WO2012177006A2 - Compound for organic electronics, organic electronics using same, and electronic device for same - Google Patents

Compound for organic electronics, organic electronics using same, and electronic device for same Download PDF

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Publication number
WO2012177006A2
WO2012177006A2 PCT/KR2012/004631 KR2012004631W WO2012177006A2 WO 2012177006 A2 WO2012177006 A2 WO 2012177006A2 KR 2012004631 W KR2012004631 W KR 2012004631W WO 2012177006 A2 WO2012177006 A2 WO 2012177006A2
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group
aryl
substituted
deuterium
mmol
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PCT/KR2012/004631
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French (fr)
Korean (ko)
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WO2012177006A3 (en
Inventor
문성윤
이선희
이범성
최대혁
김동하
박정환
박정철
김기원
주진욱
박용욱
박정근
지희선
김혜령
소기호
강문성
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덕산하이메탈(주)
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Priority claimed from KR1020110060643A external-priority patent/KR101111406B1/en
Priority claimed from KR1020110069298A external-priority patent/KR101108519B1/en
Application filed by 덕산하이메탈(주) filed Critical 덕산하이메탈(주)
Publication of WO2012177006A2 publication Critical patent/WO2012177006A2/en
Publication of WO2012177006A3 publication Critical patent/WO2012177006A3/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—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
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen 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
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to a compound and composition for an organic electric device capable of improving low voltage driving, high luminous efficiency and device life, an organic electric device including the same, and an electronic device thereof.
  • organic electroluminescent devices capable of low voltage driving with self-luminous type have superior viewing angles and contrast ratios compared to liquid crystal displays (LCDs), which are mainstream flat panel displays, and require no backlight.
  • LCDs liquid crystal displays
  • Light weight and thinness are possible, and it has an advantage in terms of power consumption.
  • the fast response speed and wide color reproduction range have attracted attention as a next generation display device.
  • an organic EL device is formed on a glass substrate in order of an anode made of a transparent electrode, an organic thin film including a light emitting region, and a metal electrode.
  • the organic thin film may include a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL), or an electron injection layer in addition to the emitting layer (EML).
  • EIL may further include an electron blocking layer (EBL) or a hole blocking layer (HBL) due to light emission characteristics of the light emitting layer.
  • EBL electron blocking layer
  • HBL hole blocking layer
  • the light emitting excitation emits light as it transitions to ground states, in which a light emitting layer (guest) is doped into the light emitting layer (host) to increase the efficiency and stability of the light emitting state.
  • a light emitting layer guest
  • host light emitting layer
  • the life of the device is important, and various studies are being conducted to increase the life of the organic electronic device.
  • various studies have been conducted on organic materials inserted into the hole transport layer or the buffer layer for excellent life characteristics of the organic electric device, and for this purpose, a thin film after deposition is provided while providing high hole transport characteristics from the anode to the organic layer.
  • a hole injection layer material having high uniformity and low crystallinity in forming.
  • the deposition method is the mainstream in the formation of the OLED device, a situation that requires a material that can withstand a long time, that is, a material having a strong heat resistance characteristics.
  • the current major challenge of the organic light emitting device is the urgent need to overcome the problems of power consumption and lifespan as the size of the panel of a mobile phone or a tablet PC is increased.
  • ⁇ Charge Trap Coefficient (Free Carrier / total Carrier)
  • An object of the present invention is to provide a compound and a composition, an organic electric device using the same, and an electronic device, which can improve the high luminous efficiency, low driving voltage, color purity and lifetime of the device.
  • the present invention provides a compound represented by the following formula (1).
  • the present invention provides a composition in which the compound represented by Chemical Formula 1 and the following Chemical Formula 2 is mixed.
  • the present invention provides a composition for an organic electric device containing a composition in which two or more different compounds from among the compounds represented by Formula 1 are mixed.
  • at least one of two or more different compounds may be a compound including deuterium, and two or more different compounds may be mixed in a range in which one compound does not exceed 90% by weight of the total weight of the composition. .
  • the present invention provides an organic electric device using the compound represented by the formula (1).
  • the present invention is an organic electroluminescent device using a composition in which two or more different compounds of the compounds represented by the formula (1) or / and the compound represented by the formula (1) and the compound represented by the formula (2) An organic electric device using the mixed composition is provided.
  • the at least one compound constituting the composition may be a compound substituted with deuterium, it may be mixed in a range not exceeding 90% by weight of the total weight of the composition.
  • the present invention is a compound represented by the formula (1), a mixture of two or more different compounds of the compound represented by the formula (1), or / and the compound represented by the formula (1) and formula (2)
  • a display device including an organic electric element comprising the mixed composition And a controller for driving the display device.
  • 1 to 6 show examples of the organic electroluminescent device to which the compound of the present invention can be applied.
  • 7 to 9 are graphs comparing the brightness, current density and efficiency of the compounds of the present invention to which deuterium is introduced and the compounds to which deuterium is not introduced, respectively.
  • halo or halogen as used herein includes fluorine, chlorine, bromine, and iodine.
  • alkyl or “alkyl group” has a carbon number of 1 to 60 unless otherwise specified, but is not limited thereto.
  • alkenyl or “alkynyl” has a double bond or a triple bond having 2 to 60 carbon atoms, respectively, unless otherwise specified, but is not limited thereto.
  • cycloalkyl refers to alkyl forming a ring having 3 to 60 carbon atoms, without being limited thereto.
  • alkoxy group used in the present invention has a carbon number of 1 to 60 unless otherwise stated, it is not limited thereto.
  • aryl group and “arylene group” have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto.
  • heteroalkyl means an alkyl having one or more heteroatoms unless otherwise indicated.
  • heteroaryl group or “heteroarylene group” means an aryl group or arylene group having 3 to 60 carbon atoms each having one or more heteroatoms unless otherwise specified, and is not limited thereto. It is not.
  • heterocycloalkyl and “heterocyclic group” include one or more heteroatoms and, unless stated otherwise, have from 2 to 60 carbon atoms.
  • heteroatom refers to N, O, S, P and Si.
  • aliphatic as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms
  • aliphatic ring means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.
  • heterocompounds or heteroradicals other than the aforementioned heterocompounds include, but are not limited to, one or more heteroatoms.
  • substituted in the term “substituted or unsubstituted” as used herein refers to deuterium, halogen, amino, nitrile, nitro, C 1 -C 20 alkyl, C 1 -C 20 alkoxy groups, C 1 to C 20 alkylamine groups, C 1 to C 20 alkylthiophene groups, C 6 to C 20 arylthiophene groups, C 2 to C 20 alkenyl groups, C 2 to C 20 alkynyl group, C 3 ⁇ C 20 cycloalkyl group, C 6 ⁇ C 60 aryl group, C 6 ⁇ C 20 aryl group substituted with deuterium, C 8 ⁇ C 20 aryl alkenyl group, silane group, boron Group, germanium group, C 5 ⁇ C 20 It is meant to be substituted with one or more substituents selected from the group consisting of, but not limited to these substituents.
  • the present invention is a method for lowering the driving voltage without introducing a plate-like molecular structure that adversely affects the life using a material having a good life, and a method for replacing deuterium at an appropriate ratio, and similarly substituted with heavy water.
  • a method of lowering the driving voltage is proposed.
  • the zero point energy that is, the energy of the ground state is lowered, and as the bond length of deuterium and carbon is shortened, the molecular hardcore volume is reduced, and thus the electrical polarization is also reduced. It was confirmed that the electrolytic polarizability can be reduced, and the thin film volume can be increased by weakening the intermolecular interaction. This property can reduce the crystallinity of the thin film, i.e., create an amorphous state, and in general, it was determined that it would be very effective to realize the necessary amorphous state in order to increase OLED lifetime and driving characteristics.
  • the present invention used an amine compound including carbazole as an excellent material for life.
  • the carbazole-based amine compound has excellent life characteristics according to the present study, but has a disadvantage in that driving voltage is increased.
  • the prior art has not proved the effect of the improvement on this part, and in particular, the prior art which improves the driving characteristics through deuterium substitution at a specific position has not been reported yet.
  • the present invention provides a compound in which an amine group substituted with deuterium is bonded to maintain the excellent properties of the organic material layers of the organic electronic device described above and to meet the requirements of the organic material.
  • deuterium may be introduced into the aryl group bonded to the amine group to improve device characteristics of the organic electroluminescent device.
  • biphenyl bi-phenl
  • the present invention provides a compound represented by the following formula (1).
  • Ar 1 to Ar 3 are each independently the same or different;
  • Halogen group amino group, nitrile group, nitro group, C 1 ⁇ C 20 alkyl group, C 2 ⁇ C 20 alkenyl group, C 1 ⁇ C 20 alkoxy group, C 3 ⁇ C 30 cycloalkyl group, C 2 ⁇ C heterocycloalkyl group, C 6 ⁇ C 60 aryl group and C 2 ⁇ C 20 with one or more substituents selected from the group consisting of heterocyclic group-substituted or unsubstituted C 6 ⁇ C 60 of the arylamine group of 30; And
  • C 1 ⁇ alkenyl group of the C 20 alkyl group C 2 ⁇ C 20 of, C 1 ⁇ C 20 alkoxy group, C 6 ⁇ aryl group of C 20 aryl group, a C 6 ⁇ C 20 substituted with deuterium, C 7 C 1 -C 50 alkyl group unsubstituted or substituted with a substituent selected from the group consisting of-C 20 arylalkyl group, C 8 ⁇ C 20 aryl alkenyl group, C 3 ⁇ C 20 heterocyclic group, nitrile group and acetylene group Selected from the group consisting of;
  • At least one of Ar 1 to Ar 3 includes one or more deuterium
  • R 1 and R 2 are each independently the same or different and are hydrogen; heavy hydrogen; halogen; Nitro group; Nitrile group; Amino group;
  • C 1 ⁇ alkenyl group of the C 20 alkyl group C 2 ⁇ C 20 of, C 1 ⁇ C 20 alkoxy group, C 6 ⁇ aryl group of C 20 aryl group, a C 6 ⁇ C 20 substituted with deuterium, C 7 C 1 -C 50 alkyl group unsubstituted or substituted with a substituent selected from the group consisting of-C 20 arylalkyl group, C 8 ⁇ C 20 aryl alkenyl group, C 3 ⁇ C 20 heterocyclic group, nitrile group and acetylene group Selected from the group consisting of;
  • R 1 and R 2 may be bonded to adjacent groups to form an alicyclic, aromatic or heterocyclic ring,
  • L is C 6 -C 60 aryl unsubstituted or substituted with one or more substituents selected from the group consisting of a nitro group, a nitrile group, a halogen group, an alkyl group, an alkoxy group, an amino group, an arylamine group and a heterocyclic group Ren group; Or a C 2 -C 60 heterocyclic group unsubstituted or substituted with one or more substituents selected from the group consisting of nitro, nitrile, halogen, alkyl, alkoxy, amino and aryl groups,
  • a is an integer of 0-4, b is an integer of 0-3, c is an integer of 0-2.
  • the present invention provides a composition in which two or more different compounds among the compounds represented by Formula 1 are mixed.
  • two or more different compounds may be mixed in a range in which one compound does not exceed 90% by weight of the total composition.
  • the present invention provides a composition for an organic electric device, a mixture of a compound represented by the formula (1) and a compound represented by the following formula (2).
  • the composition of any one compound may be mixed in the range of 90% by weight or less of the total weight of the composition.
  • Ar 1 to Ar 3 is the same as the substituent definition of Ar 1 to Ar 3 of Formula 1,
  • R 1 to R 4 is the same as the substituent definition of R 1 or R 2 in Formula 1, wherein R 1 to R 4 may be bonded to an adjacent group to form an alicyclic, aromatic or heterocycle ,
  • R 'and R are each independently the same or different, hydrogen, deuterium, halogen, amino, nitrile, nitro, C 1 -C 20 alkyl group, C 1 -C 20 alkoxy group, C 1 C 20 -C 20 alkylamine group, C 1 -C 20 alkylthiophene group, C 6 -C 20 arylthiophene group, C 2 -C 20 alkenyl group, C 2 -C 20 alkynyl group, C 3 ⁇ C 20 cycloalkyl group, C 6 ⁇ C 60 aryl group, of a C 2 ⁇ C 20 substituted by deuterium aryl group, a C 8 ⁇ C 20 aryl alkenyl group, C 6 ⁇ C 20 aryl amine group, a silane C 6 -C 60 aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of a group, a boron group, a germanium group,
  • (4) a is an integer of 1 to 3
  • b, c and d are integers of 1 to 4, respectively.
  • Ar 3 includes one or more deuterium
  • Ar 2 may be represented by the following formula.
  • R 3 and R 4 are each independently the same or different and are halogen; Nitro group; Nitrile group; Amino group;
  • C 1 ⁇ alkenyl group of the C 20 alkyl group C 2 ⁇ C 20 of, C 1 ⁇ C 20 alkoxy group, C 6 ⁇ aryl group of C 20 aryl group, a C 6 ⁇ C 20 substituted with deuterium, C 7 C 1 -C 50 alkyl group unsubstituted or substituted with a substituent selected from the group consisting of-C 20 arylalkyl group, C 8 ⁇ C 20 aryl alkenyl group, C 3 ⁇ C 20 heterocyclic group, nitrile group and acetylene group Selected from the group consisting of;
  • R 3 and R 4 may combine with adjacent groups to form an alicyclic, aromatic or heterocyclic ring,
  • R 'and R are the same as or different from each other independently, hydrogen, deuterium, halogen, amino group, nitrile group, nitro group, C 1 ⁇ C 20 alkyl group, C 1 ⁇ C 20 alkoxy group, C 1 C 20 -C 20 alkylamine group, C 1 -C 20 alkylthiophene group, C 6 -C 20 arylthiophene group, C 2 -C 20 alkenyl group, C 2 -C 20 alkynyl group, C 3 ⁇ C 20 cycloalkyl group, an aryl group of C 6 ⁇ C 60, of a C 6 ⁇ C 20 substituted with a heavy hydrogen aryl, C 8 ⁇ C 20 aryl alkenyl group, C 6 ⁇ C 20 aryl amine group, a silane C 6 -C 60 aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of a group, a boron group,
  • At least one of Ar 1 , Ar 2 , and Ar 3 may be selected from the group consisting of the following Formula 3.
  • D is deuterium
  • k and i are integers of 0 to 2
  • n, o, q, r, q 'and r' is an integer of 0 to 3
  • b, e, f, g, l, t 'and u' are integers from 0 to 4
  • a, c, c ', h, j, m, p, s, t, u and s' are integers from 0 to 5
  • b' is 0 It is an integer of -6
  • a 'and d are integers of 0-7.
  • the index may be determined such that at least one of Ar 1 to Ar 3 includes deuterium.
  • Ar 1 to Ar 3 which contains the heavy hydrogen in Ar 1 to Ar 3 of the general formula (2) is not the type is limited to such.
  • the compound represented by Formula 1 may be any one of the following Compounds (P-1) to (P-132), but is not limited thereto.
  • the compounds represented by Formula 1 may be one of the compounds shown in Formula 5, but is not limited thereto.
  • the substituents of the compounds represented by the general formula (1) are practically difficult to exemplify all the compounds in a broad relationship, the exemplary compounds have been described by way of example, but the compounds represented by the general formula (1) not shown in the general formula (5) also Some can be configured.
  • the compound represented by Formula 2 may be any one of the following Compounds (P2-1) to (P2-120), but is not limited thereto.
  • Compounds represented by Formula 2 may be one of the compounds shown in Formula 6, but is not limited thereto.
  • the substituents of the compounds represented by the formula (2) are practically difficult to exemplify all the compounds in a broad relationship, the exemplary compounds have been described by way of example, but the compounds represented by the formula (2) not shown in the formula (6) also Some can be configured.
  • compositions containing a compound having the above structural formula or a mixture thereof can be used in a soluble process.
  • the composition containing the compound or a mixture thereof may form an organic material layer of the organic electric element to be described later by a solution process (soluble process).
  • the organic material layer may be formed using a variety of polymer materials, rather than a solution process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be produced in fewer layers by methods such as law.
  • an organic electric device including a first electrode, a second electrode, and at least one organic material layer containing the compound represented by Formula 1 alone or in a mixture.
  • the mixture may be a mixture of two or more different compounds among the compounds represented by the formula (1) or a mixture of the compound represented by the formula (1) and the compound represented by the formula (2).
  • the organic material layer may be at least one of a light emitting layer, a hole injection layer, and a hole transport layer.
  • the organic electroluminescent device according to the present invention may be one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a monochromatic or white illumination device.
  • OLED organic electroluminescent device
  • OPC organic photoconductor
  • organic TFT organic transistor
  • the composition of the present invention is a metal oxide organic layer from the positive electrode electrode which is one of the causes of the hole injection layer material having high uniformity and low crystallization when forming a thin film, and shortening the life while maximizing the characteristics of the organic material layer of the organic electric device as described below Stabilization of Joule heating generated during device operation while delaying penetration diffusion into the device, namely the demand for a hole injection layer material having a high glass transition temperature, and withstanding the deposition method in the formation of an organic electroluminescent device It can meet the requirements of materials that can be used, that is, materials with strong heat resistance characteristics.
  • thermodynamic behaviors of a composition comprising a mixture of compounds substituted with deuterium or a compound not substituted with deuterium or the compound itself substituted with deuterium, and confirmed carbon, hydrogen and carbon, deuterium bonds. According to the difference in length, it was confirmed that a compound composed of carbon and deuterium having a smaller bond length has a higher luminous efficiency due to the weakening of the intermolecular van der Waals forces generated by a short bond length. As the zero point energy, or ground energy, is lowered, and the bond length of deuterium and carbon is shortened, the molecular hardcore volume is reduced, thereby reducing the electrical polarizability. Thin film volume by weakening intermolecular interactions It was confirmed that increase.
  • the properties of the compound of the present invention substituted with deuterium may create an effect of lowering the crystallinity of the thin film, that is, an amorphous state, and in general, in order to increase the lifespan and driving characteristics of the organic electroluminescent device, We decided it would be very effective to implement.
  • the mixture of the deuterium-substituted compound has a low visible light absorption characteristics than the low carbon, hydrogen bonding material, it was determined that this can be an advantage to increase the efficiency in light emitting devices such as organic electroluminescent devices.
  • the mixture of the compound of the present invention substituted with deuterium has a great increase in heat resistance.
  • Carbazole (50.2 g, 300 mmol) and bromobenzene (56.5 g, 360 mmol) were mixed in 2800 mL of toluene, followed by Pd 2 (dba) 3 (8.24 g, 9 mmol), PPh 3 (7.87 g, 30 mmol), NaO t -Bu (86.5 g, 900 mmol) was added, and the mixture was stirred at reflux for 24 hours at 100 ° C. After extraction with ether and water, the organic layer was dried over MgSO 4 , concentrated and the resulting organic was purified and recrystallized by a silica gel column to give 52.5 g (75%) of the product.
  • NBS N-bromosuccimide
  • Sub 1-2 (45.1 g, 140 mmol) obtained in the above synthesis was dissolved in 980 mL of DMF, followed by bispinacolborate (39.1 g, 154 mmol), PdCl 2 (dppf) catalyst (3.43 g, 4.2 mmol), KOAc ( 41.3 g, 420 mmol) was added sequentially, followed by stirring for 24 hours to synthesize the borate compound, and the obtained compound was separated through a silica gel column and recrystallized to obtain 35.2 g (68%) of the borate compound.
  • Sub 1-1-1 (63.88 g, 200 mmol) obtained in the above synthesis was added with 600 mL of methylene chloride and NBS (N-bromosuccimide) (59.4 g, 210 mmol) using the sub 1-2 synthesis method of Example 1 To give 55.8 g (70%) of the product.
  • reaction temperature was adjusted to 0 ° C. and a solution of 9-phenyl carbazole (2.92 g, 120 mmol) in 1,2-dichloroethane (52 mL) was added dropwise for 1 hour.
  • N-phenyl-d5-naphthalen-1-amine 22.43 g, 100 mmol
  • 2,7-dibromo-9,9-dimethyl fluorene 38.73 g, 110 mmol
  • Pd 2 (dba) 3 (2.75 g, 3 mmol)
  • PPh 3 (2.63 g, 10 mmol)
  • NaO t -Bu 28.9 g, 300 mmol
  • toluene 970 mL
  • N-phenyl-d5-naphthalen-2-amine 22.43 g, 100 mmol
  • 2,7-dibromo-9,9-diphenyl fluorene 52.38 g, 110 mmol
  • Pd 2 (dba) 3 (2.75 g, 3 mmol)
  • PPh 3 (2.63 g, 10 mmol)
  • NaO t -Bu 28.9 g, 300 mmol
  • toluene 970 mL
  • phenylaniline-d5 34.85 g, 200 mmol
  • 4-bromo-4'-iodobiphenyl 86.16 g, 240 mmol
  • Pd 2 (dba) 3 5.5 g, 6 mmol
  • PPh 3 5.25 g, 20 mmol
  • NaO t -Bu 57.7 g, 600 mmol
  • toluene (1930 mL)
  • N-phenyl-d5-naphthalen-1-amine 44.86g, 200 mmol
  • 4-bromo-4'-iodobiphenyl 86.16 g, 240 mmol
  • Pd 2 (dba) 3 5.5 g, 6 mmol
  • PPh 3 5.25 g, 20 mmol
  • NaO t -Bu 57.7 g, 600 mmol
  • toluene (1930 mL) were obtained in the same manner as in the Experiments of Sub-1b-1, to give 62.85 g (69%) of the product.
  • N-phenyl-d5-naphthalen-2-amine 44.86g, 200 mmol
  • 4-bromo-4'-iodobiphenyl 86.16 g, 240 mmol
  • Pd 2 (dba) 3 5.5 g, 6 mmol
  • PPh 3 5.25 g, 20 mmol
  • NaO t -Bu 57.7 g, 600 mmol
  • toluene (1930 mL) were obtained in the same manner as in the Experiments of Sub-1b-1 to obtain 61.93 g (68%) of the product.
  • N-phenyl-d5-biphenyl-4-amine 50.07 g, 200 mmol
  • 4-bromo-4'-iodobiphenyl 86.16 g, 240 mmol
  • Pd 2 (dba) 3 5.5 g, 6 mmol
  • PPh 3 5.25 g, 20 mmol
  • NaO t -Bu 57.7 g, 600 mmol
  • toluene (1930 mL) were obtained in the same manner as in the Experiments of Sub-1b-1, to obtain 65.48 g (68%) of the product.
  • N-phenyl-d5-phenylthiophen-2-amine 51.28g, 200 mmol
  • 4-bromo-4'-iodobiphenyl 86.16 g, 240 mmol
  • Pd 2 (dba) 3 5.5 g, 6 mmol
  • PPh 3 5.25 g, 20 mmol
  • NaO t -Bu 57.7 g, 600 mmol
  • toluene (1930 mL) were obtained in the same manner as in the Sub-1b-1 Experiment to obtain 63.37 g (65%) of the product.
  • N- (4-methoxyphenyl) -aniline-2,3,4,5,6-d5 40.86g, 200 mmol
  • 4-bromo-4'-iodobiphenyl 86.16 g, 240 mmol
  • Pd 2 (dba) 3 5.5 g, 6 mmol
  • PPh 3 5.25 g, 20 mmol
  • NaO t -Bu 57.7 g, 600 mmol
  • toluene (1930 mL) were prepared in the same manner as in Sub-1b-1. 59.21 g (68%) was obtained.
  • N-phenyl-d5-dibenzo [b, d] furan-2-amine 52.87 g, 200 mmol
  • 4-bromo-4'-iodobiphenyl 86.16 g, 240 mmol
  • Pd 2 (dba) 3 5.5 g , 6 mmol
  • PPh 3 5.25 g, 20 mmol
  • NaO t -Bu 57.7 g, 600 mmol
  • toluene (1930 mL) were prepared in the same manner as in the Experiment of Sub-1b-1, and the product was 64.40 g ( 65%).
  • N-phenyl-d5-4-fluorophenyl-1-amine 38.45 g, 200 mmol
  • 4-bromo-4'-iodobiphenyl 86.16 g, 240 mmol
  • Pd 2 (dba) 3 5.5 g, 6 mmol
  • PPh 3 5.25 g, 20 mmol
  • NaO t -Bu 57.7 g, 600 mmol
  • toluene (1930 mL) were obtained in the same manner as the Sub-1b-1 experiment to give 56.73 g (67%) of the product. .
  • naphthalene-2-anime 28.64g, 200 mmol
  • 2-bromo-9,9-dimethyl-9H-fluorene 65.56g, 240 mmol
  • Pd 2 (dba) 3 5.5 g, 6 mmol
  • PPh 3 5.25 g, 20 mmol
  • NaO t -Bu 57.7 g, 600 mmol
  • toluene (1930 mL) were obtained in the same manner as the Sub-1b-1 experiment to obtain 45.62 g (68%) of the product.
  • naphthalene-1-anime 28.64g, 200 mmol
  • 2-bromo-9,9-dimethyl-9H-fluorene 65.56g, 240 mmol
  • Pd 2 (dba) 3 5.5 g, 6 mmol
  • PPh 3 5.25 g, 20 mmol
  • NaO t -Bu 57.7 g, 600 mmol
  • toluene (1930 mL) were obtained in the same manner as in the Sub-1b-1 experiment to obtain 44.95 g (67%) of the product.
  • 1-amino-4-phenyl-naphthalene-d6 (45.06g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were prepared in the same manner as in Sub-1b-1, and the product was 53.45 g (64 %) Got.
  • each of the substituents of the compounds represented by the formula (1) or (2) is a broad relationship, the compounds represented by the formula (1) or formula (2) that is illustratively described a synthesis example of representative compounds, but not illustratively described as a synthesis example Also part of the present specification.
  • the compound which has the intrinsic property of the introduced substituent can be synthesize
  • substituents used in the hole injection layer material, the hole transport layer material, the light emitting layer material, and the electron transport layer material used in the manufacture of the organic electric device, including the organic light emitting device to satisfy the conditions required for each organic material layer Materials can be prepared.
  • the compound according to the present invention can be used for various purposes in the organic electroluminescent device according to the type and nature of the substituent.
  • the compounds of the present invention can act as various layers other than the host of the phosphorescent or fluorescent light emitting layer because they are freely controlled by the core and the substituents.
  • the organic electric device of the present invention may be manufactured by a conventional method and material for manufacturing an organic electric device except for forming one or more organic material layers using the above-described compounds.
  • the compounds of the present invention are used in other organic material layers of the organic electroluminescent device, for example, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer, it is obvious that the same effect can be obtained.
  • the compound of the present invention can be used in a soluble process.
  • the compound may form an organic material layer of the organic electronic device, which will be described later, by a solution process.
  • the organic material layer may be formed by using various polymer materials, rather than a solution process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be produced in fewer layers by the method.
  • Organic electroluminescent devices in which the compounds of the present invention may be used include, for example, organic electroluminescent devices (OLEDs), organic solar cells, organic photoconductor (OPC) drums, organic transistors (organic TFTs), and the like.
  • organic electroluminescent device As an example of the organic electroluminescent device to which the compounds of the present invention can be applied, an organic electroluminescent device (OLED) will be described.
  • OLED organic electroluminescent device
  • the present invention is not limited thereto, and the above-described compounds may be applied to various organic electroluminescent devices.
  • Another embodiment of the present invention is an organic electroluminescent device comprising a first electrode, a second electrode and an organic material layer disposed between the electrodes, wherein at least one of the organic material layer comprises an organic electroluminescent device comprising the compounds of the present invention to provide.
  • 1 to 6 show examples of the organic electroluminescent device to which the compound of the present invention can be applied.
  • the organic electroluminescent device except that at least one layer of the organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer to include the compound of the present invention.
  • a hole injection layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer to include the compound of the present invention.
  • reference numeral 101 denotes a substrate, 102 an anode, 103 a hole injection layer (HIL), 104 a hole transport layer (HTL), 105 a light emitting layer (EML), 106 an electron injection layer (EIL), 107 an electron transport layer ( ETL), 108 represents a negative electrode.
  • HIL hole injection layer
  • HTL hole transport layer
  • EML electron injection layer
  • ETL electron transport layer
  • the organic electroluminescent device further includes a hole blocking layer (HBL) that prevents the movement of holes, an electron blocking layer (EBL) that prevents the movement of electrons, a light emitting auxiliary layer that helps or assists light emission, and a protective layer. It may be located.
  • the protective layer may be formed to protect the organic material layer or the cathode at the uppermost layer.
  • the compound of the present invention may be included in one or more of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer.
  • the compound of the present invention is used in place of or in combination with one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer and a protective layer It may be used to form.
  • the organic layer may be used not only in one layer but also in two or more layers.
  • it can be used as a hole injection material, a hole transport material, an electron injection material, an electron transport material, a luminescent material and a passivation (kepping) material according to the compound of the present invention, in particular a host or in a luminescent material and host / dopant alone Can be used as a dopant, can be used as a hole injection, a hole transport layer.
  • the organic electroluminescent device is a metal having metal or conductivity on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation.
  • PVD physical vapor deposition
  • An oxide or an alloy thereof is deposited to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer is formed thereon, and then a material that can be used as a cathode is deposited thereon.
  • PVD physical vapor deposition
  • an organic electronic device may be fabricated by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.
  • the organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, but is not limited thereto and may have a single layer structure.
  • the organic layer may be formed using a variety of polymer materials, but not by a deposition process or a solvent process, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be made with a small number of layers.
  • the organic electroluminescent device according to another embodiment of the present invention may be used in a solution process such as spin coating or ink jet process.
  • the substrate is a support of the organic electroluminescent device, and a silicon wafer, a quartz or glass plate, a metal plate, a plastic film or sheet, or the like can be used.
  • the positive electrode material may be a material having a large work function to facilitate hole injection into the organic material layer.
  • Specific examples of the positive electrode material that can be used in the present invention 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 oxides with metals such as ZnO: Al or SnO 2: Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline, and the like, but are not limited thereto.
  • the hole injection layer is located on the anode.
  • the conditions required for the material of the hole injection layer are high hole injection efficiency from the anode, it should be able to transport the injected holes efficiently. This requires a small ionization potential, high transparency to visible light, and excellent hole stability.
  • the hole injection material is a material that can be injected well from the anode at a low voltage, the highest occupied molecular orbital (HOMO) of the hole injection material may be between the work function of the positive electrode material and the HOMO of the surrounding organic material layer.
  • HOMO occupied molecular orbital
  • Specific examples of hole injection materials include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene, quinacridone-based organics, perylene-based organics, Anthraquinone, polyaniline and polythiophene-based conductive polymers, but are not limited thereto.
  • the hole transport layer is positioned on the hole injection layer.
  • the hole transport layer receives holes from the hole injection layer and transports the holes to the organic light emitting layer located thereon, and serves to prevent high hole mobility, hole stability, and electrons.
  • applications for vehicle body display require heat resistance to the device, and may be a material having a glass transition temperature (Tg) of 70 ° C. or higher.
  • NPD NPB
  • spiro-arylamine compounds perylene-arylamine compounds
  • azacycloheptatriene compounds bis (diphenylvinylphenyl) anthracene and silicon germanium oxide.
  • the organic light emitting layer is positioned on the hole transport layer.
  • the organic light emitting layer is a layer for emitting light by recombination of holes and electrons injected from the anode and the cathode, respectively, and is made of a material having high quantum efficiency.
  • the light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and may be a material having good quantum efficiency for fluorescence or phosphorescence.
  • Substances or compounds that satisfy these conditions include Alq3 for green, Balq (8-hydroxyquinoline beryllium salt) for blue, DPVBi (4,4'-bis (2,2-diphenylethenyl) -1,1'- biphenyl) series, Spiro material, Spiro-DPVBi (Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazoyl) -phenollithium salt ), Bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complex, metal complexes of imidazole, thiazole and oxazole, and the like, perylene, and BczVBi (3,3 '[ (1,1'-biphenyl) -4,4'-diyldi-2,1-ethenediyl] bis (9-ethyl) -9H-carbazole; D
  • DCJTB [2- (1,1-dimethylethyl) -6- [2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H
  • doping such as -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile
  • a polymer of polyphenylene vinylene (PPV) -based polymer or poly fluorene may be used for the organic light emitting layer.
