CN117580837A - Compound and organic light emitting device comprising the same - Google Patents

Compound and organic light emitting device comprising the same Download PDF

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CN117580837A
CN117580837A CN202280045827.7A CN202280045827A CN117580837A CN 117580837 A CN117580837 A CN 117580837A CN 202280045827 A CN202280045827 A CN 202280045827A CN 117580837 A CN117580837 A CN 117580837A
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金旼俊
李勇翰
许东旭
洪性佶
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LG Chem Ltd
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Abstract

The present specification relates to a compound of chemical formula 1 and an organic light emitting device including the same.

Description

Compound and organic light emitting device comprising the same
Technical Field
The present application claims priority from korean patent application No. 10-2021-0181870, filed to the korean patent office on 12 months 17 of 2021, the entire contents of which are incorporated herein.
The present specification relates to a compound and an organic light emitting device including the same.
Background
In this specification, an organic light-emitting device is a light-emitting device using an organic semiconductor substance, and communication of holes and/or electrons between an electrode and the organic semiconductor substance is required. Organic light emitting devices can be broadly classified into the following two types according to the operation principle. The first is a light-emitting device in which an exciton (exiton) is formed in an organic layer by photons flowing into the device from an external light source, and the exciton is separated into an electron and a hole, and the electron and the hole are transferred to different electrodes to be used as a current source (voltage source). The second type is a light-emitting device in which a voltage or a current is applied to 2 or more electrodes, holes and/or electrons are injected into an organic semiconductor material layer forming an interface with the electrodes, and the injected electrons and holes operate.
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 generally has a structure including an anode and a cathode and an organic layer therebetween. Here, in order to improve efficiency and stability of the organic light-emitting device, the organic layer is often formed of a multilayer structure composed of different substances, and may be formed of, for example, a hole injection layer, a hole transport layer, a light-emitting layer, an electron suppression 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 are formed, and light is emitted when the excitons re-transition to a ground state. Such an organic light emitting device is known to have characteristics of self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and the like.
Materials used as an organic layer in an organic light emitting device can be classified into a light emitting material and a charge transporting material, such as a hole injecting material, a hole transporting material, an electron inhibiting substance, an electron transporting material, an electron injecting material, and the like, according to functions. Depending on the emission color, the luminescent materials are blue, green, red luminescent materials, and yellow and orange luminescent materials, which are required to achieve better natural colors.
In addition, for the purpose of an increase in color purity and an increase in luminous efficiency based on energy transfer, as a light emitting material, a host/dopant system may be used. The principle is that when a dopant having a smaller band gap and excellent light emission efficiency than a host mainly constituting the light emitting layer is mixed in a small amount in the light emitting layer, excitons generated in the host are transferred to the dopant to emit light with high efficiency. At this time, since the wavelength of the host is shifted to the wavelength range of the dopant, light of a desired wavelength can be obtained according to the kind of the dopant to be used.
In order to fully develop the excellent characteristics of the organic light-emitting device, materials constituting the organic layer in the device, for example, hole injection materials, hole transport materials, light-emitting materials, electron-suppressing materials, electron transport materials, electron injection materials, and the like are stable and effective materials, and therefore development of new materials is continuously demanded.
Disclosure of Invention
Technical problem
The present specification describes compounds and organic light emitting devices comprising the same.
Solution to the problem
An embodiment of the present specification provides a compound of the following chemical formula 1.
[ chemical formula 1]
Ar-L-Z
In the above-mentioned chemical formula 1,
l is a direct bond; a substituted or unsubstituted arylene group; substituted or unsubstituted monocyclic, bicyclic, or tetracyclic heteroarylene; substituted or unsubstituted 2-valent benzothienopyrimidinyl; substituted or unsubstituted 2-valent benzofuropyrimidinyl; substituted or unsubstituted phenanthrene of valence 2 An azole group; substituted or unsubstituted phenanthrothiazolyl of valence 2; substituted or unsubstituted phenanthroline group of 2 valence; or substituted or unsubstituted 2Valence naphtho->An azole group, an azole group and an azole group,
z is represented by the following chemical formula 2 or 3,
[ chemical formula 2]
[ chemical formula 3]
Except for the position bonded to L, the above chemical formula 2 or 3 is substituted or unsubstituted with deuterium, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,
ar is hydrogen; deuterium; substituted or unsubstituted alkyl; substituted or unsubstituted alkoxy; substituted or unsubstituted aryl; substituted or unsubstituted monocyclic, bicyclic, or tetracyclic heteroaryl groups; substituted or unsubstituted benzothienopyrimidinyl; substituted or unsubstituted benzofuropyrimidinyl; substituted or unsubstituted phenanthreneAn azole group; substituted or unsubstituted phenanthrothiazolyl; a substituted or unsubstituted phenanthroline group; substituted or unsubstituted naphtho->An azole group; a substituted or unsubstituted amine group; or a substituted or unsubstituted phosphine oxide group,
when L is a direct bond, ar is not hydrogen or deuterium.
In addition, according to an embodiment of the present invention, there is provided an organic light emitting device including: a first electrode, a second electrode provided opposite to the first electrode, and 1 or more organic layers provided between the first electrode and the second electrode, wherein 1 or more of the organic layers contains the compound.
Effects of the invention
The compound of the present invention can be used as a material of an organic layer of an organic light emitting device. When the compound of the present invention is contained in a hole blocking layer, an electron injection layer, an electron transport layer, or an electron injection and transport layer of an organic light emitting device, an organic light emitting device having characteristics of low voltage, high efficiency, and long life can be manufactured.
Drawings
Fig. 1 and 2 illustrate examples of an organic light emitting device according to the present invention.
[ description of the symbols ]
1: substrate board
2: anode
3: organic layer
4: cathode electrode
5: hole injection layer
6: hole transport layer
7: hole transport auxiliary layer
8: light-emitting layer
9: hole blocking layer
10: electron injection and transport layers
Detailed Description
The present specification will be described in more detail below.
In the present specification, when a certain component is referred to as "including/comprising" a certain component, unless otherwise specified, it means that other components may be further included, rather than excluded.
In this specification, when it is stated that a certain member is located "on" another member, it includes not only the case where the certain member is connected to the other member but also the case where another member exists between the two members.
In the present specification, examples of substituents are described below, but are not limited thereto.
The term "substituted" as used herein means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the substituted position is not limited as long as it is a position where a hydrogen atom can be substituted, that is, a position where a substituent can be substituted, and when 2 or more substituents are substituted, 2 or more substituents may be the same or different from each other.
In the present specification, the term "substituted or unsubstituted" means substituted with 1 or 2 or more substituents selected from deuterium, halogen group, cyano (-CN), silyl, boron group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group, and substituted or unsubstituted heterocyclic group, or substituted with 2 or more substituents bonded to the above exemplified substituents, or does not have any substituent. 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.
Examples of the above substituents are described below, but are not limited thereto.
In the present specification, examples of the halogen group include fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).
In the present specification, the silyl group may be represented by the chemical formula of-SiY 1Y2Y3, and each of the above Y1, Y2 and Y3 may be hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. The silyl group is specifically, but 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 may be represented BY the chemical formula of-BY 4Y5, and each of the above Y4 and Y5 may be hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Examples of the boron group include, but are not limited to, dimethylboronyl, diethylboronyl, t-butylmethylboronyl, diphenylboronyl, phenylboronyl, and the like.
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 60. According to one embodiment, the alkyl group has 1 to 30 carbon atoms. According to another embodiment, the above alkyl group has 1 to 20 carbon atoms. According to another embodiment, the above alkyl group has 1 to 10 carbon atoms. Specific examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, and the like.
