CN113519073B - Organic light emitting device - Google Patents
Organic light emitting device Download PDFInfo
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- CN113519073B CN113519073B CN202080015506.3A CN202080015506A CN113519073B CN 113519073 B CN113519073 B CN 113519073B CN 202080015506 A CN202080015506 A CN 202080015506A CN 113519073 B CN113519073 B CN 113519073B
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- 125000004434 sulfur atom Chemical group 0.000 description 1
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- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical group C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
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- 239000011135 tin Substances 0.000 description 1
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- 125000001425 triazolyl group Chemical group 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical group CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical group CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical group C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical class [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- H10K85/649—Aromatic compounds comprising a hetero atom
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- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present disclosure relates to organic light emitting devices having improved driving voltages, efficiencies, and lifetimes.
Description
Technical Field
Cross Reference to Related Applications
The present application claims the benefit of the filing date of korean patent application No. 10-2019-0143630 filed 11 at 11.2019 and the filing date of korean patent application No. 10-2020-0150222 filed 11 at 11.2020, the contents of which are incorporated herein by reference in their entireties.
The present disclosure relates to organic light emitting devices having improved driving voltages, efficiencies, and lifetimes.
Background
In general, an organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy by using an organic material. An organic light emitting device using the organic light emitting phenomenon has characteristics such as a wide viewing angle, excellent contrast, a fast response time, excellent brightness, driving voltage, and response speed, and thus many researches have been conducted.
The organic light emitting device generally has a structure including an anode, a cathode, and an organic material layer interposed between the anode and the cathode. The organic material layer generally has a multi-layered structure including different materials to improve efficiency and stability of the organic light emitting device, 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, holes are injected from an anode into an organic material layer and electrons are injected from a cathode into the organic material layer, and excitons are formed when the injected holes and electrons meet each other, and light is emitted when the excitons fall to a ground state again.
Among the organic light emitting devices described above, there is a continuous need to develop an organic light emitting device having improved driving voltage, efficiency, and lifetime.
[ Prior Art literature ]
[ patent literature ]
(patent document 0001) Korean unexamined patent publication No. 10-2000-0051826
Disclosure of Invention
Technical problem
The present disclosure relates to organic light emitting devices having improved driving voltages, efficiencies, and lifetimes.
Technical proposal
Provided herein are the following organic light emitting devices:
an organic light-emitting device is provided, which comprises a substrate,
comprising the following steps:
an anode, a cathode, and a light emitting layer interposed between the anode and the cathode.
Wherein the light emitting layer includes a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2:
[ chemical formula 1]
In the chemical formula 1, the chemical formula is shown in the drawing,
x is O or S, and the X is O or S,
each Y is independently N or CH, provided that at least one Y is N,
L 1 is a single bond, or substituted or unsubstituted C 6-60 An arylene group,
Ar 1 and Ar is a group 2 Each independently is a substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-60 A heteroaryl group, which is a group,
[ chemical formula 2]
In the chemical formula 2, the chemical formula is shown in the drawing,
L 2 is C substituted or unsubstituted 6-60 An arylene group,
L 3 and L 4 Each independently is a single bond, or a substituted or unsubstituted C 6-60 An arylene group,
Ar 3 and Ar is a group 4 Each independently is a substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-60 A heteroaryl group, which is a group,
r is hydrogen, deuterium, or substituted or unsubstituted C 6-60 Aryl group
n is an integer from 0 to 9.
Advantageous effects
By including the compound represented by chemical formula 1 and the compound represented by chemical formula 2 in the light emitting layer, the above organic light emitting device has excellent driving voltage, efficiency, and lifetime.
Drawings
Fig. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
Fig. 2 shows an example of an organic light emitting device including a substrate 1, an anode 2, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6, and a cathode 4.
Detailed Description
Hereinafter, embodiments of the present disclosure will be described in more detail to facilitate understanding of the present invention.
As used herein, a symbolOr->Meaning a bond to another substituent.
As used herein, the term "substituted or unsubstituted" means 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; alkylthio; arylthio; an alkylsulfonyl group; arylsulfonyl; a silyl group; a boron base; an alkyl group; cycloalkyl; alkenyl groups; an aryl group; an aralkyl group; aralkenyl; alkylaryl groups; an alkylamino group; an aralkylamine group; heteroaryl amine groups; an arylamine group; aryl phosphino; or heteroaryl containing at least one of N, O and S atoms, or unsubstituted or substituted with substituents attached through two or more of the substituents exemplified above. For example, a "substituent to which two or more substituents are attached" may be a biphenyl group. That is, biphenyl may be aryl, or it may also be interpreted as a substituent to which two phenyl groups are attached.
In the present disclosure, the carbon number of the carbonyl group is not particularly limited, but is preferably 1 to 40. Specifically, the carbonyl group may be a group having the following structural formula, but is not limited thereto.
In the present disclosure, the ester group may have a structure in which oxygen of the ester group may be substituted with a linear, branched, 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 group having the following structural formula, but is not limited thereto.
In the present disclosure, the carbon number of the imide group is not particularly limited, but is preferably 1 to 25.
Specifically, the imide group may be a group having the following structural formula, but is not limited thereto.
In the present disclosure, the silyl group specifically includes, but is not limited to, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, and the like.
In the present disclosure, the boron group specifically includes trimethylboron group, triethylboron group, t-butyldimethylboroyl group, triphenylboron group, and phenylboron group, but is not limited thereto.
In the present disclosure, examples of halogen groups include fluorine, chlorine, bromine, or iodine.
In the present disclosure, the alkyl group may be straight or branched, and the carbon number thereof is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has a carbon number of 1 to 20. According to another embodiment, the alkyl group has a carbon number of 1 to 10. According to another embodiment, the alkyl group has a carbon number of 1 to 6. Specific examples of the alkyl group include, but are not limited to, 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-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl and the like.
In the present disclosure, the alkenyl group may be straight or branched, and the carbon number thereof is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has a carbon number of 2 to 20. According to another embodiment, the alkenyl group has a carbon number of 2 to 10. According to yet another embodiment, the alkenyl group has a carbon number of 2 to 6. Specific examples thereof include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-diphenylvinyl-1-yl, 2-phenyl-2- (naphthalen-1-yl) vinyl-1-yl, 2-bis (diphenyl-1-yl) vinyl-1-yl, stilbene, styryl and the like, but are not limited thereto.
In the present disclosure, the cycloalkyl group is not particularly limited, but the carbon number thereof is preferably 3 to 60. According to one embodiment, the cycloalkyl group has a carbon number of 3 to 30. According to another embodiment, the cycloalkyl group has a carbon number of 3 to 20. According to yet another embodiment, the cycloalkyl group has a carbon number of 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-t-butylcyclohexyl, cycloheptyl, cyclooctyl and the like, but are not limited thereto.
In the present disclosure, the 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 aryl group has a carbon number of 6 to 30. According to one embodiment, the aryl group has a carbon number of 6 to 20. As the monocyclic aryl group, an aryl group may be phenyl, biphenyl, terphenyl, or the like, but is not limited thereto. Polycyclic aryl groups include naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl,A radical, a fluorenyl radical, etc., but is not limited thereto.
In the present disclosure, the fluorenyl group may be substituted, and two substituents may be linked to each other to form a spiro structure. In the case where the fluorenyl group is substituted, it may be formed Etc. However, the structure is not limited thereto.
In the present disclosure, the heterocyclic group is a heterocyclic group containing one or more of O, N, si and S as a heteroatom, and the carbon number thereof is not particularly limited, but is preferably 2 to 60. Examples of heterocyclyl groups include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl,Azolyl, (-) -and (II) radicals>Diazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinoPyrazinyl, isoquinolinyl, indolyl, carbazolyl, benzo +.>Oxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothiophenyl, benzofuranyl, phenanthrolinyl, and i ∈ ->Oxazolyl, thiadiazolyl, phenothiazinyl, dibenzofuranyl, and the like, but are not limited thereto.
