Patent Application
20240114776
The present disclosure relates to a novel compound and an organic light emitting device including the same.
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.
The present disclosure relates to a novel compound and an organic light emitting device including the same.
In the present disclosure, there is provided a compound represented by the following Chemical Formula 1 or 2:
in Chemical Formulae 1 and 2,
In addition, there is provided an organic light emitting device including: a first electrode; a second electrode that is disposed to face the first electrode; and an organic material layer including one or more layers between the first electrode and the second electrode, wherein one or more layers of the organic material layer include the compound represented by the Chemical Formula 1 or 2.
The compound represented by the Chemical Formula 1 or Chemical Formula 2 may be used as a material for an organic material layer of an organic light emitting device, and may improve efficiency, low driving voltage, and/or lifespan of the organic light emitting device. In particular, the compound represented by the Chemical Formula 1 or 2 may be used as a material for hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection.
Hereinafter, embodiments of the present disclosure will be described in more detail to facilitate understanding of the invention.
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 hydroxyl 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 in 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 also 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 formulae, but is not limited thereto.
In the present disclosure, an ester group may have a structure in which oxygen of the ester group is 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 formulae, 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 formulae, 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, 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 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 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 monocyclic aryl group includes a phenyl group, a biphenyl group, a terphenyl group and the like, 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 substituents 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 at least one heteroatom of O, N, Si and S as a heterogeneous element, 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. In the present disclosure, the heteroaryl in the heteroarylamine can apply 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 heterocycle is not a monovalent group but formed by combining two substituent groups.
In the Chemical Formula 1, at least one hydrogen may be substituted with deuterium.
Preferably, Ar is substituted or unsubstituted C6-12 aryl. More preferably, Ar is phenyl, biphenyl, or naphthyl.
Preferably, L is a single bond, or substituted or unsubstituted C6-12 arylene. More preferably, L is a single bond, phenylene, biphenyldiyl, terphenyldiyl, naphthylene, or -(phenylene)-(naphthylene)-. More preferably, L is a single bond, 1,4-phenylene, 4,4′-biphenyldiyl, or 2,6-naphthylene.
Preferably, L1 and L2 are each independently a single bond, or substituted or unsubstituted C6-12 arylene. More preferably, L1 and L2 are each independently a single bond, phenylene, or biphenyldiyl. More preferably, L1 and L2 are each independently a single bond, 1,4-phenylene, or 4,4′-biphenyldiyl.
Preferably, Ar1 and Ar2 are each independently phenyl, biphenylyl, terphenylyl, naphthyl, naphthylphenyl, phenylnaphthyl, phenanthrenyl, dimethylfluorenyl, diphenylfluorenyl, dibenzofuranyl, dibenzothiophenyl, 9H-carbazol-9-yl, or 9-phenyl-9H-carbazolyl.
Preferably, one of R1 to R4 is the Chemical Formula 3, and the rest are each independently hydrogen or deuterium; and R5 and R6 are each independently hydrogen or deuterium.
Preferably, R1 to R4 are each independently hydrogen, or deuterium; and one of R5 and R6 is the Chemical Formula 3, and the rest is hydrogen or deuterium. Herein, preferably, L1 is phenylene or biphenyldiyl, and Ar is biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dimethylfluorenyl, or diphenylfluorenyl; or L1 is a single bond, phenylene, or biphenyldiyl, and Ar is dibenzofuranyl, dibenzothiophenyl, 9H-carbazol-9-yl, or 9-phenyl-9H-carbazolyl. More preferably, Ar1 and Ar2 are each independently terphenylyl, naphthyl, phenanthrenyl, dimethylfluorenyl, diphenylfluorenyl, dibenzofuranyl, dibenzothiophenyl, 9H-carbazol-9-yl, or 9-phenyl-9H-carbazolyl. Alternatively, preferably, Ar is phenyl and Ar2 is phenyl, biphenyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, 9H-carbazol-9-yl, or 9-phenyl-9H-carbazolyl; or Ar is biphenylyl, and Ar2 is terphenylyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, 9H-carbazol-9-yl, or 9-phenyl-9H-carbazolyl. Herein, preferably, L1 and L2 are each independently a single bond, phenylene, or biphenyldiyl, and more preferably, L1 and L2 are each independently a single bond, 1,4-phenylene, or 4,4′-biphenyldiyl.
Representative examples of the compound represented by the Chemical Formula 1 or 2 areas follows:
In addition, the present disclosure provides a method for preparing a compound represented by the Chemical Formula 1 in which R1 is the Chemical Formula 3 as shown in Reaction Scheme 1 below, and the other compounds represented by the Chemical Formulae 1 and 2 may also be prepared in a similar manner.
in the Reaction Scheme 1, definitions of other substituents except for X and Y are the same as defined above, and X is halogen, preferably bromo, or chloro. Y is hydrogen when L is a single bond, and —B(OH)2 when L is not a single bond. The Reaction Scheme 1 is an amine substitution reaction or a Suzuki coupling reaction, and preferably performed in the presence of a palladium catalyst and a base. In addition, the reactive group for each reaction may be appropriately changed, and the preparation method may be more specifically described in Preparation Examples described below.
In addition, according to another aspect of the present disclosure, there is provided an organic light emitting device including the above-mentioned compound represented by the Chemical Formula 1 or Chemical Formula 2. As an example, there is provided an organic light emitting device including: a first electrode; a second electrode disposed to face the first electrode; and an organic material layer including one or more layers between the first electrode and the second electrode, wherein one or more layers of the organic material layer include the compound represented by the Chemical Formula 1 or 2.
