CN115191039A - Organic light emitting device - Google Patents
Organic light emitting device Download PDFInfo
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- CN115191039A CN115191039A CN202180013222.5A CN202180013222A CN115191039A CN 115191039 A CN115191039 A CN 115191039A CN 202180013222 A CN202180013222 A CN 202180013222A CN 115191039 A CN115191039 A CN 115191039A
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Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- 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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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present invention provides an organic light emitting device having improved driving voltage, efficiency and lifetime.
Description
Technical Field
Cross reference to related applications
This application claims priority based on korean patent application No. 10-2020-0057863, on year 2020, 5/14/and korean patent application No. 10-2021-0062251, on year 2021, 5/13/inclusive, the entire contents disclosed in the documents of this korean patent application are incorporated as part of this specification.
The present invention relates to an organic light emitting device with improved driving voltage, efficiency and lifetime.
Background
In general, the organic light emitting phenomenon refers to a phenomenon of converting electric energy into light energy using an organic substance. An organic light emitting device using an organic light emitting phenomenon has a wide viewing angle, excellent contrast, a fast response time, and excellent luminance, driving voltage, and response speed characteristics, and thus a great deal of research is being conducted.
An organic light emitting device generally has a structure including an anode and a cathode, and an organic layer between the anode and the cathode. In order to improve the efficiency and stability of the organic light emitting device, the organic layer is often formed of a multilayer structure formed of different materials, and may be formed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, or the like. With the structure of such an organic light emitting device, if a voltage is applied between the two electrodes, holes are injected from the anode into the organic layer, electrons are injected from the cathode into the organic layer, and when the injected holes and electrons meet, an exciton (exiton) is formed, and light is emitted when the exciton falls back to the ground state.
For the organic light emitting device as described above, development of an organic light emitting device having improved driving voltage, efficiency, and lifetime is continuously demanded.
Documents of the prior art
Patent document
(patent document 1) Korean patent laid-open publication No. 10-2000-0051826
Disclosure of Invention
Technical subject
The present invention relates to an organic light emitting device with improved driving voltage, efficiency and lifetime.
Means for solving the problems
The present invention provides the following organic light emitting device:
an organic light emitting device, comprising:
an anode, a cathode, and a light-emitting layer between the anode and the cathode,
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 above-mentioned chemical formula 1,
Ar 1 and Ar 2 Each independently is 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 (ii) a heteroaryl group, wherein,
L 1 to L 3 Each independently is a single bond, or substituted or unsubstituted C 6-60 An arylene group, a cyclic or cyclic alkylene group,
R 1 is hydrogen; deuterium; 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 (ii) a heteroaryl group, wherein,
a is an integer of 0 to 7,
[ chemical formula 2]
In the above-described chemical formula 1,
Ar 3 and Ar 4 Each independently is 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 (ii) a heteroaryl group, wherein,
L 4 to L 6 Each independently a single bond, or a substituted or unsubstituted C 6-60 An arylene group.
Effects of the invention
The above organic light emitting device may achieve an improvement in efficiency, a lower driving voltage, and/or an improvement in life span characteristics in the organic light emitting device by including the compound represented by the above chemical formula 1 and the compound represented by the above chemical formula 2 in the light emitting layer.
Drawings
Fig. 1 illustrates an example of an organic light-emitting device composed of a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.
Fig. 2 illustrates an example of an organic light-emitting device composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light-emitting layer 3, a hole blocking layer 8, an electron transport layer 9, an electron injection layer 10, and a cathode 4.
Detailed Description
Hereinafter, the present invention will be described in more detail to assist understanding thereof.
In the context of the present specification,
represents a bond to another substituent.
In the present specification, the term "substituted or unsubstituted" means substituted with a substituent selected from 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 radicals
Arylthio radicals
Alkylsulfonyl radicals
Aryl sulfonyl radical
A silyl group; a boron group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; aralkyl group; an aralkenyl group; an alkylaryl group; an alkylamino group; an aralkylamino group; a heteroaryl amino group; an arylamine group; an aryl phosphine group; or 1 or more substituents of 1 or more heterocyclic groups containing N, O and S atoms, or substituents formed by connecting 2 or more substituents of the above-exemplified substituents. For example, "a substituent in which 2 or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which 2 phenyl groups are linked.
In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40. Specifically, the substituent may be a substituent having the following structure, but is not limited thereto.
In the present specification, in the ester group, the oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms; or aryl having 6 to 25 carbon atoms. Specifically, the substituent may be a substituent represented by the following structural formula, but is not limited thereto.
In the present specification, the number of carbon atoms in the imide group is not particularly limited, but is preferably 1 to 25. Specifically, the substituent may be a substituent having the following structure, but is not limited thereto.
In the present specification, specific examples of the silyl group include, but are not limited to, a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, and a phenylsilyl group.
In the present specification, the boron group specifically includes a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron group, and the like, but is not limited thereto.
In the present specification, as examples of the halogen group, there are fluorine, chlorine, bromine or iodine.
In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. 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, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, and 5-methylhexyl.
In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the number of carbon atoms of the alkenyl group is 2 to 20. According to another embodiment, the number of carbon atoms of the alkenyl group is 2 to 10. According to another embodiment, the number of carbon atoms of the above alkenyl group is 2 to 6. Specific examples thereof include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylethen-1-yl, 2-phenylethen-1-yl, 2,2-diphenylethen-1-yl, 2-phenyl-2- (naphthalen-1-yl) ethen-1-yl, 2,2-bis (biphenyl-1-yl) ethen-1-yl, stilbene-yl, styryl and the like, but the present invention is not limited thereto.
In the present specification, the cycloalkyl group is not particularly limited, but is preferably a cycloalkyl group having 3 to 60 carbon atoms, and according to one embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 30. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the number of carbon atoms of the above cycloalkyl group is 3 to 6. Specifically, there are mentioned, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like.
In the present specification, the aryl group is not particularly limited, but is preferably an aryl group having 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aromatic group may be a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a perylene group,
And a fluorenyl group, but is not limited thereto.
In the present specification, the fluorenyl group may be substituted, and 2 substituents may be combined with each other to form a spiro structure. When the fluorenyl group is substituted, the substituted fluorenyl group may be
And the like. But is not limited thereto.
In the present specification, the heterocyclic group is a heterocyclic group containing 1 or more of O, N, si and S as a hetero element, and the number of carbon atoms is not particularly limited, but preferably 2 to 60. Examples of the heterocyclic group include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, thienyl,
Azolyl group,
Oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzobenzoxazinyl
Azolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, benzofuranyl, phenanthrolinyl (phenanthroline), isoquinoyl
Oxazolyl, thiadiazolyl, phenothiazinyl, dibenzofuranyl, and the like, but is not limited thereto.
In the present specification, the aryl group in the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the above-mentioned aryl group. In the present specification, the alkyl group in the aralkyl group, the alkylaryl group, and the alkylamino group is the same as the above-mentioned alkyl group. In the present specification, the heteroaryl group in the heteroarylamine can be applied to the above description about the heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is exemplified by the same alkenyl groups as described above. In the present specification, the arylene group is a 2-valent group, and the above description of the aryl group can be applied thereto. In this specification, the heteroarylene group is a 2-valent group, and the above description of the heterocyclic group can be applied thereto. In the present specification, the hydrocarbon ring is not a 1-valent group but is formed by combining 2 substituents, and in addition to this, the above description about the aryl group or the cycloalkyl group can be applied. In the present specification, the heterocyclic group is not a 1-valent group but a combination of 2 substituents, and the above description of the heterocyclic group can be applied.
The present invention will be described in detail below with reference to the respective configurations.
An anode and a cathode
The anode and the cathode used in the present invention refer to electrodes used in an organic light emitting device.
The anode material is preferably a material having a large work function in order to smoothly inject holes into the organic layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, and gold, and alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); znO-Al or SnO 2 A combination of a metal such as Sb and an oxide; poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene]Conductive polymers such as (PEDOT), polypyrrole, and polyaniline, but the present invention is not limited thereto.
The cathode material is preferably a material having a small work function in order to easily inject electrons into the organic 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, and alloys thereof; liF/Al or LiO 2 And a multilayer structure material such as Al, but not limited thereto.
Hole injection layer
The organic light emitting device according to the present invention may further include a hole injection layer on the anode as needed.
The hole injection layer is a layer for injecting holes from the electrode, and the following compounds are preferable as the hole injection substance: a compound having an ability to transport holes, having an effect of injecting holes from an anode, having an excellent hole injection effect for a light-emitting layer or a light-emitting material, preventing excitons generated in the light-emitting layer from migrating to an electron injection layer or an electron injection material, and having an excellent thin film-forming ability. Further, it is preferable that the HOMO (highest occupied molecular orbital) of the hole injecting substance is between the work function of the anode substance and the HOMO of the surrounding organic layer.
Specific examples of the hole injecting substance include, but are not limited to, metalloporphyrin (porphyrin), oligothiophene, arylamine-based organic substances, hexanitrile-hexaazatriphenylene-based organic substances, quinacridone-based organic substances, perylene-based organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers.
Hole transport layer
The organic light emitting device according to the present invention may include a hole transport layer on the anode (or on the hole injection layer when present) as 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, and the hole transport substance is a substance that can receive holes from the anode or the hole injection layer and transport the holes to the light-emitting layer, and is preferably a substance having a high mobility to holes.
Specific examples of the hole transporting substance include, but are not limited to, arylamine-based organic substances, conductive polymers, and block copolymers in which a conjugated portion and a non-conjugated portion are present simultaneously.
Electron blocking layer
The organic light emitting device according to the present invention may include an electron blocking layer on the hole transport layer as needed.
The electron blocking layer is a layer interposed between the hole transport layer and the light emitting layer in order to prevent electrons injected from the cathode from being transferred to the hole transport layer without being recombined in the light emitting layer, and is also referred to as an electron blocking layer or an electron suppressing layer. The electron-blocking layer is preferably a substance having a small electrophilic ability as compared with the electron-transporting layer.