In the present disclosure, the aryl groups in the aralkyl group, the aralkenyl group, the alkylaryl group, and the arylamine group are the same as the examples of the foregoing aryl groups. In the present disclosure, the alkyl groups in the aralkyl group, alkylaryl group, and alkylamino group are the same as the examples of the aforementioned alkyl groups. In the present disclosure, heteroaryl groups in heteroaryl amines may employ the foregoing description of heterocyclyl groups. In the present disclosure, alkenyl groups in aralkenyl groups are the same as the examples of alkenyl groups described previously. In the present disclosure, the foregoing description of aryl groups may be applied in addition to arylene groups being divalent groups. In the present disclosure, the foregoing description of heteroaryl groups may be applied in addition to the heteroarylene groups being divalent groups. In the present disclosure, the foregoing description of aryl or cycloalkyl groups may be applied in addition to the hydrocarbon ring being not a monovalent group but formed by combining two substituents. In the disclosure, the foregoing description of the heterocyclic group may be applied, except that the heterocyclic ring is not a monovalent group but is formed by combining two substituents.
Hereinafter, the present disclosure will be described in detail for each configuration.
Anode and cathode
The anode and cathode used in the present disclosure mean electrodes used in an organic light emitting device.
As the anode material, a material having a large work function is generally 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, chromium, copper, zinc and gold, or alloys thereof; metal oxides, e.g. zinc oxideOxides, indium Tin Oxides (ITO), and Indium Zinc Oxides (IZO); combinations of metals and oxides, e.g. ZnO, al or SNO 2 Sb; conductive polymers, e.g. poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxythiophene)](PEDOT), polypyrrole and polyaniline; etc., but is not limited thereto.
As the cathode material, it is generally preferable to use a material having a small work function 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 alloys thereof; multilayer structural materials, e.g. LiF/Al or LiO 2 Al; etc., but is not limited thereto.
Hole injection layer
The organic light emitting device according to the present disclosure may further include a hole injection layer on the anode, if necessary.
The hole injection layer is a layer that injects holes from the electrode, and the hole injection material is preferably a compound of: which has an ability to transport holes, an effect of injecting holes in an anode, and an excellent hole injection effect to a light emitting layer or a light emitting material, prevents excitons generated in the light emitting layer from moving to an electron injection layer or an electron injection material, and has an excellent thin film forming ability. Preferably, the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer.
Specific examples of the hole injection material include metalloporphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazabenzophenanthrene-based organic material, quinacridone-based organic material, perylene-based organic material, anthraquinone, polyaniline, and polythiophene-based conductive polymer, and the like, but are not limited thereto.
Hole transport layer
The organic light emitting device according to the present disclosure may include a hole transport layer on the anode (or on the hole injection layer when the hole injection layer is present), if necessary.
The hole transport layer is a layer that receives holes from the anode or the hole injection layer and transports the holes to the light emitting layer. The hole transport material is suitably a material having a large hole mobility, which can receive holes from the anode or the hole injection layer and transport the holes to the light emitting layer.
Specific examples of the hole transport material include an arylamine-based organic material, a conductive polymer, a block copolymer in which a conjugated moiety and a non-conjugated moiety are simultaneously present, and the like, but are not limited thereto.
Light-emitting layer
The light emitting layer used in the present disclosure means a layer that can emit light in the visible light region by combining holes and electrons transported from an anode and a cathode. Generally, the light emitting layer includes a host material and a dopant material, and in the present disclosure, a compound represented by chemical formula 1 and a compound represented by chemical formula 2 are included as hosts.
In chemical formula 1, preferably, all Y are N.
Preferably L 1 Is a single bond, phenylene or naphthylene. More preferably L 1 Is a single bond,Or->
Preferably Ar 1 And Ar is a group 2 Each independently is phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, (phenyl) naphthyl, (naphthyl) phenyl, dimethylfluorenyl, diphenylfluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazol-9-yl, 9-phenyl-9H-carbazolyl, ar 1 And Ar is a group 2 Each independently unsubstituted or substituted with at least one deuterium. When Ar is 1 Or Ar 2 When substituted with at least one deuterium, preferably, each is any one selected from the group consisting of:
preferably Ar 1 Is phenyl, biphenyl or naphthyl, ar 1 Unsubstituted or substituted with at least one deuterium; ar, ar 2 Is phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, (phenyl) naphthyl, (naphthyl) phenyl, dimethylfluorenyl, diphenylfluorenyl, dibenzofuranyl, dibenzothienyl, carbazole-9-yl, 9-phenyl-9H-carbazolyl, ar 2 Unsubstituted or substituted with at least one deuterium.
Representative examples of the compound represented by chemical formula 1 are as follows:
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also provided herein is a method for preparing the compound represented by chemical formula 1 as shown in reaction scheme 1 below.
Reaction scheme 1
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In reaction scheme 1, the definition of the remaining substituents other than X 'is the same as defined above, and X' is halogen, preferably bromine or chlorine. The above reaction is a Suzuki coupling reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactive groups for the Suzuki coupling reaction may be varied as known in the art. The above preparation method may be further presented in the preparation examples described below.
In chemical formula 2, preferably, chemical formula 2 is represented by the following chemical formula 2-1:
[ chemical formula 2-1]
Wherein in the chemical formula 2-1,
R 1 is hydrogen, deuterium or phenyl and is preferably hydrogen,
n1 is an integer of 0 to 8,
L 2 、L 3 、L 4 、Ar 3 、Ar 4 and R is as defined above.
Preferably L 2 Is phenylene, or phenylene substituted with at least one deuterium. The phenylene substituted with at least one deuterium is preferably any one selected from the group consisting of:
preferably L 3 And L 4 Each independently is a single bond, phenylene, biphenyldiyl or naphthylene, L 3 And L 4 Each independently unsubstituted or substituted with at least one deuterium. When L 3 Or L 4 When substituted with at least one deuterium, preferably, each is any one selected from the group consisting of:
preferably Ar 3 And Ar is a group 4 Each independently is phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, (benzene)Group) phenanthryl, triphenylene, phenylnaphthyl, naphthylphenyl, dimethylfluorenyl, diphenylfluorenyl, dibenzofuranyl, (phenyl) dibenzofuranyl, dibenzothienyl, (phenyl) dibenzothienyl, carbazol-9-yl or 9-phenyl-9H-carbazolyl, ar 3 And Ar is a group 4 Each independently unsubstituted or substituted with at least one deuterium. When Ar is 3 Or Ar 4 When substituted with at least one deuterium, each is preferably any one selected from the group consisting of:
Representative examples of the compound represented by chemical formula 2 are as follows:
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also provided herein is a method for preparing the compound represented by chemical formula 2 as shown in reaction scheme 2 below.
Reaction scheme 2
Wherein in reaction scheme 2, the definition of the remaining substituents other than X 'is the same as defined above, and X' is halogen, preferably bromine or chlorine. The above reaction is an amine substitution reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactive groups for the amine substitution reaction may be changed as known in the art. The above preparation method may be further presented in the preparation examples described below.
Preferably, in the light emitting layer, the weight ratio of the compound represented by chemical formula 1 to the compound represented by chemical formula 2 is 10:90 to 90:10, more preferably 20:80 to 80:20, 30:70 to 70:30, or 40:60 to 60:40.
Meanwhile, the light emitting layer may further include a dopant in addition to the host. The dopant material is not particularly limited as long as it is a material for an organic light emitting device. As examples, aromatic amine derivatives, styrene amine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like can be mentioned. Specific examples of the aromatic amine derivative include substituted or unsubstituted fused aromatic ring derivatives having an arylamino group, examples of which include pyrene, anthracene having an arylamino group, And bisindenopyrene, etc. The styrylamine compound is a compound in which at least one arylvinyl group is substituted in a substituted or unsubstituted arylamine, wherein one or two or more substituents selected from the group consisting of aryl, silyl, alkyl, cycloalkyl, and arylamino groups are substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styrylenediamine, styrylenetriamine, styrenetetramine, and the like. Further, examples of the metal complex include iridium complex, platinum complex, and the like, but are not limited thereto.
Electron transport layer
The organic light emitting device according to the present disclosure may include an electron transport layer on the light emitting layer, if necessary.
The electron transporting layer is a layer that receives electrons from the cathode or an electron injecting layer formed on the cathode and transports the electrons to the light emitting layer, and suppresses transfer of holes from the light emitting layer, and the electron transporting material is suitably a material such as: which can well receive electrons from the cathode and transfer the electrons to the light emitting layer, and has a large electron mobility.
Specific examples of the electron transport material include: al complexes of 8-hydroxyquinoline; comprising Alq 3 Is a complex of (a) and (b); an organic radical compound; hydroxyflavone-metal complexes; etc., but is not limited thereto. The electron transport layer may be used with any desired cathode material as used according to conventional techniques. In particular, suitable examples of cathode materials are typical materials with a low work function, followed by an aluminum layer or a silver layer. Specific examples thereof include cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.