  • the electron transport layer is positioned on the organic light emitting layer.
  • the electron transport layer needs a material having high electron injection efficiency from the cathode positioned thereon and capable of efficiently transporting the injected electrons. To this end, it must be made of a material having high electron affinity and electron transfer speed and excellent stability to electrons.
  • Examples of the electron transport material that satisfies such conditions include Al complexes of 8-hydroxyquinoline; Complexes including Alq3; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.
  • the electron injection layer is stacked on the electron transport layer.
  • the electron injection layer is a metal complex compound such as Balq, Alq3, Be (bq) 2, Zn (BTZ) 2, Zn (phq) 2, PBD, spiro-PBD, TPBI, Tf-6P, aromatic compound with imidazole ring, It can be produced using a low molecular weight material containing boron compounds and the like.
  • the electron injection layer may be formed in a thickness range of 100 ⁇ 300 ⁇ .
  • the cathode is positioned on the electron injection layer. This cathode serves to inject electrons.
  • the material used as the cathode may use the material used for the anode, and may be a metal having a low work function for efficient electron injection.
  • a suitable metal such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or a suitable alloy thereof can be used.
  • electrodes having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum having a thickness of 100 ⁇ m or less may also be used.
  • the compound of the present invention can be used as a hole injection material, a hole transport material, a light emitting material, an electron transport material, and an electron injection material suitable for fluorescence and phosphorescent devices of all colors such as red, green, blue, and white, It can be used as a host or dopant material of various colors.
  • the organic electroluminescent device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used.
  • the present invention includes a display device including the organic electric element described above, and a terminal including a control unit for driving the display device.
  • This terminal means a current or future wired or wireless communication terminal.
  • the terminal according to the present invention described above may be a mobile communication terminal such as a mobile phone, and includes all terminals such as a PDA, an electronic dictionary, a PMP, a remote control, a navigation device, a game machine, various TVs, various computers, and the like.
  • Various compounds of the present invention obtained through synthesis were used as light emitting host materials or hole transport layers, respectively, to fabricate organic electroluminescent devices according to a conventional method.
  • a 2-TNATA film was vacuum-deposited as a hole injection layer on the ITO layer (anode) formed on the organic substrate, and formed into a thickness of 10 nm.
  • the compound of the present invention (compounds 1 and 2) was vacuum deposited to a thickness of 20 nm to form a hole transport layer.
  • tris (8-quinolinol) aluminum was deposited to a thickness of 40 nm with an electron injection layer.
  • LiF an alkyl halide metal, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm to prepare an organic electroluminescent device using this Al / LiF as a cathode.
  • An organic electric device was manufactured in the same manner as above, but the following compound was used as the hole transport layer material.
  • the electroluminescence (EL) characteristics were measured by PR-650 of photoresearch company .
  • the T90 lifetime was measured using a life-time measurement device manufactured by McScience Inc. at 300 cd / m 2 reference luminance. The results are shown in the following table.
  • the driving voltage decreases, it is judged to have high efficiency and long life, and it is expected to solve the short life problem due to the high driving voltage which is a problem in the OLED device.
  • the compounds of the present invention are used in other organic material layers of the organic electroluminescent device, for example, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer, it is obvious that the same effect can be obtained.

Abstract

The present invention relates to organic electronics including a hole injection layer material and a hole transport layer, having improved low-voltage driving of the organic electronics and device service life and high light emitting efficiency, by mixing and using a material including heavy hydrogen and having superior driving characteristics and a material having a superior service life.

Description

유기전기소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치Compound for organic electric device, organic electric device using same and electronic device thereof
본 발명은 저전압 구동, 높은 발광효율 및 소자수명을 향상시킬 수 있는 유기전기소자용 화합물과 조성물, 이를 포함하는 유기전기소자 및 그 전자 장치에 관한 것이다.The present invention relates to a compound and composition for an organic electric device capable of improving low voltage driving, high luminous efficiency and device life, an organic electric device including the same, and an electronic device thereof.
평판 표시소자는 최근 들어 급성장세를 보이고 있는 인터넷을 중심으로 고도의 영상 정보화 사회를 지탱하는 매우 중요한 역할을 수행하고 있다. 특히, 자체 발광형으로 저전압 구동이 가능한 유기전기발광소자(유기EL소자)는, 평판 표시소자의 주류인 액정디스플레이(liquid crystal display, LCD)에 비해 시야각 및 명암비 등이 우수하고, 백라이트가 불필요하여 경량 및 박형이 가능하며, 소비전력 측면에서도 유리한 장점을 가진다. 또한, 응답속도가 빠르며, 색 재현 범위가 넓어 차세대 표시소자로서 주목을 받고 있다. 일반적으로, 유기EL소자는 투명전극으로 이루어진 양극(anode), 발광영역을 포함하는 유기박막 및 금속전극(cathode)의 순으로 유리기판 위에 형성된다. 이때, 유기박막은 발광층(emitting layer, EML) 외에 정공 주입층(hole injection layer,HIL), 정공 수송층(hole transport layer, HTL), 전자 수송층(electron transport layer, ETL) 또는 전자 주입층(electroninjection layer, EIL)을 포함할 수 있으며, 발광층의 발광특성상 전자 차단층(electron blocking layer, EBL) 또는 정공 차단층(hole blocking layer, HBL)을 추가로 포함할 수 있다. 이러한 구조의 유기EL소자에 전기장이 가해지면 양극으로부터 정공이 주입되고 음극으로부터 전자가 주입되며, 주입된 정공과 전자는 각각 정공 수송층과 전자 수송층을 거쳐 발광층에서 재조합(recombination)하여 발광 여기자(exitons)를 형성한다. 형성된 발광여기자는 바닥상태(ground states)로 전이하면서 빛을 방출하는데, 이때, 발광 상태의 효율과 안정성을 증가시키기 위해 발광 색소(게스트)를 발광층(호스트)에 도핑하기도 한다. 이러한 유기전기소자를 다양한 디스플레이 매체에 활용하기 위해서는 무엇보다 소자의 수명이 중요하며, 현재 유기전기소자의 수명을 증가시키기 위한 여러 연구들이 진행되고 있다. 특히, 유기전기소자의 우수한 수명 특성을 위해 정공 수송층 또는 완충층(buffer layer)으로 삽입되는 유기물질에 관해 여러 연구가 진행되고 있으며, 이를 위해 양극으로부터 유기층으로의 높은 정공 이동 특성을 부여하면서 증착 후 박막 형성시 균일도가 높고 결정화도가 낮은 정공 주입층 재료가 요구되고 있다. The flat panel display plays a very important role in supporting a highly visual information society, centered on the internet which is rapidly growing in recent years. In particular, organic electroluminescent devices (organic EL devices) capable of low voltage driving with self-luminous type have superior viewing angles and contrast ratios compared to liquid crystal displays (LCDs), which are mainstream flat panel displays, and require no backlight. Light weight and thinness are possible, and it has an advantage in terms of power consumption. In addition, the fast response speed and wide color reproduction range have attracted attention as a next generation display device. In general, an organic EL device is formed on a glass substrate in order of an anode made of a transparent electrode, an organic thin film including a light emitting region, and a metal electrode. In this case, the organic thin film may include a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL), or an electron injection layer in addition to the emitting layer (EML). , EIL), and may further include an electron blocking layer (EBL) or a hole blocking layer (HBL) due to light emission characteristics of the light emitting layer. When an electric field is applied to the organic EL device having such a structure, holes are injected from the anode and electrons are injected from the cathode, and the injected holes and electrons are recombined in the emission layer through the hole transport layer and the electron transport layer, respectively, to emit light excitons. To form. The light emitting excitation emits light as it transitions to ground states, in which a light emitting layer (guest) is doped into the light emitting layer (host) to increase the efficiency and stability of the light emitting state. In order to utilize the organic electronic device in various display media, the life of the device is important, and various studies are being conducted to increase the life of the organic electronic device. In particular, various studies have been conducted on organic materials inserted into the hole transport layer or the buffer layer for excellent life characteristics of the organic electric device, and for this purpose, a thin film after deposition is provided while providing high hole transport characteristics from the anode to the organic layer. There is a need for a hole injection layer material having high uniformity and low crystallinity in forming.
유기전기소자의 수명단축의 원인 중 하나인 양극전극(ITO)으로부터 금속 산화물이 유기층으로 침투 확산되는 것을 지연시키며, 소자 구동시 발생되는 주울열(Joule heating)에 대해서도 안정된 특성, 즉 높은 유리 전이 온도를 갖는 정공 주입층 재료에 대한 개발이 필요하다. 또한 정공 수송층 재료의 낮은 유리전이 온도는 소자 구동시에 박막 표면의 균일도가 무너지는 특성에 따라 소자수명에 큰 영향을 미치는 것으로 보고되고 있다. 또한, OLED 소자의 형성에 있어서 증착방법이 주류를 이루고 있으며, 이러한 증착방법에 오랫동안 견딜 수 있는 재료 즉 내열성 특성이 강한 재료가 필요한 실정이다. Delays penetration of metal oxide into the organic layer from the anode electrode (ITO), which is one of the causes of the shortening of the life of the organic electric device, and stable properties for Joule heating generated when driving the device, that is, high glass transition temperature. There is a need for development of a hole injection layer material having In addition, the low glass transition temperature of the hole transport layer material has been reported to have a significant effect on the device life, depending on the characteristics of the uniformity of the surface of the thin film when driving the device. In addition, the deposition method is the mainstream in the formation of the OLED device, a situation that requires a material that can withstand a long time, that is, a material having a strong heat resistance characteristics.
특히, 현재 유기발광소자의 주요 극복과제는 모바일용 휴대폰이이나 테블릿 PC 등의 패널 사이즈가 대형화되면서, 소비전력 및 수명에 대한 문제 극복이 시급한 실정이다.In particular, the current major challenge of the organic light emitting device is the urgent need to overcome the problems of power consumption and lifespan as the size of the panel of a mobile phone or a tablet PC is increased.
그러나, 정공 수송층 물질로서 구동전압과 수명을 동시에 극복하기는 어려움이 있다. 그러한 이유는 구동전압을 낮추기 위해 정공 수송능력이 뛰어난, 즉 정공 이동도가 높은 재료들은 대부분은 전자가 풍부한 평면구조를 갖는 경우가 대부분이다. 예를 들면, 나프틸, 플루오렌 및 펜안쓰렌 들이다. 그러나 정공 수송물질에 위와 같은 구조의 화합물을 치환기로 도입하였을 때, 일정 개수까지는 정공 이동도가 높아지며, 수명에도 좋은 영향을 주지만, 현재 산업에서 요구되는 저전압 구동 목표에 도달하기 위해서 분자에 도입 개수를 늘리면, 구동전압이 내려가면서 저전압 구동이 가능 하지만 수명 특성이 급격히 나빠지는 결과들을 보인다. 이러한 이유는 전자가 풍부한 평면구조들이 과도하게 도입된 분자의 경우 소자 수명 평가시에 일정한 전류를 계속해서 공급할 때, 판상 구조들의 사이에 홀이 트랩되어 안정화되며, 이는 정공 이동도를 낮추게 되며, 따라서 일정 전류를 가하기 위해 구동전압이 상승하게 됨에 따라, 소자 수명이 급격히 안 좋아지는 결과를 보인다. 이는 하기식으로 표현된다.However, it is difficult to simultaneously overcome the driving voltage and the lifetime as the hole transport layer material. The reason for this is that most of the materials having excellent hole transporting ability, that is, high hole mobility, have a planar structure rich in electrons in order to lower the driving voltage. Examples are naphthyl, fluorene and phenanthrene. However, when the compound of the above structure is introduced into the hole transport material as a substituent, the hole mobility increases to a certain number and has a good effect on the lifetime, but the number of introduction into the molecule is required to reach the low voltage driving target required by the current industry. Increasingly, the driving voltage is lowered, but the low voltage driving is possible, but the life characteristics are rapidly worsened. This is because in the case of molecules in which electron-rich planar structures are excessively introduced, when a constant current is continuously supplied during device life evaluation, holes are trapped and stabilized between the plate structures, which lowers hole mobility, thus As the driving voltage increases in order to apply a constant current, the device life is drastically deteriorated. This is represented by the following formula.
Figure PCTKR2012004631-appb-I000001
Figure PCTKR2012004631-appb-I000001
J = Space Charge limited current J = Space Charge limited current
ε = Permittibility ε = Permittibility
μ = Mobility Coefficient  μ = Mobility Coefficient
θ = Charge Trap Coefficient (Free Carrier/total Carrier) θ = Charge Trap Coefficient (Free Carrier / total Carrier)
V = Voltage V = Voltage
d = Thickness d = Thickness
트랩(Trap) 현상으로 자유 전하(Free Carrier)의 숫자가 적어지면, θ 값이 적어지며 따라서 일정한 전류(current)가 필요한 전류구동방식의 유기전기발광소자에서는 구동전압이 상승하며 이는 수명에 매우 치명적인 결과를 가져올 수 있다. 따라서 전술한 바와 같이 정공 이동도를 높일 수 있는 전자가 풍부한 판상구조의 일정 이상의 도입은 수명에 악영향을 줌으로써 이를 이용해서 구동전압을 낮출 수 있는 가능성은 크지 않다. When the number of free carriers is reduced due to the trap phenomenon, the value of θ decreases. Therefore, the driving voltage increases in the current-driven organic electroluminescent device which requires a constant current, which is very fatal for life. You can get results. Therefore, as described above, the introduction of a certain number of electron-rich plate structures capable of increasing hole mobility adversely affects the lifespan, so the possibility of using the same to lower the driving voltage is not great.
본 발명은 소자의 높은 발광효율, 낮은 구동전압, 색순도 및 수명을 향상시킬 수 있는 화합물과 조성물 및 이를 이용한 유기전기소자 그리고 그 전자장치를 제공하는 것을 목적으로 한다.An object of the present invention is to provide a compound and a composition, an organic electric device using the same, and an electronic device, which can improve the high luminous efficiency, low driving voltage, color purity and lifetime of the device.
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><Formula 1>
Figure PCTKR2012004631-appb-I000002
Figure PCTKR2012004631-appb-I000002
다른 측면에서, 본 발명은 상기 화학식 1과 하기 화학식 2로 표시되는 화합물을 혼합한 조성물을 제공한다.In another aspect, the present invention provides a composition in which the compound represented by Chemical Formula 1 and the following Chemical Formula 2 is mixed.
<화학식 2><Formula 2>
Figure PCTKR2012004631-appb-I000003
Figure PCTKR2012004631-appb-I000003
또 다른 측면에서, 본 발명은 상기 화학식 1로 표시되는 화합물들 중 서로 다른 2종 이상의 화합물이 혼합된 조성물을 함유하는 유기전기소자용 조성물을 제공한다. 이때, 서로 다른 2종 이상의 화합물 중 적어도 하나는 중수소를 포함하는 화합물일 수 있으며, 서로 다른 2종 이상의 화합물은 어느 하나의 화합물이 조성물 전체 중량의 90중량%를 초과하지 않는 범위에서 혼합될 수 있다.In another aspect, the present invention provides a composition for an organic electric device containing a composition in which two or more different compounds from among the compounds represented by Formula 1 are mixed. In this case, at least one of two or more different compounds may be a compound including deuterium, and two or more different compounds may be mixed in a range in which one compound does not exceed 90% by weight of the total weight of the composition. .
또 다른 측면에서, 본 발명은 상기 화학식 1로 표시되는 화합물을 이용하는 유기전기소자를 제공한다.In another aspect, the present invention provides an organic electric device using the compound represented by the formula (1).
또 다른 측면에서, 본 발명은 상기 화학식 1로 표시되는 화합물들 중 서로 다른 2종 이상의 화합물이 혼합된 조성물을 이용한 유기전기소자 또는/및 상기 화학식 1로 표시되는 화합물과 상기 화학식 2로 표시되는 화합물이 혼합된 조성물을 이용한 유기전기소자를 제공한다. 이때, 조성물을 이루는 적어도 하나의 화합물은 중수소로 치환된 화합물일 수 있으며, 조성물 전체 중량의 90중량%를 초과하지 않는 범위에서 혼합될 수 있다.In another aspect, the present invention is an organic electroluminescent device using a composition in which two or more different compounds of the compounds represented by the formula (1) or / and the compound represented by the formula (1) and the compound represented by the formula (2) An organic electric device using the mixed composition is provided. At this time, the at least one compound constituting the composition may be a compound substituted with deuterium, it may be mixed in a range not exceeding 90% by weight of the total weight of the composition.
또 다른 측면에서, 본 발명은 상기 화학식 1로 표시되는 화합물, 상기 화학식 1로 표시되는 화합물들 중 서로 다른 2종 이상의 화합물이 혼합된 조성물, 또는/및 상기 화학식 1과 상기 화학식 2로 표시되는 화합물이 혼합된 조성물을 포함하는 유기전기소자를 포함하는 디스플레이장치; 및 상기 디스플레이장치를 구동하는 제어부;를 포함하는 전자장치를 제공한다. In another aspect, the present invention is a compound represented by the formula (1), a mixture of two or more different compounds of the compound represented by the formula (1), or / and the compound represented by the formula (1) and formula (2) A display device including an organic electric element comprising the mixed composition; And a controller for driving the display device.
본 발명에 따른 화합물 및/또는 조성물을 이용함으로써 소자의 높은 발광효율, 낮은 구동전압, 우수한 색순도 및 수명을 크게 향상시킬 수 있다. By using the compound and / or composition according to the present invention, it is possible to greatly improve the high luminous efficiency, low driving voltage, excellent color purity and lifetime of the device.
도 1 내지 도 6은 본 발명의 화합물을 적용할 수 있는 유기전기발광소자의 예를 도시한 것이다.1 to 6 show examples of the organic electroluminescent device to which the compound of the present invention can be applied.
도 7 내지 도 9는 각각 중수소가 도입된 본 발명의 화합물과 중수소가 도입되지 않은 화합물의 휘도, 전류밀도 및 효율을 비교한 그래프이다.7 to 9 are graphs comparing the brightness, current density and efficiency of the compounds of the present invention to which deuterium is introduced and the compounds to which deuterium is not introduced, respectively.
이하에서 본 발명의 일부 실시예들을 예시적인 도면을 통해 상세하게 설명한다.Hereinafter, some embodiments of the present invention will be described in detail through exemplary drawings.
각 도면의 구성요소들에 참조부호를 부가함에 있어서, 동일한 구성요소들에 대해서는 비록 다른 도면상에 표시되더라도 가능한 한 동일한 부호를 가지도록 하고 있음에 유의해야 한다. 또한, 본 발명을 설명함에 있어, 관련된 공지 구성 또는 기능에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명은 생략한다.In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In addition, in describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.
또한, 본 발명의 구성 요소를 설명하는 데 있어서, 제 1, 제 2, A, B, (a),(b) 등의 용어를 사용할 수 있다. 이러한 용어는 그 구성 요소를 다른 구성 요소와 구별하기 위한 것일 뿐, 그 용어에 의해 해당 구성 요소의 본질이나 차례 또는 순서 등이 한정되지 않는다. 어떤 구성 요소가 다른 구성요소에 "연결", "결합" 또는 "접속"된다고 기재된 경우, 그 구성 요소는 그 다른 구성요소에 직접적으로 연결되거나 또는 접속될 수 있지만, 각 구성 요소 사이에 또 다른 구성 요소가 "연결", "결합" 또는 "접속"될 수도 있다고 이해되어야 할 것이다.In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It is to be understood that the elements may be "connected", "coupled" or "connected".
본 명세서에서 사용된 용어 "할로" 또는 "할로겐"은 불소, 염소, 브롬, 및 요오드를 포함한다. The term "halo" or "halogen" as used herein includes fluorine, chlorine, bromine, and iodine.
본 발명에 사용된 용어 "알킬" 또는 "알킬기"는 다른 설명이 없는 한 1 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다.As used herein, the term "alkyl" or "alkyl group" has a carbon number of 1 to 60 unless otherwise specified, but is not limited thereto.
본 발명에 사용된 용어 "알케닐" 또는 "알키닐"은 다른 설명이 없는 한 각각 2 내지 60의 탄소수의 이중결합 또는 삼중결합을 가지며, 여기에 제한되는 것은 아니다.As used herein, the term "alkenyl" or "alkynyl" has a double bond or a triple bond having 2 to 60 carbon atoms, respectively, unless otherwise specified, but is not limited thereto.
본 발명에 사용된 용어 "시클로알킬"은 다른 설명이 없는 한 3 내지 60의 탄소수를 갖는 고리를 형성하는 알킬을 의미하며, 여기에 제한되는 것은 아니다.The term "cycloalkyl" as used herein, unless otherwise stated, refers to alkyl forming a ring having 3 to 60 carbon atoms, without being limited thereto.
본 발명에 사용된 용어 "알콕시기"는 다른 설명이 없는 한 1 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다.The term "alkoxy group" used in the present invention has a carbon number of 1 to 60 unless otherwise stated, it is not limited thereto.
본 발명에 사용된 용어 "아릴기" 및 "아릴렌기"는 다른 설명이 없는 한 각각 6 내지 60의 탄소수를 가지며, 이에 제한되는 것은 아니다. As used herein, the terms "aryl group" and "arylene group" have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto.
본 명세서에서 사용된 용어 "헤테로알킬"은 다른 설명이 없는 한 하나 또는 그 이상의 헤테로원자를 갖는 알킬을 의미한다.As used herein, the term “heteroalkyl” means an alkyl having one or more heteroatoms unless otherwise indicated.
본 발명에 사용된 용어 "헤테로아릴기" 또는 "헤테로아릴렌기"는 다른 설명이 없는 한 각각 하나 또는 그 이상의 헤테로원자를 갖는 탄소수 3 내지 60의 아릴기 또는 아릴렌기를 의미하며, 여기에 제한되는 것은 아니다. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or arylene group having 3 to 60 carbon atoms each having one or more heteroatoms unless otherwise specified, and is not limited thereto. It is not.
본 발명에 사용된 용어 "헤테로시클로알킬", "헤테로고리기"는 다른 설명이 없는 한 하나 또는 그 이상의 헤테로원자를 포함하고, 2 내지 60의 탄소수를 갖는다.As used herein, the terms "heterocycloalkyl" and "heterocyclic group" include one or more heteroatoms and, unless stated otherwise, have from 2 to 60 carbon atoms.
본 명세서에서 사용된 용어 "헤테로원자"는 N, O, S, P 및 Si를 나타낸다. The term "heteroatom" as used herein refers to N, O, S, P and Si.
다른 설명이 없는 한, 본 발명에 사용된 용어 "지방족"은 탄소수 1 내지 60의 지방족 탄화수소를 의미하며, "지방족고리"는 탄소수 3 내지 60의 지방족 탄화수소 고리를 의미한다. Unless otherwise stated, the term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms, and the "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.
전술한 헤테로화합물 이외의 그 밖의 다른 헤테로화합물 또는 헤테로라디칼은 하나 이상의 헤테로원자를 포함하며, 여기에 제한되는 것은 아니다. Other heterocompounds or heteroradicals other than the aforementioned heterocompounds include, but are not limited to, one or more heteroatoms.
또한 명시적인 설명이 없는 한, 본 발명에서 사용된 용어 "치환 또는 비치환된"에서 "치환"은 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C1~C20의 알콕시기, C1~C20의 알킬아민기, C1~C20의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20의 알케닐기, C2~C20의 알키닐기, C3~C20의 시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C8~C20의 아릴알케닐기, 실란기, 붕소기, 게르마늄기, C5~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환됨을 의미하며, 이들 치환기에 제한되는 것은 아니다. Also, unless expressly stated, the term "substituted" in the term "substituted or unsubstituted" as used herein refers to deuterium, halogen, amino, nitrile, nitro, C 1 -C 20 alkyl, C 1 -C 20 alkoxy groups, C 1 to C 20 alkylamine groups, C 1 to C 20 alkylthiophene groups, C 6 to C 20 arylthiophene groups, C 2 to C 20 alkenyl groups, C 2 to C 20 alkynyl group, C 3 ~ C 20 cycloalkyl group, C 6 ~ C 60 aryl group, C 6 ~ C 20 aryl group substituted with deuterium, C 8 ~ C 20 aryl alkenyl group, silane group, boron Group, germanium group, C 5 ~ C 20 It is meant to be substituted with one or more substituents selected from the group consisting of, but not limited to these substituents.
본 발명은 수명이 좋은 재료를 이용하여, 수명에 악영향을 주는 판상구조의 분자구조를 도입하지 않고, 구동전압을 낮출 수 있는 방법으로, 중수소를 적절한 비율로 치환하는 방법과, 중수로로 치환된 유사구조의 화합물을 혼합하여 사용함으로써, 구동전압을 낮추는 방법을 제시한다.The present invention is a method for lowering the driving voltage without introducing a plate-like molecular structure that adversely affects the life using a material having a good life, and a method for replacing deuterium at an appropriate ratio, and similarly substituted with heavy water. By mixing and using a compound of the structure, a method of lowering the driving voltage is proposed.
중수소로 치환된 화합물은 비치환된 화합물과 비교하여 많은 열역학적 거동을 보이는 것을 확인하였다. 이러한 열적학적 특성 중, 이리듐 화합물이 중수소로 치환될 경우, 탄소, 수소 및 탄소, 중수소 결합길이의 차이에 따라서, 결합길이가 더욱 짧은 탄소, 중수소로 이루어진 화합물이 결합길이가 짧음에 따라 발생하는 분자간 반데르발스 힘의 약화로 인해 더 높은 발광효율을 가질 수 있음을 확인하였다. Compounds substituted with deuterium showed much thermodynamic behavior compared to unsubstituted compounds. Among these thermal properties, when the iridium compound is substituted with deuterium, the intermolecular molecules generated by the shorter bond length of the compound consisting of carbon and deuterium having a shorter bond length according to the difference in carbon, hydrogen, carbon, and deuterium bond lengths It was confirmed that due to the weakening of van der Waals force can have a higher luminous efficiency.
또한 중수소로 치환된 경우에는 제로포인트 에너지(Zero Point Energy) 즉 바닥상태의 에너지가 낮아지며, 중수소, 탄소의 결합길이가 짧아짐에 따라, 분자 중심 부피(Molecular hardcore volume)가 줄어들고, 이에 따라 전기적 극성화도(Electroical polarizability)를 줄일 수 있으며, 분자간 상호작용(Intermolecular interaction)을 약하게 함으로써, 박막 부피를 증가시킬 수 있음을 확인하였다. 이러한 특성은 박막의 결정화도를 낮추는 효과 즉, 비결정질(Amorphous) 상태를 만들 수 있으며, 일반적으로 OLED 수명 및 구동특성을 높이기 위하여, 반드시 필요한 비결정질 상태를 구현하는데 매우 효과적일 것이라고 판단하였다.In addition, when deuterium is substituted, the zero point energy, that is, the energy of the ground state is lowered, and as the bond length of deuterium and carbon is shortened, the molecular hardcore volume is reduced, and thus the electrical polarization is also reduced. It was confirmed that the electrolytic polarizability can be reduced, and the thin film volume can be increased by weakening the intermolecular interaction. This property can reduce the crystallinity of the thin film, i.e., create an amorphous state, and in general, it was determined that it would be very effective to realize the necessary amorphous state in order to increase OLED lifetime and driving characteristics.
그러나, 중수소로 치환하여 구동전압을 낮추는, 즉 정공 수송물질의 정공수송도(Mobility)를 높이는 방법은 현재 많은 연구가 진행되어 있지 않으며, 본 연구에서는 그러한 특성을 확인하기 위하여 다양한 종류의 화합물을 이용하여, 많은 실험을 진행하였다. 또한 중수소로 치환된 유사구조의 화합물을 혼합하여 박막을 형성하였을 때, 박막의 정공 이동도에 많은 영향을 줄 수 있는 비정질 유리상태(Amorphous glass)를 만들기 때문에, 매우 유리할 수 있으며, 이러한 비정질 유리상태는 등방성(Isotropic)과 균등질(Homogeneous) 특성을 통해서 결정립의 경계(Grain boundary)를 줄임으로써, 전하의 흐름 즉 정공 이동도를 빠르게 할 수 있다는 것을 확인하였다.However, there have not been many studies on the method of lowering the driving voltage by increasing the deuterium, that is, increasing the mobility of the hole transport material, and in this study, various kinds of compounds are used to confirm such characteristics. Thus, many experiments were conducted. In addition, when a thin film is formed by mixing a compound having a similar structure substituted with deuterium, it can be very advantageous because it creates an amorphous glass state that can greatly affect the hole mobility of the thin film, and this amorphous glass state By reducing the grain boundary through the isotropic and homogeneous properties, it is confirmed that the flow of charges, or hole mobility, can be increased.
본 발명을 좀더 상세히 설명하면, 수명의 우수한 재료로서 카바졸을 포함하는 아민화합물을 이용하였다. 특히 주목할 것은 카바졸계 아민 화합물은 본 연구에 따르면 수명 특성이 우수하나, 구동전압이 상승하는 단점이 있다. 그러나 종래 기술에서는 이러한 부분에 대한 개선의 효과를 입증한 바는 없으며, 특히 특정 위치에 중수소 치환을 통해 구동특성을 개선한 종래 기술은 아직 보고된 바가 없다. In more detail, the present invention used an amine compound including carbazole as an excellent material for life. In particular, the carbazole-based amine compound has excellent life characteristics according to the present study, but has a disadvantage in that driving voltage is increased. However, the prior art has not proved the effect of the improvement on this part, and in particular, the prior art which improves the driving characteristics through deuterium substitution at a specific position has not been reported yet.
이러한 발명자들의 연구개발의 결과로 전술한 유기전기소자의 유기물층들의 뛰어난 특성을 유지하면서도 유기재료의 요구특성에 부합하도록 본 발명은 중수소로 치환된 아민기가 결합된 화합물을 제공한다.As a result of the research and development of these inventors, the present invention provides a compound in which an amine group substituted with deuterium is bonded to maintain the excellent properties of the organic material layers of the organic electronic device described above and to meet the requirements of the organic material.
특히, 본 발명의 일 실시예에 따른 화합물 중 카바졸과 아릴아민이 아릴렌 등으로 연결된 코어구조의 경우, 아민기에 결합된 아릴기에 중수소를 도입함으로써 유기전기발광소자의 소자 특성을 향상시킬 수 있다. 예컨대, 아민기에 비페닐(bi-phenl)이 결합되어 있고, 비페닐 중 말단 페닐기에 수소 대신 중수소를 도입함으로써 보다 안정적으로 유기물층을 증착시킬 수 있게 되고, 계면특성을 향상시킬 수 있으며, 에너지 밴드갭을 미세하게 조절하는 것이 용이하므로 우수한 유기전기 소자 특성을 갖는 유기전기소자를 제작할 수 있게 된다. In particular, in the case of a core structure in which carbazole and arylamine are connected to arylene among the compounds according to an embodiment of the present invention, deuterium may be introduced into the aryl group bonded to the amine group to improve device characteristics of the organic electroluminescent device. . For example, biphenyl (bi-phenl) is bonded to the amine group, and by introducing deuterium instead of hydrogen in the terminal phenyl group of the biphenyl, it is possible to more stably deposit the organic layer, improve the interfacial properties, energy band gap Since it is easy to finely adjust the it is possible to manufacture an organic electronic device having excellent organic electrical device properties.
