CN116710459A - Novel compound and organic light emitting device comprising the same - Google Patents

Novel compound and organic light emitting device comprising the same Download PDF

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Publication number
CN116710459A
CN116710459A CN202280008925.3A CN202280008925A CN116710459A CN 116710459 A CN116710459 A CN 116710459A CN 202280008925 A CN202280008925 A CN 202280008925A CN 116710459 A CN116710459 A CN 116710459A
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mmol
stirred
organic layer
added
separated
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金旼俊
李东勋
全贤秀
金永锡
金宰垠
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from PCT/KR2022/004519 external-priority patent/WO2022211498A1/en
Publication of CN116710459A publication Critical patent/CN116710459A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems
    • 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
    • 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]
    • H10K50/18—Carrier blocking layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The present disclosure relates to novel compounds and organic light emitting devices comprising the same.

Description

Novel compound and organic light emitting device comprising the same
Technical Field
Cross Reference to Related Applications
The present application claims the benefits of korean patent application No. 10-2021-0041274 filed on 3 months of 2021 to the korean intellectual property office and korean patent application No. 10-2022-0039606 filed on 3 months of 2022 to the korean intellectual property office, the disclosures of which are incorporated herein by reference in their entireties.
The present disclosure relates to novel compounds and organic light emitting devices comprising the same.
Background
In general, an organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy by using an organic material. An organic light emitting device using the organic light emitting phenomenon has characteristics such as wide viewing angle, excellent contrast, fast response time, excellent brightness, driving voltage, and response speed, and thus many researches have been conducted.
The organic light emitting device generally has a structure including an anode, a cathode, and an organic material layer interposed between the anode and the cathode. The organic material layer generally has a multi-layered structure including different materials to improve efficiency and stability of the organic light emitting device, for example, the organic material layer may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of the organic light emitting device, if a voltage is applied between two electrodes, holes are injected from an anode into an organic material layer, and electrons are injected from a cathode into the organic material layer, excitons are formed when the injected holes and electrons meet each other, and light is emitted when the excitons fall to a ground state again.
There is a continuing need to develop new materials for organic materials used in organic light emitting devices as described above.
[ Prior Art literature ]
(patent document 0001) Korean unexamined patent publication No. 10-2000-0051826
Disclosure of Invention
Technical problem
The present disclosure relates to novel compounds and organic light emitting devices comprising the same.
Technical proposal
In the present disclosure, there is provided a compound represented by the following chemical formula 1:
[ chemical formula 1]
In the chemical formula 1, the chemical formula is shown in the drawing,
A 1 represented by the following chemical formula 1-a,
[ chemical formula 1-a ]
In the chemical formula 1-a, a radical of formula 1,
the dashed line is fused to an adjacent ring,
x is O or S, and the X is O or S,
Ar 1 is C substituted or unsubstituted 6-60 An aryl group; or C comprising at least one heteroatom selected from N, O and S, substituted or unsubstituted 2-60 Heteroaryl, and
l is a single bond; substituted or unsubstituted C 6-60 Arylene groups; or C comprising at least one heteroatom selected from N, O and S, substituted or unsubstituted 2-60 Heteroarylene, and
A 2 represented by the following chemical formula 1-b or 1-c,
[ chemical formula 1-b ]
[ chemical formula 1-c ]
In chemical formulas 1-b and 1-c,
L 1 and L 2 Each independently is a single bond; substituted or unsubstituted C 6-60 Arylene groups; or C comprising at least one heteroatom selected from N, O and S, substituted or unsubstituted 2-60 A heteroarylene group,
Ar 2 to Ar 5 Each independently is substituted or unsubstitutedC 6-60 An aryl group; or C comprising at least one heteroatom selected from N, O and S, substituted or unsubstituted 2-60 A heteroaryl group, which is a group,
d is deuterium, and
n is an integer from 0 to 5.
Further, there is provided an organic light emitting device including: a first electrode; a second electrode disposed opposite to the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein at least one of the organic material layers comprises a compound represented by chemical formula 1.
Advantageous effects
The compound represented by chemical formula 1 may be used as a material of an organic material layer for an organic light emitting device, and may improve efficiency, a low driving voltage, and/or lifetime of the organic light emitting device. In particular, the compound represented by chemical formula 1 may be used as a material for hole injection, hole transport, hole injection and transport, electron blocking, light emission, electron transport, or electron injection.
Drawings
Fig. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, an organic material layer 3, and a cathode 4.
Fig. 2 shows an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 8, a hole blocking layer 9, an electron transport layer 10, an electron injection layer 11, and a cathode 4.
Fig. 3 shows an example of an organic light emitting device including 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 8, a hole blocking layer 9, an electron injection and transport layer 12, and a cathode 4.
Detailed Description
Hereinafter, embodiments of the present disclosure will be described in more detail to facilitate understanding of the present invention.
In the present disclosure, a compound represented by chemical formula 1 is provided.
As used herein, a symbolOr->Meaning a bond to another substituent.
As used herein, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium; a halogen group; a nitrile group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; alkylthio; arylthio; an alkylsulfonyl group; arylsulfonyl; a silyl group; a boron base; an alkyl group; cycloalkyl; alkenyl groups; an aryl group; an aralkyl group; aralkenyl; alkylaryl groups; an alkylamino group; an aralkylamine group; heteroaryl amine groups; an arylamine group; aryl phosphino; and a heterocyclic group comprising at least one of N, O and S atoms, or a substituent which is unsubstituted or linked via two or more of the substituents exemplified above. For example, a "substituent to which two or more substituents are attached" may be a biphenyl group. That is, biphenyl may be aryl, or it may also be interpreted as a substituent to which two phenyl groups are attached.
In the present disclosure, the carbon number of the carbonyl group is not particularly limited, but is preferably 1 to 40. Specifically, the carbonyl group may be a compound having the following structural formula, but is not limited thereto.
In the present disclosure, the ester group may have a structure in which oxygen of the ester group is substituted with a linear, branched, or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, the ester group may be a compound having the following structural formula, but is not limited thereto.
In the present disclosure, the carbon number of the imide group is not particularly limited, but is preferably 1 to 25. Specifically, the imide group may be a compound having the following structural formula, but is not limited thereto.
In the present disclosure, the silyl group specifically includes, but is not limited to, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, and the like.
In the present disclosure, the boron group specifically includes trimethylboron group, triethylboron group, t-butyldimethylboroyl group, triphenylboron group, phenylboron group, and the like, but is not limited thereto.
In the present disclosure, examples of halogen groups include fluorine, chlorine, bromine, or iodine.
In the present disclosure, the alkyl group may be linear or branched, and the carbon number thereof is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has a carbon number of 1 to 20. According to another embodiment, the alkyl group has a carbon number of 1 to 10. According to another embodiment, the alkyl group has a carbon number of 1 to 6. Specific examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like.
In the present disclosure, the alkenyl group may be linear or branched, and the carbon number thereof is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has a carbon number of 2 to 20. According to another embodiment, the alkenyl group has a carbon number of 2 to 10. According to another embodiment, the alkenyl group has a carbon number of 2 to 6. Specific examples thereof include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-diphenylvinyl-1-yl, 2-phenyl-2- (naphthalen-1-yl) vinyl-1-yl, 2-bis (diphenyl-1-yl) vinyl-1-yl, stilbene, styryl and the like, but are not limited thereto.
In the present disclosure, the cycloalkyl group is not particularly limited, but the carbon number thereof is preferably 3 to 60. According to one embodiment, the cycloalkyl group has a carbon number of 3 to 30. According to another embodiment, the cycloalkyl group has a carbon number of 3 to 20. According to another embodiment, the cycloalkyl group has a carbon number of 3 to 6. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-t-butylcyclohexyl, cycloheptyl, cyclooctyl and the like, but are not limited thereto.
In the present disclosure, the aryl group is not particularly limited, but the carbon number thereof is preferably 6 to 60, and it may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has a carbon number of 6 to 30. According to one embodiment, the aryl group has a carbon number of 6 to 20. Monocyclic aryl groups include phenyl, biphenyl, terphenyl, and the like, but are not limited thereto. Polycyclic aryl groups include naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl,A radical, a fluorenyl radical, etc., but is not limited thereto.
In the present disclosure, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. In which the fluorenyl group is substituted In this case, it is possible to formEtc. However, the structure is not limited thereto.
In the present disclosure, the heterocyclic group is a heterocyclic group containing at least one heteroatom of O, N, si and S as a hetero element, and the carbon number thereof is not particularly limited, but is preferably 2 to 60. Examples of heterocyclyl groups include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl,Azolyl, (-) -and (II) radicals>Diazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolinyl, indolyl, carbazolyl, benzo->Oxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothiophenyl, benzofuranyl, phenanthrolinyl, and i ∈ ->Oxazolyl, thiadiazolyl, phenothiazinyl, dibenzofuranyl, and the like, but are not limited thereto.
In the present disclosure, the aryl groups in the aralkyl group, the aralkenyl group, the alkylaryl group, and the arylamine group are the same as the examples of the foregoing aryl groups. In the present disclosure, the alkyl groups in the aralkyl group, alkylaryl group, and alkylamino group are the same as the examples of the aforementioned alkyl groups. In the present disclosure, heteroaryl groups in heteroaryl amines may employ the foregoing description of heterocyclyl groups. In the present disclosure, alkenyl groups in aralkenyl groups are the same as the examples of alkenyl groups described previously. In the present disclosure, the foregoing description of aryl groups may be applied, except that arylene groups are divalent groups. In the present disclosure, the foregoing description of heterocyclyl groups may be applied, except that the heteroarylene group is a divalent group. In the present disclosure, the foregoing description of aryl or cycloalkyl groups may be applied, except that the hydrocarbon ring is not a monovalent group but is formed by combining two substituents. In the present disclosure, the foregoing description of the heterocyclic group may be applied, except that the heterocyclic ring is not a monovalent group but is formed by combining two substituents.
The compound represented by chemical formula 1 has a benzo group thereinThe azole or benzothiazole ring is fused to the core of the benzothiophene ring and includes a triazine or amine substituent bonded thereto. Since the above structure is satisfied, the compound represented by chemical formula 1 exhibits low voltage when applied to an organic light emitting device, and has excellent efficiency and lifetime.
Chemical formula 1 may be specifically represented by any one of the following chemical formulas 1-1 to 1-4:
[ chemical formula 1-1]
[ chemical formulas 1-2]
[ chemical formulas 1-3]
[ chemical formulas 1-4]
In chemical formulas 1-1 to 1-4,
L、X、L 1 、L 2 、Ar 1 to Ar 5 D and n are as defined in chemical formula 1.
Preferably, L is a single bond; substituted or unsubstituted C 6-20 Arylene groups; or C comprising at least one heteroatom selected from N, O and S, substituted or unsubstituted 2-20 Heteroarylene group. More specifically, it is a single bond; a phenylene group; biphenyldiyl; naphthalene diyl; dibenzofurandiyl; or dibenzothiophenediyl.
Preferably Ar 1 Is C substituted or unsubstituted 6-20 An aryl group; or C comprising at least one heteroatom selected from N, O and S, substituted or unsubstituted 2-20 Heteroaryl groups.
More preferably Ar 1 Is phenyl; a biphenyl group; a naphthyl group; dibenzofuranyl; or dibenzothienyl.
Preferably Ar 2 To Ar 5 Each independently is a substituted or unsubstituted C 6-20 An aryl group; or C which is substituted or unsubstituted and comprises at least one heteroatom selected from O and S 2-20 Heteroaryl groups.
Preferably Ar 2 And Ar is a group 3 Each independently is phenyl; a biphenyl group; a terphenyl group; a naphthyl group; phenanthryl; naphthylphenyl (i.e., phenyl substituted with one naphthyl); phenanthrylphenyl (i.e., phenyl substituted with one phenanthryl); phenyl naphthyl (i.e., naphthyl substituted with one phenyl); dibenzofuranyl; or dibenzothienyl.
Preferably L 1 And L 2 Each independently is a single bond; or C which is substituted or unsubstituted 6-20 Arylene groups.
More preferably L 1 And L 2 Each independently is a single bond; a phenylene group; biphenyldiyl; or a naphthalenediyl group.
Preferably Ar 4 And Ar is a group 5 Each independently is phenyl; a biphenyl group; a terphenyl group; a naphthyl group; phenyl naphthyl; a naphthylphenyl group; phenanthryl; 9, 9-dimethylfluorenyl; 9-phenylcarbazolyl; dibenzofuranyl; or dibenzothiazepineA phenone group.
Meanwhile, in the compound represented by chemical formula 1, at least one hydrogen may be substituted with deuterium. That is, n in chemical formula 1 may be an integer of 1 or more, and/or L, L in chemical formula 1 1 To L 2 And Ar is a group 1 To Ar 5 At least one substituent of (c) may be substituted with deuterium.
Representative examples of the compound represented by chemical formula 1 are as follows:
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further, a method for preparing the compound represented by chemical formula 1 is provided.
For example, chemical formula 1 may be prepared by a preparation method as in the following reaction scheme 1.
Reaction scheme 1
In reaction scheme 1, the definition of the other substituents other than X 'is the same as that defined in chemical formula 1, and X' is halogen, preferably chlorine or bromine.
Reaction scheme 1 is a Suzuki coupling reaction and is preferably carried out in the presence of a palladium catalyst and a base. Furthermore, the reactive groups used for the Suzuki coupling reaction may be suitably altered as known in the art.
Alternatively, when A is in chemical formula 1 2 In the case of chemical formula 1-c and L is a single bond, the compound of chemical formula 1 can be prepared by a preparation method as in the following reaction scheme 2.
Reaction scheme 2
In the above, the definition of the other substituents other than X 'is the same as that defined in chemical formula 1, and X' is halogen, preferably chlorine or bromine.
Reaction scheme 2 is an amine substitution reaction and is preferably carried out in the presence of a palladium catalyst and a base. Furthermore, the reactive groups used for the amine substitution reaction may be suitably altered as known in the art.
