CN117837301A - Organic light emitting device - Google Patents

Organic light emitting device Download PDF

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Publication number
CN117837301A
CN117837301A CN202280056278.3A CN202280056278A CN117837301A CN 117837301 A CN117837301 A CN 117837301A CN 202280056278 A CN202280056278 A CN 202280056278A CN 117837301 A CN117837301 A CN 117837301A
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mmol
compound
added
mixture
organic layer
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Chinese (zh)
Inventor
金旼俊
李东勋
徐尚德
金永锡
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020220152016A external-priority patent/KR20230071086A/en
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority claimed from PCT/KR2022/018004 external-priority patent/WO2023085908A1/en
Publication of CN117837301A publication Critical patent/CN117837301A/en
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Abstract

The present disclosure provides an organic light emitting device having improved driving voltage, efficiency, and lifetime.

Description

Organic light emitting device
Technical Field
Cross Reference to Related Applications
The present application claims the benefits of korean patent application No. 10-2021-0156950, filed on 11.15 of 2021, and korean patent application No. 10-2022-0152016, filed on 11.14 of 2022, the contents of which are incorporated herein by reference in their entirety.
The present disclosure relates to organic light emitting devices having improved driving voltages, efficiencies, and lifetimes.
Background
In general, an organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy by using an organic material. An organic light emitting device using the organic light emitting phenomenon has characteristics such as a wide viewing angle, excellent contrast, 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 literature ]
Patent document 1: korean unexamined patent publication No. 10-2000-0051826
Disclosure of Invention
Technical problem
It is an object of the present disclosure to provide an organic light emitting device having improved driving voltage, efficiency and lifetime.
Technical proposal
The present disclosure provides the following organic light emitting device:
an organic light emitting device, comprising:
an anode;
a cathode; and
a light-emitting layer interposed between the anode and the cathode,
wherein the light emitting layer includes a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2.
[ chemical formula 1]
In the chemical formula 1, the chemical formula is shown in the drawing,
X 1 to X 7 Each independently is CR 1 Or N, provided that X 1 To X 7 At least one of which is N,
each R is 1 Independently hydrogen; deuterium; substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-60 A heteroaryl group, which is a group,
L 1 to L 3 Each independently is a single bond; substituted or unsubstituted C 6-60 Arylene groups; or substituted or unsubstituted C comprising at least one selected from N, O and S 2-60 Heteroarylene group
Ar 1 And Ar is a group 2 Each independently is a substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C comprising at least one selected from N, O and S 2-60 A heteroaryl group, which is a group,
[ chemical formula 2]
In the chemical formula 2, the chemical formula is shown in the drawing,
Y 1 is N and Y 2 Is O; or Y 1 Is O and Y 2 Is a number of N, and is defined as,
r 'and R' 1 To R'. 6 In (a) and (b)Any one is a substituent represented by the following chemical formula 2A, and the remainder are hydrogen; deuterium; or C which is substituted or unsubstituted 6-60 An aryl group,
[ chemical formula 2A ]
In the chemical formula 2A, a compound having a chemical formula,
L' 1 to L' 3 Each independently is a single bond; or C which is substituted or unsubstituted 6-60 Arylene group
Ar' 1 And Ar' 2 Each independently is a substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C comprising at least one selected from N, O and S 2-60 Heteroaryl groups.
Advantageous effects
The above-described organic light emitting device includes the compound represented by chemical formula 1 and the compound represented by chemical formula 2, and thus can improve efficiency, achieve a low driving voltage, and/or improve lifetime characteristics in the organic light emitting device.
Drawings
Fig. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
Fig. 2 shows an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4.
Detailed Description
Hereinafter, embodiments of the present disclosure will be described in more detail to facilitate understanding of the present invention.
As used herein, a symbolOr->Meaning and additionallyA bond to which a substituent of (c) is attached.
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 heteroaryl groups comprising at least one of N, O and S atoms, or substituted with substituents that are unsubstituted or linked with two or more of the substituents exemplified above. For example, a "substituent in which two or more substituents are linked" may be a biphenyl group. That is, biphenyl may be aryl, or it may be interpreted as a substituent to which two phenyl groups are linked.
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 substituent having the following structural formula, but is not limited thereto.
In the present disclosure, the ester group may have a structure in which oxygen of the ester group may be substituted with a linear, branched, or cyclic alkyl group having 1 to 25 carbon atoms, or an aryl group having 6 to 25 carbon atoms. Specifically, the ester group may be a substituent 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 substituent having the following structural formula, but is not limited thereto.
In the present disclosure, the silyl group specifically includes, but is not limited to, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, and the like.
In the present disclosure, the boron group specifically includes trimethylboron group, triethylboron group, t-butyldimethylboroyl group, triphenylboron group, and phenylboron group, but is not limited thereto.
In the present disclosure, examples of halogen groups include fluorine, chlorine, bromine, or iodine.
In the present disclosure, the alkyl group may be straight or branched, and the carbon number thereof is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has a carbon number of 1 to 20. According to another embodiment, the alkyl group has a carbon number of 1 to 10. According to another embodiment, the alkyl group has a carbon number of 1 to 6. Specific examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like.
In the present disclosure, the alkenyl group may be straight or branched, and the carbon number thereof is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has a carbon number of 2 to 20. According to another embodiment, the alkenyl group has a carbon number of 2 to 10. According to yet another embodiment, the alkenyl group has a carbon number of 2 to 6. Specific examples thereof include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-diphenylvinyl-1-yl, 2-phenyl-2- (naphthalen-1-yl) vinyl-1-yl, 2-bis (diphenyl-1-yl) vinyl-1-yl, stilbene, styryl and the like, but are not limited thereto.
In the present disclosure, the cycloalkyl group is not particularly limited, but the carbon number thereof is preferably 3 to 60. According to one embodiment, the cycloalkyl group has a carbon number of 3 to 30. According to another embodiment, the cycloalkyl group has a carbon number of 3 to 20. According to yet another embodiment, the cycloalkyl group has a carbon number of 3 to 6. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-t-butylcyclohexyl, cycloheptyl, cyclooctyl and the like, but are not limited thereto.
In the present disclosure, the aryl group is not particularly limited, but the carbon number thereof is preferably 6 to 60, and it may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has a carbon number of 6 to 30. According to one embodiment, the aryl group has a carbon number of 6 to 20. As the monocyclic aryl group, an aryl group may be phenyl, biphenyl, terphenyl, or the like, but is not limited thereto. Polycyclic aryl groups include naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl,A base, etc., but is not limited thereto.
In the present disclosure, the fluorenyl group may be substituted, and two substituents may be linked to each other to form a spiro structure. In the case where the fluorenyl group is substituted, it may be formed Etc. However, the structure is not limited thereto.
In the present disclosure, heteroaryl groupsIs a heteroaryl group containing one or more of O, N, si and S as a heteroatom, and the carbon number thereof is not particularly limited, but is preferably 2 to 60. According to one embodiment, the heteroaryl group has a carbon number of 6 to 30. According to one embodiment, the heteroaryl group has a carbon number of 6 to 20. Examples of heteroaryl 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 foregoing examples of the aryl groups. In the present disclosure, the alkyl groups in the aralkyl group, alkylaryl group, and alkylamino group are the same as the aforementioned examples of the alkyl group. In the present disclosure, heteroaryl groups in heteroaryl amines may employ the foregoing description of heteroaryl groups. In the present disclosure, alkenyl groups in aralkenyl groups are the same as the aforementioned examples of alkenyl groups. 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 heteroaryl 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 heteroaryl groups may be applied, except that heteroaryl groups are not monovalent groups but are formed by combining two substituents.
Hereinafter, the present disclosure will be described in detail for each configuration.
Anode and cathode
The anode and cathode used in the present disclosure mean electrodes used in an organic light emitting device.
As the anode material, a material having a large work function is generally preferably used so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material include: metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides 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-dioxy) thiophene](PEDOT), polypyrrole and polyaniline; etc., but is not limited thereto.
As the cathode material, it is generally preferable to use a material having a small work function so that electrons can be easily injected into the organic material layer. Specific examples of the cathode material include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayer structural materials, e.g. LiF/Al or LiO 2 Al; etc., but is not limited thereto.
Hole injection layer
The organic light emitting device according to the present disclosure may further include a hole injection layer on the anode, if necessary.
The hole injection layer is a layer that injects holes from the electrode, and the hole injection material is preferably a compound of: it has a capability of transporting holes, has an effect of injecting holes in an anode and has an excellent hole injection effect to a light emitting layer or a light emitting material, prevents excitons generated in the light emitting layer from moving to an electron injection layer or an electron injection material, and is excellent in a capability of forming a thin film. Further, it is preferable that 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, polythiophene-based conductive polymer, and the like, but are not limited thereto.
Hole transport layer
The organic light emitting device according to the present disclosure may include a hole transport layer on the anode (or on the hole injection layer if present), if necessary.
The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer. The hole transport material is suitably a material having a large hole mobility, which can receive injection of holes from the anode or the hole injection layer and transfer the holes to the light emitting layer.
Specific examples of the hole transport material include an arylamine-based organic material, a conductive polymer, a block copolymer in which a conjugated moiety and a non-conjugated moiety are simultaneously present, and the like, but are not limited thereto.
Electron blocking layer
If necessary, the organic light emitting device according to the present disclosure includes an electron blocking layer on the hole transport layer.
The electron blocking layer means a layer disposed between the hole transport layer and the light emitting layer to prevent electrons injected in the cathode from being transferred to the hole transport layer without being recombined in the light emitting layer, and may also be referred to as an electron blocking layer or an electron suppressing layer. The electron blocking layer is preferably a material having a smaller electron affinity than the electron transport layer.
Light-emitting layer
The light emitting layer used in the present disclosure is a layer that can emit light in the visible light region by combining holes and electrons transported from the anode and the cathode. Generally, the light emitting layer includes a host material and a dopant material, and in the present disclosure, a compound represented by chemical formula 1 and a compound represented by chemical formula 2 are included as hosts.