In the present specification, the amine group may be selected from the group consisting of-NH 2 The alkyl amine group, the N-alkylaryl amine group, the aryl amine group, the N-arylheteroaryl amine group, the N-alkylheteroaryl amine group and the heteroaryl amine group are not particularly limited, but are preferably 1 to 30 in carbon number. Specific examples of the amine group include a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a phenylamine group, a naphthylamino group, a biphenylamino group, an anthracenylamino group, a 9-methylanthracenylamine group, a diphenylamino group, a xylylamino group, an N-phenyltolylamino group, a triphenylamino group, an N-phenylbiphenylamino group, an N-phenylnaphthylamino group, an N-biphenylnaphthylamino group, an N-naphthylfluorenylamino group, an N-phenylphenanthrylamino group, an N-biphenylphenanthrenylamino group, an N-phenylfluorenylamino group, an N-phenylterphenylamino group, an N-biphenylfluorenylamino group, and the like, but are not limited thereto.
In the present specification, the N-alkylaryl amine group means an amine group in which an alkyl group and an aryl group are substituted on N of the amine group.
In the present specification, an N-arylheteroarylamino group means an amino group substituted with an aryl group and a heteroaryl group on N of the amino group.
In the present specification, an N-alkylheteroarylamino group means an amino group in which an alkyl group and a heteroaryl group are substituted on N of the amino group.
In the present specification, alkylamino, N-arylalkylamino, alkylthio Alkylsulfonyl radicalsThe alkyl group in the N-alkylheteroaryl amine group is the same as exemplified above for the alkyl group. Specifically, the alkylthio group includes a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group, an octylthio group, and the like, and the alkylsulfonyl group includes a methanesulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and the like, but is 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, cyclohexyl, cycloheptyl, cyclooctyl 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, triphenylenyl, A group, a fluorenyl group, etc., but is not limited thereto.
In the present specification, the heteroaryl group is a cyclic group containing 1 or more of N, O, P, S, si and Se as a hetero atom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60. According to one embodiment, the heterocyclic group has 2 to 30 carbon atoms. Examples of the heterocyclic group include, but are not limited to, pyridyl, pyrrolyl, pyrimidinyl, pyridazinyl, furyl, thienyl, imidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, and carbazolyl.
In the present specification, the definition of arylene is the same as that of aryl described above except that arylene is a 2-valent group.
In the present specification, the heteroaryl group is defined as in the above heteroaryl group except that the heteroaryl group is a 2-valent group.
According to an embodiment of the present specification, the above chemical formula 2 or 3 is substituted or unsubstituted with deuterium except for the site to which L is bonded.
According to an embodiment of the present specification, the above chemical formula 1 is any one of the following chemical formulas 1-1 to 1-4.
In the above chemical formulas 1-1 to 1-4, ar and L are as defined in the above chemical formula 1.
According to an embodiment of the present specification, the above chemical formula 1 is any one of the following chemical formulas 1-5 to 1-8.
In the above chemical formulas 1-5 to 1-8, ar and L are as defined in the above chemical formula 1.
According to an embodiment of the present specification, the above chemical formula 1 is any one of the following chemical formulas 1-1-1 to 1-1-12.
In the above chemical formulas 1-1-1 to 1-1-12, the above L and Ar are as defined in the above chemical formula 1.
According to an embodiment of the present specification, the above chemical formula 1 is any one of the following chemical formulas 2-1-1 to 2-1-12.
In the above chemical formulas 2-1-1 to 2-1-12, the above L and Ar are as defined in the above chemical formula 1.
According to an embodiment of the present disclosure, L is a direct bond; a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; substituted or unsubstituted monocyclic, bicyclic or tetracyclic heteroarylene of 3 to 30 carbon atoms; substituted or unsubstituted 2-valent benzothienopyrimidinyl; substituted or unsubstituted 2-valent benzofuropyrimidinyl; substituted or unsubstituted phenanthrene of valence 2An azole group; substituted or unsubstituted phenanthrothiazolyl of valence 2; substituted or unsubstituted phenanthroline group of 2 valence; or substituted or unsubstituted naphtho ∈2-valent>An azole group.
According to an embodiment of the present disclosure, L is a direct bond; a substituted or unsubstituted arylene group having 6 to 20 carbon atoms; substituted or unsubstituted monocyclic, bicyclic or tetracyclic heteroarylene of 3 to 20 carbon atoms; substituted or unsubstituted 2-valent benzothienopyrimidinyl; substituted or unsubstituted 2-valent benzofuropyrimidinyl; substituted or unsubstituted phenanthrene of valence 2 An azole group; substituted or unsubstituted phenanthrothiazolyl of valence 2; substituted or unsubstituted phenanthroline group of 2 valence; or substituted or unsubstituted naphtho ∈2-valent>An azole group.
According to an embodiment of the present disclosure, L is a direct bond; a substituted or unsubstituted arylene group having 6 to 15 carbon atoms; substituted or unsubstituted monocyclic, bicyclic or tetracyclic heteroarylene of 3 to 15 carbon atoms; substituted or unsubstituted 2-valent benzothienopyrimidinyl; substitution ofOr unsubstituted 2-valent benzofuropyrimidinyl; substituted or unsubstituted phenanthrene of valence 2An azole group; substituted or unsubstituted phenanthrothiazolyl of valence 2; substituted or unsubstituted phenanthroline group of 2 valence; or substituted or unsubstituted naphtho ∈2-valent>An azole group.
According to an embodiment of the present specification, L is a directly bonded, deuterium-substituted or unsubstituted phenylene group, deuterium-substituted or unsubstituted biphenyl group of 2 valency, deuterium-substituted or unsubstituted naphthyl group of 2 valency, deuterium-substituted or unsubstituted quinazolinyl group of 2 valency, deuterium-substituted or unsubstituted quinolinyl group of 2 valency, deuterium-substituted or unsubstituted quinoxalinyl group of 2 valency, substituted or unsubstituted benzothiophenopyrimidinyl group of 2 valency, substituted or unsubstituted benzofuranopyrimidinyl group of 2 valency, substituted or unsubstituted phenanthro-p-phenylene group of 2 valency An oxazolyl group, a substituted or unsubstituted phenanthrothiazolyl group of 2 valences, a substituted or unsubstituted phenanthroline group of 2 valences, or a substituted or unsubstituted naphtho +.>An azole group.
According to an embodiment of the present specification, L is a direct bond, phenylene, biphenyl having a valence of 2, naphthyl having a valence of 2, quinazolinyl having a valence of 2, quinolinyl having a valence of 2, quinoxalinyl having a valence of 2, benzofuranopyrimidinyl having a valence of 2, or benzothiophenopyrimidinyl having a valence of 2.
According to one embodiment of the present specification, L is an arylene group having 6 to 30 carbon atoms.
According to one embodiment of the present specification, L is a substituted or unsubstituted monocyclic, bicyclic or tetracyclic heteroarylene group having 3 to 30 carbon atoms; substituted or unsubstituted 2-valent benzothienopyrimidinylThe method comprises the steps of carrying out a first treatment on the surface of the Substituted or unsubstituted 2-valent benzofuropyrimidinyl; substituted or unsubstituted phenanthrene of valence 2An azole group; substituted or unsubstituted phenanthrothiazolyl of valence 2; substituted or unsubstituted phenanthroline group of 2 valence; or substituted or unsubstituted naphtho ∈2-valent>An azole group.
According to an embodiment of the present disclosure, L is a direct bond; arylene groups; monocyclic, bicyclic, or tetracyclic heteroarylene; benzothiophenopyrimidinyl of valence 2; benzofuropyrimidinyl of valence 2; phenanthrene of valence 2 An azole group; phenanthrothiazolyl of valence 2; phenanthroline group of 2 valence; or 2-valent naphtho->An azole group, an azole group and an azole group,
the substituent is substituted or unsubstituted with one or more groups selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 3 to 30 carbon atoms.
According to an embodiment of the present disclosure, L is a direct bond.
According to an embodiment of the present specification, L is phenylene, biphenyl having 2 valences, or naphthyl having 2 valences.
According to an embodiment of the present specification, L is a 2-valent quinazolinyl group, a 2-valent quinolinyl group, a 2-valent quinoxalinyl group, a 2-valent benzofuropyrimidinyl group, or a 2-valent benzothiophenopyrimidinyl group.