Luminescent layer
The light-emitting layer used in the present invention is a layer capable of combining holes and electrons received from the anode and the cathode to emit light in the visible region. In general, the light emitting layer includes a host material and a dopant material, and the compound represented by the above chemical formula 1 and the compound represented by the above chemical formula 2 are included as hosts in the present invention.
Preferably, the compound represented by the above chemical formula 1 may be represented by any one of the following chemical formulae 1-1 to 1-3:
[ chemical formula 1-1]
[ chemical formulas 1-2]
[ chemical formulas 1-3]
In the above chemical formulas 1-1 to 1-3,
Ar 1 、Ar 2 、L 1 to L 3 And R 1 The same as defined in chemical formula 1.
Preferably, ar 1 And Ar 2 May each independently be substituted or unsubstituted C 6-20 An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-20 (ii) a heteroaryl group, wherein,
more preferably, ar 1 And Ar 2 Can each independently be phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, dibenzofuranyl, or dibenzothiophenyl,
most preferably, ar 1 And Ar 2 May each independently be any one selected from the following groups:
preferably, L 1 To L 3 May each independently be a single bond, or a substituted or unsubstituted C 6-20 An arylene group, a heterocyclic group, or a heterocyclic group,
more preferably, L 1 To L 3 May each independently be a single bond, phenylene, biphenylene or naphthylene,
most preferably, L 1 To L 3 May each independently be a single bond, or any one selected from the following groups:
preferably, R 1 May each independently be hydrogen; deuterium; substituted or unsubstituted C 6-20 An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-20 (ii) a heteroaryl group, wherein,
more preferably, R 1 May each independently be hydrogen, deuterium, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, naphthylphenyl, phenylnaphthyl, fluoranthenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, or benzonaphthothiophenyl.
Preferably, a may be 0 or 1. More preferably, a may be 1.
Preferably, ar 1 、Ar 2 And R 1 At least one of which may be naphthyl, phenylnaphthyl, naphthylphenyl, phenanthryl, fluoranthenyl, dibenzofuranyl, dibenzothienyl, benzonaphthofuranyl, or benzonaphthothienyl.
More preferably, ar 1 、Ar 2 And R 1 At least one of which may be naphthyl, phenylnaphthyl, naphthylphenyl, fluoranthenyl, dibenzofuranyl, benzonaphthofuranyl, or benzonaphthothienyl.
Representative examples of the compound represented by the above chemical formula 1 are as follows:
as an example, the compound represented by the above chemical formula 1 may be produced by a production method as shown in the following reaction formula 1, and the remaining compounds except for this may be produced by a similar method.
[ reaction formula 1]
In the above reaction scheme 1, ar 1 、Ar 2 、L 1 To L 3 、R 1 And a is as defined in the above chemical formula 1, X 1 Is halogen, preferably, X 1 Is chlorine or bromine.
The above reaction formula 1 is a suzuki coupling reaction, preferably carried out in the presence of a palladium catalyst and a base, and the reactive group used for the suzuki coupling reaction may be modified according to the techniques known in the art. The above-described manufacturing method can be further embodied in the manufacturing examples described later.
Preferably, ar 3 And Ar 4 May each independently be substitutedOr unsubstituted C 6-20 An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-20 (ii) a heteroaryl group, wherein,
more preferably, ar 3 And Ar 4 May each independently be phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthryl, naphthylphenyl, phenylnaphthyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, carbazolyl, phenylcarbazolyl, dibenzofuranyl, dibenzothiophenyl, or benzonaphthofuranyl,
most preferably, ar 3 And Ar 4 May each independently be any one selected from the following groups:
preferably, L 4 To L 6 May each independently be a single bond, or a substituted or unsubstituted C 6-20 An arylene group, a cyclic or cyclic alkylene group,
more preferably, L 4 To L 6 May each independently be a single bond, phenylene, biphenylene, naphthylene, or dimethylfluorenylene group,
most preferably, L 4 To L 6 May each independently be a single bond, or any one selected from the following groups:
representative examples of the compound represented by the above chemical formula 2 are as follows:
as an example, the compound represented by the above chemical formula 2 may be produced by a production method as shown in the following reaction formula 2, and the remaining compounds other than the above may be produced by a similar method.
[ reaction formula 2]
In the above reaction formula 2, ar 3 、Ar 4 And L 4 To L 6 As defined in the above chemical formula 2, X 2 Is halogen, preferably, X 2 Is chlorine or bromine.
The above reaction formula 2 is an amine substitution reaction, and is preferably carried out in the presence of a palladium catalyst and a base, and the reactive group used for the amine substitution reaction may be modified according to a technique known in the art. The above-described manufacturing method can be further embodied in the manufacturing examples described later.
Preferably, in the light-emitting layer, the weight ratio of the compound represented by the above chemical formula 1 to the compound represented by the above chemical formula 2 is 10.
On the other hand, the light-emitting layer may further contain a dopant in addition to the host. The dopant material is not particularly limited as long as it is a material used for an organic light-emitting device. As examples, there are aromatic amine derivatives, styryl amine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivative is an aromatic fused ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, or the like having an arylamino group,
Diindenopyrene, and the like, and styrylamine compounds are compounds in which at least 1 arylvinyl group is substituted on a substituted or unsubstituted arylamine, and are substituted or unsubstituted with 1 or 2 or more substituents selected from aryl, silyl, alkyl, cycloalkyl, and arylamino groups. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltrimethylamine, and styryltretramine. The metal complex includes, but is not limited to, iridium complexes and platinum complexes.
Hole blocking layer
The organic light emitting device according to the present invention may include an electron transport layer on the above light emitting layer as necessary.
The hole blocking layer is a layer interposed between the electron transport layer and the light emitting layer to prevent holes injected from the anode from being transferred to the electron transport layer without being recombined in the light emitting layer, and is also referred to as a hole inhibiting layer or a hole blocking layer. The hole blocking layer is preferably formed using a substance having a large ionization energy.
Electron transport layer
The organic light emitting device according to the present invention may include an electron transport layer on the above light emitting layer (or hole blocking layer) as necessary.
The electron transport layer is a layer that receives electrons from the cathode or an electron injection 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 transport material is a material that can favorably receive electrons from the cathode and transfer the electrons to the light-emitting layer, and is preferably a material having a high mobility for electrons.
Specific examples of the electron-transporting substance include Al complexes of 8-hydroxyquinoline and Al complexes containing Alq 3 The complex of (a), an organic radical compound, a hydroxyflavone-metal complex, etc., but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in the art. Examples of suitable cathode substances are, in particular, the customary substances having a low work function and accompanied by an aluminum or silver layer. In particular cesium, barium, calcium, ytterbium and samarium, in each case accompanied by an aluminum or silver layer.
Electron injection layer
The organic light emitting device according to the present invention may further include an electron injection layer on the above light emitting layer (or on the electron transport layer when the electron transport layer is present), as necessary.
The electron injection layer is a layer for injecting electrons from the electrode, and the following compounds are preferably used: a compound having an ability to transport electrons, having an effect of injecting electrons from a cathode, having an excellent electron injection effect with respect to a light-emitting layer or a light-emitting material, preventing excitons generated in the light-emitting layer from migrating to a hole-injecting layer, and having an excellent thin-film-forming ability.
Specific examples of the substance that can be used in the electron injection layer include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, and the like,
Azole,
Oxadiazole, oxadiazole IIIExamples of the metal complex include, but are not limited to, oxazoles, imidazoles, perylene tetracarboxylic acids, fluorenylidene methanes, anthrones, derivatives thereof, metal complexes, and nitrogen-containing five-membered ring derivatives.
Examples of the metal complex include, but are not limited to, lithium 8-quinolinolato, zinc bis (8-quinolinolato), copper bis (8-quinolinolato), manganese bis (8-quinolinolato), aluminum tris (2-methyl-8-quinolinolato), gallium tris (8-quinolinolato), beryllium bis (10-hydroxybenzo [ h ] quinoline), zinc bis (10-hydroxybenzo [ h ] quinoline), gallium bis (2-methyl-8-quinolinolato) chloride, gallium bis (2-methyl-8-quinolinolato) (o) gallium, bis (2-methyl-8-quinolinolato) (1-naphthol) aluminum, and gallium bis (2-methyl-8-quinolinolato) (2-naphthol) gallium.
On the other hand, in the present invention, the "electron injection and transport layer" is a layer that exerts all the functions of the electron injection layer and the electron transport layer, and a substance that exerts the functions of the layers may be used alone or in a mixture of two or more, but the present invention is not limited thereto.
Organic light emitting device
The structure of the organic light emitting device according to the present invention is illustrated in fig. 1 and 2. Fig. 1 illustrates an example of an organic light-emitting device composed of a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4. Fig. 2 illustrates an example of an organic light-emitting device composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light-emitting layer 3, a hole blocking layer 8, an electron transport layer 9, an electron injection layer 10, and a cathode 4.
The organic light emitting device according to the present invention can be manufactured by sequentially stacking the above-described constitutions. This can be produced as follows: the anode is formed by depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate by a PVD (physical Vapor Deposition) method such as a sputtering method or an electron beam evaporation method, the above layers are formed on the anode, and a substance which can be used as a cathode is deposited thereon. In addition to this method, an organic light emitting device can be manufactured by sequentially evaporating a cathode substance to an anode substance on a substrate in the reverse order of the above-described constitution (WO 2003/012890). In addition, the host and the dopant can be formed into the light-emitting layer not only by a vacuum deposition method but also by a solution coating method. Here, the solution coating method refers to spin coating, dip coating, blade coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.
On the other hand, the organic light emitting device according to the present invention may be a bottom emission (bottom emission) device, a top emission (top emission) device, or a bi-directional light emitting device, and particularly, may be a bottom emission device requiring relatively high light emitting efficiency.
In the following, preferred embodiments are suggested to aid in understanding the present invention. However, the following examples are provided for easier understanding of the present invention, and the present invention is not limited thereto.