Preferably X 1 To X 7 Any one of them is N and the others can be CR 1 。
Preferably, chemical formula 1 may be represented by any one of the following chemical formulas 1-1 to 1-7:
in chemical formulas 1-1 to 1-7,
R 1 、L 1 to L 3 、Ar 1 And Ar is a group 2 As defined in chemical formula 1.
Preferably, each R 1 May independently be hydrogen; deuterium; substituted or unsubstituted C 6-20 An aryl group; or substituted or unsubstituted C comprising at least one selected from N, O and S 2-20 Heteroaryl groups. More preferably, R 1 Is hydrogen, phenyl, biphenyl, naphthyl, carbazolyl, fluoranthenyl, phenanthryl, triphenylene, benzo [ a ]]Carbazolyl, benzo [ b ]]Carbazolyl and benzo [ c ]]Carbazolyl, dibenzofuranyl and benzo [ d ]]Naphtho [1,2-b]Furanyl and benzo [ d ]]Naphtho [2,3-b]Furanyl and benzo [ d ]]Naphtho [2,1-b]Furanyl and benzo [ d ]]Naphtho [1,2-b]Thienyl, benzo [ d ]]Naphtho [2,3-b]Thienyl, benzo [ d ]]Naphtho [2,1-b]Thienyl, benzo [ c ]]Phenanthryl group,A radical, phenyl naphthyl, or naphthylphenyl, provided that when R 1 When the compound is not hydrogen or deuterium, R 1 May be unsubstituted or substituted with at least one deuterium.
Preferably, R 1 One of them is phenyl, biphenyl, naphthyl, carbazolyl, fluoranthenyl, phenanthryl, triphenylene, benzo [ a ] ]Carbazolyl, benzo [ b ]]Carbazolyl and benzo [ c ]]Carbazolyl, dibenzofuranyl, and,Benzo [ d ]]Naphtho [1,2-b]Furanyl and benzo [ d ]]Naphtho [2,3-b]Furanyl and benzo [ d ]]Naphtho [2,1-b]Furanyl and benzo [ d ]]Naphtho [1,2-b]Thienyl, benzo [ d ]]Naphtho [2,3-b]Thienyl, benzo [ d ]]Naphtho [2,1-b]Thienyl, benzo [ c ]]Phenanthryl group,A radical, phenylnaphthyl, or naphthylphenyl, and the remainder may be hydrogen or deuterium, or each R 1 And may independently be hydrogen or deuterium.
Preferably L 1 To L 3 Each independently is a single bond; substituted or unsubstituted C 6-20 Arylene groups; or substituted or unsubstituted C comprising at least one selected from N, O and S 2-20 Heteroarylene group. More preferably L 1 To L 3 Each independently is a single bond, phenylene, naphthylene,provided that when L 1 To L 3 When not a single bond, L 1 To L 3 Unsubstituted or substituted with at least one deuterium.
Preferably L 1 Is a single bond, a naphthalene diyl group, L and 2 and L 3 Can be independently a single bond, phenylene, naphthylene,
preferably Ar 1 And Ar is a group 2 May each independently be a substituted or unsubstituted C 6-20 An aryl group; or substituted or unsubstituted C comprising at least one selected from N, O and S 2-20 Heteroaryl groups. More preferably Ar 1 And Ar is a group 2 Each independently ofThe three places are phenyl, biphenyl, terphenyl, naphthyl, fluoranthenyl, phenanthryl, dibenzofuranyl, dibenzothienyl, and the like,Radical, or benzo [ c ]]Phenanthryl, provided that Ar 1 And Ar is a group 2 May be unsubstituted or substituted with at least one deuterium.
Representative examples of the compound represented by chemical formula 1 are as follows:
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wherein X is 1 Is N, X 2 Is CR (CR) 1 And X 3 To X 7 The compound represented by chemical formula 1, which is CH, may be prepared by a preparation method as shown in the following reaction scheme 1-1 as an example, wherein X 1 Is N and X 2 To X 7 The compounds that are CH can be prepared by the preparation methods as shown in the following reaction schemes 1-2 as examples, and other remaining compounds can be prepared in a similar manner.
[ reaction scheme 1-1]
[ reaction schemes 1-2]
In schemes 1-1 and 1-2, R 1 、L 1 To L 3 、Ar 1 And Ar is a group 2 Z is the same as defined in chemical formula 1 1 And Z 2 Each independently is halogen, preferably Z 1 And Z 2 Each of which is a single pieceIndependently chlorine or bromine.
Schemes 1-1 and 1-2 are Suzuki coupling reactions, which are preferably carried out in the presence of a palladium catalyst and a base, and the reactive groups for the Suzuki coupling reactions may be varied as known in the art. Furthermore, an amine substitution reaction may be accompanied if necessary, and in this case, it is preferably carried out in the presence of a palladium catalyst and a base, and the reactive group for the amine substitution reaction may be changed as known in the art. The preparation method may be further embodied in the preparation examples described below.
Preferably, R 'and R' 1 To R'. 6 Any one of them is a substituent represented by the following chemical formula 2A, and the remainder may be hydrogen; deuterium; or C which is substituted or unsubstituted 6-20 Aryl groups. More preferably, R 'and R' 1 To R'. 6 Any one of them is a substituent represented by the following chemical formula 2A, and the remainder may be hydrogen; deuterium; phenyl unsubstituted or substituted with 1 to 5 deuterium; or naphthyl which is unsubstituted or substituted by 1 to 7 deuterium.
Preferably, chemical formula 2 may be represented by the following chemical formula 2-1 or chemical formula 2-2:
[ chemical formula 2-1]
[ chemical formula 2-2]
In chemical formula 2-1 and chemical formula 2-2,
Y 1 、Y 2 、R'、L' 1 to L' 3 、Ar' 1 And Ar' 2 As defined in chemical formula 2.
Preferably L' 1 To L' 3 Each independently may be a single bond; or C which is substituted or unsubstituted 6-20 Arylene groups. More preferably, L' 1 To L' 3 Can be independently a single bond, phenylene, biphenyldiyl, terphenyldiyl, naphthalenediyl, and, Provided that when L' 1 To L' 3 When not being a single bond, L' 1 To L' 3 May be unsubstituted or substituted with at least one deuterium. More preferably, L' 1 To L' 3 Each independently is a single bond, phenylene, biphenyldiyl, < >>Naphthalene diyl group, Provided that when L' 1 To L' 3 When not being a single bond, L' 1 To L' 3 Unsubstituted or substituted with at least one deuterium.
Preferably L' 1 Is a single bond, phenylene, biphenyldiyl, naphthalenediyl, orL 'and L' 2 And L' 3 Each independently may be a single bond or phenylene.
Preferably Ar' 1 And Ar' 2 May each independently be a substituted or unsubstituted C 6-20 An aryl group; or substituted or unsubstituted C comprising at least one selected from N, O and S 2-20 Heteroaryl groups. More preferably Ar' 1 And Ar' 2 Each independently is phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, dibenzofuranyl, dibenzothienyl, dimethylfluorenyl, carbazolyl, or phenylcarbazolyl, and Ar' 1 And Ar' 2 Can be unsubstituted or taken up by at least one deuteriumAnd (3) replacing.
Representative examples of the compound represented by chemical formula 2 are as follows:
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wherein L' 1 The compound represented by chemical formula 2, which is not a single bond and R 'is chemical formula 2A, can be prepared by a preparation method as shown in the following reaction scheme 2-1 as an example, wherein L' 1 The compound represented by chemical formula 2, which is a single bond and R' is chemical formula 2A, may be prepared by a preparation method as shown in the following reaction scheme 2-2 as an example, and other remaining compounds may be prepared in a similar manner.
[ reaction scheme 2-1]
[ reaction scheme 2-2]
In schemes 2-1 and 2-2, R' 1 To R'. 6 、Y 1 、Y 2 、L' 1 To L' 3 、Ar' 1 And Ar' 2 Identical to that defined in chemical formula 1, and Z' 1 And Z' 2 Is halogen, preferably Z 1 And Z 2 Is chlorine or bromine.
Reaction scheme 2-1 is a Suzuki coupling reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactive groups for the Suzuki coupling reaction may be varied as known in the art. Furthermore, reaction scheme 2-2 is an amine substitution reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactive groups for the amine substitution reaction may be varied as known in the art. The preparation method may be further embodied in the preparation examples described below.
Preferably, the weight ratio of the compound represented by chemical formula 1 to the compound represented by chemical formula 2 in the light emitting layer may be 10:90 to 90:10, more preferably 20:80 to 80:20, 30:70 to 70:30, or 40:60 to 60:40.
Meanwhile, the light emitting layer may further include a dopant in addition to the host. The dopant material is not particularly limited as long as it is a material for an organic light emitting device. As examples, aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like can be mentioned. Specific examples of the aromatic amine derivative include substituted or unsubstituted fused aromatic ring derivatives having an arylamino group, examples of which include pyrene, anthracene having an arylamino group, And bisindenopyrene, etc. Styrylamine compounds are compounds 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 styrylamine, styrylenediamine, styrylenetriamine, styrylenetetramine, and the like, but are not limited thereto. Further, examples of the metal complex include iridium complex, platinum complex, and the like, but are not limited thereto. At the position ofIn one example, one or more selected from the group consisting of, but not limited to, the following may be used as the dopant material: />
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Hole blocking layer
The organic light emitting device according to the present disclosure may include a hole blocking layer on the light emitting layer, if necessary.
The hole blocking layer is a layer provided between the electron transport layer and the light emitting layer to prevent holes injected in the anode from being transferred to the electron transport layer without being recombined in the light emitting layer, and may also be referred to as a hole suppressing layer or a hole blocking layer. The hole blocking layer is preferably a material having a large ionization energy.
Electron transport layer
The organic light emitting device according to the present disclosure may include an electron transport layer on the light emitting layer (or hole blocking layer), if necessary.
The electron transporting layer is a layer that receives electrons from the cathode or an electron injecting layer formed on the cathode and transports the electrons to the light emitting layer, and suppresses transfer of holes from the light emitting layer, and the electron transporting material is suitably a material such as: which can well receive injection of electrons from the cathode and transfer the electrons to the light emitting layer, and has a large electron mobility.
Specific examples of the electron transport material include: al complexes of 8-hydroxyquinoline; comprising Alq 3 Is a complex of (a) and (b); an organic radical compound; hydroxyflavone-metal complexes; etc., but is not limited thereto. The electron transport layer may be used with any desired cathode material as used according to conventional techniques. In particular, suitable examples of cathode materials are typical materials having a low work function, followed by an aluminum layer or a silver layer. Specific examples thereof include cesium and bariumCalcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.
Electron injection layer
The organic light emitting device according to the present disclosure may further include an electron injection layer on the light emitting layer (or on the electron transport layer if present) if necessary.
The electron injection layer is a layer that injects electrons from an electrode, and is preferably a compound that: it has an ability to transport electrons, has an effect of injecting electrons from a cathode and an excellent effect of injecting electrons into a light emitting layer or a light emitting material, prevents excitons generated from the light emitting layer from moving to a hole injecting layer, and is also excellent in an ability to form a thin film.
Specific examples of the electron injection layer 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.
Organic light emitting device
The structure of an organic light emitting device according to 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, a light emitting layer 3, and a cathode 4. Fig. 2 shows an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4.
The organic light emitting device according to the present disclosure may be manufactured by sequentially stacking the above-described structures. In this case, the organic light emitting device may be manufactured by: the respective layers described above are formed on the anode by depositing a metal, a metal oxide having conductivity, or an alloy thereof on the substrate using a PVD (physical vapor deposition) method such as a sputtering method or an electron beam evaporation method to form the anode, and then a material that can function as a cathode is deposited thereon. In addition to such a method, the organic light emitting device may also be manufactured by sequentially depositing a cathode material to an anode material on a substrate in the reverse order of the above-described configuration (WO 2003/012690). In addition, the light emitting layer may be formed by subjecting the host and the dopant to a vacuum deposition method and a solution coating method. Herein, the solution coating method means spin coating, dip coating, knife coating, ink jet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.