According to an embodiment of the present specification, ar is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; substituted or unsubstituted monocyclic, bicyclic or tetracyclic heteroaryl groups having 3 to 30 carbon atoms; substituted or unsubstituted benzothienopyrimidinyl; substituted or unsubstituted benzofuranoPyrimidinyl; substituted or unsubstituted phenanthreneAn azole group; substituted or unsubstituted phenanthrothiazolyl; a substituted or unsubstituted phenanthroline group; substituted or unsubstituted naphtho->An azole group; or a phosphine oxide group.
According to an embodiment of the present specification, ar is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; substituted or unsubstituted monocyclic, bicyclic or tetracyclic heteroaryl groups having 3 to 20 carbon atoms; substituted or unsubstituted benzothienopyrimidinyl; substituted or unsubstituted benzofuropyrimidinyl; substituted or unsubstituted phenanthreneAn azole group; substituted or unsubstituted phenanthrothiazolyl; a substituted or unsubstituted phenanthroline group; substituted or unsubstituted naphtho->An azole group; or a phosphine oxide group.
According to an embodiment of the present specification, ar is a substituted or unsubstituted aryl group having 6 to 15 carbon atoms; substituted or unsubstituted monocyclic, bicyclic or tetracyclic heteroaryl groups having 3 to 15 carbon atoms; substituted or unsubstituted benzothienopyrimidinyl; substituted or unsubstituted benzofuropyrimidinyl; substituted or unsubstituted phenanthreneAn azole group; substituted or unsubstituted phenanthrothiazolyl; a substituted or unsubstituted phenanthroline group; substituted or unsubstituted naphtho->An azole group; or a phosphine oxide group.
According to one embodiment of the present disclosure, ar is substituted or unsubstituted with deuteriumSubstituted aryl groups having 6 to 30 carbon atoms; heteroaryl groups of 3 to 30 carbon atoms of a single, double or four rings substituted or unsubstituted by alkyl or aryl; benzothienopyrimidinyl substituted or unsubstituted with alkyl or aryl; benzofuropyrimidinyl substituted or unsubstituted with alkyl or aryl; phenanthro substituted or unsubstituted by alkyl or aryl An azole group; phenanthrothiazolyl substituted or unsubstituted with alkyl or aryl; phenanthroline groups substituted or unsubstituted with alkyl or aryl groups; naphtho +.>An azole group; or by alkyl or aryl phosphine oxide groups.
According to an embodiment of the present specification, ar is an aryl group having 6 to 30 carbon atoms which is substituted or unsubstituted with deuterium; heteroaryl groups of 3 to 30 carbon atoms of a single, double or four rings substituted or unsubstituted by alkyl or aryl; benzothienopyrimidinyl substituted or unsubstituted with alkyl or aryl; benzofuropyrimidinyl substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms; phenanthro substituted or unsubstituted by alkyl having 1 to 10 carbon atoms or aryl having 6 to 30 carbon atomsAn azole group; phenanthrothiazolyl substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms; phenanthroline group substituted or unsubstituted with alkyl group having 1 to 10 carbon atoms or aryl group having 6 to 30 carbon atoms; naphtho ∈1-10 alkyl group or 6-30 aryl group substituted or unsubstituted>An azole group; or an arylphosphine oxide group having 6 to 30 carbon atoms and having 1 to 10 carbon atoms.
According to an embodiment of the present specification, ar is any one of a substituent substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 3 to 30 carbon atoms.
According to an embodiment of the present specification, ar is any one of the substituents described below, and is substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 3 to 30 carbon atoms.
According to an embodiment of the present specification, ar is any one of the substituents described below, and is substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 3 to 30 carbon atoms.
According to an embodiment of the present specification, the chemical formula 1 is any one of the following structural formulas.
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The substituents of the compound of the above chemical formula 1 may be combined by a method known in the art, and the kind, position or number of the substituents may be changed according to a technique known in the art.
In addition, by introducing various substituents into the core structure of the structure described above, a compound having the inherent characteristics of the introduced substituents can be synthesized. For example, a substance satisfying the conditions required for each organic layer can be synthesized by introducing substituents mainly used in the hole injection layer substance, the hole transport substance, the light emitting layer substance, and the electron transport layer substance used in manufacturing the organic light emitting device into the above-described core structure.
In addition, the organic light emitting device according to the present invention is characterized by comprising: a first electrode, a second electrode disposed opposite to the first electrode, and 1 or more organic layers disposed between the first electrode and the second electrode, wherein 1 or more of the organic layers contains the above-mentioned compound.
The organic light-emitting device of the present invention can be manufactured by a usual method and material for manufacturing an organic light-emitting device, except that one or more organic layers are formed using the above-described compound.
The compound may be used not only in the vacuum vapor deposition method but also in the solution coating method to form an organic layer in the production of an organic light-emitting device. Here, the solution coating method refers to spin coating, dip coating, inkjet printing, screen printing, spray coating, roll coating, and the like, but is not limited thereto.
The organic layer of the organic light-emitting device of the present invention may be formed of a single-layer structure or a multilayer structure in which 2 or more organic layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a layer that performs hole injection and hole transport simultaneously, a light emitting layer, an electron transport layer, an electron injection layer, and the like as an organic layer. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller number of organic layers or a greater number of organic layers.
In the organic light emitting device of the present invention, the organic layer includes a hole blocking layer, and the hole blocking layer may include a compound represented by chemical formula 1.
In the organic light emitting device of the present invention, the organic layer may include 1 or more of an electron transport layer, an electron injection layer, and a layer in which electron injection and electron transport are simultaneously performed, and 1 or more of the layers may include the compound represented by the chemical formula 1.
In another organic light emitting device, the organic layer may include an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer may include the compound represented by the chemical formula 1.
In the organic light emitting device of the present invention, the organic layer may include 1 or more layers of a hole injection layer, a hole transport layer, and a layer in which hole injection and hole transport are simultaneously performed, and 1 or more layers of the layers may include the compound represented by the chemical formula 1.
In another organic light emitting device, the organic layer may include a hole injection layer or a hole transport layer, and the hole transport layer or the hole injection layer may include a compound represented by chemical formula 1.
In the present invention, the first electrode is an anode, the second electrode is a cathode, the organic layer includes a light-emitting layer, and an organic layer containing the compound is provided between the cathode and the light-emitting layer.
In the present invention, the organic layer includes a light-emitting layer, and the compound is contained between the light-emitting layer and the cathode.
In the present specification, the organic layer includes a hole blocking layer, and the hole blocking layer includes the compound.
In the specification of the present invention, an electron injection layer, an electron transport layer, or an electron injection and transport layer is included between the hole blocking layer and the second electrode.
In the present specification, the hole blocking layer and the electron injection and transport layer are connected to each other.
In one embodiment of the present disclosure, the first electrode is an anode, and the second electrode is a cathode.
According to another embodiment, the first electrode is a cathode, and the second electrode is an anode.
(1) Anode/hole transport layer/light emitting layer/cathode
(2) Anode/hole injection layer/hole transport layer/light emitting layer/cathode
(3) Anode/hole injection layer/hole buffer layer/hole transport layer/light emitting layer/cathode
(4) Anode/hole transport layer/light emitting layer/electron transport layer/cathode
(5) Anode/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode
(6) Anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/cathode
(7) Anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode
(8) Anode/hole injection layer/hole buffer layer/hole transport layer/light emitting layer/electron transport layer/cathode
(9) Anode/hole injection layer/hole buffer layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode
(10) Anode/hole transport layer/electron suppression layer/light emitting layer/electron transport layer/cathode
(11) Anode/hole transport layer/electron suppression layer/light emitting layer/electron transport layer/electron injection layer/cathode
(12) Anode/hole injection layer/hole transport layer/electron suppression layer/light emitting layer/electron transport layer/cathode
(13) Anode/hole injection layer/hole transport layer/electron suppression layer/light emitting layer/electron transport layer/electron injection layer/cathode
(14) Anode/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/cathode
(15) Anode/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode
(16) Anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/cathode
(17) Anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode
(18) Anode/hole injection layer/hole transport layer/electron suppression layer/light emitting layer/hole blocking layer/electron injection and transport layer/cathode
The structure of the organic light emitting device of the present invention may have the structure shown in fig. 1 and 2, but is not limited thereto.
