Patent Application
20220109114
The present disclosure relates to an organic light emitting device.
In general, an organic light emitting phenomenon refers to a phenomenon where electric energy is converted into light energy by using an organic material. The organic light emitting device using the organic light emitting phenomenon has characteristics such as a wide viewing angle, an excellent contrast, a fast response time, an excellent luminance, driving voltage and response speed, and thus many studies have proceeded.
The organic light emitting device generally has a structure which comprises an anode, a cathode, and an organic material layer interposed between the anode and the cathode. The organic material layer frequently has a multilayered structure that comprises different materials in order to enhance efficiency and stability of the organic light emitting device, and for example, the organic material layer may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and the like. In the structure of the organic light emitting device, if a voltage is applied between two electrodes, the holes are injected from an anode into the organic material layer and the electrons are injected from the cathode into the organic material layer, and when the injected holes and electrons meet each other, an exciton is formed, and light is emitted when the exciton falls to a ground state again.
There is a continuing need for the development of new materials for the organic materials used in the organic light emitting devices as described above.
(Patent Literature 0001) Korean Unexamined Patent Publication No. 10-2000-0051826
It is an object of the present disclosure to provide an organic light emitting device.
Provided herein is an organic light emitting comprising: an anode; a cathode that is provided to face the anode; and one or more organic material layers that are provided between the anode and the cathode, wherein one or more layers of the organic material layers include a compound represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2:
in the Chemical Formula 1,
X1 to X3 are each independently N or CR5′, and at least one of X1 to X3 is N,
Ar1 and Ar2 are each independently a substituted or unsubstituted C6-60 aryl; or a substituted or unsubstituted C2-60 heteroaryl containing at least one heteroatom selected from the group consisting of O, N, Si and S,
R1 to R5 and R5′ are each independently hydrogen; deuterium; halogen; hydroxy; nitrile; nitro; amino; a substituted or unsubstituted C2-60 alkyl; a substituted or unsubstituted C2-60 alkoxy; a substituted or unsubstituted C2-60 alkenyl; a substituted or unsubstituted C6-60 aryl; a substituted or unsubstituted C2-60 heteroaryl containing at least one heteroatom selected from the group consisting of O, N, Si and S, or R1 to R3 combine with an adjacent group among R1 to R3 to form a condensed ring,
one of A and B is a substituent represented by the following Chemical Formula 1-1, and the other is hydrogen or deuterium,
in the Chemical Formula 1-1,
R6 to R10 are each independently hydrogen; deuterium; halogen; hydroxy; nitrile; nitro; amino; a substituted or unsubstituted C2-60 alkyl; a substituted or unsubstituted C2-60 alkoxy; a substituted or unsubstituted C2-60 alkenyl; a substituted or unsubstituted C6-60 aryl; a substituted or unsubstituted C2-60 heteroaryl containing at least one heteroatom selected from the group consisting of O, N, Si and S, or R6 to R9 combine with an adjacent group among R6 to R9 to form a condensed ring,
a is an integer of 1 to 6,
in the Chemical Formula 2,
Ar3 and Ar4 are each independently a substituted or unsubstituted C6-60 aryl; or a substituted or unsubstituted C2-60 heteroaryl containing at least one heteroatom selected from the group consisting of O, N, Si and S,
L1 and L2 are each independently a single bond; or a substituted or unsubstituted C6-60 arylene,
R11 to R14 are each independently hydrogen; deuterium; halogen; hydroxy; nitrile; nitro; amino; a substituted or unsubstituted C2-60 alkyl; a substituted or unsubstituted C2-60 alkoxy; a substituted or unsubstituted C2-60 alkenyl; a substituted or unsubstituted C6-60 aryl; a substituted or unsubstituted C2-60 heteroaryl containing at least one heteroatom selected from the group consisting of O, N, Si and S,
b and e are each independently an integer of 1 to 4, and
c and d are each independently an integer of 1 to 3.
Improved efficiency, low driving voltage and/or improved lifetime characteristics of the organic light emitting device can be provided by using the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 as a host material of the light emitting layer.
Hereinafter, embodiments of the present disclosure will be described in more detail to facilitate understanding of the disclosure.
According one embodiment of the present disclosure, there is provided an organic light emitting comprising: an anode; a cathode that is provided to face the anode; and one or more organic material layers that are provided between the anode and the cathode, wherein one or more layers of the organic material layers include a compound represented by Chemical Formula 1 and a compound represented by Chemical Formula 2.
As used herein, the notation or
means a bond linked to another substituent group.
As used herein, the term “substituted or unsubstituted” means being unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a nitrile group; a nitro group; a hydroxy group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; an alkylthioxy group; an arylthioxy group; an alkylsulfoxy group; an arylsulfoxy group; a silyl group; a boron group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; an aralkyl group; an aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; a heteroarylamine group; an arylamine group; an arylphosphine group; and a heterocyclic group containing at least one of N, O and S atoms, or being unsubstituted or substituted with a substituent to which two or more substituents of the above-exemplified substituents are connected. For example, “a substituent in which two or more substituents are connected” may be a biphenyl group. Namely, a biphenyl group may be an aryl group, or it may be interpreted as a substituent in which two phenyl groups are connected.
In the present disclosure, the carbon number of a carbonyl group is not particularly limited, but is preferably 1 to 40. Specifically, the carbonyl group may be a compound having the following structural formulas, but is not limited thereto.
In the present disclosure, an ester group may have a structure in which oxygen of the ester group may be substituted by a straight-chain, branched-chain, or cyclic alkyl group having 1 to 25 carbon atoms, or an aryl group having 6 to 25 carbon atoms. Specifically, the ester group may be a compound having the following structural formulas, but is not limited thereto.