Meanwhile, the organic light emitting device according to the present disclosure may be a bottom light emitting device, a top light emitting device, or a double-sided light emitting device, and in particular, may be a bottom light emitting device requiring relatively high light emitting efficiency.
In the following, preferred embodiments are presented to aid in the understanding of the present disclosure. The following examples are provided for a better understanding of the present disclosure only and are not intended to limit the disclosure.
Synthesis example 1-1
Compound A (15 g,45.5 mmol) and compound Trz1 (15.2 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (-)0.2g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound sub A-1. (yield: 63%, MS: [ M+H) ] + ＝485)
Compound sub A-1 (15 g,30.9 mmol) and compound sub1 (7.2 g,32.5 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (12.8 g,92.8 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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: 60%, MS: [ M+H)] + ＝627)
Synthesis examples 1 to 2
Compound B (15 g,45.5 mmol) and compound Trz2 (12.8 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. Passing the concentrated compound through a silica gel column Purification by chromatography gave 13.6g of compound subsB-1. (yield: 69%, MS: [ M+H)] + ＝435)
Compound sub B-1 (15 g,34.5 mmol) and compound sub2 (9.9 g,36.2 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (14.3 g,103.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound 1-2. (yield: 67%, MS: [ M+H)] + ＝627)
Synthesis examples 1 to 3
Compound C (15 g,45.5 mmol) and compound Trz2 (12.8 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 the compound sub-1. (yield: 64%, MS: [ M+H ] ] + ＝435)
The compound sub-1 (15 g,34.5 mmol) and the compound sub3 (8.9 g,36.2 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (14.3 g,103.5 mmol) was dissolved in 100ml water and added to the mixtureThe mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compounds 1 to 3. (yield: 68%, MS: [ M+H)] + ＝601)
Synthesis examples 1 to 4
Compound D (15 g,45.5 mmol) and compound Trz3 (21.2 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 subD-1. (yield: 76%, MS: [ M+H) ] + ＝611)
Compound sub D-1 (15 g,24.5 mmol) and compound sub4 (3.1 g,25.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (10.2 g,73.6 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. Dissolving in chloroform again, washing twice with water, separating organic layer, adding anhydrous magnesium sulfate, stirring, and passingFiltered and the filtrate distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8g of compounds 1 to 4. (yield: 80%, MS: [ M+H)] + ＝653)
Synthesis examples 1 to 5
Compound E (15 g,50.8 mmol) and compound Trz4 (25 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.4g of compounds 1 to 5. (yield: 67%, MS: [ M+H) ] + ＝601)
Synthesis examples 1 to 6
Compound E (15 g,50.8 mmol) and compound Trz5 (25.8 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.4g of compounds 1-6. (yield: 65%, MS: [ M+H)] + ＝617)
Synthesis examples 1 to 7
Compound E (15 g,50.8 mmol) and compound Trz6 (28.5 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compounds 1 to 7. (yield: 61%, MS: [ M+H) ] + ＝667)
Synthesis examples 1 to 8
Compound E (15 g,50.8 mmol) and compound Trz7 (26.4 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.2g of compounds 1 to 8. (yield: 76%, MS: [ M+H)] + ＝627)
Synthesis examples 1 to 9
Compound F (15 g,45.5 mmol) and compound Trz8 (19.5 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17g of compound sub F-1. (yield: 65%, MS: [ M+H) ] + ＝575)
Compound sub F-1 (15 g,26.1 mmol) and compound sub4 (3.3 g,27.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (10.8 g,78.3 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 9. (yield: 80%, MS: [ M+H)] + ＝617)
Synthesis examples 1 to 10
Compound G (15G, 45.5 mmol) and compound Trz9 (20.7G, 47.8 mmol) were added to 300ml THF and mixedThe mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.9g of compound sub G-1. (yield: 80%, MS: [ M+H) ] + ＝601)
Compound sub G-1 (15 g,25 mmol) and compound sub5 (4.5 g,26.2 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (10.3 g,74.9 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 10. (yield: 75%, MS: [ M+H)] + ＝693)
Synthesis examples 1 to 11
Compound G (15G, 45.5 mmol) and compound Trz2 (12.8G, 47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. Re-dissolving it in In chloroform, the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound sub G-2. (yield: 70%, MS: [ M+H ]] + ＝435)
Compound sub G-2 (15 g,34.5 mmol) and compound sub6 (17.5 g,36.2 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (14.3 g,103.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 11. (yield: 65%, MS: [ M+H)] + ＝627)
Synthesis examples 1 to 12
Compound G (15G, 45.5 mmol) and compound Trz10 (16.4G, 47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound sub G-3. (yield: 61%, MS: [ M+H) ] + ＝511)
Under nitrogen atmosphere, combiningSubG-3 (10 g,19.6 mmol), compound sub7 (4.3 g,20 mmol) and sodium tert-butoxide (2.4 g,25.4 mmol) were added to 200ml of xylene and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. After the reaction was completed after 5 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.5g of compounds 1 to 12. (yield: 70%, MS: [ M+H ]] + ＝692)
Synthesis examples 1 to 13
Compound H (15 g,45.5 mmol) and compound Trz11 (17.1 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.2g of compound subH-1. (yield: 68%, MS: [ M+H) ] + ＝525)
Compound sub H-1 (15 g,28.6 mmol) and compound sub5 (5.2 g,30 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (11.8 g,85.7 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compounds 1 to 13. (yield: 62%, MS: [ M+H)] + ＝617)
Synthesis examples 1 to 14
Compound I (15 g,50.8 mmol) and compound Trz12 (23.7 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compounds 1 to 14. (yield: 60%, MS: [ M+H) ] + ＝577)
Synthesis examples 1 to 15
Compound I (15 g,50.8 mmol) and compound Trz13 (25 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. Dissolving in chloroform again, washing twice with water, separating organic layer, adding anhydrous sulfurMagnesium acid, stirring, then filtering, and distilling the filtrate under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.7g of compounds 1 to 15. (yield: 71%, MS: [ M+H)] + ＝601)
Synthesis examples 1 to 16
Compound I (15 g,50.8 mmol) and compound Trz14 (25.1 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.4g of compounds 1 to 16. (yield: 70%, MS: [ M+H ] ] + ＝603)
Synthesis examples 1 to 17
Compound J (15 g,45.5 mmol) and compound Trz15 (17.6 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. Passing the concentrated compound through siliconPurification by gel column chromatography to prepare 15.6g of compound subJ-1. (yield: 64%, MS: [ M+H ]] + ＝535)
Compound sub J-1 (15 g,28 mmol) and compound sub5 (5.1 g,29.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (11.6 g,84.1 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 compounds 1 to 17. (yield: 78%, MS: [ M+H) ] + ＝627)
Synthesis examples 1 to 18
Compound K (15 g,45.5 mmol) and compound Trz1 (15.2 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound subK-1. (yield: 63%, MS: [ M+H)] + ＝485)
Compound sub K-1 (15 g,30.9 mmol) and compound sub8 (6.9 g,32.5 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (12.8 g,92.8 mmol) was dissolved in 100ml water and added to the mixtureTo the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 18. (yield: 65%, MS: [ M+H) ] + ＝617)
Synthesis examples 1 to 19
Compound L (15 g,45.5 mmol) and compound Trz2 (12.8 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound subL-1. (yield: 69%, MS: [ M+H)] + ＝435)
Compound sub L-1 (15 g,34.5 mmol) and compound sub9 (8.9 g,36.2 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (14.3 g,103.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. Dissolving in chloroform again, washing twice with water, separating organic layer, adding anhydrous magnesium sulfate, stirring, and then Post-filtration and distillation of the filtrate under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2g of compounds 1 to 19. (yield: 64%, MS: [ M+H ]] + ＝601)
Synthesis examples 1 to 20
Compound sub L-1 (15 g,34.5 mmol) and compound sub10 (10.1 g,36.2 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (14.3 g,103.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.4g of compounds 1 to 20. (yield: 66%, MS: [ M+H)] + ＝633)
Synthesis examples 1 to 21
Compound K (15 g,45.5 mmol) and compound Trz16 (17.9 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. Subjecting the concentrated compound to silica gel column chromatography Purified to prepare 16.7g of compound subK-2. (yield: 68%, MS: [ M+H)] + ＝541)
Compound sub K-2 (10 g,18.5 mmol), compound sub11 (3.2 g,18.9 mmol) and sodium tert-butoxide (2.3 g,24 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 the reaction was completed after 5 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.8g of compounds 1 to 21. (yield: 63%, MS: [ M+H)] + ＝672)
Synthesis examples 1 to 22
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Compound K (15 g,45.5 mmol) and compound Trz17 (16.4 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.3g of compound subK-3. (yield: 66%, MS: [ M+H) ] + ＝511)
Compound sub K-3 (15 g,29.4 mmol) and compound sub5 (5.3 g,30.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (12.2 g,88.1 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, then bis (tri-t-butyl) was addedPalladium (0) (0.2 g,0.3 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compounds 1 to 22. (yield: 78%, MS: [ M+H)] + ＝603)
Synthesis examples 1 to 23
Compound M (15 g,50.8 mmol) and compound Trz18 (25.1 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 1 to 23. (yield: 65%, MS: [ M+H) ] + ＝603)
Synthesis examples 1 to 24
Compound M (15 g,50.8 mmol) and compound Trz19 (25 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, howeverThe organic and aqueous layers were then separated and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.4g of compounds 1 to 24. (yield: 67%, MS: [ M+H)] + ＝601)
Synthesis examples 1 to 25
Compound M (15 g,50.8 mmol) and compound Trz20 (25.8 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compounds 1 to 25. (yield: 63%, MS: [ M+H) ] + ＝617)
Synthesis examples 1 to 26
Compound N (15 g,45.5 mmol) and compound Trz1 (15.2 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. Dissolving in chloroform again, and using waterThe organic layer was then separated, anhydrous magnesium sulfate was added, 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 subN-1. (yield: 72%, MS: [ M+H)] + ＝485)
Compound sub N-1 (15 g,30.9 mmol) and compound sub5 (5.6 g,32.5 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (12.8 g,92.8 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compounds 1 to 26. (yield: 71%, MS: [ M+H ] +=577)
Synthesis examples 1 to 27
Compound O (15 g,45.5 mmol) and compound Trz2 (12.8 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15g of compound subO-1. (yield: 76%, MS: [ M+H)] + ＝435)
The compound sub O-1 (15 g,34.5 mmol) and the compound sub12 (9.9 g,36.2 mmol) was added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (14.3 g,103.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.8g of compounds 1 to 27. (yield: 73%, MS: [ M+H) ] + ＝627)
Synthesis examples 1 to 28
Compound N (15 g,45.5 mmol) and compound Trz8 (12.8 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.4g of compound subN-2. (yield: 78%, MS: [ M+H)] + ＝575)
Compound sub N-2 (15 g,26.1 mmol) and compound sub13 (5.4 g,27.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (10.8 g,78.3 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, and then the organic layer and the aqueous layer were separated The organic layer was separated and distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 28. (yield: 60%, MS: [ M+H)] + ＝693)
Synthesis examples 1 to 29
Compound P (15 g,45.5 mmol) and compound Trz1 (15.2 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 subP-1. (yield: 62%, MS: [ M+H)] + ＝485)
Compound sub P-1 (10 g,20.6 mmol), compound sub11 (3.5 g,21 mmol) and sodium tert-butoxide (2.6 g,26.8 mmol) were added to 200ml of xylene under nitrogen atmosphere and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.2 mmol) was added thereto. After the reaction was completed after 4 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.5g of compounds 1 to 29. (yield: 51%, MS: [ M+H ] ] + ＝616)
Synthesis examples 1 to 30
Compound Q (15 g,45.5 mmol) and compound Trz21 (17.1 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound subQ-1. (yield: 69%, MS: [ M+H)] + ＝525)
Compound sub Q-1 (15 g,28.6 mmol) and compound sub14 (5.9 g,30 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (11.8 g,85.7 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compounds 1 to 30. (yield: 80%, MS: [ M+H) ] + ＝643)