Fig. 1 illustrates a structure of an organic light emitting device in which an anode 2, an organic layer 3, and a cathode 4 are sequentially stacked on a substrate 1. In the structure as described above, the compound represented by the above chemical formula 1 may be contained in the above organic layer 3.
Fig. 2 illustrates a structure of an organic light-emitting device in which an anode 2, a hole injection layer 5, a hole transport layer 6, a hole transport auxiliary layer 7, a light-emitting layer 8, a hole blocking layer 9, an electron injection and transport layer 10, and a cathode 4 are sequentially stacked on a substrate 1. In the structure as described above, the compound represented by the above chemical formula 1 may be contained in the above hole blocking layer 9, or the electron injection and transport layer 10.
For example, the organic light emitting device according to the present invention may be manufactured as follows: PVD (physical vapor deposition) such as sputtering (sputtering) or electron beam evaporation (e-beam evaporation) is used to deposit a metal or a metal oxide having conductivity or an alloy thereof on a substrate to form an anode, and then an organic layer including 1 or more layers selected from a hole injection layer, a hole transport layer, a layer in which hole transport and hole injection are performed simultaneously, a light emitting layer, an electron transport layer, an electron injection layer, and a layer in which electron transport and electron injection are performed simultaneously is formed on the anode, and then a substance usable as a cathode is deposited on the organic layer to manufacture the anode. In addition to this method, an organic light-emitting device may be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate.
The organic layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and the like, but is not limited thereto, and may have a single-layer structure. The organic layer may be formed into a smaller number of layers by a solvent process (solvent process) other than vapor deposition, such as spin coating, dip coating, knife coating, screen printing, ink jet printing, or thermal transfer printing, using various polymer materials.
The anode is an electrode for injecting holes, and is preferably a substance having a large work function as an anode substance in order to allow holes to be smoothly injected into the organic layer. Specific examples of the anode material that can be used in the present invention 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, indium Zinc Oxide); 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.
The cathode is an electrode for injecting electrons, and is preferably a substance having a small work function as a cathode substance 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.
The hole injection layer is a layer that functions to smooth injection of holes from the anode to the light-emitting layer, and the hole injection substance is a substance that can well receive holes from the anode at a low voltage, and preferably has a HOMO (highest occupied molecular orbital ) 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, but are not limited to, 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. The thickness of the hole injection layer may be 1 to 150nm. When the thickness of the hole injection layer is 1nm or more, there is an advantage that the degradation of the hole injection characteristic can be prevented, and when the thickness of the hole injection layer is 150nm or less, there is an advantage that the increase of the driving voltage for improving the migration of holes can be prevented.
According to an embodiment of the present specification, the hole injection layer includes a compound represented by the following chemical formula HI-1, but is not limited thereto.
[ chemical formula HI-1]
In the above-mentioned chemical formula HI-1,
at least one of X '1 to X'6 is N, the remainder are CH,
r309 to R314 are the same or different from each other, and are each independently hydrogen, deuterium, a nitrile group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amine group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or are combined with each other with an adjacent group to form a substituted or unsubstituted ring.
According to an embodiment of the present specification, X '1 to X'6 are N.
According to one embodiment of the present disclosure, R309 to R314 are nitrile groups.
According to one embodiment of the present specification, the above formula HI-1 is represented by the following compound.
According to an embodiment of the present specification, the hole injection layer includes a compound represented by the following chemical formula HI-2, but is not limited thereto.
[ chemical formula HI-2]
In the above-mentioned chemical formula HI-2,
r400 to R402 are the same or different from each other and are each independently any one selected from hydrogen, deuterium, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted amino, substituted or unsubstituted heteroaryl, and combinations thereof, or are combined with each other with adjacent groups to form a substituted or unsubstituted ring,
L402 is a substituted or unsubstituted arylene, or a substituted or unsubstituted heteroarylene.
According to an embodiment of the present specification, the above R400 to R402 are the same as or different from each other, each independently is any one selected from the group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted amine group, a substituted or unsubstituted heteroaryl group, and a combination thereof.
According to an embodiment of the present specification, R402 is any one selected from phenyl substituted with carbazolyl or arylamino, biphenyl substituted with carbazolyl or arylamino, and a combination thereof.
According to an embodiment of the present specification, R400 and R401 are the same or different from each other, and each is independently a substituted or unsubstituted aryl group, or are combined with each other to form an alkyl-substituted aromatic hydrocarbon ring.
According to an embodiment of the present specification, R400 and R401 are the same or different from each other, and each is independently an aryl group substituted or unsubstituted with an alkyl group.
According to an embodiment of the present specification, R400 and R401 are the same or different from each other, and each is independently biphenyl or dimethylfluorenyl.
According to one embodiment of the present specification, the above formula HI-1 is the following compound.
The hole transport layer can function to smooth the transport of holes. The hole-transporting substance is a substance capable of receiving holes from the anode or the hole-injecting layer and transferring the holes to the light-emitting layer, and a substance having a large mobility to the holes is suitable. Specific examples include, but are not limited to, arylamine-based organic substances, conductive polymers, and block copolymers having both conjugated and unconjugated portions.
According to an embodiment of the present specification, the hole transport layer includes a compound represented by the following chemical formula HT-1, but is not limited thereto.
[ chemical formula HT-1]
In the above-mentioned chemical formula HT-1,
r403 to R406 are the same or different from each other and are each independently any one selected from hydrogen, deuterium, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted amino, substituted or unsubstituted heteroaryl, and combinations thereof, or are combined with each other with adjacent groups to form a substituted or unsubstituted ring,
l403 is a substituted or unsubstituted arylene, or a substituted or unsubstituted heteroarylene,
l403 is an integer of 1 to 3, and when L403 is 2 or more, L403 is the same or different from each other.
According to an embodiment of the present specification, the above R403 to R406 are the same or different from each other, and each is independently any one selected from the group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted amine group, a substituted or unsubstituted heteroaryl group, and a combination thereof.
According to an embodiment of the present specification, the above-mentioned R403 to R406 are the same or different from each other, and each is independently an aryl group having 6 to 30 carbon atoms.
According to an embodiment of the present specification, the above-mentioned R403 to R406 are the same or different from each other, and each is independently a phenyl group, a biphenyl group or a naphthyl group.
According to an embodiment of the present specification, the above-mentioned R403 to R406 are the same or different from each other, and each is independently a phenyl group.
According to an embodiment of the present specification, L403 is an arylene group having 6 to 30 carbon atoms or a heteroarylene group having 3 to 30 carbon atoms substituted with an arylene group.
According to an embodiment of the present specification, L403 is a phenylene group, a 2-valent biphenyl group, or a 2-valent carbazole group substituted or unsubstituted with an aryl group.
According to one embodiment of the present specification, L403 is a carbazolyl group substituted with a naphthyl group.
According to one embodiment of the present specification, the above formula HT-1 is the following compound.
A hole buffer layer may be further provided between the hole injection layer and the hole transport layer, and may include a hole injection or transport material known in the art.
A hole transport auxiliary layer may be provided between the hole transport layer and the light emitting layer. The hole transport auxiliary layer may use the spiro compound described above or a material known in the art. The hole transport auxiliary layer is a layer that suppresses electrons and contributes to smooth transport of holes to the light-emitting layer.
According to an embodiment of the present specification, the hole transport auxiliary layer includes a compound represented by the following chemical formula EB-1, but is not limited thereto.