In the present disclosure, the carbon number of an imide group is not particularly limited, but is preferably 1 to 25. Specifically, the imide group may be a compound having the following structural formulas, but is not limited thereto.
In the present disclosure, a silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group and the like, but is not limited thereto.
In the present disclosure, a boron group specifically includes a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, and a phenylboron group, but is not limited thereto.
In the present disclosure, examples of a halogen group include fluorine, chlorine, bromine, or iodine.
In the present disclosure, the alkyl group may be straight-chain or branched-chain, and the carbon number thereof is not particularly limited, but is preferably 1 to 40. According to one embodiment, the carbon number of the alkyl group is 1 to 20. According to another embodiment, the carbon number of the alkyl group is 1 to 10. According to another embodiment, the carbon number of the alkyl group is 1 to 6. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.
In the present disclosure, the alkenyl group may be straight-chain or branched-chain, and the carbon number thereof is not particularly limited, but is preferably 2 to 40. According to one embodiment, the carbon number of the alkenyl group is 2 to 20. According to another embodiment, the carbon number of the alkenyl group is 2 to 10. According to still another embodiment, the carbon number of the alkenyl group is 2 to 6. Specific examples thereof include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, a stilbenyl group, a styrenyl group, and the like, but are not limited thereto.
In the present disclosure, a cycloalkyl group is not particularly limited, but the carbon number thereof is preferably 3 to 60. According to one embodiment, the carbon number of the cycloalkyl group is 3 to 30. According to another embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to still another embodiment, the carbon number of the cycloalkyl group is 3 to 6. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.
In the present disclosure, an aryl group is not particularly limited, but the carbon number thereof is preferably 6 to 60, and it may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 30. According to one embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group or the like as the monocyclic aryl group, but is not limited thereto. The polycyclic aryl group includes a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group or the like, but is not limited thereto.
In the present disclosure, a fluorenyl group may be substituted, and two substituent groups may be bonded to each other to form a spiro structure. In the case where the fluorenyl group is substituted,
and the like can be formed. However, the structure is not limited thereto.
In the present disclosure, a heterocyclic group is a heterocyclic group containing one or more of O, N, Si and S as a heteroatom, and the carbon number thereof is not particularly limited, but is preferably 2 to 60. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazol group, an oxadiazol group, a triazol group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, an acridyl group, a pyridazine group, a pyrazinyl group, a quinolinyl group, a quinazoline group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, a pyridopyrazinyl group, a pyrazinopyrazinyl group, an isoquinoline group, an indole group, a carbazole group, a benzoxazole group, a benzoimidazole group, a benzothiazol group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline group, an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, a dibenzofuranyl group, and the like, but are not limited thereto.
In the present disclosure, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group and the arylamine group is the same as the aforementioned examples of the aryl group. In the present disclosure, the alkyl group in the aralkyl group, the alkylaryl group and the alkylamine group is the same as the aforementioned examples of the alkyl group. n the present disclosure, the heteroaryl in the heteroarylamine can be applied to the aforementioned description of the heterocyclic group. In the present disclosure, the alkenyl group in the aralkenyl group is the same as the aforementioned examples of the alkenyl group. In the present disclosure, the aforementioned description of the aryl group may be applied except that the arylene is a divalent group. In the present disclosure, the aforementioned description of the heterocyclic group can be applied except that the heteroarylene is a divalent group. In the present disclosure, the aforementioned description of the aryl group or cycloalkyl group can be applied except that the hydrocarbon ring is not a monovalent group but formed by combining two substituent groups. In the present disclosure, the aforementioned description of the heterocyclic group can be applied, except that the heterocyclic group is not a monovalent group but formed by combining two substituent groups.
According one embodiment of the present disclosure, there is provided an organic light emitting comprising: an anode; a cathode that is provided to face the anode; and one or more organic material layers that are provided between the anode and the cathode, wherein one or more layers of the organic material layers include a compound represented by Chemical Formula 1 and a compound represented by Chemical Formula 2.
In the organic light emitting device, by using the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 as a host material of the light emitting layer, improved efficiency, low driving voltage and/or improved lifetime characteristics of the organic light emitting device can be provided.
Hereinafter, the present disclosure will be described in detail for each configuration.
Anode and Cathode
As the anode material, generally, a material having a large work function is preferably used so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material include metals such as vanadium, chrome, copper, zinc, and gold, or an alloy thereof; metal oxides such as zinc oxides, indium oxides, indium tin oxides (ITO), and indium zinc oxides (IZO); a combination of metals and oxides, such as ZnO:Al or SNO2:Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, and the like, but are not limited thereto.
As the cathode material, generally, a material having a small work function is preferably used so that electrons can be easily injected into the organic material layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or an alloy thereof; a multilayered structure material such as LiF/Al or LiO2/Al, and the like, but are not limited thereto.
Further, a hole injection layer may be additionally included on the anode. The hole injection layer is composed of a hole injection material, wherein the hole injection material is preferably a compound which has a capability of transporting the holes, thus has a hole injecting effect in the anode and an excellent hole injecting effect to the light emitting layer or the light emitting material, prevents excitons produced in the light emitting layer from moving to a hole injection layer or the electron injection material, and is excellent in the ability to form a thin film.
It is preferable that a HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the anode material and a HOMO of a peripheral organic material layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, an arylamine-based organic material, a hexanitrilehexaazatriphenylene-based organic material, a quinacridone-based organic material, a perylene-based organic material, anthraquinone, polyaniline and polythiophene-based conductive polymer, and the like, but are not limited thereto.
Light Emitting Layer
The light emitting material included in the light emitting layer is preferably a material which may receive holes and electrons transported from a hole transport layer and an electron transport layer, respectively, and combine the holes and the electrons to emit light in a visible ray region, and has good quantum efficiency to fluorescence or phosphorescence.