Electron injection layer
The organic light emitting device according to the present disclosure may further include an electron injection layer on the light emitting layer (or on the electron transport layer when the electron transport layer is present), if necessary.
The electron injection layer is a layer that injects electrons from an electrode, and is preferably a compound that: it has an ability to transport 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 generated by the light emitting layer from moving to a hole injecting layer, and is also excellent in an ability to form a thin film.
Specific examples of materials that can be used as the electron injection layer include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide,Azole,/->Diazoles, triazoles, imidazoles, tetracarboxylic acids, fluorenylidene methane, anthrone, and the like, and derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives,etc., but is not limited thereto.
Examples of the metal complex compound include, but are not limited to, lithium 8-hydroxyquinoline, zinc bis (8-hydroxyquinoline), copper bis (8-hydroxyquinoline), manganese bis (8-hydroxyquinoline), aluminum tris (2-methyl-8-hydroxyquinoline), gallium tris (8-hydroxyquinoline), beryllium bis (10-hydroxybenzo [ h ] quinoline), zinc bis (2-methyl-8-quinoline) chlorogallium, gallium bis (2-methyl-8-quinoline) (o-cresol), aluminum bis (2-methyl-8-quinoline) (1-naphthol), gallium bis (2-methyl-8-quinoline) (2-naphthol), and the like.
Organic light emitting device
Fig. 1 and 2 illustrate the structure of an organic light emitting device according to the present disclosure. Fig. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. Fig. 2 shows an example of an organic light emitting device including a substrate 1, an anode 2, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6, and a cathode 4.
The organic light emitting device according to the present disclosure may be manufactured by sequentially stacking the above-described structures. In this case, the organic light emitting device may be manufactured by: the above layers are formed on an anode by depositing a metal, a metal oxide having conductivity, or an alloy thereof on a substrate using a PVD (physical vapor deposition) method such as a sputtering method or an electron beam evaporation method to form the anode, and then a material that can function as a cathode is deposited thereon. In addition to such a method, the organic light emitting device may also be manufactured by sequentially depositing from a cathode material to an anode material on a substrate in the reverse order of the above-described configuration (WO 2003/012690). In addition, the light emitting layer may be formed by subjecting the host and the dopant to a vacuum deposition method and a solution coating method. Herein, the solution coating method means spin coating, dip coating, doctor blade coating, ink jet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.
On the other hand, the organic light emitting device according to the present disclosure may be of a front-side emission type, a rear-side emission type, or a double-side emission type, depending on the materials used.
The preparation of an organic light emitting device including the compound represented by chemical formula 1 and the compound represented by chemical formula 2 will be described in detail in the following examples. However, these examples are given for illustrative purposes only and are not intended to limit the scope of the present disclosure.
Preparation example
PREPARATION EXAMPLE 1-1
Compound sub1 (15 g,40.8 mmol) and compound a (11.8 g,44.9 mmol) were added to THF (300 ml) under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (16.9 g,122.3 mmol) was dissolved in water (51 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 9 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 1 (14.6 g). (yield: 65%, MS: [ M+H) ] + ＝550)
PREPARATION EXAMPLES 1-2
Compound sub2 (15 g,47.2 mmol) and compound a (13.6 g,51.9 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (19.6 g,141.6 mmol) was dissolved in water (59 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After reacting for 10 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. Dissolving in chloroform again, washing twice with water, separating organic layer, and concentratingAnhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 2 (14.4 g). (yield: 61%, MS: [ M+H)] + ＝500)
Preparation examples 1 to 3
Compound sub3 (15 g,38.1 mmol) and compound a (11 g,41.9 mmol) were added to THF (300 ml) under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (15.8 g,114.3 mmol) was dissolved in water (47 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 9 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 3 (13.4 g). (yield: 61%, MS: [ M+H) ] + ＝576)
Preparation examples 1 to 4
Compound sub4 (15 g,43.6 mmol) and compound a (12.6 g,48 mmol) were added to THF (300 ml) under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (18.1 g,130.9 mmol) was dissolved in water (54 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 9 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. Dissolving in chloroform again, washing twice with water, separating organic layer, adding anhydrous magnesium sulfate, mixingThe mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 4 (18.3 g). (yield: 80%, MS: [ M+H)] + ＝526)
Preparation examples 1 to 5
Compound sub5 (15 g,35.7 mmol) and compound a (10.3 g,39.3 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14.8 g,107.2 mmol) was dissolved in water (44 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 5 (15.2 g). (yield: 71%, MS: [ M+H) ] + ＝602)
Preparation examples 1 to 6
Compound sub6 (15 g,35.9 mmol) and compound a (10.3 g,39.5 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14.9 g,107.7 mmol) was dissolved in water (45 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. Dissolving in chloroform again, washing twice with water, separating organic layer, adding anhydrous magnesium sulfate, stirring and filtering the mixture, and filtering the filtrateDistillation was carried out under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 6 (13.1 g). (yield: 61%, MS: [ M+H)] + ＝600)
Preparation examples 1 to 7
Compound sub7 (15 g,35.7 mmol) and compound a (10.3 g,39.3 mmol) were added to THF (300 ml) under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (14.8 g,107.2 mmol) was dissolved in water (44 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 7 (14.2 g). (yield: 66%, MS: [ M+H) ] + ＝602)
Preparation examples 1 to 8
Compound sub8 (15 g,40.8 mmol) and compound a (11.8 g,44.9 mmol) were added to THF (300 ml) under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (16.9 g,122.3 mmol) was dissolved in water (51 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. Will be concentratedThe compound was purified by silica gel column chromatography to obtain compound 8 (13.4 g). (yield: 60%, MS: [ M+H)] + ＝550)
Preparation examples 1 to 9
Compound sub9 (15 g,40.8 mmol) and compound a (11.8 g,44.9 mmol) were added to THF (300 ml) under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (16.9 g,122.3 mmol) was dissolved in water (51 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 9 (14.1 g). (yield: 63%, MS: [ M+H) ] + ＝550)
Preparation examples 1 to 10
Compound sub10 (15 g,38.1 mmol) and compound a (11 g,41.9 mmol) were added to THF (300 ml) under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (15.8 g,114.3 mmol) was dissolved in water (47 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. Subjecting the concentrated compound to silica gel column chromatographyPurification gave compound 10 (15.8 g). (yield: 72%, MS: [ M+H)] + ＝576)
Preparation examples 1 to 11
Compound sub11 (15 g,38.1 mmol) and compound a (11 g,41.9 mmol) were added to THF (300 ml) under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (15.8 g,114.3 mmol) was dissolved in water (47 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 11 (16.6 g). (yield: 76%, MS: [ M+H) ] + ＝576)
Preparation examples 1 to 12
Compound sub12 (15 g,41.9 mmol) and compound a (12.1 g,46.1 mmol) were added to THF (300 ml) under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (17.4 g,125.8 mmol) was dissolved in water (52 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. Purifying the concentrated compound by silica gel column chromatography to obtain compound 12%13.8 g). (yield: 61%, MS: [ M+H)] + ＝540)
Preparation examples 1 to 13
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Compound sub13 (15 g,41.9 mmol) and compound a (12.1 g,46.1 mmol) were added to THF (300 ml) under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (17.4 g,125.8 mmol) was dissolved in water (52 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 9 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 13 (15.4 g). (yield: 68%, MS: [ M+H) ] + ＝540)
Preparation examples 1 to 14
Compound sub14 (15 g,36.8 mmol) and compound a (10.6 g,40.5 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (15.2 g,110.3 mmol) was dissolved in water (46 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 11 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 14 (16.3 g). (yield: 75%,MS：[M+H] + ＝590)
