에서 사용된 화합물 IC-1 대신 준비예 2에서 얻은 화합물 IC-3 (3 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 12와 동일한 과정을 수행하여 화합물 Inv-21 (2.07 g, 수율: 68 %)를 얻었다.Except for using the compound IC-3 (3 g, 10.63 mmol) obtained in Preparation Example 2 instead of the compound IC-1 used in Synthesis Example 12, the compound Inv-21 ( 2.07 g, yield: 68%).
GC-Mass (이론치: 714.85 g/mol, 측정치: 714 g/mol)GC-Mass (Theoretical value: 714.85 g / mol, Measured value: 714 g / mol)
[합성예 22] 화합물 Inv-22의 합성Synthesis Example 22 Synthesis of Compound Inv-22
Figure PCTKR2013007821-appb-I000144
Figure PCTKR2013007821-appb-I000144
합성예 13에서 사용된 화합물 IC-1 대신 준비예 2에서 얻은 화합물 IC-3 (3 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 13과 동일한 과정을 수행하여 화합물 Inv-22 (1.36 g, 수율: 50 %)를 얻었다.Except for using the compound IC-3 (3 g, 10.63 mmol) obtained in Preparation Example 2 instead of the compound IC-1 used in Synthesis Example 13, the compound Inv-22 ( 1.36 g, yield: 50%) was obtained.
GC-Mass (이론치: 638.76 g/mol, 측정치: 638 g/mol)GC-Mass (Theoretical value: 638.76 g / mol, Measured value: 638 g / mol)
[합성예 23] 화합물 Inv-23의 합성Synthesis Example 23 Synthesis of Compound Inv-23
Figure PCTKR2013007821-appb-I000145
Figure PCTKR2013007821-appb-I000145
합성예 14에서 사용된 화합물 IC-1 대신 준비예 2에서 얻은 화합물 IC-3 (3 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 14와 동일한 과정을 수행하여 화합물 Inv-23 (1.73 g, 수율: 57 %)를 얻었다.A compound Inv-23 (Ind-23) was obtained by the same procedure as in Synthesis Example 14, except that Compound IC-3 (3 g, 10.63 mmol) obtained in Preparation Example 2 was used instead of Compound IC-1 used in Synthesis Example 14. 1.73 g, yield: 57%) was obtained.
GC-Mass (이론치: 714.85 g/mol, 측정치: 714 g/mol)GC-Mass (Theoretical value: 714.85 g / mol, Measured value: 714 g / mol)
[합성예 24] 화합물 Inv-24의 합성Synthesis Example 24 Synthesis of Compound Inv-24
Figure PCTKR2013007821-appb-I000146
Figure PCTKR2013007821-appb-I000146
합성예 15에서 사용된 화합물 IC-1 대신 준비예 2에서 얻은 화합물 IC-3 (3 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 15와 동일한 과정을 수행하여 화합물 Inv-24 (1.22 g, 수율: 40 %)를 얻었다.Except for using the compound IC-3 (3 g, 10.63 mmol) obtained in Preparation Example 2 instead of the compound IC-1 used in Synthesis Example 15, the compound Inv-24 ( 1.22 g, yield: 40%) was obtained.
GC-Mass (이론치: 717.82 g/mol, 측정치: 717 g/mol)GC-Mass (Theoretical value: 717.82 g / mol, Measured value: 717 g / mol)
[합성예 25] 화합물 Inv-25의 합성Synthesis Example 25 Synthesis of Compound Inv-25
Figure PCTKR2013007821-appb-I000147
Figure PCTKR2013007821-appb-I000147
합성예 11에서 사용된 화합물 IC-1 대신 준비예 4에서 얻은 화합물 IC-6 (3 g, 10.63 mmol)을 사용하는 것을 제외하고는, 상기 합성예 11과 동일한 과정을 수행하여 화합물 Inv-25 (1.55 g, 수율: 49 %)를 얻었다.Except for using the compound IC-6 (3 g, 10.63 mmol) obtained in Preparation Example 4 instead of the compound IC-1 used in Synthesis Example 11, the compound Inv-25 ( 1.55 g, yield: 49%) was obtained.
GC-Mass (이론치: 742.91 g/mol, 측정치: 742 g/mol)GC-Mass (Theoretical value: 742.91 g / mol, Measured value: 742 g / mol)
[합성예 26] 화합물 Inv-26의 합성Synthesis Example 26 Synthesis of Compound Inv-26
Figure PCTKR2013007821-appb-I000148
Figure PCTKR2013007821-appb-I000148
합성예 11에서 사용된 화합물 IC-1 대신 준비예 3에서 얻은 화합물 IC-5 (3 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 11과 동일한 과정을 수행하여 화합물 Inv-26 (1.58 g, 수율: 50 %)를 얻었다.Except for using the compound IC-5 (3 g, 10.63 mmol) obtained in Preparation Example 3 instead of the compound IC-1 used in Synthesis Example 11, the compound Inv-26 ( 1.58 g, yield: 50%) was obtained.
GC-Mass (이론치: 742.91 g/mol, 측정치: 742 g/mol)GC-Mass (Theoretical value: 742.91 g / mol, Measured value: 742 g / mol)
[합성예 27] 화합물 Inv-27의 합성Synthesis Example 27 Synthesis of Compound Inv-27
Figure PCTKR2013007821-appb-I000149
Figure PCTKR2013007821-appb-I000149
합성예 11에서 사용된 화합물 IC-1 대신 준비예 1에서 얻은 화합물 IC-2 (3 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 11과 동일한 과정을 수행하여 화합물 Inv-27 (1.95 g, 수율: 62 %)를 얻었다.A compound Inv-27 (Comparative Example 11) was carried out in the same manner as in Synthesis Example 11, except that Compound IC-2 (3 g, 10.63 mmol) obtained in Preparation Example 1 was used instead of Compound IC-1 used in Synthesis Example 11. 1.95 g, yield: 62%).
GC-Mass (이론치: 742.91 g/mol, 측정치: 742 g/mol)GC-Mass (Theoretical value: 742.91 g / mol, Measured value: 742 g / mol)
[합성예 28] 화합물 Inv-28의 합성Synthesis Example 28 Synthesis of Compound Inv-28
Figure PCTKR2013007821-appb-I000150
Figure PCTKR2013007821-appb-I000150
합성예 11에서 사용된 화합물 IC-1 대신 준비예 2에서 얻은 화합물 IC-4 (3 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 11과 동일한 과정을 수행하여 화합물 Inv-28 (1.90 g, 수율: 60 %)를 얻었다.Except for using the compound IC-4 (3 g, 10.63 mmol) obtained in Preparation Example 2 instead of the compound IC-1 used in Synthesis Example 11, the compound Inv-28 ( 1.90 g, yield: 60%).
GC-Mass (이론치: 742.91 g/mol, 측정치: 742 g/mol)GC-Mass (Theoretical value: 742.91 g / mol, Measured value: 742 g / mol)
[합성예 29] 화합물 Inv-29의 합성Synthesis Example 29 Synthesis of Compound Inv-29
Figure PCTKR2013007821-appb-I000151
Figure PCTKR2013007821-appb-I000151
합성예 15에서 사용된 화합물 IC-1 대신 준비예 4에서 얻은 화합물 IC-6 (3 g, 10.63 mmol)을 사용하는 것을 제외하고는, 상기 합성예 15와 동일한 과정을 수행하여 화합물 Inv-29 (1.71 g, 수율: 56 %)를 얻었다.A compound Inv-29 (Compound Inv-29 ( 1.71 g, yield: 56%) was obtained.
GC-Mass (이론치: 717.82 g/mol, 측정치: 717 g/mol)GC-Mass (Theoretical value: 717.82 g / mol, Measured value: 717 g / mol)
[합성예 30] 화합물 Inv-30의 합성Synthesis Example 30 Synthesis of Compound Inv-30
Figure PCTKR2013007821-appb-I000152
Figure PCTKR2013007821-appb-I000152
합성예 15에서 사용된 화합물 IC-1 대신 준비예 3에서 얻은 화합물 IC-5 (3 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 15와 동일한 과정을 수행하여 화합물 Inv-30 (1.92 g, 수율: 63 %)를 얻었다.A compound Inv-30 (Synthesis Example 15) was performed in the same manner as in Synthesis Example 15, except that Compound IC-5 (3 g, 10.63 mmol) obtained in Preparation Example 3 was used instead of Compound IC-1 used in Synthesis Example 15. 1.92 g, yield: 63%).
GC-Mass (이론치: 717.82 g/mol, 측정치: 717 g/mol)GC-Mass (Theoretical value: 717.82 g / mol, Measured value: 717 g / mol)
[합성예 31] 화합물 Inv-31의 합성Synthesis Example 31 Synthesis of Compound Inv-31
Figure PCTKR2013007821-appb-I000153
Figure PCTKR2013007821-appb-I000153
합성예 15에서 사용된 화합물 IC-1 대신 준비예 1에서 얻은 화합물 IC-2 (3 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 15와 동일한 과정을 수행하여 화합물 Inv-31 (1.86 g, 수율: 61 %)를 얻었다.Except for using the compound IC-2 (3 g, 10.63 mmol) obtained in Preparation Example 1 instead of the compound IC-1 used in Synthesis Example 15, the compound Inv-31 ( 1.86 g, yield: 61%).
GC-Mass (이론치: 717.82 g/mol, 측정치: 717 g/mol)GC-Mass (Theoretical value: 717.82 g / mol, Measured value: 717 g / mol)
[합성예 32] 화합물 Inv-32의 합성Synthesis Example 32 Synthesis of Compound Inv-32
Figure PCTKR2013007821-appb-I000154
Figure PCTKR2013007821-appb-I000154
합성예 15에서 사용된 화합물 IC-1 대신 준비예 2에서 얻은 화합물 IC-4 (3 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 15와 동일한 과정을 수행하여 화합물 Inv-32 (1.47 g, 수율: 48 %)를 얻었다.A compound Inv-32 (Compound Inv-32 ( 1.47 g, yield: 48%) was obtained.
GC-Mass (이론치: 717.82 g/mol, 측정치: 717 g/mol)GC-Mass (Theoretical value: 717.82 g / mol, Measured value: 717 g / mol)
[합성예 33] 화합물 Inv-33의 합성Synthesis Example 33 Synthesis of Compound Inv-33
Figure PCTKR2013007821-appb-I000155
Figure PCTKR2013007821-appb-I000155
합성예 1에서 사용된 화합물 IC-1 대신 준비예 17에서 얻은 화합물 IC-19 (6.40 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-33 (2.30 g, 수율: 40 %)를 얻었다.Except for using the compound IC-19 (6.40 g, 10.63 mmol) obtained in Preparation Example 17 instead of the compound IC-1 used in Synthesis Example 1, the compound Inv-33 ( 2.30 g, yield: 40%).
GC-Mass (이론치: 1355.55 g/mol, 측정치: 1355 g/mol)GC-Mass (Theoretical value: 1355.55 g / mol, Measured value: 1355 g / mol)
[합성예 34] 화합물 Inv-34의 합성Synthesis Example 34 Synthesis of Compound Inv-34
Figure PCTKR2013007821-appb-I000156
Figure PCTKR2013007821-appb-I000156
합성예 1에서 사용된 화합물 IC-1 대신 준비예 9에서 얻은 화합물 IC-11 (4.61 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-34 (2.47 g, 수율: 57 %)를 얻었다.Except for using the compound IC-11 (4.61 g, 10.63 mmol) obtained in Preparation Example 9 instead of the compound IC-1 used in Synthesis Example 1, the compound Inv-34 ( 2.47 g, yield: 57%).
GC-Mass (이론치: 1019.24 g/mol, 측정치: 1018 g/mol)GC-Mass (Theoretical value: 1019.24 g / mol, Measured value: 1018 g / mol)
[합성예 35] 화합물 Inv-35의 합성Synthesis Example 35 Synthesis of Compound Inv-35
Figure PCTKR2013007821-appb-I000157
Figure PCTKR2013007821-appb-I000157
합성예 1에서 사용된 화합물 IC-1 대신 준비예 16에서 얻은 화합물 IC-18 (4.75 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-35 (2.40 g, 수율: 54 %)를 얻었다.Except for using the compound IC-18 (4.75 g, 10.63 mmol) obtained in Preparation Example 16 instead of the compound IC-1 used in Synthesis Example 1, the compound Inv-35 ( 2.40 g, yield: 54%).
GC-Mass (이론치: 1045.23 g/mol, 측정치: 1044 g/mol)GC-Mass (Theoretical value: 1045.23 g / mol, Measured value: 1044 g / mol)
[합성예 36] 화합물 Inv-36의 합성Synthesis Example 36 Synthesis of Compound Inv-36
Figure PCTKR2013007821-appb-I000158
Figure PCTKR2013007821-appb-I000158