The light emitting layer may include a host material and a dopant material. In particular, in the present disclosure, the host material includes the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2.
The Chemical Formula 1 may be any one selected from compounds represented by the following Chemical Formulas 1-A, 1-B and 1-C.
in the Chemical Formulas 1-A, 1-B and 1-C,
X1, X2, X3, Ar1, Ar2, A and B are the same as defined above.
In the Chemical Formula 1, X1 to X3 all may be N.
In the Chemical Formula 1, Ar1 and Ar2 may be each independently any one selected from the group consisting of:
The substituent of Chemical Formula 1-1 may be any one selected from the group consisting of the following.
The compound represented by Chemical Formula 1 may be selected from the group consisting of the following compounds.
The compound represented by Chemical Formula 1 may be prepared by the method as shown in Reaction Scheme 1 or 2 below.
in the Reaction Schemes 1 and 2, the remaining substituents excluding Q are the same as defined above, and Q is halogen, more preferably bromo, or chloro. The above reaction is a Suzuki-coupling reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and a reactive group for the Suzuki-coupling reaction can be modified as known in the art. The above preparation method will be more specifically described in the Preparation Examples described hereinafter.
Further, as the host material, a compound represented by Chemical Formula 1 and a compound represented by Chemical Formula 2 may be used together.
The compound represented by Chemical Formula 2 may be a compound represented by Chemical Formula 2-1.
in the Chemical Formula 2-1,
Ar3, Ar4, L1 and L2 are the same as defined above.
In Chemical Formula 2, Ar3 and Ar4 may be each independently any one selected from the group consisting of:
In Chemical Formula 2, L1 and L2 may be each independently a single bond or any one selected from the group consisting of:
In Chemical Formula 2, R11 to R14 may be hydrogen.
The compound represented by Chemical Formula 2 may be selected from the group consisting of the following compounds.
The compound represented by Chemical Formula 2 may be prepared by the method as shown in Reaction Scheme 3 below. The preparation method will be more specifically described in the Preparation Examples described hereinafter.
in the Reaction Scheme 3, the remaining substituents excluding Q′ are the same as defined above, and Q′ is halogen, more preferably bromo, or chloro. The above reaction is a Suzuki-coupling reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and a reactive group for the Suzuki-coupling reaction can be modified as known in the art. The above preparation method will be more specifically described in the Preparation Examples described hereinafter.
The light emitting layer may further include a host material known in the technical field to which the present disclosure pertains, in addition to the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2. Specific examples of such host materials include fused aromatic ring derivatives or heteroring-containing compounds or the like. Specifically, the fused aromatic ring derivative includes anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds and the like, and the heteroring-containing compound includes carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives and the like, but the material is not limited thereto.
Meanwhile, the light emitting layer may include a dopant material. The dopant material includes aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes and the like. Specifically, the aromatic amine derivative is a fused aromatic ring derivative having a substituted or unsubstituted arylamino group and includes pyrene, anthracene, chrysene, peryflanthene and the like, which have an arylamino group, and the styrylamine compound is a compound in which substituted or unsubstituted arylamine is substituted with at least one arylvinyl group, and one, two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetramine or the like is included, but the styrylamine compound is not limited thereto. In addition, the metal complex includes iridium complexes, platinum complexes or the like, but is not limited thereto.
For example, the dopant may be any one selected from the following Dp-1 to Dp-38.
Hole Transport Layer
The hole transport layer is a layer that receives holes from an anode or a hole injection layer formed on the anode and transports the holes to the light emitting layer. The hole transport material is suitably a material having large mobility to the holes, which may receive holes from the anode or the hole injection layer and transfer the holes to the light emitting layer.
Specific examples thereof include an arylamine-based organic material, a conductive polymer, a block copolymer in which a conjugate portion and a non-conjugate portion are present together, and the like, but are not limited thereto.
Hole Regulating Layer
The hole regulating layer refers to a layer that serves to regulate a movement of holes according to the energy level of the light emitting layer in the organic light emitting device.
Electron Transport Layer
The electron transport layer is layer which receives electrons from an electron injection layer and transports the electrons to a light emitting layer, and the electron transport material is suitably a material which may receive electrons well from a cathode and transfer the electrons to a light emitting layer, and has a large mobility for electrons. Specific examples of the electron transport material include: a pyridine derivative; a pyrimidine derivative; triazole derivative; an Al complex of 8-hydroxyquinoline; a complex including Alq3; an organic radical compound; a hydroxyflavone-metal complex, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material, as used according to the related art. In particular, appropriate examples of the cathode material are a typical material which has a low work function, followed by an aluminum layer or a silver layer. Specific examples thereof include cesium, barium, calcium, ytterbium, and samarium, in each case followed by an aluminum layer or a silver layer.
Electron Injection Layer
The organic light emitting device according to the present disclosure may include an electron injection layer between the electron transport layer and the cathode, if necessary. The electron injection layer is a layer which injects electrons from a cathode, and is preferably a compound which has a capability of transporting electrons, has an effect of injecting electrons from a cathode and an excellent effect of injecting electrons into a light emitting layer or a light emitting material, prevents excitons produced from the light emitting layer from moving to a hole injection layer, and is also excellent in the ability to form a thin film. Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, and the like, and derivatives thereof, a metal complex compound, a nitrogen-containing 5-membered ring derivative, and the like, but are not limited thereto.
Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h]quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)(o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, and the like, but are not limited thereto.