아민기와 말단 아릴기 사이에 존재하는 아릴기에 중수소를 도입하더라도 우수한 소자 특성을 갖는 유기전기소자를 제작할 수 있지만, 아민기에 결합된 아릴기 중 말단의 아릴기, 예컨대 말단의 페닐기에 중수소를 도입하는 것이 보다 우수한 소자 제작에 유리하다. 또한, 아민기에 결합된 아릴기 중 말단의 아릴기, 예컨대 페닐기에 중수소를 도입하되 다른 치환기와 결합되는 탄소를 제외한 모든 탄소에 수소 대신 중수소를 치환하는 것이 보다 우수한 소자 제작에 유리하다.Even if deuterium is introduced into the aryl group present between the amine group and the terminal aryl group, an organic electric device having excellent device characteristics can be manufactured. However, introducing deuterium into an aryl group such as a terminal phenyl group among the aryl groups bonded to the amine group It is advantageous for better device fabrication. In addition, introducing deuterium into an aryl group, such as a phenyl group, among the aryl groups bonded to the amine group, and deuterium instead of hydrogen to all carbons other than the carbon bonded to other substituents is advantageous for the fabrication of a superior device.
본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다.The present invention provides a compound represented by the following formula (1).
화학식 1
Figure PCTKR2012004631-appb-C000001
 Formula 1
Figure PCTKR2012004631-appb-C000001
상기 화학식 1에서,In Chemical Formula 1,
(1) Ar1 내지 Ar3은 각각 독립적으로 동일하거나 상이하며, (1) Ar 1 to Ar 3 are each independently the same or different;
수소, 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C1~C20의 알콕시기, C1~C20의 알킬아민기, C1~C20 의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20의 알케닐기, C2~C20의 알키닐기, C3~C20의 시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C8~C20의 아릴알케닐기, C6~C20의 아릴아민기, 실란기, 붕소기, 게르마늄기 및 C3~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴기; Hydrogen, deuterium, halogen, amino group, nitrile group, nitro group, C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxy group, C 1 ~ C 20 alkylamine group, C 1 ~ C 20 alkylthiophene group, C 6 ~ C 20 aryl thiophene group, a C 2 ~ C 20 alkenyl group, C 2 ~ C 20 alkynyl group, C of 3 ~ C 20 cycloalkyl group, C 6 ~ C 60 aryl group, a heavy hydrogen of the C 6 ~ C 20 aryl group, C 8 ~ C 20 aryl alkenyl group, C 6 ~ C 20 arylamine group, silane group, boron group, germanium group and C 3 ~ C 20 heterocyclic group C 6 ~ C 60 aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of;
수소, 중수소, 할로겐기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴아민기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C3~C20의 헤테로고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 1개 이상의 치환기로 치환 또는 비치환되고 O, N 및 S 중 적어도 하나를 포함하는 C2~C60의 헤테로고리기; Hydrogen, deuterium, halogen, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 6 -C 20 arylamine group, C 6 -C 60 aryl A C 6 to C 20 aryl group, a C 7 to C 20 arylalkyl group, a C 8 to C 20 arylalkenyl group, a C 3 to C 20 heterocyclic group, a nitrile group and an acetylene group C 2 ~ C 60 heterocyclic group which is unsubstituted or substituted with one or more substituents in the group and includes at least one of O, N and S;
수소, 중수소, 할로겐기, 아미노기, 니트릴기, 니트로기, C1~C20 의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C3~C30의 시클로알킬기, C2~C30의 헤테로시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기 및 C2~C20의 헤테로고리기로 구성된 군에서 선택된 1개 이상의 치환기로 치환 또는 비치환된 C1~C30의 알콕시기; Hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 3 -C 30 cycloalkyl group, At least one substituent selected from the group consisting of a C 2 to C 30 heterocycloalkyl group, a C 6 to C 60 aryl group, a C 6 to C 20 aryl group substituted with deuterium, and a C 2 to C 20 heterocyclic group Substituted or unsubstituted C 1 ~ C 30 Alkoxy group;
수소, 중수소, 할로겐기, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C3~C30의 시클로알킬기, C2~C30의 헤테로시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기 및 C2~C20의 헤테로고리기로 구성된 군으로부터 선택된 1개 이상의 치환기로 치환 또는 비치환된 C6~C30아릴옥시기; Hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 3 -C 30 cycloalkyl group, At least one substituent selected from the group consisting of a C 2 to C 30 heterocycloalkyl group, a C 6 to C 60 aryl group, a C 6 to C 20 aryl group substituted with deuterium, and a C 2 to C 20 heterocyclic group A substituted or unsubstituted C 6 ~ C 30 aryloxy group;
할로겐기, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C3~C30의 시클로알킬기, C2~C30의 헤테로시클로알킬기, C6~C60의 아릴기 및 C2~C20의 헤테로고리기로 구성된 군에서 선택된 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴아민기; 및 Halogen group, amino group, nitrile group, nitro group, C 1 ~ C 20 alkyl group, C 2 ~ C 20 alkenyl group, C 1 ~ C 20 alkoxy group, C 3 ~ C 30 cycloalkyl group, C 2 ~ C heterocycloalkyl group, C 6 ~ C 60 aryl group and C 2 ~ C 20 with one or more substituents selected from the group consisting of heterocyclic group-substituted or unsubstituted C 6 ~ C 60 of the arylamine group of 30; And
C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C3~C20의 헤테로고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 선택된 치환기로 치환 또는 비치환된 C1~C50의 알킬기;로 이루어진 군에서 선택되며, C 1 ~ alkenyl group of the C 20 alkyl group, C 2 ~ C 20 of, C 1 ~ C 20 alkoxy group, C 6 ~ aryl group of C 20 aryl group, a C 6 ~ C 20 substituted with deuterium, C 7 C 1 -C 50 alkyl group unsubstituted or substituted with a substituent selected from the group consisting of-C 20 arylalkyl group, C 8 ~ C 20 aryl alkenyl group, C 3 ~ C 20 heterocyclic group, nitrile group and acetylene group Selected from the group consisting of;
여기서 Ar1~Ar3 중 적어도 하나는 중수소를 1개 이상 포함하고,Wherein at least one of Ar 1 to Ar 3 includes one or more deuterium,
(2) R1 및 R2는 각각 독립적으로 동일하거나 상이하며, 수소; 중수소; 할로겐; 니트로기; 니트릴기; 아미노기; (2) R 1 and R 2 are each independently the same or different and are hydrogen; heavy hydrogen; halogen; Nitro group; Nitrile group; Amino group;
수소, 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C1~C20의 알콕시기, C1~C20의 알킬아민기, C1~C20 의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20 의 알케닐기, C2~C20의 알키닐기, C3~C20의 시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C8~C20의 아릴알케닐기, C6~C20의 아릴아민기, 실란기, 붕소기, 게르마늄기 및 C3~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴기; Hydrogen, deuterium, halogen, amino group, nitrile group, nitro group, C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxy group, C 1 ~ C 20 alkylamine group, C 1 ~ C 20 alkylthiophene group, C 6 ~ C 20 aryl thiophene group, a C 2 ~ C 20 alkenyl group, C 2 ~ C 20 alkynyl group, C of 3 ~ C 20 cycloalkyl group, C 6 ~ C 60 aryl group, a heavy hydrogen of the C 6 ~ C 20 aryl group, C 8 ~ C 20 aryl alkenyl group, C 6 ~ C 20 arylamine group, silane group, boron group, germanium group and C 3 ~ C 20 heterocyclic group C 6 ~ C 60 aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of;
수소, 중수소, 할로겐기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴아민기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C3~C20의 헤테로고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 1개 이상의 치환기로 치환 또는 비치환 되고 O, N 및 S 중 적어도 하나를 포함하는 C2~C60의 헤테로고리기; Hydrogen, deuterium, halogen, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 6 -C 20 arylamine group, C 6 -C 60 aryl A C 6 to C 20 aryl group, a C 7 to C 20 arylalkyl group, a C 8 to C 20 arylalkenyl group, a C 3 to C 20 heterocyclic group, a nitrile group and an acetylene group C 2 ~ C 60 heterocyclic group which is unsubstituted or substituted with one or more substituents in the group and includes at least one of O, N and S;
수소, 중수소, 할로겐기, 아미노기, 니트릴기, 니트로기, C1~C20 의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C3~C30의 시클로알킬기, C2~C30의 헤테로시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기 및 C2~C20의 헤테로고리기로 구성된 군으로부터 선택된 1개 이상의 치환기로 치환 또는 비치환된 C1~C30의 알콕시기; Hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 3 -C 30 cycloalkyl group, At least one substituent selected from the group consisting of a C 2 to C 30 heterocycloalkyl group, a C 6 to C 60 aryl group, a C 6 to C 20 aryl group substituted with deuterium, and a C 2 to C 20 heterocyclic group Substituted or unsubstituted C 1 ~ C 30 Alkoxy group;
수소, 중수소, 할로겐기, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C3~C30의 시클로알킬기, C2~C30의 헤테로시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기 및 C2~C20의 헤테로고리기로 구성된 군으로부터 선택된 1개 이상의 치환기로 치환 또는 비치환된 C6~C30의 아릴옥시기; 및Hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 3 -C 30 cycloalkyl group, At least one substituent selected from the group consisting of a C 2 to C 30 heterocycloalkyl group, a C 6 to C 60 aryl group, a C 6 to C 20 aryl group substituted with deuterium, and a C 2 to C 20 heterocyclic group Substituted or unsubstituted C 6 ~ C 30 An aryloxy group; And
C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C3~C20의 헤테로고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 선택된 치환기로 치환 또는 비치환된 C1~C50의 알킬기;로 이루어진 군에서 선택되며, C 1 ~ alkenyl group of the C 20 alkyl group, C 2 ~ C 20 of, C 1 ~ C 20 alkoxy group, C 6 ~ aryl group of C 20 aryl group, a C 6 ~ C 20 substituted with deuterium, C 7 C 1 -C 50 alkyl group unsubstituted or substituted with a substituent selected from the group consisting of-C 20 arylalkyl group, C 8 ~ C 20 aryl alkenyl group, C 3 ~ C 20 heterocyclic group, nitrile group and acetylene group Selected from the group consisting of;
여기서, R1 및 R2는 인접한 기와 서로 결합하여 지환족, 방향족 또는 헤테로고리를 형성할 수 있고, Wherein R 1 and R 2 may be bonded to adjacent groups to form an alicyclic, aromatic or heterocyclic ring,
(3) L은 니트로기, 니트릴기, 할로겐기, 알킬기, 알콕시기, 아미노기, 아릴아민기 및 헤테로고리기로 이루어진 군에서 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴렌기; 또는 니트로, 니트릴, 할로겐, 알킬기, 알콕시기, 아미노기 및 아릴기로 이루어진 군에서 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C2~C60의 헤테로고리기이며,(3) L is C 6 -C 60 aryl unsubstituted or substituted with one or more substituents selected from the group consisting of a nitro group, a nitrile group, a halogen group, an alkyl group, an alkoxy group, an amino group, an arylamine group and a heterocyclic group Ren group; Or a C 2 -C 60 heterocyclic group unsubstituted or substituted with one or more substituents selected from the group consisting of nitro, nitrile, halogen, alkyl, alkoxy, amino and aryl groups,
(4) a는 0~4의 정수, b는 0~3의 정수, c는 0~2의 정수이다.(4) a is an integer of 0-4, b is an integer of 0-3, c is an integer of 0-2.
다른 측면에서, 본 발명은 상기 화학식 1로 표시되는 화합물들 중 서로 다른 2종 이상의 화합물이 혼합된 조성물을 제공한다. 이때, 서로 다른 2종 이상의 화합물은 하나의 화합물이 조성물 전체의 90중량%를 초과하지 않는 범위에서 혼합될 수 있다.In another aspect, the present invention provides a composition in which two or more different compounds among the compounds represented by Formula 1 are mixed. In this case, two or more different compounds may be mixed in a range in which one compound does not exceed 90% by weight of the total composition.
또 다른 측면에서, 본 발명은 상기 화학식 1로 표시되는 화합물과 하기 화학식 2로 표시되는 화합물이 혼합된 유기전기소자용 조성물을 제공한다. 이때, 조성물은 어느 하나의 화합물이 조성물 전체 중량의 90중량% 이하의 범위로 혼합될 수 있다.In another aspect, the present invention provides a composition for an organic electric device, a mixture of a compound represented by the formula (1) and a compound represented by the following formula (2). At this time, the composition of any one compound may be mixed in the range of 90% by weight or less of the total weight of the composition.
화학식 2
Figure PCTKR2012004631-appb-C000002
 Formula 2
Figure PCTKR2012004631-appb-C000002
상기 화학식 2에서,In Chemical Formula 2,
(1) Ar1 내지 Ar3은 상기 화학식 1의 Ar1 내지 Ar3의 치환기 정의와 동일하며, (1) Ar 1 to Ar 3 is the same as the substituent definition of Ar 1 to Ar 3 of Formula 1,
(2) R1 내지 R4는 상기 화학식 1의 R1 또는 R2의 치환기 정의와 동일하며, 여기서, R1 내지 R4는 인접한 기와 서로 결합하여 지환족, 방향족 또는 헤테로고리를 형성할 수 있으며,(2) R 1 to R 4 is the same as the substituent definition of R 1 or R 2 in Formula 1, wherein R 1 to R 4 may be bonded to an adjacent group to form an alicyclic, aromatic or heterocycle ,
(3) R' 및 R"는 각각 독립적으로 동일하거나 상이하며, 수소, 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C1~C20의 알콕시기, C1~C20의 알킬아민기, C1~C20 의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20 의 알케닐기, C2~C20의 알키닐기, C3~C20의 시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C2~C20의 아릴기, C8~C20의 아릴알케닐기, C6~C20의 아릴아민기, 실란기, 붕소기, 게르마늄기, C3~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴기; 또는 C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴기, 중수소로 치환된 C2~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C3~C20의 헤테로 고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 선택된 치환기로 치환 또는 비치환된 C1~C50의 알킬기이며, 여기서, R' 및 R"는 서로 결합하여 지환족, 방향족, 헤테로고리, 또는 스피로화합물을 형성할 수 있으며,(3) R 'and R "are each independently the same or different, hydrogen, deuterium, halogen, amino, nitrile, nitro, C 1 -C 20 alkyl group, C 1 -C 20 alkoxy group, C 1 C 20 -C 20 alkylamine group, C 1 -C 20 alkylthiophene group, C 6 -C 20 arylthiophene group, C 2 -C 20 alkenyl group, C 2 -C 20 alkynyl group, C 3 ~ C 20 cycloalkyl group, C 6 ~ C 60 aryl group, of a C 2 ~ C 20 substituted by deuterium aryl group, a C 8 ~ C 20 aryl alkenyl group, C 6 ~ C 20 aryl amine group, a silane C 6 -C 60 aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of a group, a boron group, a germanium group, a C 3 -C 20 heterocyclic group, or a C 1 -C 20 alkyl group, C 2 ~ C 20 alkenyl group, C 1 ~ C 20 alkoxy group, C 6 ~ C 20 aryl group, C 2 ~ C 20 aryl group substituted with deuterium, C 7 ~ C 20 arylalkyl group, C 8 to C 20 arylalkenyl group, C 3 to C 20 heterocyclic group, nitrile group and ar C 1 ~ C 50 is an alkyl group substituted or unsubstituted with a substituent selected from the group consisting of cetylene, wherein R 'and R "may be combined with each other to form an alicyclic, aromatic, heterocyclic, or spiro compound ,
(4) a는 1 내지 3의 정수이고, b, c 및 d는 각각 1 내지 4의 정수이다.(4) a is an integer of 1 to 3, and b, c and d are integers of 1 to 4, respectively.
더욱 구체적으로, 상기 화학식 1에서, Ar3은 중수소를 1개 이상 포함하며, Ar2는 다음 화학식으로 표시될 수 있다.More specifically, in Formula 1, Ar 3 includes one or more deuterium, Ar 2 may be represented by the following formula.
Figure PCTKR2012004631-appb-I000004
Figure PCTKR2012004631-appb-I000004
상기 화학식에서,In the above formula,
(1) R3 및 R4는 각각 독립적으로 동일하거나 상이하며, 할로겐; 니트로기; 니트릴기; 아미노기;(1) R 3 and R 4 are each independently the same or different and are halogen; Nitro group; Nitrile group; Amino group;
수소, 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C1~C20의 알콕시기, C1~C20의 알킬아민기, C1~C20 의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20 의 알케닐기, C2~C20의 알키닐기, C3~C20의 시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C8~C20의 아릴알케닐기, C6~C20의 아릴아민기, 실란기, 붕소기, 게르마늄기 및 C3~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴기;Hydrogen, deuterium, halogen, amino group, nitrile group, nitro group, C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxy group, C 1 ~ C 20 alkylamine group, C 1 ~ C 20 alkylthiophene group, C 6 ~ C 20 aryl thiophene group, a C 2 ~ C 20 alkenyl group, C 2 ~ C 20 alkynyl group, C of 3 ~ C 20 cycloalkyl group, C 6 ~ C 60 aryl group, a heavy hydrogen of the C 6 ~ C 20 aryl group, C 8 ~ C 20 aryl alkenyl group, C 6 ~ C 20 arylamine group, silane group, boron group, germanium group and C 3 ~ C 20 heterocyclic group C 6 ~ C 60 aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of;
수소, 중수소, 할로겐기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴아민기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C8~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C3~C20의 헤테로고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 1개 이상의 치환기로 치환 또는 비치환 되고 O, N 및 S 중 적어도 하나를 포함하는 C2~C60의 헤테로고리기; Hydrogen, deuterium, halogen, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 6 -C 20 arylamine group, C 6 -C 60 aryl A C 6 to C 20 aryl group, a C 8 to C 20 arylalkyl group, a C 8 to C 20 arylalkenyl group, a C 3 to C 20 heterocyclic group, a nitrile group and an acetylene group C 2 ~ C 60 heterocyclic group which is unsubstituted or substituted with one or more substituents in the group and includes at least one of O, N and S;
수소, 중수소, 할로겐기, 아미노기, 니트릴기, 니트로기, C1~C20 의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C3~C30의 시클로알킬기, C2~C30의 헤테로시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기 및 C2~C20의 헤테로고리기로 구성된 군으로부터 선택된 1개 이상의 치환기로 치환 또는 비치환된 C1~C30의 알콕시기;Hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 3 -C 30 cycloalkyl group, At least one substituent selected from the group consisting of a C 2 to C 30 heterocycloalkyl group, a C 6 to C 60 aryl group, a C 6 to C 20 aryl group substituted with deuterium, and a C 2 to C 20 heterocyclic group Substituted or unsubstituted C 1 ~ C 30 Alkoxy group;
수소, 중수소, 할로겐기, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C3~C30의 시클로알킬기, C2~C30의 헤테로시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기 및 C2~C20의 헤테로고리기로 구성된 군으로부터 선택된 1개 이상의 치환기로 치환 또는 비치환된 C6~C30의 아릴옥시기; 및 Hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 3 -C 30 cycloalkyl group, At least one substituent selected from the group consisting of a C 2 to C 30 heterocycloalkyl group, a C 6 to C 60 aryl group, a C 6 to C 20 aryl group substituted with deuterium, and a C 2 to C 20 heterocyclic group Substituted or unsubstituted C 6 ~ C 30 An aryloxy group; And
C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C3~C20의 헤테로고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 선택된 치환기로 치환 또는 비치환된 C1~C50의 알킬기;로 이루어진 군에서 선택되며, C 1 ~ alkenyl group of the C 20 alkyl group, C 2 ~ C 20 of, C 1 ~ C 20 alkoxy group, C 6 ~ aryl group of C 20 aryl group, a C 6 ~ C 20 substituted with deuterium, C 7 C 1 -C 50 alkyl group unsubstituted or substituted with a substituent selected from the group consisting of-C 20 arylalkyl group, C 8 ~ C 20 aryl alkenyl group, C 3 ~ C 20 heterocyclic group, nitrile group and acetylene group Selected from the group consisting of;
여기서, R3 및 R4는 인접한 기와 서로 결합하여 지환족, 방향족 또는 헤테로고리를 형성할 수 있으며,Wherein R 3 and R 4 may combine with adjacent groups to form an alicyclic, aromatic or heterocyclic ring,
(2) R' 및 R"는 각각 독립적으로 동일하거나 상이하며, 수소, 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C1~C20의 알콕시기, C1~C20의 알킬아민기, C1~C20 의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20의 알케닐기, C2~C20의 알키닐기, C3~C20의 시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C8~C20의 아릴알케닐기, C6~C20의 아릴아민기, 실란기, 붕소기, 게르마늄기 및 C3~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴기; 또는 C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C3~C20의 헤테로고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 선택된 치환기로 치환 또는 비치환된 C1~C50의 알킬기이며, 여기서, R', R"는 서로 결합하여 지환족, 방향족, 헤테로고리, 또는 스피로화합물을 형성할 수 있으며,(2) R 'and R "are the same as or different from each other independently, hydrogen, deuterium, halogen, amino group, nitrile group, nitro group, C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxy group, C 1 C 20 -C 20 alkylamine group, C 1 -C 20 alkylthiophene group, C 6 -C 20 arylthiophene group, C 2 -C 20 alkenyl group, C 2 -C 20 alkynyl group, C 3 ~ C 20 cycloalkyl group, an aryl group of C 6 ~ C 60, of a C 6 ~ C 20 substituted with a heavy hydrogen aryl, C 8 ~ C 20 aryl alkenyl group, C 6 ~ C 20 aryl amine group, a silane C 6 -C 60 aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of a group, a boron group, a germanium group and a C 3 -C 20 heterocyclic group; or a C 1 -C 20 alkyl group, C alkenyl group of 2 ~ C 20, C 1 ~ C 20 alkoxy group, C 6 ~ C 20 aryl group, of a C 6 ~ C 20 substituted by deuterium aryl group, C 7 ~ C 20 aryl group, C of 8 ~ C 20 arylalkenyl group, a heterocyclic group of C 3 ~ C 20, the nitrile group, and With a substituent selected from the group consisting of a three ethylene and an alkyl group of a substituted or unsubstituted C 1 ~ C 50, where, R ', R "may be combined with each other to form an alicyclic, aromatic, heterocyclic, or a spiro compound, and ,
(3) e는 1~4의 정수, d는 1~3의 정수이다.(3) e is an integer of 1-4, d is an integer of 1-3.
상기 화학식 1에서, Ar1, Ar2, 및 Ar3 중 적어도 하나는 다음 화학식 3으로 구성된 군으로부터 선택될 수 있다.In Formula 1, at least one of Ar 1 , Ar 2 , and Ar 3 may be selected from the group consisting of the following Formula 3.
[화학식 3][Formula 3]
Figure PCTKR2012004631-appb-I000005
,
Figure PCTKR2012004631-appb-I000006
,
Figure PCTKR2012004631-appb-I000007
Figure PCTKR2012004631-appb-I000008
,
Figure PCTKR2012004631-appb-I000009
,
Figure PCTKR2012004631-appb-I000010
,
Figure PCTKR2012004631-appb-I000011
,
Figure PCTKR2012004631-appb-I000012
Figure PCTKR2012004631-appb-I000005
,
Figure PCTKR2012004631-appb-I000006
,
Figure PCTKR2012004631-appb-I000007
Figure PCTKR2012004631-appb-I000008
,
Figure PCTKR2012004631-appb-I000009
,
Figure PCTKR2012004631-appb-I000010
,
Figure PCTKR2012004631-appb-I000011
,
Figure PCTKR2012004631-appb-I000012
Figure PCTKR2012004631-appb-I000013
,
Figure PCTKR2012004631-appb-I000014
,
Figure PCTKR2012004631-appb-I000015
Figure PCTKR2012004631-appb-I000013
,
Figure PCTKR2012004631-appb-I000014
,
Figure PCTKR2012004631-appb-I000015
상기 화학식 3에서, D는 중수소이며, k 및 i는 0~2의 정수이고, n, o, q, r, q' 및 r'은 0~3의 정수이며, b, e, f, g, l, t' 및 u'은 0~4의 정수이고, a, c, c', h, j, m, p, s, t, u 및 s'은 0~5의 정수이며, b'은 0~6의 정수이며, a' 및 d는 0~7의 정수이다. 이때, Ar1~Ar3 중 적어도 하나가 중수소를 포함하도록 상기 지수가 결정될 수 있을 것이다.In Formula 3, D is deuterium, k and i are integers of 0 to 2, n, o, q, r, q 'and r' is an integer of 0 to 3, b, e, f, g, l, t 'and u' are integers from 0 to 4, a, c, c ', h, j, m, p, s, t, u and s' are integers from 0 to 5, b' is 0 It is an integer of -6, and a 'and d are integers of 0-7. In this case, the index may be determined such that at least one of Ar 1 to Ar 3 includes deuterium.
상기 화학식 3에 제시된 구조식에서, 예를 들어,
Figure PCTKR2012004631-appb-I000016
는 a가 0 내지 5인 경우 각각에 대하여 다음 구조식에 대응한다.In the structural formula shown in Formula 3, for example,
Figure PCTKR2012004631-appb-I000016
Corresponds to the following structural formula for each when a is 0 to 5.
Figure PCTKR2012004631-appb-I000017
Figure PCTKR2012004631-appb-I000017
나머지 구조식에 대하여도 동일하게 적용된다. The same applies to the remaining structural formulas.
더욱 구체적으로, 상기 화학식 1 및 화학식 2의 Ar1 내지 Ar3에서 중수소를 함유하는 Ar1 내지 Ar3은 하기와 같이 나타내어지며 그 종류가 이에 한정되는 것은 아니다.More specifically, it is represented as follows has the general formula (1) and Ar 1 to Ar 3 which contains the heavy hydrogen in Ar 1 to Ar 3 of the general formula (2) is not the type is limited to such.
화학식 4
Figure PCTKR2012004631-appb-C000003
 Formula 4
Figure PCTKR2012004631-appb-C000003
더욱 구체적으로, 상기 화학식 1로 표시되는 화합물은 아래 화합물 (P-1) 내지 (P-132) 중 어느 하나일 수 있으며, 여기에 제한되는 것은 아니다.More specifically, the compound represented by Formula 1 may be any one of the following Compounds (P-1) to (P-132), but is not limited thereto.
화학식 5
Figure PCTKR2012004631-appb-C000004
 Formula 5
Figure PCTKR2012004631-appb-C000004
Figure PCTKR2012004631-appb-I000018
Figure PCTKR2012004631-appb-I000018
Figure PCTKR2012004631-appb-I000019
Figure PCTKR2012004631-appb-I000019
Figure PCTKR2012004631-appb-I000020
Figure PCTKR2012004631-appb-I000020
Figure PCTKR2012004631-appb-I000021
Figure PCTKR2012004631-appb-I000021
Figure PCTKR2012004631-appb-I000022
Figure PCTKR2012004631-appb-I000022
Figure PCTKR2012004631-appb-I000024
Figure PCTKR2012004631-appb-I000024
Figure PCTKR2012004631-appb-I000025
Figure PCTKR2012004631-appb-I000025
Figure PCTKR2012004631-appb-I000026
Figure PCTKR2012004631-appb-I000026
Figure PCTKR2012004631-appb-I000027
Figure PCTKR2012004631-appb-I000027
Figure PCTKR2012004631-appb-I000028
Figure PCTKR2012004631-appb-I000028
Figure PCTKR2012004631-appb-I000029
Figure PCTKR2012004631-appb-I000029
Figure PCTKR2012004631-appb-I000030
Figure PCTKR2012004631-appb-I000030
Figure PCTKR2012004631-appb-I000031
Figure PCTKR2012004631-appb-I000031
Figure PCTKR2012004631-appb-I000032
Figure PCTKR2012004631-appb-I000032
Figure PCTKR2012004631-appb-I000033
Figure PCTKR2012004631-appb-I000033
Figure PCTKR2012004631-appb-I000034
Figure PCTKR2012004631-appb-I000034
Figure PCTKR2012004631-appb-I000035
Figure PCTKR2012004631-appb-I000035
상기 화학식 1로 표시되는 화합물들은 상기 화학식 5에 제시된 화합물들 중 하나일 수 있으나 이에 제한되지 않는다. 이때 화학식 1로 표시되는 화합물들의 각 치환기들은 광범위한 관계로 모든 화합물들을 예시하는 것은 현실적으로 어려우므로 대표적인 화합물들을 예시적으로 설명한 것이나, 상기 화학식 5에 제시되지 않은 화학식 1로 표시되는 화합물들도 본 명세서의 일부를 구성할 수 있다. The compounds represented by Formula 1 may be one of the compounds shown in Formula 5, but is not limited thereto. In this case, since the substituents of the compounds represented by the general formula (1) are practically difficult to exemplify all the compounds in a broad relationship, the exemplary compounds have been described by way of example, but the compounds represented by the general formula (1) not shown in the general formula (5) also Some can be configured.
더욱 구체적으로, 상기 화학식 2로 표시되는 화합물은 아래 화합물 (P2-1) 내지 (P2-120) 중 어느 하나일 수 있으며, 여기에 제한되는 것은 아니다.More specifically, the compound represented by Formula 2 may be any one of the following Compounds (P2-1) to (P2-120), but is not limited thereto.
화학식 6
Figure PCTKR2012004631-appb-C000005
 Formula 6
Figure PCTKR2012004631-appb-C000005
Figure PCTKR2012004631-appb-I000036
Figure PCTKR2012004631-appb-I000036
Figure PCTKR2012004631-appb-I000037
Figure PCTKR2012004631-appb-I000037
Figure PCTKR2012004631-appb-I000038
Figure PCTKR2012004631-appb-I000038
Figure PCTKR2012004631-appb-I000039
Figure PCTKR2012004631-appb-I000039
Figure PCTKR2012004631-appb-I000040
Figure PCTKR2012004631-appb-I000040
Figure PCTKR2012004631-appb-I000041
Figure PCTKR2012004631-appb-I000041
Figure PCTKR2012004631-appb-I000042
Figure PCTKR2012004631-appb-I000042
Figure PCTKR2012004631-appb-I000043
Figure PCTKR2012004631-appb-I000043
Figure PCTKR2012004631-appb-I000044
Figure PCTKR2012004631-appb-I000044
Figure PCTKR2012004631-appb-I000045
Figure PCTKR2012004631-appb-I000045
Figure PCTKR2012004631-appb-I000046
Figure PCTKR2012004631-appb-I000046
Figure PCTKR2012004631-appb-I000047
Figure PCTKR2012004631-appb-I000047
Figure PCTKR2012004631-appb-I000048
Figure PCTKR2012004631-appb-I000048
Figure PCTKR2012004631-appb-I000049
Figure PCTKR2012004631-appb-I000049
Figure PCTKR2012004631-appb-I000050
Figure PCTKR2012004631-appb-I000050
Figure PCTKR2012004631-appb-I000051
Figure PCTKR2012004631-appb-I000051
상기 화학식 2로 표시되는 화합물들은 상기 화학식 6에 제시된 화합물들 중 하나일 수 있으나 이에 제한되지 않는다. 이때 화학식 2로 표시되는 화합물들의 각 치환기들은 광범위한 관계로 모든 화합물들을 예시하는 것은 현실적으로 어려우므로 대표적인 화합물들을 예시적으로 설명한 것이나, 상기 화학식 6에 제시되지 않은 화학식 2로 표시되는 화합물들도 본 명세서의 일부를 구성할 수 있다. Compounds represented by Formula 2 may be one of the compounds shown in Formula 6, but is not limited thereto. In this case, since the substituents of the compounds represented by the formula (2) are practically difficult to exemplify all the compounds in a broad relationship, the exemplary compounds have been described by way of example, but the compounds represented by the formula (2) not shown in the formula (6) also Some can be configured.
상기 구조식을 가지는 화합물 또는 이들의 혼합물을 함유하는 조성물은 용액 공정(soluble process)에 사용될 수 있다. 다시 말해 상기 화합물 또는 이들의 혼합물을 함유하는 조성물은 용액 공정(soluble process)에 의해 후술할 유기전기소자의 유기물층을 형성할 수 있다. 즉 상기 화합물 또는 조성물을 유기물층으로 사용할 때 유기물층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용액 공정 또는 솔벤트 프로세스(solvent process), 예컨대 스핀 코팅, 딥 코팅, 닥터 블레이딩, 스크린 프린팅, 잉크젯 프린팅 또는 열 전사법 등의 방법에 의하여 더 적은 수의 층으로 제조될 수 있다.Compositions containing a compound having the above structural formula or a mixture thereof can be used in a soluble process. In other words, the composition containing the compound or a mixture thereof may form an organic material layer of the organic electric element to be described later by a solution process (soluble process). In other words, when the compound or composition is used as an organic material layer, the organic material layer may be formed using a variety of polymer materials, rather than a solution process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be produced in fewer layers by methods such as law.
