CN116261922A - Organic light emitting device - Google Patents
Organic light emitting device Download PDFInfo
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- CN116261922A CN116261922A CN202180066041.9A CN202180066041A CN116261922A CN 116261922 A CN116261922 A CN 116261922A CN 202180066041 A CN202180066041 A CN 202180066041A CN 116261922 A CN116261922 A CN 116261922A
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- compound
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- reduced pressure
- emitting device
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Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present invention provides an organic light emitting device including: an anode; a cathode disposed opposite to the anode; and a light emitting layer disposed between the anode and the cathode, wherein the light emitting layer contains 2 host compounds, whereby efficiency, driving voltage, and lifetime characteristics of the organic light emitting device can be improved.
Description
Technical Field
Cross reference to related applications
The present application claims priority based on korean patent application No. 10-2020-0136882 at 10 months and korean patent application No. 10-2021-01393 at 19 at 2021, the entire contents of the disclosures of the korean patent application are incorporated as part of the present specification.
The present invention relates to an organic light emitting device.
Background
In general, the organic light emitting phenomenon refers to a phenomenon of converting electric energy into light energy using an organic substance. An organic light emitting device using an organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, and excellent brightness, driving voltage, and response speed characteristics, and thus a great deal of research is being conducted.
The organic light emitting device generally has a structure including an anode and a cathode and an organic layer between the anode and the cathode. In order to improve efficiency and stability of the organic light-emitting device, the organic layer is often formed of a multilayer structure formed of different materials, and may be formed of a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, or the like. In such a structure of an organic light emitting device, if a voltage is applied between both electrodes, holes are injected into the organic layer from the anode and electrons are injected into the organic layer from the cathode, and when the injected holes and electrons meet, excitons (exiton) are formed, and light is emitted when the excitons transition to the ground state again.
As for the organic matter used for the organic light emitting device as described above, development of new materials is continuously demanded.
Prior art literature
Patent literature
(patent document 0001) Korean patent laid-open No. 10-2000-0051826
Disclosure of Invention
Technical problem
The present invention relates to an organic light emitting device.
Solution to the problem
The present invention provides the following organic light emitting device.
An organic light emitting device comprising:
an anode;
a cathode disposed opposite to the anode; and
a light-emitting layer disposed between the anode and the cathode,
wherein the light emitting layer includes a first compound represented by the following chemical formula 1 and a second compound represented by the following chemical formula 2:
[ chemical formula 1]
In the above-mentioned chemical formula 1,
A 1 and A 2 Each independently is a benzene or naphthalene ring fused to an adjacent five-membered ring,
l is a substituted or unsubstituted dibenzofuranylene group, or a substituted or unsubstituted benzonaphthofuranylene group,
L 1 and L 2 Each independently is a single bond, or a substituted or unsubstituted C 6-60 An arylene group,
Ar 1 and Ar is a group 2 Each independently is a substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C containing more than 1 heteroatom in N, O and S 2-60 A heteroaryl group, which is a group,
R 1 and R is 2 Each independently is hydrogen, deuterium, or substituted or unsubstituted C 6-60 An aryl group,
the A is as described above 1 And A 2 Each of which is a benzene ring, a and b are each independently an integer of 0 to 4,
the A is as described above 1 And A 2 Each of which is a naphthalene ring, a and b are each independently an integer of 0 to 6,
[ chemical formula 2]
In the above-mentioned chemical formula 2,
l' is substituted or unsubstituted C 6-60 An arylene group,
L 3 and L 4 Each independently is a single bond, or a substituted or unsubstituted C 6-60 An arylene group,
Ar 3 and Ar is a group 4 Each independently is a substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C containing more than 1 heteroatom in N, O and S 2-60 A heteroaryl group, which is a group,
R 3 is hydrogen or deuterium, and is preferably selected from the group consisting of,
c is an integer from 0 to 9.
In this case, when a, b and c are each 2 or more, the substituents in parentheses are the same or different from each other.
Effects of the invention
The organic light emitting device described above contains 2 host compounds in the light emitting layer, and efficiency, driving voltage, and/or lifetime characteristics can be improved in the organic light emitting device.
Drawings
Fig. 1 illustrates an example of an organic light-emitting device constituted by a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.
Fig. 2 illustrates an example of an organic light-emitting device constituted by a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron suppression 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
In the following, the invention will be described in more detail in order to aid understanding thereof.
In the present description of the invention,
represents a bond to other substituent, D represents deuterium, and Ph represents phenyl.
In the present specification, the term "substituted or unsubstituted" means that it is selected from deuterium; a halogen group; a nitrile group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; alkylthio group
Arylthio->
Alkylsulfonyl->
Arylsulfonyl->
A silyl group; a boron base; an alkyl group; cycloalkyl; alkenyl groups; an aryl group; an aralkyl group; aralkenyl; alkylaryl groups; an alkylamino group; an aralkylamine group; heteroaryl amine groups; an arylamine group; aryl phosphino; or a substituent comprising N, O and 1 or more substituents in a heterocyclic group comprising 1 or more of S atoms, or a substituent which is bonded to 2 or more substituents in the above-exemplified substituents. For example, the "substituent in which 2 or more substituents are linked" may be a biphenyl group. That is, biphenyl may be aryl or may be interpreted as a substituent in which 2 phenyl groups are linked. As an example, the term "substituted or unsubstituted" may be understood as "unsubstituted or substituted or as being selected from deuterium, halogen, C 1-10 Alkyl, C 1-10 Alkoxy and C 6-20 More than 1, for example, 1 to 5 substituents in the aryl group are substituted. In addition, in the present specification, the term "substituted with 1 or more substituents" may be understood as meaning "substituted with 1 to 5 substituents" or "substituted with 1 or 2 substituents", for example.
In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40. Specifically, the substituent may have the following structure, but is not limited thereto.
In the present specification, in the ester group, 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 substituent may be a substituent of the following structural formula, but is not limited thereto.
In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25. Specifically, the substituent may have the following structure, but is not limited thereto.
In the present specification, the silyl group specifically includes, but is not limited to, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like.
In the present specification, the boron group specifically includes trimethylboron group, triethylboron group, t-butyldimethylboroyl group, triphenylboron group, phenylboron group, and the like, but is not limited thereto.
In the present specification, examples of the halogen group include fluorine, chlorine, bromine, and iodine.
In the present specification, the alkyl group may be a straight chain or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the above alkyl group has 1 to 10 carbon atoms. According to another embodiment, 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-ethylbutyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-ethyl-propyl, 1-dimethylpropyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, isohexyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2, 4-trimethyl-1-pentyl, 2, 4-trimethyl-2-pentyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl and the like.
In the present specification, the alkenyl group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another embodiment, the alkenyl group has 2 to 6 carbon atoms. 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-phenylene1-yl, 2-diphenylethylene1-yl, 2-phenyl-2- (naphthalen-1-yl) ethylene1-yl, 2-bis (diphenyl-1-yl) ethylene1-yl, stilbene, styryl and the like, but are not limited thereto.
In the present specification, cycloalkyl is not particularly limited, but is preferably cycloalkyl having 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, there are cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, adamantyl (amantadinyl) and the like, but not limited thereto.
In the present specification, the aryl group is not particularly limited, but is preferably an aryl group having 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group, such as phenyl, biphenyl, and terphenyl, but is not limited thereto. The polycyclic aryl group may be naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, and the like,
A group, a fluorenyl group, etc., but is not limited thereto.
In this specification, a fluorenyl group may be substituted, and 2 substituents may be combined with each other to form a spiro structure. In the case where the above-mentioned fluorenyl group is substituted,
can become
Etc. However, the present invention is not limited thereto.
In the present specification, the heteroaryl group is a heterocyclic group containing 1 or more heteroatoms in O, N, si and S as hetero elements, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60. Examples of heteroaryl groups include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, and the like,
Azolyl, (-) -and (II) radicals>
Diazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl A group, isoquinolyl, indolyl, carbazolyl, benzo +.>
Oxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothiophenyl, benzofuranyl, phenanthroline (phenanthrinyl), iso>
Oxazolyl, thiadiazolyl, phenothiazinyl, dibenzofuranyl, and the like, but are not limited thereto.
In the present specification, the aryl groups in the aralkyl group, the aralkenyl group, the alkylaryl group, the arylamine group, and the arylsilyl group are the same as those exemplified for the aryl groups described above. In the present specification, the alkyl group in the aralkyl group, alkylaryl group, and alkylamino group is the same as the above-mentioned alkyl group. In this specification, the heteroaryl group in the heteroaryl amine may be as described above with respect to the heteroaryl group. In the present specification, the alkenyl group in the aralkenyl group is the same as the above-described examples of alkenyl groups. In this specification, arylene is a 2-valent group, and the above description of aryl can be applied in addition to this. In this specification, the heteroarylene group is a 2-valent group, and the above description of the heteroaryl group can be applied thereto. In this specification, the hydrocarbon ring is not a 1-valent group, but a combination of 2 substituents, and the above description of the aryl group or cycloalkyl group can be applied. In this specification, a heterocyclic ring is not a 1-valent group but a combination of 2 substituents, and the above description of heteroaryl groups can be applied thereto.