Organic Light Emitting Device
The structure of the organic light emitting device according to one embodiment is illustrated in
The organic light emitting device according to the present disclosure may be manufactured by sequentially laminating the above-mentioned components. In this case, the organic light emitting device may be manufactured may be manufactured by depositing a metal, metal oxides having conductivity, or an alloy thereof on the substrate using a PVD (physical vapor deposition) method such as a sputtering method or an e-beam evaporation method to form an anode, forming the above-mentioned respective layers thereon, and then depositing a material that can be used as the cathode thereon. In addition to such a method, the organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer and an anode material on a substrate. Further, the light emitting layer may be formed using the host and the dopant by a solution coating method as well as a vacuum deposition method. Herein, the solution coating method means a spin coating, a dip coating, a doctor blading, an inkjet printing, a screen printing, a spray method, a roll coating, or the like, but is not limited thereto.
In addition to such a method, the organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer and an anode material on a substrate (International Publication WO2003/012890). However, the manufacturing method is not limited thereto.
Meanwhile, the organic light emitting device according to the present disclosure may be a front side emission type, a backside emission type, or a double-sided emission type according to the used material.
The preparation of the organic light emitting device will be described in detail in the following examples. However, these examples are presented for illustrative purposes only, and are not intended to limit the scope of the present disclosure.
1) Preparation of Intermediate a-1
Naphthalen-2-amine (300.0 g, 1.0 eq), 1-bromo-2-iodobenzene (592.7 g, 1.0 eq), sodium tert-butoxide (NaOtBu, 302.0 g, 1.5 eq), palladium acetate (Pd(OAc)2, 4.70 g, 0.01 eq), xantphos (12.12 g, 0.01 eq) were dissolved in 1,4-dioxane (5 L), and the mixture was refluxed and stirred. When the reaction was terminated after 3 hours, the solvent was removed under reduced pressure. Then, the reaction mixture was completely dissolved in ethyl acetate, washed with water, and then approximately 70% of the solvent was removed under reduced pressure again. Under reflux again, crystals were dropped while adding hexane thereto, and the result was cooled and then filtered. This was subjected to column chromatography to give Intermediate a-1. (443.5 g, yield: 71%, [M+H]+=299) 2) Preparation of Intermediate a (5H-benzo[b]carbazole)
Intermediate a-1 (443.5 g, 1.0 eq), bis(tri-tert-butylphosphine)palladium (0) (Pd(t-Bu3P)2, 8.56 g, 0.01 eq) and potassium carbonate (K2CO3, 463.2 g, 2.00 eq) were added to diethylacetamide (4 L), and the mixture was refluxed and stirred. After 3 hours, the reaction solution was poured into water, crystals were dropped, and filtered. The filtered solid was completely dissolved in 1,2-dichlorobenzene, washed with water, and the solution in which the product was dissolved was concentrated under reduced pressure, and crystals were dropped, and the result was cooled and then filtered. This was purified by column chromatography to give Intermediate a (5H-benzo[b]carbazole). (174.8 g, yield: 48%, [M+H]+=218)
The following Intermediate b (7H-dibenzo[b,g]carbazole) was obtained in the same manner as in Preparation Example 1-1, except that 1-bromo-2-iodonaphthalene was used instead of 1-bromo-2-iodobenzene.
The following Intermediate c (6H-dibenzo[b,h]carbazole) was obtained in the same manner as in Preparation Example 1-1, except that 2,3-dibromonaphthalene was used instead of 1-bromo-2-iodobenzene.
The following Intermediate d (13H-dibenzo[a,h]carbazole) was obtained in the same manner as in Preparation Example 1, except that 2-bromo-1-iodonaphthalene was used instead of 1-bromo-2-iodobenzene.
1) Preparation of Intermediate e-2
1-Bromo-3-fluoro-2-iodobenzene (200.0 g, 1.0 eq), (4-chloro-2-hydroxyphenyl)boronic acid (82.3 g, 1.0 eq), potassium carbonate (K2CO3, 164.6 g, 2.0 eq) and tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4, 13.77 g, 0.02 eq) were dissolved in tetrahydrofuran (THF, 3 L), and the mixture was refluxed and stirred. When the reaction was terminated after 2 hours, the solvent was removed under reduced pressure. Then, the reaction mixture was completely dissolved in ethyl acetate, washed with water, and then approximately 80% of the solvent was removed under reduced pressure again. Under reflux again, crystals were dropped while adding hexane thereto, and the result was cooled and then filtered. This was subjected to column chromatography to give Intermediate e-2. (129.5 g, yield: 72%, [M+H]+=300)
2) Preparation of Intermediate e-1
Intermediate e-2 (129.5 g, 1.0 eq) and potassium carbonate (K2CO3, 118.5 g, 2.00 eq) were added to diethylacetamide (2 L), and the mixture was refluxed and stirred. After 1 hour, the reaction solution was poured into water, crystals were dropped and filtered. The filtered solid was completely dissolved in ethyl acetate, washed with water, and then approximately 70% of the solvent was removed under reduced pressure again. Under reflux again, crystals were dropped while adding hexane thereto, and the result was cooled and then filtered. This was subjected to column chromatography to give Intermediate e-1. (101.6 g, yield: 84%, [M+H]+=280)
3) Preparation of Intermediate e
Intermediate e-1 (101.6 g, 1.0 eq), bis(pinacolato)diboron (119.1 g, 1.3 eq), 1,1-bis(diphenylphosphino) ferrocene-palladium (II) dichloride (Pd(dppf)Cl2, 5.28 g, 0.02 eq) and potassium acetate (KOAc, 40.4 g, 2.00 eq) were added to dioxane (2 L), and the mixture was refluxed and stirred. When the reaction was terminated after 3 hours, the solvent was removed under reduced pressure. The filtered solid was completely dissolved in chloroform (CHCl3), washed with water, and the solution in which the product was dissolved was concentrated under reduced pressure to remove approximately 90% of the solvent. Under reflux again, crystals were dropped while adding ethanol thereto, and the result was cooled and then filtered to give Intermediate e. (103.1 g, yield: 87%, [M+H]+=329)
The following Intermediate f was obtained in the same manner as in Preparation Example 1-5, except that (5-chloro-2-hydroxyphenyl)boronic acid was used instead of (4-chloro-2-hydroxyphenyl)boronic acid.