Synthesis examples 1 to 31
Compound R (15 g,50.8 mmol) and compound Trz22 (23.7 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. However, the method is thatAfter that, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.7g of compounds 1 to 31. (yield: 64%, MS: [ M+H ]] + ＝577)
Synthesis examples 1 to 32
Compound R (15 g,50.8 mmol) and compound Trz23 (23.6 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.1g of compounds 1 to 32. (yield: 79%, MS: [ M+H) ] + ＝575)
Synthesis examples 1 to 33
Compound R (15 g,50.8 mmol) and compound Trz24 (29.9 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and mixedThe mixture was stirred well and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was then added. After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26g of compounds 1 to 33. (yield: 74%, MS: [ M+H)] + ＝693)
Synthesis examples 1 to 34
Compound S (15 g,45.5 mmol) and compound Trz15 (17.6 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19g of compound subS-1. (yield: 78%, MS: [ M+H) ] + ＝535)
Compound sub-S-1 (15 g,28 mmol) and compound sub-15 (6.5 g,29.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (11.6 g,84.1 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. Dissolving in chloroform again, washing twice with water, separating organic layer, adding anhydrous magnesium sulfate, stirring, filtering, and concentrating the filtrateDistillation under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3g of compounds 1 to 34. (yield: 70%, MS: [ M+H ]] + ＝677)
Synthesis examples 1 to 35
Compound T (15 g,45.5 mmol) and compound Trz2 (12.8 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.4g of compound subT-1. (yield: 73%, MS: [ M+H) ] + ＝435)
Compound sub T-1 (15 g,34.5 mmol) and compound sub16 (9.5 g,36.2 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (14.3 g,103.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17g of compounds 1 to 35. (yield: 80%, MS: [ M+H)] + ＝617)
Synthesis examples 1 to 36
Compound S (15 g,45.5 mmol) and compound Trz25 (18.8 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound subS-2. (yield: 77%, MS: [ M+H) ] + ＝561)
Compound sub-S-2 (10 g,17.8 mmol), compound sub-17 (4 g,18.2 mmol) and sodium tert-butoxide (2.2 g,23.2 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,0.2 mmol) was added thereto. After the reaction was completed after 5 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.3g of compounds 1 to 36. (yield: 55%, MS: [ M+H)] + ＝742)
Synthesis examples 1 to 37
Compound U (15 g,45.5 mmol) and compound Trz26 (17.9 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Potassium carbonate (18.9 g,136.5 mmol) was then dissolved in 100ml of water and added to the mixture, and the mixture was stirred well before bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.7g of compound subU-1. (yield: 76%, MS: [ M+H) ] + ＝541)
Compound sub U-1 (15 g,27.7 mmol) and compound sub18 (6.6 g,29.1 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (11.5 g,83.2 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 37. (yield: 71%, MS: [ M+H)] + ＝689)
Synthesis examples 1 to 38
Compound V (15 g,50.8 mmol) and compound Trz27 (22.3 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. Purifying the concentrated compound by silica gel column chromatography To prepare 16.8g of compounds 1-38. (yield: 60%, MS: [ M+H)] + ＝551)
Synthesis examples 1 to 39
Compound V (15 g,50.8 mmol) and compound Trz28 (23.2 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compounds 1 to 39. (yield: 70%, MS: [ M+H ]] + ＝567)
Synthesis examples 1 to 40
Compound V (15 g,50.8 mmol) and compound Trz29 (30.4 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.6g of compounds 1 to 40. (yield: 69%, MS: [ M+H) ] + ＝703)
Synthesis examples 1 to 41
Compound V (15 g,50.8 mmol) and compound Trz30 (25.8 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.8g of compounds 1 to 41. (yield: 76%, MS: [ M+H)] + ＝617)
Synthesis examples 1 to 42
Compound W (15 g,45.5 mmol) and compound Trz2 (12.8 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound sub w-1. (yield: 66%, MS: [ M+H) ] + ＝435)
The compound sub W-1 (15 g,34.5 mmol) and the compound sub19 (9.9 g,36.2 mmol) were addedTo 300ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (14.3 g,103.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 42. (yield: 76%, MS: [ M+H)] + ＝627)
Synthesis examples 1 to 43
Compound X (15 g,45.5 mmol) and compound Trz2 (12.8 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound subX-1. (yield: 71%, MS: [ M+H) ] + ＝435)
Compound sub X-1 (15 g,34.5 mmol) and compound sub20 (10.1 g,36.2 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (14.3 g,103.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and there wasThe layers were distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 43. (yield: 64%, MS: [ M+H ]] + ＝633)
Synthesis examples 1 to 44
Compound Y (15 g,45.5 mmol) and compound Trz2 (12.6 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.8g of compound sub-1. (yield: 80%, MS: [ M+H) ] + ＝435)
Compound sub-1 (15 g,34.5 mmol) and compound sub21 (9.5 g,36.2 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (14.3 g,103.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 44. (yield: 70%, MS: [ M+H ]] + ＝617)
Synthesis examples 1 to 45
Compound X (15 g,45.5 mmol) and compound Trz31 (18.8 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 subX-2. (yield: 71%, MS: [ M+H) ] + ＝561)
Compound sub X-2 (15 g,26.7 mmol) and compound sub22 (7.6 g,28.1 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (11.1 g,80.2 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.7g of compounds 1 to 45. (yield: 78%, MS: [ M+H)] + ＝753)
Synthesis examples 1 to 46
Compound Z (15 g,50.8 mmol) and compound Trz32 (21 g,53.4 mmol) were added to 300ml THFAnd the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.6g of compounds 1 to 46. (yield: 62%, MS: [ M+H) ] + ＝527)
Synthesis examples 1 to 47
Compound Z (15 g,50.8 mmol) and compound Trz33 (22.3 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compounds 1 to 47. (yield: 69%, MS: [ M+H)] + ＝551)
Synthesis examples 1 to 48
Compound Z (15 g,50.8 mmol) and compound Trz34 (25.7 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Potassium carbonate (21.1 g,152.5 mmol) was then dissolved in 100ml of waterAnd added to the mixture, and the mixture was stirred well, followed by the addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.1g of compounds 1 to 48. (yield: 74%, MS: [ M+H) ] + ＝615)
Synthesis examples 1 to 49
Compound Z (15 g,50.8 mmol) and compound Trz35 (25.8 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.9g of compounds 1 to 49. (yield: 73%, MS: [ M+H)] + ＝617)
Synthesis examples 1 to 50
Compound Z (15 g,50.8 mmol) and compound Trz36 (25.8 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, and then bis (tri-t-butylphosphine) palladium (0)) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compounds 1 to 50. (yield: 62%, MS: [ M+H) ] + ＝617)
Synthesis examples 1 to 51
Compound Z (15 g,50.8 mmol) and compound Trz37 (27.8 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 1 to 51. (yield: 60%, MS: [ M+H)] + ＝653)
Synthesis examples 1 to 52
Compound AA (15 g,45.5 mmol) and compound Trz1 (15.2 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, and then the organic matter was taken out The layers were separated from the aqueous layer and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound sub AA-1. (yield: 78%, MS: [ M+H)] + ＝485)
Compound sub AA-1 (15 g,30.9 mmol) and compound sub23 (7.4 g,32.5 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (12.8 g,92.8 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compounds 1 to 52. (yield: 71%, MS: [ M+H)] + ＝633)
Synthesis examples 1 to 53
Compound AB (15 g,45.5 mmol) and compound Trz2 (12.8 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound subeb-1. (yield: 71%, MS: [ M+H) ] + ＝435)
Compound sub AB-1 (14 g,32 mmol) and compound sub24 (8.9 g,33.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (13.3 g,96.6 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 5 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.5g of compounds 1 to 53. (yield: 62%, MS: [ M+H)] + ＝617)
Synthesis examples 1 to 54
Compound AA (15 g,45.5 mmol) and compound Trz2 (12.8 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 sub aa-2. (yield: 64%, MS: [ M+H ] ] + ＝435)
Compound sub AA-2 (15 g,34.5 mmol) and compound sub25 (10.1 g,36.2 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (14.3 g,103.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, then bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 compounds 1 to 54. (yield: 61%, MS: [ M+H)] + ＝633)
Synthesis examples 1 to 55
Compound AB (15 g,45.5 mmol) and compound Trz21 (17.1 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound subeb-2. (yield: 65%, MS: [ M+H) ] + ＝525)
Compound sub AB-2 (15 g,28.6 mmol) and compound sub26 (7.4 g,30 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (11.8 g,85.7 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by column chromatography on silica gelPurification by chromatography gave 12.5g of compounds 1-55. (yield: 63%, MS: [ M+H)] + ＝693)
Synthesis examples 1 to 56
Compound AB (15 g,45.5 mmol) and compound Trz38 (20.1 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.4g of compound subeb-3. (yield: 69%, MS: [ M+H) ] + ＝587)
Compound sub AB-3 (15 g,25.6 mmol) and compound sub27 (5.7 g,26.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (10.6 g,76.7 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.1 g,0.3 mmol). After 4 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compounds 1 to 56. (yield: 73%, MS: [ M+H)] + ＝719)
Synthesis examples 1 to 57
Compound AC (15 g,50.8 mmol) and compound Trz39 (22.3 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.1g of compounds 1 to 57. (yield: 79%, MS: [ M+H) ] + ＝551)
Synthesis examples 1 to 58
Compound AC (15 g,50.8 mmol) and compound Trz40 (23.7 g,53.4 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compounds 1 to 58. (yield: 66%, MS: [ M+H)] + ＝577)
Synthesis examples 1 to 59
Compound AC (15 g,50.8 mmol) and compound Trz41 (28.5 g,53.4 mmol) was added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g,152.5 mmol) was dissolved in 100ml of water and added to the mixture, and the mixture was stirred well, followed by addition of bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol). After 3 hours of reaction, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.7g of compounds 1 to 59. (yield: 73%, MS: [ M+H) ] + ＝667)
Synthesis example 2-1
Compound 2-AA (10 g,35.8 mmol), compound amine 1 (16 g,35.8 mmol) and sodium tert-butoxide (11.4 g,53.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After completion of the reaction after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 16.8g of compound 2-1. (yield: 68%, MS: [ M+H)] + ＝691)
Synthesis example 2-2
Compound 2-AB (10 g,35.8 mmol), compound amine 2 (12.9 g,35.8 mmol) and sodium tert-butoxide (11.4 g,53.6 mmol) were added to 200ml of xylene under nitrogen, and the mixture was stirred and refluxed. Then, a double is added thereto(tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol). After completion of the reaction after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.2g of compound 2-2. (yield: 61%, MS: [ M+H) ] + ＝605)
Synthesis examples 2 to 3
Compound 2-AC (10 g,35.8 mmol), compound amine 3 (16 g,35.8 mmol) and sodium tert-butoxide (11.4 g,53.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After completion of the reaction after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 17.3g of compound 2-3. (yield: 70%, MS: [ M+H ]] + ＝691)
Synthesis examples 2 to 4
Compound 2-AD (10 g,35.8 mmol), compound amine 4 (10.6 g,35.8 mmol) and sodium tert-butoxide (11.4 g,53.6 mmol) were added to 200ml of xylene under nitrogen atmosphere and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 3 hours the reaction was completed, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, and water was used The organic layer was then separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.7g of compound 2-4. (yield: 66%, MS: [ M+H)] + ＝539)
Synthesis examples 2 to 5
Compound 2-AE (10 g,35.8 mmol), compound amine 5 (13.3 g,35.8 mmol) and sodium tert-butoxide (11.4 g,53.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After completion of the reaction after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.4g of compound 2-5. (yield: 61%, MS: [ M+H)] + ＝615)
Synthesis examples 2 to 6
Compound 2-AE (10 g,35.8 mmol), compound amine 6 (12 g,35.8 mmol) and sodium tert-butoxide (11.4 g,53.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 3 hours the reaction was completed, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.4g of compound 2-6. (production) The rate is as follows: 65%, MS: [ M+H ]] + ＝579)
Synthesis examples 2 to 7
Compound 2-AF (10 g,35.8 mmol), compound amine 7 (12.3 g,35.8 mmol) and sodium tert-butoxide (11.4 g,53.6 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After completion of the reaction after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.5g of compound 2-7. (yield: 64%, MS: [ M+H ]] + ＝589)