합성예 1에서 사용된 화합물 IC-1 대신 준비예 30에서 얻은 화합물 IC-32 (5.45 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-36 (3.25 g, 수율: 65 %)를 얻었다.Except for using the compound IC-32 (5.45 g, 10.63 mmol) obtained in Preparation Example 30 instead of the compound IC-1 used in Synthesis Example 1, the compound Inv-36 ( 3.25 g, yield: 65%) was obtained.
GC-Mass (이론치: 1177.36 g/mol, 측정치: 1177 g/mol)GC-Mass (Theoretical value: 1177.36 g / mol, Measured value: 1177 g / mol)
[합성예 37] 화합물 Inv-37의 합성Synthesis Example 37 Synthesis of Compound Inv-37
Figure PCTKR2013007821-appb-I000159
Figure PCTKR2013007821-appb-I000159
합성예 1에서 사용된 화합물 IC-1 대신 준비예 8에서 얻은 화합물 IC-10 (3.80 g, 10.63 mmol)을 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-37 (2.28 g, 수율: 62 %)를 얻었다.Except for using the compound IC-10 (3.80 g, 10.63 mmol) obtained in Preparation Example 8 instead of the compound IC-1 used in Synthesis Example 1, the compound Inv-37 ( 2.28 g, yield: 62%).
GC-Mass (이론치: 867.05 g/mol, 측정치: 867 g/mol)GC-Mass (Theoretical value: 867.05 g / mol, Measured value: 867 g / mol)
[합성예 38] 화합물 Inv-38의 합성Synthesis Example 38 Synthesis of Compound Inv-38
Figure PCTKR2013007821-appb-I000160
Figure PCTKR2013007821-appb-I000160
합성예 1에서 사용된 화합물 IC-1 대신 준비예 11에서 얻은 화합물 IC-13 (3.80 g, 10.63 mmol)을 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-38 (2.14 g, 수율: 58 %)를 얻었다.Except for using the compound IC-13 (3.80 g, 10.63 mmol) obtained in Preparation Example 11 instead of the compound IC-1 used in Synthesis Example 1, the compound Inv-38 ( 2.14 g, yield: 58%).
GC-Mass (이론치: 867.05 g/mol, 측정치: 867 g/mol)GC-Mass (Theoretical value: 867.05 g / mol, Measured value: 867 g / mol)
[합성예 39] 화합물 Inv-39의 합성Synthesis Example 39 Synthesis of Compound Inv-39
Figure PCTKR2013007821-appb-I000161
Figure PCTKR2013007821-appb-I000161
<단계 1> 3,7-diphenyl-3,10-dihydropyrrolo[3,2-a]carbazole의 합성<Step 1> Synthesis of 3,7-diphenyl-3,10-dihydropyrrolo [3,2-a] carbazole
질소 기류 하에서 준비예 5에서 얻은 화합물 IC-7 (7-bromo-3-phenyl-3,10-dihydropyrrolo[3,2-a]carbazole) (5 g, 13.84 mmol)과 phenylboronic acid (2.03 g, 16.61 mmol), NaOH (1.66 g, 41.52 mmol) 및 THF/H2O(100 ml/500 ml)를 혼합한 다음, 40 ℃에서 Pd(PPh3)4 (0.80 g, 5 mol%)를 넣고, 80 ℃에서 12시간 동안 교반하였다. Compound IC-7 (7-bromo-3-phenyl-3,10-dihydropyrrolo [3,2-a] carbazole) (5 g, 13.84 mmol) and phenylboronic acid (2.03 g, 16.61) obtained in Preparation Example 5 under a nitrogen stream. mmol), NaOH (1.66 g, 41.52 mmol) and THF / H 2 O (100 ml / 500 ml) were mixed, and then Pd (PPh 3 ) 4 (0.80 g, 5 mol%) was added at 40 ° C, and 80 Stir at 12 ° C. for 12 h.
반응 종결 후 메틸렌클로라이드로 추출한 다음, MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:EA = 3:1 (v/v))로 정제하여 3,7-diphenyl-3,10-dihydropyrrolo[3,2-a]carbazole을 얻었다.After completion of the reaction was extracted with methylene chloride, MgSO 4 was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: EA = 3: 1 (v / v)) to obtain 3,7-diphenyl-3,10-dihydropyrrolo [3,2-a] carbazole.
<단계 2> 화합물 Inv-39의 합성Step 2 Synthesis of Compound Inv-39
합성예 1에서 사용된 화합물 IC-1 대신 상기 합성예 39의 <단계 1>에서 얻은 3,7-diphenyl-3,10-dihydropyrrolo[3,2-a]carbazole (3.80 g, 10.63 mmol)을 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-39 (1.47 g, 수율: 40 %)를 얻었다. Instead of compound IC-1 used in Synthesis Example 1, 3,7-diphenyl-3,10-dihydropyrrolo [3,2-a] carbazole (3.80 g, 10.63 mmol) obtained in <Step 1> of Synthesis Example 39 was used. A compound Inv-39 (1.47 g, yield: 40%) was obtained in the same manner as in Synthesis Example 1, except that.
GC-Mass (이론치: 867.05 g/mol, 측정치: 867 g/mol)GC-Mass (Theoretical value: 867.05 g / mol, Measured value: 867 g / mol)
[합성예 40] 화합물 Inv-40의 합성Synthesis Example 40 Synthesis of Compound Inv-40
Figure PCTKR2013007821-appb-I000162
Figure PCTKR2013007821-appb-I000162
합성예 1에서 사용된 화합물 IC-1 대신 준비예 18에서 얻은 화합물 IC-20 (3.80 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-40 (2.62 g, 수율: 71 %)를 얻었다.A compound Inv-40 was prepared in the same manner as in Synthesis Example 1, except that Compound IC-20 (3.80 g, 10.63 mmol) obtained in Preparation Example 18 was used instead of Compound IC-1 used in Synthesis Example 1. 2.62 g, yield: 71%).
GC-Mass (이론치: 867.05 g/mol, 측정치: 867 g/mol)GC-Mass (Theoretical value: 867.05 g / mol, Measured value: 867 g / mol)
[합성예 41] Inv-41의 합성Synthesis Example 41 Synthesis of Inv-41
Figure PCTKR2013007821-appb-I000163
Figure PCTKR2013007821-appb-I000163
합성예 1에서 사용된 화합물 IC-1 대신 준비예 16에서 얻은 화합물 IC-16 (4.61 g, 10.63 mmol)을 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-41 (1.77 g, 수율: 41 %)를 얻었다.Compound Inv-41 (Complete Example 1) was carried out in the same manner as in Synthesis Example 1, except that Compound IC-16 (4.61 g, 10.63 mmol) obtained in Preparation Example 16 was used instead of Compound IC-1 used in Synthesis Example 1. 1.77 g, yield: 41%).
GC-Mass (이론치: 1019.24 g/mol, 측정치: 1019 g/mol)GC-Mass (Theoretical value: 1019.24 g / mol, Measured value: 1019 g / mol)
[합성예 42] 화합물 Inv-42의 합성Synthesis Example 42 Synthesis of Compound Inv-42
Figure PCTKR2013007821-appb-I000164
Figure PCTKR2013007821-appb-I000164
합성예 1에서 사용된 화합물 IC-1 대신 준비예 15에서 얻은 화합물 IC-17 (5.45 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-42 (3.00 g, 수율: 60 %)를 얻었다.Except for using the compound IC-17 (5.45 g, 10.63 mmol) obtained in Preparation Example 15 instead of the compound IC-1 used in Synthesis Example 1, and the compound Inv-42 ( 3.00 g, yield: 60%) was obtained.
GC-Mass (이론치: 1177.36 g/mol, 측정치: 1177 g/mol)GC-Mass (Theoretical value: 1177.36 g / mol, Measured value: 1177 g / mol)
[합성예 43] 화합물 Inv-43의 합성Synthesis Example 43 Synthesis of Compound Inv-43
Figure PCTKR2013007821-appb-I000165
Figure PCTKR2013007821-appb-I000165
합성예 1에서 사용된 화합물 IC-1 대신 준비예 13에서 얻은 화합물 IC-15 (3.80 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-43 (1.44 g, 수율: 39 %)를 얻었다.Except for using the compound IC-15 (3.80 g, 10.63 mmol) obtained in Preparation Example 13 instead of the compound IC-1 used in Synthesis Example 1, the compound Inv-43 ( 1.44 g, yield: 39%) was obtained.
GC-Mass (이론치: 867.05 g/mol, 측정치: 867 g/mol)GC-Mass (Theoretical value: 867.05 g / mol, Measured value: 867 g / mol)
[합성예 44] 화합물 Inv-44의 합성Synthesis Example 44 Synthesis of Compound Inv-44
Figure PCTKR2013007821-appb-I000166
Figure PCTKR2013007821-appb-I000166
합성예 39에서 사용된 화합물 IC-1 대신 준비예 12에서 얻은 화합물 IC-14 (3.80 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-44 (2.54 g, 수율: 69 %)를 얻었다.Compound Inv-44 (Compound Inv-44 (Compound 1-4) (3.80 g, 10.63 mmol) obtained in Preparation Example 12 was used instead of compound IC-1 used in Synthesis Example 39. 2.54 g, yield: 69%).
GC-Mass (이론치: 867.05 g/mol, 측정치: 867 g/mol)GC-Mass (Theoretical value: 867.05 g / mol, Measured value: 867 g / mol)
[합성예 45] 화합물 Inv-45의 합성Synthesis Example 45 Synthesis of Compound Inv-45
Figure PCTKR2013007821-appb-I000167
Figure PCTKR2013007821-appb-I000167
합성예 39의 <단계 1>에서 사용된 화합물 IC-7 대신 준비예 6에서 얻은 화합물 IC-8 (3.80 g, 10.63 mmol)을 사용하는 것을 제외하고는, 합성예 39와 동일하게 수행하여 화합물 Inv-45 (1.80 g, 수율: 49 %)를 얻었다.Compound Inv was carried out in the same manner as in Synthesis Example 39, except that Compound IC-8 (3.80 g, 10.63 mmol) obtained in Preparation Example 6 was used instead of Compound IC-7 used in <Step 1> of Synthesis Example 39. -45 (1.80 g, yield: 49%) was obtained.
GC-Mass (이론치: 867.05 g/mol, 측정치: 867 g/mol)GC-Mass (Theoretical value: 867.05 g / mol, Measured value: 867 g / mol)
[합성예 46] 화합물 Inv-46의 합성Synthesis Example 46 Synthesis of Compound Inv-46
Figure PCTKR2013007821-appb-I000168
Figure PCTKR2013007821-appb-I000168
합성예 1에서 사용된 화합물 IC-1 대신 준비예 19에서 얻은 화합물 IC-21 (3.80 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-46 (1.88 g, 수율: 51 %)를 얻었다.Except for using the compound IC-21 (3.80 g, 10.63 mmol) obtained in Preparation Example 19 instead of the compound IC-1 used in Synthesis Example 1, the compound Inv-46 ( 1.88 g, yield: 51%) was obtained.
GC-Mass (이론치: 867.05 g/mol, 측정치: 867 g/mol)GC-Mass (Theoretical value: 867.05 g / mol, Measured value: 867 g / mol)
[합성예 47] 화합물 Inv-47의 합성Synthesis Example 47 Synthesis of Compound Inv-47
Figure PCTKR2013007821-appb-I000169
Figure PCTKR2013007821-appb-I000169
합성예 1에서 사용된 화합물 IC-1 대신 준비예 27에서 얻은 화합물 IC-29 (3.00 g, 10.63 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-47 (1.88 g, 수율: 62 %)를 얻었다.Except for using the compound IC-29 (3.00 g, 10.63 mmol) obtained in Preparation Example 27 instead of the compound IC-1 used in Synthesis Example 1, and the compound Inv-47 ( 1.88 g, yield: 62%).
GC-Mass (이론치: 714.85 g/mol, 측정치: 714 g/mol)GC-Mass (Theoretical value: 714.85 g / mol, Measured value: 714 g / mol)
[합성예 48] 화합물 Inv-48의 합성Synthesis Example 48 Synthesis of Compound Inv-48
Figure PCTKR2013007821-appb-I000170
Figure PCTKR2013007821-appb-I000170
합성예 1에서 사용된 화합물 IC-1 대신 준비예 28에서 얻은 화합물 IC-30 (3.00 g, 10.63 mmol)을 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-48 (1.67 g, 수율: 58 %)를 얻었다.Except for using the compound IC-30 (3.00 g, 10.63 mmol) obtained in Preparation Example 28 instead of the compound IC-1 used in Synthesis Example 1, the compound Inv-48 ( 1.67 g, yield: 58%) was obtained.