The following Intermediate g was obtained in the same manner as in Preparation Example 1-5, except that 3-bromo-1-fluoro-2-iodonaphthalene was used instead of 1-bromo-3-fluoro-2-iodobenzene.
The following Intermediate h was obtained in the same manner as in Preparation Example 1-7, except that (4-chloro-2-hydroxyphenyl)boronic acid was used instead of (4-chloro-2-hydroxyphenyl)boronic acid.
The following Intermediate i was obtained in the same manner as in Preparation Example 1-5, except that 1-bromo-3-fluoro-2-iodonaphthalene was used instead of 1-bromo-3-fluoro-2-iodobenzene.
The following Intermediate j was obtained in the same manner as in Preparation Example 1-9, except that (5-chloro-2-hydroxyphenyl)boronic acid was used instead of (4-chloro-2-hydroxyphenyl)boronic acid.
Intermediate 1-1 (20.0 g, 46.2 mmol), Intermediate a (10.0 g, 46.2 mmol), and sodium tert-butoxide (8.9 g, 92.4 mmol) were added to xylene (400 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added thereto. When the reaction was terminated after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 1. (14.7 g, yield: 52%, MS: [M+H]+=615)
Intermediate 2-1 (20.0 g, 46.2 mmol), Intermediate a (10.0 g, 46.2 mmol) and sodium tert-butoxide (8.9 g, 92.4 mmol) were added to xylene (400 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added thereto. When the reaction was terminated after 3 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2. (19.3 g, yield: 68%, MS: [M+H]+=615)
Intermediate 3-1 (20.0 g, 41.4 mmol), Intermediate a (9 g, 41.4 mmol) and sodium tert-butoxide (8 g, 82.8 mmol) were added to xylene (400 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added thereto. When the reaction was terminated after 3 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 3. (16.8 g, yield: 61%, MS: [M+H]+=665)
Intermediate 4-1 (20.0 g, 41.4 mmol), Intermediate a (9 g, 41.4 mmol) and sodium tert-butoxide (8 g, 82.8 mmol) were added to xylene (400 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added thereto. When the reaction was terminated after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 4. (16.2 g, yield: 59%, MS: [M+H]+=665)
Intermediate 5-1 (20.0 g, 41.4 mmol), Intermediate a (9 g, 41.4 mmol) and sodium tert-butoxide (8 g, 82.8 mmol) were added to xylene (400 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added thereto. When the reaction was terminated after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 5. (13.7 g, yield: 50%, MS: [M+H]+=665)
Intermediate 6-1 (20.0 g, 36.4 mmol), Intermediate b (9.7 g, 36.4 mmol) and sodium tert-butoxide (7 g, 72.8 mmol) were added to xylene (400 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added thereto. When the reaction was terminated after 3 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 6. (14.8 g, yield: 61%, MS: [M+H]+=665)
Intermediate 7-1 (20.0 g, 46.2 mmol), Intermediate b (12.3 g, 46.2 mmol) and sodium tert-butoxide (8.9 g, 92.4 mmol) were added to xylene (400 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added thereto. When the reaction was terminated after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 7. (18.4 g, yield: 60%, MS: [M+H]+=665)
Intermediate 8-1 (20.0 g, 41.4 mmol), Intermediate b (11.1 g, 41.4 mmol) and sodium tert-butoxide (8 g, 82.8 mmol) were added to xylene (400 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added thereto. When the reaction was terminated after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 8. (14.8 g, yield: 50%, MS: [M+H]+=715)
Intermediate 9-1 (20.0 g, 46.2 mmol), Intermediate c (12.3 g, 46.2 mmol) and sodium tert-butoxide (8.9 g, 92.4 mmol) were added to xylene (400 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added thereto. When the reaction was terminated after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 9. (17.8 g, yield: 58%, MS: [M+H]+=665)
Intermediate 10-1 (20.0 g, 46.2 mmol), Intermediate c (12.3 g, 46.2 mmol) and sodium tert-butoxide (8.9 g, 92.4 mmol) were added to xylene (400 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added thereto. When the reaction was terminated after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 10. (15.3 g, yield: 50%, MS: [M+H]+=665)
Intermediate 11-1 (20.0 g, 41.4 mmol), Intermediate c (11.1 g, 41.4 mmol) and sodium tert-butoxide (8 g, 82.8 mmol) were added to xylene (400 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added thereto. When the reaction was terminated after 3 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 11. (16.9 g, yield: 57%, MS: [M+H]+=715)
Intermediate 12-1 (20.0 g, 37.5 mmol), Intermediate d (10.0 g, 37.5 mmol) and sodium tert-butoxide (7.2 g, 75 mmol) were added to xylene (400 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added thereto. When the reaction was terminated after 3 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 12. (15.2 g, yield: 53%, MS: [M+H]+=765)
Intermediate 13-1 (20.0 g, 40.9 mmol), Intermediate a (8.9 g, 40.9 mmol) and sodium tert-butoxide (7.9 g, 81.7 mmol) were added to xylene (400 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added thereto. When the reaction was terminated after 3 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 13. (15 g, yield: 52%, MS: [M+H]+=706)
Intermediate 14-1 (20.0 g, 42.1 mmol), Intermediate a (9.1 g, 42.1 mmol) and sodium tert-butoxide (8.1 g, 84.1 mmol) were added to xylene (400 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added thereto. When the reaction was terminated after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 14. (20 g, yield: 69%, MS: [M+H]+=692)
Intermediate 15-1 (20.0 g, 31.7 mmol), Intermediate a (6.9 g, 31.7 mmol) and sodium tert-butoxide (6.1 g, 63.3 mmol) were added to xylene (400 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was terminated after 3 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 15. (18.5 g, yield: 69%, MS: [M+H]+=848)