preparation examples 1 to 15
Compound sub15 (15 g,36.8 mmol) and compound a (10.6 g,40.5 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (15.2 g,110.3 mmol) was dissolved in water (46 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 15 (15.2 g). (yield: 70%, MS: [ M+H ] ] + ＝590)
Preparation examples 1 to 16
Compound sub16 (15 g,40.1 mmol) and compound a (11.6 g,44.1 mmol) were added to THF (300 ml) under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (16.6 g,120.4 mmol) was dissolved in water (50 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 16 (13.8 g). (yield: 62%, MS: [ M+H)] + ＝556)
Preparation examples 1 to 17
Compound sub17 (15 g,40.1 mmol) and compound a (11.6 g,44.1 mmol) were added to THF (300 ml) under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (16.6 g,120.4 mmol) was dissolved in water (50 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 9 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 17 (15.1 g). (yield: 68%, MS: [ M+H) ] + ＝556)
PREPARATION EXAMPLES 1 to 18
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Compound sub18 (15 g,40.1 mmol) and compound a (11.6 g,44.1 mmol) were added to THF (300 ml) under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (16.6 g,120.4 mmol) was dissolved in water (50 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 9 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 18 (17.8 g). (yield: 80%, MS: [ M+H)] + ＝556)
Preparation examples 1 to 19
Compound sub19 (15 g,34.6 mmol) and compound a (10 g,38.1 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14.4 g,103.9 mmol) was dissolved in water (43 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After reacting for 10 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 19 (15.5 g). (yield: 73%, MS: [ M+H) ] + ＝615)
Preparation examples 1 to 20
Compound sub20 (15 g,34.6 mmol) and compound a (10 g,38.1 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14.4 g,103.9 mmol) was dissolved in water (43 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After reacting for 11 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 20 (17 g). (yield: 80%, MS: [ M+H)] + ＝615)
Preparation examples 1 to 21
Compound sub21 (15 g,42 mmol) and compound a (12.1 g,46.2 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.4 g,126.1 mmol) was dissolved in water (52 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 9 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 21 (14.5 g). (yield: 64%, MS: [ M+H ] ] + ＝539)
PREPARATION EXAMPLES 1 to 22
Compound sub22 (15 g,31.1 mmol) and compound a (9 g,34.2 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (12.9 g,93.2 mmol) was dissolved in water (39 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After reacting for 11 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 22 (12.4 g). (yield: 60%, MS: [ M+H)] + ＝665)
PREPARATION EXAMPLES 1 to 23
Compound sub2 (15 g,47.2 mmol) and compound B (7.4 g,47.2 mmol) were added to THF (300 ml) under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (19.6 g,141.6 mmol) was dissolved in water (59 ml), added to the mixture, and the mixture was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.5 g,0.5 mmol). After reacting for 10 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound subsubb-1 (13.9 g). (yield: 75%, MS: [ M+H) ] + ＝394)
Compound sub B-1 (15 g,38.1 mmol) and compound A (11 g,41.9 mmol) were added to THF (300 ml) under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (15.8 g,114.3 mmol) was dissolved in water (47 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 23 (15.3 g). (yield: 70%, MS: [ M+H ]] + ＝576)
Preparation examples 1 to 24
Compound sub23 (15 g,35.7 mmol) and compound B (5.6 g,35.7 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14.8 g,107.2 mmol) was dissolved in water (44 ml), added to the mixture, and the mixture was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.4 g,0.4 mmol). After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound subsubb-2 (12 g). (yield: 68%, MS: [ M+H) ] + ＝496)
Compound sub B-2 (15 g,30.2 mmol) and compound A (8.7 g,33.3 mmol) were added to THF (300 ml) under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (12.5 g,90.7 mmol) was dissolved in water (38 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 24 (13.1 g). (yield: 64%, MS: [ M+H ]] + ＝678)
Preparation examples 1 to 25
Compound sub12 (15 g,41.9 mmol) and compound B (6.6 g,41.9 mmol) were added to THF (300 ml) under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (17.4 g,125.8 mmol) was dissolved in water (52 ml), added to the mixture, and the mixture was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.5 g,0.4 mmol). After reacting for 10 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound subsubb-3 (12.9 g). (yield: 71%, MS: [ M+H) ] + ＝434)
Compound sub B-3 (15 g,34.6 mmol) and compound A (10 g,38 mmol) were added to THF (300 ml) under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (14.3 g,103.7 mmol) was dissolved in water (43 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 25 (17 g). (yield: 80%, MS: [ M+H)] + ＝616)
PREPARATION EXAMPLES 1 to 26
The compound was reacted under nitrogen atmospheresub17 (15 g,40.1 mmol) and compound B (6.3 g,40.1 mmol) were added to THF (300 ml) and the mixture was stirred and refluxed. Then, potassium carbonate (16.6 g,120.4 mmol) was dissolved in water (50 ml), added to the mixture, and the mixture was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.5 g,0.4 mmol). After reacting for 11 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound subsubB-4 (12.1 g). (yield: 67%, MS: [ M+H) ] + ＝450)
Compound sub B-4 (15 g,33.3 mmol) and compound A (9.6 g,36.7 mmol) were added to THF (300 ml) under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (13.8 g,100 mmol) was dissolved in water (41 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After reacting for 11 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 26 (15.8 g). (yield: 75%, MS: [ M+H)] + ＝632)
PREPARATION EXAMPLES 1 to 27
Compound sub3 (15 g,38.1 mmol) and compound B (10 g,38.1 mmol) were added to THF (300 ml) under nitrogen atmosphere andthe mixture was stirred and refluxed. Then, potassium carbonate (15.8 g,114.3 mmol) was dissolved in water (47 ml), added to the mixture, and the mixture was stirred well, followed by addition of tetrakis (triphenylphosphine) palladium (0) (0.4 g,0.4 mmol). After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound subsubB-5 (14.1 g). (yield: 79%, MS: [ M+H) ] + ＝470)
Compound sub B-5 (15 g,31.9 mmol) and compound A (9.2 g,35.1 mmol) were added to THF (300 ml) under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (13.2 g,95.8 mmol) was dissolved in water (40 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After reacting for 10 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 27 (12.5 g). (yield: 60%, MS: [ M+H)] + ＝652)
PREPARATION EXAMPLES 1 to 28
Compound sub24 (15 g,35.4 mmol) and compound B (5.5 g,35.4 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14.7 g,106.2 mmol) was dissolvedIn water (44 ml) was added to the mixture, and the mixture was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.4 g,0.4 mmol). After reacting for 9 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound subsubB-6 (12.5 g). (yield: 71%, MS: [ M+H) ] + ＝500)
Compound sub B-6 (15 g,30 mmol) and compound A (8.6 g,33 mmol) were added to THF (300 ml) under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (12.4 g,90 mmol) was dissolved in water (37 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 28 (14.9 g). (yield: 73%, MS: [ M+H)] + ＝682)
Preparation examples 1 to 29
Compound sub25 (15 g,56 mmol) and compound C (11.6 g,56 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (23.2 g,168.1 mmol) was dissolved in water (70 ml), added to the mixture, and the mixture was stirred well, then addedTetrakis (triphenylphosphine) palladium (0) (0.6 g,0.6 mmol). After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain the compound sub-c-1 (16.7 g). (yield: 76%, MS: [ M+H) ] + ＝394)
Compound sub-1 (15 g,38.1 mmol) and compound A (10 g,38.1 mmol) were added to THF (300 ml) under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (15.8 g,114.3 mmol) was dissolved in water (47 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 11 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 29 (16 g). (yield: 73%, MS: [ M+H)] + ＝576)
Preparation examples 1 to 30
Compound sub2 (15 g,47.2 mmol) and compound C (9.7 g,47.2 mmol) were added to THF (300 ml) under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (19.6 g,141.6 mmol) was dissolved in water (59 ml), added to the mixture, and the mixture was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.5 g,0.5 mmol). After 8 hours of reaction, the reaction was mixed The composition was cooled to room temperature and the organic and aqueous layers were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain the compound sub-2 (14 g). (yield: 67%, MS: [ M+H)] + ＝444)