On the other hand, the organic light emitting device according to an embodiment includes an anode, a cathode disposed opposite to the anode, and a light emitting layer disposed between the anode and the cathode, the light emitting layer including a first compound represented by the chemical formula 1 and a second compound represented by the chemical formula 2.
The organic light emitting device according to the present invention simultaneously contains 2 kinds of compounds having a specific structure as host materials in the light emitting layer, so that efficiency, driving voltage, and/or lifetime characteristics of the organic light emitting device can be improved.
The present invention will be described in detail with reference to the following configurations.
Anode and cathode
As the anode material, a material having a large work function is generally preferable in order to allow holes to be smoothly injected into the organic layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, and gold, and alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); znO of Al or SnO 2 A combination of metals such as Sb and the like and oxides; poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene]Conductive polymers such as (PEDOT), polypyrrole and polyaniline, but not limited thereto.
As the cathode material, a material having a small work function is generally preferred in order to facilitate injection of electrons into the organic layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, and alloys thereof; liF/Al or LiO 2 And/or Al, but is not limited thereto.
Hole injection layer
The organic light emitting device according to the present invention may include a hole injection layer between the anode and a hole transport layer described later as needed.
The hole injection layer is a layer that injects holes from the anode and contains a hole injection substance, and is located on the anode. As such a hole injection substance, the following compounds are preferable: a compound which has a hole transporting ability, has an effect of injecting holes from the anode, has an excellent hole injecting effect for the light emitting layer or the light emitting material, prevents excitons generated in the light emitting layer from migrating to the electron injecting layer or the electron injecting material, and has an excellent thin film forming ability. In particular, it is suitable that the HOMO (highest occupied molecular orbital ) of the hole-injecting substance is interposed between the work function of the anode substance and the HOMO of the surrounding organic layer.
Specific examples of the hole injection substance include metalloporphyrin (porphyrin), oligothiophene, arylamine-based organic substance, hexanitrile hexaazabenzophenanthrene-based organic substance, quinacridone-based organic substance, perylene-based organic substance, anthraquinone, polyaniline, and polythiophene-based conductive polymer, but are not limited thereto.
Hole transport layer
The organic light emitting device according to the present invention may include a hole transport layer between the anode and the light emitting layer. The hole-transporting layer is a layer that receives holes from the anode or a hole-injecting layer formed on the anode and transports the holes to the light-emitting layer, and contains a hole-transporting substance. The hole-transporting substance is preferably a substance which can receive holes from the anode or the hole-injecting layer and transfer the holes to the light-emitting layer, and has a large mobility to the holes. Specific examples thereof include an arylamine-based organic substance, a conductive polymer, and a block copolymer having both conjugated and unconjugated portions, but are not limited thereto.
Electron suppression layer
The organic light emitting device according to the present invention may include an electron suppressing layer between the hole transporting layer and the light emitting layer as needed. The electron suppression layer refers to the following layer: the hole transport layer is preferably formed on the light emitting layer, and is preferably provided in contact with the light emitting layer, and serves to improve the efficiency of the organic light emitting device by adjusting the hole mobility, thereby preventing excessive migration of electrons and improving the probability of hole-electron bonding. The electron blocking layer contains an electron blocking material, and as an example of such an electron blocking material, an arylamine-based organic material or the like can be used, but the electron blocking material is not limited thereto.
Light-emitting layer
An organic light-emitting device according to the present invention includes a light-emitting layer including the above-described first compound and the above-described second compound as host substances between an anode and a cathode. Specifically, the first compound functions as an N-type host material having a superior electron transport ability to that of the hole transport material, and the second compound functions as a P-type host material having a superior hole transport ability to that of the electron transport material, so that the ratio of holes to electrons in the light-emitting layer can be appropriately maintained. Accordingly, the excitons uniformly emit light in the entire light emitting layer, so that the light emitting efficiency and the lifetime characteristics of the organic light emitting device can be simultaneously improved.
Next, the first compound and the second compound will be described in order.
(first Compound)
The first compound is represented by chemical formula 1. Specifically, the first compound is a compound in which a triazinyl group is bonded to the N atom of the carbazole-based core through a linking group L, and is characterized in that the linking group L is a dibenzofuranylene group or a benzonaphthofuranylene group. In particular, the above-described first compound has a further improved electron transporting ability and efficiently transfers electrons to the dopant substance as compared with a compound having a linking group other than the dibenzofuranylene group and the benzonaphthofuranylene group as L, and thus the electron-hole recombination probability in the light-emitting layer can be improved.
According to one embodiment, in the above chemical formula 1,
A 1 and A 2 Each independently is a benzene ring fused to an adjacent five-membered ring; or alternatively
A 1 And A 2 One of them is a benzene ring condensed with an adjacent five-membered ring, and the other is a naphthalene ring condensed with an adjacent five-membered ring; or alternatively
A 1 And A 2 Each independently is a naphthalene ring fused to an adjacent five-membered ring.
In chemical formula 1, a represents R 1 Is an integer of 0 to 6. Specifically, A 1 In the case of benzene rings, a is 0, 1, 2, 3 or 4, A 1 In the case of naphthalene ring, b is 0, 1, 2, 3, 4, 5 or 6.
In addition, b represents R 2 Is an integer of 0 to 6. Specifically, A 2 When the compound is benzene ring, b is 0, 1, 2, 3 or 4, A 2 In the case of naphthalene ring, b is 0, 1, 2, 3, 4, 5 or 6.
At this time, a+b may be an integer of 0 to 4. Alternatively, a+b may be 0 or 1.
More haveIn the general formula 1, the substituent
Can be represented by any one of the following chemical formulas 1a to 1 j: />
In the above chemical formulas 1a to 1j,
a 'and b' are each independently integers from 0 to 4,
a "and b" are each independently integers from 0 to 6,
R 1 and R is 2 The same definition as in the above chemical formula 1.
More specifically, in the above chemical formulas 1a to 1j,
a ', b', a "and b" may each independently be 0, 1 or 2.
For example, in the above chemical formula 1a, a '+b' is 0 or 1,
in the above chemical formulas 1b to 1d, a "+b' is 0 or 1,
in the above chemical formulas 1e to 1j, a "+b" is 0 or 1.
Thus, the above-mentioned first compound may be represented by any one of the following chemical formulas 1-1 to 1-10:
in the above 1-1 to 1-10,
a 'and b' are each independently integers from 0 to 4,
a "and b" are each independently integers from 0 to 6,
L、L 1 、L 2 、Ar 1 、Ar 2 、R 1 and R is 2 The same definition as in the above chemical formula 1.
More specifically, in the above 1-1 to 1-10,
a ', b', a "and b" may each independently be 0, 1 or 2.
For example, in the above chemical formula 1-1, a '+b' is 0 or 1,
in the above chemical formulas 1-2 to 1-4, a "+b' is 0 or 1,
in the above chemical formulas 1-5 to 1-10, a "+b" is 0 or 1.
In addition, in the above chemical formula 1, L may be dibenzoylene, benzo (b) naphtho (1, 2-d) furanyl, benzo (b) naphtho (2, 3-d) furanyl or benzo (b) naphtho (2, 1-d) furanyl,
here, the above L may be unsubstituted or substituted with 1 or more deuterium.
More specifically, L may be any one selected from the following groups.
More specifically, L may be dibenzofuranylene or benzo (b) naphtho (2, 3-d) furanyl.
For example, L may be any one selected from the following groups:
in the chemical formula 1, L 1 And L 2 Each independently may be a single bond, or C which is unsubstituted or substituted with 1 or more deuterium 6-20 Arylene groups.
Specifically, L 1 And L 2 Each independently may be a single bond or phenylene.
More specifically, L 1 And L 2 May be single bonds.
In addition, in the above chemical formula 1, ar 1 And Ar is a group 2 Each independently can be unsubstitutedOr C substituted by more than 1 deuterium 6-20 Aryl, or C containing 1 hetero atom in O and S, unsubstituted or substituted with more than 1 deuterium 2-20 Heteroaryl groups.
Specifically, ar 1 And Ar is a group 2 Each independently may be phenyl, biphenyl, naphthyl, or dibenzofuranyl.
At this time, ar 1 And Ar is a group 2 At least one of which may be phenyl.