The organic material layer of the organic light emitting device of the present disclosure may have a single-layer structure, or it may have a multilayered structure in which two or more organic layers are stacked. For example, the organic light emitting device of the present disclosure may have a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like as the organic material layer. However, the structure of the organic light emitting device is not limited thereto, and it may include a smaller number of organic layers.
The organic material layer may include a light emitting layer, and the light emitting layer may include a compound represented by the Chemical Formula 1 or Chemical Formula 2. In particular, the compound according to the present disclosure can be used as a dopant in the light emitting layer.
In addition, the organic material layer may include an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer may include a compound represented by the Chemical Formula 1 or Chemical Formula 2.
In addition, the organic material layer may include an electron transport and injection layer, and the electron transport and injection layer may include a compound represented by the Chemical Formula 1 or Chemical Formula 2.
In addition, the organic material layer may include a light emitting layer and an electron transport layer, and the electron transport layer may include a compound represented by the Chemical Formula 1 or Chemical Formula 2.
In addition, the organic material layer may include an electron blocking layer, and the electron blocking layer may include a compound represented by the Chemical Formula 1 or Chemical Formula 2.
Further, the organic light emitting device according to the present disclosure may be a normal type organic light emitting device in which an anode, one or more layers of an organic material layer and a cathode are sequentially stacked on a substrate. Further, the organic light emitting device according to the present disclosure may be an inverted type organic light emitting device in which a cathode, one or more layers of an organic material layer and an anode are sequentially stacked on a substrate. For example, the structure of an organic light emitting device according to an embodiment of the present disclosure is illustrated in
The organic light emitting device according to the present disclosure may be manufactured using materials and methods known in the art, except that one or more layers of the organic material layer include the compound represented by Chemical Formula 1 or Chemical Formula 2. Moreover, when the organic light emitting device includes the organic material layer comprising a plurality of organic layers, the organic layers may be formed of the same material or different materials.
For example, the organic light emitting device according to the present disclosure can be manufactured by sequentially stacking a first electrode, an organic material layer and a second electrode on a substrate. In this case, the organic light emitting device 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 an organic material layer including the hole injection layer, the hole transport layer, the light emitting layer and the electron transport layer 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 compound represented by Chemical Formula 1 or Chemical Formula 2 may be formed into an organic material layer by a solution coating method as well as a vacuum deposition method at the time of manufacturing an organic light emitting device. 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.
For example, the first electrode is an anode and the second electrode is a cathode, or alternatively, the first electrode is a cathode and the second electrode is an anode.
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.
The hole injection layer is a layer for injecting holes from the electrode, and 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 an electron 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.
In addition, the hole transport layer is a layer that receives holes from a hole injection layer 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.
The light emitting material is suitably a material capable of emitting light in a visible ray region by receiving holes and electrons from the hole transport layer and the electron transport layer, respectively, to combine them, and having good quantum efficiency to fluorescence or phosphorescence. Specific examples thereof include 8-hydroxy-quinoline aluminum complex (Alq3); a carbazole-based compound; a dimerized styryl compound; BAlq; a 10-hydroxybenzo quinoline-metal compound; a benzoxazole-, benzthiazole- and benzimidazole-based compound; a poly(p-phenylenevinylene) (PPV)-based polymer; a spiro compound; polyfluorene, rubrene, and the like, but are not limited thereto.
In addition, the light emitting layer may include a host material and a dopant material. The host material may be a fused aromatic ring derivative or a heterocycle-containing compound. Specific examples of the fused aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like. Examples of the heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
The dopant material includes an aromatic amine derivative, a styrylamine compound, a boron complex, a fluoranthene compound, a metal complex, and the like. Specifically, the aromatic amine derivative is a substituted or unsubstituted fused aromatic ring derivative having an arylamino group, and examples thereof include pyrene, anthracene, chrysene, periflanthene and the like, which have an arylamino group. The styrylamine compound is a compound where at least one arylvinyl group is substituted in substituted or unsubstituted arylamine, in which one or two or more substituent groups 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. Specific examples thereof include styrylamine, styryldiamine, styryltriamine, styryltetramine, and the like, but are not limited thereto. Further, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.
The electron transport layer is a layer which receives electrons from an electron injection layer and transports the electrons to a light emitting layer, and an electron transport material used is suitably a material which can receive electrons well from a cathode and transfer the electrons to a light emitting layer and has large mobility for electrons. Specifically, examples thereof may include 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.
The electron injection layer is a layer which injects electrons from an electrode, 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.
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 compound represented by the Chemical Formula 1 or Chemical Formula 2 and the organic light emitting device including the same 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-bromo-3-chloronaphthalen-2-amine (15 g, 58.5 mmol) and benzoyl chloride (9.9 g, 70.2 mmol) were added to chloroform (300 ml) under a nitrogen atmosphere, and stirred. After that, pyridine (6.9 g, 87.7 mmol) was added dropwise. After 9 hours of reaction at room temperature, ethanol (600 ml) was added for solidification. The resulting solid was filtered, dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17 g of Compound AA_P1 (Yield 81%, MS: [M+H]+=360).