GC-Mass (이론치: 714.85 g/mol, 측정치: 714 g/mol)GC-Mass (Theoretical value: 714.85 g / mol, Measured value: 714 g / mol)
[합성예 49] 화합물 Inv-49의 합성Synthesis Example 49 Synthesis of Compound Inv-49
Figure PCTKR2013007821-appb-I000171
Figure PCTKR2013007821-appb-I000171
<단계 1> 10-(4'-bromo-[1,1'-biphenyl]-4-yl)-3-phenyl-3,10-dihydropyrrolo[3,2-a]carbazole의 합성Synthesis of 10- (4'-bromo- [1,1'-biphenyl] -4-yl) -3-phenyl-3,10-dihydropyrrolo [3,2-a] carbazole
질소 기류 하에서 준비예 1에서 얻은 화합물 IC-1 (1.2 g, 4.25 mmol), 4,4'-dibromo-1,1'-biphenyl (1.33 g, 4.25 mmol), Cu powder (0.03 g, 0.43 mmol), K2CO3 (0.59 g, 0.43 mmol), Na2SO4 (0.6 g, 0.43 mmol), nitrobenzene (50 ml)를 혼합한 다음, 210 ℃에서 24시간 동안 교반하였다. Compound IC-1 (1.2 g, 4.25 mmol), 4,4'-dibromo-1,1'-biphenyl (1.33 g, 4.25 mmol), Cu powder (0.03 g, 0.43 mmol) obtained in Preparation Example 1 under nitrogen stream , K 2 CO 3 (0.59 g, 0.43 mmol), Na 2 SO 4 (0.6 g, 0.43 mmol) and nitrobenzene (50 ml) were mixed and then stirred at 210 ° C. for 24 hours.
반응 종결 후 nitrobenzene을 제거한 다음, 메틸렌클로라이드로 유기층을 분리하고, MgSO4를 사용하여 분리된 유기층에서 물을 제거하였다. 물이 제거된 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:MC = 1:1 (v/v))로 정제하여 10-(4'-bromo-[1,1'-biphenyl]-4-yl)-3-phenyl-3,10-dihydropyrrolo[3,2-a]carbazole 을 얻었다.After completion of the reaction, nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed from the separated organic layer using MgSO 4 . The solvent was removed from the organic layer, and then purified by column chromatography (Hexane: MC = 1: 1 (v / v)) to obtain 10- (4'-bromo- [1,1'-biphenyl] -4-yl ) -3-phenyl-3,10-dihydropyrrolo [3,2-a] carbazole was obtained.
<단계 2> 화합물 Inv-49의 합성Step 2 Synthesis of Compound Inv-49
합성예 1에서 사용된 화합물 IC-1 대신 9H-carbazole (0.71 g, 4.25 mmol)을 사용하고, 4,4'-dibromo-1,1'-biphenyl 대신 상기 합성예 49의 <단계 1>에서 얻은 10-(4'-bromo-[1,1'-biphenyl]-4-yl)-3-phenyl-3,10-dihydropyrrolo[3,2-a]carbazole (2.18 g, 4.25 mmol)을 사용하는 것을 제외하고는, 합성예 1과 동일하게 수행하여 화합물 Inv-49 (0.74 g, 수율: 29 %)를 얻었다. 9H-carbazole (0.71 g, 4.25 mmol) was used instead of the compound IC-1 used in Synthesis Example 1, and it was obtained in <Step 1> of Synthesis Example 49 instead of 4,4'-dibromo-1,1'-biphenyl. Using 10- (4'-bromo- [1,1'-biphenyl] -4-yl) -3-phenyl-3,10-dihydropyrrolo [3,2-a] carbazole (2.18 g, 4.25 mmol) A compound Inv-49 (0.74 g, yield: 29%) was obtained in the same manner as in Synthesis example 1 except for the same.
GC-Mass (이론치: 599.72 g/mol, 측정치: 599 g/mol)GC-Mass (Theoretical value: 599.72 g / mol, Measured value: 599 g / mol)
[합성예 50] 화합물 Inv-50의 합성Synthesis Example 50 Synthesis of Compound Inv-50
Figure PCTKR2013007821-appb-I000172
Figure PCTKR2013007821-appb-I000172
합성예 49의 <단계 1>에서 사용된 화합물 IC-1 대신 준비예 4에서 얻은 화합물 IC-6 (1.2 g, 4.25 mmol)를 사용하는 것을 제외하고는, 상기 합성예 49와 동일한 과정을 수행하여 화합물 Inv-50 (0.59 g, 수율: 23 %)를 얻었다.The same procedure as in Synthesis Example 49 was carried out except that Compound IC-6 (1.2 g, 4.25 mmol) obtained in Preparation Example 4 was used instead of Compound IC-1 used in <Step 1> of Synthesis Example 49. Compound Inv-50 (0.59 g, yield: 23%) was obtained.
GC-Mass (이론치: 599.72 g/mol, 측정치: 599 g/mol)GC-Mass (Theoretical value: 599.72 g / mol, Measured value: 599 g / mol)
[합성예 51] 화합물 Inv-51의 합성Synthesis Example 51 Synthesis of Compound Inv-51
Figure PCTKR2013007821-appb-I000173
Figure PCTKR2013007821-appb-I000173
합성예 49의 <단계 2>에서 사용된 9H-carbazole 대신 준비예 4에서 얻은 화합물 IC-6 (1.2 g, 4.25 mmol)를 사용하는 것을 제외하고는, 상기 합성예 49와 동일한 과정을 수행하여 화합물 Inv-51 (0.40 g, 수율: 13 %)를 얻었다.A compound was prepared in the same manner as in Synthesis Example 49, except that Compound IC-6 (1.2 g, 4.25 mmol) obtained in Preparation Example 4 was used instead of 9H-carbazole used in <Step 2> of Synthesis Example 49. Inv-51 (0.40 g, yield: 13%) was obtained.
GC-Mass (이론치: 714.85 g/mol, 측정치: 714 g/mol)GC-Mass (Theoretical value: 714.85 g / mol, Measured value: 714 g / mol)
[합성예 52] 화합물 Inv-52의 합성Synthesis Example 52 Synthesis of Compound Inv-52
Figure PCTKR2013007821-appb-I000174
Figure PCTKR2013007821-appb-I000174
<단계 1> 7-(4-(9H-carbazol-9-yl)phenyl)-3-phenyl-3,10-dihydropyrrolo[3,2-a]carbazole의 합성Synthesis of 7- (4- (9H-carbazol-9-yl) phenyl) -3-phenyl-3,10-dihydropyrrolo [3,2-a] carbazole
질소 기류 하에서 준비예 5에서 얻은 화합물 IC-7 (5 g, 13.84 mmol)과 (4-(9H-carbazol-9-yl)phenyl)boronic acid (4.78 g, 16.61 mmol), NaOH (1.66 g, 41.52 mmol) 및 THF/H2O(100 ml/500 ml)를 혼합한 다음, 40 ℃에서 Pd(PPh3)4 (0.80 g, 5 mol%)를 넣은 후, 80 ℃에서 12시간 동안 교반하였다. Compounds IC-7 (5 g, 13.84 mmol) and (4- (9H-carbazol-9-yl) phenyl) boronic acid (4.78 g, 16.61 mmol), NaOH (1.66 g, 41.52) obtained in Preparation Example 5 under a nitrogen stream. mmol) and THF / H 2 O (100 ml / 500 ml) were mixed and Pd (PPh 3 ) 4 (0.80 g, 5 mol%) was added at 40 ° C., followed by stirring at 80 ° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출한 다음, MgSO4를 넣고 여과하여 유기층을 얻었다. 얻은 유기층에서 용매를 제거한 후, 컬럼 크로마토그래피 (Hexane:EA = 3:1 (v/v))로 정제하여 7-(4-(9H-carbazol-9-yl)phenyl)-3-phenyl-3,10-dihydropyrrolo[3,2-a]carbazole을 얻었다.After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered to obtain an organic layer. The solvent was removed from the organic layer obtained, and then purified by column chromatography (Hexane: EA = 3: 1 (v / v)) to obtain 7- (4- (9H-carbazol-9-yl) phenyl) -3-phenyl-3 , 10-dihydropyrrolo [3,2-a] carbazole was obtained.
<단계 2> 화합물 Inv-52의 합성Step 2 Synthesis of Compound Inv-52
질소 기류 하에서 상기 합성예 52의 <단계 1>에서 얻은 7-(4-(9H-carbazol-9-yl)phenyl)-3-phenyl-3,10-dihydropyrrolo[3,2-a]carbazole (2.23 g, 4.25 mmol)을, iodobenzene (2.17 g, 10.63 mmol), Cu powder (0.07 g, 1.06 mmol), K2CO3 (1.47 g, 10.63 mmol), Na2SO4 (1.51 g, 10.63 mmol), 및 nitrobenzene (100 ml)과 혼합한 다음, 210 ℃에서 24시간 동안 교반하였다. 7- (4- (9H-carbazol-9-yl) phenyl) -3-phenyl-3,10-dihydropyrrolo [3,2-a] carbazole (2.23) obtained in <Step 1> of Synthesis Example 52 under a nitrogen stream. g, 4.25 mmol), iodobenzene (2.17 g, 10.63 mmol), Cu powder (0.07 g, 1.06 mmol), K 2 CO 3 (1.47 g, 10.63 mmol), Na 2 SO 4 (1.51 g, 10.63 mmol), And nitrobenzene (100 ml) and then stirred at 210 ° C. for 24 hours.
반응 종결 후 nitrobenzene을 제거한 다음, 메틸렌클로라이드로 유기층을 분리한 후, MgSO4를 사용하여 분리된 유기층에서 물을 제거하였다. 물이 제거된 유기층에서 용매를 제거한 후, 컬럼 크로마토그래피 (Hexane:MC = 1:1 (v/v))로 정제하여 화합물 Inv-52 (1.10g, 수율: 43 %)을 얻었다. After completion of the reaction, nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed from the separated organic layer using MgSO 4 . After the solvent was removed from the organic layer, the water was removed, and purified by column chromatography (Hexane: MC = 1: 1 (v / v)) to give the compound Inv-52 (1.10g, yield: 43%).
GC-Mass (이론치: 599.72 g/mol, 측정치: 599 g/mol)GC-Mass (Theoretical value: 599.72 g / mol, Measured value: 599 g / mol)
[합성예 53] 화합물 Inv-53의 합성Synthesis Example 53 Synthesis of Compound Inv-53
Figure PCTKR2013007821-appb-I000175
Figure PCTKR2013007821-appb-I000175
합성예 52의 <단계 1>에서 사용된 화합물 IC-1 대신 준비예 4에서 얻은 화합물 IC-6 (1.2 g, 4.25 mmol)를 사용하는 것을 제외하고는, 상기 합성예 52와 동일한 과정을 수행하여 화합물 Inv-53 (1.02 g, 수율: 40 %)를 얻었다.The same procedure as in Synthesis Example 52 was carried out except that Compound IC-6 (1.2 g, 4.25 mmol) obtained in Preparation Example 4 was used instead of Compound IC-1 used in <Step 1> of Synthesis Example 52. Compound Inv-53 (1.02 g, yield: 40%) was obtained.
GC-Mass (이론치: 599.72 g/mol, 측정치: 599 g/mol)GC-Mass (Theoretical value: 599.72 g / mol, Measured value: 599 g / mol)
[합성예 54] 화합물 Inv-54의 합성Synthesis Example 54 Synthesis of Compound Inv-54
Figure PCTKR2013007821-appb-I000176
Figure PCTKR2013007821-appb-I000176
합성예 1에서 사용된 4,4'-dibromo-1,1'-biphenyl 대신 2,5-bis(4-bromophenyl)-1,3,4-oxadiazole (1.62 g, 4.25 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-54 (1.83 g, 수율: 55 %)를 얻었다.Except using 2,5-bis (4-bromophenyl) -1,3,4-oxadiazole (1.62 g, 4.25 mmol) instead of 4,4'-dibromo-1,1'-biphenyl used in Synthesis Example 1 Then, the same procedure as in Synthesis Example 1 was performed to obtain compound Inv-54 (1.83 g, yield: 55%).
GC-Mass (이론치: 782.89 g/mol, 측정치: 782 g/mol)GC-Mass (Theoretical value: 782.89 g / mol, Measured value: 782 g / mol)
[합성예 55] 화합물 Inv-55의 합성Synthesis Example 55 Synthesis of Compound Inv-55
합성예 1에서 사용된 화합물 IC-1 대신 준비예 4에서 얻은 화합물 IC-6 (3 g, 10.63 mmol)를 사용하고, 4,4'-dibromo-1,1'-biphenyl 대신 2,5-bis(4-bromophenyl)-1,3,4-oxadiazole (1.62 g, 4.25 mmol)를 사용하는 것을 제외하고는, 상기 합성예 54 1과 동일한 과정을 수행하여 화합물 Inv-55 (1.76 g, 수율: 53 %)를 얻었다.Compound IC-6 (3 g, 10.63 mmol) obtained in Preparation Example 4 was used instead of compound IC-1 used in Synthesis Example 1, and 2,5-bis instead of 4,4'-dibromo-1,1'-biphenyl Compound Inv-55 (1.76 g, yield: 53 was carried out in the same manner as in Synthesis Example 54 1, except that (4-bromophenyl) -1,3,4-oxadiazole (1.62 g, 4.25 mmol) was used. %) Was obtained.
GC-Mass (이론치: 782.89 g/mol, 측정치: 782 g/mol)GC-Mass (Theoretical value: 782.89 g / mol, Measured value: 782 g / mol)
[합성예 56] 화합물 Inv-56의 합성Synthesis Example 56 Synthesis of Compound Inv-56
Figure PCTKR2013007821-appb-I000178
Figure PCTKR2013007821-appb-I000178