In addition, ar 1 And Ar is a group 2 May be the same or different from each other.
In addition, R 1 And R is 2 Each independently can be hydrogen or C 6-20 Aryl groups.
For example, R 1 And R is 2 Each independently may be phenyl, biphenyl, or naphthyl.
On the other hand, representative examples of the first compound represented by the above chemical formula 1 are as follows:
on the other hand, as an example, the first compound can be produced by a production method shown in the following reaction formula 1.
[ reaction type 1]
In the above reaction formula 1, X is halogen, preferably bromine or chlorine, and the definition of other substituents is the same as the above description.
Specifically, the compound represented by the above chemical formula 1 can be produced by an amine substitution reaction of the starting materials A1 and A2. Such an amine substitution reaction is preferably carried out in the presence of a palladium catalyst and a base, and the reactive groups used for the amine substitution reaction may be appropriately changed. The method for producing the compound represented by the above chemical formula 1 can be more specifically described in the production examples described later.
(second Compound)
The second compound is represented by chemical formula 2. Specifically, the second compound is characterized by having a 9-phenanthryl group as one of the substituents of the amino group and having a substituted or unsubstituted C as the remaining substituent 6-60 Aryl or substituted or unsubstituted C containing more than 1 hetero atom in N, O and S 2-15 Heteroaryl groups. In particular, the second compound can efficiently transfer holes to a dopant substance as compared with i) a compound having no 9-phenanthryl group but one of substituents of 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, or 4-phenanthryl as an amino group, and ii) a compound in which an N atom of an amino group and a phenanthryl group are linked by a single bond, and thus can improve recombination probability of holes and electrons in a light emitting layer together with the first compound having excellent electron transporting ability.
In addition, L' may be C which is unsubstituted or substituted by deuterium 6-20 Arylene groups.
Specifically, each L' independently may be phenylene, biphenyldiyl, or naphthylene.
More specifically, L' may be any one selected from the following groups:
for example, L' may be any one selected from the following groups:
in addition, L 3 And L 4 Each independently may be a single bond, or C which is unsubstituted or substituted with 1 or more deuterium 6-20 Arylene groups.
For example, L 3 And L 4 Each independently may be a single bond, phenylene, biphenyldiyl or naphthylene.
At this time, L 3 And L 4 May be the same or different from each other.
In addition, ar 3 And Ar is a group 4 Each independently may be unsubstituted or selected from deuterium, C 1-10 Alkyl and C 6-20 C substituted by more than 1 substituent in aryl 6-20 An aryl group; or is unsubstituted or selected from deuterium, C 1-10 Alkyl and C 6-20 C comprising 1 hetero atom in N, O and S substituted by more than 1 substituent in aryl 2-20 Heteroaryl groups.
Specifically, ar 3 And Ar is a group 4 Each independently is phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, carbazolyl, dibenzofuranyl, dibenzothienyl or benzonaphthofuranyl,
ar as described above 3 And Ar is a group 4 May be unsubstituted or substituted by phenyl or naphthyl.
For example, ar 3 And Ar is a group 4 Each independently may be phenyl, phenylnaphthyl, biphenyl, terphenyl, naphthyl, naphthylphenyl, phenanthryl, triphenylene, or a group selected fromAny one of:
here, the terphenyl group is any one selected from the group consisting of:
at this time, ar 3 And Ar is a group 4 May be the same or different from each other.
In addition, R 3 Is hydrogen or deuterium, c represents R 3 Is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9. Specifically, R 3 Are hydrogen or deuterium. For example, R 3 Are all hydrogen.
On the other hand, representative examples of the compounds represented by the above chemical formula 2 are shown below:
on the other hand, as an example, the compound represented by the above chemical formula 2 can be produced by a production method shown in the following reaction formula 2:
[ reaction type 2]
In the above reaction formula 2, X' is halogen, preferably bromine or chlorine, and the definition of other substituents is the same as the above description.
Specifically, the compound represented by the above chemical formula 1 can be produced by an amine substitution reaction of the starting materials A3 and A4. Such an amine substitution reaction is preferably carried out in the presence of a palladium catalyst and a base, and the reactive groups used for the amine substitution reaction may be appropriately changed. The method for producing the compound represented by the above chemical formula 2 can be more specifically described in the production examples described later.
In addition, the first compound and the second compound may be contained in the light emitting layer at a weight ratio of 1:99 to 99:1. At this time, the above-described first compound and the above-described second compound are more preferably contained in a weight ratio of 30:70 to 70:30, a weight ratio of 40:60 to 60:40, or a weight ratio of 50:50 in terms of appropriately maintaining the ratio of holes and electrons in the light-emitting layer.
On the other hand, the light-emitting layer may contain a dopant substance in addition to the 2 host substances. Examples of such dopant substances include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is an aromatic condensed ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene having an arylamino group,
Bisindenopyrene, and the like, and a styrylamine compound is a compound in which at least 1 arylvinyl group is substituted on a substituted or unsubstituted arylamine, and is substituted or unsubstituted with 1 or more substituents selected from the group consisting of aryl, silyl, alkyl, cycloalkyl, and arylamino groups. Specifically, there are styrylamine, styrylenediamine, styrylenetriamine, styrylenetetramine, and the like, but the present invention is not limited thereto. The metal complex includes, but is not limited to, iridium complex, platinum complex, and the like. / >
Hole blocking layer
The organic light emitting device according to the present invention may include a hole blocking layer between the light emitting layer and an electron transport layer described later as needed. The hole blocking layer refers to the following layer: the layer formed on the light-emitting layer is preferably provided in contact with the light-emitting layer, and serves to improve the efficiency of the organic light-emitting device by preventing excessive migration of holes and increasing the probability of hole-electron bonding by adjusting the electron mobility. The hole blocking layer contains a hole blocking substance, and as examples of such a hole blocking substance, azine derivatives including triazines, triazole derivatives, and the like can be used,
The compound having an electron withdrawing group introduced therein, such as an diazole derivative, a phenanthroline derivative, and a phosphine oxide derivative, but is not limited thereto.
Electron injection and transport layers
The electron injection and transport layer is a layer which injects electrons from an electrode and transports the received electrons to a light emitting layer and functions as both an electron transport layer and an electron injection layer, and is formed on the light emitting layer or the hole blocking layer. Such an electron injection and transport substance is a substance that can well receive electrons from the cathode and transfer them to the light-emitting layer, and is suitable for a substance having high electron mobility. As specific examples of the electron injecting and transporting substance, there are Al complexes of 8-hydroxyquinoline containing Alq 3 But not limited to, complexes of (c) with (c), organic radical compounds, hydroxyflavone-metal complexes, triazine derivatives, and the like. Or can be mixed with fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide,
Azole,/->
Diazoles, triazoles, imidazoles, perylenetetracarboxylic acids, fluorenylenemethanes, anthrones, and the like, and their derivatives, metal complexes, nitrogen-containing five-membered ring derivatives, and the like are used together,however, the present invention is not limited thereto.
The electron injection and transport layer may be formed as separate layers such as an electron injection layer and an electron transport layer. In this case, an electron transporting layer is formed over the light emitting layer or the hole blocking layer, and the electron injecting and transporting substance can be used as the electron transporting substance contained in the electron transporting layer. Further, an electron injection layer is formed on the electron transport layer, and LiF, naCl, csF, li, may be used as an electron injection material contained in the electron injection layer 2 O, baO fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide,
Azole,/->
Diazoles, triazoles, imidazoles, perylenetetracarboxylic acids, fluorenylenemethanes, anthrones, and the like, and their derivatives, metal complexes, and nitrogen-containing five-membered ring derivatives, and the like.
Examples of the metal complex 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 (10-hydroxybenzo [ h ] quinoline), gallium chloride bis (2-methyl-8-quinoline) (o-cresol) gallium, aluminum bis (2-methyl-8-quinoline) (1-naphthol), gallium bis (2-methyl-8-quinoline) (2-naphthol).
Organic light emitting device
A structure of an organic light emitting device according to the present invention is illustrated in fig. 1. Fig. 1 illustrates an example of an organic light-emitting device constituted by a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4. In the structure described above, the first compound and the second compound may be contained in the light-emitting layer.
Fig. 2 illustrates an example of an organic light-emitting device constituted by a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron suppression layer 7, a light-emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4. In the structure described above, the first compound and the second compound may be contained in the light-emitting layer.