Compound sub-2 (15 g,33.8 mmol) and compound A (8.9 g,33.8 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14 g,101.4 mmol) was dissolved in water (42 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After reacting for 9 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 30 (13.1 g). (yield: 62%, MS: [ M+H) ] + ＝626)
PREPARATION EXAMPLES 1 to 31
Compound sub26 (15 g,40.8 mmol) and compound C (8.4 g,40.8 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (16.9 g,122.3 mmol) was dissolved in water (51 ml), added to the mixture, and the mixture was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.5 g,0.4 mmol). After reacting for 11 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain the compound sub-c-3 (13.5 g). (yield: 67%, MS: [ M+H)] + ＝494)
Compound sub-3 (15 g,30.4 mmol) and compound A (8 g,30.4 mmol) were added to THF (300 ml) under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (12.6 g,91.1 mmol) was dissolved in water (38 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After reacting for 10 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 31 (15.6 g). (yield: 76%, MS: [ M+H) ] + ＝676)
PREPARATION EXAMPLES 1 to 32
Compound sub4 (15 g,43.6 mmol) and compound C (9 g,43.6 mmol) were added to THF (300 ml) under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (18.1 g,130.9 mmol) was dissolved in water (54 ml), added to the mixture, and the mixture was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.5 g,0.4 mmol). After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, and then the organic layer was separated,anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain the compound sub-c-4 (16.4 g). (yield: 80%, MS: [ M+H)] + ＝470)
Compound sub-4 (15 g,31.9 mmol) and compound A (8.4 g,31.9 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (13.2 g,95.8 mmol) was dissolved in water (40 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 32 (13.5 g). (yield: 65%, MS: [ M+H) ] + ＝652)
PREPARATION EXAMPLES 1 to 33
Compound sub10 (15 g,38.1 mmol) and compound C (7.9 g,38.1 mmol) were added to THF (300 ml) under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (15.8 g,114.3 mmol) was dissolved in water (47 ml), added to the mixture, and the mixture was stirred well, followed by addition of tetrakis (triphenylphosphine) palladium (0) (0.4 g,0.4 mmol). After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. Dissolving in chloroform again, washing twice with water, separating organic layer, adding anhydrous magnesium sulfate, stirring and filtering the mixture, and filtering the filtrateDistillation was carried out under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain the compound sub-c-5 (14.2 g). (yield: 72%, MS: [ M+H)] + ＝520)
Compound sub-5 (15 g,28.8 mmol) and compound A (7.6 g,28.8 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (12 g,86.5 mmol) was dissolved in water (36 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After reacting for 9 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 33 (12.1 g). (yield: 60%, MS: [ M+H) ] + ＝702)
PREPARATION EXAMPLES 1 to 34
Compound sub27 (15 g,40.8 mmol) and compound C (8.4 g,40.8 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (16.9 g,122.3 mmol) was dissolved in water (51 ml), added to the mixture, and the mixture was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.5 g,0.4 mmol). After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. Purifying the concentrated compound by silica gel column chromatography to obtainTo compound sub-6 (15.7 g). (yield: 78%, MS: [ M+H)] + ＝494)
Compound sub-6 (15 g,30.4 mmol) and compound A (8 g,30.4 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (12.6 g,91.1 mmol) was dissolved in water (38 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After reacting for 10 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 34 (15.2 g). (yield: 74%, MS: [ M+H) ] + ＝676)
PREPARATION EXAMPLES 1 to 35
Compound sub34 (15 g,39.1 mmol) and compound C (8.1 g,39.1 mmol) were added to THF (300 ml) under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (16.2 g,117.2 mmol) was dissolved in water (49 ml), added to the mixture, and the mixture was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.5 g,0.4 mmol). After reacting for 9 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain the compound sub-c-7 (15.9 g). (yield: 80%, MS: [ M+H)] + ＝510)
Compound sub-7 (15 g,29.4 mmol) and compound A (7.7 g,29.4 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (12.2 g,88.2 mmol) was dissolved in water (37 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After reacting for 9 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 35 (14.2 g). (yield: 70%, MS: [ M+H ] ] + ＝692)
PREPARATION EXAMPLES 1 to 36
Compound sub28 (15 g,34.6 mmol) and compound C (7.2 g,34.6 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14.4 g,103.9 mmol) was dissolved in water (43 ml), added to the mixture, and the mixture was stirred well, followed by addition of tetrakis (triphenylphosphine) palladium (0) (0.4 g,0.3 mmol). After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain the compound sub-c-8 (13.3 g). (yield: 69%, MS: [ M+H)] + ＝559)
Compound sub-8 (15 g,26.8 mmol) and compound A (7 g,26.8 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (11.1 g,80.5 mmol) was dissolved in water (33 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 36 (15.5 g). (yield: 78%, MS: [ M+H) ] + ＝741)
PREPARATION EXAMPLES 1 to 37
Compound sub19 (15 g,34.6 mmol) and compound C (7.2 g,34.6 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14.4 g,103.9 mmol) was dissolved in water (43 ml), added to the mixture, and the mixture was stirred well, followed by addition of tetrakis (triphenylphosphine) palladium (0) (0.4 g,0.3 mmol). After reacting for 10 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain the compound sub-c-9 (13.9 g). (yield: 72%, MS: [ M+H)] + ＝559)
Compound sub-9 (15 g,26.8 mmol) and compound A (7 g,26.8 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (11.1 g,80.5 mmol) was dissolved in water (33 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After reacting for 11 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 37 (14.5 g). (yield: 73%, MS: [ M+H) ] + ＝741)
PREPARATION EXAMPLES 1 to 38
Compound sub12 (15 g,41.9 mmol) and compound C (8.7 g,41.9 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.4 g,125.8 mmol) was dissolved in water (52 ml), added to the mixture, and the mixture was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.5 g,0.4 mmol). After reacting for 9 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain the compound sub-c-10 (14.2 g). (yield: 70%, MS: [ M+H ]] + ＝484)
Compound sub-10 (15 g,31 mmol) and compound A (8.1 g,31 mmol) were added to THF (300 ml) under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (12.9 g,93 mmol) was dissolved in water (39 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After reacting for 10 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 38 (13.4 g). (yield: 65%, MS: [ M+H) ] + ＝666)
PREPARATION EXAMPLES 1 to 39
Compound sub14 (15 g,36.8 mmol) and compound C (7.6 g,36.8 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (15.2 g,110.3 mmol) was dissolved in water (46 ml), added to the mixture, and the mixture was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.4 g,0.4 mmol). After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain the compound sub-c-11 (12.9 g). (yield: 66%, MS: [ M+H)] + ＝534)
Compound sub-11 (15 g,28.1 mmol) and compound A (7.4 g,28.1 mm) were combined under nitrogenol) was added to THF (300 ml) and the mixture was stirred and refluxed. Then, potassium carbonate (11.6 g,84.3 mmol) was dissolved in water (35 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After reacting for 9 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 39 (14.5 g). (yield: 72%, MS: [ M+H) ] + ＝716)
PREPARATION EXAMPLES 1 to 40
Compound sub29 (15 g,36.8 mmol) and compound C (7.6 g,36.8 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (15.2 g,110.3 mmol) was dissolved in water (46 ml), added to the mixture, and the mixture was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.4 g,0.4 mmol). After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain the compound sub-c-12 (12.9 g). (yield: 66%, MS: [ M+H)] + ＝534)
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Compound sub-12 (15 g,28.1 mmol) and compound A (7.4 g,28.1 mmol) were added to THF (300 ml) under nitrogen, and the mixture was stirred and refluxed. Then, carbon is addedPotassium acid (11.6 g,84.3 mmol) was dissolved in water (35 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After reacting for 9 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 40 (12.7 g). (yield: 63%, MS: [ M+H) ] + ＝716)
PREPARATION EXAMPLES 1 to 41
Compound sub30 (15 g,35.5 mmol) and compound C (7.3 g,35.5 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14.7 g,106.4 mmol) was dissolved in water (44 ml), added to the mixture, and the mixture was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.4 g,0.4 mmol). After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain the compound sub-c-13 (14.6 g). (yield: 75%, MS: [ M+H)] + ＝550)