또 다른 측면에서, 제 1전극, 제 2전극 및 상기 화학식 1로 표시되는 화합물을 단독 또는 혼합물로 함유하는 1층 이상의 유기물층을 포함하는 유기전기소자를 제공한다. 이때, 혼합물은 화학식 1로 표시되는 화합물들 중 서로 다른 2종 이상의 화합물이 혼합되거나 상기 화학식 1로 표시되는 화합물과 화학식 2로 표시되는 화합물의 혼합물일 수 있다. 유기물층은 발광층, 정공 주입층 및 정공 수송층 중 적어도 일층일 수 있다.In still another aspect, there is provided an organic electric device including a first electrode, a second electrode, and at least one organic material layer containing the compound represented by Formula 1 alone or in a mixture. In this case, the mixture may be a mixture of two or more different compounds among the compounds represented by the formula (1) or a mixture of the compound represented by the formula (1) and the compound represented by the formula (2). The organic material layer may be at least one of a light emitting layer, a hole injection layer, and a hole transport layer.
본 발명에 따른 유기전기소자는 유기전기발광소자(OLED ), 유기태양전지, 유기감광체(OPC), 유기트랜지스터(유기 TFT), 단색 또는 백색 조명용 소자 중 하나일 수 있다.The organic electroluminescent device according to the present invention may be one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a monochromatic or white illumination device.
본 발명의 조성물은 후술하는 바와 같이 유기전기소자의 유기물층의 특성을 최대한 살리면서 박막 형성시 균일도가 높고 결정화가 낮은 정공 주입층 재료의 요구, 수명단축의 원인 중 하나인 양극전극으로부터 금속산화물이 유기층에 침투 확산되는 것을 지연시키면서 소자 구동시 발생되는 주울열(Joule heating)에 대해서도 안정된 특성, 즉 높은 유리 전이 온도를 갖는 정공 주입층 재료의 요구, 유기전기발광소자의 형성에 있어서 증착 방법에 오랫동안 견딜 수 있는 재료 즉 내열성 특성이 강한 재료의 요구를 만족할 수 있다. The composition of the present invention is a metal oxide organic layer from the positive electrode electrode which is one of the causes of the hole injection layer material having high uniformity and low crystallization when forming a thin film, and shortening the life while maximizing the characteristics of the organic material layer of the organic electric device as described below Stabilization of Joule heating generated during device operation while delaying penetration diffusion into the device, namely the demand for a hole injection layer material having a high glass transition temperature, and withstanding the deposition method in the formation of an organic electroluminescent device It can meet the requirements of materials that can be used, that is, materials with strong heat resistance characteristics.
전술한 바와 같이 본 발명자들은 중수소로 치환된 화합물의 혼합물을 포함하는 조성물을 중수소로 치환되지 않은 화합물 또는 중수소로 치환된 화합물 자체와 비교하여 많은 열역학적 거동을 확인하고, 탄소, 수소 및 탄소, 중수소 결합길이의 차이에 따라서, 결합길이가 보다 작은 탄소, 중수소로 이루어진 화합물이 결합길이가 짧음에 따라 발생하는 분자간 반데르발스 힘의 약화로 인해 더 높은 발광효율을 가짐을 확인하고 중수소로 치환된 경우에는 제로포인트 에너지(Zero Point Energy) 즉 바닥상태의 에너지가 낮아지며, 중수소, 탄소의 결합길이가 짧아짐에 따라, 분자 중심 부피(Molecular hardcore volume)가 줄어들고, 이에 따라 전기적 극성화도(Electroical polarizability)를 줄일 수 있으며, 분자간 상호작용(Intermolecular interaction)을 약하게 함으로써, 박막 부피를 증가시킬 수 있음을 확인하였다. As described above, the inventors have found many thermodynamic behaviors of a composition comprising a mixture of compounds substituted with deuterium or a compound not substituted with deuterium or the compound itself substituted with deuterium, and confirmed carbon, hydrogen and carbon, deuterium bonds. According to the difference in length, it was confirmed that a compound composed of carbon and deuterium having a smaller bond length has a higher luminous efficiency due to the weakening of the intermolecular van der Waals forces generated by a short bond length. As the zero point energy, or ground energy, is lowered, and the bond length of deuterium and carbon is shortened, the molecular hardcore volume is reduced, thereby reducing the electrical polarizability. Thin film volume by weakening intermolecular interactions It was confirmed that increase.
이러한 중수소로 치환된 본 발명의 화합물의 특성은 박막의 결정화도를 낮추는 효과 즉, 비결정질(Amorphous) 상태를 만들 수 있으며, 일반적으로 유기전기발광소자의 수명 및 구동특성을 높이기 위하여, 반드시 필요한 비결정질 상태를 구현하는데 매우 효과적일 것이라고 판단하였다.The properties of the compound of the present invention substituted with deuterium may create an effect of lowering the crystallinity of the thin film, that is, an amorphous state, and in general, in order to increase the lifespan and driving characteristics of the organic electroluminescent device, We decided it would be very effective to implement.
결과적으로 중수소로 치환된 화합물의 혼합물의 특성 중에 낮은 탄소, 수소 결합물질보다 낮은 가시광선 흡수율 특성을 가지며, 이는 유기전기발광소자와 같은 발광소자에서 효율을 높일 수 있는 장점이 될 수 있다고 판단하였다. 또한 중수소로 치환된 본 발명의 화합물의 혼합물은 내열성도 많은 증가가 있을 것으로 판단하였다.As a result, among the characteristics of the mixture of the deuterium-substituted compound, it has a low visible light absorption characteristics than the low carbon, hydrogen bonding material, it was determined that this can be an advantage to increase the efficiency in light emitting devices such as organic electroluminescent devices. In addition, it was determined that the mixture of the compound of the present invention substituted with deuterium has a great increase in heat resistance.
제조예Production Example
이하에서 상기 화학식 1 또는 화학식 2에 속하는 화합물들에 대한 제조예 또는 합성예를 설명한다. 다만, 화학식 1 또는 화학식 2에 속하는 화합물들의 수가 많기 때문에 화학식 1 또는 화학식 2에 속하는 화합물들 중 일부를 예시적으로 설명한다. 본 발명이 속하는 기술분야의 통상의 지식을 가진 자, 즉 당업자라면 하기에서 설명한 제조예들을 통해, 예시하지 않은 본 발명에 속하는 화합물을 제조할 수 있다.Hereinafter, the preparation or synthesis examples of the compounds belonging to Formula 1 or Formula 2 will be described. However, some of the compounds belonging to the general formula (1) or the formula (2) because of the large number of compounds belonging to the general formula (1) or (2) will be described as an example. Those skilled in the art to which the present invention pertains, that is, those skilled in the art can prepare the compounds belonging to the present invention which are not illustrated through the preparation examples described below.
일반적인 합성 방법General Synthetic Method
본 발명의 화합물의 일반적인 합성 방법은 다음과 같다.General synthetic methods of the compounds of the present invention are as follows.
i) 화학식 1 화합물의 일반적 합성 방법i) General Synthesis of Compounds of Formula 1
Figure PCTKR2012004631-appb-I000052
Figure PCTKR2012004631-appb-I000052
ii) 화학식 2 화합물의 일반적 합성 방법ii) General Synthesis of Compounds of Formula 2
Figure PCTKR2012004631-appb-I000053
Figure PCTKR2012004631-appb-I000053
화학식 1 화합물의 합성Synthesis of Compound of Formula 1
1) Sub 1 합성법 예시 : (Ar1) Example of Sub 1 synthesis: (Ar 1One , L=Phenyl), L = Phenyl)
Sub 1-1 합성 : 9-phenyl-9H-carbazole Sub 1-1 Synthesis: 9-phenyl-9H-carbazole
Figure PCTKR2012004631-appb-I000054
Figure PCTKR2012004631-appb-I000054
카바졸 (50.2 g, 300 mmol)과 브로모벤젠 (56.5 g, 360 mmol)을 톨루엔 2800mL에 혼합 후에 Pd2(dba)3 (8.24 g, 9 mmol), PPh3 (7.87 g, 30 mmol), NaOt-Bu (86.5 g, 900mmol) 을 각각 첨가한 뒤, 100℃에서 24시간 교반 환류 시킨다. 에테르와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 실리카겔 칼럼으로 정제 및 재결정하여 생성물을 52.5 g (75%) 얻었다. Carbazole (50.2 g, 300 mmol) and bromobenzene (56.5 g, 360 mmol) were mixed in 2800 mL of toluene, followed by Pd 2 (dba) 3 (8.24 g, 9 mmol), PPh 3 (7.87 g, 30 mmol), NaO t -Bu (86.5 g, 900 mmol) was added, and the mixture was stirred at reflux for 24 hours at 100 ° C. After extraction with ether and water, the organic layer was dried over MgSO 4 , concentrated and the resulting organic was purified and recrystallized by a silica gel column to give 52.5 g (75%) of the product.
Sub 1-2 합성 : 3-bromo-9-phenyl-9H-carbazoleSub 1-2 synthesis: 3-bromo-9-phenyl-9H-carbazole
Figure PCTKR2012004631-appb-I000055
Figure PCTKR2012004631-appb-I000055
상기 합성에서 얻어진 Sub 1-1 (48.66 g, 200 mmol) 에 메틸렌 크로라이드 600 mL 에 녹인후, NBS(N-bromosuccimide) (59.4 g, 210 mmol) 을 서서히 첨가한 뒤, 상온에서 24시간 교반시킨다.After dissolving in 600 mL of methylene chloride in Sub 1-1 (48.66 g, 200 mmol) obtained in the above synthesis, NBS (N-bromosuccimide) (59.4 g, 210 mmol) was slowly added, followed by stirring at room temperature for 24 hours. .
반응이 종료되면 5% 농도의 HCl 300 mL 을 첨가한 뒤, 물 300 mL 을 첨가하여, 잔존 NBS 를 제거한 뒤, 에테르와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 실리카겔 칼럼으로 정제 및 재결정하여 생성물을 47.7 (74%) 얻었다. After the reaction was completed, 300 mL of 5% HCl was added, 300 mL of water was added to remove residual NBS, and extracted with ether and water. The organic layer was dried over MgSO 4 , concentrated, and the resulting organic substance was purified by silica gel column. Purification and recrystallization were carried out to give 47.7 (74%) of the product.
Sub 1-3 합성 : 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazoleSub 1-3 Synthesis: 9-phenyl-3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole
Figure PCTKR2012004631-appb-I000056
Figure PCTKR2012004631-appb-I000056
상기 합성에서 얻어진 Sub 1-2 (45.1 g, 140 mmol) 을 DMF 980mL 에 녹인 후에, 비스피나콜보레이트 (39.1 g, 154 mmol), PdCl2(dppf) 촉매 (3.43 g, 4.2 mmol), KOAc (41.3 g, 420 mmol)을 순서대로 첨가한 후 24 시간 교반하여 보레이트 화합물을 합성한 후에, 얻어진 화합물을 실리카겔 칼럼 및 재결정을 걸쳐서 분리한 후 보레이트 화합물을 35.2 g (68 %)얻는다. Sub 1-2 (45.1 g, 140 mmol) obtained in the above synthesis was dissolved in 980 mL of DMF, followed by bispinacolborate (39.1 g, 154 mmol), PdCl 2 (dppf) catalyst (3.43 g, 4.2 mmol), KOAc ( 41.3 g, 420 mmol) was added sequentially, followed by stirring for 24 hours to synthesize the borate compound, and the obtained compound was separated through a silica gel column and recrystallized to obtain 35.2 g (68%) of the borate compound.
Sub 1 합성 : 3-(4-bromophenyl)-9-phenyl-9H-carbazoleSub 1 Synthesis: 3- (4-bromophenyl) -9-phenyl-9H-carbazole
Figure PCTKR2012004631-appb-I000057
Figure PCTKR2012004631-appb-I000057
상기 합성에서 얻어진 Sub 1-3 (29.5 g, 80 mmol) 을 THF 360 mL 에 녹인 후에, 1-브로모-4-아이오도 벤젠 (23.8 g, 84 mmol), Pd(PPh3)4 (2.8 g, 2.4mmol), NaOH (9.6 g, 240mmol), 물 180 mL 을 첨가한 후, 교반 환류시킨다. 반응이 완료되면 에테르와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 실리카겔 칼럼으로 정제 및 재결정하여 생성물을 22.9 g (72 %) 얻었다.Sub 1-3 (29.5 g, 80 mmol) obtained in the above synthesis was dissolved in 360 mL of THF, followed by 1-bromo-4-iodo benzene (23.8 g, 84 mmol), Pd (PPh 3 ) 4 (2.8 g , 2.4 mmol), NaOH (9.6 g, 240 mmol), 180 mL of water are added, followed by stirring under reflux. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO 4 , concentrated, and the resulting organic was purified and recrystallized by a silica gel column to obtain 22.9 g (72%) of the product.
2) R2) R 1One 치환 합성법 예시: (Ar Example substitution synthesis: (Ar 1One , R, R 1One , L=Phenyl), L = Phenyl)
Sub 1-1-1 합성 : 3,9-diphenyl-9H-carbazoleSub 1-1-1 Synthesis: 3,9-diphenyl-9H-carbazole
Figure PCTKR2012004631-appb-I000058
Figure PCTKR2012004631-appb-I000058
상기 실시예 1에서 얻어진 Sub 1-2 (25.8 g, 80 mmol) 을 THF 360 mL 에 녹인 후에, Phenyl boronic acid (10.7 g, 88mmol), Pd(PPh3)4 (2.8 g, 2.4mmol), NaOH (9.6 g, 240mmol), 물 180 mL 을 실시예 sub 1 합성법을 사용하여 18.9 g (74 %) 의 생성물을 얻었으며, scale-up 반응 시 동일한 실험방법으로 진행하여 동일한 수득률을 나타냈다. Sub 1-2 (25.8 g, 80 mmol) obtained in Example 1 was dissolved in 360 mL of THF, followed by Phenyl boronic acid (10.7 g, 88 mmol), Pd (PPh 3 ) 4 (2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol) and 180 mL of water were used to obtain 18.9 g (74%) of the product using the synthesis method of Example sub 1, and the same yield was obtained when the scale-up reaction proceeded to the same experimental method.
Sub 1-2 합성 : 3-bromo-6,9-diphenyl-9H-carbazoleSub 1-2 synthesis: 3-bromo-6,9-diphenyl-9H-carbazole
Figure PCTKR2012004631-appb-I000059
Figure PCTKR2012004631-appb-I000059
상기 합성에서 얻어진 Sub 1-1-1 (63.88 g, 200 mmol) 에 메틸렌 크로라이드 600 mL, NBS(N-bromosuccimide) (59.4 g, 210 mmol) 을 상기 실시예 1의 sub 1-2 합성법을 사용하여 55.8 g (70%)의 생성물을 얻었다. Sub 1-1-1 (63.88 g, 200 mmol) obtained in the above synthesis was added with 600 mL of methylene chloride and NBS (N-bromosuccimide) (59.4 g, 210 mmol) using the sub 1-2 synthesis method of Example 1 To give 55.8 g (70%) of the product.
Sub 1-3 합성 : 3,9-diphenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazoleSub 1-3 Synthesis: 3,9-diphenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole
Figure PCTKR2012004631-appb-I000060
Figure PCTKR2012004631-appb-I000060
상기 합성에서 얻어진 Sub-1-2 (55.8 g, 140 mmol), DMF 980mL, 비스피나콜보레이트를 (39.1 g, 154 mmol), PdCl2(dppf) 촉매 (3.43 g, 4.2 mmol), KOAc (41.3 g, 420 mmol)을 상기 실시예 1의 sub 1-3의 합성법을 사용하여 40.5 g (65 %)의 생성물을 얻었다. Sub-1-2 obtained in the above synthesis (55.8 g, 140 mmol), DMF 980 mL, bispinacolborate (39.1 g, 154 mmol), PdCl 2 (dppf) catalyst (3.43 g, 4.2 mmol), KOAc (41.3) g, 420 mmol) was obtained using the synthesis method of sub 1-3 of Example 1 to obtain 40.5 g (65%) of the product.
Sub 1 합성 : 3-(4-bromophenyl)-6,9-diphenyl-9H-carbazoleSub 1 Synthesis: 3- (4-bromophenyl) -6,9-diphenyl-9H-carbazole
Figure PCTKR2012004631-appb-I000061
Figure PCTKR2012004631-appb-I000061
상기 합성에서 얻어진 Sub-1-3 (35.6 g, 80 mmol) 을 THF 360 mL 에 녹인 후에, 1-브로모-4-아이오도 벤젠 (23.8 g, 84 mmol), Pd(PPh3)4 (2.8 g, 2.4mmol), NaOH (9.6 g, 240mmol), 물 180 mL 을 첨가한 후, 교반 환류 시킨다. 반응이 완료되면 에테르와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 실리카겔 칼럼으로 정제 및 재결정하여 생성물을 27.7 g (73 %) 얻었다.Sub-1-3 (35.6 g, 80 mmol) obtained in the above synthesis was dissolved in 360 mL of THF, followed by 1-bromo-4-iodo benzene (23.8 g, 84 mmol), Pd (PPh 3 ) 4 (2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol) and 180 mL of water were added, followed by stirring under reflux. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic was purified and recrystallized by a silica gel column to obtain a product 27.7 g (73%).
3) Dibenzothiophene 를 포함하는 출발물질 합성법 예시 3) Example of starting material synthesis method containing Dibenzothiophene
Figure PCTKR2012004631-appb-I000062
Figure PCTKR2012004631-appb-I000062
중간체 A의 합성Synthesis of Intermediate A
2-Bromothioanisole을 glacial acetic acid 용매에 녹인 후, 반응물의 온도를 0℃로 낮춘 후에 Hydrogen peroxide 를 천천히 적가시킨다. 적가가 완료되면 반응물의 온도를 상온으로 올린 후 12시간동안 교반하면서 반응을 진행시켰다. 반응이 종료되면 감압장치를 이용하여 용매를 제거 한 후 CH2Cl2로 추출하고, NaHCO3 수용액으로 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 중간체 A를 43 g (98%)의 수율로 얻었다. Dissolve 2-Bromothioanisole in a glacial acetic acid solvent, lower the temperature of the reaction to 0 ° C, and then slowly add Hydrogen peroxide. When the addition was completed, the reaction was heated to room temperature and stirred for 12 hours to proceed with the reaction. After the reaction was completed, the solvent was removed using a pressure reduction apparatus, extracted with CH 2 Cl 2 , and washed with NaHCO 3 aqueous solution. A small amount of water was removed with anhydrous MgSO 4 , filtered under reduced pressure, and the organic solvent was concentrated and the resulting product was separated using column chromatography to give the desired intermediate A in a yield of 43 g (98%).
중간체 B의 합성Synthesis of Intermediate B
중간체 A와 2-Bromocarbazole, Pd(PPh3)4, Na2CO3를 무수 THF와 소량의 물에 녹이고 난 후 24시간동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아 주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 중간체 B를 30.6 g (51%) 얻었다. Intermediate A, 2-Bromocarbazole, Pd (PPh 3 ) 4 , and Na 2 CO 3 were dissolved in anhydrous THF and a small amount of water and refluxed for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with CH 2 Cl 2 , and washed with water. A small amount of water was removed with anhydrous MgSO 4 , filtered under reduced pressure, and the organic solvent was concentrated. The resulting product was separated using column chromatography to obtain 30.6 g (51%) of the desired intermediate B.
중간체 C의 합성Synthesis of Intermediate C
상기 합성에서 얻어진 중간체 B (30.5 g, 100 mmol) 에 메틸렌 크로라이드 300 mL, NBS(N-bromosuccimide) (29.7 g, 105 mmol) 을 상기 실시예 1의 sub 1-2 합성법을 사용하여 28.058 g (73%)의 생성물을 얻었다. To Intermediate B (30.5 g, 100 mmol) obtained in the above synthesis, 300 mL of methylene chloride and NBS (N-bromosuccimide) (29.7 g, 105 mmol) were prepared using 28.058 g ( 73%) of the product.
중간체 D의 합성Synthesis of Intermediate D
중간체 C를 trifluoromethanesulfonic acid 용매에 녹인 후 상온에서 48시간 동안 교반시켰다. Intermediate C was dissolved in trifluoromethanesulfonic acid solvent and stirred at room temperature for 48 hours.
반응이 종료되면 반응물을 물과 pyridine 혼합용매를 붓고, 20분동안 환류시켰다. 반응물의 온도를 상온으로 식히고 CH2Cl2로 추출하고 물을 닦아주었다, 소량의 물을 MgSO4로 제거하고 감압 여과후 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 중간체 D를 21.1 g (82%)얻었다. After the reaction was completed, the reaction was poured into a mixture of water and pyridine solvent and refluxed for 20 minutes. The reaction mixture was cooled to room temperature, extracted with CH2Cl2, and washed with water. A small amount of water was removed with MgSO4, filtered under reduced pressure, and the organic solvent was concentrated. The resulting product was separated by column chromatography to obtain 21.1 g of the desired intermediate D. (82%) got.
출발물질 합성Starting material synthesis
중간체 D (21.1g, 60 mmol), Iodobenzene (18.4 g, 90 mmol), DMF 300mL, K2CO3 (12.4 g, 90 mmol), Cu powder (4.2 g, 66 mmol), 18-crown-6 (1.6 g, 6 mmol)에 둥근바닥플라스크에 넣은 후에 170℃에서 24시간 환류시켰다. 반응이 완료되면 물과 CH2Cl2로 추출하고 5% HCl 수용액으로 닦아준다. 마지막으로 brine 으로 닦아준다. 얻어진 유기층을 MgSO4로 수분제거 후 감압여과하여 농축한고 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 출발물질을 19 g (74%) 얻었다.Intermediate D (21.1 g, 60 mmol), Iodobenzene (18.4 g, 90 mmol), DMF 300 mL, K 2 CO 3 (12.4 g, 90 mmol), Cu powder (4.2 g, 66 mmol), 18-crown-6 ( 1.6 g, 6 mmol) was added to a round bottom flask and refluxed at 170 ° C. for 24 hours. After the reaction is completed, the mixture is extracted with water and CH2Cl2 and washed with 5% aqueous HCl solution. Finally clean it with brine. The obtained organic layer was dried with MgSO 4, filtered, and concentrated under reduced pressure. The resulting product was separated using column chromatography to obtain 19 g (74%) of the desired starting material.
4) 3-Cyano-9-phenylcarbazole 합성 예시4) Example of 3-Cyano-9-phenylcarbazole synthesis
Figure PCTKR2012004631-appb-I000063
Figure PCTKR2012004631-appb-I000063
중간체 A의 합성Synthesis of Intermediate A
DMF (43.4 mL)을 둥근바닥플라스크에 넣은 후에 질소대상태를 만들고 반응온도를 0℃로 조절한다. 그런다음 phosphoryl chloride (32 g, 200 mmol)을 천천히 적가하고 상온으로 온도를 높인 후에 1시간동안 교반시킨다. After adding DMF (43.4 mL) to the round bottom flask, create a nitrogen zone and adjust the reaction temperature to 0 ℃. Then, slowly add dropwise phosphoryl chloride (32 g, 200 mmol), raise the temperature to room temperature, and stir for 1 hour.
반응온도를 다시 0℃로 조절하고 9-phenyl carbazole(2.92 g, 120 mmol) 을 1,2-dichloroethane (52 mL)에 녹인 용액을 1시간동안 적가한다. The reaction temperature was adjusted to 0 ° C. and a solution of 9-phenyl carbazole (2.92 g, 120 mmol) in 1,2-dichloroethane (52 mL) was added dropwise for 1 hour.
반응온도를 90℃로 8시간동안 교반 시킨 후에 반응이 완료되면 얼음물과 CH2Cl2 로 추출하고 얻어진 유기층을 MgSO4 로 수분제거 및 컬럼크로마토그래피를 이용하여 분리하고 ethanol 과 hexane 으로 재결정하여 31.4g (75%)의 3-aldehyde-9-phenyl carbazole (중간체 A) 화합물을 얻었다. After the reaction temperature was stirred at 90 ° C. for 8 hours and the reaction was completed, the mixture was extracted with ice water and CH 2 Cl 2 , and the obtained organic layer was separated using MgSO 4, water removal and column chromatography. 75%) of 3-aldehyde-9-phenyl carbazole (Intermediate A) compound was obtained.
중간체 B의 합성Synthesis of Intermediate B
상기에서 얻어진 3-aldehyde-9-phenyl carbazole (31.4 g, 116 mmol), hydroxylamine hydrochloride (10 g, 140.4 mmol), acetic acid (25.1 g, 418 mmol), pyridine (16.72 g, 209 mmol), DMF (83 mL)를 순서대로 반응플라스크에 넣은 후에 140℃에서 5시간동안 교반시킨다. 3-aldehyde-9-phenyl carbazole (31.4 g, 116 mmol) obtained above, hydroxylamine hydrochloride (10 g, 140.4 mmol), acetic acid (25.1 g, 418 mmol), pyridine (16.72 g, 209 mmol), DMF ( 83 mL) was added to the reaction flask in order and stirred at 140 ° C. for 5 hours.
반응이 완료되면 물과 CH2Cl2 를 이용하여 추출하고 얻어진 유기층을 MgSO4로 수분제거 및 컬럼크로마토그래피를 이용하여 분리하고 ethanol 과 hexane 으로 재결정하여 23 g (74%)의 3-cyano-9-phenylcarbazole(중간체 B) 화합물을 얻었다.After completion of the reaction, the mixture was extracted with water and CH 2 Cl 2 , and the obtained organic layer was separated with MgSO 4 by water removal and column chromatography, and recrystallized with ethanol and hexane to give 23 g (74%) of 3-cyano-9. -phenylcarbazole (intermediate B) compound was obtained.
중간체 C의 합성Synthesis of Intermediate C
상기 합성에서 얻어진 중간체 B (23 g, 85.72 mmol) 에 메틸렌 크로라이드 80 mL, NBS(N-bromosuccimide) (25.46 g, 90 mmol) 을 상기 실시예 1의 sub 1-2 합성법을 사용하여 20.54 g (69%)의 생성물을 얻었다. In intermediate B (23 g, 85.72 mmol) obtained in the above synthesis, 80 mL of methylene chromide (N-bromosuccimide) (25.46 g, 90 mmol) was added to 20.54 g ( 69%) of the product.
5) Sub 2 합성법 예시5) Sub 2 Synthesis Example
Figure PCTKR2012004631-appb-I000064
Figure PCTKR2012004631-appb-I000064
Figure PCTKR2012004631-appb-I000065
Figure PCTKR2012004631-appb-I000065
Figure PCTKR2012004631-appb-I000066
Figure PCTKR2012004631-appb-I000066
Figure PCTKR2012004631-appb-I000067
Figure PCTKR2012004631-appb-I000067
Sub 2-1 의 합성 Synthesis of Sub 2-1
Figure PCTKR2012004631-appb-I000068
Figure PCTKR2012004631-appb-I000068
Aniline-d5 (23.56 g, 240 mmol), bromobenzene-d5 (32.41 g, 200 mmol)을 플라스크에 혼합후, Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 첨가 한뒤 24시간 교반 환류시킨다. 반응이 완료되면 에테르와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 실리카겔 칼럼으로 정제 및 재결정하여 생성물을 26.17 g (73 %)얻었다.Aniline-d5 (23.56 g, 240 mmol) and bromobenzene-d5 (32.41 g, 200 mmol) were mixed into the flask, followed by Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol) , NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were added and then stirred under reflux for 24 hours. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO 4 , concentrated, and the resulting organic was purified and recrystallized by a silica gel column to obtain 26.17 g (73%) of the product.
Sub 2-2 의 합성Synthesis of Sub 2-2
Figure PCTKR2012004631-appb-I000069
Figure PCTKR2012004631-appb-I000069
Aniline-d5 (23.56 g, 240 mmol), 1-bromo-4-fluorobenzene (35 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 26.14 g (68 %)얻었다.Aniline-d5 (23.56 g, 240 mmol), 1-bromo-4-fluorobenzene (35 g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the Experiments of Sub-2-1 to obtain 26.14 g (68%) of the product.
Sub 2-3 의 합성Synthesis of Sub 2-3
Figure PCTKR2012004631-appb-I000070
Figure PCTKR2012004631-appb-I000070
Aniline-d5 (23.56 g, 240 mmol), bromobenzene (31.4 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 26.14 g (75 %)얻었다.Aniline-d5 (23.56 g, 240 mmol), bromobenzene (31.4 g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the Experiments of Sub-2-1 to obtain 26.14 g (75%) of the product.
Sub 2-4 의 합성Synthesis of Sub 2-4
Figure PCTKR2012004631-appb-I000071
Figure PCTKR2012004631-appb-I000071
Aniline-d5 (23.56 g, 240 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (54.6 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 41.24 g (71 %)얻었다.Aniline-d5 (23.56 g, 240 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (54.6 g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the experimental method of Sub-2-1 to obtain 41.24 g (71%) of a product.
Sub 2-5 의 합성Synthesis of Sub 2-5
Aniline-d5 (23.56 g, 240 mmol), 2-bromo-9,9-diphenyl-9H-fluorene (79.5 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 57.2 g (69 %)얻었다.Aniline-d5 (23.56 g, 240 mmol), 2-bromo-9,9-diphenyl-9H-fluorene (79.5 g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the experimental method of Sub-2-1 to give 57.2 g (69%) of the product.
Sub 2-6 의 합성Synthesis of Sub 2-6
Figure PCTKR2012004631-appb-I000073
Figure PCTKR2012004631-appb-I000073
Aniline-d5 (23.56 g, 240 mmol), 2-bromo-9,9-diphenyl-9H-fluorene (79.5 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 57.2 g (69 %)얻었다.Aniline-d5 (23.56 g, 240 mmol), 2-bromo-9,9-diphenyl-9H-fluorene (79.5 g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the experimental method of Sub-2-1 to give 57.2 g (69%) of the product.
Sub 2-7 의 합성Synthesis of Sub 2-7
Figure PCTKR2012004631-appb-I000074
Figure PCTKR2012004631-appb-I000074
1-naphtylamine (34.37 g, 240 mmol), 4'-bromo-2,3,4,5,6-d5-biphenyl (47.63 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 44.5 g (74 %)얻었다.1-naphtylamine (34.37 g, 240 mmol), 4'-bromo-2,3,4,5,6-d5-biphenyl (47.63 g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol) , PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were prepared in the same manner as in the Experiment of Sub-2-1 to obtain 44.5 g (74%) of the product. .
Sub 2-8 의 합성Synthesis of Sub 2-8
Figure PCTKR2012004631-appb-I000075
Figure PCTKR2012004631-appb-I000075
Aniline-d5 (23.56 g, 240 mmol), 2-bromonaphthalene (41.41 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 32.3 g (72 %)얻었다.Aniline-d5 (23.56 g, 240 mmol), 2-bromonaphthalene (41.41 g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were prepared in the same manner as in the Experiment of Sub-2-1, to obtain 32.3 g (72%) of a product.
Sub 2-9 의 합성Synthesis of Sub 2-9
Figure PCTKR2012004631-appb-I000076
Figure PCTKR2012004631-appb-I000076
Aniline-d5 (23.56 g, 240 mmol), 4-bromobiphenyl (46.62 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 36.55 g (73 %)얻었다.Aniline-d5 (23.56 g, 240 mmol), 4-bromobiphenyl (46.62 g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the Experiments of Sub-2-1 to obtain 36.55 g (73%) of the product.