The organic light emitting device according to the present invention can be manufactured by sequentially laminating the above-described constitution. This can be manufactured as follows: PVD (physical Vapor Deposition) such as sputtering (sputtering) or electron beam evaporation (physical vapor deposition) is used to deposit a metal or a metal oxide having conductivity or an alloy thereof on a substrate to form an anode, and each layer is formed on the anode, and then a substance that can be used as a cathode is deposited thereon. In addition to this method, an organic light-emitting device can be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate. In addition, the host and the dopant may be formed into the light-emitting layer not only by a vacuum vapor deposition method but also by a solution coating method. Here, the solution coating method refers to spin coating, dip coating, blade coating, inkjet printing, screen printing, spray coating, roll coating, and the like, but is not limited thereto.
In addition to this method, an organic light-emitting device can be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited thereto.
On the other hand, the organic light emitting device according to the present invention may be a bottom emission (bottom emission) device, a top emission (top emission) device, or a bi-directional light emitting device, and in particular, may be a bottom emission device requiring relatively high light emitting efficiency.
In addition, the compound according to the present invention may be contained in an organic solar cell or an organic transistor in addition to the organic light emitting device.
The fabrication of the above-described organic light emitting device is specifically described in the following examples. However, the following examples are given by way of illustration of the present invention, and the scope of the present invention is not limited thereto.
Synthesis example 1-1: production of Compound 1-1
Substance (sub) 1 (15 g,56 mmol) and intermediate a (15.2 g,61.6 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (potassium carbonate) (23.2 g,168.1 mmol) was dissolved in 70mL of water and the mixture was poured, and after stirring the mixture sufficiently, bis (tri-tert-butylphosphine) palladium (0) (bis (tris-tert-butylphenyl) palladium (0)) (0.9 g,1.7 mmol) was poured. After reacting for 12 hours, cooling to normal temperature, separating the organic layer from the water layer, and distilling the organic layer. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 16.5g of substance 1-1 was produced. (yield 68%, MS: [ M+H) ] + ＝434)
Compound A (10 g,46 mmol), material 1-1 (22 g,50.6 mmol), sodium tert-butoxide (8.8 g,92.1 mmol) were added to 200mL of Xylene (Xylene) under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 3 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 18.4g of compound 1-1 was obtained. (yield 65%, MS: [ M+H ]] + ＝615)
Synthesis examples 1 to 2: production of Compounds 1-2
Substance 1 (15 g,56 mmol) and intermediate b (15.2 g,61.6 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (23.2 g,168.1 mmol) was dissolved in 70mL of water and added thereto, and after stirring sufficiently, bis (tri-tertiary) was added theretoButylphosphine) palladium (0) (0.9 g,1.7 mmol). After reacting for 10 hours, cooling to normal temperature, separating the organic layer from the water layer, and distilling the organic layer. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to thereby produce 16g of substance 1-2. (yield 66%, MS: [ M+H) ] + ＝434)
Compound A (10 g,46 mmol), material 1-2 (22 g,50.6 mmol), sodium tert-butoxide (8.8 g,92.1 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 3 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 15.3g of compound 1-2 was obtained. (yield 54%, MS: [ M+H)] + ＝615)
Synthesis examples 1 to 3: production of Compounds 1-3
Compound B (10 g,37.4 mmol), material 1-2 (17.9 g,41.1 mmol), sodium t-butoxide (7.2 g,74.8 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 mmol) was charged. After 2 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 12.7g of compounds 1 to 3 was obtained. (yield 51%, MS: [ M+H ] ] + ＝665)
Synthesis examples 1 to 4: production of Compounds 1-4
Substance 2 (15 g,41.9 mmol) and intermediate c (11.4 g,46.1 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (17.4 g,125.8 mmol) was dissolved in 52mL of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.3 mmol) was added thereto. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to thereby produce 17.3g of substances 1 to 3. (yield 79%, MS: [ M+H)] + ＝524)
Material 1-3 (10 g,19.1 mmol), compound E (3.4 g,20 mmol), sodium t-butoxide (2.8 g,28.6 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8..1g of compound 1-4 was obtained. (yield 65%, MS: [ M+H ] ] + ＝655)
Synthesis examples 1 to 5: production of Compounds 1-5
Substance 1 (15 g,56 mmol) and intermediate d (15.2 g,61.6 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (23.2 g,168.1 mmol) was dissolved in 70mL of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.9 g,1.7 mmol) was added thereto. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. Dissolving in chloroform again, washing with water for 2 times, and separatingThe organic layer was separated, anhydrous magnesium sulfate was added thereto, and after stirring, filtration was performed, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 15.3g of substances 1 to 4 were produced. (yield 63%, MS: [ M+H)] + ＝434)
Compound A (10 g,46 mmol), materials 1-4 (22 g,50.6 mmol), sodium tert-butoxide (8.8 g,92.1 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 3 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 17g of compounds 1 to 5 were obtained. (yield 60%, MS: [ M+H) ] + ＝615)
Synthesis examples 1 to 6: production of Compounds 1-6
Substance 1 (15 g,56 mmol) and intermediate e (15.2 g,61.6 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (23.2 g,168.1 mmol) was dissolved in 70mL of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.9 g,1.7 mmol) was added thereto. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 18.9g of substances 1 to 5 were produced. (yield 78%, MS: [ M+H)] + ＝434)
Compound A (10 g,46 mmol), materials 1-5 (22 g,50.6 mmol), sodium tert-butoxide (8.8 g,92.1 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 3 hours, cooling to normal temperature and decompressing to remove the solvent when the reaction is finishedAnd (3) an agent. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 14.1g of compounds 1 to 6 was obtained. (yield 50%, MS: [ M+H) ] + ＝615)
Synthesis examples 1 to 7: production of Compounds 1-7
Substance 1 (15 g,56 mmol) and intermediate f (15.2 g,61.6 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (23.2 g,168.1 mmol) was dissolved in 70mL of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.9 g,1.7 mmol) was added thereto. After reacting for 10 hours, cooling to normal temperature, separating the organic layer from the water layer, and distilling the organic layer. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to thereby produce 17.7g of substances 1 to 6. (yield 73%, MS: [ M+H)] + ＝434)
Compound A (10 g,46 mmol), materials 1-6 (22 g,50.6 mmol), sodium tert-butoxide (8.8 g,92.1 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 2 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 17.5g of compounds 1 to 7 was obtained. (yield 62%, MS: [ M+H) ] + ＝615)
Synthesis examples 1 to 8: production of Compounds 1-8
Compound B (10 g,37.4 mmol), materials 1-6 (17.9 g,41.1 mmol), sodium t-butoxide (7.2 g,74.8 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 mmol) was charged. After 3 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 16.9g of compounds 1 to 8 were obtained. (yield 68%, MS: [ M+H)] + ＝665)
Synthesis examples 1 to 9: production of Compounds 1-9
Material 1 (15 g,56 mmol) and intermediate g (15.2 g,61.6 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (23.2 g,168.1 mmol) was dissolved in 70mL of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.9 g,1.7 mmol) was added thereto. After reacting for 8 hours, cooling to normal temperature, separating the organic layer from the water layer, and distilling the organic layer. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to thereby produce 18g of substances 1 to 7. (yield 74%, MS: [ M+H ] ] + ＝434)
Compound A (10 g,46 mmol), materials 1-7 (22 g,50.6 mmol), sodium tert-butoxide (8.8 g,92.1 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 3 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound is usedPurification by silica gel column chromatography gave 19.8g of compounds 1-9. (yield 70%, MS: [ M+H)] + ＝615)
Synthesis examples 1 to 10: production of Compounds 1 to 10
Material 3 (15 g,43.6 mmol) and intermediate h (11.8 g,48 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (18.1 g,130.9 mmol) was dissolved in 54mL of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.7 g,1.3 mmol) was added thereto. After reacting for 12 hours, cooling to normal temperature, separating the organic layer from the water layer, and distilling the organic layer. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to thereby produce 14.2g of substances 1 to 8. (yield 64%, MS: [ M+H) ] + ＝510)