Compound sub-13 (15 g,27.3 mmol) and compound A (7.1 g,27.3 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (11.3 g,81.8 mmol) was dissolved in water (34 ml), added to the mixture, andthe mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 41 (13.6 g). (yield: 68%, MS: [ M+H) ] + ＝732)
PREPARATION EXAMPLES 1 to 42
Compound sub17 (15 g,40.1 mmol) and compound C (8.3 g,40.1 mmol) were added to THF (300 ml) under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (16.6 g,120.4 mmol) was dissolved in water (50 ml), added to the mixture, and the mixture was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.5 g,0.4 mmol). After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain the compound sub-14 (13 g). (yield: 65%, MS: [ M+H)] + ＝500)
Compound sub-14 (15 g,30 mmol) and compound A (7.9 g,30 mmol) were added to THF (300 ml) under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (12.4 g,90 mmol) was dissolved in water (37 ml), added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 42 (14.7 g). (yield: 72%, MS: [ M+H)] + ＝682)
PREPARATION EXAMPLE 2-1
Compound F (15 g,58.3 mmol) and compound B (10 g,64.2 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (24.2 g,175 mmol) was dissolved in water (73 ml), added to the mixture, and the mixture was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.7 g,0.6 mmol). After reacting for 11 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub A-1 (10.4 g). (yield: 62%, MS: [ M+H) ] + ＝289)
Compound sub A-1 (10 g,34.6 mmol), compound sub E-1 (11.1 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene (200 ml) under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 3 hours of reaction, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform,the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound 2-1 (13.3 g). (yield: 67%, MS: [ M+H)] + ＝574)
PREPARATION EXAMPLE 2-2
Compound sub A-1 (10 g,34.6 mmol), compound sub E-2 (12.9 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound 2-2 (11 g). (yield: 51%, MS: [ M+H ] ] + ＝624)
PREPARATION EXAMPLES 2-3
Compound sub A-1 (10 g,34.6 mmol), compound sub E-3 (14.6 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. Purifying the concentrated compound by silica gel column chromatography to obtain2-3 (14 g). (yield: 60%, MS: [ M+H)] + ＝674)
PREPARATION EXAMPLES 2 to 4
Compound sub A-1 (10 g,34.6 mmol), compound sub E-4 (13.8 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound 2-4 (12.4 g). (yield: 55%, MS: [ M+H) ] + ＝650)
PREPARATION EXAMPLES 2 to 5
Compound sub A-1 (10 g,34.6 mmol), compound sub E-5 (12.9 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound 2-5 (12.7 g). (yield: 59%, MS: [ M+H)] + ＝624)
Preparation examples 2 to 6
Compound sub A-1 (10 g,34.6 mmol), compound sub E-6 (14.3 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound 2-6 (15.4 g). (yield: 67%, MS: [ M+H) ] + ＝664)
Preparation examples 2 to 7
Compound sub A-1 (10 g,34.6 mmol), compound sub E-7 (17.4 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene (200 ml) under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound 2-7 (17.3 g). (yield: 66%, MS: [ M+H)] + ＝756)
Preparation examples 2 to 8
Will be under nitrogen atmosphereCompound sub A-1 (10 g,34.6 mmol), compound sub E-8 (11.6 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene (200 ml), and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound 2-8 (13.8 g). (yield: 68%, MS: [ M+H) ] + ＝588)
Preparation examples 2 to 9
Compound sub A-1 (10 g,34.6 mmol), compound sub E-9 (11.6 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene (200 ml) under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compounds 2 to 9 (10.6 g). (yield: 52%, MS: [ M+H)] + ＝588)
Preparation examples 2 to 10
Compound sub A-1 (10 g,34.6 mmol), compound sub E-10 (12.5 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, it is theretoBis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound 2-10 (11.5 g). (yield: 54%, MS: [ M+H) ] + ＝614)
PREPARATION EXAMPLES 2 to 11
Compound sub A-1 (10 g,34.6 mmol), compound sub E-11 (15.2 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound 2-11 (13.6 g). (yield: 57%, MS: [ M+H)] + ＝690)
PREPARATION EXAMPLES 2 to 12
Compound sub A-1 (10 g,34.6 mmol), compound sub E-12 (13.9 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene (200 ml) under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the mixture is combined The material was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound 2-12 (15.8 g). (yield: 70%, MS: [ M+H ]] + ＝654)
PREPARATION EXAMPLES 2 to 13
Compound sub A-1 (10 g,34.6 mmol), compound sub E-13 (115.5 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 2-13 (13.8 g). (yield: 68%, MS: [ M+H)] + ＝588)
PREPARATION EXAMPLES 2 to 14
Compound sub A-1 (10 g,34.6 mmol), compound sub E-14 (13.8 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene (200 ml) under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. Concentrating the mixture The resultant was purified by silica gel column chromatography to obtain compound 2-14 (14.8 g). (yield: 66%, MS: [ M+H)] + ＝650)
PREPARATION EXAMPLES 2 to 15
Compound sub A-1 (10 g,34.6 mmol), compound sub E-15 (13.8 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound 2-15 (14.4 g). (yield: 64%, MS: [ M+H ]] + ＝650)
PREPARATION EXAMPLES 2 to 16
Compound sub A-1 (10 g,34.6 mmol), compound sub E-16 (16.4 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound 2-16 (13.1 g). (yield: 52%, MS: [ M+H) ] + ＝726)
PREPARATION EXAMPLES 2 to 17
Compound sub A-1 (10 g,34.6 mmol), compound sub E-17 (16.4 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene (200 ml) under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound 2-17 (16.6 g). (yield: 66%, MS: [ M+H)] + ＝726)
PREPARATION EXAMPLES 2 to 18
Compound sub A-1 (10 g,34.6 mmol), compound sub E-18 (11.1 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 2-18 (11.1 g). (yield: 56%, MS: [ M+H) ] + ＝572)
PREPARATION EXAMPLES 2 to 19
Compound sub A-1 (10 g,34.6 mmol), compound sub E-19 (15 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compounds 2 to 19 (16.4 g). (yield: 69%, MS: [ M+H)] + ＝687)
PREPARATION EXAMPLES 2 to 20
Compound sub A-1 (10 g,34.6 mmol), compound sub E-20 (13.7 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene (200 ml) under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound 2-20 (15 g). (yield: 67%, MS: [ M+H) ] + ＝648)
PREPARATION EXAMPLES 2 to 21
Compound sub A-1 (10 g,34.6 mmol), compound sub E-21 (11.1 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene under nitrogen atmosphere(200 ml) and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound 2-21 (10.5 g). (yield: 53%, MS: [ M+H)] + ＝572)
PREPARATION EXAMPLES 2 to 22
Compound F (15G, 58.3 mmol) and compound G (10G, 64.2 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (24.2 g,175 mmol) was dissolved in water (73 ml), added to the mixture, and the mixture was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.7 g,0.6 mmol). After reacting for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub A-2 (12.4 g). (yield: 74%, MS: [ M+H) ] + ＝289)
Compound sub A-2 (10 g,34.6 mmol), compound sub E-22 (12 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction was reversedThe mixture should be cooled to room temperature and the solvent removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound 2-22 (14.1 g). (yield: 68%, MS: [ M+H)] + ＝598)
PREPARATION EXAMPLES 2 to 23
Compound sub A-1 (10 g,34.6 mmol), compound sub E-23 (12 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 2-23 (11 g). (yield: 53%, MS: [ M+H) ] + ＝598)
PREPARATION EXAMPLES 2 to 24
Compound sub A-2 (10 g,34.6 mmol), compound sub E-24 (17.7 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to xylene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, and washed with anhydrous magnesium sulfateAnd then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound 2-24 (15.3 g). (yield: 58%, MS: [ M+H)] + ＝763)
PREPARATION EXAMPLES 2 to 25
Compound sub E-25 (10 g,59.1 mmol), compound sub A-1 (34.1 g,118.2 mmol) and sodium tert-butoxide (17 g,177.3 mmol) were added to xylene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound 2-25 (27.1 g). (yield: 68%, MS: [ M+H) ] + ＝674)
PREPARATION EXAMPLES 2 to 26
Compound sub E-26 (10 g,51.7 mmol), compound sub A-1 (29.9 g,103.5 mmol) and sodium tert-butoxide (14.9 g,155.2 mmol) were added to xylene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compounds 2 to 26 (18 g). (yield: 50%, MS: [ M+H)] + ＝698)
PREPARATION EXAMPLES 2 to 27
Compound sub E-27 (10 g,30 mmol), compound sub A-1 (17.3 g,60 mmol) and sodium tert-butoxide (8.6 g,90 mmol) were added to xylene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound 2-27 (14.6 g). (yield: 58%, MS: [ M+H) ] + ＝838)
PREPARATION EXAMPLES 2 to 28
Compound sub A-2 (10 g,34.6 mmol), compound sub E-28 (7.2 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to toluene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub A-2-1 (11.2 g). (yield: 70%, MS: [ M+H ]] + ＝462)
Compound sub A-2-1 (10 g,21.7 mmol), compound sub A-1 (6.3 g,21.7 mmol) and sodium tert-butoxide (4.2 g,43.3 mmol) were added to xylene (200 ml) under nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compounds 2 to 28 (10.7 g). (yield: 69%, MS: [ M+H) ] + ＝714)