Synthesis examples 2 to 8
Compound 2-AA (15 g,53.6 mmol) and compound amine 8 (25.6 g,56.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.9g of compounds 2 to 8. (yield: 68%, MS: [ M+H) ] + ＝655)
Synthesis examples 2 to 9
Compound 2-AB (15 g,53.6 mmol) and compound amine 9 (29.9 g,56.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.9g of compounds 2 to 9. (yield: 61%, MS: [ M+H)] + ＝730)
Synthesis examples 2 to 10
Compound 2-AC (15 g,53.6 mmol) and compound amine 10 (29.9 g,56.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.2g of compounds 2 to 10. (yield: 62%, MS: [ M+H) ] + ＝730)
Synthesis examples 2 to 11
Compound 2-AD (15 g,53.6 mmol) and compound amine 11 (24.9 g,56.3 mmol) were added to 300ml THF under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compounds 2 to 11. (yield: 61%, MS: [ M+H)] + ＝641)
Synthesis examples 2 to 12
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Compound 2-AD (15 g,53.6 mmol) and compound amine 12 (30.5 g,56.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.8g of compounds 2 to 12. (yield: 65%, MS: [ M+H) ] + ＝741)
Synthesis examples 2 to 13
Compound 2-AE (15 g,53.6 mmol) and compound amine 13 (21.4 g,56.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compounds 2 to 13. (yield: 60%, MS: [ M+H)] + ＝579)
Synthesis examples 2 to 14
Compound 2-AE (15 g,53.6 mmol) and compound amine 14 (23.4 g,56.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.1g of compounds 2 to 14. (yield: 67%, MS: [ M+H) ] + ＝615)
Synthesis examples 2 to 15
Compound 2-AE (15 g,53.6 mmol) and compound amine 15 (29.9 g,56.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.2g of compounds 2 to 15. (yield: 62%, MS: [ M+H)] + ＝730)
Synthesis examples 2 to 16
Compound 2-AE (15 g,53.6 mmol) and compound amine 11 (24.9 g,56.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23g of compounds 2 to 16. (yield: 67%, MS: [ M+H) ] + ＝641)
Synthesis examples 2 to 17
Compound 2-AF (15 g,53.6 mmol) and compound amine 16 (27.9 g,56.3 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.5g of compound 2-17. (yield: 63%, MS: [ M+H)] + ＝695)
Synthesis examples 2 to 18
Compound 2-AA (15 g,53.6 mmol) and compound amine 17 (36.2 g,56.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 28.5g of compounds 2 to 18. (yield: 63%, MS: [ M+H) ] + ＝843)
Synthesis examples 2 to 19
Under nitrogen atmosphereCompound 2-AD (15 g,53.6 mmol) and compound amine 18 (24.9 g,56.3 mmol) were added to 300ml THF, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.3g of compounds 2 to 19. (yield: 68%, MS: [ M+H)] + ＝641)
Synthesis examples 2 to 20
Compound 2-AF (15 g,53.6 mmol) and compound amine 19 (34.8 g,56.3 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.6g of compound 2-20. (yield: 63%, MS: [ M+H) ] + ＝817)
Synthesis examples 2 to 21
Compound 2-AA (15 g,53.6 mmol) and Compound were combined under nitrogen atmosphereThe amine 20 (33.3 g,56.3 mmol) was added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.5g of compound 2-21. (yield: 65%, MS: [ M+H)] + ＝791)
Synthesis examples 2 to 22
Compound 2-AD (15 g,53.6 mmol) and compound amine 21 (32 g,56.3 mmol) were added to 300ml THF under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.9g of compound 2-22. (yield: 68%, MS: [ M+H) ] + ＝767)
Synthesis examples 2 to 23
Compound 2-AE (15 g,53.6 mmol) and compound amine 22 (23.4 g,56.3 mmol) were added to 300ml T under nitrogen atmosphereIn HF, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compounds 2 to 23. (yield: 68%, MS: [ M+H)] + ＝615)
Synthesis examples 2 to 24
Compound 2-AH (10 g,28.1 mmol), compound amine 23 (11.2 g,28.1 mmol) and sodium tert-butoxide (8.9 g,42.2 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, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 14.1g of compounds 2 to 24. (yield: 70%, MS: [ M+H ] ] + ＝717)
Synthesis examples 2 to 25
Compound 2-AJ (10 g,28.1 mmol), compound amine 24 (12.6 g,28.1 mmol) and sodium tert-butoxide (8.9 g,42.2 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, bis (tri-t-butyl) was added theretoPhosphine) palladium (0) (0.1 g,0.3 mmol). After completion of the reaction after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.1g of compound 2-25. (yield: 61%, MS: [ M+H)] + ＝767)
Synthesis examples 2 to 26
Compound 2-AJ (10 g,28.1 mmol), compound amine 25 (10.4 g,28.1 mmol) and sodium tert-butoxide (8.9 g,42.2 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 completion of the reaction after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.8g of compounds 2 to 26. (yield: 61%, MS: [ M+H) ] + ＝691)
Synthesis examples 2 to 27
Compound 2-AK (10 g,28.1 mmol), compound amine 26 (9.8 g,28.1 mmol) and sodium tert-butoxide (8.9 g,42.2 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 completion of the reaction after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform and washed with waterThe organic layer was then separated twice, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.6g of compounds 2 to 27. (yield: 62%, MS: [ M+H)] + ＝669)
Synthesis examples 2 to 28
Compound 2-AK (15 g,42.2 mmol) and compound amine 27 (16.2 g,44.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g,126.5 mmol) was dissolved in 52ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.4 mmol) was then added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.2g of compounds 2 to 28. (yield: 60%, MS: [ M+H) ] + ＝641)
Synthesis examples 2 to 29
Compound 2-AI (15 g,42.2 mmol) and compound amine 28 (19.5 g,44.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g,126.5 mmol) was dissolved in 52ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.4 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. Dissolving in chloroform again, washing twice with water, separating organic layer, adding anhydrousMagnesium 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 compounds 2 to 29. (yield: 60%, MS: [ M+H)] + ＝717)
Synthesis examples 2 to 30
Compound 2-AG (15 g,42.2 mmol) and compound amine 29 (25.1 g,44.3 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Then, potassium carbonate (17.5 g,126.5 mmol) was dissolved in 52ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.4 mmol) was then added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 2-30. (yield: 64%, MS: [ M+H ] ] + ＝843)
Synthesis examples 2 to 31
Compound 2-AJ (15 g,42.2 mmol) and compound amine 30 (22.9 g,44.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g,126.5 mmol) was dissolved in 52ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.4 mmol) was then added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. Dissolving in chloroform again, washing twice with water, separating organic layer, adding anhydrous magnesium sulfate, stirring, filtering, and concentratingThe filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.4g of compounds 2 to 31. (yield: 67%, MS: [ M+H)] + ＝793)
Synthesis examples 2 to 32
Compound 2-AI (15 g,42.2 mmol) and compound amine 31 (21.8 g,44.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g,126.5 mmol) was dissolved in 52ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.4 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.6g of compound 2-32. (yield: 70%, MS: [ M+H ] ] + ＝767)
Synthesis examples 2 to 33
Compound 2-AL (15 g,42.2 mmol) and compound amine 32 (22.9 g,44.3 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g,126.5 mmol) was dissolved in 52ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.4 mmol) was then added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. By column color of silica gelThe concentrated compound was purified by chromatography to prepare 23.4g of compound 2-33. (yield: 70%, MS: [ M+H ]] + ＝793)
Synthesis examples 2 to 34
Compound 2-AK (15 g,42.2 mmol) and compound amine 33 (25.1 g,44.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g,126.5 mmol) was dissolved in 52ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.4 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.3g of compounds 2 to 34. (yield: 60%, MS: [ M+H) ] + ＝843)
Synthesis examples 2 to 35
Compound 2-AI (15 g,42.2 mmol) and compound amine 34 (22.4 g,44.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g,126.5 mmol) was dissolved in 52ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.4 mmol) was then added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. Purification of the concentrated compound by silica gel column chromatography to prepare22.7g of Compound 2-35. (yield: 69%, MS: [ M+H)] + ＝781)
Synthesis examples 2 to 36
Compound 2-AH (15 g,42.2 mmol) and compound amine 35 (22.8 g,44.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g,126.5 mmol) was dissolved in 52ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.4 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23g of compounds 2 to 36. (yield: 69%, MS: [ M+H) ] + ＝791)
Synthesis examples 2 to 37
Compound 2-AQ (10 g,30.3 mmol), compound amine 36 (11.1 g,30.3 mmol) and sodium tert-butoxide (9.7 g,45.5 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, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.6g of compound 2-37. (yield: 68%, MS: [ M+H)] + ＝659)
Synthesis examples 2 to 38
Compound 2-AO (10 g,30.3 mmol), compound amine 37 (13.6 g,30.3 mmol) and sodium tert-butoxide (9.7 g,45.5 mmol) were added to 200ml of xylene under 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 completion of the reaction after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 14.4g of compound 2-38. (yield: 64%, MS: [ M+H ] ] + ＝741)
Synthesis examples 2 to 39
Compound 2-AQ (10 g,30.3 mmol), compound amine 38 (10.2 g,30.3 mmol) and sodium tert-butoxide (9.7 g,45.5 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 completion of the reaction after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12g of compound 2-39. (yield: 63%, MS: [ M+H)] + ＝629)
Synthesis examples 2 to 40
Compound 2-AQ (15 g,45.5 mmol) and compound amine 27 (17.4 g,47.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 57ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.5 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.4g of compounds 2 to 40. (yield: 66%, MS: [ M+H) ] + ＝615)
Synthesis examples 2 to 41
Compound 2-AN (15 g,45.5 mmol) and compound amine 39 (24.7 g,47.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 57ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.5 mmol) was then added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 2-41. (yield: 60%, MS: [ M+H)] + ＝767)
Synthesis examples 2 to 42
In nitrogen atmosphereCompound 2-AR (15 g,45.5 mmol) and compound amine 40 (21.1 g,47.8 mmol) were added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 57ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.5 mmol) was then added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 2-42. (yield: 66%, MS: [ M+H) ] + ＝691)
Synthesis examples 2 to 43
Compound 2-AP (15 g,45.5 mmol) and compound amine 41 (27.8 g,47.8 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 57ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.5 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.1g of compounds 2 to 43. (yield: 69%, MS: [ M+H)] + ＝831)
Synthesis examples 2 to 44
Compound 2-AQ (15 g,45.5 mmol) and Compound under nitrogen atmosphereAmine 42 (23.5 g,47.8 mmol) was added to 300ml THF and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 57ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.5 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.9g of compounds 2 to 44. (yield: 68%, MS: [ M+H) ] + ＝741)
Synthesis examples 2 to 45
Compound 2-AN (15 g,45.5 mmol) and compound amine 43 (27.1 g,47.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 57ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.5 mmol) was then added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26g of compounds 2 to 45. (yield: 70%, MS: [ M+H ]] + ＝817)
Synthesis examples 2 to 46
Compound 2-AQ (15 g,45.5 mmol) and compound amine 44 (27.1 g,47.8 mmol) were added to 300ml TH under nitrogenF, and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 57ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.5 mmol) was then added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.3g of compounds 2 to 46. (yield: 60%, MS: [ M+H) ] + ＝817)
Synthesis examples 2 to 47
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Compound 2-AO (15 g,43.4 mmol) and compound amine 45 (25.8 g,45.5 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (18 g,130.1 mmol) was dissolved in 54ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.4 mmol) was then added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compounds 2 to 47. (yield: 54%, MS: [ M+H)] + ＝833)
Synthesis examples 2 to 48
Compound 2-AP (15 g,45.5 mmol) and compound amine 46 (23.5 g,47.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. ThenPotassium carbonate (18.9 g,136.5 mmol) was dissolved in 57ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.5 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compounds 2 to 48. (yield: 60%, MS: [ M+H) ] + ＝741)
Synthesis examples 2 to 49