Compound AA_P1 (15 g, 41.6 mmol) and potassium carbonate (17.2 g, 124.8 mmol) were added to DMF (150 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. After sufficient stirring, copper iodide (0.1 g, 0.4 mmol) and 1,10-phenanthroline (0.1 g, 0.8 mmol) were added thereto. After 11 hours of reaction, cooling was performed to at room temperature and water (300 ml) was added for solidification. The resulting solid was filtered, dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.6 g of Compound AA (Yield 83%, MS: [M+H]+=280).
Compound AB was prepared in the same manner as in Preparation Example 1, except that 1-bromo-4-chloronaphthalen-2-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound AC was prepared in the same manner as in Preparation Example 1, except that 1-bromo-5-chloronaphthalen-2-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound AD was prepared in the same manner as in Preparation Example 1, except that 1-bromo-6-chloronaphthalen-2-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound AE was prepared in the same manner as in Preparation Example 1, except that 1-bromo-7-chloronaphthalen-2-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound AF was prepared in the same manner as in Preparation Example 1, except that 1-bromo-8-chloronaphthalen-2-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound AG was prepared in the same manner as in Preparation Example 1, except that [1,1′-biphenyl]-4-carbonyl chloride was used instead of benzoyl chloride.
Compound AH was prepared in the same manner as in Preparation Example 1, except that [1,1′-biphenyl]-4-carbonyl chloride was used instead of benzoyl chloride, and 1-bromo-4-chloronaphthalen-2-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound AH was prepared in the same manner as in Preparation Example 1, except that [1,1′-biphenyl]-4-carbonyl chloride was used instead of benzoyl chloride, and 1-bromo-5-chloronaphthalen-2-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound AJ was prepared in the same manner as in Preparation Example 1, except that [1,1′-biphenyl]-4-carbonyl chloride was used instead of benzoyl chloride, and 1-bromo-6-chloronaphthalen-2-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound AK was prepared in the same manner as in Preparation Example 1, except that [1,1′-biphenyl]-4-carbonyl chloride was used instead of benzoyl chloride, and 1-bromo-7-chloronaphthalen-2-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound AL was prepared in the same manner as in Preparation Example 1, except that [1,1′-biphenyl]-4-carbonyl chloride was used instead of benzoyl chloride, and 1-bromo-8-chloronaphthalen-2-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound AM was prepared in the same manner as in Preparation Example 1, except that 2-naphthoyl chloride was used instead of benzoyl chloride.
Compound AN was prepared in the same manner as in Preparation Example 1, except that 2-naphthoyl chloride was used instead of benzoyl chloride, and 1-bromo-4-chloronaphthalen-2-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound AO was prepared in the same manner as in Preparation Example 1, except that 2-naphthoyl chloride was used instead of benzoyl chloride, and 1-bromo-5-chloronaphthalen-2-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound AP was prepared in the same manner as in Preparation Example 1, except that 2-naphthoyl chloride was used instead of benzoyl chloride, and 1-bromo-6-chloronaphthalen-2-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound AQ was prepared in the same manner as in Preparation Example 1, except that 2-naphthoyl chloride was used instead of benzoyl chloride, and 1-bromo-7-chloronaphthalen-2-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound AR was prepared in the same manner as in Preparation Example 1, except that 2-naphthoyl chloride was used instead of benzoyl chloride, and 1-bromo-8-chloronaphthalen-2-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound BA was prepared in the same manner as in Preparation Example 1, except that 2-bromo-3-chloronaphthalen-1-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound BB was prepared in the same manner as in Preparation Example 1, except that 2-bromo-4-chloronaphthalen-1-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound BC was prepared in the same manner as in Preparation Example 1, except that 2-bromo-5-chloronaphthalen-1-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound BD was prepared in the same manner as in Preparation Example 1, except that 2-bromo-6-chloronaphthalen-1-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound BE was prepared in the same manner as in Preparation Example 1, except that 2-bromo-7-chloronaphthalen-1-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound BF was prepared in the same manner as in Preparation Example 1, except that 2-bromo-8-chloronaphthalen-1-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound BG was prepared in the same manner as in Preparation Example 1, except that [1,1′-biphenyl]-4-carbonyl chloride was used instead of benzoyl chloride, and 2-bromo-3-chloronaphthalen-1-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound BH was prepared in the same manner as in Preparation Example 1, except that [1,1′-biphenyl]-4-carbonyl chloride was used instead of benzoyl chloride, and 2-bromo-4-chloronaphthalen-1-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound BI was prepared in the same manner as in Preparation Example 1, except that [1,1′-biphenyl]-4-carbonyl chloride was used instead of benzoyl chloride, and 2-bromo-3-chloronaphthalen-1-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound BJ was prepared in the same manner as in Preparation Example 1, except that [1,1′-biphenyl]-4-carbonyl chloride was used instead of benzoyl chloride, and 2-bromo-6-chloronaphthalen-1-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound BK was prepared in the same manner as in Preparation Example 1, except that [1,1′-biphenyl]-4-carbonyl chloride was used instead of benzoyl chloride, and 2-bromo-7-chloronaphthalen-1-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound BL was prepared in the same manner as in Preparation Example 1, except that [1,1′-biphenyl]-4-carbonyl chloride was used instead of benzoyl chloride, and 2-bromo-8-chloronaphthalen-1-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound BM was prepared in the same manner as in Preparation Example 1, except that 2-naphthoyl chloride was used instead of benzoyl chloride, and 2-bromo-3-chloronaphthalen-1-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound BN was prepared in the same manner as in Preparation Example 1, except that 2-naphthoyl chloride was used instead of benzoyl chloride, and 2-bromo-4-chloronaphthalen-1-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound BO was prepared in the same manner as in Preparation Example 1, except that 2-naphthoyl chloride was used instead of benzoyl chloride, and 2-bromo-5-chloronaphthalen-1-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound BP was prepared in the same manner as in Preparation Example 1, except that 2-naphthoyl chloride was used instead of benzoyl chloride, and 2-bromo-6-chloronaphthalen-1-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound BQ was prepared in the same manner as in Preparation Example 1, except that 2-naphthoyl chloride was used instead of benzoyl chloride, and 2-bromo-7-chloronaphthalen-1-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound BR was prepared in the same manner as in Preparation Example 1, except that 2-naphthoyl chloride was used instead of benzoyl chloride, and 2-bromo-8-chloronaphthalen-1-amine was used instead of 1-bromo-3-chloronaphthalen-2-amine.