The preparation method of the compound of chemical formula 1 may be more specifically described in preparation examples and synthesis examples described below.
Further, an organic light emitting device including the compound represented by chemical formula 1 is provided. As an example, there is provided an organic light emitting device including: a first electrode; a second electrode disposed opposite to the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein at least one of the organic material layers comprises a compound represented by chemical formula 1.
The organic material layer of the organic light emitting device of the present disclosure may have a single layer structure, or it may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present disclosure may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like as an organic material layer. However, the structure of the organic light emitting device is not limited thereto, and it may include a smaller number of organic layers.
Further, the organic material layer may include a light emitting layer, and the light emitting layer includes a compound represented by chemical formula 1. In particular, the compounds according to the present disclosure may be used as hosts for light emitting layers.
Further, the organic material layer may include a hole injection layer, a hole transport layer, or an electron blocking layer, and the hole injection layer, the hole transport layer, or the electron blocking layer contains a compound represented by chemical formula 1.
Further, the organic light emitting device according to the present disclosure may be a normal organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. Further, the organic light emitting device according to the present disclosure may be an inverted organic light emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light emitting device according to one embodiment of the present disclosure is shown in fig. 1 and 2.
Fig. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, an organic material layer 3, and a cathode 4. In such a structure, the compound represented by chemical formula 1 may be included in the light emitting layer.
Fig. 2 shows an example of an organic light emitting device including 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 8, a hole blocking layer 9, an electron transport layer 10, an electron injection layer 11, and a cathode 4. In such a structure, the compound represented by chemical formula 1 may be included in at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.
Fig. 3 shows an example of an organic light emitting device including 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 8, a hole blocking layer 9, an electron injection and transport layer 12, and a cathode 4. In such a structure, the compound represented by chemical formula 1 may be included in at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, and an electron injection and transport layer. For example, the compound represented by chemical formula 1 may be included in the light emitting layer or the electron blocking layer.
The organic light emitting device according to the present disclosure may be manufactured using materials and methods known in the art, except that at least one of the organic material layers includes a compound represented by chemical formula 1. In addition, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.
For example, an organic light emitting device according to the present disclosure may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. In this case, the organic light emitting device may be manufactured by: a metal, a metal oxide having conductivity, or an alloy thereof is deposited on a substrate using a PVD (physical vapor deposition) method such as a sputtering method or an electron beam evaporation method to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed on the anode, and then a material that can function as a cathode is deposited on the organic material layer. In addition to such a method, the organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.
In addition, in manufacturing an organic light emitting device, the compound represented by chemical formula 1 may be formed into an organic material layer by a solution coating method as well as a vacuum deposition method. Herein, the solution coating method means spin coating, dip coating, knife coating, ink jet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.
In addition to such a method, the organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate (international publication WO 2003/012890). However, the manufacturing method is not limited thereto.
For example, the first electrode is an anode and the second electrode is a cathode, or alternatively, the first electrode is a cathode and the second electrode is an anode.
As the anode material, it is generally preferable to use a material having a large work function so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combinations of metals and oxides, e.g. ZnO, al or SnO 2 Sb; conductive polymers, e.g. poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxythiophene) ](PEDOT), polypyrrole and polyaniline; etc., but is not limited thereto.
As the cathode material, it is generally preferable to use a material having a small work function so that electrons can be easily injected into the organic material layer. Specific examples of the cathode material include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayer structural materials, e.g. LiF/Al or LiO 2 Al; etc., but is not limited thereto.
The hole injection layer is a layer for injecting holes from the electrode, and the hole injection material is preferably a compound of: it has a capability of transporting holes, and thus has a hole injection effect in the anode and an excellent hole injection effect to the light emitting layer or the light emitting material, prevents excitons generated in the light emitting layer from moving to the electron injection layer or the electron injection material, and is excellent in the capability of forming a thin film. Preferably, the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metalloporphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazabenzophenanthrene-based organic material, quinacridone-based organic material, perylene-based organic material, anthraquinone, polyaniline-based and polythiophene-based conductive polymer, and the like, but are not limited thereto.
The hole-transporting layer is a layer that receives holes from the hole-injecting layer and transports the holes to the light-emitting layer. The hole transport material is suitably a material having a large hole mobility, which can receive holes from the anode or the hole injection layer and transfer the holes to the light emitting layer. Specific examples thereof include an arylamine-based organic material, a conductive polymer, a block copolymer in which a conjugated moiety and a non-conjugated moiety are simultaneously present, and the like, but are not limited thereto.
The electron blocking layer serves to improve efficiency of the organic light emitting device by inhibiting electrons injected from the cathode from being transferred to the anode without being recombined in the light emitting layer. Preferably, the material represented by chemical formula 1 of the present disclosure may be used as an electron blocking material.
The light emitting material is suitably a material capable of emitting light in the visible light region by receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, so that they combine and having good quantum efficiency for fluorescence or phosphorescence. Specific examples thereof include 8-hydroxy-quinoline aluminum complex (Alq 3 ) The method comprises the steps of carrying out a first treatment on the surface of the Carbazole-based compounds; a dimeric styryl compound; BAlq; 10-hydroxybenzoquinoline-metal compounds; based on benzo Oxazole, benzothiazole-based and benzimidazole-based compounds; poly (p-phenylene vinylene) (PPV) based polymers; a spiro compound; polyfluorene and rubrene; etc., but is not limited thereto.
In addition, the light emitting layer may include a host material and a dopant material. The host material may be a fused aromatic ring derivative or a heterocycle-containing compound. Specific examples of the condensed aromatic ring derivative include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like. Examples of the heterocycle-containing compound include carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, and the like, but are not limited thereto. In particular, in the present disclosure, the compound represented by chemical formula 1 may be used as a host material for a light emitting layer, and in this case, low voltage, high efficiency, and/or long life of an organic light emitting device may be achieved.
Specifically, in chemical formula 1, when A 2 In the case of the triazine substituent represented by the chemical formula 1-b, it may be suitably used as an N-type host material when A 2 Being an amine substituent represented by chemical formula 1-c, it may be suitable for use as a P-type host material. Thus, in chemical formula 1, at least one of which A 2 A compound which is a triazine substituent represented by the formula 1-b and at least one of the compounds wherein A 2 The compound which is an amine substituent represented by chemical formula 1-c may be simultaneously contained in the light emitting layer.
Dopant materials include aromatic amine derivatives, styrene amine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivative is a substituted or unsubstituted fused aromatic ring derivative having an arylamino group, and examples thereof include pyrene, anthracene having an arylamino group,Bisindenopyrene, and the like. The styrylamine compound is a compound in which at least one arylvinyl group is substituted in a substituted or unsubstituted arylamine, wherein one or two or more substituents selected from the group consisting of aryl, silyl, alkyl, cycloalkyl, and arylamino groups are substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styrylenediamine, styrylenetriamine, styrenetetramine, and the like. Further, the metal complex includes iridium complex, platinum complex, and the like, but is not limited thereto.
Electron transportThe layer is a layer that receives electrons from the electron injection layer and transmits electrons to the light emitting layer, and the electron transport material used is suitably a material such as: which can well receive electrons from the cathode and transfer the electrons to the light emitting layer, and has a large electron mobility. Specifically, examples thereof may include Al complexes of 8-hydroxyquinoline; comprising Alq 3 Is a complex of (a) and (b); an organic radical compound; hydroxyflavone-metal complexes; etc., but is not limited thereto. The electron transport layer may be used with any desired cathode material as used according to the related art. In particular, suitable examples of cathode materials are typical materials having a low work function followed by an aluminum layer or a silver layer. Specific examples thereof include cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.
The electron injection layer is a layer that injects electrons from an electrode, and is preferably a compound that: it has an ability to transport electrons, has an effect of injecting electrons from a cathode and an excellent effect of injecting electrons into a light emitting layer or a light emitting material, prevents excitons generated by the light emitting layer from moving to a hole injecting layer, and is also excellent in an ability to form a thin film. Specific examples thereof include: fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide,Azole,/->Diazoles, triazoles, imidazoles, perylenetetracarboxylic acids, fluorenylenemethanes, anthrones, and the like, and derivatives thereof; a metal complex compound; a nitrogen-containing 5-membered ring derivative; etc., but is not limited thereto.
Examples of the metal complex compound include, but are not limited to, lithium 8-hydroxyquinoline, zinc bis (8-hydroxyquinoline), copper bis (8-hydroxyquinoline), manganese bis (8-hydroxyquinoline), aluminum tris (2-methyl-8-hydroxyquinoline), gallium tris (8-hydroxyquinoline), beryllium bis (10-hydroxybenzo [ h ] quinoline), zinc bis (2-methyl-8-quinoline) chlorogallium, gallium bis (2-methyl-8-quinoline) (o-cresol), aluminum bis (2-methyl-8-quinoline) (1-naphthol), gallium bis (2-methyl-8-quinoline) (2-naphthol), and the like.
According to one embodiment of the present disclosure, the electron transporting material and the electron injecting material may be deposited simultaneously to form the electron injecting and transporting layer as a single layer.
The organic light emitting device according to the present disclosure may be a bottom emission device, a top emission device, or a double-sided light emitting device, and in particular, may be a bottom emission device requiring relatively high light emitting efficiency.
In addition, the compound represented by chemical formula 1 may be contained in an organic solar cell or an organic transistor in addition to the organic light emitting device.
The preparation of the compound represented by chemical formula 1 and the organic light emitting device including the same will be described in detail in the following examples. However, these examples are presented for illustrative purposes only and are not intended to limit the scope of the present disclosure.
Examples (example)
< preparation example: preparation of core of Compound of chemical formula 1 ]
(synthetic schemes of preparation examples 1 to 4)
Preparation example 1: synthesis of chemical formula AA
2-amino-5-bromophenol (15 g,79.8 mmol) and (3-chloro-2- (methylthio) phenyl) boronic acid (17 g,83.8 mmol) were added to 300ml of THF under a nitrogen atmosphere and the mixture stirred and refluxed. Then, potassium carbonate (33.1 g,239.3 mmol) was dissolved in 99ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.8 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.1g of the formula aa_p1 (yield 76%, MS: [ m+h ] +=266).
Formula AA_P1 (15 g,56.6 mmol) and hydrogen peroxide (3.8 g,113.2 mmol) were added to 300ml of acetic acid under nitrogen and the mixture was stirred and refluxed. After reacting for 10 hours, cooling to room temperature was performed, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.8g of the formula aa_p2 (yield 74%, MS: [ m+h ] +=282).
Chemical formula AA_P2 (15 g,53.2 mmol) and trifluoromethanesulfonic acid (12 g,79.9 mmol) were added to 300ml pyridine under nitrogen atmosphere and stirred at room temperature. After 11 hours of reaction, it was poured into 600ml of water to solidify, and then filtered. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.2g of the formula aa_p3 (yield 62%, MS: [ m+h ] +=250).
Formula AA_P3 (15 g,60.2 mmol), carbon disulphide (5.5 g,72 mmol) and potassium hydroxide (4.1 g,77 mmol) are added to 150ml EtOH under nitrogen and the mixture is stirred and refluxed. After the reaction for 12 hours, cooling to room temperature was performed, and then the organic solvent was distilled under reduced pressure. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.9g of the formula aa_p4 (yield 64%, MS: [ m+h ] +=258).
Chemical formula aa_p4 (15 g,58.4 mmol) and phosphorus pentachloride (12.2 g,70 mmol) were added to 150ml toluene under nitrogen atmosphere and the mixture was stirred and refluxed. After the reaction for 12 hours, cooling to room temperature was performed, and then the organic solvent was distilled under reduced pressure. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.1g of the compound of formula AA (yield 67%, MS: [ m+h ] +=260).
Preparation example 2: synthesis of chemical formula AB
Chemical formula AB was prepared in the same manner as in preparation example 1 except that (4-chloro-2- (methylthio) phenyl) boronic acid was used instead of (3-chloro-2- (methylthio) phenyl) boronic acid.
Preparation example 3: synthesis of chemical AC
Chemical formula AC was prepared in the same manner as in preparation example 1, except that (5-chloro-2- (methylthio) phenyl) boronic acid was used instead of (3-chloro-2- (methylthio) phenyl) boronic acid.
Preparation example 4: synthesis of chemical AD
Chemical formula AD was prepared in the same manner as in preparation example 1 except that (2-chloro-6- (methylthio) phenyl) boronic acid was used instead of (3-chloro-2- (methylthio) phenyl) boronic acid.
(synthetic schemes of preparation examples 5 to 6)
Preparation example 5: synthesis of chemical AE
The formula AE was produced in the same manner as in production example 1, except that 2-amino-5-bromo-3-chlorophenol was used instead of 2-amino-5-bromophenol, and (2- (methylthio) phenyl) boronic acid was used instead of (3-chloro-2- (methylthio) phenyl) boronic acid.
Preparation example 6: synthesis of chemical AF
The formula AE was produced in the same manner as in production example 1, except that 6-amino-3-bromo-2-chlorophenol was used instead of 2-amino-6-bromophenol, and (2- (methylthio) phenyl) boronic acid was used instead of (3-chloro-2- (methylthio) phenyl) boronic acid.
Preparation example 7: synthesis of chemical formula AG
Chemical formula AG was prepared in the same manner as in preparation example 1, except that (2- (methylthio) phenyl) boronic acid was used instead of (3-chloro-2- (methylthio) phenyl) boronic acid.
(synthetic schemes of preparation examples 8 to 11)
Preparation example 8: synthesis of chemical formula BA
Chemical formula BA was prepared in the same manner as in preparation example 1, except that 2-amino-4-bromophenol was used instead of 2-amino-5-bromophenol.
Preparation example 9: synthesis of chemical formula BB
Chemical formula BB was prepared in the same manner as in preparation example 1, except that 2-amino-4-bromophenol was used instead of 2-amino-5-bromophenol, and (4-chloro-2- (methylthio) phenyl) boronic acid was used instead of (3-chloro-2- (methylthio) phenyl) boronic acid.