Compound 2-AN (15 g,45.5 mmol) and compound amine 47 (23.5 g,47.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 57ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.5 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compounds 2 to 49. (yield: 64%, MS: [ M+H ]] + ＝741)
Synthesis examples 2 to 50
Compound 2-BA (10 g,30.3 mmol), compound amine 48 (12.1 g,30.3 mmol) and sodium tert-butoxide (9.7 g,45.5 mmol) were added to 200ml of xylene under nitrogen and the mixture was stirred and refluxed. Then, the process is carried out,to this was added bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After completion of the reaction after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.8g of compound 2-50. (yield: 61%, MS: [ M+H) ] + ＝641)
Synthesis examples 2 to 51
Compound 2-BA (10 g,30.3 mmol), compound amine 49 (11.3 g,30.3 mmol) and sodium tert-butoxide (9.7 g,45.5 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, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.7g of compound 2-51. (yield: 63%, MS: [ M+H)] + ＝615)
Synthesis examples 2 to 52
Compound 2-BB (10 g,30.3 mmol), compound amine 50 (12.9 g,30.3 mmol) and sodium tert-butoxide (9.7 g,45.5 mmol) were added to 200ml of xylene under 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 completion of the reaction after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound is completely dissolved again The solution was dissolved in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 14g of compound 2-52. (yield: 69%, MS: [ M+H)] + ＝668)
Synthesis examples 2 to 53
Compound 2-BC (10 g,30.3 mmol), compound amine 51 (14 g,30.3 mmol) and sodium tert-butoxide (9.7 g,45.5 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 completion of the reaction after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.8g of compound 2-53. (yield: 60%, MS: [ M+H)] + ＝704)
Synthesis examples 2 to 54
Compound 2-BD (10 g,30.3 mmol), compound amine 52 (13.6 g,30.3 mmol) and sodium tert-butoxide (9.7 g,45.5 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 completion of the reaction after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. Purifying the concentrated compound by silica gel column chromatography to obtain To 12.6g of Compound 2-54. (yield: 60%, MS: [ M+H)] + ＝691)
Synthesis examples 2 to 55
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Compound 2-BE (10 g,30.3 mmol), compound amine 53 (12.1 g,30.3 mmol) and sodium tert-butoxide (9.7 g,45.5 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 completion of the reaction after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.2g of compound 2-55. (yield: 68%, MS: [ M+H)] + ＝641)
Synthesis examples 2 to 56
Compound 2-BA (15 g,53.6 mmol) and compound amine 54 (27.1 g,56.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.9g of compounds 2 to 56. (yield: 60%, MS: [ M+H) ] + ＝681)
Synthesis examples 2 to 57
Compound 2-BC (15 g,53.6 mmol) and compound amine 55 (26.5 g,56.3 mmol) are added to 300ml THF under nitrogen and the mixture is stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23g of compounds 2 to 57. (yield: 64%, MS: [ M+H ]] + ＝671)
Synthesis examples 2 to 58
Compound 2-BC (15 g,53.6 mmol) and compound amine 56 (24.9 g,56.3 mmol) are added to 300ml THF under nitrogen and the mixture is stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compounds 2 to 58. (yield: 66%, MS: [ M+H) ] + ＝641)
Synthesis examples 2 to 59
Compound 2-BE (15 g,53.6 mmol) and compound amine 57 (22.3 g,56.3 mmol) are added to 300ml THF under nitrogen, and the mixture is stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.3g of compound 2-59. (yield: 70%, MS: [ M+H ]] + ＝595)
Synthesis examples 2 to 60
Compound 2-BF (15 g,53.6 mmol) and compound amine 58 (32.7 g,56.3 mmol) were added to 300ml THF under a nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.5g of compound 2-60. (yield: 61%, MS: [ M+H) ] + ＝780)
Synthesis examples 2 to 61
Compound 2-BE (15 g,53.6 mmol) and compound amine 59 (36.2 g,56.3 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 31.6g of compound 2-61. (yield: 70%, MS: [ M+H ]] + ＝843)
Synthesis examples 2 to 62
Compound 2-BC (15 g,53.6 mmol) and compound amine 60 (29.9 g,56.3 mmol) are added to 300ml THF under nitrogen and the mixture is stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.2g of compound 2-62. (yield: 67%, MS: [ M+H) ] + ＝730)
Synthesis examples 2 to 63
Compound 2-BD (15 g,53.6 mmol) and compound amine 61 (27.7 g,56.3 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 2-63. (yield: 60%, MS: [ M+H)] + ＝691)
Synthesis examples 2 to 64
Compound 2-BE (15 g,53.6 mmol) and compound amine 62 (23.4 g,56.3 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compounds 2 to 64. (yield: 64%, MS: [ M+H ] ] + ＝615)
Synthesis examples 2 to 65
Compound 2-BD (15 g,53.6 mmol) and compound amine 63 (22.8 g,56.3 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound 2-65. (yield: 67%, MS: [ M+H)] + ＝605)
Synthesis examples 2 to 66
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Compound 2-BF (15 g,53.6 mmol) and compound amine 64 (31.6 g,56.3 mmol) were added to 300ml THF under a nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.9g of compound 2-66. (yield: 66%, MS: [ M+H) ] + ＝760)
Synthesis examples 2 to 67
Compound 2-BB (15 g,53.6 mmol) and compound amine 65 (32 g,56.3 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.1g of compounds 2 to 67. (yield: 66%, MS: [ M+H)] + ＝767)
Synthesis examples 2 to 68
Compound 2-BC (15 g,53.6 mmol) and compound amine 66 (32 g,56.3 mmol) are added to 300ml THF under nitrogen and the mixture is stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.8g of compound 2-68. (yield: 65%, MS: [ M+H) ] + ＝569)
Synthesis examples 2 to 69
Under nitrogen atmosphere to be converted intoCompound 2-BB (15 g,53.6 mmol) and compound amine 67 (29.1 g,56.3 mmol) were added to 300ml THF, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.5g of compounds 2 to 69. (yield: 69%, MS: [ M+H)] + ＝717)
Synthesis examples 2 to 70
Compound 2-BF (15 g,53.6 mmol) and compound amine 68 (30.5 g,56.3 mmol) were added to 300ml THF under a nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25g of compound 2-70. (yield: 63%, MS: [ M+H) ] + ＝741)
Synthesis examples 2 to 71
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2-BC (15 g,53.6 mmol) and amine 69 [. Sup.26.2g,56.3 mmol) are added to 300ml THF and the mixture is stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.1g of compounds 2 to 71. (yield: 62%, MS: [ M+H)] + ＝665)
Synthesis examples 2 to 72
Compound 2-BF (15 g,53.6 mmol) and compound amine 70 (23.4 g,56.3 mmol) were added to 300ml THF under a nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound 2-72. (yield: 66%, MS: [ M+H) ] + ＝615)
Synthesis examples 2 to 73
Compound 2-BE (15 g,53.6 mmol) and compound amine 71 (32 g,56.3 mmol) were added to 300ml THF under a nitrogen atmosphere, andthe mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.5g of compound 2-73. (yield: 62%, MS: [ M+H)] + ＝767)
Synthesis examples 2 to 74
Compound 2-BD (15 g,53.6 mmol) and compound amine 72 (36.2 g,56.3 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 30.7g of compound 2-74. (yield: 68%, MS: [ M+H) ] + ＝843)
Synthesis examples 2 to 75
Compound 2-BC (15 g,53.6 mmol) and compound amine 73 (39.1 g,56.3 mmol) are added to 300ml THF under nitrogen and the mixture is stirred and refluxed. Then, willPotassium carbonate (22.2 g,160.9 mmol) was dissolved in 67ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,0.5 mmol) was then added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 29.7g of compound 2-75. (yield: 62%, MS: [ M+H)] + ＝893)
Synthesis examples 2 to 76
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Compound 2-BG (10 g,28.1 mmol), compound amine 74 (10.4 g,28.1 mmol) and sodium tert-butoxide (8.9 g,42.2 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 completion of the reaction after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.6g of compounds 2 to 76. (yield: 65%, MS: [ M+H) ] + ＝691)
Synthesis examples 2 to 77
Compound 2-BI (10 g,28.1 mmol), compound amine 75 (9.4 g,28.1 mmol) and sodium tert-butoxide (8.9 g,42.2 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. The reaction was completed after 2 hoursAt this time, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11g of compound 2-77. (yield: 60%, MS: [ M+H)] + ＝655)
Synthesis examples 2 to 78
Compound 2-BJ (10 g,28.1 mmol), compound amine 76 (10.4 g,28.1 mmol) and sodium tert-butoxide (8.9 g,42.2 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, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.8g of compound 2-78. (yield: 61%, MS: [ M+H) ] + ＝691)
Synthesis examples 2 to 79
Compound 2-BK (10 g,28.1 mmol), compound amine 77 (11.8 g,28.1 mmol) and sodium tert-butoxide (8.9 g,42.2 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 completion of the reaction after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, and then the organic layer was separated, and washed with anhydrous magnesium sulfateAnd then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.1g of compound 2-79. (yield: 63%, MS: [ M+H)] + ＝741)
Synthesis examples 2 to 80
Compound 2-BJ (15 g,42.2 mmol) and compound amine 78 (16.2 g,44.3 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g,126.5 mmol) was dissolved in 52ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.4 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 2-80. (yield: 67%, MS: [ M+H) ] + ＝641)
Synthesis examples 2 to 81
Compound 2-BG (15 g,42.2 mmol) and compound amine 79 (21.8 g,44.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g,126.5 mmol) was dissolved in 52ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.4 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. Dissolving in chloroform again, washing twice with water, separating organic layer, adding anhydrous magnesium sulfate, stirring, filtering, and concentrating the filtrate under reduced pressureAnd (5) distilling. The concentrated compound was purified by silica gel column chromatography to prepare 19.7g of compound 2-81. (yield: 61%, MS: [ M+H)] + ＝767)
Synthesis examples 2 to 82
Compound 2-BI (15 g,42.2 mmol) and compound amine 80 (26.3 g,44.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g,126.5 mmol) was dissolved in 52ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.4 mmol) was then added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.9g of compound 2-82. (yield: 68%, MS: [ M+H) ] + ＝869)
Synthesis examples 2 to 83
Compound 2-BH (15 g,42.2 mmol) and compound amine 81 (20.2 g,44.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g,126.5 mmol) was dissolved in 52ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.4 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. Concentrating by silica gel column chromatographyThe condensed compound was purified to prepare 19.7g of compound 2-83. (yield: 64%, MS: [ M+H ]] + ＝731)
Synthesis examples 2 to 84
Compound 2-BG (15 g,42.2 mmol) and compound amine 82 (21.8 g,44.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g,126.5 mmol) was dissolved in 52ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.4 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 84. (yield: 62%, MS: [ M+H) ] + ＝767)
Synthesis examples 2 to 85
Compound 2-BL (15 g,42.2 mmol) and compound amine 83 (22.9 g,44.3 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g,126.5 mmol) was dissolved in 52ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.4 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 the compound2-85. (yield: 60%, MS: [ M+H)] + ＝793)
Synthesis examples 2 to 86
Compound 2-BG (15 g,42.2 mmol) and compound amine 84 (23.5 g,44.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g,126.5 mmol) was dissolved in 52ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.4 mmol) was then added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.5g of compounds 2 to 86. (yield: 69%, MS: [ M+H) ] + ＝807)
Synthesis examples 2 to 87
Compound 2-BI (15 g,42.2 mmol) and compound amine 85 (22.4 g,44.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g,126.5 mmol) was dissolved in 52ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.4 mmol) was then added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compounds 2 to 87. (yield: 69%, MS: [ M+H)] + ＝781)
Synthesis examples 2 to 88
Compound 2-BJ (15 g,42.2 mmol) and compound amine 86 (20.6 g,44.3 mmol) were added to 300ml THF under nitrogen, and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g,126.5 mmol) was dissolved in 52ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.4 mmol) was then added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 2 to 88. (yield: 66%, MS: [ M+H) ] + ＝741)
Synthesis examples 2 to 89
Compound 2-BI (15 g,42.2 mmol) and compound amine 87 (22.4 g,44.3 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (17.5 g,126.5 mmol) was dissolved in 52ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.4 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.4g of compound 2-89. (yield: 62%, MS: [ M+H)] + ＝781)
Synthesis examples 2 to 90