[ chemical formula EB-1]
In the above-mentioned chemical formula EB-1,
l311 to L313 are the same or different from each other and are each independently a direct bond, a substituted or unsubstituted arylene, or a substituted or unsubstituted heteroarylene,
r311 to R313 are the same as or different from each other, each independently is any one selected from hydrogen, deuterium, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and combinations thereof, or combine with each other with an adjacent group to form a substituted or unsubstituted ring.
According to an embodiment of the present specification, the above R311 to R313 are the same as or different from each other, each independently is any one selected from the group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and a combination thereof.
According to an embodiment of the present specification, the above-mentioned R311 to R313 are the same as or different from each other, and each is independently a phenyl group, a biphenyl group or a phenanthryl group.
According to an embodiment of the present specification, the above-mentioned R311 to R313 are the same as or different from each other, and each is independently a phenyl group or a phenanthryl group.
According to an embodiment of the present specification, the above-mentioned L311 to L313 are the same or different from each other, and each is independently a direct bond, arylene or heteroarylene.
According to an embodiment of the present disclosure, the above L311 to L313 are a direct bond or phenylene group.
According to one embodiment of the present specification, the above formula EB-1 is represented by the following compound.
The light-emitting layer may emit red, green, or blue light, and may be formed of a phosphorescent material or a fluorescent material. The light-emitting substance is a substance capable of receiving holes and electrons from the hole-transporting layer and the electron-transporting layer, respectively, and combining them to emit light in the visible light region, and is preferably a substance having high quantum efficiency for fluorescence or phosphorescence. Specifically, there are 8-hydroxy-quinoline aluminum complex (Alq 3 ) The method comprises the steps of carrying out a first treatment on the surface of the Carbazole-based compounds; dimeric styryl (dimerized styryl) compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; benzo (E) benzo (EAzole, benzothiazole, and benzimidazole compounds; poly (p-phenylene vinylene) (PPV) based polymers; spiro (spiro) compounds; polyfluorene, rubrene, etc., but not limited toThis is done.
Examples of the host material of the light-emitting layer include an aromatic condensed ring derivative and a heterocyclic compound. Specifically, examples of the aromatic condensed ring derivative include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and examples of the heterocyclic compound include carbazole derivatives, dibenzofuran derivatives, and ladder-type furan compounds Pyrimidine derivatives, etc., but are not limited thereto.
According to an embodiment of the present specification, the body includes a compound represented by the following chemical formula H-1, but is not limited thereto.
[ chemical formula H-1]
In the above-mentioned chemical formula H-1,
l20 and L21 are the same or different from each other and each independently is a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heterocyclic group of 2 valency,
ar20 and Ar21 are the same as or different from each other, and each is independently hydrogen, deuterium, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group,
r201 is hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group,
r201 is an integer of 1 to 8, and when R201 is 2 or more, 2 or more R201 are the same or different from each other.
In one embodiment of the present specification, L20 and L21 are the same or different from each other, and each is independently a direct bond, a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms, or a monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms.
In an embodiment of the present specification, the above L20 and L21 are the same or different from each other, and each is independently a direct bond, a deuterium-substituted or unsubstituted phenylene group, a deuterium-substituted or unsubstituted biphenylene group, a deuterium-substituted or unsubstituted naphthylene group, a 2-valent dibenzofuranyl group, or a 2-valent dibenzothienyl group.
In one embodiment of the present specification, ar20 is a substituted or unsubstituted heterocyclic group, and Ar21 is a substituted or unsubstituted aryl group.
In one embodiment of the present specification, ar20 and Ar21 are the same or different from each other, and each is independently a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms.
In one embodiment of the present specification, ar20 and Ar21 are the same or different from each other, and each is independently a substituted or unsubstituted monocyclic to tetracyclic aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted monocyclic to tetracyclic heterocyclic group having 6 to 20 carbon atoms.
In an embodiment of the present specification, the above Ar20 and Ar21 are the same or different from each other, and are each independently a phenyl group substituted or unsubstituted with deuterium or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms, a biphenyl group substituted or unsubstituted with deuterium or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms, a naphthyl group substituted or unsubstituted with a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms, a thienyl group substituted or unsubstituted with a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, a dibenzofuranyl group substituted or unsubstituted with a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms, a naphthobenzofuranyl group substituted or unsubstituted with a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms, a dibenzothienyl group substituted or unsubstituted with a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms, or a naphthobenzothienyl group substituted or unsubstituted with a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.
In an embodiment of the present specification, ar20 and Ar21 are the same or different from each other, and each is independently a phenyl group substituted or unsubstituted with deuterium, a biphenyl group substituted or unsubstituted with deuterium, a terphenyl group, a naphthyl group substituted or unsubstituted with deuterium, a thienyl group substituted or unsubstituted with phenyl group, a phenanthryl group, a dibenzofuranyl group, a naphthobenzofuranyl group, a dibenzothienyl group, or a naphthobenzothienyl group.
In one embodiment of the present specification, ar20 and Ar21 are the same or different from each other, and each is independently a 1-naphthyl group or a 2-naphthyl group.
According to an embodiment of the present disclosure, R201 is hydrogen.
According to an embodiment of the present specification, the above formula H-1 is represented by the following compound.
When the light-emitting layer emits red light, as a light-emitting dopant, a phosphorescent substance such as PIQIr (acac) (bis (1-phenylisoquinoline) acetylacetonide), PQIr (acac) (bis (1-phenylquinoline) acetylacetonate iridium), bis (1-phenylquinoline) acetylacetonate iridium), PQIr (tris (1-phenylquinoline) irium, tris (1-phenylquinoline) iridium), ptOEP (octaethylporphyrin platinum, platinum octaethylporphyrin), or Alq may be used 3 Fluorescent substances such as (tris (8-hydroxyquinoline) aluminum, etc., but not limited thereto. When the light emitting layer emits green light, ir (ppy) can be used as a light emitting dopant 3 Phosphorescent substances such as (factris (2-phenylpyridine) iridium, planar tris (2-phenylpyridine) iridium), or Alq 3 Fluorescent substances such as (tris (8-hydroxyquinoline) aluminum), but are not limited thereto. When the light-emitting layer emits blue light, as the light-emitting dopant, (4, 6-F 2 ppy) 2 Examples of the fluorescent substance include, but are not limited to, phosphorescent substances such as Irpic, fluorescent substances such as spiro-DPVBi (spiro-DPVBi), spiro-6P (spiro-6P), distyrylbenzene (DSB), distyrylarylene (DSA), PFO-based polymers, and PPV-based polymers.
According to an embodiment of the present specification, the dopant includes a compound represented by the following chemical formula D-1, but is not limited thereto.
[ chemical formula D-1]
In the above-mentioned chemical formula D-1,
t1 to T6 are identical to or different from each other and are each independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl,
t5 and t6 are each an integer of 1 to 4,
when T5 is 2 or more, T5 of 2 or more are the same or different from each other,
When T6 is 2 or more, T6 s of 2 or more are the same or different from each other.
According to an embodiment of the present specification, T1 to T6 are the same or different from each other, and each is independently hydrogen, a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms.
According to an embodiment of the present specification, T1 to T6 are the same or different from each other, and each is independently hydrogen, a linear or branched alkyl group having 1 to 30 carbon atoms, a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms substituted or unsubstituted with a nitrile group or a linear or branched alkyl group having 1 to 30 carbon atoms, or a monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms substituted or unsubstituted with a linear or branched alkyl group having 1 to 30 carbon atoms.
According to an embodiment of the present specification, the above-mentioned T1 to T6 are the same or different from each other, and each is independently hydrogen, phenyl substituted with methyl, or dibenzofuranyl.
According to an embodiment of the present specification, the above chemical formula D-1 is represented by the following compound.
A hole blocking layer may be provided between the electron transport layer and the light emitting layer, and materials known in the art may be used.