[ production example ]
Production example 1-1: production of Compound 1-1
Under a nitrogen atmosphere, the compound 1-A (15g, 60.9mmol) and the compound Trz27 (25.6g, 60.9mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (bis (0)) (0.3g, 0.6 mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 19.1g of the compound substance (sub) 1-A-1 (yield 65%, MS: [ M + H ]] + ＝484)。
In nitrogenThe compound substance 1-A-1 (15g, 31mmol) and the compound substance 1 (6.1g, 31mmol) were added to 300ml of THF under the atmosphere, stirred and refluxed. Then, potassium carbonate (8.6 g, 62mmol) was dissolved in 26ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2 g, 0.3mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.3g of Compound 1-1 (yield 66%, MS: [ M + H ]] + ＝602)。
Production examples 1 and 2: production of Compound 1-2
Under a nitrogen atmosphere, compound 1-A (15g, 60.9 mmol) and compound Trz2 (16.3g, 60.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 19.5g of the compound substance 1-A-2 (yield 74%, MS: [ M + H ]] + ＝434)。
Under a nitrogen atmosphere, the compound substance 1-A-2 (15g, 34.6 mmol) and the compound substance 2 (9.4g, 34.6 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (9.6 g,69.1 mmol) was dissolved in 29ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.2g, 0) was charged.3 mmol). After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 14.3g of Compound 1-2 (yield 66%, MS: [ M + H ]] + ＝626)。
Production examples 1 to 3: production of Compounds 1 to 3
Under a nitrogen atmosphere, the compound 1-A (15g, 60.9mmol) and the compound Trz3 (19.3g, 60.9mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 23.2g of the compound substance 1-A-3 (yield 79%, MS: [ M + H ]] + ＝484)。
Under a nitrogen atmosphere, compound substance 1-A-3 (15g, 31mmol) and compound substance 3 (7.1g, 31mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (8.6 g, 62mmol) was dissolved in 26ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2g, 0.3mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound is applied to silica gelPurification was performed by column chromatography to thereby produce 12.9g of the compounds 1 to 3 (yield 66%, MS: [ M + H ]] + ＝632)。
Production examples 1 to 4: production of Compounds 1 to 4
Under a nitrogen atmosphere, compound 1-A (15g, 60.9 mmol) and compound Trz4 (27g, 60.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 26g of the compound substance 1-A-4 (yield 70%, MS: [ M + H ]] + ＝610)。
Under a nitrogen atmosphere, the compound substance 1-A-4 (15g, 24.6mmol) and the compound substance 4 (5.6g, 24.6mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (6.8g, 49.2mmol) was dissolved in 20ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.1g, 0.2mmol) was charged. After 11 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 11.2g of compounds 1 to 4 (yield 60%, MS: [ M + H ]] + ＝758)。
Production examples 1 to 5: production of Compounds 1 to 5
Under a nitrogen atmosphere, compound 1-B (15g, 60.9 mmol) and compound Trz5 (24g, 60.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 26.2g of the compound substance 1-B-1 (yield 77%, MS: [ M + H ]] + ＝560)。
Compound 1-B-1 (15g, 26.8mmol) and compound 5 (3.3g, 26.8mmol) were added to 300ml of THF under a nitrogen atmosphere, and stirring and refluxing were carried out. Then, potassium carbonate (7.4 g,53.6 mmol) was dissolved in 22ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.1 g,0.3 mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.9g of compounds 1 to 5 (yield 80%, MS: [ M + H ]] + ＝602)。
Production examples 1 to 6: production of Compounds 1 to 6
Under a nitrogen atmosphere, compound 1-B (15g, 60.9 mmol) and compound Trz3 (19.3g, 60.9 mmol) were added to 300ml of THF with stirringStirring and refluxing. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 18.2g of the compound substance 1-B-2 (yield 62%, MS: [ M + H ]] + ＝484)。
The compound substance 1-B-2 (15g, 31mmol) and the compound substance 6 (7.6g, 31mmol) were added to 300ml of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (8.6 g, 62mmol) was dissolved in 26ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2g, 0.3mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 15.3g of compounds 1 to 6 (yield 76%, MS: [ M + H ]] + ＝650)。
Production examples 1 to 7: production of Compounds 1 to 7
Under a nitrogen atmosphere, compound 1-B (15g, 60.9 mmol) and compound Trz2 (16.3g, 60.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. Dissolving it againAfter washing with chloroform and water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 20.8g of the compound substance 1-B-3 (yield 79%, MS: [ M + H ]] + ＝434)。
The compound substance 1-B-3 (15g, 34.6 mmol) and the compound substance 7 (8.6 g,34.6 mmol) were added to 300ml of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (9.6 g,69.1 mmol) was dissolved in 29ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2 g,0.3 mmol) was charged. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 15.4g of compounds 1 to 7 (yield 74%, MS: [ M + H ]] + ＝602)。
Production examples 1 to 8: production of Compounds 1 to 8
Under a nitrogen atmosphere, the compound substance 1-B-2 (15g, 31mmol) and the compound substance 8 (8.1g, 31mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (8.6 g, 62mmol) was dissolved in 26ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2g, 0.3mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 15.5g of compounds 1 to 8 (yield 75%, MS: [ M + H ]] + ＝666)。
Production examples 1 to 9: production of Compounds 1 to 9
Compound 1-B (15g, 60.9 mmol) and compound Trz6 (22.4g, 60.9 mmol) were added to 300ml of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 23.7g of the compound substance 1-B-4 (yield 73%, MS: [ M + H ]] + ＝534)。
Under a nitrogen atmosphere, the compound substance 1-B-4 (15g, 28.1mmol) and the compound substance 9 (6g, 28.1mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (7.8g, 56.2mmol) was dissolved in 23ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.1g, 0.3mmol) was charged. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 11.6g of compounds 1 to 9 (yield 62%, MS: [ M + H ]] + ＝666)。
Production examples 1 to 10: production of Compounds 1 to 10
Under a nitrogen atmosphere, the compound 1-B (15g, 60.9 mmol) and the compound Trz7 (28.6g, 60.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 28.6g of compound substance 1-B-5 (yield 74%, MS: [ M + H ]] + ＝636)。
Under a nitrogen atmosphere, compound substance 1-B-5 (15g, 23.6 mmol) and compound substance 5 (2.9g, 23.6 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (6.5g, 47.2mmol) was dissolved in 20ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.2mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 10.4g of compounds 1 to 10 (yield 65%, MS: [ M + H ]] + ＝678)。
Production examples 1 to 11: production of Compounds 1 to 11
Under a nitrogen atmosphere, the compound 1-B (15g, 60.9mmol) and the compound Trz8 (21.8g, 60.9mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and charged, and the mixture was sufficiently stirredThen, bis (tri-tert-butylphosphine) palladium (0) (0.3g, 0.6 mmol) was charged. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 20.1g of Compound substance 1-B-6 (yield 63%, MS: [ M + H ]] + ＝524)。
Under a nitrogen atmosphere, the compound substance 1-B-6 (15g, 28.6 mmol) and the compound substance 10 (4.9g, 28.6 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (7.9 g, 57.3mmol) was dissolved in 24ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3mmol) was charged. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 11.4g of compounds 1 to 11 (yield 65%, MS: [ M + H ]] + ＝616)。
Production examples 1 to 12: production of Compounds 1 to 12
Under a nitrogen atmosphere, compound 1-C (15g, 60.9 mmol) and compound Trz3 (19.3g, 60.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and introduced, followed by sufficient stirring, and then bis (tri-tert-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was introduced. After 11 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. Dissolving in chloroform again, washing with water for 2 times, separating organic layer, adding anhydrous magnesium sulfate, stirring, and filteringFiltering, and distilling the filtrate under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 17.6g of the compound substance 1-C-1 (yield 60%, MS: [ M + H ]] + ＝484)。
Under a nitrogen atmosphere, compound 1-C-1 (15g, 31mmol) and compound 10 (5.3g, 31mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (8.6 g, 62mmol) was dissolved in 26ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2 g, 0.3mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.8g of compounds 1 to 12 (yield 72%, MS: [ M + H ]] + ＝576)。
Production examples 1 to 13: production of Compounds 1 to 13
Under a nitrogen atmosphere, compound 1-C (15g, 60.9 mmol) and compound Trz9 (24g, 60.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 23.5g of Compound substance 1-C-2 (yield 69%, MS: [ M + H ]] + ＝560)。
Under a nitrogen atmosphere, compound 1-C-2 (15g, 26.8mmol) and compound 10 (4.6g, 26.8mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (7.4 g,53.6 mmol) was dissolved in 22ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.1 g,0.3 mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 14g of compounds 1 to 13 (yield 80%, MS: [ M + H ]] + ＝652)。
Production examples 1 to 14: production of Compounds 1 to 14
Under a nitrogen atmosphere, compound 1-C (15g, 60.9 mmol) and compound Trz10 (20.9 g,60.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 20.5g of the compound substance 1-C-3 (yield 66%, MS: [ M + H ]] + ＝510)。
Under a nitrogen atmosphere, compound substance 1-C-3 (15g, 29.4mmol) and Compound substance 11 (7.3g, 29.4mmol) were added to 300mlIn THF, stirred and refluxed. Then, potassium carbonate (8.1g, 58.8mmol) was dissolved in 24ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2g, 0.3mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 15.3g of compounds 1 to 14 (yield 77%, MS: [ M + H ]] + ＝678)。
Production examples 1 to 15: production of Compounds 1 to 15
Under a nitrogen atmosphere, compound 1-C (15g, 60.9 mmol) and compound Trz2 (16.3g, 60.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and introduced, followed by sufficient stirring, and then bis (tri-tert-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was introduced. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 18.7g of Compound substance 1-C-4 (yield 71%, MS: [ M + H ]] + ＝434)。