Preparation example 10: synthesis of chemical BC
Chemical formula BC was prepared in the same manner as in preparation example 1, except that 2-amino-4-bromophenol was used instead of 2-amino-5-bromophenol, and (5-chloro-2- (methylthio) phenyl) boronic acid was used instead of (3-chloro-2- (methylthio) phenyl) boronic acid.
Preparation example 11: synthesis of chemical BD
Chemical formula BD was prepared in the same manner as in preparation example 1, except that 2-amino-4-bromophenol was used instead of 2-amino-5-bromophenol, and (2-chloro-6- (methylthio) phenyl) boronic acid was used instead of (3-chloro-2- (methylthio) phenyl) boronic acid.
(synthetic schemes of preparation examples 12 to 13)
Preparation example 12: synthesis of chemical BE
The formula BE was produced in the same manner as in production example 1, except that 2-amino-4-bromo-5-chlorophenol was used instead of 2-amino-5-bromophenol, and (2- (methylthio) phenyl) boronic acid was used instead of (3-chloro-2- (methylthio) phenyl) boronic acid.
Preparation example 13: synthesis of chemical BF
The formula BF was prepared in the same manner as in preparation example 1, except that 2-amino-4-bromo-3-chlorophenol was used instead of 2-amino-5-bromophenol, and (2- (methylthio) phenyl) boronic acid was used instead of (3-chloro-2- (methylthio) phenyl) boronic acid.
Preparation example 14: synthesis of chemical formula BG
Formula BG was prepared in the same manner as in preparation example 1 except that 2-amino-4-bromophenol was used instead of 2-amino-5-bromophenol and (2- (methylthio) phenyl) boronic acid was used instead of (3-chloro-2- (methylthio) phenyl) boronic acid.
(synthetic schemes of preparation examples 15 to 18)
Preparation example 15: synthesis of chemical CA
4-bromo-2-fluoroaniline (15 g,78.9 mmol) and (3-chloro-2- (methylthio) phenyl) boronic acid (24 g,118.4 mmol) were added to 300ml of THF under a nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (32.7 g,236.8 mmol) was dissolved in 98ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.8 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.8g of the formula ca_p1 (yield 51%, MS: [ m+h ] +=268).
Formula CA_P1 (15 g,56.2 mmol) and hydrogen peroxide (2.9 g,84.3 mmol) were added to 300ml of acetic acid under nitrogen and the mixture was stirred and refluxed. After reacting for 10 hours, cooling to room temperature was performed, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.6g of the formula ca_p2 (yield 54%, MS: [ m+h ] +=284).
Chemical formula CA_P2 (15 g,53 mmol) and trifluoromethanesulfonic acid (11.9 g,79.5 mmol) were added to 300ml of pyridine under nitrogen atmosphere and stirred at room temperature. After 11 hours of reaction, it was poured into 600ml of water to solidify, and then filtered. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.9g of the formula ca_p3 (yield 52%, MS: [ m+h ] +=252).
Chemical formula CA_P3 (15 g,59.7 mmol) and potassium O-ethyldithiocarbonate (21.0 g,131 mmol) were added to 150ml DMF under nitrogen and the mixture was stirred and refluxed. After the reaction for 9 hours, cooling to room temperature was performed, and then the organic solvent was distilled under reduced pressure. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.7g of the formula ca_p4 (yield 80%, MS: [ m+h ] +=308).
Add formula CA_P4 (15 g,48.7 mmol) to 150ml CHCl under nitrogen atmosphere 3 In and cooled to 0 ℃ with an ice bath. Thionyl chloride (12.8 g,107.5 mmol) was then slowly added dropwise followed by stirring. After 4 hours of reaction, cooling to room temperature was performed, and then the organic solvent was distilled under reduced pressure. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.3g of the formula CA_P5 (yield 68%, MS: [ M+H)]+＝310)。
Preparation example 16: synthesis of chemical CB
Chemical formula CB was prepared in the same manner as in preparation example 15 except that (4-chloro-2- (methylthio) phenyl) boronic acid was used instead of (3-chloro-2- (methylthio) phenyl) boronic acid.
Preparation example 17: synthesis of chemical formula CC
Chemical formula CC was prepared in the same manner as in preparation example 15 except that (5-chloro-2- (methylthio) phenyl) boronic acid was used instead of (3-chloro-2- (methylthio) phenyl) boronic acid.
Preparation example 18: synthesis of chemical CD
Chemical formula CD was prepared in the same manner as in preparation example 15, except that (2-chloro-6- (methylthio) phenyl) boronic acid was used instead of (3-chloro-2- (methylthio) phenyl) boronic acid.
(synthetic schemes of preparation examples 19 to 20)
Preparation example 19: synthesis of chemical CE
Chemical formula CE was prepared in the same manner as in preparation example 15, except that 4-bromo-2-chloro-6-fluoroaniline was used instead of 4-bromo-2-fluoroaniline, and (2- (methylthio) phenyl) boric acid was used instead of (3-chloro-2- (methylthio) phenyl) boric acid.
Preparation example 20: synthesis of chemical formula CF
The formula CF was produced in the same manner as in production example 15, except that 4-bromo-3-chloro-2-fluoroaniline was used instead of 4-bromo-2-fluoroaniline, and (2- (methylthio) phenyl) boric acid was used instead of (3-chloro-2- (methylthio) phenyl) boric acid.
Preparation example 21: synthesis of chemical formula CG
Chemical formula CG was prepared in the same manner as in preparation example 15, except that (2- (methylthio) phenyl) boronic acid was used instead of (3-chloro-2- (methylthio) phenyl) boronic acid.
(synthetic schemes of preparation examples 22 to 25)
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Preparation example 22: synthesis of chemical formula DA
The chemical formula DA was produced in the same manner as in preparation example 15, except that 5-bromo-2-fluoroaniline was used instead of 4-bromo-2-fluoroaniline.
Preparation example 23: synthesis of formula DB
Formula DB was prepared in the same manner as in preparation example 15 except that 5-bromo-2-fluoroaniline was used instead of 4-bromo-2-fluoroaniline, and (4-chloro-2- (methylthio) phenyl) boronic acid was used instead of (3-chloro-2- (methylthio) phenyl) boronic acid.
Preparation example 24: synthesis of chemical DC
Chemical formula DC was prepared in the same manner as in preparation example 15, except that 5-bromo-2-fluoroaniline was used instead of 4-bromo-2-fluoroaniline, and (5-chloro-2- (methylthio) phenyl) boronic acid was used instead of (3-chloro-2- (methylthio) phenyl) boronic acid.
Preparation example 25: synthesis of chemical DD
Chemical formula DD was prepared in the same manner as in preparation example 15, except that 5-bromo-2-fluoroaniline was used instead of 4-bromo-2-fluoroaniline, and (2-chloro-6- (methylthio) phenyl) boronic acid was used instead of (3-chloro-2- (methylthio) phenyl) boronic acid.
(synthetic schemes of preparation examples 26 to 27)
Preparation example 26: synthesis of formula DE
Chemical formula DE was prepared in the same manner as in preparation example 15 except that 5-bromo-3-chloro-2-fluoroaniline was used instead of 4-bromo-2-fluoroaniline, and (2- (methylthio) phenyl) boric acid was used instead of (3-chloro-2- (methylthio) phenyl) boric acid.
Preparation example 27: synthesis of chemical formula DF
Chemical formula DE was prepared in the same manner as in preparation example 15 except that 3-bromo-2-chloro-6-fluoroaniline was used instead of 4-bromo-2-fluoroaniline, and (2- (methylthio) phenyl) boric acid was used instead of (3-chloro-2- (methylthio) phenyl) boric acid.
Preparation example 28: synthesis of chemical DG
Chemical formula DG was prepared in the same manner as in preparation example 15, except that 5-bromo-2-fluoroaniline was used instead of 4-bromo-2-fluoroaniline, and (2- (methylthio) phenyl) boric acid was used instead of (3-chloro-2- (methylthio) phenyl) boric acid.
< synthesis example: preparation of Compound of chemical formula 1
Synthesis example 1-1
Formula AA (15 g,51 mmol) and [1,1' -biphenyl ] -4-ylboronic acid (10.6 g,53.5 mmol) were added to 300ml THF under a nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8g of sub AA-1 (yield 66%, MS: [ M+H ] +=412).
SubAA-1 (15 g,36.4 mmol) and bis (pinacolato) diboron (10.2 g,40.1 mmol) were added to 300ml of 1, 4-bis under nitrogen atmosphere In an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (5.4 g,54.6 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.6 g,1.1 mmol) and tricyclohexylphosphine (0.6 g,2.2 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.9g of sub AA-2 (yield 65%, MS: [ M+H)]+＝504)。
SubAA-2 (15 g,29.8 mmol) and Trz1 (12.3 g,31.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (12.4 g,89.4 mmol) was dissolved in 37ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6g of compound 1-1 (yield 53%, MS: [ m+h ] + =735).
Synthesis examples 1 to 2
Chemical formula AA (15 g,51 mmol) and phenylboronic acid (6.5 g,53.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.1g of sub AA-3 (yield 59%, MS: [ M+H ] +=336).
SubAA-3 (15 g,44.7 mmol) and Trz2 (18.9 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.8g of compound 1-2 (yield 57%, MS: [ m+h ] +=659).
Synthesis examples 1 to 3
Chemical formula AB (15 g,51 mmol) and phenylboronic acid (6.5 g,53.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.8g of subeb-1 (yield 69%, MS: [ m+h ] +=336).
SubAB-1 (15 g,44.7 mmol) and Trz3 (18.9 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.5g of compounds 1 to 3 (yield 56%, MS: [ m+h ] +=659).
Synthesis examples 1 to 4
SubAB-1 (15 g,44.7 mmol) and bis (pinacolato) diboron (12.5 g,49.1 mmol) were added to 300ml of 1, 4-bis under nitrogen atmosphereIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (6.6 g,67 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.8 g,1.3 mmol) and tricyclohexylphosphine (0.8 g,2.7 mmol). After 6 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12g of subeb-2 (yield 63%, MS: [ m+h)]+＝428)
SubAB-2 (15 g,35.1 mmol) and Trz4 (13.6 g,36.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14.6 g,105.3 mmol) was dissolved in 44ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.3g of compounds 1 to 4 (yield 51%, MS: [ m+h ] +=633).
Synthesis examples 1 to 5
Chemical formula AC (15 g,51 mmol) and naphthalen-2-ylboronic acid (9.2 g,53.5 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6g of subarac-1 (yield 69%, MS: [ m+h ] + =385).
SubAC-1 (15 g,38.9 mmol) and bis (pinacolato) diboron (10.9 g,42.8 mmol) were added to 300ml of 1, 4-bis under nitrogen atmosphereIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (5.7 g,58.3 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.7 g,1.2 mmol) and tricyclohexylphosphine (0.7 g,2.3 mmol). After 7 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.5g of subAC-2 (yield 73%, MS: [ M+H) ]+＝478)
SubAC-2 (15 g,31.4 mmol) and Trz1 (13 g,33 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (13 g,94.3 mmol) was dissolved in 39ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.1g of compounds 1 to 5 (yield 50%, MS: [ m+h ] +=709).
Synthesis examples 1 to 6
Chemical formula AD (15 g,51 mmol) and phenylboronic acid (6.5 g,53.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.8g of subAD-1 (yield 63%, MS: [ m+h ] +=336).
SubAD-1 (15 g,44.7 mmol) and bis (pinacolato) diboron (12.5 g,49.1 mmol) were added to 300ml of 1, 4-di under nitrogen atmosphereIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (6.6 g,67 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.8 g,1.3 mmol) and tricyclohexylphosphine (0.8 g,2.7 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13g of subAD-2 (yield 68%, MS: [ M+H ]]+＝428)。
SubAD-2 (15 g,35.1 mmol) and Trz5 (9.9 g,36.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14.6 g,105.3 mmol) was dissolved in 44ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5g of compounds 1 to 6 (yield 67%, MS: [ m+h ] +=533).
Synthesis examples 1 to 7
SubAD-2 (15 g,35.1 mmol) and Trz6 (13.2 g,36.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14.6 g,105.3 mmol) was dissolved in 44ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.1g of compounds 1 to 7 (yield 51%, MS: [ m+h ] +=623).
Synthesis examples 1 to 8
SubAD-1 (15 g,44.7 mmol) and Trz7 (23.1 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.7g of compounds 1 to 8 (yield 65%, MS: [ m+h ] +=749).
Synthesis examples 1 to 9
SubAD-1 (15 g,44.7 mmol) and Trz8 (18.9 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.8g of compounds 1 to 9 (yield 64%, MS: [ m+h ] +=659).
Synthesis examples 1 to 10
SubAD-2 (15 g,35.1 mmol) and Trz9 (14.9 g,36.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14.6 g,105.3 mmol) was dissolved in 44ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2g of compounds 1 to 10 (yield 53%, MS: [ m+h ] +=659).
Synthesis examples 1 to 11
Chemical formula AD (15 g,51 mmol) and dibenzo [ b, d ] thiophen-4-ylboronic acid (1.5 g,53.5 mmol) were added to 300ml of THF under a nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2g of subAD-3 (yield 63%, MS: [ M+H ] +=442).
SubAD-3 (15 g,33.9 mmol) and bis (pinacolato) diboron (9.5 g,37.3 mmol) were added to 300ml of 1, 4-bis under nitrogen atmosphereIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (5 g,50.9 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.6 g,1 mmol) and tricyclohexyl Phosphine (0.6 g,2 mmol). After 7 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.1g of subAD-4 (yield 78%, MS: [ M+H ]]+＝534)。
SubAD-4 (15 g,28.1 mmol) and Trz5 (7.9 g,29.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (11.7 g,84.4 mmol) was dissolved in 35ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4g of compounds 1 to 11 (yield 69%, MS: [ m+h ] +=639).