The electron transport layer can play a role in enabling electron transport to be smooth. The electron transporting 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 mobility of electrons. Specifically, there is an Al complex of 8-hydroxyquinoline containing Alq 3 But not limited to, complexes of (c) and (d), organic radical compounds, hydroxyflavone-metal complexes, and the like. The thickness of the electron transport layer may be 1 to 50nm. When the thickness of the electron transport layer is 1nm or more, there is an advantage that the degradation of the electron transport property can be prevented, and when it is 50nm or less, there is an advantage that the increase of the driving voltage for the purpose of improving the electron transfer can be prevented when the thickness of the electron transport layer is too thick.
The electron injection layer can perform a function of smoothly injecting electrons. As the electron injecting substance, the following compounds are preferable: a compound which has an ability to transport electrons, an effect of injecting electrons from a cathode, an excellent electron injection effect for a light-emitting layer or a light-emitting material, prevents excitons generated in the light-emitting layer from migrating to a hole injection layer, and has excellent thin film forming ability. Specifically, fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, and the like, Azole,/->Examples of the compound include, but are not limited to, diazoles, triazoles, imidazoles, perylenetetracarboxylic acids, fluorenylenemethanes, anthrones, derivatives thereof, metal complexes, and nitrogen-containing five-membered ring derivatives.
The electron injection and transport layer is a layer that facilitates injection and transport of electrons, and may be formed using the above-described electron transport layer material or electron injection layer material alone or together with other materials.
According to an embodiment of the present specification, the electron injection and transport layer includes a compound of the following chemical formula EI-1.
[ chemical formula EI-1]
In the above-mentioned chemical formula EI-1,
at least one of Z11 to Z13 is N, the rest is CH,
at least one of Z14 to Z16 is N, the rest is CH,
l701 is a direct bond, a substituted or unsubstituted arylene, or a substituted or unsubstituted heteroarylene,
ar701 to Ar704 are the same or different from each other and are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group,
l701 is an integer of 1 to 4, and L701 is the same or different from each other when L701 is a complex number.
According to an embodiment of the present specification, L701 is a substituted or unsubstituted monocyclic or polycyclic arylene group having 6 to 30 carbon atoms.
According to one embodiment of the present specification, the L701 is phenylene, biphenylene, or naphthylene.
According to one embodiment of the present disclosure, the L701 is phenylene or naphthylene.
According to an embodiment of the present specification, the above-mentioned Ar701 to Ar704 are the same as or different from each other, and each is independently a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 3 to 30 carbon atoms.
According to an embodiment of the present specification, ar701 to Ar704 are phenyl groups.
According to an embodiment of the present specification, the above chemical formula EI-1 is represented by the following compound.
According to an embodiment of the present disclosure, the electron injection and transport layer may further include a metal complex.
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).
The hole blocking layer is a layer that prevents holes from reaching the cathode, and can be formed generally under the same conditions as those of the hole injection layer. Specifically, there areThe diazole derivative, triazole derivative, phenanthroline derivative, BCP, aluminum complex (aluminum complex), and the like, but are not limited thereto.
The organic light emitting device according to the present invention may be of a top emission type, a bottom emission type, or a bi-directional emission type, depending on the materials used.
Modes for carrying out the invention
The organic light-emitting device of the present invention can be manufactured by a usual method and material for manufacturing an organic light-emitting device, except that one or more organic layers are formed using the above-described compound.
The method of manufacturing the compound of the above chemical formula 1 and the manufacture of an organic light emitting device using the same are 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.
In the following reaction formulae, the kinds and numbers of substituents can be synthesized into various types of intermediates with appropriately selecting known starting materials by those skilled in the art. The type of reaction and the reaction conditions may utilize techniques known in the art.
Synthesis example 1
Sub1 (15 g,38.1 mmol) and sub1-1 (16.7 g,40 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (potassium carbonate) (15.8 g,114.3 mmol) was dissolved in 100ml of water and added thereto, and after stirring sufficiently, bis (tri-tert-butylphosphine) palladium (0) (bis (tris-tert-butylphenyl) palladium (0)) (0.2 g,0.4 mmol) was added thereto. After 4 hours of reaction, 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 19g of compound 1 was produced. (yield 77%, MS: [ M+H)] + ＝650)
Synthesis example 2
Sub2 (15 g,38.6 mmol) and sub1-1 (16.9 g,40.5 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (16 g,115.7 mmol) was dissolved in 100ml of water and added thereto, and after stirring sufficiently, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 4 hours of reaction, 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 17.1g of compound 2 was produced. (yield 69%, MS: [ M+H) ] + ＝645)
Synthesis example 3
Sub3 (15 g,40.9 mmol) and sub1-1 (18 g,42.9 mmol) were added to 30In 0ml of THF, stirring and refluxing were carried out. Then, potassium carbonate (17 g,122.7 mmol) was dissolved in 100ml of water and added thereto, and after stirring sufficiently, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 3 hours of reaction, 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 20.1g of compound 3 was produced. (yield 79%, MS: [ M+H)] + ＝623)
Synthesis example 4
Sub4 (15 g,35.8 mmol) and sub1-1 (15.7 g,37.6 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (14.8 g,107.4 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 2 hours of reaction, 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 15g of compound 4 was produced. (yield 62%, MS: [ M+H) ] + ＝675)
Synthesis example 5
Sub5 (15 g,38.2 mmol) and sub1-2 (16.8 g,40.1 mmol) are added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (15.8 g,114.5 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 4 hours of reaction, 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 separating organicThe mixture was stirred 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 5 was produced. (yield 60%, MS: [ M+H)] + ＝649)
Synthesis example 6
Sub6 (15 g,45.3 mmol) and sub1-2 (19.9 g,47.6 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (18.8 g,136 mmol) was dissolved in 100ml of water and charged, and after stirring well, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was charged. After 4 hours of reaction, 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 17.5g of compound 6 was produced. (yield 66%, MS: [ M+H) ] + ＝587)
Synthesis example 7
Sub7 (15 g,50.5 mmol) and sub1-2 (22.2 g,53.1 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (21 g,151.6 mmol) was dissolved in 100ml of water and charged, and after stirring sufficiently, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 5 hours of reaction, 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 17.9g of compound 7 was produced. (yield 64%, MS: [ M+H)] + ＝553)
Synthesis example 8
Sub8 (15 g,38.8 mmol) and sub1-3 (17 g,40.7 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (16.1 g,116.3 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 2 hours of reaction, 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 15.9g of compound 8 was produced. (yield 64%, MS: [ M+H) ] + ＝643)
Synthesis example 9
Sub9 (15 g,43.8 mmol) and sub1-3 (19.2 g,45.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (18.1 g,131.3 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 2 hours of reaction, 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 16.5g of compound 9 was produced. (yield 63%, MS: [ M+H)] + ＝599)
Synthesis example 10
Sub10 (15 g,49.2 mmol) and sub1-4 (21.6 g,51.7 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (20.4 g,147.6 mmol) was dissolved in 100ml of water and chargedAfter stirring, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was added. After 5 hours of reaction, 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 17.4g of compound 10 was produced. (yield 63%, MS: [ M+H) ] + ＝561)
Synthesis example 11
Sub11 (15 g,38.2 mmol) and sub1-4 (16.8 g,40.1 mmol) are added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (15.8 g,114.5 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 2 hours of reaction, 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 18.1g of compound 11 was produced. (yield 73%, MS: [ M+H)] + ＝649)
Synthesis example 12
Sub12 (15 g,47.3 mmol) and sub1-5 (20.8 g,49.7 mmol) are added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (19.6 g,142 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. After 3 hours of reaction, 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 is treated with silicon Purification by column chromatography produced 18.7g of compound 12. (yield 69%, MS: [ M+H)] + ＝573)
Synthesis example 13