합성예 1에서 사용된 4,4'-dibromo-1,1'-biphenyl 대신 2,5-bis(4-bromophenyl)-1,3,4-thiadiazole (1.68 g, 4.25 mmol)를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 Inv-56 (1.70 g, 수율: 50 %)를 얻었다.Except using 2,5-bis (4-bromophenyl) -1,3,4-thiadiazole (1.68 g, 4.25 mmol) instead of 4,4'-dibromo-1,1'-biphenyl used in Synthesis Example 1 Then, the same procedure as in Synthesis Example 1 was performed to obtain compound Inv-56 (1.70 g, yield: 50%).
GC-Mass (이론치: 798.95 g/mol, 측정치: 799 g/mol)GC-Mass (Theoretical value: 798.95 g / mol, Measured value: 799 g / mol)
[합성예 57] 화합물 Inv-57의 합성Synthesis Example 57 Synthesis of Compound Inv-57
Figure PCTKR2013007821-appb-I000179
Figure PCTKR2013007821-appb-I000179
합성예 1에서 사용된 화합물 IC-1 대신 준비예 4에서 얻은 화합물 IC-6 (3 g, 10.63 mmol)를 사용하고, 4'-dibromo-1,1'-biphenyl 대신 2,5-bis(4-bromophenyl)-1,3,4-thiadiazole (1.68 g, 4.25 mmol)를 사용하는 것을 제외하고는, 상기 합성예 56 1과 동일한 과정을 수행하여 화합물 Inv-57 (1.63 g, 수율: 48 %)를 얻었다.Compound IC-6 (3 g, 10.63 mmol) obtained in Preparation Example 4 was used instead of compound IC-1 used in Synthesis Example 1, and 2,5-bis (4) instead of 4'-dibromo-1,1'-biphenyl was used. Compound Inv-57 (1.63 g, Yield: 48%) was carried out in the same manner as in Synthesis Example 56 1, except that -bromophenyl) -1,3,4-thiadiazole (1.68 g, 4.25 mmol) was used. Got.
GC-Mass (이론치: 798.95 g/mol, 측정치: 799 g/mol)GC-Mass (Theoretical value: 798.95 g / mol, Measured value: 799 g / mol)
[합성예 58] 화합물 Inv-58의 합성Synthesis Example 58 Synthesis of Compound Inv-58
Figure PCTKR2013007821-appb-I000180
Figure PCTKR2013007821-appb-I000180
질소 기류 하에서 준비예 2에서 얻은 화합물 IC-3 (3 g, 10.63 mmol), 2-(biphenyl-4-yl)-4,6-dibromo-1,3,5-triazine (1.66 g, 4.25 mmol), Cu powder (0.07 g, 1.06 mmol), K2CO3 (1.47 g, 10.63 mmol), Na2SO4 (1.51 g, 10.63 mmol), nitrobenzene (100 ml)를 혼합한 다음, 210 ℃에서 24시간 동안 교반하였다. Compound IC-3 (3 g, 10.63 mmol), 2- (biphenyl-4-yl) -4,6-dibromo-1,3,5-triazine (1.66 g, 4.25 mmol) obtained in Preparation Example 2 under nitrogen stream , Cu powder (0.07 g, 1.06 mmol), K 2 CO 3 (1.47 g, 10.63 mmol), Na 2 SO 4 (1.51 g, 10.63 mmol), nitrobenzene (100 ml) were mixed and then stirred at 210 ° C. for 24 hours. Was stirred.
반응 종결 후 nitrobenzene을 제거한 다음, 메틸렌클로라이드로 유기층을 분리하고, MgSO4를 사용하여 분리된 유기층에서 물을 제거하였다. 물이 제거된 유기층에서 용매를 제거한 다음, 컬럼 크로마토그래피 (Hexane:MC = 1:1 (v/v))로 정제하여 화합물 Inv-58 (2.06g, 수율: 61 %)을 얻었다. After completion of the reaction, nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed from the separated organic layer using MgSO 4 . The solvent was removed from the organic layer, which was freed of water, and then purified by column chromatography (Hexane: MC = 1: 1 (v / v)) to obtain a compound Inv-58 (2.06 g, yield: 61%).
GC-Mass (이론치: 793.91 g/mol, 측정치: 793 g/mol)GC-Mass (Theoretical value: 793.91 g / mol, Measured value: 793 g / mol)
[합성예 59] 화합물 Inv-59의 합성Synthesis Example 59 Synthesis of Compound Inv-59
Figure PCTKR2013007821-appb-I000181
Figure PCTKR2013007821-appb-I000181
합성예 58 에서 사용된 화합물 2-(biphenyl-4-yl)-4,6-dibromo-1,3,5-triazine 대신 2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazine (1.98 g, 4.25 mmol)를 사용하는 것을 제외하고는, 상기 합성예 58과 동일한 과정을 수행하여 화합물 Inv-59 (2.03 g, 수율: 55 %)를 얻었다.Compound 2- (biphenyl-4-yl) -4,6-dibromo-1,3,5-triazine instead of 2- (3,5-dibromophenyl) -4,6-diphenyl-1,3 used in Synthesis Example 58 A compound Inv-59 (2.03 g, yield: 55%) was obtained in the same manner as the Synthesis Example 58, except that, 5-triazine (1.98 g, 4.25 mmol) was used.
GC-Mass (이론치: 870.01 g/mol, 측정치: 870 g/mol)GC-Mass (Theoretical value: 870.01 g / mol, Measured value: 870 g / mol)
[합성예 60] 화합물 Inv-60의 합성Synthesis Example 60 Synthesis of Compound Inv-60
Figure PCTKR2013007821-appb-I000182
Figure PCTKR2013007821-appb-I000182
질소 기류 하에서 준비예 2에서 얻은 화합물 IC-3 (4.31 g, 15.3 mmol), 1,3,5-tribromobenzene (1.33 g, 4.25 mmol), Cu powder (0.10 g, 1.53 mmol), K2CO3 (2.11 g, 15.3 mmol), Na2SO4 (2.17 g, 15.3 mmol), nitrobenzene (100 ml)를 혼합한 다음, 210 ℃에서 24시간 동안 교반하였다. Compound IC-3 (4.31 g, 15.3 mmol) obtained in Preparation Example 2, 1,3,5-tribromobenzene (1.33 g, 4.25 mmol), Cu powder (0.10 g, 1.53 mmol), and K 2 CO 3 (under nitrogen stream) 2.11 g, 15.3 mmol), Na 2 SO 4 (2.17 g, 15.3 mmol) and nitrobenzene (100 ml) were mixed and then stirred at 210 ° C. for 24 hours.
반응 종결 후 nitrobenzene을 제거한 다음, 메틸렌클로라이드로 유기층을 분리하고, MgSO4를 사용하여 분리된 유기층에서 물을 제거하였다. 물이 제거된 유기층에서 용매를 제거한 다음, 컬럼 크로마토그래피 (Hexane:MC = 1:1 (v/v))로 정제하여 화합물 Inv-60 (1.76g, 수율: 45 %)을 얻었다. After completion of the reaction, nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed from the separated organic layer using MgSO 4 . The solvent was removed from the organic layer, which was freed of water, and then purified by column chromatography (Hexane: MC = 1: 1 (v / v)) to obtain a compound Inv-60 (1.76 g, yield: 45%).
GC-Mass (이론치: 922.04 g/mol, 측정치: 922 g/mol)GC-Mass (Theoretical value: 922.04 g / mol, Measured value: 922 g / mol)
[실시예 1] 유기 EL 소자의 제조Example 1 Fabrication of Organic EL Device
합성예 1에서 합성된 화합물 Inv-1을 통상적으로 알려진 방법으로 고순도 승화정제를 한 후, 아래의 과정에 따라 녹색 유기 EL 소자를 제작하였다.The compound Inv-1 synthesized in Synthesis Example 1 was subjected to high purity sublimation purification by a commonly known method, and then a green organic EL device was manufactured according to the following procedure.
먼저, ITO (Indium tin oxide)가 1500 Å 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) having a thickness of 1500 mm 3 was washed with distilled water ultrasonic waves. After washing with distilled water, ultrasonic washing with a solvent such as isopropyl alcohol, acetone, methanol, and drying was carried out. The substrate was transferred to a vacuum evaporator.
상기와 같이 준비된 ITO 투명 전극 위에, m-MTDATA (60 nm)/TCTA (80 nm)/화합물 Inv-1+ 10 % Ir(ppy)3 (30Å0nm)/BCP (10 nm)/Alq3 (30 nm)/LiF (1 nm)/Al (200 nm) 순으로 적층하여 유기 EL 소자를 제작하였다. On the prepared ITO transparent electrode, m-MTDATA (60 nm) / TCTA (80 nm) / Compound Inv-1 + 10% Ir (ppy) 3 (30 (0nm) / BCP (10 nm) / Alq 3 (30 nm) ) / LiF (1 nm) / Al (200 nm) was laminated in order to produce an organic EL device.
소자 제작에 사용된 m-MTDATA, TCTA, Ir(ppy)3, CBP 및 BCP의 구조는 하기와 같다.The structures of m-MTDATA, TCTA, Ir (ppy) 3 , CBP, and BCP used in device fabrication are as follows.
Figure PCTKR2013007821-appb-I000183
Figure PCTKR2013007821-appb-I000183
Figure PCTKR2013007821-appb-I000184
Figure PCTKR2013007821-appb-I000184
[실시예 2 ~ 57] 유기 EL 소자의 제조Examples 2 to 57 Fabrication of Organic EL Device
실시예 1에서 발광층의 형성시 호스트 물질로 사용된 화합물 Inv-1 대신 합성예 2 내지 57에서 각각 합성된 화합물 Inv-2 내지 Inv-57를 사용하는 것을 제외하고는, 실시예 1과 동일하게 수행하여 유기 EL 소자를 제조하였다.Except for using the compounds Inv-2 to Inv-57 synthesized in Synthesis Examples 2 to 57 instead of the compound Inv-1 used as a host material in the formation of the light emitting layer in Example 1, the same as in Example 1 To an organic EL device.
[비교예 1] 유기 EL 소자의 제작Comparative Example 1 Fabrication of Organic EL Device
실시예 1에서 발광층의 형성시 발광 호스트 물질로서 사용된 화합물 Inv-1 대신 CBP를 사용하는 것을 제외하고는, 실시예 1과 동일한 과정으로 유기 EL 소자를 제작하였다.An organic EL device was manufactured in the same manner as in Example 1, except that CBP was used instead of the compound Inv-1 used as the light emitting host material in forming the emission layer in Example 1.
사용된 CBP의 구조는 하기와 같다.The structure of CBP used is as follows.
Figure PCTKR2013007821-appb-I000185
Figure PCTKR2013007821-appb-I000185
[평가예 1][Evaluation Example 1]
실시예 1 내지 57, 및 비교예 1에서 각각 제작된 유기 EL 소자에 대하여, 전류밀도 10 mA/㎠에서의 구동전압 및 전류효율을 측정하였고, 그 결과를 하기 표 1에 나타내었다.For organic EL devices fabricated in Examples 1 to 57 and Comparative Example 1, driving voltage and current efficiency at current density of 10 mA / cm 2 were measured, and the results are shown in Table 1 below.
표 1
샘플 호스트 구동 전압 (V) 전류효율 (cd/A)
실시예 1 화합물 Inv-1 6.68 41.1
실시예 2 화합물 Inv-2 6.68 41.2
실시예 3 화합물 Inv-3 6.85 40.9
실시예 4 화합물 Inv-4 6.83 41.3
실시예 5 화합물 Inv-5 6.85 39.2
실시예 6 화합물 Inv-6 6.89 41.7
실시예 7 화합물 Inv-7 6.91 38.9
실시예 8 화합물 Inv-8 6.67 40.9
실시예 9 화합물 Inv-9 6.65 42.1
실시예 10 화합물 Inv-10 6.63 41.1
실시예 11 화합물 Inv-11 6.65 39.1
실시예 12 화합물 Inv-12 6.66 40.3
실시예 13 화합물 Inv-13 6.7 41.2
실시예 14 화합물 Inv-14 6.73 39.8
실시예 15 화합물 Inv-15 6.75 39.3
실시예 16 화합물 Inv-16 6.88 39.4
실시예 17 화합물 Inv-17 6.88 38.8
실시예 18 화합물 Inv-18 6.72 41.3
실시예 19 화합물 Inv-19 6.69 41.3
실시예 20 화합물 Inv-20 6.69 38.8
실시예 21 화합물 Inv-21 6.68 38.9
실시예 22 화합물 Inv-22 6.65 40.5
실시예 23 화합물 Inv-23 6.61 40.8
실시예 24 화합물 Inv-24 6.65 40.3
실시예 25 화합물 Inv-25 6.65 41.9
실시예 26 화합물 Inv-26 6.68 40.8
실시예 27 화합물 Inv-27 6.69 41.8
실시예 28 화합물 Inv-28 6.73 40.5
실시예 29 화합물 Inv-29 6.74 41.1
실시예 30 화합물 Inv-30 6.75 39.5
실시예 31 화합물 Inv-31 6.83 41.2
실시예 32 화합물 Inv-32 6.73 42.2
실시예 33 화합물 Inv-33 6.87 42.8
실시예 34 화합물 Inv-34 6.91 43.2
실시예 35 화합물 Inv-35 6.88 39.1
실시예 36 화합물 Inv-36 6.91 39.4
실시예 37 화합물 Inv-37 6.69 38.5
실시예 38 화합물 Inv-38 6.67 41.2
실시예 39 화합물 Inv-39 6.63 41.3
실시예 40 화합물 Inv-40 6.61 41.5
실시예 41 화합물 Inv-41 6.6 39.3
실시예 42 화합물 Inv-42 6.63 39.1
실시예 43 화합물 Inv-43 6.62 40.9
실시예 44 화합물 Inv-44 6.66 41
실시예 45 화합물 Inv-45 6.68 40.5
실시예 46 화합물 Inv-46 6.67 39.5
실시예 47 화합물 Inv-47 6.65 41.3
실시예 48 화합물 Inv-48 6.74 40.9
실시예 49 화합물 Inv-49 6.85 41.2
실시예 50 화합물 Inv-50 6.89 42.6
실시예 51 화합물 Inv-51 6.83 40.7