Sub 2-10 의 합성Synthesis of Sub 2-10
Figure PCTKR2012004631-appb-I000077
Figure PCTKR2012004631-appb-I000077
Aniline-d5 (23.56 g, 240 mmol), 1-(4-bromophenyl)naphthalene (56.63 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 41.46 g (69%)얻었다.Aniline-d5 (23.56 g, 240 mmol), 1- (4-bromophenyl) naphthalene (56.63 g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol) , NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were prepared in the same manner as in the Experiments of Sub-2-1 to obtain 41.46 g (69%) of the product.
Sub 2-11 의 합성Synthesis of Sub 2-11
Figure PCTKR2012004631-appb-I000078
Figure PCTKR2012004631-appb-I000078
Aniline-d5 (23.56 g, 240 mmol), 2-(4-bromophenyl)naphthalene (56.63 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 40.86 g (68%)얻었다.Aniline-d5 (23.56 g, 240 mmol), 2- (4-bromophenyl) naphthalene (56.63 g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol) , NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were prepared in the same manner as in the Experiments of Sub-2-1 to obtain 40.86 g (68%) of the product.
Sub 2-12 의 합성Synthesis of Sub 2-12
Figure PCTKR2012004631-appb-I000079
Figure PCTKR2012004631-appb-I000079
Aniline-d5 (23.56 g, 240 mmol), 1-bromo-4-phenylnaphthalene (56.63 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 39.05 g (65 %)얻었다.Aniline-d5 (23.56 g, 240 mmol), 1-bromo-4-phenylnaphthalene (56.63 g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the Experiments of Sub-2-1 to obtain 39.05 g (65%) of the product.
Sub 2-13 의 합성Synthesis of Sub 2-13
Figure PCTKR2012004631-appb-I000080
Figure PCTKR2012004631-appb-I000080
Aniline-d5 (23.56 g, 240 mmol), 2-bromo-6-phenylnaphthalene (56.63 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 39.05 g (65 %)얻었다.Aniline-d5 (23.56 g, 240 mmol), 2-bromo-6-phenylnaphthalene (56.63 g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the Experiments of Sub-2-1 to obtain 39.05 g (65%) of the product.
Sub 2-14 의 합성Synthesis of Sub 2-14
Figure PCTKR2012004631-appb-I000081
Figure PCTKR2012004631-appb-I000081
Aniline-d5 (23.56 g, 240 mmol), 3,5-diphenyl bromobenzene (61.84 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 44.4 g (68 %)얻었다.Aniline-d5 (23.56 g, 240 mmol), 3,5-diphenyl bromobenzene (61.84 g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t- Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the Experiments of Sub-2-1 to obtain 44.4 g (68%) of the product.
Sub 2-15 의 합성Synthesis of Sub 2-15
Figure PCTKR2012004631-appb-I000082
Figure PCTKR2012004631-appb-I000082
Aniline-d5 (23.56 g, 240 mmol), 4-bromo-N,N-diphenylaniline (64.84 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 45.76 g (67 %)얻었다.Aniline-d5 (23.56 g, 240 mmol), 4-bromo-N, N-diphenylaniline (64.84 g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol ), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were prepared in the same manner as in the Experiments of Sub-2-1 to obtain 45.76 g (67%) of the product.
Sub 2-16 의 합성Synthesis of Sub 2-16
Figure PCTKR2012004631-appb-I000083
Figure PCTKR2012004631-appb-I000083
Aniline-d5 (23.56 g, 240 mmol), 2-bromo-dibenzothiophene (52.63 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 39.82 g (71 %)얻었다.Aniline-d5 (23.56 g, 240 mmol), 2-bromo-dibenzothiophene (52.63 g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the Experiments of Sub-2-1 to obtain 39.82 g (71%) of the product.
Sub 2-17 의 합성Synthesis of Sub 2-17
Figure PCTKR2012004631-appb-I000084
Figure PCTKR2012004631-appb-I000084
Aniline-d5 (23.56 g, 240 mmol), 2-bromo-dibenzofuran (49.42 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 37 g (70 %)얻었다.Aniline-d5 (23.56 g, 240 mmol), 2-bromo-dibenzofuran (49.42 g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were prepared in the same manner as in the Experiment of Sub-2-1 to obtain 37 g (70%) of the product.
Sub 2-18 의 합성Synthesis of Sub 2-18
Figure PCTKR2012004631-appb-I000085
Figure PCTKR2012004631-appb-I000085
Aniline-d5 (23.56 g, 240 mmol), 1-bromonaphthalene-d7 (42.82 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 34.24 g (74 %)얻었다.Aniline-d5 (23.56 g, 240 mmol), 1-bromonaphthalene-d7 (42.82 g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the Experiment of Sub-2-1 to obtain 34.24 g (74%) of the product.
Sub 2-19 의 합성Synthesis of Sub 2-19
Figure PCTKR2012004631-appb-I000086
Figure PCTKR2012004631-appb-I000086
Aniline-d5 (23.56 g, 240 mmol), 2-bromonaphthalene-d7 (42.82 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 33.32 g (72 %)얻었다.Aniline-d5 (23.56 g, 240 mmol), 2-bromonaphthalene-d7 (42.82 g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the Experiments of Sub-2-1 to obtain 33.32 g (72%) of the product.
Sub 2-20 의 합성Synthesis of Sub 2-20
Figure PCTKR2012004631-appb-I000087
Figure PCTKR2012004631-appb-I000087
Aniline-d5 (23.56 g, 240 mmol), 4'-bromo-2,3,4,5,6-d5-biphenyl (47.63 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 36.77 g (72 %)얻었다.Aniline-d5 (23.56 g, 240 mmol), 4'-bromo-2,3,4,5,6-d5-biphenyl (47.63 g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol) , PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the Experiments of Sub-2-1 to obtain 36.77 g (72%) of the product. .
Sub 2-21 의 합성Synthesis of Sub 2-21
Figure PCTKR2012004631-appb-I000088
Figure PCTKR2012004631-appb-I000088
Aniline-d5 (23.56 g, 240 mmol), 1-(4-bromophenyl)-2,3,4,5,6,7,8-d7-naphthalene (58.04 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 43.04 g (70 %)얻었다.Aniline-d5 (23.56 g, 240 mmol), 1- (4-bromophenyl) -2,3,4,5,6,7,8-d7-naphthalene (58.04 g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were prepared in the same manner as in the Experiment of Sub-2-1. 43.04 g (70%) was obtained.
Sub 2-22 의 합성Synthesis of Sub 2-22
Figure PCTKR2012004631-appb-I000089
Figure PCTKR2012004631-appb-I000089
Aniline-d5 (23.56 g, 240 mmol), 2-(4-bromo-2,3,5,6-d4-phenyl)naphthalene (57.44 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 43.23 g (71 %)얻었다.Aniline-d5 (23.56 g, 240 mmol), 2- (4-bromo-2,3,5,6-d4-phenyl) naphthalene (57.44 g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were prepared in the same manner as in Sub-2-1, and the product was 43.23 g (71%). )
Sub 2-23 의 합성Synthesis of Sub 2-23
Figure PCTKR2012004631-appb-I000090
Figure PCTKR2012004631-appb-I000090
Aniline-d5 (23.56 g, 240 mmol), 1-bromo-4-(2,3,4,5,6-d5-phenyl)naphthalene (57.64 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 42.15 g (69 %)얻었다.Aniline-d5 (23.56 g, 240 mmol), 1-bromo-4- (2,3,4,5,6-d5-phenyl) naphthalene (57.64 g, 200 mmol), Pd 2 (dba) 3 (5.5 g , 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol), toluene (1930 mL) were prepared in the same manner as in Sub-2-1, and the product was 42.15 g ( 69%).
Sub 2-24 의 합성Synthesis of Sub 2-24
Figure PCTKR2012004631-appb-I000091
Figure PCTKR2012004631-appb-I000091
Aniline-d5 (23.56 g, 240 mmol), 2-bromo-6-(2,3,4,5,6-d5-phenyl)naphthalene (57.64 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 42.15 g (69 %)얻었다.Aniline-d5 (23.56 g, 240 mmol), 2-bromo-6- (2,3,4,5,6-d5-phenyl) naphthalene (57.64 g, 200 mmol), Pd 2 (dba) 3 (5.5 g , 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol), toluene (1930 mL) were prepared in the same manner as in Sub-2-1, and the product was 42.15 g ( 69%).
Sub 2-25 의 합성Synthesis of Sub 2-25
Figure PCTKR2012004631-appb-I000092
Figure PCTKR2012004631-appb-I000092
Aniline-d5 (23.56 g, 240 mmol), 3,6-Diphenyl-d10-bromobenzene (63.85 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 43.07 g (64 %)얻었다.Aniline-d5 (23.56 g, 240 mmol), 3,6-Diphenyl-d10-bromobenzene (63.85 g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol ), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were prepared in the same manner as in the Experiments of Sub-2-1 to obtain 43.07 g (64%) of the product.
Sub 2-26 의 합성Synthesis of Sub 2-26
Figure PCTKR2012004631-appb-I000093
Figure PCTKR2012004631-appb-I000093
4-Phenyl-d5-Aniline (41.82 g, 240 mmol), 4'-bromo-2,3,4,5,6-d5-biphenyl (47.63 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 45.08 g (68 %)얻었다.4-Phenyl-d5-Aniline (41.82 g, 240 mmol), 4'-bromo-2,3,4,5,6-d5-biphenyl (47.63 g, 200 mmol), Pd 2 (dba) 3 (5.5 g , 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol), toluene (1930 mL) were prepared in the same manner as in Sub-2-1, and the product was 45.08 g ( 68%).
표 1
Figure PCTKR2012004631-appb-T000001
 Table 1
Figure PCTKR2012004631-appb-T000001
6) Sub 3 합성법 예시 6) Sub 3 Synthesis Example
Figure PCTKR2012004631-appb-I000094
Figure PCTKR2012004631-appb-I000094
Figure PCTKR2012004631-appb-I000095
Figure PCTKR2012004631-appb-I000095
Sub 3-1 의 합성Synthesis of Sub 3-1
Figure PCTKR2012004631-appb-I000096
Figure PCTKR2012004631-appb-I000096
Sub 2-7 (30.04 g, 100 mmol), 2,5-dibromothiophene (26.61 g, 110 mmol), Pd2(dba)3 (2.75 g, 3 mmol), PPh3 (2.63 g, 10 mmol), NaOt-Bu (28.9 g, 300mmol), toluene (970 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 30.92 g (67 %)얻었다.Sub 2-7 (30.04 g, 100 mmol), 2,5-dibromothiophene (26.61 g, 110 mmol), Pd 2 (dba) 3 (2.75 g, 3 mmol), PPh 3 (2.63 g, 10 mmol), NaO t- Bu (28.9 g, 300 mmol) and toluene (970 mL) were prepared in the same manner as in the Experiments of Sub-2-1 to obtain 30.92 g (67%) of the product.
Sub 3-2 의 합성Synthesis of Sub 3-2
Figure PCTKR2012004631-appb-I000097
Figure PCTKR2012004631-appb-I000097
N-(2,3,5,6-d4-biphenyl-4-yl)naphthalen-1-amine (29.94 g, 100 mmol), 2-bromo-5-(4-iodophenyl)thiophene (40.15 g, 110 mmol), Pd2(dba)3 (2.75 g, 3 mmol), PPh3 (2.63 g, 10 mmol), NaOt-Bu (28.9 g, 300mmol), toluene (970 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 33.80 g (63 %)얻었다.N- (2,3,5,6-d4-biphenyl-4-yl) naphthalen-1-amine (29.94 g, 100 mmol), 2-bromo-5- (4-iodophenyl) thiophene (40.15 g, 110 mmol ), Pd 2 (dba) 3 (2.75 g, 3 mmol), PPh 3 (2.63 g, 10 mmol), NaO t -Bu (28.9 g, 300 mmol), toluene (970 mL) were obtained from Sub-2-1. In the same manner as in the experimental method, 33.80 g (63%) of a product were obtained.
Sub 3-3 의 합성Synthesis of Sub 3-3
Figure PCTKR2012004631-appb-I000098
Figure PCTKR2012004631-appb-I000098
bis(2',3',4',5',6'-d5-biphenyl-4-yl)amine (33.15 g, 100 mmol), 2,6-dibromopyridine (26.06 g, 110 mmol), Pd2(dba)3 (2.75 g, 3 mmol), PPh3 (2.63 g, 10 mmol), NaOt-Bu (28.9 g, 300mmol), toluene (970 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 31.68 g (65 %)얻었다.bis (2 ', 3', 4 ', 5', 6'-d5-biphenyl-4-yl) amine (33.15 g, 100 mmol), 2,6-dibromopyridine (26.06 g, 110 mmol), Pd 2 ( dba) 3 (2.75 g, 3 mmol), PPh 3 (2.63 g, 10 mmol), NaO t -Bu (28.9 g, 300 mmol), toluene (970 mL) were prepared in the same manner as in the Experiment of Sub-2-1. To give 31.68 g (65%) of the product.
Sub 3-4 의 합성Synthesis of Sub 3-4
Figure PCTKR2012004631-appb-I000099
Figure PCTKR2012004631-appb-I000099
N-phenyl-d5-naphthalen-1-amine (22.43 g, 100 mmol), 2,7-dibromo-9,9-dimethyl fluorene (38.73 g, 110 mmol), Pd2(dba)3 (2.75 g, 3 mmol), PPh3 (2.63 g, 10 mmol), NaOt-Bu (28.9 g, 300mmol), toluene (970 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 34.19 g (69 %)얻었다.N-phenyl-d5-naphthalen-1-amine (22.43 g, 100 mmol), 2,7-dibromo-9,9-dimethyl fluorene (38.73 g, 110 mmol), Pd 2 (dba) 3 (2.75 g, 3 mmol), PPh 3 (2.63 g, 10 mmol), NaO t -Bu (28.9 g, 300 mmol) and toluene (970 mL) were prepared in the same manner as in the Sub-2-1 experiment to obtain 34.19 g (69%). )
Sub 3-5 의 합성Synthesis of Sub 3-5
Figure PCTKR2012004631-appb-I000100
Figure PCTKR2012004631-appb-I000100
N-phenyl-d5-naphthalen-2-amine (22.43 g, 100 mmol), 2,7-dibromo-9,9-diphenyl fluorene (52.38 g, 110 mmol), Pd2(dba)3 (2.75 g, 3 mmol), PPh3 (2.63 g, 10 mmol), NaOt-Bu (28.9 g, 300mmol), toluene (970 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 41.51 g (67 %)얻었다.N-phenyl-d5-naphthalen-2-amine (22.43 g, 100 mmol), 2,7-dibromo-9,9-diphenyl fluorene (52.38 g, 110 mmol), Pd 2 (dba) 3 (2.75 g, 3 mmol), PPh 3 (2.63 g, 10 mmol), NaO t -Bu (28.9 g, 300 mmol) and toluene (970 mL) were prepared in the same manner as in the above Experiment of Sub-2-1 to obtain 41.51 g (67%). )
Sub 3-6 의 합성Synthesis of Sub 3-6
Figure PCTKR2012004631-appb-I000101
Figure PCTKR2012004631-appb-I000101
Sub 2-3 (17.43 g, 100 mmol), 2,7-dibromo-9,9'-spirobi[fluorene] (52.16 g, 110 mmol), Pd2(dba)3 (2.75 g, 3 mmol), PPh3 (2.63 g, 10 mmol), NaOt-Bu (28.9 g, 300mmol), toluene (970 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 38.02 g (67 %)얻었다.Sub 2-3 (17.43 g, 100 mmol), 2,7-dibromo-9,9'-spirobi [fluorene] (52.16 g, 110 mmol), Pd 2 (dba) 3 (2.75 g, 3 mmol), PPh 3 (2.63 g, 10 mmol), NaO t -Bu (28.9 g, 300 mmol) and toluene (970 mL) were obtained in the same manner as in the Experiment of Sub-2-1 to obtain 38.02 g (67%) of the product.
Sub 3-7 의 합성Synthesis of Sub 3-7
Figure PCTKR2012004631-appb-I000102
Figure PCTKR2012004631-appb-I000102
Sub 2-2 (19.22 g, 100 mmol), 2,7-dibromophenanthrene (36.96 g, 110 mmol), Pd2(dba)3 (2.75 g, 3 mmol), PPh3 (2.63 g, 10 mmol), NaOt-Bu (28.9 g, 300mmol), toluene (970 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 29.53 g (66 %)얻었다.Sub 2-2 (19.22 g, 100 mmol), 2,7-dibromophenanthrene (36.96 g, 110 mmol), Pd 2 (dba) 3 (2.75 g, 3 mmol), PPh 3 (2.63 g, 10 mmol), NaO t- Bu (28.9 g, 300 mmol) and toluene (970 mL) were prepared in the same manner as in the Experiment of Sub-2-1 to obtain 29.53 g (66%) of the product.
Sub 3-8 의 합성Synthesis of Sub 3-8
Figure PCTKR2012004631-appb-I000103
Figure PCTKR2012004631-appb-I000103
Sub 2-3 (17.43 g, 100 mmol), 4,4'-dibromobiphenyl (34.32 g, 110 mmol), Pd2(dba)3 (2.75 g, 3 mmol), PPh3 (2.63 g, 10 mmol), NaOt-Bu (28.9 g, 300mmol), toluene (970 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 27.97 g (69 %)얻었다.Sub 2-3 (17.43 g, 100 mmol), 4,4'-dibromobiphenyl (34.32 g, 110 mmol), Pd 2 (dba) 3 (2.75 g, 3 mmol), PPh 3 (2.63 g, 10 mmol), NaO t -Bu (28.9 g, 300 mmol) and toluene (970 mL) were obtained in the same manner as in the Experiments of Sub-2-1 to obtain 27.97 g (69%) of the product.
Sub 3-9 의 합성Synthesis of Sub 3-9
Figure PCTKR2012004631-appb-I000104
Figure PCTKR2012004631-appb-I000104
Sub 2-3 (17.43 g, 100 mmol), 2,6-dibromonaphthalene (31.46 g, 110 mmol), Pd2(dba)3 (2.75 g, 3 mmol), PPh3 (2.63 g, 10 mmol), NaOt-Bu (28.9 g, 300mmol), toluene (970 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 26.17 g (69 %)얻었다.Sub 2-3 (17.43 g, 100 mmol), 2,6-dibromonaphthalene (31.46 g, 110 mmol), Pd 2 (dba) 3 (2.75 g, 3 mmol), PPh 3 (2.63 g, 10 mmol), NaO t- Bu (28.9 g, 300 mmol) and toluene (970 mL) were obtained in the same manner as in the Experiments of Sub-2-1 to obtain 26.17 g (69%) of the product.
Sub 3-10 의 합성Synthesis of Sub 3-10
Figure PCTKR2012004631-appb-I000105
Figure PCTKR2012004631-appb-I000105
Sub 2-3 (17.43 g, 100 mmol), 1,4-dibromonaphthalene (31.46 g, 110 mmol), Pd2(dba)3 (2.75 g, 3 mmol), PPh3 (2.63 g, 10 mmol), NaOt-Bu (28.9 g, 300mmol), toluene (970 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 25.79 g (68 %)얻었다.Sub 2-3 (17.43 g, 100 mmol), 1,4-dibromonaphthalene (31.46 g, 110 mmol), Pd 2 (dba) 3 (2.75 g, 3 mmol), PPh 3 (2.63 g, 10 mmol), NaO t- Bu (28.9 g, 300 mmol) and toluene (970 mL) were obtained in the same manner as in the Experiments of Sub-2-1 to obtain 25.79 g (68%) of the product.
Sub 3-11 의 합성Synthesis of Sub 3-11
Figure PCTKR2012004631-appb-I000106
Figure PCTKR2012004631-appb-I000106
Sub 2-3 (17.43 g, 100 mmol), 1,5-dibromonaphthalene (31.46 g, 110 mmol), Pd2(dba)3 (2.75 g, 3 mmol), PPh3 (2.63 g, 10 mmol), NaOt-Bu (28.9 g, 300mmol), toluene (970 mL) 을 상기 Sub-2-1의 실험방법과 동일하게 하여 생성물을 25.41 g (67 %)얻었다.Sub 2-3 (17.43 g, 100 mmol), 1,5-dibromonaphthalene (31.46 g, 110 mmol), Pd 2 (dba) 3 (2.75 g, 3 mmol), PPh 3 (2.63 g, 10 mmol), NaO t- Bu (28.9 g, 300 mmol) and toluene (970 mL) were obtained in the same manner as in the Experiments of Sub-2-1 to obtain 25.41 g (67%) of the product.
표 2
Figure PCTKR2012004631-appb-T000002
 TABLE 2
Figure PCTKR2012004631-appb-T000002
최종 생성물(Final Product) 합성법 Final Product Synthesis
Figure PCTKR2012004631-appb-I000107
Figure PCTKR2012004631-appb-I000107
Method 1 합성법Method 1 Synthesis
둥근바닥플라스크에 Sub 1 (1 당량), Sub 2 (1 당량), Pd2(dba)3 (0.05 mol%), PPh3 (0.1 당량), NaOt-Bu (3 당량), toluene (10.5 mL / 1 mmol) 을 넣은 후에 100 ℃에서 반응을 진행한다. 반응이 완료되면 에테르와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 실리카겔 칼럼으로 정제 및 재결정하여 생성물을 얻었다.Sub 1 (1 equiv), Sub 2 (1 equiv), Pd 2 (dba) 3 (0.05 mol%), PPh 3 (0.1 equiv), NaO t -Bu (3 equiv), toluene (10.5 mL) / 1 mmol) and then proceed with the reaction at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic was purified and recrystallized by a silica gel column to obtain a product.
Method 2 합성법 Method 2 Synthesis
둥근바닥플라스크에 Sub 1-3 (1당량), Sub 3 (1.1당량), Pd(PPh3)4 (0.05 당량), NaOH (3당량), THF (3 mL / 1 mmol), 물 (1.5 mL / 1 mmol)을 넣는다.In a round bottom flask, Sub 1-3 (1 equiv), Sub 3 (1.1 equiv), Pd (PPh 3 ) 4 (0.05 equiv), NaOH (3 equiv), THF (3 mL / 1 mmol), water (1.5 mL / 1 mmol).
그런 후에 80℃~90℃ 상태에서 가열 환류시킨다. 반응이 완료되면 상온에서 증류수를 넣어 희석시킨다. 그런후에 메틸렌클로라이드와 물로 추출하고 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 실리카겔 칼럼으로 정제 및 재결정하여 생성물을 얻었다.Thereafter, the mixture is heated to reflux at 80 ° C to 90 ° C. After the reaction is completed, distilled water is diluted at room temperature. Thereafter, the mixture was extracted with methylene chloride and water, the organic layer was dried over MgSO 4 , concentrated, and the resulting compound was purified and recrystallized by a silica gel column to obtain a product.
최종적으로 합성된 화합물의 구조분석을 위해 아래와 같이 질량분석법 HRMS 를 측정하였으며, 순도를 확인하기 위하여 시마츠사에 제조된 HPLC(Model, SPB-20A) 를 이용해서 THF 를 Eluent 용매로 사용하여 순도를 측정하였다.Finally, the mass spectrometry HRMS was measured for structural analysis of the synthesized compound, and purity was measured using THF as an eluent solvent using HPLC (Model, SPB-20A) manufactured by Shimadzu Corporation to confirm the purity. It was.
표 3
Figure PCTKR2012004631-appb-T000003
 TABLE 3
Figure PCTKR2012004631-appb-T000003
Figure PCTKR2012004631-appb-I000108
Figure PCTKR2012004631-appb-I000108
화학식 2 화합물의 합성Synthesis of Compound of Formula 2
1) Sub 1b 합성법 예시:1) Sub 1b Synthesis Example:
Figure PCTKR2012004631-appb-I000109
Figure PCTKR2012004631-appb-I000109
Sub 1b-1 의 합성Synthesis of Sub 1b-1
Figure PCTKR2012004631-appb-I000110
Figure PCTKR2012004631-appb-I000110
Aniline-d5 (19.63 g, 200 mmol), bromobenzene (37.68 g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 첨가 한 뒤 24시간 교반 환류시킨다. 반응이 완료되면 에테르와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 실리카겔 칼럼으로 정제 및 재결정하여 생성물을 26.14 g (75 %)얻었다.Aniline-d5 (19.63 g, 200 mmol), bromobenzene (37.68 g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600mmol) and toluene (1930 mL) were added and then stirred at reflux for 24 hours. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO 4 , concentrated, and the resulting organic was purified and recrystallized by a silica gel column to obtain 26.14 g (75%) of the product.
Sub 1b-2 의 합성Synthesis of Sub 1b-2
Figure PCTKR2012004631-appb-I000111
Figure PCTKR2012004631-appb-I000111
Aniline-d5 (19.63 g, 200 mmol), 1-bromonaphthalene (49.70 g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 32.3 g (72 %)얻었다.Aniline-d5 (19.63 g, 200 mmol), 1-bromonaphthalene (49.70 g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were prepared in the same manner as in the Experiment of Sub-1b-1, to obtain 32.3 g (72%) of a product.
Sub 1b-3 의 합성Synthesis of Sub 1b-3
Figure PCTKR2012004631-appb-I000112
Figure PCTKR2012004631-appb-I000112
Aniline-d5 (19.63 g, 200 mmol), 2-bromonaphthalene (49.70 g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 32.3 g (72 %)얻었다.Aniline-d5 (19.63 g, 200 mmol), 2-bromonaphthalene (49.70 g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were prepared in the same manner as in the Experiment of Sub-1b-1, to obtain 32.3 g (72%) of a product.
Sub 1b-4 의 합성Synthesis of Sub 1b-4
Figure PCTKR2012004631-appb-I000113
Figure PCTKR2012004631-appb-I000113
Aniline-d5 (19.63 g, 200 mmol), 4-bromobiphenyl (55.94 g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 36.55 g (73 %)얻었다.Aniline-d5 (19.63 g, 200 mmol), 4-bromobiphenyl (55.94 g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the Experiments of Sub-1b-1, to obtain 36.55 g (73%) of the product.
Sub 1b-5 의 합성Synthesis of Sub 1b-5
Figure PCTKR2012004631-appb-I000114
Figure PCTKR2012004631-appb-I000114
Aniline-d5 (19.63 g, 200 mmol), 2-bromo-5-phenylthiophene (57.39 g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 35.89 g (70 %)얻었다.Aniline-d5 (19.63 g, 200 mmol), 2-bromo-5-phenylthiophene (57.39 g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were prepared in the same manner as in the Sub-1b-1 experiment to obtain 35.89 g (70%) of the product.
Sub 1b-6 의 합성Synthesis of Sub 1b-6
Figure PCTKR2012004631-appb-I000115
Figure PCTKR2012004631-appb-I000115
Aniline-d5 (19.63 g, 200 mmol), 1-bromo-4-methoxybenzene (44.89 g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 29.42 g (72 %)얻었다.Aniline-d5 (19.63 g, 200 mmol), 1-bromo-4-methoxybenzene (44.89 g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were prepared in the same manner as in the Experiments of Sub-1b-1 to obtain 29.42 g (72%) of the product.
Sub 1b-7 의 합성Synthesis of Sub 1b-7
Figure PCTKR2012004631-appb-I000116
Figure PCTKR2012004631-appb-I000116
Aniline-d5 (19.63 g, 200 mmol), 2-bromodibenzo[b,d]furan (59.30 g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 35.95 g (68 %)얻었다.Aniline-d5 (19.63 g, 200 mmol), 2-bromodibenzo [b, d] furan (59.30 g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol ), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were prepared in the same manner as in the Experiments of Sub-1b-1 to obtain 35.95 g (68%) of the product.
Sub 1b-8 의 합성Synthesis of Sub 1b-8
Figure PCTKR2012004631-appb-I000117
Figure PCTKR2012004631-appb-I000117
Aniline-d5 (19.63 g, 200 mmol), 1-bromo-4-fluorobenzene (42 g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 23.84 g (62 %)얻었다.Aniline-d5 (19.63 g, 200 mmol), 1-bromo-4-fluorobenzene (42 g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were prepared in the same manner as in the Sub-1b-1 experiment to obtain 23.84 g (62%) of the product.
Sub 1b-9 의 합성Synthesis of Sub 1b-9
Figure PCTKR2012004631-appb-I000118
Figure PCTKR2012004631-appb-I000118
Aniline-d5 (19.63 g, 200 mmol), 4-bromobenzonitrile (43.68 g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 26.30 g (66 %)얻었다.Aniline-d5 (19.63 g, 200 mmol), 4-bromobenzonitrile (43.68 g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the Experiments of Sub-1b-1, to obtain 26.30 g (66%) of the product.
표 4
Figure PCTKR2012004631-appb-T000004
 Table 4
Figure PCTKR2012004631-appb-T000004
2) Sub 2b 합성법 예시:2) Example of Sub 2b Synthesis:
Figure PCTKR2012004631-appb-I000119
Figure PCTKR2012004631-appb-I000119
Sub 2b-1 의 합성Synthesis of Sub 2b-1
Figure PCTKR2012004631-appb-I000120
Figure PCTKR2012004631-appb-I000120
phenylaniline-d5 (34.85 g, 200 mmol), 4-bromo-4'-iodobiphenyl (86.16 g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 55.13 g (68 %)얻었다.phenylaniline-d5 (34.85 g, 200 mmol), 4-bromo-4'-iodobiphenyl (86.16 g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol) , NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were prepared in the same manner as in the Experiments of Sub-1b-1 to obtain 55.13 g (68%) of the product.
Sub 2b-2 의 합성Synthesis of Sub 2b-2
Figure PCTKR2012004631-appb-I000121
Figure PCTKR2012004631-appb-I000121
N-phenyl-d5-naphthalen-1-amine (44.86g, 200 mmol), 4-bromo-4'-iodobiphenyl (86.16 g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 62.85 g (69 %)얻었다.N-phenyl-d5-naphthalen-1-amine (44.86g, 200 mmol), 4-bromo-4'-iodobiphenyl (86.16 g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the Experiments of Sub-1b-1, to give 62.85 g (69%) of the product.
Sub 2b-3 의 합성Synthesis of Sub 2b-3
Figure PCTKR2012004631-appb-I000122
Figure PCTKR2012004631-appb-I000122
N-phenyl-d5-naphthalen-2-amine (44.86g, 200 mmol), 4-bromo-4'-iodobiphenyl (86.16 g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 61.93 g (68 %)얻었다.N-phenyl-d5-naphthalen-2-amine (44.86g, 200 mmol), 4-bromo-4'-iodobiphenyl (86.16 g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the Experiments of Sub-1b-1 to obtain 61.93 g (68%) of the product.
Sub 2b-4 의 합성Synthesis of Sub 2b-4
Figure PCTKR2012004631-appb-I000123
Figure PCTKR2012004631-appb-I000123
N-phenyl-d5-biphenyl-4-amine (50.07 g, 200 mmol), 4-bromo-4'-iodobiphenyl (86.16 g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 65.48 g (68 %)얻었다.N-phenyl-d5-biphenyl-4-amine (50.07 g, 200 mmol), 4-bromo-4'-iodobiphenyl (86.16 g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the Experiments of Sub-1b-1, to obtain 65.48 g (68%) of the product.
Sub 2b-5 의 합성Synthesis of Sub 2b-5
Figure PCTKR2012004631-appb-I000124
Figure PCTKR2012004631-appb-I000124
N-phenyl-d5-phenylthiophen-2-amine (51.28g, 200 mmol), 4-bromo-4'-iodobiphenyl (86.16 g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 63.37 g (65 %)얻었다.N-phenyl-d5-phenylthiophen-2-amine (51.28g, 200 mmol), 4-bromo-4'-iodobiphenyl (86.16 g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the Sub-1b-1 Experiment to obtain 63.37 g (65%) of the product.