Compound 1-C-4 (15g, 37.1mmol) and compound 12 (9.7g, 37.1mmol) were added to 300ml of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (10.3g, 74.3mmol) was dissolved in 31ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphine) palladium (0) (0.2g, 0.4 mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 14.6g of compounds 1 to 15 (yield 64%, MS: [ M + H ]] + ＝616)。
Production examples 1 to 16: production of Compounds 1 to 16
Compound 1-C-3 (15g, 26.8mmol) and compound 13 (7.4g, 26.8mmol) were added to 300ml of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (7.4 g,53.6 mmol) was dissolved in 22ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.1 g,0.3 mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 16.2g of compounds 1 to 16 (yield 80%, MS: [ M + H ]] + ＝758)。
Production examples 1 to 17: production of Compounds 1 to 17
Under a nitrogen atmosphere, the compound substance 1-C-4 (15g, 34.6 mmol) and the compound substance 14 (7.7g, 34.6 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (9.6 g,69.1 mmol) was dissolved in 29ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2g, 0.3 mmol) was charged. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. Subjecting the concentrated compound to silica gel column chromatographyPurification was performed to thereby produce 12.3g of compounds 1 to 17 (yield 62%, MS: [ M + H ]] + ＝576)。
Production examples 1 to 18: production of Compounds 1-18
Under a nitrogen atmosphere, the compound substance 1-C-1 (15g, 31mmol) and the compound substance 9 (6.6g, 31mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (8.6 g, 62mmol) was dissolved in 26ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2g, 0.3mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12g of compounds 1 to 18 (yield 63%, MS: [ M + H ]] + ＝616)。
Production examples 1 to 19: production of Compounds 1 to 19
Compound 1-C (15g, 60.9 mmol) and compound Trz11 (22.4g, 60.9 mmol) were added to 300ml of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 22.4g of Compound substance 1-C-5 (yield 69%, MS: [ M + H ]] + ＝534)。
Under a nitrogen atmosphere, the compound substance 1-C-5 (15g, 28.1mmol) and the compound substance 15 (6g, 28.1mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (7.8g, 56.2mmol) was dissolved in 23ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.1g, 0.3mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.3g of compounds 1 to 19 (yield 71%, MS: [ M + H ]] + ＝666)。
Production examples 1 to 20: production of Compounds 1 to 20
Under a nitrogen atmosphere, the compound 1-C (15g, 60.9 mmol) and the compound Trz12 (21.8g, 60.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and introduced, followed by sufficient stirring, and then bis (tri-tert-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was introduced. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 21g of the compound substance 1-C-6 (yield 66%, MS: [ M + H ]] + ＝524)。
Under a nitrogen atmosphere, compound substance 1-C-6 (15g, 28.6 mmol) and compound substance 10 (4.9g, 28.6 mmol) were added to 300ml of THFStirring and refluxing. Then, potassium carbonate (11.9 g,85.9 mmol) was dissolved in 36ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.1 g,0.3 mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.3g of compounds 1 to 20 (yield 70%, MS: [ M + H ]] + ＝616)。
Production examples 1 to 21: production of Compounds 1 to 21
Under a nitrogen atmosphere, compound 1-C (15g, 60.9 mmol) and compound Trz13 (24g, 60.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 26.2g of Compound substance 1-C-7 (yield 77%, MS: [ M + H ]] + ＝560)。
Compound 1-C-7 (15g, 26.8mmol) and compound 5 (3.3g, 26.8mmol) were added to 300ml of THF under a nitrogen atmosphere, and stirring and refluxing were carried out. Then, potassium carbonate (11.1g, 80.3mmol) was dissolved in 33ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphine) palladium (0) (0.1g, 0.3mmol) was charged. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. Will be provided withIt was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added, 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 give 10.5g of compounds 1 to 21 (yield 65%, MS: [ M + H ]] + ＝602)。
Production examples 1 to 22: production of Compounds 1-22
Under a nitrogen atmosphere, compound 1-D (15g, 60.9 mmol) and compound Trz14 (19.3g, 60.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and introduced, followed by sufficient stirring, and then bis (tri-tert-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was introduced. After 11 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 23.9g of the compound substance 1-D-1 (yield 67%, MS: [ M + H ]] + ＝586)。
The compound substance 1-D-1 (15g, 25.6 mmol) and the compound substance 5 (3.1g, 25.6 mmol) were added to 300ml of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (10.6 g,76.8 mmol) was dissolved in 32ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.1g, 0.3 mmol) was charged. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 10.3g of compounds 1 to 22 (yield 64%, MS: [ M + H ]] + ＝628)。
Production examples 1 to 23: production of Compounds 1 to 23
Under a nitrogen atmosphere, compound 1-D (15g, 60.9 mmol) and compound Trz2 (16.3g, 60.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and introduced, followed by sufficient stirring, and then bis (tri-tert-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was introduced. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 20g of the compound substance 1-D-2 (yield 76%, MS: [ M + H ]] + ＝434)。
The compound substance 1-D-2 (15g, 34.6 mmol) and the compound substance 16 (9.1g, 34.6 mmol) were added to 300ml of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (14.3g, 103.7mmol) was dissolved in 43ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2g, 0.3mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 14g of compounds 1 to 23 (yield 66%, MS: [ M + H ]] + ＝616)。
Production examples 1 to 24: production of Compounds 1-24
Under a nitrogen atmosphere, compound 1-D (15g, 60.9 mmol) and compound Trz10 (20.9 g,60.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 20.8g of the compound substance 1-D-3 (yield 67%, MS: [ M + H ]] + ＝510)。
Compound 1-D-3 (15g, 29.4mmol) and compound 17 (7.7g, 29.4mmol) were added to 300ml of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (12.2 g,88.2 mmol) was dissolved in 37ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2 g,0.3 mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.4g of compounds 1 to 24 (yield 61%, MS: [ M + H ]] + ＝692)。
Production examples 1 to 25: production of Compounds 1 to 25
Under a nitrogen atmosphere, the compound 1-D (15g, 60.9mmol) and the compound Trz15 (21.8g, 60.9mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76After stirring sufficiently, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 21.3g of the compound substance 1-D-4 (yield 67%, MS: [ M + H ]] + ＝524)。
Under a nitrogen atmosphere, the compound substance 1-D-4 (15g, 28.6 mmol) and the compound substance 10 (4.9g, 28.6 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (11.9 g,85.9 mmol) was dissolved in 36ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.1 g,0.3 mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 10.7g of compounds 1 to 25 (yield 61%, MS: [ M + H ]] + ＝616)。
Production examples 1 to 26: production of Compounds 1 to 26
Under a nitrogen atmosphere, compound substance 1-D-3 (15g, 29.4mmol) and compound substance 18 (6.2g, 29.4mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (12.2 g,88.2 mmol) was dissolved in 37ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2 g,0.3 mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. Dissolving in chloroform again, washing with water for 2 times, and separating organic phaseTo the layer, anhydrous magnesium sulfate was added, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 14.3g of compounds 1 to 26 (yield 76%, MS: [ M + H ]] + ＝642)。
Production examples 1 to 27: production of Compounds 1 to 27
Under a nitrogen atmosphere, compound 1-D (15g, 60.9 mmol) and compound Trz16 (27g, 60.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and introduced, followed by sufficient stirring, and then bis (tri-tert-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was introduced. After 11 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 27.1g of the compound substance 1-D-5 (yield 73%, MS: [ M + H ]] + ＝610)。
Under a nitrogen atmosphere, the compound substance 1-D-5 (15g, 24.6mmol) and the compound substance 9 (5.2g, 24.6mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (10.2g, 73.8 mmol) was dissolved in 31ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.1g, 0.2mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.8g of compounds 1 to 27 (yield 70%, MS: [ M + H ]] + ＝742)。
Production examples 1 to 28: production of Compounds 1-28
Under a nitrogen atmosphere, compound 1-D (15g, 60.9 mmol) and compound Trz13 (24g, 60.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and introduced, followed by sufficient stirring, and then bis (tri-tert-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was introduced. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 20.8g of Compound substance 1-D-6 (yield 61%, MS: [ M + H ]] + ＝560)。
Under a nitrogen atmosphere, compound 1-D-6 (15g, 26.8mmol) and compound 10 (4.6g, 26.8mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (11.1g, 80.3mmol) was dissolved in 33ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphine) palladium (0) (0.1g, 0.3mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.2g of compounds 1 to 28 (yield 70%, MS: [ M + H ]] + ＝652)。
Production examples 1 to 29: production of Compounds 1 to 29
Under a nitrogen atmosphere, the compound 1-E (15g, 60.9mmol) and the compound Trz2 (16.3g, 60.9mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 17.1g of the compound substance 1-E-1 (yield 65%, MS: [ M + H ]] + ＝434)。
Compound 1-E-1 (15g, 34.6 mmol) and compound 2 (9.4g, 34.6 mmol) were added to 300ml of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (14.3g, 103.7mmol) was dissolved in 43ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2g, 0.3mmol) was charged. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 14.5g of compounds 1 to 29 (yield 67%, MS: [ M + H ]] + ＝626)。