Synthesis examples 1 to 12
Formula AE (15 g,51 mmol) and phenylboronic acid (6.5 g,53.5 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.4g of sub ae-1 (yield 61%, MS: [ m+h ] +=336).
SubAE-1 (15 g,44.7 mmol) and Trz10 (21.3 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.3g of compounds 1 to 12 (yield 58%, MS: [ m+h ] +=709).
Synthesis examples 1 to 13
Formula AE (15 g,51 mmol) and naphthalen-2-ylboronic acid (9.2 g,53.5 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.4g of sub ae-2 (yield 53%, MS: [ m+h ] + =385).
SubAE-2 (15 g,38.9 mmol) and bis (pinacolato) diboron (10.9 g,42.8 mmol) were added to 300ml of 1, 4-bis under nitrogen atmosphereIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (5.7 g,58.3 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.7 g,1.2 mmol) and tricyclohexylphosphine (0.7 g,2.3 mmol). After 7 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.9g of subAE-3 (yield 64%, MS: [ M+H ] ]+＝478)。
SubAE-3 (15 g,31.4 mmol) and Trz11 (15.8 g,33 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (13 g,94.3 mmol) was dissolved in 39ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3g of compounds 1 to 13 (yield 58%, MS: [ m+h ] +=785).
Synthesis examples 1 to 14
Formula AF (15 g,51 mmol) and phenylboronic acid (6.5 g,53.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.9g of sub AF-1 (yield 52%, MS: [ M+H ] +=336).
SubAF-1 (15 g,44.7 mmol) and bis (pinacolato) diboron (12.5 g,49.1 mmol) were added to 300ml of 1, 4-bis under nitrogenIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (6.6 g,67 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.8 g,1.3 mmol) and tricyclohexylphosphine (0.8 g,2.7 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13g of sub AF-2 (yield 68%, MS: [ M+H ]]+＝428)。
SubAF-2 (15 g,35.1 mmol) and Trz12 (14.5 g,36.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14.6 g,105.3 mmol) was dissolved in 44ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5g of compounds 1 to 14 (yield 54%, MS: [ m+h ] + =659).
Synthesis examples 1 to 15
Formula AF (15 g,51 mmol) and [1,1' -biphenyl ] -4-ylboronic acid (10.6 g,53.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.2g of sub AF-3 (yield 54%, MS: [ M+H ] +=336).
SubAF-3 (15 g,36.4 mmol) and bis (pinacolato) diboron (10.2 g,40.1 mmol) were added to 300ml of 1, 4-bis under nitrogen atmosphereIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (5.4 g,54.6 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.6 g,1.1 mmol) and tricyclohexylphosphine (0.6 g,2.2 mmol). After 7 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1g of subeF-4 (yield 66%, MS: [ M+H ] ]+＝504)。
SubAF-4 (15 g,29.8 mmol) and Trz13 (12.3 g,31.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (12.4 g,89.4 mmol) was dissolved in 37ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2g of compounds 1 to 15 (yield 65%, MS: [ m+h ] + =735).
Synthesis examples 1 to 16
Chemical formula BA (15 g,51 mmol) and dibenzo [ b, d ] furan-2-ylboronic acid (11.4 g,53.5 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.5g of subBA-1 (yield 53%, MS: [ m+h ] +=426).
SubBA-1 (15 g,35.2 mmol) and bis (pinacolato) diboron (9.8 g,38.7 mmol) were added to 300ml of 1, 4-bis under nitrogen atmosphereIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (5.2 g,52.8 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.6 g,1.1 mmol) and tricyclohexylphosphine (0.6 g,2.1 mmol). After 8 hours of reaction, cooling to room temperature was performed. However, the method is thatAfter that, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 0.4g of subBA-2 (yield 69%, MS: [ M+H ]]+＝18)。
SubBA-2 (15 g,29 mmol) and Trz5 (8.1 g,30.4 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (12 g,87 mmol) was dissolved in 36ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.6g of compounds 1 to 16 (yield 53%, MS: [ m+h ] +=623).
Synthesis examples 1 to 17
Chemical formula BA (15 g,51 mmol) and phenylboronic acid (6.5 g,53.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.6g of subBA-3 (yield 62%, MS: [ m+h ] +=336).
SubBA-3 (15 g,44.7 mmol) and Trz14 (20.8 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.8g of compounds 1 to 17 (yield 57%, MS: [ m+h ] +=699).
Synthesis examples 1 to 18
Chemical formula BB (15 g,51 mmol) and phenylboronic acid (6.5 g,53.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.8g of subeb-1 (yield 69%, MS: [ m+h ] +=336).
SubBB-2 (15 g,35.1 mmol) and Trz15 (11.7 g,36.9 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (14.6 g,105.3 mmol) was dissolved in 44ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3g of compounds 1 to 18 (yield 60%, MS: [ m+h ] +=583).
Synthesis examples 1 to 19
Chemical formula BC (15 g,51 mmol) and dibenzo [ b, d ] thiophen-4-ylboronic acid (12.2 g,53.5 mmol) were added to 300ml THF under a nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.5g of subBC-1 (yield 51%, MS: [ m+h ] +=442).
SubBB-1 (15 g,44.7 mmol) and bis (pinacolato) diboron (12.5 g,49.1 mmol) were added to 300ml of 1, 4-diboron under a nitrogen atmosphereIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (6.6 g,67 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.8 g,1.3 mmol) and tricyclohexylphosphine (0.8 g,2.7 mmol). After 5 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water And (3) separating and distilling. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8g of subBB-2 (yield 67%, MS: [ M+H)]+＝428)。
SubBB-4 (15 g,29 mmol) and Trz5 (8.1 g,30.4 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (12 g,87 mmol) was dissolved in 36ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.5g of compounds 1 to 19 (yield 58%, MS: [ m+h ] +=623).
Synthesis examples 1 to 20
Chemical formula BD (15 g,51 mmol) and phenylboronic acid (6.5 g,53.5 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.6g of subBD-1 (yield 56%, MS: [ M+H ] +=336).
SubBC-1 (15 g,33.9 mmol) and bis (pinacolato) diboron (9.5 g,37.3 mmol) are added to 300ml of 1, 4-bis under nitrogenIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (5 g,50.9 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.6 g,1 mmol) and tricyclohexylphosphine (0.6 g,2 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.9g of subBC-2 (yield 77%, MS: [ M+H ]]+＝534)。
SubBC-2 (15 g,28.1 mmol) and Trz5 (7.9 g,29.5 mmol) are added to 300ml THF under nitrogen and the mixture is stirred and refluxed. Then, potassium carbonate (11.7 g,84.4 mmol) was dissolved in 35ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.6g of compounds 1 to 20 (yield 59%, MS: [ m+h ] +=639).
Synthesis examples 1 to 21
Chemical formula BD (15 g,51 mmol) and phenylboronic acid (6.5 g,53.5 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.5g of subBD-1 (yield 50%, MS: [ M+H ] +=336).
SubBD-1 (15 g,44.7 mmol) and bis (pinacolato) diboron (12.5 g,49.1 mmol) were added to 300ml of 1, 4-diboron under a nitrogen atmosphereIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (6.6 g,67 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.8 g,1.3 mmol) and tricyclohexylphosphine (0.8 g,2.7 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.1g of subBD-2 (yield 74%, MS: [ M+H ] ]+＝428)。
SubBD-2 (15 g,35.1 mmol) and Trz5 (9.9 g,36.9 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (14.6 g,105.3 mmol) was dissolved in 44ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.3g of compounds 1 to 21 (yield 50%, MS: [ m+h ] +=533).
Synthesis examples 1 to 22
SubBD-2 (15 g,35.1 mmol) and Trz16 (14.9 g,36.9 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (14.6 g,105.3 mmol) was dissolved in 44ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6g of compounds 1 to 22 (yield 63%, MS: [ m+h ] +=659).
Synthesis examples 1 to 23
SubBD-2 (15 g,35.1 mmol) and Trz6 (13.2 g,36.9 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (14.6 g,105.3 mmol) was dissolved in 44ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2g of compounds 1 to 23 (yield 56%, MS: [ m+h ] +=623).
Synthesis examples 1 to 24
SubBD-1 (15 g,44.7 mmol) and Trz9 (18.9 g,46.9 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.9g of compounds 1 to 24 (yield 61%, MS: [ m+h ] +=659).
Synthesis examples 1 to 25
SubBD-1 (15 g,44.7 mmol) and Trz14 (20.8 g,46.9 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.8g of compounds 1 to 25 (yield 57%, MS: [ m+h ] +=699).
Synthesis examples 1 to 26
Chemical formula BE (15 g,51 mmol) and phenylboronic acid (6.5 g,53.5 mmol) were added to 300ml THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12g of subee-1 (yield 70%, MS: [ m+h ] +=336).
Sube-1 (15 g,44.7 mmol) and Trz17 (16.6 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.5g of compounds 1 to 26 (yield 68%, MS: [ m+h ] +=609).
Synthesis examples 1 to 27
Formula BE (15 g,51 mmol) and naphthalen-2-ylboronic acid (9.2 g,53.5 mmol) were added to 300ml THF under a nitrogen atmosphere and the mixture stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2g of subee-2 (yield 67%, MS: [ m+h ] + =385).
SubBE-2 (15 g,38.9 mmol) and bis (pinacolato) diboron (10.9 g,42.8 mmol) were added to 300ml of 1, 4-bis under a nitrogen atmosphereIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (5.7 g,58.3 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.7 g,1.2 mmol) and tricyclohexylphosphine (0.7 g,2.3 mmol). After 5 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.1g of subee-3 (yield 60%, MS: [ M+H)]+＝478)。
Sube-3 (15 g,31.4 mmol) and Trz18 (11.8 g,33 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (13 g,94.3 mmol) was dissolved in 39ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11g of compounds 1 to 27 (yield 52%, MS: [ m+h ] +=673).
Synthesis examples 1 to 28
Chemical formula BF (15 g,51 mmol) and phenylboronic acid (6.5 g,53.5 mmol) were added to 300ml THF under a nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.9g of subBF-1 (yield 58%, MS: [ m+h ] +=336).
SubBF-1 (15 g,44.7 mmol) and Trz19 (18.9 g,46.9 mmol) were added to 300ml THF under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.6g of compounds 1 to 28 (yield 70%, MS: [ m+h ] + =659).
Synthesis examples 1 to 29
Chemical formula BF (15 g,51 mmol) and naphthalen-2-ylboronic acid (9.2 g,53.5 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.6g of subBF-2 (yield 64%, MS: [ m+h ] + =385).
SubBF-2 (15 g,38.9 mmol) and bis (pinacolato) diboron (10.9 g,42.8 mmol) were added to 300ml of 1, 4-bis under a nitrogen atmosphereIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (5.7 g,58.3 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.7 g,1.2 mmol) and tricyclohexylphosphine (0.7 g,2.3 mmol). After 6 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13g of subBF-3 (yield 70%, MS: [ M+H) ]+＝478)。
SubBF-3 (15 g,31.4 mmol) and Trz18 (11.8 g,33 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (13 g,94.3 mmol) was dissolved in 39ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2g of compounds 1 to 29 (yield 53%, MS: [ m+h ] +=673).
Synthesis examples 1 to 30
Formula CA (15 g,51 mmol) and phenylboronic acid (6.5 g,53.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.1g of subCA-1 (yield 62%, MS: [ M+H ] +=352).
SubCA-1 (15 g,42.6 mmol) and bis (pinacolato) diboron (11.9 g,46.9 mmol) are added to 300ml of 1, 4-bis under nitrogen atmosphereIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (6.3 g,63.9 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.7 g,1.3 mmol) and tricyclohexylphosphine (0.7 g,2.6 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and waterAnd distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.7g of subCA-2 (yield 78%, MS: [ M+H ]]+＝444)。
SubCA-2 (15 g,33.8 mmol) and Trz20 (12.7 g,35.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14 g,101.5 mmol) was dissolved in 42ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.5g of compounds 1 to 30 (yield 67%, MS: [ m+h ] +=639).
Synthesis examples 1 to 31
Formula CA (15 g,51 mmol) and naphthalen-2-ylboronic acid (9.2 g,53.5 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.5g of subCA-3 (yield 56%, MS: [ m+h ] +=402).
SubCA-3 (15 g,37.3 mmol) and Trz21 (15.8 g,39.2 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (15.5 g,112 mmol) was dissolved in 46ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.1g of compounds 1 to 31 (yield 56%, MS: [ m+h ] +=725).
Synthesis examples 1 to 32
Chemical formula CB (15 g,51 mmol) and naphthalen-2-ylboronic acid (9.2 g,53.5 mmol) are added to 300ml THF under nitrogen and the mixture is stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.9g of subCB-1 (yield 68%, MS: [ m+h ] +=402).
SubCB-1 (15 g,37.3 mmol) and bis (pinacolato) diboron (10.4 g,41.1 mmol) are added to 300ml of 1, 4-diboron under a nitrogen atmosphereIn an alkane and stirring the mixtureAnd refluxed. Then, potassium acetate (5.5 g,56 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.6 g,1.1 mmol) and tricyclohexylphosphine (0.6 g,2.2 mmol). After 7 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11g of subCB-2 (yield 60%, MS: [ M+H ] ]+＝494)。/>
SubCB-2 (15 g,30.4 mmol) and Trz15 (10.1 g,31.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (12.6 g,91.2 mmol) was dissolved in 38ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.6g of compounds 1 to 32 (yield 64%, MS: [ m+h ] +=649).
Synthesis examples 1 to 33
Chemical formula CB (15 g,51 mmol) and phenylboronic acid (6.5 g,53.5 mmol) are added to 300ml THF under nitrogen and the mixture is stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.9g of subCB-3 (yield 61%, MS: [ m+h ] +=352).
SubCB-3 (15 g,42.6 mmol) and Trz3 (18 g,44.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.7 g,127.9 mmol) was dissolved in 53ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.9g of compounds 1 to 33 (yield 52%, MS: [ m+h ] +=675).