Sub 2b-6 의 합성Synthesis of Sub 2b-6
Figure PCTKR2012004631-appb-I000125
Figure PCTKR2012004631-appb-I000125
N-(4-methoxyphenyl)-aniline-2,3,4,5,6-d5 (40.86g, 200 mmol), 4-bromo-4'-iodobiphenyl (86.16 g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 59.21 g (68 %)얻었다.N- (4-methoxyphenyl) -aniline-2,3,4,5,6-d5 (40.86g, 200 mmol), 4-bromo-4'-iodobiphenyl (86.16 g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were prepared in the same manner as in Sub-1b-1. 59.21 g (68%) was obtained.
Sub 2b-7 의 합성Synthesis of Sub 2b-7
Figure PCTKR2012004631-appb-I000126
Figure PCTKR2012004631-appb-I000126
N-phenyl-d5-dibenzo[b,d]furan-2-amine (52.87 g, 200 mmol), 4-bromo-4'-iodobiphenyl (86.16 g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 64.40 g (65 %)얻었다.N-phenyl-d5-dibenzo [b, d] furan-2-amine (52.87 g, 200 mmol), 4-bromo-4'-iodobiphenyl (86.16 g, 240 mmol), Pd 2 (dba) 3 (5.5 g , 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol), toluene (1930 mL) were prepared in the same manner as in the Experiment of Sub-1b-1, and the product was 64.40 g ( 65%).
Sub 2b-8 의 합성Synthesis of Sub 2b-8
Figure PCTKR2012004631-appb-I000127
Figure PCTKR2012004631-appb-I000127
N-phenyl-d5-4-fluorophenyl-1-amine (38.45 g, 200 mmol), 4-bromo-4'-iodobiphenyl (86.16 g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 56.73 g (67 %)얻었다.N-phenyl-d5-4-fluorophenyl-1-amine (38.45 g, 200 mmol), 4-bromo-4'-iodobiphenyl (86.16 g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol) , PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as the Sub-1b-1 experiment to give 56.73 g (67%) of the product. .
Sub 2b-9 의 합성Synthesis of Sub 2b-9
Figure PCTKR2012004631-appb-I000128
Figure PCTKR2012004631-appb-I000128
4-(phenyl-d5-amino)benzonitrile (39.85 g, 200 mmol), 4-bromo-4'-iodobiphenyl (86.16 g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 59.39 g (69 %)얻었다.4- (phenyl-d5-amino) benzonitrile (39.85 g, 200 mmol), 4-bromo-4'-iodobiphenyl (86.16 g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the Experiments of Sub-1b-1 to obtain 59.39 g (69%) of the product.
표 5
Figure PCTKR2012004631-appb-T000005
 Table 5
Figure PCTKR2012004631-appb-T000005
3) Sub 3b 합성법 예시:3) Sub 3b synthesis example:
Figure PCTKR2012004631-appb-I000129
Figure PCTKR2012004631-appb-I000129
Figure PCTKR2012004631-appb-I000130
Figure PCTKR2012004631-appb-I000130
Figure PCTKR2012004631-appb-I000131
Figure PCTKR2012004631-appb-I000131
Sub 3b-1의 합성Synthesis of Sub 3b-1
Figure PCTKR2012004631-appb-I000132
Figure PCTKR2012004631-appb-I000132
aniline (18.63g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 38.81 g (68 %)얻었다.aniline (18.63 g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56 g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the Sub-1b-1 experiment to obtain 38.81 g (68%) of the product.
Sub 3b-2의 합성Synthesis of Sub 3b-2
Figure PCTKR2012004631-appb-I000133
Figure PCTKR2012004631-appb-I000133
naphthalene-2-anime (28.64g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 45.62 g (68 %)얻었다.naphthalene-2-anime (28.64g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as the Sub-1b-1 experiment to obtain 45.62 g (68%) of the product.
Sub 3b-3의 합성Synthesis of Sub 3b-3
Figure PCTKR2012004631-appb-I000134
Figure PCTKR2012004631-appb-I000134
naphthalene-1-anime (28.64g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 44.95 g (67 %)얻었다.naphthalene-1-anime (28.64g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the Sub-1b-1 experiment to obtain 44.95 g (67%) of the product.
Sub 3b-4의 합성Synthesis of Sub 3b-4
Figure PCTKR2012004631-appb-I000135
Figure PCTKR2012004631-appb-I000135
biphenyl-4-amine (33.84g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 49.88 g (69 %)얻었다.biphenyl-4-amine (33.84g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the Experiments of Sub-1b-1 to obtain 49.88 g (69%) of the product.
Sub 3b-5의 합성Synthesis of Sub 3b-5
Figure PCTKR2012004631-appb-I000136
Figure PCTKR2012004631-appb-I000136
9,9-dimethyl-9H-fluoren-2-amine (41.86 g, 200 mmol), 2-bromo-5-phenylthiophene (57.39 g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 47.78 g (65 %)얻었다.9,9-dimethyl-9H-fluoren-2-amine (41.86 g, 200 mmol), 2-bromo-5-phenylthiophene (57.39 g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as the Experimental Method of Sub-1b-1 to obtain 47.78 g (65%) of the product.
Sub 3b-6의 합성Synthesis of Sub 3b-6
Figure PCTKR2012004631-appb-I000137
Figure PCTKR2012004631-appb-I000137
4-methoxyaniline (24.63g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 43.53 g (69 %)얻었다.4-methoxyaniline (24.63g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the Experiments of Sub-1b-1 to obtain 43.53 g (69%) of the product.
Sub 3b-7의 합성Synthesis of Sub 3b-7
Figure PCTKR2012004631-appb-I000138
Figure PCTKR2012004631-appb-I000138
9,9-dimethyl-9H-fluoren-2-amine (41.86 g, 200 mmol), 2-bromodibenzo[b,d]furan (59.3 g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 47.31 g (63 %)얻었다.9,9-dimethyl-9H-fluoren-2-amine (41.86 g, 200 mmol), 2-bromodibenzo [b, d] furan (59.3 g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol ), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were prepared in the same manner as in Sub-1b-1, and the product was 47.31 g (63%). Got it.
Sub 3b-8의 합성Synthesis of Sub 3b-8
Figure PCTKR2012004631-appb-I000139
Figure PCTKR2012004631-appb-I000139
d5-aniline (32.65g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 38.91 g (67 %)얻었다.d5-aniline (32.65 g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56 g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the Experiments of Sub-1b-1 to obtain 38.91 g (67%) of the product.
Sub 3b-9의 합성Synthesis of Sub 3b-9
Figure PCTKR2012004631-appb-I000140
Figure PCTKR2012004631-appb-I000140
4-phenyl-d5-phenyl-1-amine (34.85 g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 50.58 g (69 %)얻었다.4-phenyl-d5-phenyl-1-amine (34.85 g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol), toluene (1930 mL) were prepared in the same manner as in Sub-1b-1, and the product was 50.58 g (69 %) Got.
Sub 3b-10의 합성Synthesis of Sub 3b-10
Figure PCTKR2012004631-appb-I000141
Figure PCTKR2012004631-appb-I000141
2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), 2-Aminonaphthalene-d7 (30.05g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 45.89 g (67 %)얻었다.2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), 2-Aminonaphthalene-d7 (30.05g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as in the Experiments of Sub-1b-1, to obtain 45.89 g (67%) of the product.
Sub 3b-11의 합성Synthesis of Sub 3b-11
Figure PCTKR2012004631-appb-I000142
Figure PCTKR2012004631-appb-I000142
2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), biphenyl-d9-4-amine (35.66g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 48.91 g (66 %)얻었다.2-bromo-9,9-dimethyl-9H-fluorene (65.56 g, 240 mmol), biphenyl-d9-4-amine (35.66 g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were obtained in the same manner as the Sub-1b-1 experiment to obtain 48.91 g (66%) of the product.
Sub 3b-12의 합성Synthesis of Sub 3b-12
Figure PCTKR2012004631-appb-I000143
Figure PCTKR2012004631-appb-I000143
1-amino-4-phenyl-naphthalene-d6 (45.06g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 53.45 g (64 %)얻었다.1-amino-4-phenyl-naphthalene-d6 (45.06g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were prepared in the same manner as in Sub-1b-1, and the product was 53.45 g (64 %) Got.
Sub 3b-13의 합성Synthesis of Sub 3b-13
Figure PCTKR2012004631-appb-I000144
Figure PCTKR2012004631-appb-I000144
2-amino-6-phenyl-naphthalene-d6 (45.06g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 54.28 g (65 %)얻었다.2-amino-6-phenyl-naphthalene-d6 (45.06g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were prepared in the same manner as in Sub-1b-1, and the product was 54.28 g (65 %) Got.
Sub 3b-14의 합성Synthesis of Sub 3b-14
Figure PCTKR2012004631-appb-I000145
Figure PCTKR2012004631-appb-I000145
4-(naphthalen-1-yl-d7)aniline (45.26 g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 51.90 g (62 %)얻었다.4- (naphthalen-1-yl-d7) aniline (45.26 g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), Pd 2 (dba) 3 (5.5 g , 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol), toluene (1930 mL) were prepared in the same manner as in the Sub-1b-1, and the product was 51.90 g ( 62%).
Sub 3b-15의 합성Synthesis of Sub 3b-15
Figure PCTKR2012004631-appb-I000146
Figure PCTKR2012004631-appb-I000146
2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), 4-(naphthalen-2-yl)aniline-d11 (46.07 g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 53.25 g (63 %)얻었다.2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), 4- (naphthalen-2-yl) aniline-d11 (46.07 g, 200 mmol), Pd 2 (dba) 3 (5.5 g , 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol) and toluene (1930 mL) were prepared in the same manner as in the Sub-1b-1, and the product was 53.25 g ( 63%).
Sub 3b-16의 합성Synthesis of Sub 3b-16
Figure PCTKR2012004631-appb-I000147
Figure PCTKR2012004631-appb-I000147
4-(biphenyl-4-yl-d9)-aniline (50.87 g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 56.28 g (63 %)얻었다.4- (biphenyl-4-yl-d9) -aniline (50.87 g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol), toluene (1930 mL) were prepared in the same manner as in Sub-1b-1, and the product was 56.28 g. Got (63%).
Sub 3b-17의 합성Synthesis of Sub 3b-17
Figure PCTKR2012004631-appb-I000148
Figure PCTKR2012004631-appb-I000148
9,9-dimethyl-9H-fluoren-2-amine (41.86 g, 200 mmol), 4'-bromo-3-phenyl-d5-biphenyl-d4 (76.38 g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 54.49 g (61 %)얻었다.9,9-dimethyl-9H-fluoren-2-amine (41.86 g, 200 mmol), 4'-bromo-3-phenyl-d5-biphenyl-d4 (76.38 g, 240 mmol), Pd 2 (dba) 3 ( 5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol), toluene (1930 mL) were prepared in the same manner as in Sub-1b-1, and the product was 54.49. g (61%) was obtained.
Sub 3b-18의 합성Synthesis of Sub 3b-18
Figure PCTKR2012004631-appb-I000149
Figure PCTKR2012004631-appb-I000149
9,9-dimethyl-9H-fluoren-2-amine (41.86 g, 200 mmol), 2-bromo-5-phenyl-d5-thiophene (57.39 g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 47.69 g (64 %)얻었다.9,9-dimethyl-9H-fluoren-2-amine (41.86 g, 200 mmol), 2-bromo-5-phenyl-d5-thiophene (57.39 g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol), toluene (1930 mL) were prepared in the same manner as in Sub-1b-1, and the product was 47.69 g (64 %) Got.
Sub 3b-19의 합성Synthesis of Sub 3b-19
Figure PCTKR2012004631-appb-I000150
Figure PCTKR2012004631-appb-I000150
9,9-dimethyl-7-phenyl-d5-9H-fluoren-2-amine (58.08g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 64.68 g (67 %)얻었다.9,9-dimethyl-7-phenyl-d5-9H-fluoren-2-amine (58.08g, 200 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol), toluene (1930 mL) are the same as the experimental method of Sub-1b-1. To give 64.68 g (67%) of the product.
Sub 3b-20의 합성Synthesis of Sub 3b-20
Figure PCTKR2012004631-appb-I000151
Figure PCTKR2012004631-appb-I000151
2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), 7-(phenyl-d5)-9,9-diphenyl-9H-fluoren-2-amine (82.91g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 78.88 g (65 %)얻었다.2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), 7- (phenyl-d5) -9,9-diphenyl-9H-fluoren-2-amine (82.91g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol), toluene (1930 mL) were tested for Sub-1b-1. In the same manner to give 78.88 g (65%) of the product.
Sub 3b-21의 합성Synthesis of Sub 3b-21
Figure PCTKR2012004631-appb-I000152
Figure PCTKR2012004631-appb-I000152
2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), 7-(phenyl-d5)-9,9' spirobi[fluoren]-2-amine (82.51g, 200 mmol), Pd2(dba)3 (5.5 g, 6 mmol), PPh3 (5.25 g, 20 mmol), NaOt-Bu (57.7 g, 600mmol), toluene (1930 mL) 을 상기 Sub-1b-1의 실험방법과 동일하게 하여 생성물을 72.57 g (60 %)얻었다.2-bromo-9,9-dimethyl-9H-fluorene (65.56g, 240 mmol), 7- (phenyl-d5) -9,9 'spirobi [fluoren] -2-amine (82.51g, 200 mmol), Pd 2 (dba) 3 (5.5 g, 6 mmol), PPh 3 (5.25 g, 20 mmol), NaO t -Bu (57.7 g, 600 mmol), toluene (1930 mL) and the experimental method of Sub-1b-1 In the same manner, 72.57 g (60%) of a product were obtained.
표 6
Figure PCTKR2012004631-appb-T000006
 Table 6
Figure PCTKR2012004631-appb-T000006
최종 생성물(Final Product) 합성법 예시Example of Final Product Synthesis
Figure PCTKR2012004631-appb-I000153
Figure PCTKR2012004631-appb-I000153
둥근바닥플라스크에 Sub2b의 화합물 (1.2당량), Sub3b의 화합물 (1당량), Pd2(dba)3 (0.06~0.1 mmol), PPh3 (0.2당량), NaOt-Bu (6당량), toluene (10.5 mL / 1 mmol)을 넣은 후에 100 ℃에서 반응을 진행한다. 반응이 완료되면 에테르와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 실리카겔 칼럼으로 정제 및 재결정하여 생성물을 얻었다.Compound of Sub2b (1.2 equiv), Compound of Sub3b (1 equiv), Pd 2 (dba) 3 (0.06 ~ 0.1 mmol), PPh 3 (0.2 equiv), NaO t -Bu (6 equiv), toluene (10.5 mL / 1 mmol) was added and the reaction proceeds at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic was purified and recrystallized by a silica gel column to obtain a product.
표 7
Figure PCTKR2012004631-appb-T000007
 TABLE 7
Figure PCTKR2012004631-appb-T000007
Figure PCTKR2012004631-appb-I000154
Figure PCTKR2012004631-appb-I000154
한편, 화학식 1 또는 화학식 2로 표시되는 화합물들의 각 치환기들은 광범위한 관계로, 대표적인 화합물들의 합성예를 예시적으로 설명하였으나, 합성예로 예시적으로 설명하지 않은 화학식 1 또는 화학식 2로 표시되는 화합물들도 본 명세서의 일부를 구성할 수 있다.On the other hand, each of the substituents of the compounds represented by the formula (1) or (2) is a broad relationship, the compounds represented by the formula (1) or formula (2) that is illustratively described a synthesis example of representative compounds, but not illustratively described as a synthesis example Also part of the present specification.
또한, 상기와 같은 구조의 코어 구조에 다양한 치환기를 도입함으로써 도입된 치환기의 고유 특성을 갖는 화합물을 합성할 수 있다. 예컨대, 유기발광소자를 비롯한 유기전기소자의 제조시 사용되는 정공주입층 물질, 정공수송층 물질, 발광층 물질, 및 전자 수송층 물질에 사용되는 치환기를 상기 구조에 도입함으로써 각 유기물층에서 요구하는 조건들을 충족시키는 물질을 제조할 수 있다.Moreover, the compound which has the intrinsic property of the introduced substituent can be synthesize | combined by introducing various substituents into the core structure of the above structure. For example, by introducing substituents used in the hole injection layer material, the hole transport layer material, the light emitting layer material, and the electron transport layer material used in the manufacture of the organic electric device, including the organic light emitting device to satisfy the conditions required for each organic material layer Materials can be prepared.
본 발명에 따른 화합물은 치환기의 종류 및 성질에 따라 유기전기발광소자에서 다양한 용도로 사용될 수 있다.The compound according to the present invention can be used for various purposes in the organic electroluminescent device according to the type and nature of the substituent.
본 발명의 화합물은 코어와 치환체에 의해 조절이 자유롭기 때문에 인광 또는 형광 발광층의 호스트 이외의 다양한 층으로 작용할 수 있다.The compounds of the present invention can act as various layers other than the host of the phosphorescent or fluorescent light emitting layer because they are freely controlled by the core and the substituents.
본 발명의 유기전기소자는 전술한 화합물들을 이용하여 한층 이상의 유기물층을 형성하는 것을 제외하고는, 통상의 유기전기소자의 제조방법 및 재료에 의하여 제조될 수 있다.The organic electric device of the present invention may be manufactured by a conventional method and material for manufacturing an organic electric device except for forming one or more organic material layers using the above-described compounds.
본 발명의 화합물들을 유기전기발광소자의 다른 유기물층들, 예를 들어 발광 보조층, 전자주입층, 전자수송층, 및 정공주입층에 사용되더라도 동일한 효과를 얻을 수 있는 것은 자명하다.When the compounds of the present invention are used in other organic material layers of the organic electroluminescent device, for example, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer, it is obvious that the same effect can be obtained.
한편 본 발명의 화합물은 용액 공정(soluble process)에 사용될 수 있다. 다시 말해 상기 화합물을 용액 공정(soluble process)에 의해 후술할 유기전기소자의 유기물층을 형성할 수 있다. 즉 상기 화합물을 유기물층으로 사용할 때 유기물층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용액 공정 또는 솔벤트 프로세스(solvent process), 예컨대 스핀 코팅, 딥 코팅, 닥터 블레이딩, 스크린 프린팅, 잉크젯 프린팅 또는 열 전사법 등의 방법에 의하여 더 적은 수의 층으로 제조될 수 있다.Meanwhile, the compound of the present invention can be used in a soluble process. In other words, the compound may form an organic material layer of the organic electronic device, which will be described later, by a solution process. In other words, when the compound is used as an organic material layer, the organic material layer may be formed by using various polymer materials, rather than a solution process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be produced in fewer layers by the method.
본 발명의 화합물들이 사용될 수 있는 유기전기소자는 예를 들어, 유기전기발광소자(OLED), 유기태양전지, 유기감광체(OPC) 드럼, 유기트랜지스트(유기 TFT) 등이 있다.Organic electroluminescent devices in which the compounds of the present invention may be used include, for example, organic electroluminescent devices (OLEDs), organic solar cells, organic photoconductor (OPC) drums, organic transistors (organic TFTs), and the like.
본 발명의 화합물들이 적용될 수 있는 유기전기소자 중 일예로 유기전기발광소자(OLED)에 대하여 설명하나, 본 발명은 이에 제한되지 않고 다양한 유기전기소자에 위에서 설명한 화합물들이 적용될 수 있다.As an example of the organic electroluminescent device to which the compounds of the present invention can be applied, an organic electroluminescent device (OLED) will be described. However, the present invention is not limited thereto, and the above-described compounds may be applied to various organic electroluminescent devices.
본 발명의 다른 실시예는 제1 전극, 제2 전극 및 이들 전극 사이에 배치된 유기물층을 포함하는 유기전기소자에 있어서, 상기 유기물층 중 1층 이상이 본 발명의 화합물들을 포함하는 유기전기발광소자를 제공한다.Another embodiment of the present invention is an organic electroluminescent device comprising a first electrode, a second electrode and an organic material layer disposed between the electrodes, wherein at least one of the organic material layer comprises an organic electroluminescent device comprising the compounds of the present invention to provide.
도 1 내지 도 6은 본 발명의 화합물을 적용할 수 있는 유기전기발광소자의 예를 도시한 것이다.1 to 6 show examples of the organic electroluminescent device to which the compound of the present invention can be applied.
본 발명의 다른 실시예에 따른 유기전기발광소자는, 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층을 포함하는 유기물층 중 1층 이상을 본 발명의 화합물을 포함하도록 형성하는 것을 제외하고는, 당 기술 분야에 통상의 제조 방법 및 재료를 이용하여 당 기술 분야에 알려져 있는 구조로 제조될 수 있다.The organic electroluminescent device according to another embodiment of the present invention, except that at least one layer of the organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer to include the compound of the present invention. Can be prepared with a structure known in the art using conventional manufacturing methods and materials in the art.
본 발명에 다른 실시예에 따른 유기전기발광소자의 구조는 도 1 내지 6에 예시되어 있으나, 이들 구조에만 한정된 것은 아니다. 이때, 도면번호 101은 기판, 102는 양극, 103은 정공주입층(HIL), 104는 정공수송층(HTL), 105는 발광층(EML), 106은 전자주입층(EIL), 107은 전자수송층(ETL), 108은 음극을 나타낸다. The structure of the organic electroluminescent device according to another embodiment of the present invention is illustrated in Figures 1 to 6, but is not limited to these structures. In this case, reference numeral 101 denotes a substrate, 102 an anode, 103 a hole injection layer (HIL), 104 a hole transport layer (HTL), 105 a light emitting layer (EML), 106 an electron injection layer (EIL), 107 an electron transport layer ( ETL), 108 represents a negative electrode.
미도시하였지만, 이러한 유기전기발광소자는 정공의 이동을 저지하는 정공저지층(HBL), 전자의 이동을 저지하는 전자저지층(EBL), 발광을 돕거나 보조하는 발광보조층 및 보호층이 더 위치할 수도 있다. 보호층의 경우 최상위층에서 유기물층을 보호하거나 음극을 보호하도록 형성될 수 있다.Although not shown, the organic electroluminescent device further includes a hole blocking layer (HBL) that prevents the movement of holes, an electron blocking layer (EBL) that prevents the movement of electrons, a light emitting auxiliary layer that helps or assists light emission, and a protective layer. It may be located. The protective layer may be formed to protect the organic material layer or the cathode at the uppermost layer.
이때, 본 발명의 화합물은 정공주입층, 정공수송층, 발광층 및 전자수송층을 포함하는 유기물층 중 하나 이상에 포함될 수 있다.In this case, the compound of the present invention may be included in one or more of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer.
구체적으로, 본 발명의 화합물은 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층, 정공저지층, 전자저지층, 발광보조층 및 보호층 중 하나 이상을 대신하여 사용되거나 이들과 함께 층을 형성하여 사용될 수도 있다. 물론 유기물층 중 한층에만 사용되는 것이 아니라 두층 이상에 사용될 수 있다.Specifically, the compound of the present invention is used in place of or in combination with one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer and a protective layer It may be used to form. Of course, the organic layer may be used not only in one layer but also in two or more layers.
특히, 본 발명의 화합물에 따라서 정공주입 재료, 정공수송 재료, 전자주입 재료, 전자수송 재료, 발광 재료 및 패시베이션(케핑) 재료로 사용될 수 있고, 특히 단독으로 발광물질 및 호스트/도판트에서 호스트 또는 도판트로 사용될 수 있으며, 정공 주입, 정공수송층으로 사용될 수 있다.In particular, it can be used as a hole injection material, a hole transport material, an electron injection material, an electron transport material, a luminescent material and a passivation (kepping) material according to the compound of the present invention, in particular a host or in a luminescent material and host / dopant alone Can be used as a dopant, can be used as a hole injection, a hole transport layer.
예컨대, 본 발명의 다른 실시예에 따른 유기전기발광소자는 스퍼터링(sputtering)이나 전자빔 증발(e-beam evaporation)과 같은 PVD(physical vapor deposition) 방법을 이용하여, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고, 그 위에 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층을 포함하는 유기물층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다.For example, the organic electroluminescent device according to another embodiment of the present invention is a metal having metal or conductivity on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. An oxide or an alloy thereof is deposited to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer is formed thereon, and then a material that can be used as a cathode is deposited thereon. Can be prepared.
이와 같은 방법 외에도, 기판 상에 음극 물질부터 유기물층, 양극 물질을 차례로 증착시켜 유기전기소자를 만들 수도 있다. 상기 유기물층은 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 등을 포함하는 다층 구조일 수도 있으나, 이에 한정되지 않고 단층 구조일 수 있다. In addition to the above method, an organic electronic device may be fabricated by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, but is not limited thereto and may have a single layer structure.
또한, 상기 유기물층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용액 공정 또는 솔벤트 프로세스(solvent process), 예컨대 스핀 코팅, 딥 코팅, 닥터 블레이딩, 스크린 프린팅, 잉크젯 프린팅 또는 열 전사법 등의 방법에 의하여 더 적은 수의 층으로 제조할 수 있다.In addition, the organic layer may be formed using a variety of polymer materials, but not by a deposition process or a solvent process, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be made with a small number of layers.
본 발명의 다른 실시예에 따른 유기전기발광소자는 위에서 설명한 화합물을 스핀 코팅(spin coating)이나 잉크젯(ink jet) 공정과 같은 용액 공정(soluble process)에 사용될 수도 있다.The organic electroluminescent device according to another embodiment of the present invention may be used in a solution process such as spin coating or ink jet process.
기판은 유기전기발광소자의 지지체이며, 실리콘 웨이퍼, 석영 또는 유리판, 금속판, 플라스틱 필름이나 시트 등이 사용될 수 있다.The substrate is a support of the organic electroluminescent device, and a silicon wafer, a quartz or glass plate, a metal plate, a plastic film or sheet, or the like can be used.
기판 위에는 양극이 위치된다. 이러한 양극은 그 위에 위치되는 정공주입층으로 정공을 주입한다. 양극 물질로는 통상 유기물층으로 정공주입이 원활할 수 있도록 일함수가 큰 물질일 수 있다. 본 발명에서 사용될 수 있는 양극 물질의 구체적인 예로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연산화물, 인듐산화물, 인듐주석 산화물(ITO), 인듐아연산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SnO2:Sb와 같은 금속과 산화물의 조합; 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다.An anode is positioned over the substrate. This anode injects holes into the hole injection layer located thereon. The positive electrode material may be a material having a large work function to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention 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 oxides with metals such as ZnO: Al or SnO 2: Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline, and the like, but are not limited thereto.
양극 위에는 정공주입층이 위치된다. 이러한 정공주입층의 물질로 요구되는 조건은 양극으로부터의 정공주입 효율이 높으며, 주입된 정공을 효율적으로 수송할 수 있어야 한다. 이를 위해서는 이온화 포텐셜이 작고 가시광선에 대한 투명성이 높으며, 정공에 대한 안정성이 우수해야 한다.The hole injection layer is located on the anode. The conditions required for the material of the hole injection layer are high hole injection efficiency from the anode, it should be able to transport the injected holes efficiently. This requires a small ionization potential, high transparency to visible light, and excellent hole stability.
정공주입 물질로는 낮은 전압에서 양극으로부터 정공을 잘 주입받을 수 있는 물질로서, 정공주입 물질의 HOMO(highest occupied molecular orbital)가 양극 물질의 일함수와 주변 유기물층의 HOMO 사이일 수 있다. 정공주입 물질의 구체적인 예로는 금속 포피린(porphyrine), 올리고티오펜, 아릴아민 계열의 유기물, 헥사니트릴 헥사아자트리페닐렌, 퀴나크리돈(quinacridone) 계열의 유기물, 페릴렌(perylene) 계열의 유기물, 안트라퀴논 및 폴리아닐린과 폴리티오펜 계열의 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다.The hole injection material is a material that can be injected well from the anode at a low voltage, the highest occupied molecular orbital (HOMO) of the hole injection material may be between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene, quinacridone-based organics, perylene-based organics, Anthraquinone, polyaniline and polythiophene-based conductive polymers, but are not limited thereto.
상기 정공주입층 위에는 정공수송층이 위치된다. 이러한 정공수송층은 정공주입층으로부터 정공을 전달받아 그 위에 위치되는 유기발광층으로 수송하는 역할을 하며, 높은 정공 이동도와 정공에 대한 안정성 및 전자를 막아주는 역할를 한다. 이러한 일반적 요구 이외에 차체 표시용으로 응용할 경우 소자에 대한 내열성이 요구되며, 유리 전이 온도(Tg)가 70 ℃ 이상의 값을 갖는 재료일 수 있다.The hole transport layer is positioned on the hole injection layer. The hole transport layer receives holes from the hole injection layer and transports the holes to the organic light emitting layer located thereon, and serves to prevent high hole mobility, hole stability, and electrons. In addition to these general requirements, applications for vehicle body display require heat resistance to the device, and may be a material having a glass transition temperature (Tg) of 70 ° C. or higher.
이와 같은 조건을 만족하는 물질들로는 NPD(혹은 NPB라 함), 스피로-아릴아민계화합물, 페릴렌-아릴아민계화합물, 아자시클로헵타트리엔화합물, 비스(디페닐비닐페닐)안트라센, 실리콘게르마늄옥사이드화합물, 실리콘계아릴아민화합물 등이 될 수 있다.Materials satisfying these conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene and silicon germanium oxide. Compound, a silicon-based arylamine compound, and the like.
정공수송층 위에는 유기발광층이 위치된다. 이러한 유기발광층는 양극과 음극으로부터 각각 주입된 정공과 전자가 재결합하여 발광을 하는 층이며, 양자효율이 높은 물질로 이루어져 있다. 발광 물질로는 정공수송층과 전자수송층으로부터 정공과 전자를 각각 수송받아 결합시킴으로써 가시광선 영역의 빛을 낼 수 있는 물질로서, 형광이나 인광에 대한 양자효율이 좋은 물질일 수 있다.The organic light emitting layer is positioned on the hole transport layer. The organic light emitting layer is a layer for emitting light by recombination of holes and electrons injected from the anode and the cathode, respectively, and is made of a material having high quantum efficiency. The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and may be a material having good quantum efficiency for fluorescence or phosphorescence.
이와 같은 조건을 만족하는 물질 또는 화합물로는 녹색의 경우 Alq3가, 청색의 경우 Balq(8-hydroxyquinoline beryllium salt), DPVBi(4,4'-bis(2,2-diphenylethenyl)-1,1'-biphenyl) 계열, 스피로(Spiro) 물질, 스피로-DPVBi(Spiro-4,4'-bis(2,2-diphenylethenyl)-1,1'-biphenyl), LiPBO(2-(2-benzoxazoyl)-phenollithium salt), 비스(디페닐비닐페닐비닐)벤젠, 알루미늄-퀴놀린 금속착체, 이미다졸, 티아졸 및 옥사졸의 금속착체 등이 있으며, 청색 발광 효율을 높이기 위해 페릴렌, 및 BczVBi(3,3'[(1,1'-biphenyl)-4,4'-diyldi-2,1-ethenediyl]bis(9-ethyl)-9H-carbazole; DSA(distrylamine)류)를 소량 도핑하여 사용할 수 있다. 적색의 경우는 녹색 발광 물질에 DCJTB([2-(1,1-dimethylethyl)-6-[2-(2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H-benzo(ij)quinolizin-9-yl)ethenyl]-4H-pyran-4-ylidene]-propanedinitrile)와 같은 물질을 소량 도핑하여 사용할 수 있다. Substances or compounds that satisfy these conditions include Alq3 for green, Balq (8-hydroxyquinoline beryllium salt) for blue, DPVBi (4,4'-bis (2,2-diphenylethenyl) -1,1'- biphenyl) series, Spiro material, Spiro-DPVBi (Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazoyl) -phenollithium salt ), Bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complex, metal complexes of imidazole, thiazole and oxazole, and the like, perylene, and BczVBi (3,3 '[ (1,1'-biphenyl) -4,4'-diyldi-2,1-ethenediyl] bis (9-ethyl) -9H-carbazole; DSA (distrylamine) can be used by doping in small amounts. In the case of red, DCJTB ([2- (1,1-dimethylethyl) -6- [2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H Small amounts of doping such as -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile) can be used.