실시예 52 화합물 Inv-52 6.73 41.3
실시예 53 화합물 Inv-53 6.69 39.1
실시예 54 화합물 Inv-54 6.67 39.3
실시예 55 화합물 Inv-55 6.66 40.8
실시예 56 화합물 Inv-56 6.64 41.2
실시예 57 화합물 Inv-57 6.66 40.8
비교예 1 CBP 6.93 38.2
Table 1
Sample Host Driving voltage (V) Current efficiency (cd / A)
Example 1 Compound Inv-1 6.68 41.1
Example 2 Compound Inv-2 6.68 41.2
Example 3 Compound Inv-3 6.85 40.9
Example 4 Compound Inv-4 6.83 41.3
Example 5 Compound Inv-5 6.85 39.2
Example 6 Compound Inv-6 6.89 41.7
Example 7 Compound Inv-7 6.91 38.9
Example 8 Compound Inv-8 6.67 40.9
Example 9 Compound Inv-9 6.65 42.1
Example 10 Compound Inv-10 6.63 41.1
Example 11 Compound Inv-11 6.65 39.1
Example 12 Compound Inv-12 6.66 40.3
Example 13 Compound Inv-13 6.7 41.2
Example 14 Compound Inv-14 6.73 39.8
Example 15 Compound Inv-15 6.75 39.3
Example 16 Compound Inv-16 6.88 39.4
Example 17 Compound Inv-17 6.88 38.8
Example 18 Compound Inv-18 6.72 41.3
Example 19 Compound Inv-19 6.69 41.3
Example 20 Compound Inv-20 6.69 38.8
Example 21 Compound Inv-21 6.68 38.9
Example 22 Compound Inv-22 6.65 40.5
Example 23 Compound Inv-23 6.61 40.8
Example 24 Compound Inv-24 6.65 40.3
Example 25 Compound Inv-25 6.65 41.9
Example 26 Compound Inv-26 6.68 40.8
Example 27 Compound Inv-27 6.69 41.8
Example 28 Compound Inv-28 6.73 40.5
Example 29 Compound Inv-29 6.74 41.1
Example 30 Compound Inv-30 6.75 39.5
Example 31 Compound Inv-31 6.83 41.2
Example 32 Compound Inv-32 6.73 42.2
Example 33 Compound Inv-33 6.87 42.8
Example 34 Compound Inv-34 6.91 43.2
Example 35 Compound Inv-35 6.88 39.1
Example 36 Compound Inv-36 6.91 39.4
Example 37 Compound Inv-37 6.69 38.5
Example 38 Compound Inv-38 6.67 41.2
Example 39 Compound Inv-39 6.63 41.3
Example 40 Compound Inv-40 6.61 41.5
Example 41 Compound Inv-41 6.6 39.3
Example 42 Compound Inv-42 6.63 39.1
Example 43 Compound Inv-43 6.62 40.9
Example 44 Compound Inv-44 6.66 41
Example 45 Compound Inv-45 6.68 40.5
Example 46 Compound Inv-46 6.67 39.5
Example 47 Compound Inv-47 6.65 41.3
Example 48 Compound Inv-48 6.74 40.9
Example 49 Compound Inv-49 6.85 41.2
Example 50 Compound Inv-50 6.89 42.6
Example 51 Compound Inv-51 6.83 40.7
Example 52 Compound Inv-52 6.73 41.3
Example 53 Compound Inv-53 6.69 39.1
Example 54 Compound Inv-54 6.67 39.3
Example 55 Compound Inv-55 6.66 40.8
Example 56 Compound Inv-56 6.64 41.2
Example 57 Compound Inv-57 6.66 40.8
Comparative Example 1 CBP 6.93 38.2
상기 표1에 나타낸 바와 같이, 본 발명에 따른 화합물(화합물 Inv-1 내지 Inv-57)을 발광층 재료(발광층의 호스트 물질)로 사용한 녹색 유기 EL 소자(실시예 1 내지 57에서 각각 제조된 유기 EL 소자)는, 종래 호스트 물질 CBP를 사용한 녹색 유기 EL 소자(비교예1에서 제조된 유기 EL 소자)에 비해 전류효율 및 구동전압 면에서 우수한 성능을 나타내는 것을 알 수 있다.As shown in Table 1 above, the green organic EL elements (the organic ELs produced in Examples 1 to 57, respectively) using the compounds (compounds Inv-1 to Inv-57) according to the present invention as the light emitting layer material (host material of the light emitting layer) It can be seen that the device exhibits excellent performance in terms of current efficiency and driving voltage compared to the conventional green organic EL device (organic EL device manufactured in Comparative Example 1) using the host material CBP.
[실시예 58] - 유기 EL 소자의 제조Example 58-Fabrication of Organic EL Device
합성예 15에서 합성된 화합물 Inv-15를 통상적으로 알려진 방법으로 고순도 승화정제를 한 후 아래의 과정에 따라 녹색 유기 EL 소자를 제작하였다.Compound Inv-15 synthesized in Synthesis Example 15 was subjected to high purity sublimation purification by a conventionally known method, and then a green organic EL device was manufactured according to the following procedure.
먼저, ITO (Indium tin oxide)가 1500 Å두께로 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) at a thickness of 1500 mW was washed with distilled water ultrasonic waves. After washing with distilled water, ultrasonic washing with a solvent such as isopropyl alcohol, acetone, methanol, and drying was carried out. The substrate was transferred to a vacuum evaporator.
상기와 같이 준비된 ITO (양극) 위에, DS-HIL (두산社)를 800 Å의 두께로 열 진공 증착하여 정공 주입층을 형성한 다음, 상기 정공 주입층 위에 정공 수송 물질인 α-NPB (N, N-di(naphthalene-1-yl)-N, N-diphenylbenzidine)을 150 Å의 두께로 진공 증착하여 정공 수송층을 형성하였다.On the ITO (anode) prepared as above, DS-HIL (Doosan Co., Ltd.) was thermally vacuum deposited to a thickness of 800 kPa to form a hole injection layer, and then α-NPB ( N , which is a hole transport material on the hole injection layer) N- di (naphthalene-1-yl) -N , N- diphenylbenzidine) was vacuum deposited to a thickness of 150 kPa to form a hole transport layer.
이후, 호스트 물질로서 m-CP (1,3-di(9H-carbazol-9-yl)benzene)을 사용하고, 도펀트로서 상기 합성예 1에서 합성된 화합물 Inv-15를 6 % 도핑하여, 300 Å의 두께로 상기 정공 수송층 위에 진공 증착하여 발광층을 형성하였다. Thereafter, m-CP (1,3-di (9H-carbazol-9-yl) benzene) was used as the host material and 6% of the compound Inv-15 synthesized in Synthesis Example 1 was doped as a dopant. The light emitting layer was formed by vacuum deposition on the hole transport layer to a thickness of.
이어서, 상기 발광층 위에 전자 수송 물질인 Alq3을 250 Å의 두께로 진공 증착하여 전자 수송층을 형성한 후, 전자 주입 물질인 LiF를 10 Å의 두께로 상기 전자 수송층 위에 증착하여 전자 주입층을 형성한 다음, 상기 전자 주입층 위에 알루미늄을 2000 Å의 두께로 진공 증착하여 음극을 형성하여 유기 전계 발광 소자를 제조하였다.Subsequently, an electron transporting layer was formed by vacuum depositing Alq 3 , which is an electron transporting material, to a thickness of 250 kPa on the light emitting layer, and then an electron injection layer was formed by depositing LiF, which is an electron injection material, on the electron transporting layer, having a thickness of 10 kW. Next, aluminum was vacuum deposited to a thickness of 2000 kPa on the electron injection layer to form a cathode, thereby manufacturing an organic EL device.
사용된 α-NPB 및 m-CP의 구조는 다음과 같다.The structures of α-NPB and m-CP used are as follows.
Figure PCTKR2013007821-appb-I000186
Figure PCTKR2013007821-appb-I000186
[실시예 59 내지 66] 유기 EL 소자의 제조[Examples 59 to 66] Fabrication of Organic EL Device
실시예 58에서 발광층의 형성시 도펀트로 사용된 화합물 Inv-15 대신 화합물 Inv-24, Inv-29, Inv-30, Inv-31, Inv-32, Inv-58, Inv-59, Inv-60을 각각 사용하는 것을 제외하고는, 상기 실시예 58과 동일하게 수행하여 유기 전계 발광 소자를 제조하였다.Compound Inv-24, Inv-29, Inv-30, Inv-31, Inv-32, Inv-58, Inv-59, Inv-60 instead of Compound Inv-15 used as dopants in the formation of the emission layer in Example 58 Except for each use, the organic electroluminescent device was manufactured in the same manner as in Example 58.
[비교예 2] 유기 EL 소자의 제조Comparative Example 2 Fabrication of Organic EL Device
실시예 58에서 발광층의 형성시 호스트 물질로 사용된 m-CP 대신 DS-H522 (두산社)을 사용하고, 도펀트 물질로 사용된 화합물 Inv-15 대신 C-545T를 사용하는 것을 제외하고는, 상기 실시예 58과 동일하게 수행하여 유기 전계 발광 소자를 제조하였다.In Example 58, except that DS-H522 (Doosan Corporation) was used instead of m-CP used as a host material in forming the light emitting layer, and C-545T was used instead of compound Inv-15 used as a dopant material. The organic electroluminescent device was manufactured in the same manner as in Example 58.
사용된 C-545T의 구조는 다음과 같다.The structure of C-545T used is as follows.
Figure PCTKR2013007821-appb-I000187
Figure PCTKR2013007821-appb-I000187
[평가예 2][Evaluation Example 2]
실시예 58 내지 66, 및 비교예 2 에서 각각 제작된 유기 EL 소자에 대하여, 전류밀도 10 mA/㎠에서의 구동전압, 및 전류효율을 측정하였고, 그 결과를 하기 표 2에 나타내었다.For organic EL devices fabricated in Examples 58 to 66 and Comparative Example 2, the driving voltage and current efficiency at current density of 10 mA / cm 2 were measured, and the results are shown in Table 2 below.
표 2
샘플 도펀트 구동 전압 (V) 전류효율 (cd/A)
실시예 58 화합물 Inv-15 6.1 32.5
실시예 59 화합물 Inv-24 6.3 31.7
실시예 60 화합물 Inv-29 6.2 31.9
실시예 61 화합물 Inv-30 6.0 32.2
실시예 62 화합물 Inv-31 5.5 32.9
실시예 63 화합물 Inv-32 5.9 32.3
실시예 64 화합물 Inv-58 5.8 33.1
실시예 65 화합물 Inv-59 5.7 33.5
실시예 66 화합물 Inv-60 5.6 32.0
비교예 2 C-545T 6.8 23.0
TABLE 2
Sample Dopant Driving voltage (V) Current efficiency (cd / A)
Example 58 Compound Inv-15 6.1 32.5
Example 59 Compound Inv-24 6.3 31.7
Example 60 Compound Inv-29 6.2 31.9
Example 61 Compound Inv-30 6.0 32.2
Example 62 Compound Inv-31 5.5 32.9
Example 63 Compound Inv-32 5.9 32.3
Example 64 Compound Inv-58 5.8 33.1
Example 65 Compound Inv-59 5.7 33.5
Example 66 Compound Inv-60 5.6 32.0
Comparative Example 2 C-545T 6.8 23.0
상기 표2에 나타낸 바와 같이, 본 발명에 따른 화합물(Inv-15, Inv-24, Inv-29, Inv-30, Inv-31, Inv-32, Inv-58, Inv-59, Inv-60)을 발광층 재료(발광층의 도펀트)로 사용한 녹색 형광 유기 EL 소자(실시예 58 내지 66에서 각각 제조된 유기 EL 소자)는, 종래 도펀트 C-545T를 사용한 녹색 형광 유기 EL 소자(비교예2의 유기 EL 소자)에 비해, 전류효율 및 구동전압 면에서 우수한 성능을 나타내는 것을 알 수 있다.As shown in Table 2, the compounds according to the present invention (Inv-15, Inv-24, Inv-29, Inv-30, Inv-31, Inv-32, Inv-58, Inv-59, Inv-60) The green fluorescent organic EL device (the organic EL device manufactured in each of Examples 58 to 66) using as a light emitting layer material (the dopant of the light emitting layer) is a green fluorescent organic EL device using the conventional dopant C-545T (organic EL of Comparative Example 2). Element), it can be seen that it shows excellent performance in terms of current efficiency and driving voltage.
이상을 통해 본 발명의 바람직한 실시예에 대하여 설명하였지만, 본 발명은 이에 한정되는 것이 아니고 특허청구범위와 발명의 상세한 설명의 범위 안에서 여러 가지로 변형하여 실시하는 것이 가능하고 이 또한 본 발명의 범위에 속하는 것은 당연하다. Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention. It is natural to belong.