Sub13 (15 g,37.9 mmol) and sub1-5 (16.6 g,39.8 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (15.7 g,113.7 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 3 hours of reaction, 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 16.5g of compound 13 was produced. (yield 67%, MS: [ M+H)] + ＝652)
Synthesis example 14
Sub14 (15 g,43.8 mmol) and sub1-5 (19.2 g,45.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (18.1 g,131.3 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 5 hours of reaction, 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 19.4g of compound 14 was produced. (yield 74%, MS: [ M+H ] ] + ＝599)
Synthesis example 15
Sub15 (15 g,40.9 mmol) and sub1-6 (18 g,42.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (17 g,122.7 mmol) was dissolved in 100ml of water and added thereto, and after stirring sufficiently, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 3 hours of reaction, 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 15.3g of compound 15 was produced. (yield 60%, MS: [ M+H)] + ＝623)
Synthesis example 16
Sub16 (15 g,31.9 mmol) and sub1-6 (14 g,33.5 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (13.2 g,95.8 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 3 hours of reaction, 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 13.9g of compound 16 was produced. (yield 60%, MS: [ M+H) ] + ＝726)
Synthesis example 17
Sub17 (15 g,43.8 mmol) and sub1-7 (19.2 g,45.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (18.1 g,131.3 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After the reaction time of 3 hours, the reaction time was set,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 20.7g of compound 17 was produced. (yield 79%, MS: [ M+H)] + ＝599)
Synthesis example 18
Sub18 (15 g,62.3 mmol) and sub1-7 (27.4 g,65.4 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (25.8 g,187 mmol) was dissolved in 100ml of water and the mixture was poured, and after stirring well, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was poured. After 5 hours of reaction, 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 23.2g of compound 18 was produced. (yield 75%, MS: [ M+H) ] + ＝497)
Synthesis example 19
Sub19 (15 g,45.5 mmol) and sub1-7 (20 g,47.8 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. After 5 hours of reaction, 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 21.3g of compound 19 was produced. (yield 80%, MS: [ M+H)] + ＝586)
Synthesis example 20
Sub20 (15 g,42 mmol) and sub1-8 (18.5 g,44.1 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (17.4 g,126.1 mmol) was dissolved in 100ml of water and added thereto, and after stirring well, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 2 hours of reaction, 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 18.5g of compound 20 was produced. (yield 72%, MS: [ M+H) ] + ＝613)
Synthesis example 21
Sub21 (15 g,35.8 mmol) and sub1-8 (15.7 g,37.6 mmol) are added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (14.8 g,107.4 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 2 hours of reaction, 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 18.8g of compound 21 was produced. (yield 78%, MS: [ M+H)] + ＝675)
Synthesis example 22
Sub22 (15 g,51.6mmol) and sub1-9 (22.7 g,54.2 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (21.4 g,154.8 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was added thereto. After 3 hours of reaction, 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 18g of compound 22 was produced. (yield 64%, MS: [ M+H) ] + ＝547)
Synthesis example 23
Sub23 (15 g,37 mmol) and sub1-9 (16.2 g,38.8 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (15.3 g,110.9 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 2 hours of reaction, 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 15.4g of compound 23 was produced. (yield 63%, MS: [ M+H)] + ＝662)
Synthesis example 24
Sub24 (15 g,43.8 mmol) and sub1-9 (19.2 g,45.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (18.1 g,131.3 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 2 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. Re-dissolving itAfter washing with chloroform 2 times, the organic layer was separated, anhydrous magnesium sulfate was added, and after stirring, the filtrate was filtered and distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 16.5g of compound 24 was produced. (yield 63%, MS: [ M+H) ] + ＝599)
Synthesis example 25
Sub25 (15 g,43.6 mmol) and sub1-10 (19.2 g,45.8 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (18.1 g,130.9 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 3 hours of reaction, 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 16.5g of compound 25 was produced. (yield 63%, MS: [ M+H)] + ＝600)
Synthesis example 26
Sub26 (15 g,43.8 mmol) and sub1-10 (19.2 g,45.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (18.1 g,131.3 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 4 hours of reaction, 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 18.3g of compound 26 was produced. (yield 70%, MS: [ M+H) ] + ＝599)
Synthesis example 27
Sub27 (15 g,58.4 mmol) and sub1-10 (25.7 g,61.3 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (24.2 g,175.3 mmol) was dissolved in 100ml of water and added thereto, and after stirring sufficiently, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. After 2 hours of reaction, 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 23g of compound 27 was produced. (yield 77%, MS: [ M+H)] + ＝513)
Synthesis example 28
Sub28 (15 g,53.6 mmol) and sub1-10 (23.6 g,56.3 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was added thereto. After 5 hours of reaction, 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 21.5g of compound 28 was produced. (yield 75%, MS: [ M+H) ] + ＝536)
Synthesis example 29
Sub29 (15 g,35.7 mmol) and sub1-11 (15.7 g,37.5 mmol) are added to 300ml of THF, stirred and refluxed. ThenPotassium carbonate (14.8 g,107.2 mmol) was dissolved in 100ml of water and then poured, followed by stirring thoroughly, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added. After 3 hours of reaction, 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 14.7g of compound 29 was produced. (yield 61%, MS: [ M+H)] + ＝676)
Synthesis example 30
Sub30 (15 g,47.3 mmol) and sub1-11 (20.8 g,49.7 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (19.6 g,142 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. After 2 hours of reaction, 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 21.7g of compound 30 was produced. (yield 80%, MS: [ M+H) ] + ＝573)
Synthesis example 31
Sub31 (15 g,53.6 mmol) and sub1-11 (23.6 g,56.3 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was added thereto. After 4 hours of reaction, 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 magnesium sulfateAfter stirring, filtration was carried out, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 21.8g of compound 31 was produced. (yield 76%, MS: [ M+H)] + ＝536)
Synthesis example 32
Sub32 (15 g,53.6 mmol) and sub1-11 (16.9 g,40.5 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (16 g,115.7 mmol) was dissolved in 100ml of water and added thereto, and after stirring sufficiently, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 2 hours of reaction, 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 17.9g of compound 32 was produced. (yield 72%, MS: [ M+H) ] + ＝645)
Synthesis example 33
Sub33 (15 g,42 mmol) and sub2-1 (18.5 g,44.1 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (17.4 g,126.1 mmol) was dissolved in 100ml of water and added thereto, and after stirring well, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 3 hours of reaction, 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 16g of compound 33 was produced. (yield 62%, MS: [ M+H)] + ＝613)
Synthesis example 34
Sub34 (15 g,30 mmol) and sub2-1 (13.2 g,31.5 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (12.4 g,90 mmol) was dissolved in 100ml of water and added thereto, and after stirring sufficiently, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 4 hours of reaction, 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 16.3g of compound 34 was produced. (yield 72%, MS: [ M+H) ] + ＝756)
Synthesis example 35
Sub35 (15 g,33.9 mmol) and sub2-1 (14.9 g,35.6 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (14 g,101.6 mmol) was dissolved in 100ml of water and added thereto, and after stirring sufficiently, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 3 hours of reaction, 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 17.5g of compound 35 was produced. (yield 74%, MS: [ M+H ]] + ＝699)
Synthesis example 36
Sub36 (15 g,32 mmol) and sub2-1 (14 g,33.6 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (13.3 g,96 mmol) was dissolved in 100ml of water and added thereto, and after stirring sufficiently, both were added(tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol). After 5 hours of reaction, 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 14.8g of compound 36 was produced. (yield 64%, MS: [ M+H) ] + ＝725)
Synthesis example 37
Sub37 (15 g,58.4 mmol) and sub2-1 (25.7 g,61.3 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (24.2 g,175.3 mmol) was dissolved in 100ml of water and added thereto, and after stirring sufficiently, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.6 mmol) was added thereto. After 5 hours of reaction, 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 18.3g of compound 37 was produced. (yield 61%, MS: [ M+H)] + ＝513)
Synthesis example 38
Sub38 (15 g,36 mmol) and sub2-2 (15.8 g,37.8 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (14.9 g,107.9 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 3 hours of reaction, 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. Purifying the concentrated compound by silica gel column chromatography 18.6g of compound 38 was thus produced. (yield 77%, MS: [ M+H)] + ＝673)