Compound A (10 g,46 mmol), materials 1-8 (25.4 g,50.6 mmol), sodium t-butoxide (8.8 g,92.1 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 3 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 18.1g of compounds 1 to 10 were obtained. (yield 57%, MS: [ M+H)] + ＝691)
Synthesis examples 1 to 11: production of Compounds 1-11
Substance 1 (15 g,56 mmol) and intermediate i (15.2 g,61.6 mmol) were added to 300mL of THF under nitrogen, stirred and returnedAnd (3) flow. Then, potassium carbonate (23.2 g,168.1 mmol) was dissolved in 70mL of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.9 g,1.7 mmol) was added thereto. After reacting for 10 hours, cooling to normal temperature, separating the organic layer from the water layer, and distilling the organic layer. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 18.9g of substances 1 to 9 were produced. (yield 78%, MS: [ M+H) ] + ＝434)
Compound A (10 g,46 mmol), materials 1-9 (22 g,50.6 mmol), sodium tert-butoxide (8.8 g,92.1 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 2 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 16.7g of compounds 1 to 11 was obtained. (yield 59%, MS: [ M+H)] + ＝615)
Synthesis examples 1 to 12: production of Compounds 1-12
Substance 1 (15 g,56 mmol) and intermediate j (15.2 g,61.6 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (23.2 g,168.1 mmol) was dissolved in 70mL of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.9 g,1.7 mmol) was added thereto. After reacting for 10 hours, cooling to normal temperature, separating the organic layer from the water layer, and distilling the organic layer. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to thereby produce 15.5g of substances 1 to 10. (yield 64%, MS: [ M+H) ] + ＝434)
Under nitrogen atmosphere, 1-10 (10 g,23 mmol), compound E (4 g,24.2 mmol), sodium tert-butoxide (3.3 g,34.6 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.2g of compounds 1 to 12 were obtained. (yield 55%, MS: [ M+H)] + ＝565)
Synthesis examples 1 to 13: production of Compounds 1-13
Substance 4 (15 g,47.2 mmol) and intermediate k (12.8 g,51.9 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (19.6 g,141.6 mmol) was dissolved in 59mL of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.7 g,1.4 mmol) was added thereto. After reacting for 8 hours, cooling to normal temperature, separating the organic layer from the water layer, and distilling the organic layer. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to thereby produce 15.1g of substances 1 to 11. (yield 66%, MS: [ M+H ] ] + ＝484)
Compound A (10 g,46 mmol), materials 1-11 (24.5 g,50.6 mmol), sodium t-butoxide (8.8 g,92.1 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 3 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. Purifying the concentrated compound by silica gel column chromatography to obtain15.9g of compounds 1-13 are obtained. (yield 52%, MS: [ M+H)] + ＝665)
Synthesis examples 1 to 14: production of Compounds 1-14
Substance 5 (15 g,41.9 mmol) and intermediate l (11.4 g,46.1 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (17.4 g,125.8 mmol) was dissolved in 52mL of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.3 mmol) was added thereto. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to thereby produce 14.7g of substances 1 to 12. (yield 67%, MS: [ M+H ] ] + ＝524)
Compound A (10 g,46 mmol), materials 1-12 (26.5 g,50.6 mmol), sodium t-butoxide (8.8 g,92.1 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 3 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 20.1g of compounds 1 to 14 were obtained. (yield 62%, MS: [ M+H)] + ＝705)
Synthesis examples 1 to 15: production of Compounds 1-15
Substance 2 (15 g,41.9 mmol) and intermediate m (11.4 g,46.1 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (17.4 g,125.8 mmol) was dissolved in 52mL of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.3 mmol) was added thereto. After reacting for 12 hours, cooling to normal temperature, separating the organic layer from the water layer, and distilling the organic layer. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to thereby produce 17.1g of substances 1 to 13. (yield 78%, MS: [ M+H) ] + ＝524)
Compound C (10 g,37.4 mmol), materials 1-13 (21.6 g,41.2 mmol), sodium t-butoxide (7.2 g,74.8 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 mmol) was charged. After 2 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 13.2g of compounds 1 to 15 were obtained. (yield 50%, MS: [ M+H)] + ＝705)
Synthesis examples 1 to 16: production of Compounds 1-16
Substance 6 (15 g,40.8 mmol) and intermediate n (11.1 g,44.9 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (16.9 g,122.3 mmol) was dissolved in 51mL of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.2 mmol) was added thereto. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to thereby produce 15.4g of substances 1 to 14. (yield 71%, MS: [ M+H) ] + ＝534)
Under nitrogen atmosphereCompound A (10 g,46 mmol), materials 1-14 (27 g,50.6 mmol), sodium t-butoxide (8.8 g,92.1 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 2 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 19.4g of compounds 1 to 16 were obtained. (yield 59%, MS: [ M+H)] + ＝715)
Synthesis examples 1 to 17: production of Compounds 1-17
Substance 4 (15 g,47.2 mmol) and intermediate o (12.8 g,51.9 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (19.6 g,141.6 mmol) was dissolved in 59mL of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.7 g,1.4 mmol) was added thereto. After reacting for 12 hours, cooling to normal temperature, separating the organic layer from the water layer, and distilling the organic layer. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 16.6g of substances 1 to 15 were produced. (yield 73%, MS: [ M+H) ] + ＝484)
Compound A (10 g,46 mmol), materials 1-15 (24.5 g,50.6 mmol), sodium t-butoxide (8.8 g,92.1 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 2 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 18g of compounds 1 to 17 were obtained. (collection)The rate is 59%, MS is [ M+H ]] + ＝665)
Synthesis examples 1 to 18: production of Compounds 1-18
Substance 7 (15 g,47.2 mmol) and intermediate p (12.8 g,51.9 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (19.6 g,141.6 mmol) was dissolved in 59mL of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.7 g,1.4 mmol) was added thereto. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 16.9g of substances 1 to 16 were produced. (yield 74%, MS: [ M+H ] ] + ＝484)
Compound A (10 g,46 mmol), materials 1-16 (24.5 g,50.6 mmol), sodium t-butoxide (8.8 g,92.1 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 2 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 18.3g of compounds 1 to 18 were obtained. (yield 60%, MS: [ M+H)] + ＝665)
Synthesis examples 1 to 19: production of Compounds 1 to 19
Material 3 (15 g,43.6 mmol) and intermediate b (11.8 g,48 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (18.1 g,130.9 mmol) was dissolved in 54mL of waterAfter the mixture was poured and stirred well, bis (tri-t-butylphosphine) palladium (0) (0.7 g,1.3 mmol) was poured. After reacting for 12 hours, cooling to normal temperature, separating the organic layer from the water layer, and distilling the organic layer. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to thereby produce 17.1g of substances 1 to 17. (yield 77%, MS: [ M+H) ] + ＝510)
Substances 1-17 (10 g,19.6 mmol), compound E (3.4 g,20.6 mmol), sodium t-butoxide (2.8 g,29.4 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8g of compounds 1 to 19 were obtained. (yield 64%, MS: [ M+H)] + ＝641)
Synthesis examples 1 to 20: production of Compounds 1-20
Substance 8 (15 g,35.7 mmol) and intermediate p (9.7 g,39.3 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (14.8 g,107.2 mmol) was dissolved in 44mL of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.5 g,1.1 mmol) was added thereto. After reacting for 12 hours, cooling to normal temperature, separating the organic layer from the water layer, and distilling the organic layer. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to thereby produce 13g of substances 1 to 18. (yield 62%, MS: [ M+H) ] + ＝586)
Under nitrogen atmosphere, compound A (10 g,46 mmol) was taken up1-18 (29.7 g,50.6 mmol), sodium t-butoxide (8.8 g,92.1 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 2 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 24.7g of compounds 1 to 20 were obtained. (yield 70%, MS: [ M+H)] + ＝767)
Synthesis examples 1 to 21: production of Compounds 1-21
Substance 4 (15 g,47.2 mmol) and intermediate q (12.8 g,51.9 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (19.6 g,141.6 mmol) was dissolved in 59mL of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.7 g,1.4 mmol) was added thereto. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to thereby produce 17.8g of substances 1 to 19. (yield 78%, MS: [ M+H ] ] + ＝484)