Claims (12)

  1. 하기 화학식 1로 표시되는 화합물: Compound represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2013007821-appb-I000188
    Figure PCTKR2013007821-appb-I000188
    상기 화학식 1에서,In Chemical Formula 1,
    환 A는 CR3 및 N을 함유하는 6원의 헤테로환, R3로 치환된 6원의 환, 또는 2개의 N을 함유하는 6원의 헤테로환이고;Ring A is a 6-membered heterocycle containing CR 3 and N, a 6-membered ring substituted with R 3 , or a 6-membered heterocycle containing two N;
    X1 및 X2는 각각 독립적으로 O, S, Se, N(Ar1), C(Ar2)(Ar3) 및 Si(Ar4)(Ar5)로 이루어진 군에서 선택되고, 이때, X1 및 X2 중에서 적어도 하나는 N(Ar1)이며;X 1 and X 2 are each independently selected from the group consisting of O, S, Se, N (Ar 1 ), C (Ar 2 ) (Ar 3 ) and Si (Ar 4 ) (Ar 5 ), wherein X At least one of 1 and X 2 is N (Ar 1 );
    Y1 내지 Y4은 서로 같거나 또는 상이하며, 각각 독립적으로 N 또는 CR4이고, 이때 CR4가 복수인 경우, 이들은 서로 상이하거나 동일하고;Y 1 to Y 4 are the same as or different from each other, and each independently N or CR 4, wherein, when there are a plurality of CR 4 , they are different from each other or the same;
    단, 상기 R1 내지 R4, 및 Ar1 내지 Ar5 중에서 하나는 하기 화학식 2로 표시되는 치환기이며,However, one of R 1 to R 4 , and Ar 1 to Ar 5 is a substituent represented by the following Chemical Formula 2,
    [화학식 2][Formula 2]
    Figure PCTKR2013007821-appb-I000189
    Figure PCTKR2013007821-appb-I000189
    상기 화학식 2에서,In Chemical Formula 2,
    a는 1 또는 2이고;a is 1 or 2;
    L은 치환 또는 비치환된 C6~C60의 아릴렌기, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴렌기, 치환 또는 비치환된 아릴-트라이일(aryl-triyl), 또는 치환 또는 비치환된 헤테로아릴-트라이일(heteroaryl-triyl)이며,L represents a substituted or unsubstituted C 6 to C 60 arylene group, a substituted or unsubstituted heteroarylene group having 5 to 60 nuclear atoms, a substituted or unsubstituted aryl-triyl, or a substituted or Unsubstituted heteroaryl-triyl,
    단, a가 1인 경우, L은 치환 또는 비치환된 C6~C60의 아릴렌기, 또는 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴렌기이며,Provided that when a is 1, L is a substituted or unsubstituted C 6 to C 60 arylene group, or a substituted or unsubstituted heteroarylene group having 5 to 60 nuclear atoms,
    a가 2인 경우, L은 치환 또는 비치환된 아릴-트라이일(aryl-triyl), 또는 치환 또는 비치환된 헤테로아릴-트라이일(heteroaryl-triyl)이고;when a is 2, L is substituted or unsubstituted aryl-triyl, or substituted or unsubstituted heteroaryl-triyl;
    B는 치환 또는 비치환된 카바졸기, 또는 하기 화학식 3으로 표시되는 치환기이며, 이때 B가 복수인 경우, 이들은 서로 상이하거나 동일하고;B is a substituted or unsubstituted carbazole group, or a substituent represented by the following formula (3), wherein when B is plural, they are different from each other or the same;
    [화학식 3][Formula 3]
    Figure PCTKR2013007821-appb-I000190
    Figure PCTKR2013007821-appb-I000190
    상기 화학식 3에서, In Chemical Formula 3,
    환 C는 CR7 및 N을 함유하는 6원의 헤테로환, R7로 치환된 6원의 환, 또는 2개의 N을 함유하는 6원의 헤테로환이고;Ring C is a 6-membered heterocycle containing CR 7 and N, a 6-membered ring substituted with R 7 , or a 6-membered heterocycle containing two N;
    X3 및 X4는 각각 독립적으로 O, S, Se, N(Ar6), C(Ar7)(Ar8) 및 Si(Ar9)(Ar10)로 이루어진 군에서 선택되고, X 3 and X 4 are each independently selected from the group consisting of O, S, Se, N (Ar 6 ), C (Ar 7 ) (Ar 8 ) and Si (Ar 9 ) (Ar 10 ),
    Y5 내지 Y8은 서로 같거나 또는 상이하며, 각각 독립적으로 N 또는 CR8이고, 이때 CR8이복수인 경우, 이들은 서로 상이하거나 동일하고;Y 5 to Y 8 are the same as or different from each other, and each independently N or CR 8, wherein, when a plurality of CR 8 plurals, they are different from or the same;
    상기 R5 내지 R8 및 Ar6 내지 Ar10 중에서 하나는 단일 결합으로, 상기 화학식 2의 L에 연결되고;One of R 5 to R 8 and Ar 6 to Ar 10 is a single bond, connected to L of Formula 2;
    R1 내지 R8은 서로 동일하거나 상이하며, 각각 독립적으로 수소, 중수소, 할로겐, 시아노, 니트로, 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C2~C40의 알케닐기, 치환 또는 비치환된 C2~C40의 알키닐기, 치환 또는 비치환된 C3~C40의 시클로알킬기, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로시클로알킬기, 치환 또는 비치환된 C6~C60의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기, 치환 또는 비치환된 C1~C40의 알킬옥시기, 치환 또는 비치환된 C6~C60의 아릴옥시기, 치환 또는 비치환된 C3~C40의 알킬실릴기, 치환 또는 비치환된 C6~C60의 아릴실릴기, 치환 또는 비치환된 C1~C40의 알킬보론기, 치환 또는 비치환된 C6~C60의 아릴보론기, 치환 또는 비치환된 C6~C60의 아릴포스핀기, 치환 또는 비치환된 C6~C60의 아릴포스핀옥사이드기, 및 치환 또는 비치환된 C6~C60의 아릴아민기로 구성된 군으로부터 선택되거나, 또는 인접한 기와 축합 고리를 형성하거나 또는 비형성하며;R 1 to R 8 are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano, nitro, a substituted or unsubstituted C 1 -C 40 alkyl group, a substituted or unsubstituted C 2 -C 40 Alkenyl group, substituted or unsubstituted C 2 to C 40 alkynyl group, substituted or unsubstituted C 3 to C 40 cycloalkyl group, substituted or unsubstituted heterocycloalkyl group having 3 to 40 nuclear atoms, substituted or unsubstituted Substituted C 6 ~ C 60 aryl group, substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, substituted or unsubstituted C 1 ~ C 40 alkyloxy group, substituted or unsubstituted C 6 ~ C 60 aryloxy group, substituted or unsubstituted C 3 to C 40 alkylsilyl group, substituted or unsubstituted C 6 to C 60 arylsilyl group, substituted or unsubstituted C 1 to C 40 alkylboron Groups, substituted or unsubstituted C 6 -C 60 arylborone groups, substituted or unsubstituted C 6 -C 60 arylphosphine groups, substituted or unsubstituted An arylphosphineoxide group of C 6 -C 60 and a substituted or unsubstituted C 6 -C 60 arylamine group, or form a condensed ring with an adjacent group or not form it;
    Ar1 내지 Ar10은 서로 동일하거나 또는 상이하며, 각각 독립적으로 수소, 중수소, 할로겐, 시아노, 니트로, 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C3~C40의 시클로알킬기, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로시클로알킬기, 치환 또는 비치환된 C6~C60의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기, 치환 또는 비치환된 C1~C40의 알킬옥시기, 치환 또는 비치환된 C6~C60의 아릴옥시기, 치환 또는 비치환된 C3~C40의 알킬실릴기, 치환 또는 비치환된 C6~C60의 아릴실릴기, 치환 또는 비치환된 C1~C40의 알킬보론기, 치환 또는 비치환된 C6~C60의 아릴보론기, 치환 또는 비치환된 C6~C60의 아릴포스핀기, 치환 또는 비치환된 C6~C60의 아릴포스핀옥사이드기, 및 치환 또는 비치환된 C6~C60의 아릴아민기로 구성된 군으로부터 선택되며;Ar 1 to Ar 10 are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C 1 to C 40 alkyl group, substituted or unsubstituted C 3 to C 40 A cycloalkyl group, a substituted or unsubstituted heterocycloalkyl group having 3 to 40 nuclear atoms, a substituted or unsubstituted C 6 -C 60 aryl group, a substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, Substituted or unsubstituted C 1 to C 40 alkyloxy group, substituted or unsubstituted C 6 to C 60 aryloxy group, substituted or unsubstituted C 3 to C 40 alkylsilyl group, substituted or unsubstituted C 6 ~ C 60 arylsilyl group, substituted or unsubstituted C 1 ~ C 40 Alkyl boron group, substituted or unsubstituted C 6 ~ C 60 Aryl boron group, substituted or unsubstituted C 6 ~ C 60 an aryl phosphine group, a substituted or unsubstituted C 6 ~ C aryl phosphine oxide groups of 60, and a substituted or unsubstituted C 6 ~ C 60 aryl the It is selected from the group consisting of Min - gi;
    상기 L의 아릴렌기, 헤테로아릴렌기, 아릴-트라이일, 헤테로아릴-트라이일; B의 카바졸기와; 상기 R1 내지 R8, 및 Ar1 내지 Ar10 의 알킬기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 아릴포스핀옥사이드기 및 아릴아민기에 각각 도입되는 하나 이상의 치환기는 각각 독립적으로 중수소, 할로겐, 시아노, 니트로, C1~C40의 알킬기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기로 이루어진 군에서 선택되고, 다만 상기 치환기가 복수인 경우, 이들은 서로 동일하거나 상이할 수 있다. The above arylene group, heteroarylene group, aryl-triyl, heteroaryl-triyl; Carbazole groups of B; An alkyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group, an alkyl boron group of R 1 to R 8 and Ar 1 to Ar 10 , One or more substituents respectively introduced to the arylborone group, the arylphosphine group, the arylphosphine oxide group and the arylamine group are each independently deuterium, halogen, cyano, nitro, C 1 -C 40 alkyl group, C 3 -C 40 Cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C 6 to C 60 , heteroaryl group of 5 to 60 nuclear atoms, alkyloxy group of C 1 to C 40 , C 6 to C 60 Aryloxy group, C 3 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 6 ~ C 60 If an aryl phosphine group, is selected from the group consisting of an aryl phosphine oxide of a C 6 ~ C 60, a plurality of just the above substituent, all of which are identical to each other Or it may be different.
  2. 제1항에 있어서, 상기 L은 하기 치환기 C1 내지 C76으로 이루어진 군에서 선택된 것이 특징인 화합물.The compound of claim 1, wherein L is selected from the group consisting of the following substituents C1 to C76.
    Figure PCTKR2013007821-appb-I000191
    Figure PCTKR2013007821-appb-I000191
    Figure PCTKR2013007821-appb-I000192
    Figure PCTKR2013007821-appb-I000192
    Figure PCTKR2013007821-appb-I000193