PREPARATION EXAMPLES 2 to 29
Compound sub A-2 (10 g,34.6 mmol), compound sub E-29 (8.5 g,34.6 mmol) and sodium tert-butoxide (6.7 g,69.3 mmol) were added to toluene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub A-2-2 (9.8 g). (yield: 57%, MS: [ M+H)] + ＝498)
Compound sub A-2-2 (10 g,20.1 mmol), compound sub A-1 (5.8 g,20.1 mmol) and sodium tert-butoxide (3.9 g,40.2 mmol) were added to xylene (200 ml) under nitrogen atmosphere, and the mixture was stirredThe mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compounds 2 to 29 (10.1 g). (yield: 67%, MS: [ M+H) ] + ＝750)
PREPARATION EXAMPLES 2 to 30
Compound D (15 g,45 mmol) and compound B (7.7 g,49.5 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.7 g,135 mmol) was dissolved in water (56 ml), added to the mixture, and the mixture was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.5 g,0.5 mmol). After reacting for 10 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound subD-1 (13.1 g). (yield: 80%, MS: [ M+H)] + ＝365)
Compound sub D-1 (10 g,27.4 mmol), compound sub E-22 (9.5 g,27.4 mmol) and sodium tert-butoxide (5.3 g,54.8 mmol) were added to xylene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to The solvent was removed at room temperature under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound 2-30 (9.6 g). (yield: 52%, MS: [ M+H)] + ＝674)
PREPARATION EXAMPLES 2 to 31
Compound sub D-1 (10 g,27.4 mmol), compound sub E-30 (11.5 g,27.4 mmol) and sodium tert-butoxide (5.3 g,54.8 mmol) were added to xylene (200 ml) under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 2-31 (13.9 g). (yield: 68%, MS: [ M+H)] + ＝748)
PREPARATION EXAMPLES 2 to 32
Compound D (15G, 45 mmol) and compound G (7.7G, 49.5 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.7 g,135 mmol) was dissolved in water (56 ml), added to the mixture, and the mixture was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.5 g,0.5 mmol). After reacting for 9 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was redissolved in chloroform, washed twice with water, and the organic was separated Layer, add anhydrous magnesium sulfate thereto, stir and filter the mixture, and distill the filtrate under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound subD-2 (9.3 g). (yield: 72%, MS: [ M+H)] + ＝289)
Compound sub-D-2 (10 g,27.4 mmol), compound sub-31 (12.4 g,27.4 mmol) and sodium tert-butoxide (5.3 g,54.8 mmol) were added to xylene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 2-32 (15 g). (yield: 70%, MS: [ M+H ]] + ＝780)
PREPARATION EXAMPLES 2 to 33
Compound F (15 g,58.3 mmol) and compound E (14.9 g,64.2 mmol) were added to THF (300 ml) under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (24.2 g,175 mmol) was dissolved in water (73 ml), added to the mixture, and the mixture was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.7 g,0.6 mmol). After reacting for 10 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and filtered, and the filtrate was distilled under reduced pressure. Purifying the concentrated compound by silica gel column chromatography to obtain To compound sub A-3 (14.9 g). (yield: 70%, MS: [ M+H ]] + ＝365)
Compound sub A-3 (10 g,27.4 mmol), compound sub32 (2.6 g,27.4 mmol) and sodium tert-butoxide (5.3 g,54.8 mmol) were added to toluene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound sub A-3-1 (5.8 g). (yield: 50%, MS: [ M+H)] + ＝422)
Compound sub A-3-1 (10 g,23.7 mmol), compound sub A-2 (6.9 g,23.7 mmol) and sodium tert-butoxide (4.6 g,47.4 mmol) were added to xylene (200 ml) under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 2-33 (8.9 g). (yield: 56%, MS: [ M+H) ] + ＝674)
PREPARATION EXAMPLES 2 to 34
Compound sub A-3 (10 g,27.4 mmol), compound sub33 (4.6 g,27.4 mmol) and sodium tert-butoxide (5.3 g,54.8 mmol) were added to toluene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub A-3-2 (9.1 g). (yield: 67%, MS: [ M+H)] + ＝498)
Compound sub A-3-2 (10 g,20.1 mmol), compound sub A-2 (5.8 g,20.1 mmol) and sodium tert-butoxide (3.9 g,40.2 mmol) were added to xylene (200 ml) under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound 2-34 (9.6 g). (yield: 64%, MS: [ M+H ] ] + ＝750)
PREPARATION EXAMPLES 2 to 35
Compound sub A-3-2 (10 g,20.1 mmol), compound sub A-1 (5.8 g,20.1 mmol) and sodium tert-butoxide (3.9 g,40.2 mmol) were added to xylene (2) under nitrogen00 ml), and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compounds 2 to 35 (8.6 g). (yield: 57%, MS: [ M+H)] + ＝750)
PREPARATION EXAMPLES 2 to 36
Compound sub A-3 (10 g,27.4 mmol), compound sub E-34 (4.6 g,27.4 mmol) and sodium tert-butoxide (5.3 g,54.8 mmol) were added to toluene (200 ml) under nitrogen atmosphere and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub A-3-3 (8.6 g). (yield: 63%, MS: [ M+H) ] + ＝498)
Compound sub A-3-3 (10 g,20.1 mmol), compound sub A-2 (5.8 g,20.1 mmol) and sodium tert-butoxide (3.9 g,40.2 mmol) were added to xylene (200 ml) under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the process is carried out,the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give compound 2-36 (10.4 g). (yield: 69%, MS: [ M+H)] + ＝750)
PREPARATION EXAMPLES 2 to 37
Compound sub35 (10 g,51.7 mmol), compound sub A-2 (29.9 g,103.5 mmol) and sodium tert-butoxide (14.9 g,155.2 mmol) were added to xylene (200 ml) under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 2-37 (23.8 g). (yield: 66%, MS: [ M+H) ] + ＝698)
PREPARATION EXAMPLES 2 to 38
Compound sub E-33 (10 g,107.4 mmol), compound sub D-1 (78.4 g,214.8 mmol) and sodium tert-butoxide (31 g,322.1 mmol) were added to xylene (200 ml) under nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (1.1 g,2.1 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. ConcentratingIs purified by silica gel column chromatography to give compound 2-38 (53.9 g). (yield: 67%, MS: [ M+H)] + ＝750)
Examples (example)
Example 1
Coating it withThe glass substrate of the ITO (indium tin oxide) thin film of the thickness is put into distilled water containing a detergent dissolved therein and washed by ultrasonic waves. In this case, the detergent used was a commercially available product from Fisher co. And the distilled water was distilled water filtered twice by using a commercially available filter from Millipore co. The ITO was washed for 30 minutes, and then ultrasonic washing was repeated twice by using distilled water for 10 minutes. After washing with distilled water is completed, the substrate is ultrasonically washed with isopropanol, acetone and methanol solvents and dried before being transferred to a plasma cleaner. Then, the substrate was cleaned with oxygen plasma for 5 minutes, and then transferred to a vacuum evaporator.
Forming an ITO transparent electrode having a thickness ofThe following compound HI-1 was used as a hole injection layer, but the following compound A-1 was p-doped at a concentration of 1.5 wt%. Vacuum depositing the following compound HT-1 on the hole injection layer to form a film having a thickness +.>Is provided. Then, the following compound EB-1 was vacuum deposited on the hole transport layer to form a film thickness of +.>Is a barrier to electrons. Then, the previously prepared compound 1 and compound 2-1 were vacuum deposited as a host and the following compound Dp-7 was used as a dopant on the electron blocking layer at a weight ratio of 49:49:2, respectively, to form a film thickness of +.>Is provided. Vacuum depositing the following compound HB-1 on the light-emitting layer to form a film thickness of +.>Is a hole blocking layer of (a). Vacuum depositing the following compound ET-1 and the following compound LiQ on the hole blocking layer at a ratio of 2:1 to form a film thickness +.> Electron injection and transport layers of (a) are provided. Sequentially depositing lithium fluoride (LiF) and aluminum to a thickness of +.>And->Thereby forming a cathode. />
In the above process, the deposition rate of the organic material is maintained atSecond to->Second, the deposition rates of lithium fluoride and aluminum of the cathode were maintained at +. >Second and->Second, and the vacuum during deposition was maintained at 2X 10 -7 To 5X 10 -6 And a support, thereby manufacturing an organic light emitting device.
Examples 2 to 100
An organic light-emitting device was manufactured in the same manner as in example 1, except that the compounds shown in tables 1 to 3 below were used as the main bodies of the light-emitting layers.
Comparative examples 1 to 85
An organic light-emitting device was manufactured in the same manner as in example 1, except that the compounds shown in tables 4 to 7 below were used as the main bodies of the light-emitting layers. In the following tables 6 and 7, it is meant that a single compound is used as a host of the light emitting layer, and the compounds in table 7 are as follows, respectively.
By applying a current (15 mA/cm 2 ) The driving voltage, light emitting efficiency, and lifetime were measured, and the results are shown in tables 1 to 7 below. Lifetime T95 means the time (hours) required for the luminance to decrease to 95% of the initial luminance (6000 nit).