Intermediate 16-1 (20.0 g, 39.6 mmol), Intermediate c (10.6 g, 39.6 mmol) and sodium tert-butoxide (7.6 g, 79.1 mmol) were added to xylene (400 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added thereto. When the reaction was terminated after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 16. (20.4 g, yield: 67%, MS: [M+H]+=772)
Intermediate 17-1 (20.0 g, 39.6 mmol), Intermediate b (10.6 g, 39.6 mmol) and sodium tert-butoxide (7.6 g, 79.1 mmol) were added to xylene (400 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added thereto. When the reaction was terminated after 3 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 17. (21.3 g, yield: 70%, MS: [M+H]+=772)
Intermediate 18-1 (20.0 g, 34.7 mmol), Intermediate a (7.5 g, 34.7 mmol) and sodium tert-butoxide (6.7 g, 69.5 mmol) were added to xylene (400 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added thereto. When the reaction was terminated after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 18. (17.6 g, yield: 64%, MS: [M+H]+=792)
Intermediate 19-1 (20.0 g, 39.6 mmol), Intermediate a (8.6 g, 39.6 mmol) and sodium tert-butoxide (7.6 g, 79.1 mmol) were added to xylene (400 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added thereto. When the reaction was terminated after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 19. (17.4 g, yield: 61%, MS: [M+H]+=722)
Intermediate 20-1 (20.0 g, 33.2 mmol), Intermediate a (7.2 g, 33.2 mmol) and sodium tert-butoxide (6.4 g, 66.5 mmol) were added to xylene (400 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added thereto. When the reaction was terminated after 3 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 20. (18.2 g, yield: 67%, MS: [M+H]+=818)
Intermediate 21-1 (20.0 g, 36.4 mmol), Intermediate b (9.7 g, 36.4 mmol) and sodium tert-butoxide (7 g, 72.8 mmol) were added to xylene (400 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added thereto. When the reaction was terminated after 3 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 21. (18.1 g, yield: 61%, MS: [M+H]+=816)
Intermediate 22-1 (20.0 g, 37.1 mmol), Intermediate a (8.1 g, 37.1 mmol) and sodium tert-butoxide (7.1 g, 74.1 mmol) were added to xylene (400 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added thereto. When the reaction was terminated after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 22. (19 g, yield: 68%, MS: [M+H]+=756)
Intermediate 2-1-1 (10.0 g, 25.2 mmol) and Intermediate 2-1-2 (8 g, 27.7 mmol) were added to tetrahydrofuran (THF, 200 ml) under a nitrogen atmosphere, stirred, and potassium carbonate (13.9 g, 100.7 mmol) was dissolved in water and added thereto. The mixture was sufficiently stirred and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2-1. (9 g, yield: 64%, MS: [M+H]+=561)
Intermediate 2-2-1 (10.0 g, 25.2 mmol) and Intermediate 2-2-2 (8 g, 27.7 mmol) were added to THF (200 ml) under a nitrogen atmosphere, stirred, and potassium carbonate (13.9 g, 100.7 mmol) was dissolved in water and added thereto. The mixture was sufficiently stirred and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2-2. (10.6 g, yield: 66%, MS: [M+H]+=637)
Intermediate 2-3-1 (10.0 g, 25.2 mmol) and Intermediate 2-3-2 (10.1 g, 27.7 mmol) were added to THF (200 ml) under a nitrogen atmosphere, stirred, and potassium carbonate (13.9 g, 100.7 mmol) was dissolved in water and added thereto. The mixture was sufficiently stirred and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2-3. (9 g, yield: 56%, MS: [M+H]+=637)
Intermediate 2-4-1 (10.0 g, 25.2 mmol) and Intermediate 2-4-2 (9.3 g, 27.7 mmol) were added to THF (200 ml) under a nitrogen atmosphere, stirred, and potassium carbonate (13.9 g, 100.7 mmol) was dissolved in water and added thereto. The mixture was sufficiently stirred and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2-4. (7.8 g, yield: 51%, MS: [M+H]+=611)
Intermediate 2-5-1 (10.0 g, 25.2 mmol) and Intermediate 2-5-2 (10.1 g, 27.7 mmol) were added to THF (200 ml) under a nitrogen atmosphere, stirred, and potassium carbonate (13.9 g, 100.7 mmol) was dissolved in water and added thereto. The mixture was sufficiently stirred and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2-5. (10.4 g, yield: 65%, MS: [M+H]+=637)
Intermediate 2-6-1 (10.0 g, 25.2 mmol) and Intermediate 2-6-2 (11.4 g, 27.7 mmol) were added to THF (200 ml) under a nitrogen atmosphere, stirred, and potassium carbonate (13.9 g, 100.7 mmol) was dissolved in water and added thereto. The mixture was sufficiently stirred and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2-6. (10.5 g, yield: 61%, MS: [M+H]+=687)
Intermediate 2-7-1 (10.0 g, 22.4 mmol) and Intermediate 2-7-2 (10.2 g, 24.6 mmol) were added to THF (200 ml) under a nitrogen atmosphere, stirred, and potassium carbonate (12.4 g, 89.5 mmol) was dissolved in water and added thereto. The mixture was sufficiently stirred and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2-7. (11 g, yield: 67%, MS: [M+H]+=737)
Intermediate 2-8-1 (10.0 g, 17.9 mmol) and Intermediate 2-8-2 (5.6 g, 19.7 mmol) were added to THF (200 ml) under a nitrogen atmosphere, stirred, and potassium carbonate (9.9 g, 71.5 mmol) was dissolved in water and added thereto. The mixture was sufficiently stirred and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2-8. (7.8 g, yield: 60%, MS: [M+H]+=723)
Intermediate 2-9-1 (10.0 g, 21.1 mmol) and Intermediate 2-9-2 (6.7 g, 23.3 mmol) were added to THF (200 ml) under a nitrogen atmosphere, stirred, and potassium carbonate (11.7 g, 84.6 mmol) was dissolved in water and added thereto. The mixture was sufficiently stirred and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2-9. (7.4 g, yield: 55%, MS: [M+H]+=637)