Synthesis examples 1 to 34
Chemical formula CC (15 g,51 mmol) and phenylboronic acid (6.5 g,53.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.4g of subCC-1 (yield 58%, MS: [ m+h ] +=352).
In nitrogen atmosphereSubCC-1 (15 g,42.6 mmol) and bis (pinacolato) diboron (11.9 g,46.9 mmol) are added to 300ml of 1, 4-bisIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (6.3 g,63.9 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.7 g,1.3 mmol) and tricyclohexylphosphine (0.7 g,2.6 mmol). After 5 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.7g of subC-2 (yield 67%, MS: [ M+H ]]+＝444)。
SubCC-2 (15 g,33.8 mmol) and Trz22 (14 g,35.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14 g,101.5 mmol) was dissolved in 42ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16g of compounds 1 to 34 (yield 70%, MS: [ m+h ] +=675).
Synthesis examples 1 to 35
Chemical formula CD (15 g,48.4 mmol) and phenylboronic acid (6.2 g,50.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.5g of subCD-1 (yield 56%, MS: [ M+H ] +=352).
SubCD-1 (15 g,42.6 mmol) and bis (pinacolato) diboron (11.9 g,46.9 mmol) are added to 300ml of 1, 4-diboron under a nitrogen atmosphereIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (6.3 g,63.9 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.7 g,1.3 mmol) and tricyclohexylphosphine (0.7 g,2.6 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4g of subCD-2 (yield 71%, MS: [ M+H ] ]+＝444)。
SubCD-2 (15 g,33.8 mmol) and Trz23 (14 g,35.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14 g,101.5 mmol) was dissolved in 42ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4g of compounds 1 to 35 (yield 50%, MS: [ m+h ] +=675).
Synthesis examples 1 to 36
SubCD-1 (15 g,42.6 mmol) and Trz7 (22.1 g,44.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.7 g,127.9 mmol) was dissolved in 53ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.9g of compounds 1 to 36 (yield 52%, MS: [ m+h ] +=765).
Synthesis examples 1 to 37
Chemical formula CD (15 g,48.4 mmol) and dibenzo [ b, d ] furan-2-ylboronic acid (10.8 g,50.8 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.9g of subCD-3 (yield 51%, MS: [ m+h ] +=442).
SubCD-3 (15 g,33.9 mmol) and bis (pinacolato) diboron (9.5 g,37.3 mmol) are added to 300ml of 1, 4-bis under nitrogen atmosphereIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (5 g,50.9 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.6 g,1 mmol) and tricyclohexylphosphine (0.6 g,2 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6g of subCD-4 (yield 64%, MS: [ M+H ] ]+＝534)。
SubCD-4 (15 g,28.1 mmol) and Trz5 (7.9 g,29.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (11.7 g,84.4 mmol) was dissolved in 35ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9g of compounds 1 to 37 (yield 50%, MS: [ m+h ] +=639).
Synthesis examples 1 to 38
Chemical formula CE (15 g,48.4 mmol) and [1,1' -biphenyl ] -4-ylboronic acid (10.1 g,50.8 mmol) were added to 300ml of THF under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.5g of subCE-1 (yield 51%, MS: [ m+h ] + =428).
SubCE-1 (15 g,35.1 mmol) and bis (pinacolato) diboron (9.8 g,38.6 mmol) were added to 300ml of 1, 4-di under nitrogen atmosphereIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (5.2 g,52.6 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.6 g,1.1 mmol) and tricyclohexylphosphine (0.6 g,2.1 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1g of subCE-2 (yield 72%, MS: [ M+H ]]+＝520)。
SubCE-2 (15 g,28.9 mmol) and Trz23 (11.2 g,30.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (12 g,86.6 mmol) was dissolved in 36ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3g of compounds 1 to 38 (yield 59%, MS: [ m+h ] +=725).
Synthesis examples 1 to 39
Chemical formula CE (15 g,48.4 mmol) and phenylboronic acid (6.2 g,50.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.5g of subCE-3 (yield 62%, MS: [ m+h ] +=352).
SubCE-3 (15 g,42.6 mmol) and Trz24 (18 g,44.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.7 g,127.9 mmol) was dissolved in 53ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.4g of compounds 1 to 39 (yield 57%, MS: [ m+h ] +=675).
Synthesis examples 1 to 40
Chemical formula CF (15 g,48.4 mmol) and phenylboronic acid (6.2 g,50.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9g of ubcf-1 (yield 53%, MS: [ m+h ] +=352).
SubCF-1 (15 g,42.6 mmol) and bis (pinacolato) diboron (11.9 g,46.9 mmol) are added to 300ml of 1, 4-diboron under a nitrogen atmosphereIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (6.3 g,63.9 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.7 g,1.3 mmol) and tricyclohexylphosphine (0.7 g,2.6 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.7g of subCF-2 (yield 78%, MS: [ M+H ] ]+＝444)。
SubCF-2 (15 g,33.8 mmol) and Trz25 (14.9 g,35.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14 g,101.5 mmol) was dissolved in 42ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.5g of compounds 1 to 40 (yield 57%, MS: [ m+h ] +=701).
Synthesis examples 1 to 41
Chemical formula CF (15 g,48.4 mmol) and naphthalen-2-ylboronic acid (8.7 g,50.8 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.3g of subCF-3 (yield 53%, MS: [ M+H ] +=402).
SubCF-3 (15 g,37.3 mmol) and Trz26 (17.8 g,39.2 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (15.5 g,112 mmol) was dissolved in 46ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.6g of compounds 1 to 41 (yield 68%, MS: [ m+h ] +=775).
Synthesis examples 1 to 42
Chemical formula DA (15 g,48.4 mmol) and naphthalen-2-ylboronic acid (8.7 g,50.8 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4g of subDA-1 (yield 59%, MS: [ M+H ] + =402).
SubDA-1 (15 g,37.3 mmol) and bis (pinacolato) diboron (10.4 g,41.1 mmol) are added to 300ml of 1, 4-di-under a nitrogen atmosphereIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (5.5 g,56 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.6 g,1.1 mmol) and tricyclohexylphosphine (0.6 g,2.2 mmol). After 7 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.7g of subDA-2 (yield 69%, MS: [ M+H ]]+＝494)。
SubDA-2 (15 g,30.4 mmol) and Trz6 (11.4 g,31.9 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (12.6 g,91.2 mmol) was dissolved in 38ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14g of compounds 1 to 42 (yield 67%, MS: [ m+h ] +=689).
Synthesis examples 1 to 43
Chemical formula DA (15 g,48.4 mmol) and [1,1' -biphenyl ] -4-ylboronic acid (10.1 g,50.8 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2g of subDA-3 (yield 59%, MS: [ M+H ] + =428).
SubDA-3 (15 g,35.1 mmol) and bis (pinacolato) diboron (9.8 g,38.6 mmol) are added to 300ml of 1, 4-di-under a nitrogen atmosphereIn an alkane, and the mixture was stirred and refluxed. Then, acetic acid is addedPotassium (5.2 g,52.6 mmol) was stirred thoroughly, followed by the addition of bis (dibenzylideneacetone) palladium (0) (0.6 g,1.1 mmol) and tricyclohexylphosphine (0.6 g,2.1 mmol). After 6 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.8g of subDA-4 (yield 65%, MS: [ M+H) ]+＝520)。
SubDA-4 (15 g,28.9 mmol) and Trz15 (9.6 g,30.3 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (12 g,86.6 mmol) was dissolved in 36ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13g of compounds 1 to 43 (yield 67%, MS: [ m+h ] +=675).
Synthesis examples 1 to 44
Formula DB (15 g,48.4 mmol) and phenylboronic acid (6.2 g,50.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.5g of subDB-1 (yield 56%, MS: [ M+H ] +=352).
SubDB-1 (15 g,42.6 mmol) and bis (pinacolato) diboron (11.9 g,46.9 mmol) were added to 300ml of 1, 4-bis under a nitrogen atmosphereIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (6.3 g,63.9 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.7 g,1.3 mmol) and tricyclohexylphosphine (0.7 g,2.6 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.9g of subDB-2 (yield 63%, MS: [ M+H ]]+＝444)。
SubDB-2 (15 g,33.8 mmol) and Trz6 (12.7 g,35.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14 g,101.5 mmol) was dissolved in 42ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6g of compounds 1 to 44 (yield 63%, MS: [ m+h ] +=639).
Synthesis examples 1 to 45
SubDB-2 (15 g,33.8 mmol) and Trz27 (12.2 g,35.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14 g,101.5 mmol) was dissolved in 42ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.8g of compounds 1 to 45 (yield 51%, MS: [ m+h ] +=625).
Synthesis examples 1 to 46
Formula DC (15 g,48.4 mmol) and phenylboronic acid (6.2 g,50.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.4g of subDC-1 (yield 61%, MS: [ m+h ] +=352).
SubDC-1 (15 g,42.6 mmol) and bis (pinacolato) diboron (11.9 g,46.9 mmol) were added to 300ml of 1, 4-di under nitrogen atmosphereIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (6.3 g,63.9 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.7 g,1.3 mmol) and tricyclohexylphosphine (0.7 g,2.6 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8g of subDC-2 (yield 68%, MS: [ M+H ]]+＝444)。
SubDC-2 (15 g,33.8 mmol) and Trz28 (13.3 g,35.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14 g,101.5 mmol) was dissolved in 42ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.3g of compounds 1 to 46 (yield 51%, MS: [ m+h ] +=655).
Synthesis examples 1 to 47
Chemical formula DD (15 g,48.4 mmol) and phenylboronic acid (6.2 g,50.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2g of subDD-1 (yield 66%, MS: [ M+H ] +=352).
SubDD-1 (15 g,42.6 mmol) and bis (pinacolato) diboron (11.9 g,46.9 mmol) are added to 300ml of 1, 4-diboron under a nitrogen atmosphereIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (6.3 g,63.9 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.7 g,1.3 mmol) and tricyclohexylphosphine (0.7 g,2.6 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4g of subDD-2 (yield 71%, MS: [ M+H) ]+＝444)。
SubDD-2 (15 g,33.8 mmol) and Trz22 (14 g,35.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14 g,101.5 mmol) was dissolved in 42ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.5g of compounds 1 to 47 (yield 68%, MS: [ m+h ] +=675).
Synthesis examples 1 to 48
Chemical formula DD (15 g,48.4 mmol) and [1,1' -biphenyl ] -4-ylboronic acid (10.1 g,50.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2g of subDD-3 (yield 59%, MS: [ M+H ] + =428).
SubDD-3 (15 g,35.1 mmol) and bis (pinacolato) diboron (9.8 g,38.6 mmol) are added to 300ml of 1, 4-bis under nitrogenIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (5.2 g,52.6 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.6 g,1.1 mmol) and tricyclohexylphosphine (0.6 g,2.1 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9g of subDD-4 (yield 71%, MS: [ M+H)]+＝520)。
SubDD-4 (15 g,28.9 mmol) and Trz18 (10.8 g,30.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (12 g,86.6 mmol) was dissolved in 36ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.6g of compounds 1 to 48 (yield 61%, MS: [ m+h ] +=715).
Synthesis examples 1 to 49
Chemical formula DD (15 g,48.4 mmol) and dibenzo [ b, d ] furan-2-ylboronic acid (10.8 g,50.8 mmol) were added to 300ml THF under a nitrogen atmosphere and the mixture stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.7g of subDD-5 (yield 55%, MS: [ M+H ] +=442).
SubDD-5 (15 g,33.9 mmol) and bis (pinacolato) diboron (9.5 g,37.3 mmol) are added to 300ml of 1, 4-bis under nitrogenIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (5 g,50.9 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.6 g,1 mmol) and tricyclohexylphosphine (0.6 g,2 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, will It was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11g of subDD-6 (yield 61%, MS: [ M+H ]]+＝534)。
SubDD-6 (15 g,28.1 mmol) and Trz5 (7.9 g,29.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (11.7 g,84.4 mmol) was dissolved in 35ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4g of compounds 1 to 49 (yield 69%, MS: [ m+h ] +=639).
Synthesis examples 1 to 50
Chemical formula DE (15 g,48.4 mmol) and phenylboronic acid (6.2 g,50.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.9g of subDE-1 (yield 70%, MS: [ M+H ] +=352).
SubDE-1 (15 g,42.6 mmol) and bis (pinacolato) diboron (11.9 g,46.9 mmol) are added to 300ml of 1, 4-bis under nitrogenIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (6.3 g,63.9 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.7 g,1.3 mmol) and tricyclohexylphosphine (0.7 g,2.6 mmol). After 7 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8g of subDE-2 (yield 68%, MS: [ M+H ]]+＝444)。
SubDE-2 (15 g,33.8 mmol) and Trz29 (13.3 g,35.5 mmol) are added to 300ml THF under nitrogen and the mixture is stirred and refluxed. Then, potassium carbonate (14 g,101.5 mmol) was dissolved in 42ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.6g of compound 1-50 (yield 57%, MS: [ m+h ] +=655).
Synthesis examples 1 to 51
Chemical formula DE (15 g,48.4 mmol) and naphthalen-2-ylboronic acid (8.7 g,50.8 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.1g of subDE-3 (yield 52%, MS: [ M+H ] + =402).
SubDE-3 (15 g,37.3 mmol) and bis (pinacolato) diboron (10.4 g,41.1 mmol) are added to 300ml of 1, 4-di-boron under nitrogen atmosphereIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (5.5 g,56 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.6 g,1.1 mmol) and tricyclohexylphosphine (0.6 g,2.2 mmol). After 6 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1g of subDE-4 (yield 71%, MS: [ M+H ] ]+＝494)。
SubDE-4 (15 g,30.4 mmol) and Trz27 (11 g,31.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (12.6 g,91.2 mmol) was dissolved in 38ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.9g of the compound 1-51 (yield 68%, MS: [ m+h ] +=675).
Synthesis examples 1 to 52
Formula DF (15 g,48.4 mmol) and phenylboronic acid (6.2 g,50.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11g of subDF-1 (yield 65%, MS: [ M+H ] +=352).