Compound AA (10 g, 35.8 mmol), Compound amine1 (16 g, 35.8 mmol), and sodium tert-butoxide (11.4 g, 53.6 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. Upon completion of the reaction after 2 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 16.8 g of Compound 1 (Yield 68%, MS: [M+H]+=691).
Compound AB (10 g, 35.8 mmol), Compound amine2 (12.9 g, 35.8 mmol), and sodium tert-butoxide (11.4 g, 53.6 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. Upon completion of the reaction after 2 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 13.2 g of Compound 2 (Yield 61%, MS: [M+H]+=605).
Compound AC (10 g, 35.8 mmol), Compound amine3 (16 g, 35.8 mmol), and sodium tert-butoxide (11.4 g, 53.6 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. Upon completion of the reaction after 2 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 17.3 g of Compound 3 (Yield 70%, MS: [M+H]+=691).
Compound AD (10 g, 35.8 mmol), Compound amine4 (10.6 g, 35.8 mmol), and sodium tert-butoxide (11.4 g, 53.6 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. Upon completion of the reaction after 3 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 12.7 g of Compound 4 (Yield 66%, MS: [M+H]+=539).
Compound AE (10 g, 35.8 mmol), Compound amine5 (13.3 g, 35.8 mmol), and sodium tert-butoxide (11.4 g, 53.6 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. Upon completion of the reaction after 2 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 13.4 g of Compound 5 (Yield 61%, MS: [M+H]+=615).
Compound AE (10 g, 35.8 mmol), Compound amine6 (12 g, 35.8 mmol), and sodium tert-butoxide (11.4 g, 53.6 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. Upon completion of the reaction after 3 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 13.4 g of Compound 6 (Yield 65%, MS: [M+H]+=579).
Compound AF (10 g, 35.8 mmol), Compound amine7 (12.3 g, 35.8 mmol), and sodium tert-butoxide (11.4 g, 53.6 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. Upon completion of the reaction after 2 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 13.5 g of Compound 7 (Yield 64%, MS: [M+H]+=589).
Compound AA (15 g, 53.6 mmol), and Compound amine8 (25.6 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 9 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.9 g of Compound 8 (Yield 68%, MS: [M+H]+=655).
Compound AB (15 g, 53.6 mmol) and Compound amine9 (29.9 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 9 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.9 g of Compound 9 (Yield 61%, MS: [M+H]+=730).
Compound AC (15 g, 53.6 mmol) and Compound amine10 (29.9 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 12 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.2 g of Compound 10 (Yield 62%, MS: [M+H]+=730).
Compound AD (15 g, 53.6 mmol) and Compound amine11 (24.9 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 12 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.9 g of Compound 11 (Yield 61%, MS: [M+H]+=641).
Compound AD (15 g, 53.6 mmol) and Compound amine12 (30.5 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 11 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.8 g of Compound 12 (Yield 65%, MS: [M+H]+=741).
Compound AE (15 g, 53.6 mmol) and Compound amine13 (21.4 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 10 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.6 g of Compound 13 (Yield 60%, MS: [M+H]+=579).
Compound AE (15 g, 53.6 mmol) and Compound amine14 (23.4 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 9 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.1 g of Compound 14 (Yield 67%, MS: [M+H]+=615).
Compound AE (15 g, 53.6 mmol) and Compound amine15 (29.9 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 8 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.2 g of Compound 15 (Yield 62%, MS: [M+H]+=730).
Compound AE (15 g, 53.6 mmol) and Compound amine11 (24.9 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 10 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23 g of Compound 16 (Yield 67%, MS: [M+H]+=641).
Compound AF (15 g, 53.6 mmol) and Compound amine16 (27.9 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 8 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.5 g of Compound 17 (Yield 63%, MS: [M+H]+=695).
Compound AA (15 g, 53.6 mmol) and Compound amine17 (36.2 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 11 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 28.5 g of Compound 18 (Yield 63%, MS: [M+H]+=843).
Compound AD (15 g, 53.6 mmol) and Compound amine18 (24.9 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 11 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.3 g of Compound 19 (Yield 68%, MS: [M+H]+=641).
Compound AF (15 g, 53.6 mmol) and Compound amine19 (34.8 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 8 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.6 g of Compound 20 (Yield 63%, MS: [M+H]+=817).