잉크젯프린팅, 롤코팅, 스핀코팅 등의 공정을 사용하여 발광층을 형성할 경우에, 폴리페닐렌비닐렌(PPV) 계통의 고분자나 폴리 플루오렌(poly fluorene) 등의 고분자를 유기발광층에 사용할 수 있다.When forming a light emitting layer using a process such as inkjet printing, roll coating, or spin coating, a polymer of polyphenylene vinylene (PPV) -based polymer or poly fluorene may be used for the organic light emitting layer. .
유기발광층 위에는 전자수송층이 위치된다. 이러한 전자수송층은 그 위에 위치되는 음극으로부터 전자주입 효율이 높고 주입된 전자를 효율적으로 수송할 수 있는 물질이 필요하다. 이를 위해서는 전자 친화력과 전자 이동속도가 크고 전자에 대한 안정성이 우수한 물질로 이루어져야 한다. The electron transport layer is positioned on the organic light emitting layer. The electron transport layer needs a material having high electron injection efficiency from the cathode positioned thereon and capable of efficiently transporting the injected electrons. To this end, it must be made of a material having high electron affinity and electron transfer speed and excellent stability to electrons.
이와 같은 조건을 충족시키는 전자수송 물질로는 구체적인 예로 8-히드록시퀴놀린의 Al 착물; Alq3를 포함한 착물; 유기 라디칼 화합물; 히드록시플라본-금속 착물 등이 있으나, 이들에만 한정되는 것은 아니다.Examples of the electron transport material that satisfies such conditions include Al complexes of 8-hydroxyquinoline; Complexes including Alq3; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.
전자수송층 위에는 전자주입층이 적층된다. 전자주입층은 Balq, Alq3,Be(bq)2, Zn(BTZ)2, Zn(phq)2, PBD, spiro-PBD, TPBI, Tf-6P 등과 같은 금속착제화합물, imidazole ring 을 갖는 aromatic 화합물이나 boron화합물 등을 포함하는 저분자 물질을 이용하여 제작할 수 있다. 이때, 전자주입층은 100Å ~ 300Å의 두께 범위에서 형성될 수 있다.The electron injection layer is stacked on the electron transport layer. The electron injection layer is a metal complex compound such as Balq, Alq3, Be (bq) 2, Zn (BTZ) 2, Zn (phq) 2, PBD, spiro-PBD, TPBI, Tf-6P, aromatic compound with imidazole ring, It can be produced using a low molecular weight material containing boron compounds and the like. At this time, the electron injection layer may be formed in a thickness range of 100 ~ 300Å.
전자주입층 위에는 음극이 위치된다. 이러한 음극은 전자를 주입하는 역할을 한다. 음극으로 사용하는 재료는 양극에 사용된 재료를 이용하는 것이 가능하며, 효율적인 전자주입을 위해서는 일 함수가 낮은 금속일 수 있다. 특히 주석, 마그네슘, 인듐, 칼슘, 나트륨, 리튬, 알루미늄, 은 등의 적당한 금속, 또는 그들의 적절한 합금이 사용될 수 있다. 또한 100 ㎛ 이하 두께의 리튬플루오라이드와 알루미늄, 산화리튬과 알루미늄, 스트론튬산화물과 알루미늄 등의 2 층 구조의 전극도 사용될 수 있다.The cathode is positioned on the electron injection layer. This cathode serves to inject electrons. The material used as the cathode may use the material used for the anode, and may be a metal having a low work function for efficient electron injection. In particular, a suitable metal such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or a suitable alloy thereof can be used. In addition, electrodes having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum having a thickness of 100 μm or less may also be used.
전술하였듯이, 본 발명의 화합물에 따라서 적색, 녹색, 청색, 흰색 등의 모든 칼라의 형광과 인광소자에 적합한 정공주입 재료, 정공수송 재료, 발광 재료, 전자수송 재료 및 전자주입 재료로 사용할 수 있으며, 다양한 색의 호스트 또는 도판트 물질로 사용될 수 있다.As described above, according to the compound of the present invention, it can be used as a hole injection material, a hole transport material, a light emitting material, an electron transport material, and an electron injection material suitable for fluorescence and phosphorescent devices of all colors such as red, green, blue, and white, It can be used as a host or dopant material of various colors.
본 발명에 따른 유기전기발광소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic electroluminescent device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used.
한편 본 발명은, 위에서 설명한 유기전기소자를 포함하는 디스플레이장치와, 이 디스플레이장치를 구동하는 제어부를 포함하는 단말을 포함한다. 이 단말은 현재 또는 장래의 유무선 통신단말을 의미한다. 이상에서 전술한 본 발명에 따른 단말은 휴대폰 등의 이동 통신 단말기일 수 있으며, PDA, 전자사전, PMP, 리모콘, 네비게이션, 게임기, 각종 TV, 각종 컴퓨터 등 모든 단말을 포함한다.Meanwhile, the present invention includes a display device including the organic electric element described above, and a terminal including a control unit for driving the display device. This terminal means a current or future wired or wireless communication terminal. The terminal according to the present invention described above may be a mobile communication terminal such as a mobile phone, and includes all terminals such as a PDA, an electronic dictionary, a PMP, a remote control, a navigation device, a game machine, various TVs, various computers, and the like.
유기전기소자의 제조 평가Manufacturing Evaluation of Organic Electrical Device
합성을 통해 얻은 본 발명의 여러 화합물을 각각 발광층의 발광 호스트 물질이나 정공 수송층으로 사용하여 통상적인 방법에 따라 유기전기발광소자를 제작하였다. 먼저, 유기 기판에 형성된 ITO층(양극)위에 우선 정공 주입층으로서 2-TNATA 막을 진공증착하여 10nm 두께로 형성하였다. 이어서 본 발명의 화합물(화학식1, 화학식2의 화합물)을 20nm 두께로 진공 증착하여 정공 수송층을 형성하였다. 이후, BD-052X(Idemitsu사)를 발광 도펀트로 사용하고 호스트 물질은9, 10-다이-(나프탈렌-2-안트라센)=AND]을 사용하였으며, 도핑 농도는 4%로 고정하여 비교 실험을 진행 하였다. 이어서 전자주입층으로 트리스(8-퀴놀리놀)알루미늄을 40 nm의 두께로 성막하였다. 이후, 할로겐화 알킬리 금속인 LiF를 0.2 nm의 두께로 증착하고, 이어서 Al을 150 nm의 두께로 증착하여 이 Al/LiF를 음극으로 사용하여 유기전기발광소자를 제조하였다.Various compounds of the present invention obtained through synthesis were used as light emitting host materials or hole transport layers, respectively, to fabricate organic electroluminescent devices according to a conventional method. First, a 2-TNATA film was vacuum-deposited as a hole injection layer on the ITO layer (anode) formed on the organic substrate, and formed into a thickness of 10 nm. Subsequently, the compound of the present invention (compounds 1 and 2) was vacuum deposited to a thickness of 20 nm to form a hole transport layer. Subsequently, BD-052X (Idemitsu Co., Ltd.) was used as a light emitting dopant and the host material was 9, 10-di- (naphthalene-2-anthracene) = AND], and the doping concentration was fixed at 4%. It was. Subsequently, tris (8-quinolinol) aluminum was deposited to a thickness of 40 nm with an electron injection layer. Subsequently, LiF, an alkyl halide metal, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm to prepare an organic electroluminescent device using this Al / LiF as a cathode.
비교예Comparative example
상기와 같은 방법으로 유기전기소자를 제작하되, 정공수송층 물질로 하기 화합물을 사용하였다. An organic electric device was manufactured in the same manner as above, but the following compound was used as the hole transport layer material.
Figure PCTKR2012004631-appb-I000155
Figure PCTKR2012004631-appb-I000155
한편, 상기와 같은 방법에 의해 제조된 본 발명의 유기전기발광소자 및 비교예의 유기전기발광소자에 순바이어스 직류전압을 가하여 포토리서치(photoresearch)사의 PR-650으로 전기발광(EL) 특성을 측정하였다. 300cd/m2 기준 휘도에서 맥사이언스사에서 제조된 수명 측정 장비를 통해 T90 수명을 측정하였는데, 그 결과는 하기 표와 같다.On the other hand, by applying a forward bias DC voltage to the organic electroluminescent device of the present invention and the organic electroluminescent device of the comparative example prepared by the method as described above, the electroluminescence (EL) characteristics were measured by PR-650 of photoresearch company . The T90 lifetime was measured using a life-time measurement device manufactured by McScience Inc. at 300 cd / m 2 reference luminance. The results are shown in the following table.
[표 8]TABLE 8
화학식 1의 화합물Compound of Formula 1
Figure PCTKR2012004631-appb-I000156
Figure PCTKR2012004631-appb-I000156
Figure PCTKR2012004631-appb-I000157
Figure PCTKR2012004631-appb-I000157
Figure PCTKR2012004631-appb-I000158
Figure PCTKR2012004631-appb-I000158
Figure PCTKR2012004631-appb-I000159
Figure PCTKR2012004631-appb-I000159
[표 9]TABLE 9
화학식 2의 화합물Compound of formula (2)
Figure PCTKR2012004631-appb-I000160
Figure PCTKR2012004631-appb-I000160
Figure PCTKR2012004631-appb-I000161
Figure PCTKR2012004631-appb-I000161
Figure PCTKR2012004631-appb-I000162
Figure PCTKR2012004631-appb-I000162
상기 표 8 및 표 9의 비교예와 실시예의 결과를 비교하면, 비교예 1, 2, 3에 비해 중수소로 치환된 실시예 화합물들의 구동전압이 떨어지는 특성을 나타내며, 구동전압 하강뿐만 아니라 발광효율 및 수명에서도 높은 결과를 나타내고 있다.Comparing the results of Comparative Examples and Examples of Tables 8 and 9, the driving voltages of the example compounds substituted with deuterium are lower than those of Comparative Examples 1, 2, and 3, and the luminous efficiency and The results are high even in the lifetime.
또한, 중소수 치환효과를 알아보기 위하여 하기 3가지 화합물로 실험한 결과 도 7내지 도 9의 결과를 얻었다. In addition, the results of experiments with the following three compounds in order to determine the small- and medium-substituted effect was obtained in the results of FIGS.
한편, 중수소가 도입된 경우와 도입되지 않은 경우 등의 소자 특성을 비교하기 위하여 하기 화합물로 실험한 결과 도 7 내지 도 9와 같은 결과를 얻었다. 도 7 내지 도 9는 각각 중수소가 도입된 본 발명의 화합물과 중수소가 도입되지 않은 화합물의 휘도, 전류밀도 및 효율을 비교한 그래프이다.On the other hand, in order to compare the device characteristics, such as when deuterium is introduced and when not introduced, the results as shown in Figures 7 to 9 as a result of the experiment with the following compound. 7 to 9 are graphs comparing the brightness, current density and efficiency of the compounds of the present invention to which deuterium is introduced and the compounds to which deuterium is not introduced, respectively.
Figure PCTKR2012004631-appb-I000163
Figure PCTKR2012004631-appb-I000163
도 7 내지 도 9를 참조하면, 아릴기에 중수소 도입시 말단의 아릴기에 도입한 경우(P-71 화합물) 휘도, 전류밀도 및 효율이 가장 우수함을 알 수 있다. 이로써, 중수소를 도입하지 않은 화합물(샘플 B)보다 중수소를 도입한 화합물(P-71, 샘플 A)의 소자 특성이 우수하고, 중수소를 도입시 말단의 아릴기에 도입한 경우 소자 특성이 가장 우수함을 알 수 있다. 7 to 9, when deuterium is introduced into the aryl group, when introduced into the aryl group (P-71 compound), it can be seen that the brightness, current density, and efficiency are the best. As a result, the device characteristics of the compound (P-71, Sample A) in which deuterium was introduced are superior to the compound without the introduction of deuterium (Sample B). Able to know.
한편, 비교적 높은 열안정성 및 낮은 구동전압과 높은 수명을 나타내고 있는 실시예 (70), 실시예 (71), 실시예 (72)를 이용하여 [표 9]의 물질과 50 : 50으로 혼합한 정공 수송층을 사용, 상기와 동일하게 소자를 만들어 하기와 같은 소자평가 결과를 얻었다. On the other hand, the hole mixed with the material of [Table 9] by 50:50 using Example 70, Example 71, and Example 72 which show comparatively high thermal stability, low drive voltage, and high lifetime. Using the transport layer, a device was formed in the same manner as above, and the following device evaluation results were obtained.
표 10
Figure PCTKR2012004631-appb-T000008
 Table 10
Figure PCTKR2012004631-appb-T000008
Figure PCTKR2012004631-appb-I000164
Figure PCTKR2012004631-appb-I000164
Figure PCTKR2012004631-appb-I000165
Figure PCTKR2012004631-appb-I000165
Figure PCTKR2012004631-appb-I000166
Figure PCTKR2012004631-appb-I000166
Figure PCTKR2012004631-appb-I000167
Figure PCTKR2012004631-appb-I000167
Figure PCTKR2012004631-appb-I000168
Figure PCTKR2012004631-appb-I000168
Figure PCTKR2012004631-appb-I000169
Figure PCTKR2012004631-appb-I000169
Figure PCTKR2012004631-appb-I000170
Figure PCTKR2012004631-appb-I000170
Figure PCTKR2012004631-appb-I000171
Figure PCTKR2012004631-appb-I000171
Figure PCTKR2012004631-appb-I000172
Figure PCTKR2012004631-appb-I000172
상기 [표 8]에서 비교예 화합물 (1) 인 NPB와 가장 좋은 결과를 나타내었던 실시예 70, 실시예 71, 실시예 72를 [표 10]에서 비교예로 정하고 P-70, P-71, P-72와 [표 9]의 다른 화합물들을 50:50으로 혼합한 혼합물을 정공 수송층으로 사용하여 비교 소자평가를 측정한 결과 단일화합물을 정공 수송층으로 사용했을 때보다 낮은 구동전압과 높은 효율, 수명이 월등하게 좋아지는 것을 확인할 수 있었다. Example 70, Example 71, and Example 72, which showed the best results with NPB of Comparative Example Compound (1) in [Table 8], were determined as Comparative Examples in [Table 10], and P-70, P-71, Comparative device evaluation was carried out using a mixture of P-72 and other compounds in Table 9 as 50:50 as the hole transport layer. We can see that this is getting better.
이는 중수소 치환된 화합물을 혼합하였을 경우 단일 화합물을 사용했을 때보다 좋은 모폴로지(morphology)를 나타내며, 이는 계면간에 밀접한 계면 접착성을 가지고, 이로 인해 층 간의 에너지 전이(energy transfer)가 증가되어 높은 구동전압을 낮추게 된다. This results in better morphology when mixed with deuterium-substituted compounds than when a single compound is used, which has a closer interfacial adhesion between interfaces, resulting in increased energy transfer between layers resulting in higher driving voltages. Will be lowered.
따라서 구동전압이 낮아지면서 높은 효율과 장수명을 가지게 되는 것으로 판단되며, 최근 OLED소자에서 문제시되는 높은 구동전압으로 인한 단수명의 문제점을 해결할 것으로 본다. Therefore, as the driving voltage decreases, it is judged to have high efficiency and long life, and it is expected to solve the short life problem due to the high driving voltage which is a problem in the OLED device.
본 발명의 화합물들을 유기전기발광소자의 다른 유기물층들, 예를 들어 발광 보조층, 전자주입층, 전자수송층, 및 정공 주입층에 사용되더라도 동일한 효과를 얻을 수 있는 것은 자명하다.When the compounds of the present invention are used in other organic material layers of the organic electroluminescent device, for example, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer, it is obvious that the same effect can be obtained.
이상의 설명은 본 발명을 예시적으로 설명한 것에 불과한 것으로, 본 발명이 속하는 기술분야에서 통상의 지식을 가지는 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 변형이 가능할 것이다. 따라서, 본 명세서에 개시된 실시예들은 본 발명을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시예에 의하여 본 발명의 사상과 범위가 한정되는 것은 아니다. 본 발명의 보호범위는 상기의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술은 본 발명의 권리범위에 포함하는 것으로 해석되어야 할 것이다.The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains may various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention but to describe the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The scope of protection of the present invention should be interpreted by the above claims, and all descriptions within the scope equivalent thereto should be construed as being included in the scope of the present invention.
CROSS-REFERENCE TO RELATED APPLICATIONCROSS-REFERENCE TO RELATED APPLICATION
본 특허출원은 2011년 06월 22일 한국에 출원한 특허출원번호 제 10-2011-0060643 호 및 2011년 07월 13일 한국에 출원한 특허출원번호 제 10-2011-0069298 호에 대해 미국 특허법 119(a)조 (35 U.S.C § 119(a))에 따라 우선권을 주장하며, 그 모든 내용은 참고문헌으로 본 특허출원에 병합된다. 아울러, 본 특허출원은 미국 이외에 국가에 대해서도 위와 동일한 이유로 우선권을 주장하면 그 모든 내용은 참고문헌으로 본 특허출원에 병합된다.This patent application is filed with the Korean Patent Application No. 10-2011-0060643 filed in Korea on June 22, 2011 and the patent application No. 10-2011-0069298 filed in Korea on July 13, 2011. Priority is claimed under section (a) (35 USC § 119 (a)), all of which is incorporated by reference in this patent application. In addition, if this patent application claims priority to a country other than the United States for the same reason, all its contents are incorporated into this patent application by reference.

Claims (16)

  1. 제 1전극, 제 2전극 및 하기 화학식 1로 표시되는 화합물이 단독 또는 혼합물로 함유된 1층 이상의 유기물층을 포함하는 유기전기소자.An organic electric device comprising at least one organic material layer containing a first electrode, a second electrode and a compound represented by the following formula (1) alone or in a mixture.
    <화학식 1> <Formula 1>
    Figure PCTKR2012004631-appb-I000173
    Figure PCTKR2012004631-appb-I000173
    상기 화학식 1에서,In Chemical Formula 1,
    (1) Ar1 내지 Ar3은 각각 독립적으로 동일하거나 상이하며, (1) Ar 1 to Ar 3 are each independently the same or different;
    수소, 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C1~C20의 알콕시기, C1~C20의 알킬아민기, C1~C20 의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20의 알케닐기, C2~C20의 알키닐기, C3~C20의 시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C8~C20의 아릴알케닐기, C6~C20의 아릴아민기, 실란기, 붕소기, 게르마늄기 및 C3~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴기; Hydrogen, deuterium, halogen, amino group, nitrile group, nitro group, C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxy group, C 1 ~ C 20 alkylamine group, C 1 ~ C 20 alkylthiophene group, C 6 ~ C 20 aryl thiophene group, a C 2 ~ C 20 alkenyl group, C 2 ~ C 20 alkynyl group, C of 3 ~ C 20 cycloalkyl group, C 6 ~ C 60 aryl group, a heavy hydrogen of the C 6 ~ C 20 aryl group, C 8 ~ C 20 aryl alkenyl group, C 6 ~ C 20 arylamine group, silane group, boron group, germanium group and C 3 ~ C 20 heterocyclic group C 6 ~ C 60 aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of;
    수소, 중수소, 할로겐기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴아민기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C3~C20의 헤테로고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 1개 이상의 치환기로 치환 또는 비치환되고 O, N 및 S 중 적어도 하나를 포함하는 C2~C60의 헤테로고리기; Hydrogen, deuterium, halogen, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 6 -C 20 arylamine group, C 6 -C 60 aryl A C 6 to C 20 aryl group, a C 7 to C 20 arylalkyl group, a C 8 to C 20 arylalkenyl group, a C 3 to C 20 heterocyclic group, a nitrile group and an acetylene group C 2 ~ C 60 heterocyclic group which is unsubstituted or substituted with one or more substituents in the group and includes at least one of O, N and S;
    수소, 중수소, 할로겐기, 아미노기, 니트릴기, 니트로기, C1~C20 의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C3~C30의 시클로알킬기, C2~C30의 헤테로시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기 및 C2~C20의 헤테로고리기로 구성된 군에서 선택된 1개 이상의 치환기로 치환 또는 비치환된 C1~C30의 알콕시기; Hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 3 -C 30 cycloalkyl group, At least one substituent selected from the group consisting of a C 2 to C 30 heterocycloalkyl group, a C 6 to C 60 aryl group, a C 6 to C 20 aryl group substituted with deuterium, and a C 2 to C 20 heterocyclic group Substituted or unsubstituted C 1 ~ C 30 Alkoxy group;
    수소, 중수소, 할로겐기, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C3~C30의 시클로알킬기, C2~C30의 헤테로시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기 및 C2~C20의 헤테로고리기로 구성된 군으로부터 선택된 1개 이상의 치환기로 치환 또는 비치환된 C6~C30아릴옥시기; Hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 3 -C 30 cycloalkyl group, At least one substituent selected from the group consisting of a C 2 to C 30 heterocycloalkyl group, a C 6 to C 60 aryl group, a C 6 to C 20 aryl group substituted with deuterium, and a C 2 to C 20 heterocyclic group A substituted or unsubstituted C 6 ~ C 30 aryloxy group;
    할로겐기, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C3~C30의 시클로알킬기, C2~C30의 헤테로시클로알킬기, C6~C60의 아릴기 및 C2~C20의 헤테로고리기로 구성된 군에서 선택된 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴아민기; 및 Halogen group, amino group, nitrile group, nitro group, C 1 ~ C 20 alkyl group, C 2 ~ C 20 alkenyl group, C 1 ~ C 20 alkoxy group, C 3 ~ C 30 cycloalkyl group, C 2 ~ C heterocycloalkyl group, C 6 ~ C 60 aryl group and C 2 ~ C 20 with one or more substituents selected from the group consisting of heterocyclic group-substituted or unsubstituted C 6 ~ C 60 of the arylamine group of 30; And
    C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C3~C20의 헤테로고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 선택된 치환기로 치환 또는 비치환된 C1~C50의 알킬기;로 이루어진 군에서 선택되며, C 1 ~ alkenyl group of the C 20 alkyl group, C 2 ~ C 20 of, C 1 ~ C 20 alkoxy group, C 6 ~ aryl group of C 20 aryl group, a C 6 ~ C 20 substituted with deuterium, C 7 C 1 -C 50 alkyl group unsubstituted or substituted with a substituent selected from the group consisting of-C 20 arylalkyl group, C 8 ~ C 20 aryl alkenyl group, C 3 ~ C 20 heterocyclic group, nitrile group and acetylene group Selected from the group consisting of;
    여기서 Ar1~Ar3 중 적어도 하나는 중수소를 1개 이상 포함하고,Wherein at least one of Ar 1 to Ar 3 includes one or more deuterium,
    (2) R1 및 R2는 각각 독립적으로 동일하거나 상이하며, 수소; 중수소; 할로겐; 니트로기; 니트릴기; 아미노기; (2) R 1 and R 2 are each independently the same or different and are hydrogen; heavy hydrogen; halogen; Nitro group; Nitrile group; Amino group;
    수소, 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C1~C20의 알콕시기, C1~C20의 알킬아민기, C1~C20 의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20 의 알케닐기, C2~C20의 알키닐기, C3~C20의 시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C8~C20의 아릴알케닐기, C6~C20의 아릴아민기, 실란기, 붕소기, 게르마늄기 및 C3~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴기; Hydrogen, deuterium, halogen, amino group, nitrile group, nitro group, C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxy group, C 1 ~ C 20 alkylamine group, C 1 ~ C 20 alkylthiophene group, C 6 ~ C 20 aryl thiophene group, a C 2 ~ C 20 alkenyl group, C 2 ~ C 20 alkynyl group, C of 3 ~ C 20 cycloalkyl group, C 6 ~ C 60 aryl group, a heavy hydrogen of the C 6 ~ C 20 aryl group, C 8 ~ C 20 aryl alkenyl group, C 6 ~ C 20 arylamine group, silane group, boron group, germanium group and C 3 ~ C 20 heterocyclic group C 6 ~ C 60 aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of;
    수소, 중수소, 할로겐기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴아민기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C3~C20의 헤테로고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 1개 이상의 치환기로 치환 또는 비치환 되고 O, N 및 S 중 적어도 하나를 포함하는 C2~C60의 헤테로고리기; Hydrogen, deuterium, halogen, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 6 -C 20 arylamine group, C 6 -C 60 aryl A C 6 to C 20 aryl group, a C 7 to C 20 arylalkyl group, a C 8 to C 20 arylalkenyl group, a C 3 to C 20 heterocyclic group, a nitrile group and an acetylene group C 2 ~ C 60 heterocyclic group which is unsubstituted or substituted with one or more substituents in the group and includes at least one of O, N and S;
    수소, 중수소, 할로겐기, 아미노기, 니트릴기, 니트로기, C1~C20 의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C3~C30의 시클로알킬기, C2~C30의 헤테로시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기 및 C2~C20의 헤테로고리기로 구성된 군으로부터 선택된 1개 이상의 치환기로 치환 또는 비치환된 C1~C30의 알콕시기; Hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 3 -C 30 cycloalkyl group, At least one substituent selected from the group consisting of a C 2 to C 30 heterocycloalkyl group, a C 6 to C 60 aryl group, a C 6 to C 20 aryl group substituted with deuterium, and a C 2 to C 20 heterocyclic group Substituted or unsubstituted C 1 ~ C 30 Alkoxy group;
    수소, 중수소, 할로겐기, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C3~C30의 시클로알킬기, C2~C30의 헤테로시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기 및 C2~C20의 헤테로고리기로 구성된 군으로부터 선택된 1개 이상의 치환기로 치환 또는 비치환된 C6~C30의 아릴옥시기; 및Hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 3 -C 30 cycloalkyl group, At least one substituent selected from the group consisting of a C 2 to C 30 heterocycloalkyl group, a C 6 to C 60 aryl group, a C 6 to C 20 aryl group substituted with deuterium, and a C 2 to C 20 heterocyclic group Substituted or unsubstituted C 6 ~ C 30 An aryloxy group; And
    C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C3~C20의 헤테로고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 선택된 치환기로 치환 또는 비치환된 C1~C50의 알킬기;로 이루어진 군에서 선택되며, C 1 ~ alkenyl group of the C 20 alkyl group, C 2 ~ C 20 of, C 1 ~ C 20 alkoxy group, C 6 ~ aryl group of C 20 aryl group, a C 6 ~ C 20 substituted with deuterium, C 7 C 1 -C 50 alkyl group unsubstituted or substituted with a substituent selected from the group consisting of-C 20 arylalkyl group, C 8 ~ C 20 aryl alkenyl group, C 3 ~ C 20 heterocyclic group, nitrile group and acetylene group Selected from the group consisting of;
    여기서, R1 및 R2는 인접한 기와 서로 결합하여 지환족, 방향족 또는 헤테로고리를 형성할 수 있고, Wherein R 1 and R 2 may be bonded to adjacent groups to form an alicyclic, aromatic or heterocyclic ring,
    (3) L은 니트로기, 니트릴기, 할로겐기, 알킬기, 알콕시기, 아미노기, 아릴아민기 및 헤테로고리기로 이루어진 군에서 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴렌기; 또는 니트로, 니트릴, 할로겐, 알킬기, 알콕시기, 아미노기 및 아릴기로 이루어진 군에서 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C2~C60의 헤테로고리기이며,(3) L is C 6 -C 60 aryl unsubstituted or substituted with one or more substituents selected from the group consisting of a nitro group, a nitrile group, a halogen group, an alkyl group, an alkoxy group, an amino group, an arylamine group and a heterocyclic group Ren group; Or a C 2 -C 60 heterocyclic group unsubstituted or substituted with one or more substituents selected from the group consisting of nitro, nitrile, halogen, alkyl, alkoxy, amino and aryl groups,
    (4) a는 0~4의 정수, b는 0~3의 정수, c는 0~2의 정수이다.(4) a is an integer of 0-4, b is an integer of 0-3, c is an integer of 0-2.
  2. 제 1항에 있어서,The method of claim 1,
    상기 혼합물은 상기 화학식 1로 표시되는 화합물 중 서로 다른 2종 이상의 화합물이 혼합된 것을 특징으로 하는 유기전기소자.The mixture is an organic electric device, characterized in that two or more different compounds mixed in the compound represented by the formula (1).
  3. 제 1항에 있어서,The method of claim 1,
    상기 혼합물은 하기 화학식 2로 표시되는 화합물이 포함된 것을 특징으로 하는 유기전기소자.The mixture is an organic electric device, characterized in that containing a compound represented by the formula (2).
    <화학식 2>                  <Formula 2>
    Figure PCTKR2012004631-appb-I000174
    Figure PCTKR2012004631-appb-I000174
    상기 화학식 2에서,In Chemical Formula 2,
    (1) Ar1 내지 Ar3은 상기 화학식 1의 Ar1 내지 Ar3의 치환기 정의와 동일하며, (1) Ar 1 to Ar 3 is the same as the substituent definition of Ar 1 to Ar 3 of Formula 1,
    (2) R1 내지 R4는 상기 화학식 1의 R1 또는 R2의 치환기 정의와 동일하며, 여기서, R1 내지 R4는 인접한 기와 서로 결합하여 지환족, 방향족 또는 헤테로고리를 형성할 수 있으며,(2) R 1 to R 4 is the same as the substituent definition of R 1 or R 2 in Formula 1, wherein R 1 to R 4 may be bonded to an adjacent group to form an alicyclic, aromatic or heterocycle ,
    (3) R' 및 R"는 각각 독립적으로 동일하거나 상이하며, 수소, 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C1~C20의 알콕시기, C1~C20의 알킬아민기, C1~C20 의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20 의 알케닐기, C2~C20의 알키닐기, C3~C20의 시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C2~C20의 아릴기, C8~C20의 아릴알케닐기, C6~C20의 아릴아민기, 실란기, 붕소기, 게르마늄기, C3~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴기; 또는 C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴기, 중수소로 치환된 C2~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C3~C20의 헤테로 고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 선택된 치환기로 치환 또는 비치환된 C1~C50의 알킬기이며, 여기서, R' 및 R"는 서로 결합하여 지환족, 방향족, 헤테로고리, 또는 스피로화합물을 형성할 수 있으며,(3) R 'and R "are each independently the same or different, hydrogen, deuterium, halogen, amino, nitrile, nitro, C 1 -C 20 alkyl group, C 1 -C 20 alkoxy group, C 1 C 20 -C 20 alkylamine group, C 1 -C 20 alkylthiophene group, C 6 -C 20 arylthiophene group, C 2 -C 20 alkenyl group, C 2 -C 20 alkynyl group, C 3 ~ C 20 cycloalkyl group, C 6 ~ C 60 aryl group, of a C 2 ~ C 20 substituted by deuterium aryl group, a C 8 ~ C 20 aryl alkenyl group, C 6 ~ C 20 aryl amine group, a silane C 6 -C 60 aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of a group, a boron group, a germanium group, a C 3 -C 20 heterocyclic group, or a C 1 -C 20 alkyl group, C 2 ~ C 20 alkenyl group, C 1 ~ C 20 alkoxy group, C 6 ~ C 20 aryl group, C 2 ~ C 20 aryl group substituted with deuterium, C 7 ~ C 20 arylalkyl group, C 8 to C 20 arylalkenyl group, C 3 to C 20 heterocyclic group, nitrile group and ar C 1 ~ C 50 is an alkyl group substituted or unsubstituted with a substituent selected from the group consisting of cetylene, wherein R 'and R "may be combined with each other to form an alicyclic, aromatic, heterocyclic, or spiro compound ,
    (4) a는 1 내지 3의 정수이고, b, c 및 d는 각각 1 내지 4의 정수이다.(4) a is an integer of 1 to 3, and b, c and d are integers of 1 to 4, respectively.
  4. 제 1항에 있어서, The method of claim 1,
    상기 Ar3는 중수소를 하나 이상 포함하며,Ar 3 includes at least one deuterium,
    상기 Ar2는 다음 화학식으로 표시되는 것을 특징으로 하는 유기전기소자.The Ar 2 is an organic electric device, characterized in that represented by the formula.