Production examples 1 to 30: production of Compounds 1 to 30
Under a nitrogen atmosphere, the compound 1-E (15g, 60.9mmol) and the compound Trz9 (24g, 60.9mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) was charged(0.3g, 0.6 mmol). After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 26.9g of the compound substance 1-E-2 (yield 79%, MS: [ M + H ]] + ＝560)。
Compound 1-E-2 (15g, 26.8mmol) and compound 19 (7g, 26.8mmol) were added to 300ml of THF under a nitrogen atmosphere, and stirring and refluxing were carried out. Then, potassium carbonate (11.1g, 80.3mmol) was dissolved in 33ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.3mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15.9g of compounds 1 to 30 (yield 80%, MS: [ M + H ]] + ＝742)。
Production examples 1 to 31: production of Compounds 1 to 31
Compound 1-E (15g, 60.9 mmol) and compound Trz17 (22.4g, 60.9 mmol) were added to 300ml of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. ConcentratingThe compound (2) was purified by silica gel column chromatography to give 25.3g of the compound substance 1-E-3 (yield 78%, MS: [ M + H ]] + ＝534)。
Under a nitrogen atmosphere, compound substance 1-E-3 (15g, 28.1mmol) and compound substance 20 (7.8g, 28.1mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (11.6 g,84.3 mmol) was dissolved in 35ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.1 g,0.3 mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 14.8g of compounds 1 to 31 (yield 72%, MS: [ M + H ]] + ＝732)。
Production examples 1 to 32: production of Compounds 1 to 32
Under a nitrogen atmosphere, the compound substance 1-E-1 (15g, 34.6 mmol) and the compound substance 21 (7.7g, 34.6 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (14.3g, 103.7mmol) was dissolved in 43ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2g, 0.3mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.9g of compounds 1 to 32 (yield 65%, MS: [ M + H ]] + ＝576)。
Production examples 1 to 33: production of Compounds 1 to 33
Under a nitrogen atmosphere, the compound 1-E (15g, 60.9mmol) and the compound Trz15 (21.8g, 60.9mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 25.5g of the compound substance 1-E-4 (yield 80%, MS: [ M + H ]] + ＝524)。
Under a nitrogen atmosphere, the compound substance 1-E-4 (15g, 28.6 mmol) and the compound substance 10 (4.9g, 28.6 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (11.9 g,85.9 mmol) was dissolved in 36ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.1 g,0.3 mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.6g of compounds 1 to 33 (yield 60%, MS: [ M + H ]] + ＝616)。
Production examples 1 to 34: production of Compounds 1 to 34
Under a nitrogen atmosphere, compound 1-E (15g, 60.9 mmol) and CompoundTrz3 (19.3 g,60.9 mmol) was added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and introduced, followed by sufficient stirring, and then bis (tri-tert-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was introduced. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 17.6g of Compound substance 1-E-5 (yield 60%, MS: [ M + H ]] + ＝484)。
The compound substance 1-E-5 (15g, 31mmol) and the compound substance 9 (6.6g, 31mmol) were added to 300ml of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (12.9 g, 93mmol) was dissolved in 39ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3mmol) was charged. After 11 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.4g of compounds 1 to 34 (yield 60%, MS: [ M + H ]] + ＝616)。
Production examples 1 to 35: production of Compounds 1 to 35
Under a nitrogen atmosphere, the compound 1-E (15g, 60.9 mmol) and the compound Trz10 (20.9 g,60.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was charged. After 8 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separatedAfter separation from the aqueous layer, the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 21.7g of Compound substance 1-E-6 (yield 70%, MS: [ M + H ]] + ＝510)。
Compound 1-E-6 (15g, 29.4mmol) and compound 22 (7.7g, 29.4mmol) were added to 300ml of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (12.2 g,88.2 mmol) was dissolved in 37ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2 g,0.3 mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 14.6g of compounds 1 to 35 (yield 72%, MS: [ M + H ]] + ＝692)。
Production examples 1 to 36: production of Compounds 1 to 36
Under a nitrogen atmosphere, the compound substance 1-E-5 (15g, 31mmol) and the compound substance 23 (8.1g, 31mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (12.9 g, 93mmol) was dissolved in 39ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2 g,0.3 mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 124g of compounds 1 to 36 (yield 60%, MS: [ M + H ]] + ＝666)。
Production examples 1 to 37: production of Compounds 1 to 37
Under a nitrogen atmosphere, the compound substance 1-E-5 (15g, 31mmol) and the compound substance 10 (5.3g, 31mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (12.9 g, 93mmol) was dissolved in 39ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2 g,0.3 mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 14.1g of Compound 1-37 (yield 79%, MS: [ M + H ]] + ＝576)。
Production examples 1 to 38: production of Compounds 1 to 38
Under a nitrogen atmosphere, the compound 1-E (15g, 60.9 mmol) and the compound Trz18 (27g, 60.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 24.1g of the compound substance 1-E-7 (yield 65%, MS: [ M + H ]] + ＝610)。
Under a nitrogen atmosphere, the compound substance 1-E-7 (15g, 24.6mmol) and the compound substance 5 (3g, 24.6mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (10.2g, 73.8 mmol) was dissolved in 31ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.1g, 0.2mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 10.1g of compounds 1 to 38 (yield 63%, MS: [ M + H ]] + ＝652)。
Production examples 1 to 39: production of Compounds 1 to 39
Under a nitrogen atmosphere, the compound 1-E (15g, 60.9mmol) and the compound Trz13 (24g, 60.9mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and introduced, followed by sufficient stirring, and then bis (tri-tert-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was introduced. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 26.2g of Compound substance 1-E-8 (yield 77%, MS: [ M + H ]] + ＝560)。
Under a nitrogen atmosphere, compound substance 1-E-8 (15g, 26.8mmol) and compound substance 5 (3.3g, 26.8mmol) were added to 300ml of THF, stirred and refluxed. Then, the user can use the device to perform the operation,potassium carbonate (11.1g, 80.3mmol) was dissolved in 33ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphine) palladium (0) (0.1g, 0.3mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 10.9g of compounds 1 to 39 (yield 68%, MS: [ M + H ]] + ＝602)。
Production examples 1 to 40: production of Compounds 1 to 40
Under a nitrogen atmosphere, the compound 1-F (15g, 60.9mmol) and the compound Trz2 (16.3g, 60.9mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 19.2g of the compound substance 1-F-1 (yield 73%, MS: [ M + H ]] + ＝434)。
Compound 1-F-1 (15g, 34.6 mmol) and compound 6 (8.5g, 34.6 mmol) were added to 300ml of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (14.3g, 103.7mmol) was dissolved in 43ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2g, 0.3mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. Dissolving in chloroform again, and adding waterAfter washing 2 times, the organic layer was separated, anhydrous magnesium sulfate was added, stirring was performed, filtration was performed, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.7g of compounds 1 to 40 (yield 71%, MS: [ M + H ]] + ＝600)。
Production examples 1 to 41: production of Compounds 1 to 41
Under a nitrogen atmosphere, compound 1-F (15g, 60.9 mmol) and compound Trz10 (20.9 g,60.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.2g, 182.6 mmol) was dissolved in 76ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was charged. After 11 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 21.1g of the compound substance 1-F-2 (yield 68%, MS: [ M + H ]] + ＝510)。
Compound 1-F-2 (15g, 29.4mmol) and compound 1 (5.8g, 29.4mmol) were added to 300ml of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (12.2 g,88.2 mmol) was dissolved in 37ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2 g,0.3 mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 14.2g of compounds 1 to 41 (yield 77%, MS: [ M + H ]] + ＝628)。
Production examples 1 to 42: production of Compounds 1 to 42
Under a nitrogen atmosphere, the compound Trz7 (15g, 31.9mmol) and the compound substance 9 (6.8g, 31.9mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (13.2g, 95.8mmol) was dissolved in 40ml of water and charged, followed by sufficiently stirring, and then bis (tri-tert-butylphosphino) palladium (0) (0.2g, 0.3mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 15.2g of compounds 1 to 42 (yield 79%, MS: [ M + H ]] + ＝602)。
Production examples 1 to 43: production of Compounds 1 to 43
Under a nitrogen atmosphere, compound Trz16 (15g, 33.8mmol) and compound substance 9 (7.2g, 33.8mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (14g, 101.4mmol) was dissolved in 42ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 15g of compounds 1 to 43 (yield 77%, MS: [ M + H ]] + ＝576)。
Production examples 1 to 44: production of Compounds 1-44
Under a nitrogen atmosphere, compound Trz4 (15g, 33.8mmol) and compound substance 9 (7.2g, 33.8mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (14g, 101.4mmol) was dissolved in 42ml of water and introduced, followed by sufficient stirring, and then bis (tri-t-butylphosphino) palladium (0) (0.2g, 0.3mmol) was introduced. After 11 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 14.2g of compounds 1 to 44 (yield 73%, MS: [ M + H ]] + ＝576)。
Production examples 1 to 45: production of Compounds 1 to 45
Under a nitrogen atmosphere, compound Trz1 (15g, 35.7 mmol) and compound substance 9 (7.6g, 35.7 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (14.8g, 107.2mmol) was dissolved in 44ml of water and charged, followed by stirring sufficiently, and then bis (tri-tert-butylphosphino) palladium (0) (0.2g, 0.4mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.2g of compounds 1 to 45 (yield 62%, MS: [ M + H ]] + ＝552)。
Production examples 1 to 46: production of Compounds 1-46.