SubDF-1 (15 g,42.6 mmol) and Trz30 (21.5 g,44.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.7 g,127.9 mmol) was dissolved in 53ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.5g of compounds 1 to 52 (yield 58%, MS: [ m+h ] + =751).
Synthesis examples 1 to 53
SubDF-1 (15 g,42.6 mmol) and bis (pinacolato) diboron (11.9 g,46.9 mmol) were added to 300ml of 1, 4-bis under nitrogenIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (6.3 g,63.9 mmol) was added and stirred thoroughly, followed by bis (dibenzylideneacetone) palladium (0) (0.7 g,1.3 mmol) and tricyclohexylphosphine (0.7 g,2.6 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated using chloroform and water, and distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2g of subDF-2 (yield 75%, MS: [ M+H) ]+＝444)。
SubDF-2 (15 g,33.8 mmol) and Trz31 (13.1 g,35.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14 g,101.5 mmol) was dissolved in 42ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9g of compounds 1 to 53 (yield 59%, MS: [ m+h ] +=649).
Synthesis example 2-1
SubAA-3 (10 g,29.8 mmol), amine 1 (12.6 g,29.8 mmol) and sodium tert-butoxide (9.5 g,44.7 mmol) were added to 200ml xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4g of compound 2-1 (yield 58%, MS: [ m+h ] +=721).
Synthesis example 2-2
SubAA-3 (10 g,29.8 mmol), amine 2 (10.3 g,29.8 mmol) and sodium tert-butoxide (9.5 g,44.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1g of compound 2-2 (yield 63%, MS: [ m+h ] +=645).
Synthesis examples 2 to 3
SubAA-3 (10 g,29.8 mmol), amine 3 (10.5 g,29.8 mmol) and sodium tert-butoxide (9.5 g,44.7 mmol) were added to 200ml xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4g of compound 2-3 (yield 64%, MS: [ m+h ] + =651).
Synthesis examples 2 to 4
SubAA-3 (15 g,44.7 mmol) and amine 4 (20.7 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.4g of compound 2-4 (yield 56%, MS: [ m+h ] +=697).
Synthesis examples 2 to 5
Chemical formula AA (15 g,51 mmol) and phenylboronic acid (6.5 g,53.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.2g of sub AA-4 (yield 54%, MS: [ M+H ] +=336).
SubAA-4 (15 g,38.9 mmol) and amine 5 (17 g,40.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (16.1 g,116.6 mmol) was dissolved in 48ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.3g of compound 2-5 (yield 69%, MS: [ m+h ] +=721).
Synthesis examples 2 to 6
SubAB-1 (10 g,29.8 mmol), amine 6 (12.3 g,29.8 mmol) and sodium tert-butoxide (9.5 g,44.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3g of compound 2-6 (yield 63%, MS: [ m+h ] +=711).
Synthesis examples 2 to 7
SubAB-1 (10 g,29.8 mmol), amine 7 (10.4 g,29.8 mmol) and sodium t-butoxide (9.5 g,44.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.4g of compound 2-7 (yield 54%, MS: [ m+h ] +=649).
Synthesis examples 2 to 8
SubAB-1 (15 g,44.7 mmol) and amine 8 (24.9 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.7g of compound 2-8 (yield 59%, MS: [ m+h ] +=787).
Synthesis examples 2 to 9
SubAB-1 (15 g,44.7 mmol) and amine 9 (26.6 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.6g of compound 2-9 (yield 56%, MS: [ m+h ] +=823).
Synthesis examples 2 to 10
Chemical formula AB (15 g,51 mmol) and [1,1' -biphenyl ] -4-ylboronic acid (10.6 g,53.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2g of subeb-3 (yield 58%, MS: [ m+h ] +=412).
SubAB-3 (10 g,24.3 mmol), amine 10 (6 g,24.3 mmol) and sodium tert-butoxide (7.7 g,36.4 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.4g of compound 2-10 (yield 56%, MS: [ m+h ] +=621).
Synthesis examples 2 to 11
Chemical formula AC (15 g,51 mmol) and phenylboronic acid (6.5 g,53.5 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.6g of subarc-3 (yield 56%, MS: [ m+h ] +=336).
SubAC-3 (10 g,29.8 mmol), amine 11 (13.3 g,29.8 mmol) and sodium tert-butoxide (9.5 g,44.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6g of compound 2-11 (yield 52%, MS: [ m+h ] +=747).
Synthesis examples 2 to 12
SubAC-3 (10 g,29.8 mmol), amine 12 (11.1 g,29.8 mmol) and sodium tert-butoxide (9.5 g,44.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8g of compound 2-12 (yield 64%, MS: [ m+h ] +=671).
Synthesis examples 2 to 13
SubAC-3 (10 g,29.8 mmol), amine 13 (10.8 g,29.8 mmol) and sodium tert-butoxide (9.5 g,44.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.4g of compound 2-13 (yield 53%, MS: [ m+h ] +=661).
Synthesis examples 2 to 14
SubAC-3 (15 g,44.7 mmol) and amine 14 (19.5 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.9g of compound 2-14 (yield 53%, MS: [ m+h ] +=671).
Synthesis examples 2 to 15
SubAC-3 (15 g,44.7 mmol) and amine 15 (20.7 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.9g of compound 2-15 (yield 64%, MS: [ m+h ] +=697).
Synthesis examples 2 to 16
Chemical formula AC (15 g,51 mmol) and naphthalen-2-ylboronic acid (9.2 g,53.5 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11g of subarac-4 (yield 56%, MS: [ m+h ] +=386).
SubAC-4 (10 g,25.9 mmol), amine 16 (8.3 g,25.9 mmol) and sodium tert-butoxide (8.3 g,38.9 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.7g of compound 2-16 (yield 56%, MS: [ m+h ] +=671).
Synthesis examples 2 to 17
SubAD-1 (10 g,29.8 mmol), amine 17 (12.6 g,29.8 mmol) and sodium tert-butoxide (9.5 g,44.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6g of compound 2-17 (yield 54%, MS: [ m+h ] +=721).
Synthesis examples 2 to 18
SubAD-1 (15 g,44.7 mmol) and amine 18 (26.6 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.9g of compound 2-18 (yield 57%, MS: [ m+h ] +=823).
Synthesis examples 2 to 19
SubAD-1 (10 g,29.8 mmol), amine 19 (12.2 g,29.8 mmol) and sodium tert-butoxide (9.5 g,44.7 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6g of compounds 2 to 19 (yield 55%, MS: [ m+h ] +=710).
Synthesis examples 2 to 20
SubAD-1 (15 g,44.7 mmol) and amine 20 (21.4 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.2g of compound 2-20 (yield 70%, MS: [ m+h ] +=712).
Synthesis examples 2 to 21
Chemical formula AD (15 g,51 mmol) and naphthalen-2-ylboronic acid (9.2 g,53.5 mmol) were added to 300ml of THF under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4g of subAD-5 (yield 63%, MS: [ M+H ] +=386).
SubAD-5 (10 g,25.9 mmol), amine 21 (7.7 g,25.9 mmol) and sodium t-butoxide (8.3 g,38.9 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.7g of compound 2-21 (yield 64%, MS: [ m+h ] +=645).
Synthesis examples 2 to 22
SubAE-1 (10 g,29.8 mmol), amine 22 (12.6 g,29.8 mmol) and sodium tert-butoxide (9.5 g,44.7 mmol) were added to 200ml xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6g of compound 2-22 (yield 54%, MS: [ m+h ] +=721).
Synthesis examples 2 to 23
SubAE-1 (15 g,44.7 mmol) and amine 23 (25.4 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.2g of compound 2-23 (yield 54%, MS: [ m+h ] +=797).
Synthesis examples 2 to 24
SubAE-1 (15 g,44.7 mmol) and amine 24 (23 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21g of compound 2-24 (yield 63%, MS: [ m+h ] +=747).
Synthesis examples 2 to 25
Formula AE (15 g,51 mmol) and [1,1' -biphenyl ] -4-ylboronic acid (10.6 g,53.5 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.1g of sub AE-4 (yield 53%, MS: [ M+H ] +=412).
SubAE-4 (10 g,24.3 mmol), amine 16 (7.8 g,24.3 mmol) and sodium tert-butoxide (7.7 g,36.4 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11g of compound 2-25 (yield 65%, MS: [ m+h ] +=697).
Synthesis examples 2 to 26
SubAF-1 (15 g,44.7 mmol) and amine 25 (20.7 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.6g of compound 2-26 (yield 54%, MS: [ m+h ] +=773).
Synthesis examples 2 to 27
SubBA-3 (15 g,44.7 mmol) and amine 26 (23 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20g of compounds 2 to 27 (yield 60%, MS: [ m+h ] +=747).
Synthesis examples 2 to 28
SubBA-3 (15 g,44.7 mmol) and amine 27 (22.1 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.2g of compounds 2 to 28 (yield 53%, MS: [ m+h ] +=727).
Synthesis examples 2 to 29
SubBA-3 (15 g,44.7 mmol) and amine 28 (20.7 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.4g of compounds 2 to 29 (yield 56%, MS: [ m+h ] +=697).
Synthesis examples 2 to 30
SubBB-1 (10 g,29.8 mmol), amine 29 (11.1 g,29.8 mmol) and sodium tert-butoxide (9.5 g,44.7 mmol) were added to 200ml of xylene under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.4g of compound 2-30 (yield 52%, MS: [ m+h ] +=671).
Synthesis examples 2 to 31
SubBB-1 (10 g,29.8 mmol), amine 30 (11.8 g,29.8 mmol) and sodium tert-butoxide (9.5 g,44.7 mmol) were added to 200ml of xylene under nitrogen, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2g of compound 2-31 (yield 59%, MS: [ m+h ] +=697).
Synthesis examples 2 to 32
SubBB-1 (15 g,44.7 mmol) and amine 31 (23 g,46.9 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.7g of compound 2-32 (yield 68%, MS: [ m+h ] +=747).
Synthesis examples 2 to 33
SubBB-1 (15 g,44.7 mmol) and amine 31 (23 g,46.9 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.7g of compound 2-32 (yield 68%, MS: [ m+h ] +=747).
Synthesis examples 2 to 34
Chemical formula BC (15 g,51 mmol) and phenylboronic acid (6.5 g,53.5 mmol) are added to 300ml THF under nitrogen and the mixture is stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.7g of subBC-3 (yield 57%, MS: [ m+h ] +=336).
SubBC-3 (10 g,29.8 mmol), amine 33 (12.3 g,29.8 mmol) and sodium tert-butoxide (9.5 g,44.7 mmol) are added to 200ml of xylene under nitrogen and the mixture is stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7g of compound 2-34 (yield 65%, MS: [ m+h ] +=711).
Synthesis examples 2 to 35
SubBC-3 (10 g,29.8 mmol), amine 34 (13.3 g,29.8 mmol) and sodium tert-butoxide (9.5 g,44.7 mmol) are added to 200ml of xylene under nitrogen and the mixture is stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12g of compounds 2 to 35 (yield 54%, MS: [ m+h ] +=747).
SubBC-3 (15 g,44.7 mmol) and amine 35 (19.5 g,46.9 mmol) are added to 300ml THF under nitrogen and the mixture is stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.9g of compound 2-36 (yield 53%, MS: [ m+h ] +=671).
Synthesis examples 2 to 36
SubBC-3 (15 g,44.7 mmol) and amine 36 (18.5 g,46.9 mmol) are added to 300ml THF under nitrogen and the mixture is stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16g of compound 2-37 (yield 55%, MS: [ m+h ] +=651).
Synthesis examples 2 to 37
SubBD-3 (15 g,38.9 mmol) and amine 42 (18.6 g,40.8 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (16.1 g,116.6 mmol) was dissolved in 48ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16g of compounds 2-37 (yield 54%, MS: [ m+h ] +=761).
Synthesis examples 2 to 38
Chemical formula BC (15 g,51 mmol) and [1,1' -biphenyl ] -4-ylboronic acid (10.6 g,53.5 mmol) are added to 300ml THF under nitrogen and the mixture is stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13g of subBC-4 (yield 62%, MS: [ m+h ] +=412).
SubBC-4 (10 g,24.3 mmol), amine 37 (9.7 g,24.3 mmol) and sodium tert-butoxide (7.7 g,36.4 mmol) are added to 200ml of xylene under nitrogen and the mixture is stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2g of compound 2-38 (yield 60%, MS: [ m+h ] +=773).
Synthesis examples 2 to 39
SubBD-1 (10 g,29.8 mmol), amine 38 (10.3 g,29.8 mmol) and sodium tert-butoxide (9.5 g,44.7 mmol) were added to 200ml of xylene under a nitrogen atmosphere and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3g of compound 2-39 (yield 64%, MS: [ m+h ] +=645).
Synthesis examples 2 to 40
SubBD-1 (10 g,29.8 mmol), amine 39 (11.1 g,29.8 mmol) and sodium tert-butoxide (9.5 g,44.7 mmol) were added to 200ml of xylene under a nitrogen atmosphere and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10g of compound 2-40 (yield 50%, MS: [ m+h ] +=671).
Synthesis examples 2 to 41
SubBD-1 (10 g,29.8 mmol), amine 40 (11.1 g,29.8 mmol) and sodium tert-butoxide (9.5 g,44.7 mmol) were added to 200ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11g of compound 2-41 (yield 55%, MS: [ m+h ] +=671).
Synthesis examples 2 to 42
SubBD-1 (10 g,29.8 mmol), amine 41 (13.3 g,29.8 mmol) and sodium tert-butoxide (9.5 g,44.7 mmol) were added to 200ml of xylene under a nitrogen atmosphere and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2g of compound 2-42 (yield 64%, MS: [ m+h ] +=747).
Synthesis examples 2 to 43
Chemical formula BD (15 g,51 mmol) and naphthalen-2-ylboronic acid (9.2 g,53.5 mmol) were added to 300ml THF under a nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,153 mmol) was dissolved in 63ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.6g of subBD-3 (yield 64%, MS: [ M+H ] +=386).