    Figure PCTKR2012004631-appb-I000175
    Figure PCTKR2012004631-appb-I000175
    상기 화학식에서,In the above formula,
    (1) R3 및 R4는 각각 독립적으로 동일하거나 상이하며, 할로겐; 니트로기; 니트릴기; 아미노기;(1) R 3 and R 4 are each independently the same or different and are halogen; Nitro group; Nitrile group; Amino group;
    수소, 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C1~C20의 알콕시기, C1~C20의 알킬아민기, C1~C20 의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20 의 알케닐기, C2~C20의 알키닐기, C3~C20의 시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C8~C20의 아릴알케닐기, C6~C20의 아릴아민기, 실란기, 붕소기, 게르마늄기 및 C3~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴기;Hydrogen, deuterium, halogen, amino group, nitrile group, nitro group, C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxy group, C 1 ~ C 20 alkylamine group, C 1 ~ C 20 alkylthiophene group, C 6 ~ C 20 aryl thiophene group, a C 2 ~ C 20 alkenyl group, C 2 ~ C 20 alkynyl group, C of 3 ~ C 20 cycloalkyl group, C 6 ~ C 60 aryl group, a heavy hydrogen of the C 6 ~ C 20 aryl group, C 8 ~ C 20 aryl alkenyl group, C 6 ~ C 20 arylamine group, silane group, boron group, germanium group and C 3 ~ C 20 heterocyclic group C 6 ~ C 60 aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of;
    수소, 중수소, 할로겐기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴아민기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C8~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C3~C20의 헤테로고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 1개 이상의 치환기로 치환 또는 비치환 되고 O, N 및 S 중 적어도 하나를 포함하는 C2~C60의 헤테로고리기; Hydrogen, deuterium, halogen, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 6 -C 20 arylamine group, C 6 -C 60 aryl A C 6 to C 20 aryl group, a C 8 to C 20 arylalkyl group, a C 8 to C 20 arylalkenyl group, a C 3 to C 20 heterocyclic group, a nitrile group and an acetylene group C 2 ~ C 60 heterocyclic group which is unsubstituted or substituted with one or more substituents in the group and includes at least one of O, N and S;
    수소, 중수소, 할로겐기, 아미노기, 니트릴기, 니트로기, C1~C20 의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C3~C30의 시클로알킬기, C2~C30의 헤테로시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기 및 C2~C20의 헤테로고리기로 구성된 군으로부터 선택된 1개 이상의 치환기로 치환 또는 비치환된 C1~C30의 알콕시기;Hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 3 -C 30 cycloalkyl group, At least one substituent selected from the group consisting of a C 2 to C 30 heterocycloalkyl group, a C 6 to C 60 aryl group, a C 6 to C 20 aryl group substituted with deuterium, and a C 2 to C 20 heterocyclic group Substituted or unsubstituted C 1 ~ C 30 Alkoxy group;
    수소, 중수소, 할로겐기, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C3~C30의 시클로알킬기, C2~C30의 헤테로시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기 및 C2~C20의 헤테로고리기로 구성된 군으로부터 선택된 1개 이상의 치환기로 치환 또는 비치환된 C6~C30의 아릴옥시기; 및 Hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 3 -C 30 cycloalkyl group, At least one substituent selected from the group consisting of a C 2 to C 30 heterocycloalkyl group, a C 6 to C 60 aryl group, a C 6 to C 20 aryl group substituted with deuterium, and a C 2 to C 20 heterocyclic group Substituted or unsubstituted C 6 ~ C 30 An aryloxy group; And
    C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C3~C20의 헤테로고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 선택된 치환기로 치환 또는 비치환된 C1~C50의 알킬기;로 이루어진 군에서 선택되며, C 1 ~ alkenyl group of the C 20 alkyl group, C 2 ~ C 20 of, C 1 ~ C 20 alkoxy group, C 6 ~ aryl group of C 20 aryl group, a C 6 ~ C 20 substituted with deuterium, C 7 C 1 -C 50 alkyl group unsubstituted or substituted with a substituent selected from the group consisting of-C 20 arylalkyl group, C 8 ~ C 20 aryl alkenyl group, C 3 ~ C 20 heterocyclic group, nitrile group and acetylene group Selected from the group consisting of;
    여기서, R3 및 R4는 인접한 기와 서로 결합하여 지환족, 방향족 또는 헤테로고리를 형성할 수 있으며,Wherein R 3 and R 4 may combine with adjacent groups to form an alicyclic, aromatic or heterocyclic ring,
    (2) R' 및 R"는 각각 독립적으로 동일하거나 상이하며, 수소, 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C1~C20의 알콕시기, C1~C20의 알킬아민기, C1~C20 의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20의 알케닐기, C2~C20의 알키닐기, C3~C20의 시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C8~C20의 아릴알케닐기, C6~C20의 아릴아민기, 실란기, 붕소기, 게르마늄기 및 C3~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴기; 또는 C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C3~C20의 헤테로고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 선택된 치환기로 치환 또는 비치환된 C1~C50의 알킬기이며, 여기서, R', R"는 서로 결합하여 지환족, 방향족, 헤테로고리, 또는 스피로화합물을 형성할 수 있으며,(2) R 'and R "are the same as or different from each other independently, hydrogen, deuterium, halogen, amino group, nitrile group, nitro group, C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxy group, C 1 C 20 -C 20 alkylamine group, C 1 -C 20 alkylthiophene group, C 6 -C 20 arylthiophene group, C 2 -C 20 alkenyl group, C 2 -C 20 alkynyl group, C 3 ~ C 20 cycloalkyl group, an aryl group of C 6 ~ C 60, of a C 6 ~ C 20 substituted with a heavy hydrogen aryl, C 8 ~ C 20 aryl alkenyl group, C 6 ~ C 20 aryl amine group, a silane C 6 -C 60 aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of a group, a boron group, a germanium group and a C 3 -C 20 heterocyclic group; or a C 1 -C 20 alkyl group, C alkenyl group of 2 ~ C 20, C 1 ~ C 20 alkoxy group, C 6 ~ C 20 aryl group, of a C 6 ~ C 20 substituted by deuterium aryl group, C 7 ~ C 20 aryl group, C of 8 ~ C 20 arylalkenyl group, a heterocyclic group of C 3 ~ C 20, the nitrile group, and With a substituent selected from the group consisting of a three ethylene and an alkyl group of a substituted or unsubstituted C 1 ~ C 50, where, R ', R "may be combined with each other to form an alicyclic, aromatic, heterocyclic, or a spiro compound, and ,
    (3) e는 1~4의 정수, d는 1~3의 정수이다.(3) e is an integer of 1-4, d is an integer of 1-3.
  5. 제 1항 또는 제 2항에 있어서, The method according to claim 1 or 2,
    상기 Ar1, Ar2, 및 Ar3 중 적어도 하나는 다음으로 구성된 군으로부터 선택되는 것을특징으로 하는 유기전기소자.At least one of Ar 1 , Ar 2 , and Ar 3 is selected from the group consisting of:
    Figure PCTKR2012004631-appb-I000176
    ,
    Figure PCTKR2012004631-appb-I000177
    ,
    Figure PCTKR2012004631-appb-I000178
    ,
    Figure PCTKR2012004631-appb-I000179
    ,
    Figure PCTKR2012004631-appb-I000180
    ,
    Figure PCTKR2012004631-appb-I000181
    ,
    Figure PCTKR2012004631-appb-I000182
    ,
    Figure PCTKR2012004631-appb-I000183
    Figure PCTKR2012004631-appb-I000176
    ,
    Figure PCTKR2012004631-appb-I000177
    ,
    Figure PCTKR2012004631-appb-I000178
    ,
    Figure PCTKR2012004631-appb-I000179
    ,
    Figure PCTKR2012004631-appb-I000180
    ,
    Figure PCTKR2012004631-appb-I000181
    ,
    Figure PCTKR2012004631-appb-I000182
    ,
    Figure PCTKR2012004631-appb-I000183
    Figure PCTKR2012004631-appb-I000184
    ,
    Figure PCTKR2012004631-appb-I000185
    ,
    Figure PCTKR2012004631-appb-I000186
    Figure PCTKR2012004631-appb-I000184
    ,
    Figure PCTKR2012004631-appb-I000185
    ,
    Figure PCTKR2012004631-appb-I000186
    여기서, D는 중수소이며, k 및 i는 0~2의 정수이고, n, o, q, r, q' 및 r'은 0~3의 정수이며, b, e, f, g, l, t' 및 u'은 0~4의 정수이고, a, c, c', h, j, m, p, s, t, u 및 s'은 0~5의 정수이며, b'은 0~6의 정수이며, a' 및 d는 0~7의 정수이다.Where D is deuterium, k and i are integers from 0 to 2, n, o, q, r, q 'and r' are integers from 0 to 3, and b, e, f, g, l, t 'And u' are integers from 0 to 4, a, c, c ', h, j, m, p, s, t, u and s' are integers from 0 to 5, and b' is 0 to 6 It is an integer, and a 'and d are the integers of 0-7.
  6. 제 1항 또는 제 2항에 있어서,The method according to claim 1 or 2,
    상기 Ar1, Ar2, 및 Ar3 중 적어도 하나는 다음으로 구성된 군으로부터 선택되는 것을 특징으로 하는 유기전기소자.At least one of Ar 1 , Ar 2 , and Ar 3 is selected from the group consisting of organic electroluminescent device.
    Figure PCTKR2012004631-appb-I000187
    Figure PCTKR2012004631-appb-I000187
  7. 제 1항에 있어서,The method of claim 1,
    상기 화학식 1로 표시되는 화합물은 다음으로 구성된 군으로부터 선택되는 것을 특징으로 하는 유기전기소자.Compound represented by the formula (1) is an organic electric device, characterized in that selected from the group consisting of:
    Figure PCTKR2012004631-appb-I000188
    Figure PCTKR2012004631-appb-I000188
    Figure PCTKR2012004631-appb-I000189
    Figure PCTKR2012004631-appb-I000189
    Figure PCTKR2012004631-appb-I000190
    Figure PCTKR2012004631-appb-I000190
    Figure PCTKR2012004631-appb-I000192
    Figure PCTKR2012004631-appb-I000192
    Figure PCTKR2012004631-appb-I000193
    Figure PCTKR2012004631-appb-I000193
    Figure PCTKR2012004631-appb-I000194
    Figure PCTKR2012004631-appb-I000194
    Figure PCTKR2012004631-appb-I000195
    Figure PCTKR2012004631-appb-I000195
    Figure PCTKR2012004631-appb-I000196
    Figure PCTKR2012004631-appb-I000196
    Figure PCTKR2012004631-appb-I000197
    Figure PCTKR2012004631-appb-I000197
    Figure PCTKR2012004631-appb-I000198
    Figure PCTKR2012004631-appb-I000198
    Figure PCTKR2012004631-appb-I000199
    Figure PCTKR2012004631-appb-I000199
    Figure PCTKR2012004631-appb-I000200
    Figure PCTKR2012004631-appb-I000200
    Figure PCTKR2012004631-appb-I000201
    Figure PCTKR2012004631-appb-I000201
    Figure PCTKR2012004631-appb-I000202
    Figure PCTKR2012004631-appb-I000202
    Figure PCTKR2012004631-appb-I000203
    Figure PCTKR2012004631-appb-I000203
    Figure PCTKR2012004631-appb-I000204
    Figure PCTKR2012004631-appb-I000204
    Figure PCTKR2012004631-appb-I000205
    Figure PCTKR2012004631-appb-I000205
    Figure PCTKR2012004631-appb-I000206
    Figure PCTKR2012004631-appb-I000206
  8. 제 3항에 있어서,The method of claim 3, wherein
    상기 화학식 2로 표시되는 화합물은 다음으로 구성된 군으로부터 선택되는 것을 특징으로 하는 유기전기소자.Compound represented by the formula (2) is an organic electric device, characterized in that selected from the group consisting of:
    Figure PCTKR2012004631-appb-I000207
    Figure PCTKR2012004631-appb-I000207
    Figure PCTKR2012004631-appb-I000208
    Figure PCTKR2012004631-appb-I000208
    Figure PCTKR2012004631-appb-I000209
    Figure PCTKR2012004631-appb-I000209
    Figure PCTKR2012004631-appb-I000210
    Figure PCTKR2012004631-appb-I000210
    Figure PCTKR2012004631-appb-I000211
    Figure PCTKR2012004631-appb-I000211
    Figure PCTKR2012004631-appb-I000212
    Figure PCTKR2012004631-appb-I000212
    Figure PCTKR2012004631-appb-I000213
    Figure PCTKR2012004631-appb-I000213
    Figure PCTKR2012004631-appb-I000214
    Figure PCTKR2012004631-appb-I000214
    Figure PCTKR2012004631-appb-I000215
    Figure PCTKR2012004631-appb-I000215
    Figure PCTKR2012004631-appb-I000216
    Figure PCTKR2012004631-appb-I000216
    Figure PCTKR2012004631-appb-I000217
    Figure PCTKR2012004631-appb-I000217
    Figure PCTKR2012004631-appb-I000218
    Figure PCTKR2012004631-appb-I000218
    Figure PCTKR2012004631-appb-I000219
    Figure PCTKR2012004631-appb-I000219
    Figure PCTKR2012004631-appb-I000220
    Figure PCTKR2012004631-appb-I000220
    Figure PCTKR2012004631-appb-I000221
    Figure PCTKR2012004631-appb-I000221
    Figure PCTKR2012004631-appb-I000222
    Figure PCTKR2012004631-appb-I000222
    Figure PCTKR2012004631-appb-I000223
    Figure PCTKR2012004631-appb-I000223
  9. 제 1항 내지 제 3항 중 어느 한 항에 있어서,The method according to any one of claims 1 to 3,
    상기 화합물 또는 혼합물을 용액공정(soluble process)에 의해 상기 유기물층으로 형성하는 것을 특징으로 하는 유기전기소자. And forming the compound or mixture into the organic material layer by a soluble process.
  10. 제 1항 내지 제 3항 중 어느 한 항에 있어서,The method according to any one of claims 1 to 3,
    제 1전극, 상기 유기물층 및 제 2전극이 순차적으로 적층된 유기전기발광소자인 것을 특징으로 하는 유기전기소자.An organic electroluminescent device, characterized in that an organic electroluminescent device in which a first electrode, the organic material layer and a second electrode are sequentially stacked.
  11. 제 1항 내지 제 3항 중 어느 한 항에 있어서,The method according to any one of claims 1 to 3,
    상기 유기물층은 발광층, 정공 주입층 및 정공 수송층 중 적어도 일층인 것을 특징으로 하는 유기전기소자.The organic material layer is an organic electroluminescent device, characterized in that at least one of a light emitting layer, a hole injection layer and a hole transport layer.
  12. 제 2항 또는 제 3항에 있어서,The method of claim 2 or 3,
    상기 혼합물은 어느 하나의 화합물이 혼합물 전체 중량의 90중량% 이하의 범위로 혼합된 것을 특징으로 하는 유기전기소자.The mixture is an organic electronic device, characterized in that any one compound is mixed in the range of 90% by weight or less of the total weight of the mixture.
  13. 제 1항 내지 제 3항 중 어느 한 항의 유기전기소자를 포함하는 디스플레이장치; 및Claim 1 to 3, wherein the display device comprising any one of the organic electroluminescent element; And
    상기 디스플레이장치를 구동하는 제어부;를 포함하는 전자장치.And a controller for driving the display device.
  14. 제 12항에 있어서,The method of claim 12,
    상기 유기전기소자는 유기전기발광소자(OLED), 유기태양전지, 유기감광체(OPC), 유기트랜지스터(유기 TFT), 단색 또는 백색 조명용 소자 중 하나인 것을 특징으로 하는 전자장치.The organic electroluminescent device is one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a device for monochrome or white illumination.
  15. 하기 화학식 3으로 표시되는 화합물.A compound represented by the following formula (3).
    <화학식 3><Formula 3>
    Figure PCTKR2012004631-appb-I000224
    Figure PCTKR2012004631-appb-I000224
    상기 화학식 3에서,In Chemical Formula 3,
    (1) Ar1 내지 Ar3은 각각 독립적으로 동일하거나 상이하며, (1) Ar 1 to Ar 3 are each independently the same or different;
    수소, 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C1~C20의 알콕시기, C1~C20의 알킬아민기, C1~C20 의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20의 알케닐기, C2~C20의 알키닐기, C3~C20의 시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C8~C20의 아릴알케닐기, C6~C20의 아릴아민기, 실란기, 붕소기, 게르마늄기 및 C3~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴기; Hydrogen, deuterium, halogen, amino group, nitrile group, nitro group, C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxy group, C 1 ~ C 20 alkylamine group, C 1 ~ C 20 alkylthiophene group, C 6 ~ C 20 aryl thiophene group, a C 2 ~ C 20 alkenyl group, C 2 ~ C 20 alkynyl group, C of 3 ~ C 20 cycloalkyl group, C 6 ~ C 60 aryl group, a heavy hydrogen of the C 6 ~ C 20 aryl group, C 8 ~ C 20 aryl alkenyl group, C 6 ~ C 20 arylamine group, silane group, boron group, germanium group and C 3 ~ C 20 heterocyclic group C 6 ~ C 60 aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of;
    수소, 중수소, 할로겐기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴아민기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C3~C20의 헤테로고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 1개 이상의 치환기로 치환 또는 비치환되고 O, N 및 S 중 적어도 하나를 포함하는 C2~C60의 헤테로고리기; Hydrogen, deuterium, halogen, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 6 -C 20 arylamine group, C 6 -C 60 aryl A C 6 to C 20 aryl group, a C 7 to C 20 arylalkyl group, a C 8 to C 20 arylalkenyl group, a C 3 to C 20 heterocyclic group, a nitrile group and an acetylene group C 2 ~ C 60 heterocyclic group which is unsubstituted or substituted with one or more substituents in the group and includes at least one of O, N and S;
    수소, 중수소, 할로겐기, 아미노기, 니트릴기, 니트로기, C1~C20 의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C3~C30의 시클로알킬기, C2~C30의 헤테로시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기 및 C2~C20의 헤테로고리기로 구성된 군에서 선택된 1개 이상의 치환기로 치환 또는 비치환된 C1~C30의 알콕시기; Hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 3 -C 30 cycloalkyl group, At least one substituent selected from the group consisting of a C 2 to C 30 heterocycloalkyl group, a C 6 to C 60 aryl group, a C 6 to C 20 aryl group substituted with deuterium, and a C 2 to C 20 heterocyclic group Substituted or unsubstituted C 1 ~ C 30 Alkoxy group;
    수소, 중수소, 할로겐기, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C3~C30의 시클로알킬기, C2~C30의 헤테로시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기 및 C2~C20의 헤테로고리기로 구성된 군으로부터 선택된 1개 이상의 치환기로 치환 또는 비치환된 C6~C30아릴옥시기; Hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 3 -C 30 cycloalkyl group, At least one substituent selected from the group consisting of a C 2 to C 30 heterocycloalkyl group, a C 6 to C 60 aryl group, a C 6 to C 20 aryl group substituted with deuterium, and a C 2 to C 20 heterocyclic group A substituted or unsubstituted C 6 ~ C 30 aryloxy group;
    할로겐기, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C3~C30의 시클로알킬기, C2~C30의 헤테로시클로알킬기, C6~C60의 아릴기 및 C2~C20의 헤테로고리기로 구성된 군에서 선택된 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴아민기; 및 Halogen group, amino group, nitrile group, nitro group, C 1 ~ C 20 alkyl group, C 2 ~ C 20 alkenyl group, C 1 ~ C 20 alkoxy group, C 3 ~ C 30 cycloalkyl group, C 2 ~ C heterocycloalkyl group, C 6 ~ C 60 aryl group and C 2 ~ C 20 with one or more substituents selected from the group consisting of heterocyclic group-substituted or unsubstituted C 6 ~ C 60 of the arylamine group of 30; And
    C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C3~C20의 헤테로고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 선택된 치환기로 치환 또는 비치환된 C1~C50의 알킬기;로 이루어진 군에서 선택되며, C 1 ~ alkenyl group of the C 20 alkyl group, C 2 ~ C 20 of, C 1 ~ C 20 alkoxy group, C 6 ~ aryl group of C 20 aryl group, a C 6 ~ C 20 substituted with deuterium, C 7 C 1 -C 50 alkyl group unsubstituted or substituted with a substituent selected from the group consisting of-C 20 arylalkyl group, C 8 ~ C 20 aryl alkenyl group, C 3 ~ C 20 heterocyclic group, nitrile group and acetylene group Selected from the group consisting of;
    여기서 Ar1~Ar3 중 적어도 하나는 중수소를 1개 이상 포함하고,Wherein at least one of Ar 1 to Ar 3 includes one or more deuterium,
    (2) R1 및 R2는 각각 독립적으로 동일하거나 상이하며, 수소; 중수소; 할로겐; 니트로기; 니트릴기; 아미노기; (2) R 1 and R 2 are each independently the same or different and are hydrogen; heavy hydrogen; halogen; Nitro group; Nitrile group; Amino group;
    수소, 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C1~C20의 알콕시기, C1~C20의 알킬아민기, C1~C20 의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20 의 알케닐기, C2~C20의 알키닐기, C3~C20의 시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C8~C20의 아릴알케닐기, C6~C20의 아릴아민기, 실란기, 붕소기, 게르마늄기 및 C3~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴기; Hydrogen, deuterium, halogen, amino group, nitrile group, nitro group, C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxy group, C 1 ~ C 20 alkylamine group, C 1 ~ C 20 alkylthiophene group, C 6 ~ C 20 aryl thiophene group, a C 2 ~ C 20 alkenyl group, C 2 ~ C 20 alkynyl group, C of 3 ~ C 20 cycloalkyl group, C 6 ~ C 60 aryl group, a heavy hydrogen of the C 6 ~ C 20 aryl group, C 8 ~ C 20 aryl alkenyl group, C 6 ~ C 20 arylamine group, silane group, boron group, germanium group and C 3 ~ C 20 heterocyclic group C 6 ~ C 60 aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of;
    수소, 중수소, 할로겐기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴아민기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C3~C20의 헤테로고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 1개 이상의 치환기로 치환 또는 비치환 되고 O, N 및 S 중 적어도 하나를 포함하는 C2~C60의 헤테로고리기; Hydrogen, deuterium, halogen, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 6 -C 20 arylamine group, C 6 -C 60 aryl A C 6 to C 20 aryl group, a C 7 to C 20 arylalkyl group, a C 8 to C 20 arylalkenyl group, a C 3 to C 20 heterocyclic group, a nitrile group and an acetylene group C 2 ~ C 60 heterocyclic group which is unsubstituted or substituted with one or more substituents in the group and includes at least one of O, N and S;
    수소, 중수소, 할로겐기, 아미노기, 니트릴기, 니트로기, C1~C20 의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C3~C30의 시클로알킬기, C2~C30의 헤테로시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기 및 C2~C20의 헤테로고리기로 구성된 군으로부터 선택된 1개 이상의 치환기로 치환 또는 비치환된 C1~C30의 알콕시기; Hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 3 -C 30 cycloalkyl group, At least one substituent selected from the group consisting of a C 2 to C 30 heterocycloalkyl group, a C 6 to C 60 aryl group, a C 6 to C 20 aryl group substituted with deuterium, and a C 2 to C 20 heterocyclic group Substituted or unsubstituted C 1 ~ C 30 Alkoxy group;
    수소, 중수소, 할로겐기, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C3~C30의 시클로알킬기, C2~C30의 헤테로시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기 및 C2~C20의 헤테로고리기로 구성된 군으로부터 선택된 1개 이상의 치환기로 치환 또는 비치환된 C6~C30의 아릴옥시기; 및Hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 1 -C 20 alkoxy group, C 3 -C 30 cycloalkyl group, At least one substituent selected from the group consisting of a C 2 to C 30 heterocycloalkyl group, a C 6 to C 60 aryl group, a C 6 to C 20 aryl group substituted with deuterium, and a C 2 to C 20 heterocyclic group Substituted or unsubstituted C 6 ~ C 30 An aryloxy group; And
    C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C3~C20의 헤테로고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 선택된 치환기로 치환 또는 비치환된 C1~C50의 알킬기;로 이루어진 군에서 선택되며, C 1 ~ alkenyl group of the C 20 alkyl group, C 2 ~ C 20 of, C 1 ~ C 20 alkoxy group, C 6 ~ aryl group of C 20 aryl group, a C 6 ~ C 20 substituted with deuterium, C 7 C 1 -C 50 alkyl group unsubstituted or substituted with a substituent selected from the group consisting of-C 20 arylalkyl group, C 8 ~ C 20 aryl alkenyl group, C 3 ~ C 20 heterocyclic group, nitrile group and acetylene group Selected from the group consisting of;
    여기서, R1 및 R2는 인접한 기와 서로 결합하여 지환족, 방향족 또는 헤테로고리를 형성할 수 있고, Wherein R 1 and R 2 may be bonded to adjacent groups to form an alicyclic, aromatic or heterocyclic ring,
    (3) L은 니트로기, 니트릴기, 할로겐기, 알킬기, 알콕시기, 아미노기, 아릴아민기 및 헤테로고리기로 이루어진 군에서 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴렌기; 또는 니트로, 니트릴, 할로겐, 알킬기, 알콕시기, 아미노기 및 아릴기로 이루어진 군에서 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C2~C60의 헤테로고리기이며,(3) L is C 6 -C 60 aryl unsubstituted or substituted with one or more substituents selected from the group consisting of a nitro group, a nitrile group, a halogen group, an alkyl group, an alkoxy group, an amino group, an arylamine group and a heterocyclic group Ren group; Or a C 2 -C 60 heterocyclic group unsubstituted or substituted with one or more substituents selected from the group consisting of nitro, nitrile, halogen, alkyl, alkoxy, amino and aryl groups,
    (4) a는 0~4의 정수, b는 0~3의 정수, c는 0~2의 정수이다.(4) a is an integer of 0-4, b is an integer of 0-3, c is an integer of 0-2.
  16. 제 15항의 상기 화학식 3으로 표시되는 화합물과 하기 화학식 4로 표시되는 화합물이 혼합된 유기전기소자용 조성물.The composition of claim 15, wherein the compound represented by Chemical Formula 3 and the compound represented by Chemical Formula 4 are mixed.
    <화학식 4>                  <Formula 4>
    Figure PCTKR2012004631-appb-I000225
    Figure PCTKR2012004631-appb-I000225
    상기 화학식 4에서,In Chemical Formula 4,
    (1) Ar1 내지 Ar3은 상기 화학식 1의 Ar1 내지 Ar3의 치환기 정의와 동일하며, (1) Ar 1 to Ar 3 is the same as the substituent definition of Ar 1 to Ar 3 of Formula 1,
    (2) R1 내지 R4는 상기 화학식 1의 R1 또는 R2의 치환기 정의와 동일하며, 여기서, R1 내지 R4는 인접한 기와 서로 결합하여 지환족, 방향족 또는 헤테로고리를 형성할 수 있으며,(2) R 1 to R 4 is the same as the substituent definition of R 1 or R 2 in Formula 1, wherein R 1 to R 4 may be bonded to an adjacent group to form an alicyclic, aromatic or heterocycle ,
    (3) R' 및 R"는 각각 독립적으로 동일하거나 상이하며, 수소, 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C1~C20의 알콕시기, C1~C20의 알킬아민기, C1~C20 의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20 의 알케닐기, C2~C20의 알키닐기, C3~C20의 시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C2~C20의 아릴기, C8~C20의 아릴알케닐기, C6~C20의 아릴아민기, 실란기, 붕소기, 게르마늄기, C3~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴기; 또는 C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴기, 중수소로 치환된 C2~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C3~C20의 헤테로 고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 선택된 치환기로 치환 또는 비치환된 C1~C50의 알킬기이며, 여기서, R' 및 R"는 서로 결합하여 지환족, 방향족, 헤테로고리, 또는 스피로화합물을 형성할 수 있으며,(3) R 'and R "are each independently the same or different, hydrogen, deuterium, halogen, amino, nitrile, nitro, C 1 -C 20 alkyl group, C 1 -C 20 alkoxy group, C 1 C 20 -C 20 alkylamine group, C 1 -C 20 alkylthiophene group, C 6 -C 20 arylthiophene group, C 2 -C 20 alkenyl group, C 2 -C 20 alkynyl group, C 3 ~ C 20 cycloalkyl group, C 6 ~ C 60 aryl group, of a C 2 ~ C 20 substituted by deuterium aryl group, a C 8 ~ C 20 aryl alkenyl group, C 6 ~ C 20 aryl amine group, a silane C 6 -C 60 aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of a group, a boron group, a germanium group, a C 3 -C 20 heterocyclic group, or a C 1 -C 20 alkyl group, C 2 ~ C 20 alkenyl group, C 1 ~ C 20 alkoxy group, C 6 ~ C 20 aryl group, C 2 ~ C 20 aryl group substituted with deuterium, C 7 ~ C 20 arylalkyl group, C 8 to C 20 arylalkenyl group, C 3 to C 20 heterocyclic group, nitrile group and ar C 1 ~ C 50 is an alkyl group substituted or unsubstituted with a substituent selected from the group consisting of cetylene, wherein R 'and R "may be combined with each other to form an alicyclic, aromatic, heterocyclic, or spiro compound ,
    (4) a는 1 내지 3의 정수이고, b, c 및 d는 각각 1 내지 4의 정수이다.(4) a is an integer of 1 to 3, and b, c and d are integers of 1 to 4, respectively.
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Cited By (75)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140027747A1 (en) * 2011-04-01 2014-01-30 Duksan High Metal Co., Ltd. Compound, organic electronic element using same, and electronic device using the latter
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WO2016009823A1 (en) * 2014-07-16 2016-01-21 東レ株式会社 Monoamine derivative, luminescent element material comprising same, and luminescent element
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11288783A (en) * 1998-04-01 1999-10-19 Mitsui Chem Inc Organic electroluminescent element
WO2008062636A1 (en) * 2006-11-24 2008-05-29 Idemitsu Kosan Co., Ltd. Aromatic amine derivative and organic electroluminescent element using the same
KR20090051140A (en) * 2007-11-08 2009-05-21 주식회사 엘지화학 New compound and organic light emitting device using the same
KR20100033265A (en) * 2008-09-19 2010-03-29 주식회사 엘지화학 Carbazole derivatives and organic light emitting device using the same
WO2010061824A1 (en) * 2008-11-25 2010-06-03 出光興産株式会社 Aromatic amine derivative, and organic electroluminescent element
KR20100106014A (en) * 2009-03-23 2010-10-01 다우어드밴스드디스플레이머티리얼 유한회사 Novel organic electroluminescent compounds and organic electroluminescent device using the same
KR20110041727A (en) * 2009-10-16 2011-04-22 에스에프씨 주식회사 Carbazole derivatives and organoelectroluminescent device using the same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110057078A (en) * 2009-11-23 2011-05-31 에스에프씨 주식회사 Heteroaryl amine compounds and organic light-emitting diode including the same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11288783A (en) * 1998-04-01 1999-10-19 Mitsui Chem Inc Organic electroluminescent element
WO2008062636A1 (en) * 2006-11-24 2008-05-29 Idemitsu Kosan Co., Ltd. Aromatic amine derivative and organic electroluminescent element using the same
KR20090051140A (en) * 2007-11-08 2009-05-21 주식회사 엘지화학 New compound and organic light emitting device using the same
KR20100033265A (en) * 2008-09-19 2010-03-29 주식회사 엘지화학 Carbazole derivatives and organic light emitting device using the same
WO2010061824A1 (en) * 2008-11-25 2010-06-03 出光興産株式会社 Aromatic amine derivative, and organic electroluminescent element
KR20100106014A (en) * 2009-03-23 2010-10-01 다우어드밴스드디스플레이머티리얼 유한회사 Novel organic electroluminescent compounds and organic electroluminescent device using the same
KR20110041727A (en) * 2009-10-16 2011-04-22 에스에프씨 주식회사 Carbazole derivatives and organoelectroluminescent device using the same

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