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Compound 2-BN (10 g,30.3 mmol), compound amine 88 (11.3 g,30.3 mmol) and sodium tert-butoxide (9.7 g,45.5 mmol) are added to 200ml of xylene under a nitrogen atmosphere 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, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.3g of compound 2-90. (yield: 66%, MS: [ M+H) ] + ＝665)
Synthesis examples 2 to 91
Compound 2-BM (10 g,30.3 mmol), compound amine 89 (12.8 g,30.3 mmol) and sodium tert-butoxide (9.7 g,45.5 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 completion of the reaction after 2 hours, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.4g of compound 2-91. (yield: 62%, MS: [ M+H)] + ＝715)
Synthesis examples 2 to 92
Compound 2-BP (10 g,30.3 mmol), compound amine 90 (12.1 g,30.3 mmol) and sodium tert-butoxide (9.7 g,45.5 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, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.8g of compound 2-92. (yield: 66%, MS: [ M+H) ] + ＝691)
Synthesis examples 2 to 93
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Compound 2-BQ (10 g,30.3 mmol), compound amine 91 (12.1 g,30.3 mmol) and sodium tert-butoxide (9.7 g,45.5 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, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved again in chloroform, washed twice with water, then the organic layer was separated, treated with anhydrous magnesium sulfate, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.4g of compound 2-93. (yield: 64%, MS: [ M+H ]] + ＝691)
Synthesis examples 2 to 94
Compound 2-BP (15 g,45.5 mmol) and compound amine 92 (25.6 g,47.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. However, the method is thatAfter that, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 57ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.5 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 2-94. (yield: 61%, MS: [ M+H) ] + ＝785)
Synthesis examples 2 to 95
Compound 2-BN (15 g,45.5 mmol) and compound amine 93 (26 g,47.8 mmol) are added to 300ml THF under nitrogen and the mixture is stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 57ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.5 mmol) was then added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.6g of compound 2-95. (yield: 68%, MS: [ M+H)] + ＝795)
Synthesis examples 2 to 96
Compound 2-BP (15 g,45.5 mmol) and compound amine 94 (27.1 g,47.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in57ml of water and added to the mixture, the mixture was stirred well and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.5 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.6g of compound 2-96. (yield: 69%, MS: [ M+H) ] + ＝817)
Synthesis examples 2 to 97
Compound 2-BN (15 g,45.5 mmol) and compound amine 95 (30.7 g,47.8 mmol) are added to 300ml THF under nitrogen and the mixture is stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 57ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.5 mmol) was then added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.2g of compound 2-97. (yield: 62%, MS: [ M+H)] + ＝893)
Synthesis examples 2 to 98
Compound 2-BR (15 g,45.5 mmol) and compound amine 96 (21.1 g,47.8 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Potassium carbonate (18.9 g,136.5 mmol) was then dissolved in 57ml of water and added to the mixtureThe mixture was stirred well and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.5 mmol) was then added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 2-98. (yield: 64%, MS: [ M+H ] ] + ＝691)
Synthesis examples 2 to 99
Compound 2-BP (15 g,45.5 mmol) and compound amine 97 (27.1 g,47.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 57ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.5 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23g of compound 2-99. (yield: 62%, MS: [ M+H)] + ＝817)
Synthesis examples 2 to 100
Compound 2-BN (15 g,45.5 mmol) and compound amine 98 (24.7 g,47.8 mmol) are added to 300ml THF under nitrogen and the mixture is stirred and refluxed. Potassium carbonate (18.9 g,136.5 mmol) was then dissolved in 57ml of water and added to the mixture, the mixture was stirred well and then addedBis (tri-t-butylphosphine) palladium (0) (0.5 g,0.5 mmol). After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.3g of compound 2-100. (yield: 64%, MS: [ M+H ] ] + ＝767)
Synthesis examples 2 to 101
Compound 2-BP (15 g,45.5 mmol) and compound amine 99 (27.1 g,47.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 57ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.5 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.3g of compound 101. (yield: 60%, MS: [ M+H)] + ＝817)
Synthesis examples 2 to 102
Compound 2-BM (15 g,45.5 mmol) and compound amine 100 (25.9 g,47.8 mmol) were added to 300ml THF under nitrogen and the mixture stirred and refluxed. Potassium carbonate (18.9 g,136.5 mmol) was then dissolved in 57ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.5 mmol). After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound 2-102. (yield: 60%, MS: [ M+H)] + ＝791)
Synthesis examples 2 to 103
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Compound 2-BO (15 g,45.5 mmol) and compound amine 101 (27.1 g,47.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 57ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.5 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26g of compounds 2 to 103. (yield: 70%, MS: [ M+H ] ] + ＝817)
Synthesis examples 2 to 104
Compound 2-BO (15 g,45.5 mmol) and compound amine 102 (24.1 g,47.8 mmol) were added to 300ml THF under nitrogen and the mixture was stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 57ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.5 mmol) was then added. After 10 hours of reaction, the reaction was reversedThe mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.6g of compounds 2 to 104. (yield: 63%, MS: [ M+H)] + ＝791)
Synthesis examples 2 to 105
Compound 2-BN (15 g,45.5 mmol) and compound amine 103 (27.1 g,47.8 mmol) are added to 300ml THF under nitrogen and the mixture is stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 57ml of water and added to the mixture, the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.5 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and then the organic layer was distilled. It was dissolved again in chloroform, washed twice with water, then the organic layer was separated, anhydrous magnesium sulfate was added, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.7g of compounds 2 to 105. (yield: 69%, MS: [ M+H) ] + ＝755)
Example 1
Coated with a coating having a thickness ofThe glass substrate of the ITO (indium tin oxide) film of (c) is put into distilled water containing a cleaning agent dissolved therein and washed by ultrasonic waves. In this case, the detergent used is a product commercially available from Fischer co, and the distilled water is distilled water filtered twice by using a filter commercially available from Millipore co. The ITO was washed for 30 minutes, and then ultrasonic washing was repeated twice by using distilled water for 10 minutes. After the washing with distilled water was completed,the substrate was ultrasonically cleaned with isopropyl alcohol, acetone and methanol solvents, dried, and then transferred to a plasma cleaner. Then, the substrate was cleaned with oxygen plasma for 5 minutes, and then transferred to a vacuum evaporator.
On the ITO transparent electrode thus prepared, the following compound HI-1 was formed toAs the hole injection layer, the following compound a-1 was p-doped at a concentration of 1.5 wt%. Vacuum depositing the following compound HT-1 on the hole injection layer to form a layer having a thickness +.>Is provided. Then, the following compounds EB-1 to +.>To form an electron blocking layer. Then, compound 1-1 and compound 2-1 as a host and the following compound Dp-7 as a dopant were vacuum deposited on the EB-1 deposited layer at a weight ratio of 49:49:2 to form a layer with a thickness +. >Is provided. Vacuum deposition of the following compounds HB-1 to +.>To form a hole blocking layer. Then, the following compound ET-1 and the following compound LiQ were vacuum deposited on the hole blocking layer in a weight ratio of 2:1 to form a layer having a thickness +.>Electron injection and transport layers of (a) are provided. Sequentially depositing lithium fluoride (LiF) and aluminum to a thickness of +.>And->Thereby forming a cathode.
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In the above process, the deposition rate of the organic material is maintained atSecond to->Per second, the deposition rates of lithium fluoride and aluminum of the cathode are kept at +.>Second and->Per second, and maintain the vacuum level during deposition at 2 x 10 -7 To 5X 10 -6 And a support, thereby manufacturing an organic light emitting device.
Examples 2 to 220
An organic light-emitting device was manufactured in the same manner as in example 1, except that in the organic light-emitting device of example 1, the first and second hosts described in tables 1 to 5 below were used instead of the compound 1-1 and the compound 2-1.
Comparative examples 1 to 23
An organic light-emitting device was manufactured in the same manner as in example 1, except that in the organic light-emitting device of example 1, only the compounds shown in the following table 6 were used as hosts instead of the compound 1-1 and the compound 2-1, and the hosts and the compound Dp-7 were vacuum deposited at a weight ratio of 98:2 to form a light-emitting layer.
Comparative examples 24 to 51
An organic light-emitting device was manufactured in the same manner as in example 1, except that in the organic light-emitting device of example 1, only the compounds shown in the following table 7 were used as hosts instead of the compound 1-1 and the compound 2-1, and the hosts and the compound Dp-7 were vacuum deposited at a weight ratio of 98:2 to form a light-emitting layer.
Experimental example
Voltage and efficiency were measured by applying current to the organic light emitting devices manufactured in examples 1 to 220 and comparative examples 1 to 51 (based on 15 mA/cm) 2 ) And the results are shown in tables 1 to 4 below. Lifetime T95 means the time required for the luminance to decrease to 95% of the initial luminance (6000 nit).
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
TABLE 6
TABLE 7
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When current was applied to the organic light emitting devices manufactured in examples 1 to 220 and comparative examples 1 to 51, the results shown in tables 1 to 7 were obtained. In the red organic light emitting device of comparative example 1, a conventional widely used material was used, and compound EB-1 was used as an electron blocking layer, and compound Dp-7 was used as a dopant of the red light emitting layer. As shown in table 6, when only the compound represented by chemical formula 2 of the present disclosure is used as the compound of the comparative example, the driving voltage is generally increased, and the efficiency and lifetime are reduced, as compared to the combination of the present disclosure. In table 7, as the compound of the comparative example, only the compound represented by chemical formula 1 of the present disclosure was used as the host of the light emitting layer, in which case the driving voltage, efficiency, and lifetime were improved as compared with the case of using chemical formula 2 as the host, but the dynamic voltage was increased and the efficiency and lifetime were decreased as compared with the combination of the present disclosure.
As can be determined from the above results, when a combination of the compound represented by chemical formula 1 (which is a first host of the present disclosure) and the compound represented by chemical formula 2 (which is a second host of the present disclosure) is used in an organic light emitting device, energy transfer to a red dopant in a red light emitting layer is advantageously achieved, thereby improving a driving voltage and improving efficiency and lifetime. Basically, this is considered to be because the combination of the compound represented by chemical formula 1 and the compound represented by chemical formula 2 of the present disclosure causes electrons and holes to combine in the light emitting layer through a more stable equilibrium to form excitons, thus improving efficiency and lifetime, compared to the case where a single host is used as a host in the compound of the comparative example. In summary, it was determined that when the compound represented by chemical formula 1 and the compound represented by chemical formula 2 according to the present disclosure are combined, co-evaporation is used as a host of the red light emitting layer, the driving voltage, light emitting efficiency, and lifetime characteristics of the organic light emitting device can be improved.
[ reference numerals ]
1: substrate 2: anode
3: light emitting layer 4: cathode electrode
5: hole injection layer 6: hole transport layer
7: electron blocking layer 8: hole blocking layer
9: electron injection and transport layers