Under nitrogen, substances 1-19 (10 g,20.7 mmol), compound E (3.6 g,21.7 mmol), sodium t-butoxide (3 g,31 mmol) were added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was charged. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 7.6g of compounds 1 to 21 were obtained. (yield 60%, MS: [ M+H)] + ＝615)
Synthesis examples 1 to 22: production of Compounds 1-22
Substance 1 (15 g,56 mmol) and intermediate k (15.2 g,61.6 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (23.2 g,168.1 mmol) was dissolved in 70mL of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.9 g,1.7 mmol) was added thereto. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to thereby produce 23.4g of substances 1 to 20. (yield 80%, MS: [ M+H ] ] + ＝524)
Compound A (10 g,46 mmol), materials 1-20 (26.5 g,50.6 mmol), sodium t-butoxide (8.8 g,92.1 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 3 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 16.2g of compounds 1 to 22 were obtained. (yield 50%, MS: [ M+H)] + ＝705)
Synthesis examples 1 to 23: production of Compounds 1-23
Substance 9 (15 g,41.9 mmol) and intermediate i (11.4 g,46.1 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (17.4 g,125.8 mmol) was dissolved in 52mL of water and added thereto, followed by stirring thoroughlyBis (tri-t-butylphosphine) palladium (0) (0.6 g,1.3 mmol). After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to thereby produce 14.3g of substances 1 to 21. (yield 65%, MS: [ M+H ] ] + ＝524)
Compound D (10 g,37.4 mmol), materials 1-21 (21.6 g,41.1 mmol), sodium t-butoxide (7.2 g,74.8 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.4 g,0.7 mmol) was charged. After 2 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 17.5g of compounds 1 to 23 was obtained. (yield 62%, MS: [ M+H)] + ＝755)
Synthesis examples 1 to 24: production of Compounds 1-24
Substance 10 (15 g,43.6 mmol) and intermediate r (11.8 g,48 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (18.1 g,130.9 mmol) was dissolved in 54mL of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.7 g,1.3 mmol) was added thereto. After reacting for 8 hours, cooling to normal temperature, separating the organic layer from the water layer, and distilling the organic layer. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to thereby produce 16g of substances 1 to 22. (yield 72%, MS: [ M+H) ] + ＝510)
Under nitrogen atmosphere, compound A (10 g,46 mmol), substances 1-22 (25.8 g,50.6 mmol), tert-butyl acrylateSodium butoxide (8.8 g,92.1 mmol) was added to 200mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 2 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 22.2g of compounds 1 to 24 were obtained. (yield 70%, MS: [ M+H)] + ＝691)
Synthesis examples 1 to 25: production of Compounds 1-25
Substance 10 (15 g,43.6 mmol) and intermediate s (11.8 g,48 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (18.1 g,130.9 mmol) was dissolved in 54mL of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.7 g,1.3 mmol) was added thereto. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 15.8g of substances 1 to 23 were produced. (yield 71%, MS: [ M+H) ] + ＝510)
Compound A (10 g,46 mmol), materials 1-23 (25.8 g,50.6 mmol), sodium t-butoxide (8.8 g,92.1 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 3 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 21.3g of compounds 1 to 25 were obtained. (yield 67%, MS: [ M+H)] + ＝691)
Synthesis examples 1 to 26: production of Compounds 1-26
Substance 2 (15 g,41.9 mmol) and intermediate t (11.4 g,46.1 mmol) were added to 300mL of THF under nitrogen, stirred and refluxed. Then, potassium carbonate (17.4 g,125.8 mmol) was dissolved in 52mL of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.3 mmol) was added thereto. After reacting for 10 hours, cooling to normal temperature, separating the organic layer from the water layer, and distilling the organic layer. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to thereby produce 14g of substances 1 to 24. (yield 64%, MS: [ M+H) ] + ＝524)
Compound A (10 g,46 mmol), materials 1-24 (26.5 g,50.6 mmol), sodium t-butoxide (8.8 g,92.1 mmol) were added to 200mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 3 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 22.7g of compounds 1 to 26 was obtained. (yield 70%, MS: [ M+H)] + ＝705)
Synthesis example 2-1: production of Compound 2-1
Under nitrogen, material 2-1 (10 g,38.9 mmol) and material 2-2 (6.7 g,42.8 mmol) were added to 200mL of THF, stirred and refluxed. Then, potassium carbonate (16.1 g,116.7 mmol) was dissolved in 48mL of water and added thereto, and after stirring sufficiently, tetrakis (triphenylphosphine) palladium (0) (Tetraki)s (triphenylphosphine) paladium (0)) (0.4 g,0.4 mmol). After reacting for 12 hours, cooling to normal temperature, separating the organic layer from the water layer, and distilling the organic layer. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.9g of substance 2-1-1 was produced. (yield 79%, MS: [ M+H) ] + ＝289)
Under nitrogen, material 2-1-1 (10 g,34.6 mmol), amine (amine) 1 (14.5 g,36.4 mmol), sodium t-butoxide (8.3 g,86.6 mmol) were added to 300mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 13.9g of compound 2-1 was obtained. (yield 62%, MS: [ M+H)] + ＝650)
Synthesis example 2-2: production of Compound 2-2
Under nitrogen, material 2-1-1 (10 g,34.6 mmol), amine 2 (14.5 g,36.4 mmol), sodium t-butoxide (8.3 g,86.6 mmol) were added to 300mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 13.9g of compound 2-2 was obtained. (yield 62%, MS: [ M+H) ] + ＝650)
Synthesis examples 2 to 3: production of Compounds 2-3
Under nitrogen, material 2-1-1 (10 g,34.6 mmol), amine 3 (11.7 g,36.4 mmol), sodium t-butoxide (8.3 g,86.6 mmol) were added to 300mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 13.1g of compound 2-3 was obtained. (yield 66%, MS: [ M+H)] + ＝574)
Synthesis examples 2 to 4: production of Compounds 2-4
Under nitrogen, material 2-1-1 (10 g,34.6 mmol), amine 4 (14.5 g,36.4 mmol), sodium t-butoxide (8.3 g,86.6 mmol) were added to 300mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 13.5g of compound 2-4 was obtained. (yield 60%, MS: [ M+H) ] + ＝650)
Synthesis examples 2 to 5: production of Compounds 2-5
Under nitrogen, material 2-1-1 (10 g,34.6 mmol), amine 5 (16.3 g,36.4 mmol), sodium t-butoxide (8.3 g,86.6 mmol) were added to 300mL of xylene, stirred and refluxed. Then, the process is carried out,bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 13.6g of compound 2-5 was obtained. (yield 56%, MS: [ M+H)] + ＝700)
Synthesis examples 2 to 6: production of Compounds 2-6
Under nitrogen, material 2-1-1 (10 g,34.6 mmol), amine 6 (14.5 g,36.4 mmol), sodium t-butoxide (8.3 g,86.6 mmol) were added to 300mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 11.9g of compound 2-6 was obtained. (yield 53%, MS: [ M+H) ] + ＝650)
Synthesis examples 2 to 7: production of Compounds 2-7
Material 2-1-1 (10 g,34.6 mmol), amine 7 (14.5 g,36.4 mmol), sodium t-butoxide (8.3 g,86.6 mmol) were added to 300mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound is applied to a silica gel column layerThe reaction mixture was purified by chromatography to obtain 12.8g of Compound 2-7. (yield 57%, MS: [ M+H)] + ＝650)
Synthesis examples 2 to 8: production of Compounds 2-8
Under nitrogen, material 2-1-1 (10 g,34.6 mmol), amine 8 (14.4 g,36.4 mmol), sodium t-butoxide (8.3 g,86.6 mmol) were added to 300mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 14.8g of compound 2-8 was obtained. (yield 66%, MS: [ M+H) ] + ＝648)
Synthesis examples 2 to 9: production of Compounds 2-9
Under nitrogen, material 2-1-1 (10 g,34.6 mmol), amine 9 (12.6 g,36.4 mmol), sodium t-butoxide (8.3 g,86.6 mmol) were added to 300mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 13.4g of compound 2-9 was obtained. (yield 65%, MS: [ M+H ]] + ＝598)
Synthesis examples 2 to 10: production of Compounds 2-10
Under nitrogen, material 2-1 (10 g,38.9 mmol) and material 2-3 (6.7 g,42.8 mmol) were added to 200mL of THF, stirred and refluxed. Then, potassium carbonate (16.1 g,116.7 mmol) was dissolved in 48mL of water and the mixture was stirred well, and tetrakis (triphenylphosphine) palladium (0) (0.4 g,0.4 mmol) was added thereto. After reacting for 12 hours, cooling to normal temperature, separating the organic layer from the water layer, and distilling the organic layer. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to thereby produce 9g of substance 2-1-2. (yield 80%, MS: [ M+H) ] + ＝289)
Under nitrogen, material 2-1-2 (10 g,34.6 mmol), amine 10 (14.4 g,36.4 mmol), sodium t-butoxide (8.3 g,86.6 mmol) were added to 300mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 13.7g of compound 2-10 was obtained. (yield 61%, MS: [ M+H)] + ＝648)
Synthesis examples 2 to 11: production of Compounds 2-11
Amine 11 (10 g,59.1 mmol), material 2-1-1 (35.8 g,124.1 mmol), sodium t-butoxide (19.9 g,206.8 mmol) were added to 300mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.9 g,1.8 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water for 2 times, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated under reduced pressure And (3) distilling. The concentrated compound was purified by silica gel column chromatography, whereby 27.1g of compound 2-11 was obtained. (yield 68%, MS: [ M+H)] + ＝674)