    Figure PCTKR2013007821-appb-I000193
  3. 제1항에 있어서, 상기 화학식 3으로 표시되는 치환기는 하기 화학식 3a 내지 3f로 표시되는 치환기 중에서 선택된 것이 특징인 화합물.The compound of claim 1, wherein the substituent represented by Formula 3 is selected from substituents represented by Formulas 3a to 3f.
    [화학식 3a][Formula 3a]
    Figure PCTKR2013007821-appb-I000194
    Figure PCTKR2013007821-appb-I000194
    [화학식 3b][Formula 3b]
    Figure PCTKR2013007821-appb-I000195
    Figure PCTKR2013007821-appb-I000195
    [화학식 3c][Formula 3c]
    Figure PCTKR2013007821-appb-I000196
    ;
    Figure PCTKR2013007821-appb-I000196
    ;
    [화학식 3d][Formula 3d]
    Figure PCTKR2013007821-appb-I000197
    ;
    Figure PCTKR2013007821-appb-I000197
    ;
    [화학식 3e][Formula 3e]
    Figure PCTKR2013007821-appb-I000198
    ;
    Figure PCTKR2013007821-appb-I000198
    ;
    [화학식 3f][Formula 3f]
    Figure PCTKR2013007821-appb-I000199
    Figure PCTKR2013007821-appb-I000199
    상기 화학식 3a 내지 3f에서,In Chemical Formulas 3a to 3f,
    X3 및 X4는 각각 독립적으로 O, S, Se, N(Ar6), C(Ar7)(Ar8) 및 Si(Ar9)(Ar10)로 이루어진 군에서 선택되고;X 3 and X 4 are each independently selected from the group consisting of O, S, Se, N (Ar 6 ), C (Ar 7 ) (Ar 8 ) and Si (Ar 9 ) (Ar 10 );
    다만, R5 내지 R8 및 Ar6 내지 Ar10 중에서 하나는 단일 결합으로, 상기 화학식 2의 L에 연결되며;Provided that one of R 5 to R 8 and Ar 6 to Ar 10 is a single bond and is connected to L of Formula 2;
    R5 내지 R8 및 Ar6 내지 Ar10은 각각 제1항에 정의된 바와 같고,R 5 to R 8 and Ar 6 to Ar 10 are each as defined in claim 1,
    이때, 복수의 R7은 서로 동일하거나 상이하며, 복수의 R8은 서로 동일하거나 상이하다.In this case, a plurality of R 7 are the same or different from each other, a plurality of R 8 is the same or different from each other.
  4. 제 1항에 있어서, 상기 R1 내지 R8 및 Ar1 내지 Ar10은 각각 독립적으로 치환 또는 비치환된 C6~C60의 아릴기, 및 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기로 이루어진 군에서 선택된 것이 특징인 화합물. The R 1 to R 8 and Ar 1 to Ar 10 are each independently a substituted or unsubstituted C 6 ~ C 60 aryl group, and a substituted or unsubstituted heteroatom having 5 to 60 hetero atoms A compound characterized by being selected from the group consisting of aryl groups.
  5. 제 1항에 있어서, 하기 화학식 4 내지 9로 표시되는 화합물로 이루어진 군에서 선택되는 화합물:The compound according to claim 1, wherein the compound is selected from the group consisting of compounds represented by the following Chemical Formulas 4-9:
    [화학식 4][Formula 4]
    Figure PCTKR2013007821-appb-I000200
    Figure PCTKR2013007821-appb-I000200
    [화학식 5][Formula 5]
    Figure PCTKR2013007821-appb-I000201
    Figure PCTKR2013007821-appb-I000201
    [화학식 6][Formula 6]
    Figure PCTKR2013007821-appb-I000202
    Figure PCTKR2013007821-appb-I000202
    [화학식 7][Formula 7]
    Figure PCTKR2013007821-appb-I000203
    Figure PCTKR2013007821-appb-I000203
    [화학식 8][Formula 8]
    Figure PCTKR2013007821-appb-I000204
    Figure PCTKR2013007821-appb-I000204
    [화학식 9][Formula 9]
    Figure PCTKR2013007821-appb-I000205
    Figure PCTKR2013007821-appb-I000205
    상기 화학식 4 내지 9에서, In Chemical Formulas 4 to 9,
    X1 및 X2는 각각 독립적으로 O, S, Se, N(Ar1), C(Ar2)(Ar3) 및 Si(Ar4)(Ar5)로 이루어진 군에서 선택되고, 이때, X1 및 X2 중에서 적어도 하나는 N(Ar1)이며;X 1 and X 2 are each independently selected from the group consisting of O, S, Se, N (Ar 1 ), C (Ar 2 ) (Ar 3 ) and Si (Ar 4 ) (Ar 5 ), wherein X At least one of 1 and X 2 is N (Ar 1 );
    단, 상기 R1 내지 R4, 및 Ar1 내지 Ar5 중에서 하나는 상기 화학식 2로 표시되는 치환기이며;Provided that one of R 1 to R 4 and Ar 1 to Ar 5 is a substituent represented by Formula 2;
    상기 R1 내지 R4, 및 Ar1 내지 Ar5는 각각 제1항에서 정의된 바와 같고,R 1 to R 4 , and Ar 1 to Ar 5 are each as defined in claim 1,
    이때, 복수의 R3은 서로 동일하거나 상이하며, 복수의 R4는 서로 동일하거나 상이하다.At this time, a plurality of R 3 are the same or different from each other, a plurality of R 4 is the same or different from each other.
  6. 제1항에 있어서, 하기 화학식 10으로 표시되는 화합물.The compound of claim 1, represented by the following Chemical Formula 10.
    [화학식 10][Formula 10]
    Figure PCTKR2013007821-appb-I000206
    Figure PCTKR2013007821-appb-I000206
    상기 화학식 10에서,In Chemical Formula 10,
    X1, Y1 내지 Y4, 환 A, R1, R2, L, a 및 B는 각각 제1항에 정의된 바와 같다.X 1 , Y 1 to Y 4 , Ring A, R 1 , R 2 , L, a and B are each as defined in claim 1.
  7. 제1항에 있어서, 하기 화학식 11 내지 16으로 표시되는 화합물로 이루어진 군에서 선택된 화합물.The compound according to claim 1, wherein the compound is selected from the group consisting of compounds represented by the following Chemical Formulas 11 to 16.
    [화학식 11][Formula 11]
    Figure PCTKR2013007821-appb-I000207
    Figure PCTKR2013007821-appb-I000207
    [화학식 12][Formula 12]
    Figure PCTKR2013007821-appb-I000208
    Figure PCTKR2013007821-appb-I000208
    [화학식 13][Formula 13]
    Figure PCTKR2013007821-appb-I000209
    Figure PCTKR2013007821-appb-I000209
    [화학식 14][Formula 14]
    Figure PCTKR2013007821-appb-I000210
    Figure PCTKR2013007821-appb-I000210
    [화학식 15][Formula 15]
    Figure PCTKR2013007821-appb-I000211
    Figure PCTKR2013007821-appb-I000211
    [화학식 16][Formula 16]
    Figure PCTKR2013007821-appb-I000212
    Figure PCTKR2013007821-appb-I000212
    상기 화학식 11 내지 16에서, In Chemical Formulas 11 to 16,
    X1, R1 내지 R4, L, a 및 B는 각각 제1항에 정의된 바와 같고,X 1 , R 1 to R 4 , L, a and B are each as defined in claim 1,
    이때, 복수의 R3은 서로 동일하거나 상이하며, 복수의 R4는 서로 동일하거나 상이하다.At this time, a plurality of R 3 are the same or different from each other, a plurality of R 4 is the same or different from each other.
  8. 제1항에 있어서, 하기 화학식 17로 표시되는 화합물.The compound of claim 1, wherein the compound is represented by the following Formula 17: 4.
    [화학식 17][Formula 17]
    Figure PCTKR2013007821-appb-I000213
    Figure PCTKR2013007821-appb-I000213
    상기 화학식 17에서,In Chemical Formula 17,
    X1, X3, Y1 내지 Y8, R1, R2, R5, R6, 환 A, 환 C, L 및 a는 각각 제1항에 정의된 바와 같다.X 1 , X 3 , Y 1 to Y 8 , R 1 , R 2 , R 5 , R 6 , Ring A, Ring C, L and a are each as defined in claim 1.
  9. 제1항에 있어서, 하기 화학식 18 내지 23으로 표시되는 화합물로 이루어진 군에서 선택된 화합물.The compound of claim 1, wherein the compound is selected from the group consisting of compounds represented by Formulas 18-23.
    [화학식 18][Formula 18]
    Figure PCTKR2013007821-appb-I000214
    Figure PCTKR2013007821-appb-I000214
    [화학식 19][Formula 19]
    Figure PCTKR2013007821-appb-I000215
    Figure PCTKR2013007821-appb-I000215
    [화학식 20][Formula 20]
    Figure PCTKR2013007821-appb-I000216
    Figure PCTKR2013007821-appb-I000216
    [화학식 21][Formula 21]
    Figure PCTKR2013007821-appb-I000217
    Figure PCTKR2013007821-appb-I000217
    [화학식 22][Formula 22]
    Figure PCTKR2013007821-appb-I000218
    Figure PCTKR2013007821-appb-I000218
    [화학식 23][Formula 23]
    Figure PCTKR2013007821-appb-I000219
    Figure PCTKR2013007821-appb-I000219
    상기 화학식 18 내지 23에서,In Chemical Formulas 18 to 23,
    X1, X3, Y5 내지 Y8, R1 내지 R6, 환 C, L 및 a는 각각 제1항에 정의된 바와 같고,X 1 , X 3 , Y 5 to Y 8 , R 1 to R 6 , rings C, L and a are as defined in claim 1, respectively.
    이때, 복수의 R3은 서로 동일하거나 상이하며, 복수의 R4는 서로 동일하거나 상이하다.At this time, a plurality of R 3 are the same or different from each other, a plurality of R 4 is the same or different from each other.
  10. 양극, 음극, 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하는 유기 전계 발광 소자로서, An organic electroluminescent device comprising an anode, a cathode, and at least one organic material layer interposed between the anode and the cathode.
    상기 1층 이상의 유기물층 중에서 적어도 하나는 제1항 내지 제9항 중 어느 한 항에 기재된 화합물을 포함하는 것이 특징인 유기 전계 발광 소자. At least one of the one or more organic material layers comprises the compound according to any one of claims 1 to 9.
  11. 제10항에 있어서, 상기 화합물을 포함하는 유기물층은 정공 주입층, 정공 수송층 및 발광층으로 구성된 군으로부터 선택되는 것이 특징인 유기 전계 발광 소자. The organic electroluminescent device according to claim 10, wherein the organic material layer including the compound is selected from the group consisting of a hole injection layer, a hole transport layer, and a light emitting layer.
  12. 제10 항에 있어서, 상기 화합물을 포함하는 유기물층은 발광층인 것이 특징인 유기 전계 발광 소자.The organic electroluminescent device according to claim 10, wherein the organic material layer including the compound is a light emitting layer.
PCT/KR2013/007821 2012-09-19 2013-08-30 Organic compound and electroluminescent element having same WO2014046392A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020120104250A KR101571589B1 (en) 2012-09-19 2012-09-19 Organic compound and organic electroluminescent device comprising the same
KR10-2012-0104250 2012-09-19