SubBD-3 (15 g,38.9 mmol) and amine 42 (18.6 g,40.8 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (16.1 g,116.6 mmol) was dissolved in 48ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.8g of compound 2-43 (yield 50%, MS: [ m+h ] +=761).
Synthesis examples 2 to 44
Sube-1 (15 g,44.7 mmol) and amine 43 (22 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.1g of compound 2-44 (yield 62%, MS: [ m+h ] +=725).
Synthesis examples 2 to 45
Sube-1 (15 g,44.7 mmol) and amine 44 (22.6 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21g of compound 2-45 (yield 64%, MS: [ m+h ] +=737).
Synthesis examples 2 to 46
Sube-1 (15 g,44.7 mmol) and amine 45 (24.3 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.3g of compound 2-46 (yield 53%, MS: [ m+h ] +=773).
Synthesis examples 2 to 47
Sube-2 (10 g,25.9 mmol), amine 37 (10.3 g,25.9 mmol) and sodium tert-butoxide (8.3 g,38.9 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4g of compound 2-47 (yield 64%, MS: [ m+h ] +=747).
Synthesis examples 2 to 48
SubBF-1 (15 g,44.7 mmol) and amine 46 (23 g,46.9 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.7g of compound 2-48 (yield 59%, MS: [ m+h ] +=747).
Synthesis examples 2 to 49
SubBF-1 (10 g,29.8 mmol), amine 47 (8.8 g,29.8 mmol) and sodium tert-butoxide (9.5 g,44.7 mmol) were added to 200ml of xylene under a nitrogen atmosphere and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9g of compounds 2 to 49 (yield 51%, MS: [ m+h ] +=595).
Synthesis examples 2 to 50
SubBF-1 (15 g,44.7 mmol) and amine 48 (26.6 g,46.9 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.5 g,134 mmol) was dissolved in 56ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.1g of compound 2-50 (yield 52%, MS: [ m+h ] +=823).
Synthesis examples 2 to 51
SubBF-2 (10 g,25.9 mmol), amine 49 (8.7 g,25.9 mmol) and sodium tert-butoxide (8.3 g,38.9 mmol) were added to 200ml of xylene under a nitrogen atmosphere and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.4g of compound 2-51 (yield 53%, MS: [ m+h ] +=685).
Synthesis examples 2 to 52
SubBF-2 (15 g,38.9 mmol) and amine 50 (21.1 g,40.8 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (16.1 g,116.6 mmol) was dissolved in 48ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.6g of compound 2-52 (yield 55%, MS: [ m+h ] +=823).
Synthesis examples 2 to 53
SubCA-1 (10 g,28.4 mmol), amine 51 (12.7 g,28.4 mmol) and sodium tert-butoxide (9 g,42.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11g of compound 2-53 (yield 51%, MS: [ m+h ] +=763).
Synthesis examples 2 to 54
SubCA-1 (10 g,28.4 mmol), amine 52 (11 g,28.4 mmol) and sodium tert-butoxide (9 g,42.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.9g of compound 2-54 (yield 60%, MS: [ m+h ] +=701).
Synthesis examples 2 to 55
SubCA-1 (15 g,42.6 mmol) and amine 53 (24.5 g,44.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.7 g,127.9 mmol) was dissolved in 53ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.1g of compound 2-55 (yield 52%, MS: [ m+h ] +=819).
Synthesis examples 2 to 56
SubCA-2 (15 g,37.3 mmol) and amine 35 (16.3 g,39.2 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (15.5 g,112 mmol) was dissolved in 46ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.9g of compound 2-56 (yield 65%, MS: [ m+h ] +=737).
Synthesis examples 2 to 57
SubCB-3 (10 g,28.4 mmol), amine 54 (12 g,28.4 mmol) and sodium tert-butoxide (9 g,42.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4g of compound 2-57 (yield 64%, MS: [ m+h ] +=737).
Synthesis examples 2 to 58
SubCB-3 (10 g,29.8 mmol), amine 55 (11.8 g,29.8 mmol) and sodium tert-butoxide (9.5 g,44.7 mmol) were added to 200ml xylene under nitrogen and the mixture stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4g of compound 2-58 (yield 63%, MS: [ m+h ] +=713).
Synthesis examples 2 to 59
SubCB-3 (15 g,42.6 mmol) and amine 56 (21.5 g,44.8 mmol) are added to 300ml THF under nitrogen and the mixture is stirred and refluxed. Then, potassium carbonate (17.7 g,127.9 mmol) was dissolved in 53ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.4g of compound 2-59 (yield 70%, MS: [ m+h ] +=753).
Synthesis examples 2 to 60
SubCB-3 (15 g,42.6 mmol) and amine 57 (22 g,44.8 mmol) are added to 300ml THF under nitrogen and the mixture is stirred and refluxed. Then, potassium carbonate (17.7 g,127.9 mmol) was dissolved in 53ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.1g of compound 2-60 (yield 65%, MS: [ m+h ] +=763).
Synthesis examples 2 to 61
SubCB-3 (15 g,42.6 mmol) and amine 58 (21.5 g,44.8 mmol) are added to 300ml THF under nitrogen and the mixture is stirred and refluxed. Then, potassium carbonate (17.7 g,127.9 mmol) was dissolved in 53ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.5g of compound 2-61 (yield 64%, MS: [ m+h ] +=753).
Synthesis examples 2 to 62
SubCB-3 (15 g,42.6 mmol) and amine 59 (22 g,44.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.7 g,127.9 mmol) was dissolved in 53ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.1g of compound 2-62 (yield 62%, MS: [ m+h ] +=763).
Synthesis examples 2 to 63
Chemical formula CB (15 g,48.4 mmol) and [1,1' -biphenyl ] -4-ylboronic acid (10.1 g,50.8 mmol) are added to 300ml THF under nitrogen and the mixture is stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8g of subCB-4 (yield 67%, MS: [ m+h ] + =428).
SubCB-4 (10 g,25.9 mmol), amine 10 (6.4 g,25.9 mmol) and sodium tert-butoxide (8.3 g,38.9 mmol) were added to 200ml xylene under nitrogen and the mixture stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.9g of compound 2-63 (yield 60%, MS: [ m+h ] +=637).
Synthesis examples 2 to 64
SubCC-1 (10 g,28.4 mmol), amine 60 (12.7 g,28.4 mmol) and sodium tert-butoxide (9 g,42.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.1g of compound 2-64 (yield 52%, MS: [ m+h ] +=687).
Synthesis examples 2 to 65
SubCC-1 (10 g,28.4 mmol), amine 61 (11 g,28.4 mmol) and sodium tert-butoxide (9 g,42.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2g of compound 2-65 (yield 63%, MS: [ m+h ] +=737).
Synthesis examples 2 to 66
SubCC-1 (15 g,42.6 mmol) and amine 62 (22 g,44.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.7 g,127.9 mmol) was dissolved in 53ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.5g of compound 2-66 (yield 54%, MS: [ m+h ] +=763).
Synthesis examples 2 to 67
SubCC-1 (15 g,42.6 mmol) and amine 63 (23.7 g,44.8 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (17.7 g,127.9 mmol) was dissolved in 53ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.5g of compound 2-67 (yield 57%, MS: [ m+h ] +=802).
Synthesis examples 2 to 68
Formula CC (15 g,48.4 mmol) and naphthalen-2-ylboronic acid (8.7 g,50.8 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.9g of subCC-3 (yield 51%, MS: [ m+h ] +=402).
SubCC-3 (10 g,24.9 mmol), amine 16 (8 g,24.9 mmol) and sodium tert-butoxide (7.9 g,37.3 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.1g of compound 2-68 (yield 59%, MS: [ m+h ] +=687).
Synthesis examples 2 to 69
SubCD-1 (10 g,28.4 mmol), amine 64 (10.6 g,28.4 mmol) and sodium tert-butoxide (9 g,42.6 mmol) were added to 200ml xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.7g of compounds 2 to 69 (yield 65%, MS: [ m+h ] +=687).
Synthesis examples 2 to 70
SubCD-1 (10 g,28.4 mmol), amine 65 (11.3 g,28.4 mmol) and sodium tert-butoxide (9 g,42.6 mmol) were added to 200ml xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.3g of compound 2-70 (yield 56%, MS: [ m+h ] +=713).
Synthesis examples 2 to 71
SubCD-1 (15 g,42.6 mmol) and amine 66 (25.1 g,44.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.7 g,127.9 mmol) was dissolved in 53ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.4g of compound 2-71 (yield 66%, MS: [ m+h ] +=833).
Synthesis examples 2 to 72
Chemical formula CD (15 g,48.4 mmol) and naphthalen-2-ylboronic acid (8.7 g,50.8 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.6g of subCD-5 (yield 65%, MS: [ m+h ] +=402).
SubCD-5 (10 g,24.9 mmol), amine 21 (7.3 g,24.9 mmol) and sodium tert-butoxide (7.9 g,37.3 mmol) were added to 200ml xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.5g of compound 2-72 (yield 64%, MS: [ m+h ] +=661).
Synthesis examples 2 to 73
SubCE-3 (10 g,28.4 mmol), amine 67 (12.7 g,28.4 mmol) and sodium tert-butoxide (9 g,42.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4g of compound 2-73 (yield 62%, MS: [ m+h ] +=763).
Synthesis examples 2 to 74
SubCE-3 (10 g,28.4 mmol), amine 17 (12 g,28.4 mmol) and sodium tert-butoxide (9 g,42.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.7g of compound 2-74 (yield 56%, MS: [ m+h ] +=737).
Synthesis examples 2 to 75
SubCE-3 (15 g,42.6 mmol) and amine 68 (24.2 g,44.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.7 g,127.9 mmol) was dissolved in 53ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.7g of compound 2-75 (yield 57%, MS: [ m+h ] +=813).
Synthesis examples 2 to 76
SubCE-3 (15 g,42.6 mmol) and amine 69 (22 g,44.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.7 g,127.9 mmol) was dissolved in 53ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.2g of compound 2-76 (yield 59%, MS: [ m+h ] +=763).
Synthesis examples 2 to 77
SubCE-1 (15 g,35.1 mmol) and amine 70 (13.4 g,36.8 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (14.5 g,105.2 mmol) was dissolved in 44ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.7g of compound 2-77 (yield 67%, MS: [ m+h ] +=713).
Synthesis examples 2 to 78
SubCF-1 (10 g,28.4 mmol), amine 71 (9.9 g,28.4 mmol) and sodium tert-butoxide (9 g,42.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.4g of compound 2-78 (yield 50%, MS: [ m+h ] +=665).
Synthesis examples 2 to 79
SubCF-1 (10 g,28.4 mmol), amine 72 (12.7 g,28.4 mmol) and sodium tert-butoxide (9 g,42.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13g of compound 2-79 (yield 60%, MS: [ m+h ] +=763).
Synthesis examples 2 to 80
SubCF-1 (15 g,42.6 mmol) and amine 73 (23.2 g,44.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.7 g,127.9 mmol) was dissolved in 53ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.5g of compound 2-80 (yield 64%, MS: [ m+h ] +=789).
Synthesis examples 2 to 81
Chemical formula CF (15 g,48.4 mmol) and [1,1' -biphenyl ] -4-ylboronic acid (10.1 g,50.8 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.8g of ubcf-4 (yield 57%, MS: [ m+h ] + =428).
SubCF-4 (15 g,35.1 mmol) and amine 25 (16.2 g,36.8 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (14.5 g,105.2 mmol) was dissolved in 44ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.2g of compound 2-81 (yield 55%, MS: [ m+h ] +=789).
Synthesis examples 2 to 82
Chemical formula DA (15 g,48.4 mmol) and phenylboronic acid (6.2 g,50.8 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.2g of subDA-4 (yield 60%, MS: [ M+H ] +=352).
SubDA-4 (10 g,28.4 mmol), amine 74 (12 g,28.4 mmol) and sodium tert-butoxide (9 g,42.6 mmol) were added to 200ml of xylene under nitrogen and the mixture stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.5g of compound 2-82 (yield 55%, MS: [ m+h ] +=737).
Synthesis examples 2 to 83
SubDA-4 (10 g,28.4 mmol), amine 75 (12 g,28.4 mmol) and sodium tert-butoxide (9 g,42.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.7g of compound 2-83 (yield 56%, MS: [ m+h ] +=737).
Synthesis examples 2 to 84
SubDA-4 (15 g,42.6 mmol) and amine 63 (23.7 g,44.8 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (17.7 g,127.9 mmol) was dissolved in 53ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.4g of compound 2-84 (yield 51%, MS: [ m+h ] +=802).
Synthesis examples 2 to 85
SubDB-1 (10 g,28.4 mmol), amine 40 (10.6 g,28.4 mmol) and sodium tert-butoxide (9 g,42.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.7g of compound 2-85 (yield 65%, MS: [ m+h ] +=687).
Synthesis examples 2 to 86
SubDB-1 (10 g,28.4 mmol), amine 76 (9.9 g,28.4 mmol) and sodium tert-butoxide (9 g,42.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.5g of compound 2-86 (yield 61%, MS: [ m+h ] +=665).
Synthesis examples 2 to 87
Formula DB (15 g,48.4 mmol) and [1,1' -biphenyl ] -4-ylboronic acid (10.1 g,50.8 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 9 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2g of subDB-3 (yield 54%, MS: [ M+H ] + =428).
SubDB-3 (15 g,35.1 mmol) and amine 77 (16.8 g,36.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (14.5 g,105.2 mmol) was dissolved in 44ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.9g of compound 2-87 (yield 60%, MS: [ m+h ] +=803).
Synthesis examples 2 to 88
SubDC-1 (10 g,28.4 mmol), amine 78 (9.5 g,28.4 mmol) and sodium tert-butoxide (9 g,42.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6g of compounds 2 to 88 (yield 63%, MS: [ m+h ] + =651).