Compound AA (15 g, 53.6 mmol) and Compound amine20 (33.3 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 10 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.5 g of Compound 21 (Yield 65%, MS: [M+H]+=791).
Compound AD (15 g, 53.6 mmol) and Compound amine21 (32 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 12 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.9 g of Compound 22 (Yield 68%, MS: [M+H]+=767).
Compound AE (15 g, 53.6 mmol) and Compound amine22 (23.4 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 10 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.4 g of Compound 23 (Yield 68%, MS: [M+H]+=615).
Compound AH (10 g, 28.1 mmol), Compound amine23 (11.2 g, 28.1 mmol), and sodium tert-butoxide (8.9 g, 42.2 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. Upon completion of the reaction after 3 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 14.1 g of Compound 24 (Yield 70%, MS: [M+H]+=717).
Compound AJ (10 g, 28.1 mmol), Compound amine24 (12.6 g, 28.1 mmol), and sodium tert-butoxide (8.9 g, 42.2 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. Upon completion of the reaction after 2 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 13.1 g of Compound 25 (Yield 61%, MS: [M+H]+=767).
Compound AJ (10 g, 28.1 mmol), Compound amine25 (10.4 g, 28.1 mmol), and sodium tert-butoxide (8.9 g, 42.2 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. Upon completion of the reaction after 2 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 11.8 g of Compound 26 (Yield 61%, MS: [M+H]+=691).
Compound AK (10 g, 28.1 mmol), Compound amine26 (9.8 g, 28.1 mmol), and sodium tert-butoxide (8.9 g, 42.2 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. Upon completion of the reaction after 2 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 11.6 g of Compound 27 (Yield 62%, MS: [M+H]+=669).
Compound AK (15 g, 42.2 mmol) and Compound amine27 (16.2 g, 44.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in water (52 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 12 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.2 g of Compound 28 (Yield 60%, MS: [M+H]+=641).
Compound AI (15 g, 42.2 mmol) and Compound amine28 (19.5 g, 44.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in water (52 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 11 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.1 g of Compound 29 (Yield 60%, MS: [M+H]+=717).
Compound AG (15 g, 42.2 mmol) and Compound amine29 (25.1 g, 44.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in water (52 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 12 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.7 g of Compound 30 (Yield 64%, MS: [M+H]+=843).
Compound AJ (15 g, 42.2 mmol) and Compound amine30 (22.9 g, 44.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in water (52 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 9 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.4 g of Compound 31 (Yield 67%, MS: [M+H]+=793).
Compound AI (15 g, 42.2 mmol) and Compound amine31 (21.8 g, 44.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in water (52 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 11 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.6 g of Compound 32 (Yield 70%, MS: [M+H]+=767).
Compound AL (15 g, 42.2 mmol) and Compound amine32 (22.9 g, 44.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in water (52 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 9 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.4 g of Compound 33 (Yield 70%, MS: [M+H]+=793).
Compound AK (15 g, 42.2 mmol) and Compound amine33 (25.1 g, 44.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in water (52 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 8 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.3 g of Compound 34 (Yield 60%, MS: [M+H]+=843).
Compound AI (15 g, 42.2 mmol) and Compound amine34 (22.4 g, 44.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in water (52 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 9 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.7 g of Compound 35 (Yield 69%, MS: [M+H]+=781).
Compound AH (15 g, 42.2 mmol) and Compound amine35 (22.8 g, 44.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in water (52 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 11 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23 g of Compound 36 (Yield 69%, MS: [M+H]+=791).
Compound AQ (10 g, 30.3 mmol), Compound amine36 (11.1 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. Upon completion of the reaction after 3 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 13.6 g of Compound 37 (Yield 68%, MS: [M+H]+=659).
Compound AO (10 g, 30.3 mmol), Compound amine37 (13.6 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. Upon completion of the reaction after 2 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 14.4 g of Compound 38 (Yield 64%, MS: [M+H]+=741).
Compound AQ (10 g, 30.3 mmol), Compound amine38 (10.2 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. Upon completion of the reaction after 2 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 12 g of Compound 39 (Yield 63%, MS: [M+H]+=629).
Compound AQ (15 g, 45.5 mmol) and Compound amine27 (17.4 g, 47.8 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in water (57 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 8 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.4 g of Compound 40 (Yield 66%, MS: [M+H]+=615).
Compound AN (15 g, 45.5 mmol) and Compound amine39 (24.7 g, 47.8 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in water (57 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 10 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.9 g of Compound 41 (Yield 60%, MS: [M+H]+=767).
Compound AR (15 g, 45.5 mmol) and Compound amine40 (21.1 g, 47.8 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in water (57 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 9 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.7 g of Compound 42 (Yield 66%, MS: [M+H]+=691).
Compound AP (15 g, 45.5 mmol) and Compound amine4l (27.8 g, 47.8 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in water (57 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 8 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.1 g of Compound 43 (Yield 69%, MS: [M+H]+=831).
Compound AQ (15 g, 45.5 mmol) and Compound amine42 (23.5 g, 47.8 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in water (57 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 8 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.9 g of Compound 44 (Yield 68%, MS: [M+H]+=741).
Compound AN (15 g, 45.5 mmol) and Compound amine43 (27.1 g, 47.8 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in water (57 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 12 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26 g of Compound 45 (Yield 70%, MS: [M+H]+=817).