Synthesis examples 2 to 12: production of Compounds 2-12
Amine 12 (10 g,40.8 mmol), material 2-1-1 (24.7 g,85.6 mmol), sodium tert-butoxide (13.7 g,142.7 mmol) were added to 300mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.2 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 17.7g of compound 2-12 was obtained. (yield 58%, MS: [ M+H)] + ＝750)
Synthesis examples 2 to 13: production of Compounds 2-13
Amine 13 (10 g,51.7 mmol), material 2-1-2 (31.4 g,108.7 mmol), sodium t-butoxide (17.4 g,181.1 mmol) were added to 300mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.8 g,1.6 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 23.5g of compound 2-13 was obtained. (yield 65%, MS: [ M+H ] ] + ＝698)
Synthesis examples 2 to 14: production of Compounds 2-14
Under nitrogen, material 2-1 (10 g,38.9 mmol) and material 2-4 (9.9 g,42.8 mmol) were added to 200mL of THF, stirred and refluxed. Then, potassium carbonate (16.1 g,116.7 mmol) was dissolved in 48mL of water and the mixture was stirred well, and tetrakis (triphenylphosphine) palladium (0) (0.4 g,0.4 mmol) was added thereto. After reacting for 8 hours, cooling to normal temperature, separating the organic layer from the water layer, and distilling the organic layer. It was dissolved in chloroform again, washed with water for 2 times, and then the organic layer was separated, anhydrous magnesium sulfate was added, followed by filtration under stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 10.9g of substances 2-1-3 was produced. (yield 77%, MS: [ M+H)] + ＝365)
Amine 14 (10 g,45.6 mmol), materials 2-1-3 (34.9 g,95.8 mmol), sodium t-butoxide (15.3 g,159.6 mmol) were added to 300mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.7 g,1.4 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 22g of compounds 2-14 was obtained. (yield 55%, MS: [ M+H) ] + ＝876)
Synthesis examples 2 to 15: production of Compounds 2-15
Under nitrogen, material 2-1-1 (10 g,34.6 mmol), amine 15 (12.2 g,36.4 mmol), sodium t-butoxide (8.3 g,86.6 mmol) were added to 300mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and the organic matter was separatedThe layers were 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, whereby 11.8g of compound 2-15 was obtained. (yield 58%, MS: [ M+H)] + ＝588)
Synthesis examples 2 to 16: production of Compounds 2-16
Material 2-1-1 (10 g,34.6 mmol), amine 16 (15 g,36.4 mmol), sodium t-butoxide (8.3 g,86.6 mmol) were added to 300mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 14.7g of compounds 2 to 16 was obtained. (yield 64%, MS: [ M+H) ] + ＝664)
Synthesis examples 2 to 17: production of Compounds 2-17
Material 2-1-1 (10 g,34.6 mmol), amine 17 (14 g,36.4 mmol), sodium t-butoxide (8.3 g,86.6 mmol) were added to 300mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 11.7g of compound 2-17 was obtained. (yield 53%, MS: [ M+H)] + ＝638)
Synthesis examples 2 to 18: production of Compounds 2-18
Under nitrogen, material 2-1-1 (10 g,34.6 mmol), amine 18 (12.8 g,36.4 mmol), sodium t-butoxide (8.3 g,86.6 mmol) were added to 300mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 14.4g of compounds 2 to 18 was obtained. (yield 69%, MS: [ M+H) ] + ＝604)
Synthesis examples 2 to 19: production of Compounds 2-19
Under nitrogen, material 2-1-1 (10 g,34.6 mmol), amine 19 (14.6 g,36.4 mmol), sodium t-butoxide (8.3 g,86.6 mmol) were added to 300mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 13.3g of compound 2-19 was obtained. (yield 59%, MS: [ M+H)] + ＝654)
Synthesis examples 2 to 20: production of Compounds 2-20
Under nitrogen, 2-1-1 (10 g,34.6 mmol), amine 20 (12.8 g,36.4 mmol), sodium tert-butoxide (8.3 g,86.6mmol) was added to 300mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 12.1g of compound 2-20 was obtained. (yield 58%, MS: [ M+H) ] + ＝604)
Synthesis examples 2 to 21: production of Compounds 2-21
Under nitrogen, material 2-1-1 (10 g,34.6 mmol), amine 21 (15.4 g,36.4 mmol), sodium t-butoxide (8.3 g,86.6 mmol) were added to 300mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 14.8g of compound 2-21 was obtained. (yield 63%, MS: [ M+H)] + ＝677)
Synthesis examples 2 to 22: production of Compounds 2-22
Under nitrogen, material 2-1-1 (10 g,34.6 mmol), amine 22 (15.4 g,36.4 mmol), sodium t-butoxide (8.3 g,86.6 mmol) were added to 300mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and the organic layer was separated and treated with anhydrous magnesium sulfate After filtration, the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 16.2g of compound 2-22 was obtained. (yield 69%, MS: [ M+H)] + ＝677)
Synthesis examples 2 to 23: production of Compounds 2-23
Under nitrogen, material 2-1-2 (10 g,34.6 mmol), amine 23 (15.8 g,36.4 mmol), sodium t-butoxide (8.3 g,86.6 mmol) were added to 300mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 13.6g of compound 2-23 was obtained. (yield 57%, MS: [ M+H)] + ＝688)
Synthesis examples 2 to 24: production of Compounds 2-24
Under nitrogen, material 2-1-2 (10 g,34.6 mmol), amine 24 (13.1 g,36.4 mmol), sodium t-butoxide (8.3 g,86.6 mmol) were added to 300mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 14.2g of compound 2-24 was obtained. (yield 67%, MS: [ M+H) ] + ＝612)
Synthesis examples 2 to 25: production of Compounds 2-25
Amine 25 (10 g,38.6 mmol), material 2-1-1 (23.4 g,81 mmol), sodium t-butoxide (13 g,135 mmol) were added to 300mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.6 g,1.2 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 15.6g of compound 2-15 was obtained. (yield 53%, MS: [ M+H)] + ＝764)
Synthesis examples 2 to 26: production of Compounds 2-26
Material 2-1-1 (10 g,34.6 mmol), amine 26 (14 g,36.4 mmol), sodium t-butoxide (8.3 g,86.6 mmol) were added to 300mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 11.9g of compound 2-26 was obtained. (yield 54%, MS: [ M+H) ] + ＝638)
Synthesis examples 2 to 27: production of Compounds 2-27
Under nitrogen, add substance 2-1-1 (10 g,34.6 mmol), amine 27 (17.3 g,36.4 mmol), sodium t-butoxide (8.3 g,86.6 mmol) to 300mL of dimethylStirring and refluxing the mixture in benzene. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 14.6g of compound 2-27 was obtained. (yield 58%, MS: [ M+H)] + ＝727)
Synthesis examples 2 to 28: production of Compounds 2-28
Material 2-1-1 (10 g,34.6 mmol), amine 28 (14 g,36.4 mmol), sodium t-butoxide (8.3 g,86.6 mmol) were added to 300mL of xylene under nitrogen, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,1 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 11.9g of compounds 2 to 28 was obtained. (yield 54%, MS: [ M+H) ] + ＝638)
Synthesis examples 2 to 29: production of Compounds 2-29
Under nitrogen, material 2-1 (10 g,38.9 mmol) and material 2-5 (8.8 g,42.8 mmol) were added to 200mL of THF, stirred and refluxed. Then, potassium carbonate (16.1 g,116.7 mmol) was dissolved in 48mL of water and the mixture was stirred well, and tetrakis (triphenylphosphine) palladium (0) (0.4 g,0.4 mmol) was added thereto. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. Dissolving in chloroform again, washing with water for 2 times, separating organic layer, adding anhydrous sulfuric acidMagnesium, after stirring, was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 8.8g of substances 2-1-4 was produced. (yield 67%, MS: [ M+H)] + ＝339)
Under nitrogen, materials 2-1-4 (10 g,29.5 mmol), amine 26 (11.9 g,31 mmol), sodium t-butoxide (7.1 g,73.8 mmol) were added to 300mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 12.8g of compounds 2 to 29 was obtained. (yield 63%, MS: [ M+H) ] + ＝688)
Synthesis examples 2 to 30: production of Compounds 2-30
Under nitrogen, materials 2-1-4 (10 g,29.5 mmol), amine 29 (14.2 g,31 mmol), sodium t-butoxide (7.1 g,73.8 mmol) were added to 300mL of xylene, stirred and refluxed. Then, bis (tri-t-butylphosphine) palladium (0) (0.5 g,0.9 mmol) was charged. After 5 hours, at the end of the reaction, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then, the compound was completely dissolved in chloroform again, washed with water 2 times, and then the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 12.4g of compound 2-30 was obtained. (yield 55%, MS: [ M+H)] + ＝762)
Comparative example 1: fabrication of organic light emitting devices
To ITO (indium tin oxide)
The glass substrate coated with the film is put into distilled water dissolved with detergent, and ultrasonic wave is usedWashing is performed. In this case, a product of fei he er (Fischer co.) was used as the detergent, and distilled water was filtered twice using a Filter (Filter) manufactured by millbore co. After washing the ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After the distilled water washing is completed, ultrasonic washing is performed by using solvents of isopropanol, acetone and methanol, and the obtained product is dried and then conveyed to a plasma cleaning machine. After the substrate was cleaned with oxygen plasma for 5 minutes, the substrate was transferred to a vacuum vapor deposition machine.