TABLE 1
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TABLE 2
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TABLE 3
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TABLE 4
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TABLE 5
TABLE 6
| Classification | Main body | Efficiency (cd/A) | Lifetime T95 (hours) | Luminescent color |
| Comparative example 49 | Compound 1 | 20.3 | 122 | Red color |
| Comparative example 50 | Compound 3 | 21.1 | 135 | Red color |
| Comparative example 51 | Compound 5 | 23.2 | 148 | Red color |
| Comparative example 52 | Compound 9 | 22.6 | 127 | Red color |
| Comparative example 53 | Compound 10 | 21.8 | 143 | Red color |
| Comparative example 54 | Compound 14 | 23.2 | 157 | Red color |
| Comparative example 55 | Compound 17 | 22.6 | 145 | Red color |
| Comparative example 56 | Compound 19 | 21.4 | 128 | Red color |
| Comparative example 57 | Compound 21 | 24.5 | 172 | Red color |
| Comparative example 58 | Compound 23 | 19.4 | 126 | Red color |
| Comparative example 59 | Compound 25 | 20.2 | 129 | Red color |
| Comparative example 60 | Compound 29 | 21.3 | 141 | Red color |
| Comparative example 61 | Compound 30 | 21.5 | 133 | Red color |
| Comparative example 62 | Compound 31 | 20.2 | 145 | Red color |
| Comparative example 63 | Compound 32 | 21.6 | 157 | Red color |
| Comparative example 64 | Compound 33 | 22.3 | 140 | Red color |
| Comparative example 65 | Compound 34 | 21.6 | 152 | Fiber color |
| Comparative example 66 | Compound 35 | 22.2 | 143 | Red color |
| Comparative example 67 | Compound 36 | 22.8 | 142 | Red color |
| Comparative example 68 | Compound 37 | 21.6 | 158 | Red color |
| Comparative example 69 | Compound 38 | 22.3 | 141 | Red color |
| Comparative example 70 | Compound 39 | 21.5 | 151 | Red color |
| Comparative example 71 | Compound 40 | 20.7 | 160 | Red color |
| Comparative example 72 | Compound 41 | 22.6 | 159 | Fiber color |
| Comparative example 73 | Compound 42 | 23.8 | 163 | Red color |
TABLE 7
| Classification | Main body | Efficiency (cd/A) | Lifetime T95 (hours) | Luminescent color |
| Comparative example 74 | C-1 | 17.4 | 107 | Red color |
| Comparative example 75 | C-2 | 16.1 | 83 | Red color |
| Comparative example 76 | C-3 | 16.4 | 94 | Red color |
| Comparative example 77 | C-4 | 16.0 | 87 | Red color |
| Comparative example 78 | C-5 | 18.7 | 110 | Red color |
| Comparative example 79 | C-6 | 16.5 | 47 | Red color |
| Comparative example 80 | C-7 | 15.3 | 22 | Red color |
| Comparative example 81 | C-8 | 15.1 | 37 | Red color |
| Comparative example 82 | C-9 | 17.3 | 75 | Red color |
| Comparative example 83 | C-10 | 17.5 | 92 | Red color |
| Comparative example 84 | C-11 | 15.8 | 63 | Red color |
| Comparative example 85 | C-12 | 16.1 | 78 | Red color |
As shown in the above table, the organic light emitting device of the example in which the first compound represented by chemical formula 1 and the second compound represented by chemical formula 2 were simultaneously used as the host material of the light emitting layer exhibited excellent light emitting efficiency and significantly improved lifetime characteristics, compared to the organic light emitting device of the comparative example in which only one of the compound represented by chemical formula 1 and the compound represented by chemical formula 2 (table 6) or neither of them was used (table 7). In particular, the device according to the embodiment exhibits higher efficiency and longer lifetime than the device of the comparative example in which the compound represented by chemical formula 1 is used as a single body. Further, even compared to the device of the comparative example in which the compounds C-1 to C-12 of the comparative example were used as the first host and the compound represented by chemical formula 2 was used as the second host, the device according to the embodiment exhibited improved efficiency and lifetime characteristics. Thus, it was determined that when the combination of the first compound represented by chemical formula 1 and the second compound represented by chemical formula 2 is used as a co-host, energy transfer to the red dopant is effectively performed in the red light emitting layer. This can be judged because the first compound has high electron and hole stability, and further, because the amount of holes increases with the simultaneous use of the second compound, the electrons and holes in the red light emitting layer maintain a more stable balance.
Therefore, when the first compound and the second compound are simultaneously used as a host material of the organic light emitting device, it was determined that the driving voltage, the light emitting efficiency, and/or the lifetime characteristics of the organic light emitting device can be improved. In general, considering that the light emission efficiency and lifetime characteristics of the organic light emitting device have a trade-off relationship with each other, it may be considered that the organic light emitting device employing the combination of the compounds of the present disclosure exhibits significantly improved device characteristics compared to the device of the comparative example.
Description of the reference numerals
1: substrate 2: anode
3: light emitting layer 4: cathode electrode
5: hole transport layer 6: electron transport layer
Claims (9)
1. An organic light emitting device comprising:
an anode is provided with a cathode,
cathode and method for manufacturing the same
A light emitting layer between the anode and the cathode,
wherein the light emitting layer comprises a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2:
[ chemical formula 1]
In the chemical formula 1, the chemical formula is shown in the drawing,
x is O or S, and the X is O or S,
each Y is independently N or CH, provided that at least one Y is N,
L 1 is a single bond, or substituted or unsubstituted C 6-60 An arylene group,
Ar 1 and Ar is a group 2 Each independently is a substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-60 A heteroaryl group, which is a group,
[ chemical formula 2]
In the chemical formula 2, the chemical formula is shown in the drawing,
L 2 is phenylene or phenylene substituted with at least one deuterium,
L 3 and L 4 Each independently is a single bond, phenylene, biphenyldiyl, or naphthylene, the L 3 And L 4 Each independently unsubstituted or substituted with at least one deuterium,
Ar 3 and Ar is a group 4 Each independently is phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, phenylphenanthryl, triphenylenyl, phenylnaphthyl or naphthylphenyl, said Ar 3 And Ar is a group 4 Each independently unsubstituted or substituted with at least one deuterium,
r is hydrogen, deuterium, or substituted or unsubstituted C 6-60 Aryl group
n is an integer from 0 to 9.
2. The organic light-emitting device according to claim 1,
wherein all Y are N.
3. The organic light-emitting device according to claim 1,
wherein L is 1 Is a single bond, phenylene or naphthylene.
4. The organic light-emitting device according to claim 1,
wherein L is 1 Is a single bond,
5. The organic light-emitting device according to claim 1,
wherein Ar is 1 And Ar is a group 2 Each independently is phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, phenylnaphthyl, naphthylphenyl, dimethylfluorenyl, diphenylfluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazol-9-yl, 9-phenyl-9H-carbazolyl, and
The Ar is as follows 1 And Ar is a group 2 Each independently unsubstituted or substituted with at least one deuterium.
6. The organic light-emitting device according to claim 1,
wherein Ar is 1 Is phenyl, biphenyl or naphthyl,
the Ar is as follows 1 Unsubstituted or substituted with at least one deuterium
Ar 2 Is phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, phenylnaphthyl, naphthylphenyl, dimethylfluorenyl, diphenylfluorenyl, dibenzofuranyl, dibenzothienyl, carbazole-9-yl, 9-phenyl-9H-carbazolyl,
the Ar is as follows 2 Unsubstituted or substituted with at least one deuterium.
7. The organic light-emitting device according to claim 1,
wherein the compound represented by chemical formula 1 is any one selected from the group consisting of:
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8. the organic light emitting device according to claim 1, wherein chemical formula 2 is represented by the following chemical formula 2-1: [ chemical formula 2-1]
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In the chemical formula 2-1, a radical of formula,
R 1 is hydrogen, deuterium or phenyl and is preferably hydrogen,
n1 is an integer of 0 to 8,
L 2 、L 3 、L 4 、Ar 3 、Ar 4 and R is as defined in claim 1.
9. The organic light-emitting device according to claim 1,
wherein the compound represented by chemical formula 2 is any one selected from the group consisting of:
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| WO2023201590A1 (en) * | 2022-04-20 | 2023-10-26 | 京东方科技集团股份有限公司 | Light-emitting material for organic light-emitting device, light-emitting device, and display device |
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