Intermediate 2-10-1 (10.0 g, 27 mmol) and Intermediate 2-10-2 (10.0 g, 29.6 mmol) were added to THF (200 ml) under a nitrogen atmosphere, stirred, and potassium carbonate (14.9 g, 107.8 mmol) was dissolved in water and added thereto. The mixture was sufficiently stirred and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2-10. (11 g, yield: 70%, MS: [M+H]+=585)
Intermediate 2-11-1 (10.0 g, 27 mmol) and Intermediate 2-11-2 (11.5 g, 29.6 mmol) were added to THF (200 ml) under a nitrogen atmosphere, stirred, and potassium carbonate (14.9 g, 107.8 mmol) was dissolved in water and added thereto. The mixture was sufficiently stirred and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2-11. (11.5 g, yield: 67%, MS: [M+H]+=635)
Intermediate 2-12-1 (10.0 g, 23.8 mmol) and Intermediate 2-12-2 (8.8 g, 26.1 mmol) were added to THF (200 ml) under a nitrogen atmosphere, stirred, and potassium carbonate (13.1 g, 95 mmol) was dissolved in water and added thereto. The mixture was sufficiently stirred and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2-12. (10.4 g, yield: 69%, MS: [M+H]+=635)
Intermediate 2-13-1 (10.0 g, 24.3 mmol) and Intermediate 2-13-2 (11.1 g, 26.8 mmol) were added to THF (200 ml) under a nitrogen atmosphere, stirred, and potassium carbonate (13.5 g, 97.3 mmol) was dissolved in water and added thereto. The mixture was sufficiently stirred and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2-13. (9 g, yield: 53%, MS: [M+H]+=701)
Intermediate 2-14-1 (10.0 g, 24.3 mmol) and Intermediate 2-14-2 (7.7 g, 26.8 mmol) were added to THF (200 ml) under a nitrogen atmosphere, stirred, and potassium carbonate (13.5 g, 97.3 mmol) was dissolved in water and added thereto. The mixture was sufficiently stirred and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2-14. (8.9 g, yield: 64%, MS: [M+H]+=575)
Intermediate 2-15-1 (10.0 g, 24.3 mmol) and Intermediate 2-15-2 (9 g, 26.8 mmol) were added to THF (200 ml) under a nitrogen atmosphere, stirred, and potassium carbonate (13.5 g, 97.3 mmol) was dissolved in water and added thereto. The mixture was sufficiently stirred and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2-15. (8.4 g, yield: 55%, MS: [M+H]+=625)
Intermediate 2-16-1 (10.0 g, 24.3 mmol) and Intermediate 2-16-2 (11.1 g, 26.8 mmol) were added to THF (200 ml) under a nitrogen atmosphere, stirred, and potassium carbonate (13.5 g, 97.3 mmol) was dissolved in water and added thereto. The mixture was sufficiently stirred and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2-16. (11.2 g, yield: 66%, MS: [M+H]+=701)
Intermediate 2-17-1 (10.0 g, 24.3 mmol) and Intermediate 2-17-2 (10.1 g, 26.8 mmol) were added to THF (200 ml) under a nitrogen atmosphere, stirred, and potassium carbonate (13.5 g, 97.3 mmol) was dissolved in water and added thereto. The mixture was sufficiently stirred and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2-17. (10.0 g, yield: 62%, MS: [M+H]+=665)
Intermediate 2-18-1 (10.0 g, 24.3 mmol) and Intermediate 2-18-2 (10.5 g, 26.8 mmol) were added to THF (200 ml) under a nitrogen atmosphere, stirred, and potassium carbonate (13.5 g, 97.3 mmol) was dissolved in water and added thereto. The mixture was sufficiently stirred and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2-18. (9.8 g, yield: 59%, MS: [M+H]+=681)
Intermediate 2-19-1 (10.0 g, 24.3 mmol) and Intermediate 2-19-2 (10.5 g, 26.8 mmol) were added to THF (200 ml) under a nitrogen atmosphere, stirred, and potassium carbonate (13.5 g, 97.3 mmol) was dissolved in water and added thereto. The mixture was sufficiently stirred and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2-19. (11.4 g, yield: 69%, MS: [M+H]+=681)
Intermediate 2-20-1 (10.0 g, 23.4 mmol) and Intermediate 2-20-2 (9.4 g, 25.8 mmol) were added to THF (200 ml) under a nitrogen atmosphere, stirred, and potassium carbonate (12.9 g, 93.7 mmol) was dissolved in water and added thereto. The mixture was sufficiently stirred and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2-20. (9 g, yield: 58%, MS: [M+H]+=667)
Intermediate 2-21-1 (10.0 g, 23.4 mmol) and Intermediate 2-21-2 (10.6 g, 25.8 mmol) were added to THF (200 ml) under a nitrogen atmosphere, stirred, and potassium carbonate (12.9 g, 93.7 mmol) was dissolved in water and added thereto. The mixture was sufficiently stirred and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2-21. (10.7 g, yield: 64%, MS: [M+H]+=717)
Intermediate 2-22-1 (10.0 g, 23.4 mmol) and Intermediate 2-22-2 (11.3 g, 25.8 mmol) were added to THF (200 ml) under a nitrogen atmosphere, stirred, and potassium carbonate (12.9 g, 93.7 mmol) was dissolved in water and added thereto. The mixture was sufficiently stirred and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2-22. (9 g, yield: 52%, MS: [M+H]+=743)
Intermediate 2-23-1 (10.0 g, 23.4 mmol) and Intermediate 2-23-2 (10.1 g, 25.8 mmol) were added to THF (200 ml) under a nitrogen atmosphere, stirred, and potassium carbonate (12.9 g, 93.7 mmol) was dissolved in water and added thereto. The mixture was sufficiently stirred and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give Compound 2-23. (9.1 g, yield: 56%, MS: [M+H]+=697)
A glass substrate on which ITO (indium tin oxide) was coated as a thin film to a thickness of 1,000 Å was put into distilled water in which a detergent was dissolved, and ultrasonically cleaned. A product manufactured by Fischer Co. was used as the detergent, and as the distilled water, distilled water filtered twice using a filter manufactured by Millipore Co. was used. After the ITO was cleaned for 30 minutes, ultrasonic cleaning was repeated twice using distilled water for 10 minutes. After the cleaning with distilled water was completed, the substrate was ultrasonically cleaned with solvents of isopropyl alcohol, acetone, and methanol, dried, and then transferred to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using oxygen plasma and then transferred to a vacuum depositor.