Compound AQ (15 g, 45.5 mmol) and Compound amine44 (27.1 g, 47.8 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in water (57 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 12 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.3 g of Compound 46 (Yield 60%, MS: [M+H]+=817).
Compound AQ (15 g, 43.4 mmol) and Compound amine45 (25.8 g, 45.5 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 9 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.5 g of Compound 47 (Yield 54%, MS: [M+H]+=833).
Compound AP (15 g, 45.5 mmol) and Compound amine46 (23.5 g, 47.8 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in water (57 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 11 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.2 g of Compound 48 (Yield 60%, MS: [M+H]+=741).
Compound AN (15 g, 45.5 mmol) and Compound amine47 (23.5 g, 47.8 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in water (57 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 11 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.5 g of Compound 49 (Yield 64%, MS: [M+H]+=741).
Compound BA (10 g, 30.3 mmol), Compound amine48 (12.1 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. Upon completion of the reaction after 2 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 11.8 g of Compound 50 (Yield 61%, MS: [M+H]+=641).
Compound BA (10 g, 30.3 mmol), Compound amine49 (11.3 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. Upon completion of the reaction after 3 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 11.7 g of Compound 51 (Yield 63%, MS: [M+H]+=615).
Compound BB (10 g, 30.3 mmol), Compound amine50 (12.9 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. Upon completion of the reaction after 2 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 14 g of Compound 52 (Yield 69%, MS: [M+H]+=668).
Compound BC (10 g, 30.3 mmol), Compound amine51 (14 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. Upon completion of the reaction after 2 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 12.8 g of Compound 53 (Yield 60%, MS: [M+H]+=704).
Compound BD (10 g, 30.3 mmol), Compound amine52 (13.6 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. Upon completion of the reaction after 2 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 12.6 g of Compound 54 (Yield 60%, MS: [M+H]+=691).
Compound BE (10 g, 30.3 mmol), Compound amine53 (12.1 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. Upon completion of the reaction after 2 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 13.2 g of Compound 55 (Yield 68%, MS: [M+H]+=641).
Compound BA (15 g, 53.6 mmol) and Compound amine54 (27.1 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 8 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.9 g of Compound 56 (Yield 60%, MS: [M+H]+=681).
Compound BC (15 g, 53.6 mmol) and Compound amine55 (26.5 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 8 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23 g of Compound 57 (Yield 64%, MS: [M+H]+=671).
Compound BC (15 g, 53.6 mmol) and Compound amine56 (24.9 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 8 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.7 g of Compound 58 (Yield 66%, MS: [M+H]+=641).
Compound BE (15 g, 53.6 mmol) and Compound amine57 (22.3 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 9 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.3 g of Compound 59 (Yield 70%, MS: [M+H]+=595).
Compound BF (15 g, 53.6 mmol) and Compound amine58 (32.7 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 8 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.5 g of Compound 60 (Yield 61%, MS: [M+H]+=780).
Compound BE (15 g, 53.6 mmol) and Compound amine59 (36.2 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 8 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 31.6 g of Compound 61 (Yield 70%, MS: [M+H]+=843).
Compound BC (15 g, 53.6 mmol) and Compound amine60 (29.9 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 12 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.2 g of Compound 62 (Yield 67%, MS: [M+H]+=730).
Compound BD (15 g, 53.6 mmol) and Compound amine61 (27.7 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 11 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.2 g of Compound 63 (Yield 60%, MS: [M+H]+=691).
Compound BE (15 g, 53.6 mmol) and Compound amine62 (23.4 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 9 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.1 g of Compound 64 (Yield 64%, MS: [M+H]+=615).
Compound BD (15 g, 53.6 mmol) and Compound amine63 (22.8 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 8 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.7 g of Compound 65 (Yield 67%, MS: [M+H]+=605).
Compound BF (15 g, 53.6 mmol) and Compound amine64 (31.6 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 10 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.9 g of Compound 66 (Yield 66%, MS: [M+H]+=760).
Compound BB (15 g, 53.6 mmol) and Compound amine65 (32 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 10 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.1 g of Compound 67 (Yield 66%, MS: [M+H]+=767).
Compound BC (15 g, 53.6 mmol) and Compound amine66 (32 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 10 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.8 g of Compound 68 (Yield 65%, MS: [M+H]+=569).
Compound BB (15 g, 53.6 mmol) and Compound amine67 (29.1 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 9 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.5 g of Compound 69 (Yield 69%, MS: [M+H]+=717).
Compound BF (15 g, 53.6 mmol) and Compound amine68 (30.5 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 12 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25 g of Compound 70 (Yield 63%, MS: [M+H]+=741).
Compound BC (15 g, 53.6 mmol) and Compound amine69 (26.2 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 11 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.1 g of Compound 71 (Yield 62%, MS: [M+H]+=665).
Compound BF (15 g, 53.6 mmol) and Compound amine70 (23.4 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 9 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.7 g of Compound 72 (Yield 66%, MS: [M+H]+=615).
Compound BE (15 g, 53.6 mmol) and Compound amine71 (32 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 10 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.5 g of Compound 73 (Yield 62%, MS: [M+H]+=767).
Compound BD (15 g, 53.6 mmol) and Compound amine72 (36.2 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 11 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 30.7 g of Compound 74 (Yield 68%, MS: [M+H]+=843).
Compound BC (15 g, 53.6 mmol) and Compound amine73 (39.1 g, 56.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in water (67 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol). After 10 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 29.7 g of Compound 75 (Yield 62%, MS: [M+H]+=893).