Under nitrogen atmosphere, compound Trz19 (15g, 33.8mmol) and compound substance 9 (7.2g, 33.8mmo)l) are added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (14g, 101.4mmol) was dissolved in 42ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 13.6g of compounds 1 to 46 (yield 70%, MS: [ M + H ]] + ＝576)。
Production examples 1 to 47: production of Compounds 1 to 47
Under a nitrogen atmosphere, compound Trz20 (15g, 35.9 mmol) and compound substance 9 (7.6g, 35.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (14.9g, 107.7mmol) was dissolved in 45ml of water and charged, followed by stirring well, and bis (tri-t-butylphosphino) palladium (0) (0.2g, 0.4mmol) was charged. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 15g of compounds 1 to 47 (yield 76%, MS: [ M + H ]] + ＝550)。
Production examples 1 to 48: production of Compounds 1-48
Compound Trz3 (15g, 47.2mmol) and compound 24 (9.7g, 47.2mmol) were added to 300ml of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (19.6 g,141.6 mmol) was dissolved in 59ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2g, 0.5 mmol) was charged. Reaction ofAfter 11 hours, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 13G of the compound substance 1-G-1 (yield 62%, MS: [ M + H ]] + ＝444)。
Under a nitrogen atmosphere, compound 1-G-1 (15g, 33.8mmol) and compound 9 (7.2g, 33.8mmol) were added to 300ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (14g, 101.4mmol) was dissolved in 42ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15.2g of compounds 1 to 48 (yield 78%, MS: [ M + H ]] + ＝576)。
Production examples 1 to 49: production of Compounds 1 to 49
Under a nitrogen atmosphere, the compound Trz15 (15g, 41.9mmol) and the compound substance 25 (8.7g, 41.9mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (17.4g, 125.8mmol) was dissolved in 52ml of water and introduced, followed by sufficient stirring, and then bis (tri-tert-butylphosphino) palladium (0) (0.2g, 0.4mmol) was introduced. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound is applied to silica gelPurification was performed by column chromatography to thereby produce 12.6G of the compound substance 1-G-2 (yield 62%, MS: [ M + H ]] + ＝484)。
Under a nitrogen atmosphere, the compound substance 1-G-2 (15g, 31mmol) and the compound substance 9 (6.6g, 31mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (12.9 g, 93mmol) was dissolved in 39ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2 g,0.3 mmol) was charged. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 13.7g of compounds 1 to 49 (yield 72%, MS: [ M + H ]] + ＝616)。
Production examples 1 to 50: production of Compounds 1 to 50
Under a nitrogen atmosphere, compound Trz21 (15g, 36.8mmol) and compound substance 26 (5.8g, 36.8mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (15.2 g,110.3 mmol) was dissolved in 46ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.2 g,0.4 mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.8G of the compound substance 1-G-3 (yield 72%, MS: [ M + H ]] + ＝484)。
The compound substance 1-G-3 (15g, 31mmol) and the compound substance 9 (6.6g, 31mmol) were added to 300ml of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (12.9 g, 93mmol) was dissolved in 39ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2 g,0.3 mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 13.2g of compounds 1 to 50 (yield 69%, MS: [ M + H ]] + ＝616)。
Production examples 1 to 51: production of Compounds 1 to 51
Under a nitrogen atmosphere, compound Trz16 (15g, 33.8mmol) and compound substance 27 (5.3g, 33.8mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (14g, 101.4mmol) was dissolved in 42ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.3G of compound substance 1-G-4 (yield 76%, MS: [ M + H ]] + ＝520)。
Under a nitrogen atmosphere, compound substance 1-G-4 (15g, 28.8mmol) and compound substance 9 (6.1g, 28.8mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (12g, 86)5 mmol) was dissolved in 36ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphine) palladium (0) (0.1g, 0.3mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 13.3g of compounds 1 to 51 (yield 71%, MS: [ M + H ]] + ＝652)。
Production examples 1 to 52: production of Compounds 1-52
Under a nitrogen atmosphere, compound Trz22 (15g, 36.8mmol) and compound substance 28 (5.8g, 36.8mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (15.2 g,110.3 mmol) was dissolved in 46ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.2 g,0.4 mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.8G of compound substance 1-G-5 (yield 72%, MS: [ M + H ]] + ＝484)。
Under a nitrogen atmosphere, the compound substance 1-G-5 (15g, 31mmol) and the compound substance 9 (6.6g, 31mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (12.9 g, 93mmol) was dissolved in 39ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2 g,0.3 mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. Dissolving in chloroform again, washing with water for 2 times, and separatingThe organic layer was added with anhydrous magnesium sulfate, stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 13g of compounds 1 to 52 (yield 68%, MS: [ M + H ]] + ＝616)。
Production examples 1 to 53: production of Compounds 1-53
Under a nitrogen atmosphere, compound Trz23 (15g, 34.6 mmol) and compound substance 27 (5.4g, 34.6 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (14.3g, 103.7mmol) was dissolved in 43ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2g, 0.3mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 11.3G of Compound substance 1-G-6 (yield 64%, MS: [ M + H ]] + ＝510)。
Under a nitrogen atmosphere, the compound substance 1-G-6 (15g, 31mmol) and the compound substance 9 (6.6g, 31mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (12.9 g, 93mmol) was dissolved in 39ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2 g,0.3 mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13g of compounds 1 to 53 (yield 68%, MS: [ M + H ]] + ＝616)。
Production examples 1 to 54: production of Compounds 1-54
Under a nitrogen atmosphere, the compound substance 1-G-1 (15g, 33.8mmol) and the compound 1-E (8.3g, 33.8mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (14g, 101.4mmol) was dissolved in 42ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 8 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer was separated from the aqueous layer, followed by distillation of the organic layer. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 14.4g of the compound substance 1-E-9 (yield 70%, MS: [ M + H ]] + ＝610)。
Under a nitrogen atmosphere, the compound substance 1-E-9 (15g, 24.6mmol) and the compound substance 5 (3g, 24.6mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (10.2g, 73.8 mmol) was dissolved in 31ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.1g, 0.2mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.2g of compounds 1 to 54 (yield 76%, MS: [ M + H ]] + ＝652)。
Production examples 1 to 55: production of Compounds 1 to 55
Under a nitrogen atmosphere, compound Trz2 (15g, 56mmol) and compound substance 24 (11.6g, 56mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (23.2g, 168.1mmol) was dissolved in 70ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.3g, 0.6 mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 15.6G of compound substance 1-G-7 (yield 71%, MS: [ M + H ]] + ＝394)。
Compound 1-G-7 (15g, 38.1mmol) and compound 1-B (9.4g, 38.1mmol) were added to 300ml of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (15.8g, 114.3mmol) was dissolved in 47ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2g, 0.4 mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.8g of the compound substance 1-B-7 (yield 65%, MS: [ M + H ]] + ＝560)。
Compound 1-B-7 (15g, 26.8mmol) and compound 5 (3.3g, 26.8mmol) were added to 300ml of THF under a nitrogen atmosphere, and stirring and refluxing were carried out. Then, potassium carbonate (11.1g, 80.3mmol) was dissolved in 33ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphine) palladium (0) (0.1g, 0.3mmol) was charged. After 9 hours of reaction, the mixture is cooled to normal temperatureAfter separating the organic layer from the aqueous layer, the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.9g of compounds 1 to 55 (yield 80%, MS: [ M + H ]] + ＝602)。
Production examples 1 to 56: production of Compounds 1 to 56
Compound Trz24 (15g, 38.1mmol) and Compound No. 25 (9.4g, 38.1mmol) were added to 300ml of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (15.8g, 114.3mmol) was dissolved in 47ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2g, 0.4 mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.8G of compound substance 1-G-8 (yield 65%, MS: [ M + H ]] + ＝560)。
Compound 1-G-8 (15g, 30mmol) and compound 9 (6.4g, 30mmol) were added to 300ml of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (12.4 g, 90mmol) was dissolved in 37ml of water and introduced, followed by sufficient stirring, and bis (tri-tert-butylphosphino) palladium (0) (0.2 g, 0.3mmol) was introduced. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. Purifying the concentrated compound by silica gel column chromatography to obtain13.4g of the compounds 1 to 56 (yield 71%, MS: [ M + H ]] + ＝632)。
Production examples 1 to 57: production of Compounds 1-57
Under a nitrogen atmosphere, compound Trz25 (15g, 41.9mmol) and compound substance 24 (8.7g, 41.9mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (17.4g, 125.8mmol) was dissolved in 52ml of water and introduced, followed by sufficient stirring, and then bis (tri-tert-butylphosphino) palladium (0) (0.2g, 0.4mmol) was introduced. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.4G of compound substance 1-G-9 (yield 61%, MS: [ M + H ]] + ＝484)。
The compound substance 1-G-9 (15g, 31mmol) and the compound 1-F (7.6g, 31mmol) were added to 300ml of THF under nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (12.9 g, 93mmol) was dissolved in 39ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2 g,0.3 mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.5g of the compound substance 1-F-3 (yield 62%, MS: [ M + H ]] + ＝650)。
Compound 1-F-3 (15g, 23.1mmol) and compound 5 (2.8g, 23.1mmol) were added to 300ml of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (9.6 g, 69.2mmol) was dissolved in 29ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.1 g, 0.2mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.8g of compounds 1 to 57 (yield 80%, MS: [ M + H ]] + ＝692)。
Production examples 1 to 58: production of Compounds 1 to 58
Under a nitrogen atmosphere, compound Trz26 (15g, 33.8mmol) and compound 26 (5.3g, 33.8mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (14g, 101.4mmol) was dissolved in 42ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 10.5G of compound substance 1-G-10 (yield 60%, MS: [ M + H ]] + ＝520)。
Under a nitrogen atmosphere, compound 1-G-10 (15g, 28.8mmol) and compound 1-D (7.1g, 28.8mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (12g, 86.5 mmol) was dissolved in 36ml of water and chargedAfter sufficiently stirring, bis (tri-t-butylphosphine) palladium (0) (0.1g, 0.3mmol) was added. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 15g of the compound substance 1-D-7 (yield 76%, MS: [ M + H ]] + ＝686)。
Under a nitrogen atmosphere, the compound substance 1-D-7 (15g, 21.9mmol) and the compound substance 5 (2.7g, 21.9mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (9.1g, 65.6 mmol) was dissolved in 27ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.1g, 0.2mmol) was charged. After 12 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 9.9g of compounds 1 to 58 (yield 62%, MS: [ M + H ]] + ＝728)。
Production examples 1 to 59: production of Compounds 1 to 59
Under a nitrogen atmosphere, compound Trz15 (15g, 41.9mmol) and compound substance 24 (8.7g, 41.9mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (17.4g, 125.8mmol) was dissolved in 52ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.2g, 0.4mmol) was charged. After 11 hours of the reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. Dissolving in chloroform again, washing with water for 2 times, separating organic layer, and adding anhydrous sulfuric acidMagnesium, stirring, filtering, and distilling the filtrate under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.4G of compound substance 1-G-11 (yield 61%, MS: [ M + H ]] + ＝484)。
Under a nitrogen atmosphere, the compound substance 1-G-11 (15g, 28.8 mmol) and the compound substance 1-F (7.1g, 28.8 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (12g, 86.5mmol) was dissolved in 36ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1g, 0.3mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 15g of the compound substance 1-F-7 (yield 76%, MS: [ M + H ]] + ＝686)。