Synthesis examples 2 to 89
SubDC-1 (15 g,42.6 mmol) and amine 79 (23.2 g,44.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.7 g,127.9 mmol) was dissolved in 53ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.2g of compound 2-89 (yield 60%, MS: [ m+h ] +=789).
Synthesis examples 2 to 90
Formula DC (15 g,48.4 mmol) and [1,1' -biphenyl ] -4-ylboronic acid (10.1 g,50.8 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6g of subDC-3 (yield 56%, MS: [ m+h ] + =428).
SubDC-3 (10 g,23.4 mmol), amine 37 (9.3 g,23.4 mmol) and sodium tert-butoxide (7.4 g,35.1 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.2g of compound 2-90 (yield 50%, MS: [ m+h ] +=789).
Synthesis examples 2 to 91
SubDD-1 (10 g,28.4 mmol), amine 65 (11.3 g,28.4 mmol) and sodium tert-butoxide (9 g,42.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1g of compound 2-91 (yield 60%, MS: [ m+h ] +=713).
Synthesis examples 2 to 92
SubDD-1 (10 g,28.4 mmol), amine 80 (12.7 g,28.4 mmol) and sodium tert-butoxide (9 g,42.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6g of compound 2-92 (yield 63%, MS: [ m+h ] +=763).
Synthesis examples 2 to 93
SubDD-1 (15 g,42.6 mmol) and amine 81 (20.8 g,44.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.7 g,127.9 mmol) was dissolved in 53ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.5g of compound 2-93 (yield 59%, MS: [ m+h ] +=737).
Synthesis examples 2 to 94
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SubDD-1 (15 g,42.6 mmol) and amine 82 (19.8 g,44.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.7 g,127.9 mmol) was dissolved in 53ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.6g of compound 2-94 (yield 58%, MS: [ m+h ] +=713).
Synthesis examples 2 to 95
Chemical formula DD (15 g,48.4 mmol) and naphthalen-2-ylboronic acid (8.7 g,50.8 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.9g of subDD-7 (yield 56%, MS: [ M+H ] + =402).
SubDD-7 (15 g,37.3 mmol) and amine 77 (17.8 g,39.2 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (15.5 g,112 mmol) was dissolved in 46ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.4g of compound 2-95 (yield 67%, MS: [ m+h ] +=777).
Synthesis examples 2 to 96
SubDE-1 (10 g,28.4 mmol), amine 78 (12.7 g,28.4 mmol) and sodium tert-butoxide (9 g,42.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.8g of compound 2-96 (yield 50%, MS: [ m+h ] +=763).
Synthesis examples 2 to 97
SubDE-1 (10 g,28.4 mmol), amine 79 (11.7 g,28.4 mmol) and sodium tert-butoxide (9 g,42.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4g of compound 2-97 (yield 55%, MS: [ m+h ] +=727).
Synthesis examples 2 to 98
SubDE-1 (15 g,42.6 mmol) and amine 80 (23.2 g,44.8 mmol) are added to 300ml THF under nitrogen and the mixture is stirred and refluxed. Then, potassium carbonate (17.7 g,127.9 mmol) was dissolved in 53ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 11 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.1g of compound 2-98 (yield 54%, MS: [ m+h ] +=789).
Synthesis examples 2 to 99
SubDE-1 (15 g,42.6 mmol) and amine 81 (25.4 g,44.8 mmol) are added to 300ml THF under nitrogen and the mixture is stirred and refluxed. Then, potassium carbonate (17.7 g,127.9 mmol) was dissolved in 53ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 10 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.2g of compound 2-99 (yield 65%, MS: [ m+h ] +=839).
Synthesis examples 2 to 100
SubDF-1 (10 g,28.4 mmol), amine 82 (10.6 g,28.4 mmol) and sodium t-butoxide (9 g,42.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.1g of compound 2-100 (yield 52%, MS: [ m+h ] +=687).
Synthesis examples 2 to 101
SubDF-1 (10 g,28.4 mmol), amine 19 (11.7 g,28.4 mmol) and sodium t-butoxide (9 g,42.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol) was added thereto. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.5g of compound 2-101 (yield 51%, MS: [ m+h ] +=726).
Synthesis examples 2 to 102
SubDF-1 (15 g,42.6 mmol) and amine 56 (21.5 g,44.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.7 g,127.9 mmol) was dissolved in 53ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.8g of compound 2-102 (yield 68%, MS: [ m+h ] +=753).
Synthesis examples 2 to 103
SubDF-1 (15 g,42.6 mmol) and amine 83 (21.1 g,44.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.7 g,127.9 mmol) was dissolved in 53ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.9g of compounds 2 to 103 (yield 63%, MS: [ m+h ] +=743).
Synthesis examples 2 to 104
Formula DF (15 g,48.4 mmol) and naphthalen-2-ylboronic acid (8.7 g,50.8 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (20 g,145.1 mmol) was dissolved in 60ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.6 g,0.5 mmol). After 8 hours of reaction, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.9g of subDF-3 (yield 51%, MS: [ M+H ] +=402).
SubDF-3 (15 g,37.3 mmol) and amine 50 (20.3 g,39.2 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (15.5 g,112 mmol) was dissolved in 46ml of water and then added to the mixture. After this time, it was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After reacting for 12 hours, cooling to room temperature was performed. Then, the organic layer was separated from the aqueous layer, and then the organic layer was distilled. Then, it was dissolved again in chloroform and washed twice with water. After that, the organic layer was separated, treated with anhydrous magnesium sulfate, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.6g of compounds 2 to 104 (yield 69%, MS: [ m+h ] +=839).
< examples and comparative examples >
Comparative example A
Coated with a coating having a thickness ofThe glass substrate as a thin film was put into distilled water in which a cleaning agent was dissolved, and subjected to ultrasonic cleaning. At this time, a product manufactured by Fischer co. Was used as a cleaner, and distilled water filtered twice using a filter manufactured by Millipore co. Was used as distilled water. After washing the ITO for 30 minutes, ultrasonic washing was repeated twice using distilled water for 10 minutes. After the washing with distilled water is completed, the substrate is ultrasonically washed with isopropanol, acetone and methanol solvents, dried, and then transferred to a plasma washer. In addition, the substrate was cleaned using oxygen plasma for 5 minutes and then transferred into a vacuum depositor.
On the prepared ITO transparent electrode, the following compound HI-1 was formed toThe following compound a-1 was p-doped at a concentration of 1.5% at the same time to form a hole injection layer. On the hole injection layer, the following compound HT-1 was vacuum deposited to form a thickness +.>Is provided. Then, on the hole transport layer, the following compound EB-1 was vacuum deposited to form a film having a thickness +.>Is a barrier to electrons. Then, the following compound RH-1 and the following compound Dp-7 were vacuum deposited on the EB-1 deposited film in a weight ratio of 98:2 to form a film having a thickness +. >Is provided. On the light-emitting layer, the following compound HB-1 was vacuum deposited to form a thickness +.>Is a hole blocking layer of (a). Vacuum depositing the following compound ET-1 and the following compound LiQ in a weight ratio of 2:1 on the hole blocking layer to form a thickness +.>Electron injection and transport layers of (a) are provided. Sequentially depositing lithium fluoride (LiF) and aluminum to a thickness of +.>And->To form a cathode. />
Above is passed throughIn the process, the deposition rate of the organic material is kept atTo->The deposition rate of lithium fluoride of the cathode is kept at +.>And maintaining the deposition rate of aluminum at +.>In addition, the vacuum during deposition was maintained at 2X 10 -7 To 5X 10 -6 The support, thereby manufacturing the organic light emitting device.
Examples 1 to 29
An organic light-emitting device was manufactured in the same manner as in comparative example a, except that the compound shown in table 1 was used instead of the compound RH-1 as a main body in the organic light-emitting device of comparative example a.
Comparative examples 1 to 7
An organic light-emitting device was manufactured in the same manner as in comparative example a, except that the compound shown in table 1 was used in place of the compound RH-1 in the organic light-emitting device of comparative example a as a main body. The compounds B-8 to B-14 listed in Table 1 are as follows.
Examples 30 to 75
An organic light-emitting device was manufactured in the same manner as in comparative example a, except that the compound EB-1 in the organic light-emitting device of comparative example a was replaced with the compound shown in table 2 as an electron blocking layer material.
Comparative examples 8 to 14
An organic light-emitting device was manufactured in the same manner as in comparative example a, except that the compound EB-1 in the organic light-emitting device of comparative example a was replaced with the compound shown in table 2 as an electron blocking layer material. The compounds B-1 to B-7 listed in Table 2 are as follows.
Examples 76 to 179
An organic light-emitting device was manufactured in the same manner as in comparative example a, except that the first and second hosts described in table 3 were used in a weight ratio of 1:1 instead of the compound RH-1 as a host in the organic light-emitting device of comparative example a.
< Experimental example >
For the organic light-emitting devices prepared in examples 1 to 179, comparative example a and comparative examples 1 to 14, the organic light-emitting devices were prepared by applying a current (15 mA/cm 2 ) The voltage, efficiency and lifetime were measured and the results are shown in tables 1 to 3 below. Lifetime (T95) means the time taken until the initial brightness (7,000 nits) decreases to 95%.
TABLE 1
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TABLE 2
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TABLE 3
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When current was applied to the organic light emitting devices manufactured according to examples 1 to 179 and comparative examples 1 to 14, the results shown in tables 1 to 3 were obtained.
As shown in tables 1 and 2, it can be seen that the organic light emitting device using the compound of the present disclosure for the light emitting layer or the electron blocking layer has a reduced driving voltage and increased efficiency and lifetime as compared to the case of using the compound of the comparative example.
Further, referring to Table 3, when A of chemical formula 1 therein 2 Compounds which are triazine substituents represented by the formula 1-b and wherein A 2 When the compounds which are amine substituents represented by chemical formula 1-c are co-deposited simultaneously and used as co-hosts, it can be seen that the driving voltage is reduced, and the efficiency and lifetime are increased, as compared to the case where a single material host is used.
In summary, it can be determined that when the compound of chemical formula 1 is used as a host or an electron blocking layer material of a red light emitting layer in a red device, the driving voltage, light emitting efficiency, and lifetime of the organic light emitting device can be improved.
[ reference numerals ]
1: substrate 2: anode
3: organic material layer 4: cathode electrode
5: hole injection layer 6: hole transport layer
7: electron blocking layer 8: light-emitting layer
9: hole blocking layer 10: electron transport layer 11: electron injection layer 12: electron injection and transport layers

Claims (10)

1. A compound represented by the following chemical formula 1:
[ chemical formula 1]
In the chemical formula 1 described above, a compound having the formula,
A 1 represented by the following chemical formula 1-a,
[ chemical formula 1-a ]
In the chemical formula 1-a described above,
the dashed line is fused to an adjacent ring,
x is O or S, and the X is O or S,
Ar 1 is C substituted or unsubstituted 6-60 An aryl group; or C comprising at least one heteroatom selected from N, O and S, substituted or unsubstituted 2-60 Heteroaryl, and
l is a single bond; substituted or unsubstituted C 6-60 Arylene groups; or C comprising at least one heteroatom selected from N, O and S, substituted or unsubstituted 2-60 Heteroarylene, and
A 2 represented by the following chemical formula 1-b or chemical formula 1-c,
[ chemical formula 1-b ]
[ chemical formula 1-c ]
In the chemical formulas 1-b and 1-c,
L 1 and L 2 Each independently is a single bond; substituted or unsubstituted C 6-60 Arylene groups; or C comprising at least one heteroatom selected from N, O and S, substituted or unsubstituted 2-60 A heteroarylene group,
Ar 2 to Ar 5 Each independently is a substituted or unsubstituted C 6-60 An aryl group; or C comprising at least one heteroatom selected from N, O and S, substituted or unsubstituted 2-60 A heteroaryl group, which is a group,
d is deuterium, and
n is an integer from 0 to 5.
2. A compound according to claim 1,
wherein the chemical formula 1 is represented by any one of the following chemical formulas 1-1 to 1-4:
[ chemical formula 1-1]
[ chemical formulas 1-2]
[ chemical formulas 1-3]
[ chemical formulas 1-4]
In the chemical formula 1-1 to the chemical formula 1-4,
L、X、L 1 、L 2 、Ar 1 to Ar 5 D and n are as defined in claim 1.
3. A compound according to claim 1,
wherein L is a single bond; a phenylene group; biphenyldiyl; naphthalene diyl; dibenzofurandiyl; or dibenzothiophenediyl.
4. A compound according to claim 1,
wherein Ar is 1 Is phenyl; a biphenyl group; a naphthyl group; dibenzofuranyl; or dibenzothienyl.
5. A compound according to claim 1,
wherein Ar is 2 And Ar is a group 3 Each independently is phenyl; a biphenyl group; a terphenyl group; a naphthyl group; phenanthryl; a naphthylphenyl group; phenanthryl phenyl; phenyl naphthyl; dibenzofuranyl; or dibenzothienyl.
6. A compound according to claim 1,
wherein L is 1 And L 2 Each independently is a single bond; a phenylene group; biphenyldiyl; or a naphthalenediyl group.
7. A compound according to claim 1,
wherein Ar is 4 And Ar is a group 5 Each independently is phenyl; a biphenyl group; a terphenyl group; a naphthyl group; phenyl naphthyl; a naphthylphenyl group; phenanthryl; 9, 9-dimethylfluorenyl; 9-phenylcarbazolyl; dibenzofuranyl; or dibenzothienyl.
8. A compound according to claim 1,
wherein the compound represented by chemical formula 1 is any one selected from the group consisting of:
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9. an organic light emitting device comprising: a first electrode; a second electrode disposed opposite to the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein at least one of the organic material layers comprises the compound according to any one of claims 1 to 8.
10. The organic light-emitting device according to claim 9,
wherein the organic material layer containing the compound is a light emitting layer and/or an electron blocking layer.
CN202280008925.3A 2021-03-30 2022-03-30 Novel compound and organic light emitting device comprising the same Pending CN116710459A (en)

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