Compound BG (10 g, 28.1 mmol), Compound amine74 (10.4 g, 28.1 mmol), and sodium tert-butoxide (8.9 g, 42.2 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. Upon completion of the reaction after 2 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 12.6 g of Compound 76 (Yield 65%, MS: [M+H]+=691).
Compound BI (10 g, 28.1 mmol), Compound amine75 (9.4 g, 28.1 mmol), and sodium tert-butoxide (8.9 g, 42.2 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. Upon completion of the reaction after 2 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 11 g of Compound 77 (Yield 60%, MS: [M+H]+=655).
Compound BJ (10 g, 28.1 mmol), Compound amine76 (10.4 g, 28.1 mmol), and sodium tert-butoxide (8.9 g, 42.2 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. Upon completion of the reaction after 3 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 11.8 g of Compound 78 (Yield 61%, MS: [M+H]+=691).
Compound BK (10 g, 28.1 mmol), Compound amine77 (11.8 g, 28.1 mmol), and sodium tert-butoxide (8.9 g, 42.2 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. Upon completion of the reaction after 2 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 13.1 g of Compound 79 (Yield 63%, MS: [M+H]+=741).
Compound BJ (15 g, 42.2 mmol) and Compound amine78 (16.2 g, 44.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in water (52 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 11 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.1 g of Compound 80 (Yield 67%, MS: [M+H]+=641).
Compound BG (15 g, 42.2 mmol) and Compound amine79 (21.8 g, 44.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in water (52 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 11 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.7 g of Compound 81 (Yield 61%, MS: [M+H]+=767).
Compound BI (15 g, 42.2 mmol) and Compound amine80 (26.3 g, 44.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in water (52 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 10 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.9 g of Compound 82 (Yield 68%, MS: [M+H]+=869).
Compound BH (15 g, 42.2 mmol) and Compound amine81 (20.2 g, 44.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in water (52 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 11 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.7 g of Compound 83 (Yield 64%, MS: [M+H]+=731).
Compound BG (15 g, 42.2 mmol) and Compound amine82 (21.8 g, 44.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in water (52 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 11 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20 g of Compound 84 (Yield 62%, MS: [M+H]+=767).
Compound BL (15 g, 42.2 mmol) and Compound amine83 (22.9 g, 44.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in water (52 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 11 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20 g of Compound 85 (Yield 60%, MS: [M+H]+=793).
Compound BG (15 g, 42.2 mmol) and Compound amine84 (23.5 g, 44.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in water (52 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 9 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.5 g of Compound 86 (Yield 69%, MS: [M+H]+=807).
Compound BI (15 g, 42.2 mmol) and Compound amine85 (22.4 g, 44.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in water (52 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 9 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.7 g of Compound 87 (Yield 69%, MS: [M+H]+=781).
Compound BJ (15 g, 42.2 mmol) and Compound amine86 (20.6 g, 44.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in water (52 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 12 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.6 g of Compound 88 (Yield 66%, MS: [M+H]+=741).
Compound BI (15 g, 42.2 mmol) and Compound amine87 (22.4 g, 44.3 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in water (52 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 8 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.4 g of Compound 89 (Yield 62%, MS: [M+H]+=781).
Compound BN (10 g, 30.3 mmol), Compound amine88 (11.3 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. Upon completion of the reaction after 3 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 13.3 g of Compound 90 (Yield 66%, MS: [M+H]+=665).
Compound BM (10 g, 30.3 mmol), Compound amine89 (12.8 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. Upon completion of the reaction after 2 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 13.4 g of Compound 91 (Yield 62%, MS: [M+H]+=715).
Compound BP (10 g, 30.3 mmol), Compound amine90 (12.1 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. Upon completion of the reaction after 3 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 13.8 g of Compound 92 (Yield 66%, MS: [M+H]+=691).
Compound BQ (10 g, 30.3 mmol), Compound amine91 (12.1 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to xylene (200 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. Upon completion of the reaction after 3 hours, the solvent was removed by cooling to room temperature and reducing the pressure. Then, the compound was completely dissolved again in chloroform, and washed twice with water. Thereafter, 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 prepare 13.4 g of Compound 93 (Yield 64%, MS: [M+H]+=691).
Compound BP (15 g, 45.5 mmol) and Compound amine92 (25.6 g, 47.8 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in water (57 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 8 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.8 g of Compound 94 (Yield 61%, MS: [M+H]+=785).
Compound BN (15 g, 45.5 mmol) and Compound amine93 (26 g, 47.8 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in water (57 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 9 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.6 g of Compound 95 (Yield 68%, MS: [M+H]+=795).
Compound BP (15 g, 45.5 mmol) and Compound amine94 (27.1 g, 47.8 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in water (57 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 8 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.6 g of Compound 96 (Yield 69%, MS: [M+H]+=817).
Compound BN (15 g, 45.5 mmol) and Compound amine95 (30.7 g, 47.8 mmol) were added to THF (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in water (57 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 12 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.2 g of Compound 97 (Yield 62%, MS: [M+H]+=893).
Compound BR (15 g, 45.5 mmol) and Compound amine96 (21.1 g, 47.8 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in water (57 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 10 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.1 g of Compound 98 (Yield 64%, MS: [M+H]+=691).