On the ITO transparent electrode thus prepared, as a hole injection layer, the following HI-1 compound was used
And the following a-1 compound was p-doped (p-dopping) at a concentration of 1.5%. On the hole injection layer, the following HT-1 compound was subjected to vacuum evaporation to form a film thickness +.>
Is provided. Next, on the hole transport layer, the film thickness is +.>
An electron-inhibiting layer was formed by vacuum evaporation of the EB-1 compound described below.
Next, on the EB-1 vapor deposition film, the compound 1-1 produced in the above-described Synthesis example 1-1 as a host material and the below-described Dp-7 compound as a dopant material were vacuum-deposited at a weight ratio of 98:2 to form
A red light emitting layer of thickness.
On the light-emitting layer, the film thickness is set to
The hole blocking layer was formed by vacuum evaporation of the HB-1 compound described below. Next, the cavity is formedOn the barrier layer, the following ET-1 compound and the following LiQ compound were vacuum evaporated in a weight ratio of 2:1, thereby +.>
Form an electron injection and transport layer. On the electron injection and transport layer, lithium fluoride (LiF) is sequentially added +.>
Is made of aluminum +.>
And vapor deposition is performed to form a cathode. / >
In the above process, the vapor deposition rate of the organic matter is maintained
Lithium fluoride maintenance of cathode
Is kept at>
Is to maintain a vacuum degree of 2X 10 during vapor deposition -7 ～5×10 -6 The support is thus fabricated into an organic light emitting device.
Comparative examples 2 to 15
An organic light-emitting device was manufactured in the same manner as in comparative example 1 above, except that the compound 1-1 was replaced with the compound described in table 1 below in the organic light-emitting device of comparative example 1.
Examples 1 to 104
An organic light-emitting device was manufactured in the same manner as in comparative example 1 above, except that the compound of chemical formula 1 as a first host and the compound of chemical formula 2 as a second host described in tables 2 to 4 were co-evaporated at a weight ratio of 1:1 in place of the compound 1-1 in the organic light-emitting device of comparative example 1.
Here, the structures of the compounds used in examples and comparative examples 2 to 15 are collated as follows.
Comparative examples 16 to 51
An organic light-emitting device was manufactured in the same manner as in comparative example 1, except that the organic light-emitting device of comparative example 1 was used in place of the compound 1-1 by co-evaporation of the compounds of the first and second hosts described in tables 5 and 6 below at a weight ratio of 1:1. Here, the structures of the comparative compounds RH1 to RH9 are shown below.
Experimental example 1: evaluation of device characteristics
When a current was applied to the organic light emitting devices fabricated in examples 1 to 104 and comparative examples 1 to 51, voltage, efficiency, and lifetime (10 mA/cm were measured 2 Benchmark), the results are shown in tables 1 to 5 below. Lifetime T95 refers to the time required for the luminance to decrease from the initial luminance (5000 nits) to 95%.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
As shown in tables 1 to 5 above, the organic light emitting device of the example in which the first compound represented by the above chemical formula 1 and the second compound represented by the above chemical formula 2 were simultaneously used as the host material of the light emitting layer exhibited excellent driving voltage, light emitting efficiency, and lifetime characteristics as compared to the organic light emitting device of the comparative example in which only one of the compounds represented by the above chemical formulas 1 and 2, or neither of them was used.
In particular, the device according to the embodiment improves the driving voltage, efficiency, and lifetime characteristics as compared to both the devices of comparative examples 40 to 51 in which the comparative compounds RH7 to RH9 are used as the first host, the compounds represented by the above chemical formula 2 are used as the second host, and the devices of comparative examples 16 to 39 in which the compounds represented by the above chemical formula 1 are used as the first host, and the comparative compounds RH1 to RH6 are used as the second host. From this, it was confirmed that when the combination of the first compound represented by the above chemical formula 1 and the second compound represented by the above chemical formula 2 is used as a common host, energy transfer to the red dopant is effectively achieved in the red light emitting layer. This is judged to be because the first compound has high stability to electrons and holes, and further, it is judged to be because the amount of holes is increased by the simultaneous use of the second compound while the electrons and holes maintain a more stable balance in the red light emitting layer.
Therefore, it was confirmed that when the first compound and the second compound are used as host materials of the organic light-emitting device at the same time, the driving voltage, the light-emitting efficiency, and the lifetime characteristics of the organic light-emitting device can be improved. In contrast, when considering that the light-emitting efficiency and lifetime characteristics of an organic light-emitting device normally have a Trade-off relationship with each other, it is known that an organic light-emitting device employing a combination between compounds of the present invention exhibits significantly improved device characteristics compared to a comparative example device.
[ description of the symbols ]
1: substrate 2: anode
3: light emitting layer 4: cathode electrode
5: hole injection layer 6: hole transport layer
7: electron suppression layer 8: hole blocking layer
9: electron injection and transport layers.
Claims (14)
1. An organic light emitting device comprising:
an anode;
a cathode disposed opposite to the anode; and
a light emitting layer disposed between the anode and the cathode,
wherein the light emitting layer includes a first compound represented by the following chemical formula 1 and a second compound represented by the following chemical formula 2:
chemical formula 1
In the chemical formula 1 described above, a compound having the formula,
A 1 and A 2 Each independently is a benzene or naphthalene ring fused to an adjacent five-membered ring,
l is a substituted or unsubstituted dibenzofuranylene group, or a substituted or unsubstituted benzonaphthofuranylene group,
L 1 And L 2 Each independently is a single bond, or a substituted or unsubstituted C 6-60 An arylene group,
Ar 1 and Ar is a group 2 Each independently is a substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C containing more than 1 heteroatom in N, O and S 2-60 A heteroaryl group, which is a group,
R 1 and R is 2 Each independently is hydrogen, deuterium, or substituted or unsubstituted C 6-60 An aryl group,
the A is 1 And A 2 Each of which is a benzene ring, a and b are each independently an integer of 0 to 4,
the A is 1 And A 2 In the case of naphthalene rings, a and b are each independentlyIs an integer of 0 to 6,
chemical formula 2
In the chemical formula 2 described above, the chemical formula,
l' is substituted or unsubstituted C 6-60 An arylene group,
L 3 and L 4 Each independently is a single bond, or a substituted or unsubstituted C 6-60 An arylene group,
Ar 3 and Ar is a group 4 Each independently is a substituted or unsubstituted C 6-60 An aryl group; or substituted or unsubstituted C containing more than 1 heteroatom in N, O and S 2-60 A heteroaryl group, which is a group,
R 3 is hydrogen or deuterium, and is preferably selected from the group consisting of,
c is an integer from 0 to 9.
2. The organic light-emitting device according to claim 1, wherein the first compound is represented by any one of the following chemical formulas 1-1 to 1-10:
in the 1-1 to 1-10,
a 'and b' are each independently integers from 0 to 4,
a "and b" are each independently integers from 0 to 6,
L、L 1 、L 2 、Ar 1 、Ar 2 、R 1 and R is 2 As defined in claim 1.
3. The organic light-emitting device of claim 1, wherein L is any one selected from the group consisting of:
4. the organic light-emitting device of claim 1, wherein L 1 And L 2 Is a single bond.
5. The organic light-emitting device of claim 1, wherein Ar 1 And Ar is a group 2 Each independently is phenyl, biphenyl, naphthyl, or dibenzofuranyl.
6. The organic light-emitting device of claim 1, wherein R 1 And R is 2 Each independently is phenyl, biphenyl, or naphthyl.
7. The organic light-emitting device of claim 1, wherein a+b is 0 or 1.
8. The organic light-emitting device according to claim 1, wherein the first compound is any one selected from the group consisting of:
9. the organic light-emitting device according to claim 1, wherein L' is phenylene, biphenyldiyl or naphthylene.
10. The organic light-emitting device of claim 9, wherein L' is any one selected from the group consisting of:
11. the organic light-emitting device of claim 1, wherein L 3 And L 4 Each independently is a single bond, phenylene, biphenyldiyl, or naphthylene.
12. The organic light-emitting device of claim 1, wherein Ar 3 And Ar is a group 4 Each independently is phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, carbazolyl, dibenzofuranyl, dibenzothienyl or benzonaphthofuranyl,
the Ar is as follows 3 And Ar is a group 4 Unsubstituted, or substituted by phenyl or naphthyl.
13. The organic light-emitting device of claim 1, wherein R 3 Is hydrogen.
14. The organic light-emitting device according to claim 1, wherein the second compound is any one selected from the group consisting of:
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