A compound HI-1 below was formed in a thickness of 1150 Å on the ITO transparent electrode prepared above as a hole injection layer, wherein a compound A-1 below was p-doped at a concentration of 1.5%. A compound HT-1 below was vacuum-deposited on the hole injection layer to form a hole transport layer with a film thickness of 800 Å. Then, a compound EB-1 below was vacuum-deposited in a thickness of 150 Å on the hole transport layer to form an electron blocking layer. Then, the compound 1 prepared in Preparation Example 2-1 and the compound 2-1 prepared in Preparation Example 3-1 as host materials were co-deposited at a weight ratio of 1:1 on the EB-1 deposited film, and a dopant Dp-7 compound below was vacuum-deposited at a weight ratio of 98:2 (host: dopant) to form a red light emitting layer with a thickness of 400 Å. A compound HB-1 below was vacuum-deposited in a film thickness of 30 Å on the light emitting layer to form a hole blocking layer. Then, a compound ET-1 below and a compound LiQ below were vacuum deposited at a weight ratio of 2:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 300 Å. Lithium fluoride (LiF) and aluminum were sequentially deposited to have a thickness of 12 Å and 1,000 Å, respectively, on the electron injection and transport layer, thereby forming a cathode.
In the above-mentioned process, the vapor deposition rate of the organic material was maintained at 0.4 to 0.7 Å/sec, the deposition rate of lithium fluoride of the cathode was maintained at 0.3 Å/sec, the deposition rate of aluminum was maintained at 2 Å/sec, and the degree of vacuum during the deposition was maintained at 2×10−7 to 5×10−6 torr, thereby manufacturing the organic light emitting device.
Organic light emitting devices were manufactured in the same manner as in Example 1, except that the first host and the second host described in the following Tables 1 to 5 respectively were co-deposited in a ratio of 1:1 instead of Compound 1 and Compound 2-1 used in the organic light emitting device of Example 1.
Compounds C-1 to C-14 used in Comparative Examples 1 to 56 are as follows.
For the organic light emitting devices manufactured in the Examples and Comparative Examples, the voltage and efficiency were measured at a current density of 10 mA/cm2, and the lifetime was measured at a current density of 50 mA/cm2. The results are shown in Tables 1 to 5 below. T95 means the time (hr) required for the luminance to be reduced to 95% of the initial luminance.
Referring to Tables 1 to 5 above, it was confirmed that Example 1 uses the EB-1 as the electron blocking layer, and the compound of Chemical Formula 1 and the compound of Chemical Formula 2 as the red light emitting layer, and Dp-7 as the dopant, and thereby exhibits low driving voltage and high efficiency and lifetime, as compared with the organic light emitting devices of the Comparative Examples. From this, it can be predicted that when the combination of the compound of Chemical Formula 1 which is the first host and the compound of Formula 2 which is the second host is used, energy transfer to the red dopant in the red light emitting layer is performed well and thus, the efficiency and lifetime of the organic light emitting device are effectively increased. Furthermore, it can be predicted that the Examples have higher stability to electrons and holes as compared with the Comparative Examples. In addition, it can be predicted that as the amount of holes increases depending on the use of the second host, electrons and holes in the red light emitting layer maintain a more stable balance and thereby, the efficiency and the lifetime are further increased. That is, it was confirmed that when the compound of Chemical Formula 1 and the compound of Chemical Formula 2 were vapor-deposited and used as a host of the red light emitting layer, the driving voltage, light emitting efficiency and lifetime characteristics of the organic light emitting device could be improved.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2019-0051622 | May 2019 | KR | national |
| 10-2020-0052000 | Apr 2020 | KR | national |
CROSS-REFERENCE TO RELATED APPLICATION(S) This application is a National Stage Application of International Application No. PCT/KR2020/005777 filed on Apr. 29, 2020, which claims priority to Korean Patent Application No. 10-2019-0051622 filed on May 2, 2019 and Korean Patent Application No. 10-2020-0052000 filed on Apr. 29, 2020, the disclosures of which are incorporated herein by reference in their entirety.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2020/005777 | 4/29/2020 | WO | 00 |