Compound 1-F-4 (15g, 23.1mmol) and compound 5 (2.8g, 23.1mmol) were added to 300ml of THF under a nitrogen atmosphere, stirred and refluxed. Then, potassium carbonate (9.6 g, 69.2mmol) was dissolved in 29ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.1 g, 0.2mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.1g of compounds 1 to 59 (yield 76%, MS: [ M + H ]] + ＝692)。
Production examples 1 to 60: production of Compounds 1 to 60
Under a nitrogen atmosphere, the compound Trz12 (15g, 41.9mmol) and the compound substance 28 (6.6g, 41.9mmol) were added to 300ml of THF, and stirred and refluxed. Then, potassium carbonate (17.4g, 125.8mmol) was dissolved in 52ml of water and charged, and after sufficiently stirring, bis (tri-t-butylphosphino) palladium (0) (0.2g, 0.4mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 11.1G of the compound substance 1-G-12 (yield 61%, MS: [ M + H ]] + ＝434)。
Under a nitrogen atmosphere, the compound substance 1-G-12 (15g, 34.6 mmol) and the compound 1-D (8.5g, 34.6 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (14.3g, 103.7mmol) was dissolved in 43ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphino) palladium (0) (0.2g, 0.3mmol) was charged. After 9 hours of reaction, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 13.6g of Compound substance 1-D-8 (yield 79%, MS: [ M + H ]] + ＝500)。
Under a nitrogen atmosphere, the compound substance 1-D-8 (15g, 25mmol) and the compound substance 10 (4.3g, 25mmol) were added to 300ml of THF, stirred and refluxed. Then, willPotassium carbonate (10.4 g, 75mmol) was added by dissolving it in 31ml of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2mmol) was added. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the water layer were separated, and then the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 13.3g of compounds 1 to 60 (yield 77%, MS: [ M + H ]] + ＝692)。
Production example 2-1: production of Compound 2-1
Compound H (10g, 32.6 mmol), compound amine (amine) 1 (11g, 34.2mmol), sodium t-butoxide (4.1g, 42.3 mmol) were added to 200ml of Xylene (XYLENE) under a nitrogen atmosphere, and stirring and refluxing were carried out. Then, bis (tri-tert-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 5 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.5g of Compound 2-1 (yield 70%, MS: [ M + H ]] + ＝548)。
Production example 2-2: production of Compound 2-2
Compound H (10g, 32.6 mmol), compound amine 2 (12.7g, 34.2mmol) and sodium tert-butoxide (4.1g, 42.3mmol) were added to 200ml of xylene under a nitrogen atmosphere, and stirring and refluxing were carried out. Then, bis (tri-tert-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 5 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, and washed with waterAfter washing 2 times, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13g of Compound 2-2 (yield 67%, MS: [ M + H ]] + ＝598)。
Production examples 2 to 3: production of Compound 2-3
Compound H (10g, 32.6 mmol), compound amine 3 (13.6g, 34.2mmol), and sodium t-butoxide (4.1g, 42.3mmol) were added to 200ml of xylene under a nitrogen atmosphere, and stirring and refluxing were carried out. Then, bis (tri-tert-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 5 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.4g of Compound 2-3 (yield 66%, MS: [ M + H ]] + ＝624)。
Production examples 2 to 4: production of Compounds 2-4
Compound H (10g, 32.6 mmol), compound amine 4 (12.7g, 34.2mmol) and sodium tert-butoxide (4.1g, 42.3mmol) were added to 200ml of xylene under a nitrogen atmosphere, and stirring and refluxing were carried out. Then, bis (tri-tert-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 5 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.7g of Compound 2-4 (yield 60%, MS: [ M + H ]] + ＝598)。
Production examples 2 to 5: production of Compounds 2 to 5
Compound H (10g, 32.6 mmol), compound amine 5 (15.3g, 34.2mmol), and sodium tert-butoxide (4.1g, 42.3mmol) were added to 200ml of xylene under a nitrogen atmosphere, and stirring and refluxing were carried out. Then, bis (tri-tert-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 5 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.2g of Compound 2-5 (yield 60%, MS: [ M + H ]] + ＝674)。
Production examples 2 to 6: production of Compounds 2 to 6
Compound H (10 g,32.6 mmol), compound amine 6 (10.1 g, 34.2mmol), and sodium t-butoxide (4.1 g,42.3 mmol) were added to 200ml of xylene under nitrogen atmosphere, stirred and refluxed. Then, bis (tri-tert-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 5 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.9g of compounds 2 to 6 (yield 64%, MS: [ M + H ]] + ＝522)。
Production examples 2 to 7: production of Compounds 2 to 7
Under a nitrogen atmosphere, compound H (10g, 32.6mmol), compound amine 7 (13) were introduced.6g, 34.2mmol) and sodium tert-butoxide (4.1g, 42.3mmol) were added to 200ml of xylene, stirred and refluxed. Then, bis (tri-tert-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 5 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.6g of compounds 2 to 7 (yield 62%, MS: [ M + H ]] + ＝624)。
Production examples 2 to 8: production of Compounds 2 to 8
Compound H (10g, 32.6mmol), compound amine 8 (13.6g, 34.2mmol), and sodium t-butoxide (4.1g, 42.3mmol) were added to 200ml of xylene under a nitrogen atmosphere, and stirring and refluxing were carried out. Then, bis (tri-tert-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 5 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.2g of Compound 2-8 (yield 55%, MS: [ M + H ]] + ＝624)。
Production examples 2 to 9: production of Compounds 2 to 9
Compound H (10g, 32.6 mmol), compound amine 9 (11.8g, 34.2mmol), and sodium tert-butoxide (4.1g, 42.3mmol) were added to 200ml of xylene under a nitrogen atmosphere, and stirring and refluxing were carried out. Then, bis (tri-tert-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 5 hours, the reaction was terminated, cooled to normal temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and the mixture was washed with waterThe organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.6g of compounds 2 to 9 (yield 57%, MS: [ M + H ]] + ＝572)。
Production examples 2 to 10: production of Compounds 2 to 10
Compound H (10g, 32.6 mmol), compound amine 10 (10.9g, 34.2mmol) and sodium tert-butoxide (4.1g, 42.3mmol) were added to 200ml of xylene under a nitrogen atmosphere, and stirring and refluxing were carried out. Then, bis (tri-tert-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 5 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.3g of compounds 2 to 10 (yield 58%, MS: [ M + H ]] + ＝546)。
Production examples 2 to 11: production of Compounds 2 to 11
Compound H (10g, 32.6 mmol), compound amine 11 (14.4g, 34.2mmol), and sodium tert-butoxide (4.1g, 42.3mmol) were added to 200ml of xylene under a nitrogen atmosphere, and stirring and refluxing were carried out. Then, bis (tri-tert-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 5 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.7g of compounds 2 to 11 (yield 51%, MS: [ M + H ]] + ＝648)。
Production examples 2 to 12: production of Compounds 2 to 12
Compound H (15g, 48.8 mmol) and compound I (7.6g, 48.8 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (13.5g, 97.7 mmol) was dissolved in 40ml of water and charged, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2g, 0.5mmol) was charged. After 10 hours of reaction, the reaction mixture was cooled to normal temperature, and the organic layer and the aqueous layer were separated, and the organic layer was distilled. The resulting solution was dissolved in chloroform again, washed with water for 2 times, the organic layer was separated, anhydrous magnesium sulfate was added thereto, the mixture was stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.4g of substance H-1 (yield 75%, MS: [ M + H ]] + ＝339)。
Substance H-1 (10g, 29.5mmol), compound amine 12 (7.6g, 31mmol), sodium t-butoxide (3.7g, 38.4mmol) were added to 200ml of xylene under a nitrogen atmosphere, and stirring and refluxing were carried out. Then, bis (tri-tert-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 5 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, the organic layer was separated, treated with anhydrous magnesium sulfate, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10g of compounds 2 to 12 (yield 62%, MS: [ M + H ]] + ＝548)。
Production examples 2 to 13: production of Compounds 2 to 13
Under a nitrogen atmosphere, the substance H-1 (10g, 29.5mmol), the compound amine 13 (11.5g, 31mmol), sodium tert-butoxide (3.7 g,38.4 mmol) was added to 200ml of xylene, stirred and refluxed. Then, bis (tri-tert-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 5 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.9g of compounds 2 to 13 (yield 55%, MS: [ M + H ]] + ＝674)。
Production examples 2 to 14: production of Compounds 2 to 14
Compound H (10g, 32.6mmol), compound amine 14 (14g, 34.2mmol), and sodium t-butoxide (4.1g, 42.3mmol) were added to 200ml of xylene under a nitrogen atmosphere, and stirring and refluxing were performed. Then, bis (tri-tert-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 5 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.2g of compounds 2 to 14 (yield 54%, MS: [ M + H ]] + ＝637)。
Production examples 2 to 15: production of Compounds 2 to 15
Compound H (10g, 32.6 mmol), compound amine 15 (12g, 34.2mmol), and sodium tert-butoxide (4.1g, 42.3mmol) were added to 200ml of xylene under a nitrogen atmosphere, and stirring and refluxing were carried out. Then, bis (tri-tert-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 5 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, the organic layer was separated, and anhydrous sulfur was addedMagnesium treating, filtering, and distilling the filtrate under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.6g of compounds 2 to 15 (yield 67%, MS: [ M + H ]] + ＝578)。
Production examples 2 to 16: production of Compounds 2 to 16
Compound H (10g, 32.6 mmol), compound amine 16 (15.7g, 34.2mmol), and sodium tert-butoxide (4.1g, 42.3mmol) were added to 200ml of xylene under a nitrogen atmosphere, and stirring and refluxing were carried out. Then, bis (tri-tert-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 5 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, the organic layer was separated, treated with anhydrous magnesium sulfate, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.5g of compounds 2 to 16 (yield 65%, MS: [ M + H ]] + ＝687)。
Production examples 2 to 17: production of Compounds 2 to 17
Compound H (10g, 32.6mmol), compound amine 17 (13.2g, 34.2mmol), and sodium tert-butoxide (4.1g, 42.3mmol) were added to 200ml of xylene under a nitrogen atmosphere, and stirring and refluxing were carried out. Then, bis (tri-tert-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 5 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.7g of compounds 2 to 17 (yield 59%, MS: [ M + H ]] + ＝612)。
Production examples 2 to 18: production of Compounds 2 to 18
Compound H (10g, 32.6 mmol), compound amine 18 (11.9g, 34.2mmol) and sodium tert-butoxide (4.1g, 42.3mmol) were added to 200ml of xylene under a nitrogen atmosphere, and stirring and refluxing were carried out. Then, bis (tri-tert-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 5 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.5g of compounds 2 to 18 (yield 56%, MS: [ M + H ]] + ＝576)。
Production examples 2 to 19: production of Compounds 2 to 19
Compound H (10g, 32.6 mmol), compound amine 19 (12.5g, 34.2mmol), and sodium tert-butoxide (4.1g, 42.3mmol) were added to 200ml of xylene under a nitrogen atmosphere, and stirring and refluxing were carried out. Then, bis (tri-tert-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 5 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.1g of compounds 2 to 19 (yield 63%, MS: [ M + H ]] + ＝592)。
Production examples 2 to 20: production of Compounds 2 to 20
Under nitrogen atmosphere, compound H (10g, 32.6mmol), compound amine 20 (13g, 34.2mmol) and tert-butylSodium alkoxide (4.1g, 42.3mmol) was added to 200ml of xylene, stirred and refluxed. Then, bis (tri-tert-butylphosphine) palladium (0) (0.2g, 0.3mmol) was charged. After 5 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.1g of compounds 2 to 20 (yield 56%, MS: [ M + H ]] + ＝608)。
[ examples ]
Example 1
Indium Tin Oxide (ITO) and a process for producing the same
The glass substrate coated with a thin film of (2) is put in distilled water in which a detergent is dissolved, and washed by ultrasonic waves. In this case, a product of fisher (Fischer co.) was used as the detergent, and distilled water was filtered twice with a Filter (Filter) manufactured by Millipore co. After washing ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After the completion of the distilled water washing, the resultant was ultrasonically washed with a solvent of isopropyl alcohol, acetone, or methanol, dried, and then transported to a plasma cleaning machine. After the substrate was cleaned with oxygen plasma for 5 minutes, the substrate was transported to a vacuum evaporator.