Compound BP (15 g, 45.5 mmol) and Compound amine97 (27.1 g, 47.8 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in water (57 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 8 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23 g of Compound 99 (Yield 62%, MS: [M+H]+=817).
Compound BB (15 g, 45.5 mmol) and Compound amine98 (24.7 g, 47.8 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in water (57 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 10 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.3 g of Compound 100 (Yield 64%, MS: [M+H]+=767).
Compound BP (15 g, 45.5 mmol) and Compound amine99 (27.1 g, 47.8 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in water (57 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 11 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.3 g of Compound 101 (Yield 60%, MS: [M+H]+=817).
Compound BM (15 g, 45.5 mmol) and Compound amine100 (25.9 g, 47.8 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in water (57 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 10 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.6 g of Compound 102 (Yield 60%, MS: [M+H]+=791).
Compound BO (15 g, 45.5 mmol) and Compound amine101 (27.1 g, 47.8 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in water (57 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 8 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26 g of Compound 103 (Yield 70%, MS: [M+H]+=817).
Compound BO (15 g, 45.5 mmol) and Compound amine102 (24.1 g, 47.8 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in water (57 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 10 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.6 g of Compound 104 (Yield 63%, MS: [M+H]+=791).
Compound BN (15 g, 45.5 mmol) and Compound amine103 (27.1 g, 47.8 mmol) were added to THE (300 ml) under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in water (57 ml), and then added thereto. Thereafter, it was stirred sufficiently, followed by adding bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol). After 11 hours of reaction, cooling was performed to room temperature. Then, the organic layer was separated from the water layer, and then the organic layer was distilled. Then, this was dissolved again in chloroform, and washed twice with water. Thereafter, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.7 g of Compound 105 (Yield 69%, MS: [M+H]+=755).
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. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water filtered twice using a filter manufactured by Millipore Co. was used as the distilled water. 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.
On the prepared ITO transparent electrode, the following Compound HI-1 was formed to a thickness of 1150 Å while the following Compound A-1 was p-doped at a concentration of 1.5% to form a hole injection layer. On the hole injection layer, the following Compound HT-1 was vacuum-deposited to form a hole transport layer having a thickness of 800 Å. Then, on the hole transport layer, the Compound 1 prepared above was vacuum-deposited to form an electron blocking layer having a thickness of 150 Å. On the electron blocking layer, the following Compound RH-1 as a host and the following Compound Dp-7 as a dopant were vacuum-deposited at a weight ratio of 98:2 to form a red light emitting layer having a thickness of 400 Å. On the light emitting layer, the following Compound HB-1 was vacuum-deposited to form a hole blocking layer having a thickness of 30 Å. On the hole blocking layer, the following Compound ET-1 and the following Compound LiQ were vacuum-deposited at a weight ratio of 2:1 to form an electron injection and transport layer having a thickness of 300 Å. On the electron injection and transport layer, lithium fluoride (LiF) and aluminum were sequentially deposited to a thickness of 12 Å and 1,000 Å, respectively to form a cathode.
In the above process, the 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, and the deposition rate of aluminum was maintained at 2 Å/sec. In addition, the degree of vacuum during the deposition was maintained at 2×10−7 to 5×10−6 torr, thereby manufacturing an organic light emitting device.
An organic light emitting device was manufactured in the same manner as in Experimental Example 1, except that the compound shown in Tables 1 to 5 was used instead of Compound 1.
An organic light emitting device was manufactured in the same manner as in Experimental Example 1, except that the compound shown in Table 6 was used instead of Compound 1. At this time, Compounds C-1 to C-16 listed in Table 6 are as follows.
For the organic light emitting devices prepared in Experimental Examples and Experimental Comparative Examples, the voltage and efficiency were measured by applying a current (15 mA/cm2), and the results are shown in Tables 1 to 6 below. In addition, lifespan (T95) means the time (hr) taken until the initial luminance (6000 nit) decreases to 95%.
When a current was applied to the organic light emitting devices manufactured according to Experimental Examples 1 to 105 and Comparative Experimental Examples 1 to 16, the results shown in Tables 1 to 6 were obtained. The red organic light emitting device of Experimental Example 1 used a material widely used in the prior art, and has a structure using Dp-7 as a dopant for the red light-emitting layer. In Comparative Experimental Examples 1 to 16, organic light emitting devices were prepared by using Compounds C-1 to C-16 instead of Compound 1. Referring to the results of Table 1, when the compound of the present disclosure was used as the electron blocking layer, the driving voltage was significantly lowered and the efficiency was increased compared to the case of using the material of Comparative Examples, so it was found that the energy transfer from the host to the red dopant was excellent. In addition, it was found that the lifespan could be greatly improved while maintaining high efficiency. This may be because the compound of the present disclosure has higher stability to electrons and holes than the compound of Comparative Examples. In conclusion, it can be confirmed that when the compound of the present disclosure is used as the electron blocking layer of the red light emitting layer, the driving voltage, luminous efficiency, and lifespan of the organic light emitting device can be improved.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2021-0024902 | Feb 2021 | KR | national |
This application is a National Phase entry pursuant to 35 U.S.C. § 371 of International Application No. PCT/KR2022/002695 filed on Feb. 24, 2022, and claims priority to and the benefit of Korean Patent Application No. 10-2021-0024902 filed on Feb. 24, 2021, the disclosures of which are incorporated herein by reference in their entirety.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2022/002695 | 2/24/2022 | WO |