Publications (1)

Publication Number Publication Date
WO2014046392A1 true WO2014046392A1 (en) 2014-03-27

Family

ID=50341647

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2013/007821 WO2014046392A1 (en) 2012-09-19 2013-08-30 Organic compound and electroluminescent element having same

Country Status (2)

Country Link
KR (1) KR101571589B1 (en)
WO (1) WO2014046392A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106467532A (en) * 2016-08-19 2017-03-01 江苏三月光电科技有限公司 A kind of compound with nitrogenous five-ring heterocycles as core and its application in OLED
CN106892901A (en) * 2017-04-21 2017-06-27 瑞声光电科技(常州)有限公司 Triaizine compounds and luminescent device
US10593888B2 (en) 2017-02-23 2020-03-17 Samsung Display Co., Ltd. Polycyclic compound and organic light-emitting device including the same
US10807984B2 (en) 2017-02-10 2020-10-20 Samsung Display Co., Ltd. Heterocyclic compound and organic light-emitting device including the same

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102507373B1 (en) * 2015-12-21 2023-03-08 솔루스첨단소재 주식회사 Organic light-emitting compound and organic electroluminescent device using the same
KR20200110506A (en) * 2019-03-13 2020-09-24 삼성디스플레이 주식회사 Heterocyclic compound and organic light emitting device including the same
KR20200118329A (en) 2019-04-05 2020-10-15 삼성디스플레이 주식회사 Organic electroluminescence device and compound for organic electroluminescence device

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040086745A1 (en) * 2002-03-22 2004-05-06 Idemitsu Kosan Co., Ltd. Material for organic electroluminescence devices and organic electroluminescence device using the material
JP2005347160A (en) * 2004-06-04 2005-12-15 Konica Minolta Holdings Inc Organic electroluminescent element, lighting device, and display device
KR20110105268A (en) * 2010-03-18 2011-09-26 덕산하이메탈(주) Compound containing indoloacridine and organic electronic element using the same, terminal thereof
KR20110105270A (en) * 2010-03-18 2011-09-26 덕산하이메탈(주) Compound containing indoloacridine and organic electronic element using the same, terminal thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040086745A1 (en) * 2002-03-22 2004-05-06 Idemitsu Kosan Co., Ltd. Material for organic electroluminescence devices and organic electroluminescence device using the material
JP2005347160A (en) * 2004-06-04 2005-12-15 Konica Minolta Holdings Inc Organic electroluminescent element, lighting device, and display device
KR20110105268A (en) * 2010-03-18 2011-09-26 덕산하이메탈(주) Compound containing indoloacridine and organic electronic element using the same, terminal thereof
KR20110105270A (en) * 2010-03-18 2011-09-26 덕산하이메탈(주) Compound containing indoloacridine and organic electronic element using the same, terminal thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106467532A (en) * 2016-08-19 2017-03-01 江苏三月光电科技有限公司 A kind of compound with nitrogenous five-ring heterocycles as core and its application in OLED
CN106467532B (en) * 2016-08-19 2019-05-14 江苏三月光电科技有限公司 It is a kind of using nitrogenous five-ring heterocycles as the compound of core and its application in OLED device
US10807984B2 (en) 2017-02-10 2020-10-20 Samsung Display Co., Ltd. Heterocyclic compound and organic light-emitting device including the same
US10593888B2 (en) 2017-02-23 2020-03-17 Samsung Display Co., Ltd. Polycyclic compound and organic light-emitting device including the same
CN106892901A (en) * 2017-04-21 2017-06-27 瑞声光电科技(常州)有限公司 Triaizine compounds and luminescent device

Also Published As

Publication number Publication date
KR101571589B1 (en) 2015-11-25
KR20140038060A (en) 2014-03-28

Similar Documents

Publication Publication Date Title
WO2016195441A1 (en) Nitrogen-containing condensed cyclic compound and organic light emitting element using same
WO2018038401A1 (en) Organic compound and organic electroluminescence device including same
WO2017179809A1 (en) Organic light-emitting compound and organic electroluminescent element using same
WO2018093107A1 (en) Organic compound and organic electroluminescent element comprising same
WO2018110958A1 (en) Organic light-emitting compound and organic electroluminescent element using same
WO2013094999A2 (en) Organic compound, and organic electroluminescent device using same
WO2014065498A1 (en) Organic electroluminescent device
WO2020153758A1 (en) Composition, organic optoelectronic diode, and display device
WO2018038400A1 (en) Organic compound and organic electroluminescence device including same
WO2014142488A1 (en) Organic compound and organic electroluminescent element including same
WO2014092354A1 (en) Organic compound and organic electroluminescent element comprising same
WO2014025209A1 (en) Novel compound and organic electroluminescence device comprising same
WO2011145876A2 (en) Novel hybrid organic compound and organic electroluminescent device using same
WO2014010810A1 (en) Novel compound and electroluminescent device including same
WO2014046392A1 (en) Organic compound and electroluminescent element having same
WO2018038464A1 (en) Organic compound and organic electroluminescent device comprising same
WO2016105054A2 (en) Organic light emitting compound and organic electroluminescent element using same
WO2014027822A1 (en) Novel compound and organic electroluminescent device comprising same
WO2017023125A1 (en) Organic light-emitting compound and organic electroluminescent device using same
WO2015111943A1 (en) Organic compound, and organic electroluminescent device containing same
WO2014027814A1 (en) Novel compound and organic electroluminescent device comprising same
WO2015125986A1 (en) Organic compound and organic electroluminescent device comprising same
WO2016105123A2 (en) Organic compound and organic electroluminescent device comprising same
WO2015111942A2 (en) Organic compound and organic electroluminescent element comprising same
WO2020027463A1 (en) Organic compound and organic electroluminescent device using same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13839406

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205 DATED 08.07.2015)

122 Ep: pct application non-entry in european phase

Ref document number: 13839406

Country of ref document: EP

Kind code of ref document: A1