On the ITO transparent electrode thus prepared, as a hole injection layer, the following compound HI-1 was added
And the following compound a-1 was p-doped (p-doping) at 1.5 wt%. On the hole injection layer, the following compound HT-1 was vacuum-deposited to form a film having a thickness
The hole transport layer of (1). Then, on the hole transport layer, the film thickness
The following compound EB-1 was vacuum-deposited to form an electron blocking layer. Then, the following produced compound 1-2 and compound 2-1 as the main components and compound Dp-7 as the dopant were vacuum-evaporated on the EB-1 deposition film at a weight ratio of 49
A thick red light emitting layer. On the light-emitting layer, the thickness of the film
The following compound HB-1 was vacuum-deposited to form a hole stopper layer. Next, on the hole stopper layer, the following compound ET-1 and the following compound LiQ were vacuum-deposited at a weight ratio of 2:1 to form a hole stopper layer
The thickness of (a) forms an electron injection and transport layer. On the above electron injection and transport layer, lithium fluoride (LiF) is sequentially added to
Thickness of aluminum and
is deposited to form a cathode.
In the above process, the evaporation speed of the organic material is maintained
Second, maintenance of lithium fluoride at the cathode
Vapor deposition rate per second, aluminum maintenance
A vapor deposition rate of 2 × 10/sec, and a vacuum degree maintained during vapor deposition -7 ～5*10 -6 And thus an organic light emitting device was manufactured.
Examples 2 to 132
An organic light-emitting device was manufactured in the same manner as in example 1 above, except that the first host and the second host described in table 1 were used as the hosts of the organic light-emitting device.
Comparative examples 1 to 51
An organic light emitting device was manufactured in the same manner as in example 1, except that the first host and the second host described in table 2 were used as the hosts of the organic light emitting device. Compounds B-1 to B-12 of Table 2 are shown below.
Comparative examples 52 to 99
An organic light-emitting device was produced in the same manner as in production example 1, except that the first host and the second host described in table 3 were used as the hosts of the organic light-emitting device. Compounds C-1 to C-6 of Table 2 are shown below.
[ Experimental example ]
When a current was applied to the organic light-emitting devices manufactured in the above-described examples 1 to 132 and comparative examples 1 to 99, the current (15 mA/cm) was measured 2 Reference) shows the voltage and efficiency, and the results are shown in tables 1 to 3 below. The lifetime T95 refers to the time required for the luminance to decrease from the initial luminance (6000 nit) to 95%.
[ Table 1]
[ Table 2]
[ Table 3]
Current was applied to the organic light emitting devices manufactured by examples 1 to 132 and comparative examples 1 to 99, and the results of the above tables 1 to 3 were obtained.
In an embodiment of the present invention, when the compound represented by chemical formula 1 and the compound represented by chemical formula 2 are co-evaporated to be used as a red light emitting layer, as shown in table 1, it is confirmed that the driving voltage is decreased and the efficiency and the lifetime are increased compared to the comparative example. Further, as shown in table 2, when the compounds B-1 to B-12 of comparative examples and the compound represented by chemical formula 2 of the present invention were co-evaporated to be used as a red light emitting layer, the results of an increase in driving voltage, a decrease in efficiency and a decrease in lifetime were shown in general, as compared with the combination of the present invention. As shown in table 3, the compounds C-1 to C-6 of comparative examples and the compound represented by chemical formula 1 of the present invention were co-evaporated to be used as a red light emitting layer, and also showed the results of an increase in driving voltage, a decrease in efficiency, and a decrease in lifetime.
From the above results, it was confirmed that energy transfer to the dopant is well formed when a combination of the compound represented by chemical formula 1 as the first host and the compound represented by chemical formula 2 as the second host is used as a host in the red light emitting layer as shown in one embodiment of the present invention. This can be finally inferred to be due to the combination of chemical formula 1 and chemical formula 2 of the present invention forming a more stable equilibrium in the light emitting layer than the combination with the comparative compound. Therefore, it was confirmed that efficiency and lifetime are further improved when electrons and holes are combined to form excitons in the organic light emitting device according to an embodiment of the present invention.
As described above, it was confirmed that when the compound represented by chemical formula 1 and the compound represented by chemical formula 2 of the present invention are combined and co-evaporated to be used as a host of a light emitting layer, driving voltage, light emitting efficiency, and life characteristics of an organic light emitting device can be improved.
Description of the symbols
1: substrate 2: anode
3: light-emitting layer 4: cathode electrode
5: hole injection layer 6: hole transport layer
7: electron blocking layer 8: hole blocking layer
9: electron transport layer 10: an electron injection layer.
Claims (12)
1. An organic light emitting device, comprising:
an anode;
a cathode; and
a light emitting layer between the anode and the cathode,
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 first and second organic solvents,
Ar 1 and Ar 2 Each independently is 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 (ii) a heteroaryl group, wherein,
L 1 to L 3 Each independently is a single bond, or substituted or unsubstituted C 6-60 An arylene group, a cyclic or cyclic alkylene group,
R 1 is hydrogen; deuterium; 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 (ii) a heteroaryl group, wherein,
a is an integer of 0 to 7, and,
chemical formula 2
In the chemical formula 1, the first and second organic solvents,
Ar 3 and Ar 4 Each independently is 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 (ii) a heteroaryl group, wherein,
L 4 to L 6 Each independently is a single bond, or substituted or unsubstituted C 6-60 An arylene group.
2. The organic light emitting device according to claim 1, wherein the compound represented by chemical formula 1 is represented by any one of the following chemical formulae 1-1 to 1-3:
chemical formula 1-1
Chemical formula 1-2
Chemical formulas 1 to 3
In the chemical formulas 1-1 to 1-3,
Ar 1 、Ar 2 、L 1 to L 3 And R 1 As defined in claim 1.
3. The organic light emitting device of claim 1, wherein Ar 1 And Ar 2 Each independently is phenyl, biphenyl, terphenylAn alkyl group, a naphthyl group, a phenanthryl group, a dibenzofuranyl group, or a dibenzothienyl group.
4. The organic light emitting device of claim 1, wherein L 1 To L 3 Each independently a single bond, or any one selected from the following groups:
5. the organic light emitting device of claim 1, wherein R 1 Each independently hydrogen, deuterium, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, naphthylphenyl, phenylnaphthyl, fluoranthenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, or benzonaphthothiophenyl.
6. The organic light emitting device of claim 1, wherein Ar 1 、Ar 2 And R 1 At least one of which is naphthyl, phenylnaphthyl, naphthylphenyl, phenanthryl, fluoranthenyl, dibenzofuranyl, dibenzothienyl, benzonaphthofuranyl, or benzonaphthothienyl.
7. The organic light emitting device of claim 1, wherein a is 0 or 1.
8. The organic light emitting device according to claim 1, wherein the compound represented by the chemical formula 1 is any one selected from the group consisting of:
9. the organic light emitting device of claim 1, wherein Ar 3 And Ar 4 Each independently a phenyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, a naphthyl group, a phenanthryl group, a naphthylphenyl group, a phenylnaphthyl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a spirobifluorenyl group, a carbazolyl group, a phenylcarbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, or a benzonaphthofuranyl group.
10. The organic light emitting device of claim 1, wherein Ar 3 And Ar 4 Each independently is any one selected from the group consisting of:
11. the organic light emitting device of claim 1, wherein L 4 To L 6 Each independently a single bond, phenylene, biphenylene, naphthylene, or dimethylfluorenylene.
12. 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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| KR10-2020-0057863 | 2020-05-14 | ||
| KR20200057863 | 2020-05-14 | ||
| KR1020210062251A KR102550644B1 (en) | 2020-05-14 | 2021-05-13 | Organic light emitting device |
| KR10-2021-0062251 | 2021-05-13 | ||
| PCT/KR2021/006093 WO2021230715A1 (en) | 2020-05-14 | 2021-05-14 | Organic light-emitting element |
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| CN114763351A (en) * | 2021-01-15 | 2022-07-19 | 三星Sdi株式会社 | Compound for organic photoelectric device, composition for organic photoelectric device, and display device |
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| CN110268036B (en) * | 2017-07-14 | 2022-12-20 | 株式会社Lg化学 | Organic light emitting element |
| KR20190020930A (en) * | 2017-08-22 | 2019-03-05 | (주)피엔에이치테크 | An electroluminescent compound and an electroluminescent device comprising the same |
| KR20190114764A (en) * | 2018-03-29 | 2019-10-10 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
| KR20190127272A (en) * | 2018-05-04 | 2019-11-13 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
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