Claims (11)

1. An organic light emitting device comprising:
an anode;
a cathode; and
a light emitting layer between the anode and the cathode,
wherein the light emitting layer comprises a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2.
[ chemical formula 1]
In the chemical formula 1, the chemical formula is shown in the drawing,
X 1 to X 7 Each independently is CR 1 Or N, provided that X 1 To X 7 At least one of which is N,
each R is 1 Independently hydrogen; deuterium; substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C comprising any one or more selected from N, O and S 2-60 A heteroaryl group, which is a group,
L 1 to L 3 Each independently is a single bond; substituted or unsubstituted C 6-60 Arylene groups; or substituted or unsubstituted C comprising at least one selected from N, O and S 2-60 Heteroarylene group
Ar 1 And Ar is a group 2 Each independently is a substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C comprising at least one selected from N, O and S 2-60 A heteroaryl group, which is a group,
[ chemical formula 2]
In the chemical formula 2, the chemical formula is shown in the drawing,
Y 1 is N and Y 2 Is O; or Y 1 Is O and Y 2 Is a number of N, and is defined as,
r 'and R' 1 To R'. 6 Any one of them is a substituent represented by the following chemical formula 2A, and the remainder are hydrogen; deuterium; or C which is substituted or unsubstituted 6-60 An aryl group,
[ chemical formula 2A ]
In the chemical formula 2A, a compound having a chemical formula,
L' 1 to L' 3 Each independently is a single bond; or C which is substituted or unsubstituted 6-60 Arylene group
Ar' 1 And Ar' 2 Each independently is a substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C comprising at least one selected from N, O and S 2-60 Heteroaryl groups.
2. The organic light-emitting device of claim 1, wherein:
X 1 to X 7 Any one of them is N and the rest are CR 1 。
3. The organic light-emitting device of claim 1, wherein:
R 1 is hydrogen, deuterium, phenyl, biphenyl, naphthyl, carbazolyl, fluoranthenyl, phenanthryl, triphenylene, benzo [ a ]]Carbazolyl, benzo [ b ]]Carbazolyl and benzo [ c ]]Carbazolyl, dibenzofuranyl and benzo [ d ]]Naphtho [1,2-b]Furanyl and benzo [ d ]]Naphtho [2,3-b]Furanyl and benzo [ d ]]Naphtho [2,1-b]Furyl and benzeneAnd [ d ]]Naphtho [1,2-b]Thienyl, benzo [ d ]]Naphtho [2,3-b]Thienyl, benzo [ d ]]Naphtho [2,1-b]Thienyl, benzo [ c ]]Phenanthryl group,A group, phenyl naphthyl, or naphthylphenyl.
Provided that when R 1 When the compound is not hydrogen or deuterium, R 1 Unsubstituted or substituted with at least one deuterium.
4. The organic light-emitting device of claim 1, wherein:
L 1 To L 3 Each independently is a single bond, phenylene, naphthylene,
provided that when L 1 To L 3 When not a single bond, L 1 To L 3 Unsubstituted or substituted with at least one deuterium.
5. The organic light-emitting device of claim 1, wherein:
Ar 1 and Ar is a group 2 Each independently is phenyl, biphenyl, terphenyl, naphthyl, fluoranthenyl, phenanthryl, dibenzofuranyl, dibenzothienyl,Radical, or benzo [ c ]]Phenanthryl group
The Ar is as follows 1 And Ar is a group 2 Unsubstituted or substituted with at least one deuterium.
6. The organic light-emitting device of claim 1, wherein:
the compound represented by chemical formula 1 is any one selected from the following:
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7. the organic light-emitting device of claim 1, wherein:
r 'and R' 1 To R'. 6 Any one of the substituents represented by the following chemical formula 2A, and the remainder are hydrogen; deuterium; phenyl unsubstituted or substituted with 1 to 5 deuterium; or unsubstituted or substituted with 1 to 7 deuteriumSubstituted naphthyl.
8. The organic light-emitting device of claim 1, wherein:
the chemical formula 2 is represented by the following chemical formula 2-1 or chemical formula 2-2:
[ chemical formula 2-1]
[ chemical formula 2-2]
In chemical formula 2-1 and chemical formula 2-2,
the Y is 1 、Y 2 、R'、L' 1 To L' 3 、Ar' 1 And Ar' 2 As defined in claim 1.
9. The organic light-emitting device of claim 1, wherein:
L' 1 to L' 3 Each independently is a single bond, phenylene, biphenyldiyl, terphenyldiyl, naphthalenediyl,
Provided that when L' 1 To L' 3 When not being a single bond, L' 1 To L' 3 Unsubstituted or substituted with at least one deuterium.
10. The organic light-emitting device of claim 1, wherein:
Ar' 1 and Ar' 2 Each independently selected from phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, dibenzofuranyl, dibenzothienyl, dimethylfluorenyl, carbazolyl, or phenylcarbazolyl, and
the Ar 'is' 1 And Ar' 2 Unsubstituted or substituted with at least one deuterium.
11. The organic light-emitting device of claim 1, wherein:
the compound represented by chemical formula 2 is any one selected from the following:
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CN202280056278.3A 2021-11-15 2022-11-15 Organic light emitting device Pending CN117837301A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2021-0156950 2021-11-15
KR1020220152016A KR20230071086A (en) 2021-11-15 2022-11-14 Organic light emitting device
KR10-2022-0152016 2022-11-14
PCT/KR2022/018004 WO2023085908A1 (en) 2021-11-15 2022-11-15 Organic light emitting device

Publications (1)

Publication Number Publication Date
CN117837301A true CN117837301A (en) 2024-04-05

Family

ID=90519520

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202280056278.3A Pending CN117837301A (en) 2021-11-15 2022-11-15 Organic light emitting device

Country Status (1)

Country Link
CN (1) CN117837301A (en)

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