Synthesis example 39
Sub39 (15 g,43.8 mmol) and sub2-2 (19.2 g,45.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (18.1 g,131.3 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 4 hours of reaction, 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 16.8g of compound 39 was produced. (yield 64%, MS: [ M+H)] + ＝599)
Synthesis example 40
Sub40 (15 g,45.5 mmol) and sub2-2 (20 g,47.8 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. After 5 hours of reaction, 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 19.2g of compound 40 was produced. (yield 72%, MS: [ M+H) ] + ＝586)
Synthesis example 41
Sub41 (15 g,35.7 mmol) and sub2-3 (15.7 g,37.5 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (14.8 g,107.2 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 2 hours of reaction, 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 15.9g of compound 41 was produced. (yield 66%, MS: [ M+H)] + ＝676)
Synthesis example 42
Sub42 (15 g,48 mmol) and sub2-3 (21.1 g,50.4 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (19.9 g,143.9 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. After 2 hours of reaction, 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 20.4g of compound 42 was produced. (yield 75%, MS: [ M+H) ] + ＝569)
Synthesis example 43
Sub43 (15 g,50.7 mmol) and sub2-3 (22.3 g,53.2 mmol) are added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (21 g,152.1 mmol) was dissolved in 100ml of water and added thereto, and after stirring sufficiently, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was added thereto. After 5 hours of reaction, the mixture is cooled to normal temperature and is provided withAfter separation of the organic and aqueous layers, the organic layer was 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 19.8g of compound 43 was produced. (yield 71%, MS: [ M+H)] + ＝552)
Synthesis example 44
Sub44 (15 g,31.9 mmol) and sub2-4 (14 g,33.5 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (13.2 g,95.8 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 5 hours of reaction, 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 13.9g of compound 44 was produced. (yield 60%, MS: [ M+H) ] + ＝726)
Synthesis example 45
Sub45 (15 g,40.1 mmol) and sub2-4 (17.6 g,42.1 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (16.6 g,120.4 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 2 hours of reaction, 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 20.2g of compound 45 was produced. (yield 80%, MS: [ M+H)] + ＝630)
Synthesis example 46
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Sub46 (15 g,42 mmol) and sub2-4 (18.5 g,44.1 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (17.4 g,126.1 mmol) was dissolved in 100ml of water and added thereto, and after stirring well, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 3 hours of reaction, 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 16.2g of compound 46 was produced. (yield 63%, MS: [ M+H) ] + ＝613)
Synthesis example 47
Sub47 (15 g,50.5 mmol) and sub2-4 (22.2 g,53.1 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (21 g,151.6 mmol) was dissolved in 100ml of water and charged, and after stirring sufficiently, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was charged. After 2 hours of reaction, 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 19.5g of compound 47 was produced. (yield 70%, MS: [ M+H)] + ＝553)
Synthesis example 48
Sub48 (15 g,53.6 mmol) and sub2-4 (23.6 g,56.3mmol) was added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (22.2 g,160.9 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was added thereto. After 5 hours of reaction, 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 18.7g of compound 48 was produced. (yield 65%, MS: [ M+H ] ] + ＝536)
Synthesis example 49
Sub49 (15 g,33.8 mmol) and sub2-5 (14.8 g,35.5 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (14 g,101.4 mmol) was dissolved in 100ml of water and added thereto, and after stirring sufficiently, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 5 hours of reaction, 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 15.6g of compound 49 was produced. (yield 66%, MS: [ M+H)] + ＝700)
Synthesis example 50
Sub50 (15 g,32 mmol) and sub2-5 (14 g,33.6 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (13.3 g,96 mmol) was dissolved in 100ml of water and added thereto, and after stirring sufficiently, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 2 hours of reaction, 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 timesThe organic layer was separated, anhydrous magnesium sulfate was added thereto, followed by stirring and filtration, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography, whereby 17.4g of compound 50 was produced. (yield 75%, MS: [ M+H) ] + ＝725)
Synthesis example 51
Sub51 (15 g,33.4 mmol) and sub2-6 (14.7 g,35.1 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (13.9 g,100.2 mmol) was dissolved in 100ml of water and added thereto, and after stirring well, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 5 hours of reaction, 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 14.1g of compound 51 was produced. (yield 60%, MS: [ M+H)] + ＝705)
Synthesis example 52
Sub52 (15 g,38.1 mmol) and sub2-6 (16.7 g,40 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (15.8 g,114.3 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 4 hours of reaction, 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 18.5g of compound 52 was produced. (yield 75%, MS: [ M+H) ] + ＝650)
Synthesis example 53
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Sub53 (15 g,38.6 mmol) and sub2-7 (16.9 g,40.5 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (16 g,115.7 mmol) was dissolved in 100ml of water and added thereto, and after stirring sufficiently, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 3 hours of reaction, 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 15.7g of compound 53 was produced. (yield 63%, MS: [ M+H)] + ＝645)
Synthesis example 54
Sub54 (15 g,49.2 mmol) and sub2-7 (21.6 g,51.7 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (20.4 g,147.6 mmol) was dissolved in 100ml of water and added thereto, and after stirring well, bis (tri-t-butylphosphine) palladium (0) (0.3 g,0.5 mmol) was added thereto. After 2 hours of reaction, 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 21g of compound 54 was produced. (yield 76%, MS: [ M+H) ] + ＝561)
Synthesis example 55
Sub55 (15 g,37.8 mmol) and sub2-7 (16.6 g,39.7 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (15.7 g,113.4 mmol) was dissolvedAfter pouring 100ml of water and stirring thoroughly, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was poured. After 3 hours of reaction, 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 18.7g of compound 55 was produced. (yield 76%, MS: [ M+H)] + ＝653)
Synthesis example 56
Sub56 (15 g,40.8 mmol) and sub2-8 (17.9 g,42.8 mmol) are added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (16.9 g,122.3 mmol) was dissolved in 100ml of water and the mixture was poured, and after stirring well, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was poured. After 3 hours of reaction, 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 18.3g of compound 56 was produced. (yield 72%, MS: [ M+H) ] + ＝624)
Synthesis example 57
Sub57 (15 g,33.9 mmol) and sub2-8 (14.9 g,35.6 mmol) are added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (14 g,101.6 mmol) was dissolved in 100ml of water and added thereto, and after stirring sufficiently, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 2 hours of reaction, 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 magnesium sulfate, stirring, filtering, and vacuum distilling the filtrate. The concentrated compound was purified by silica gel column chromatography, whereby 18g of compound 57 was produced. (yield 76%, MS: [ M+H)] + ＝699)
Synthesis example 58
Sub58 (15 g,40.9 mmol) and sub2-9 (18 g,42.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (17 g,122.7 mmol) was dissolved in 100ml of water and added thereto, and after stirring sufficiently, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 4 hours of reaction, 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 19.8g of compound 58 was produced. (yield 78%, MS: [ M+H) ] + ＝623)
Synthesis example 59
Sub59 (15 g,45.5 mmol) and sub2-9 (20 g,47.8 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (18.9 g,136.5 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mmol) was added thereto. After 3 hours of reaction, 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 20.2g of compound 59 was produced. (yield 76%, MS: [ M+H)] + ＝586)
Synthesis example 60
Sub60 (15 g,33.9 mmol) and sub2-9 (14.9 g,35.6 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (14 g,101.6 mmol) was dissolved in 100ml of water and added thereto, and after stirring sufficiently, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.3 mmol) was added thereto. After 5 hours of reaction, 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 16.3g of compound 60 was produced. (yield 69%, MS: [ M+H) ] + ＝699)
Synthesis example 61
Sub61 (15 g,36.9 mmol) and sub2-10 (16.2 g,38.7 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (15.3 g,110.6 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 3 hours of reaction, 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 19g of compound 61 was produced. (yield 78%, MS: [ M+H)] + ＝663)
Synthesis example 62
Sub62 (15 g,47.3 mmol) and sub2-10 (20.8 g,49.7 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (19.6 g,142 mmol) was dissolved in 100ml of water and added thereto, and after stirring sufficiently, bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.5 mm)And (3) an ol). After 4 hours of reaction, 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 17.6g of compound 62 was produced. (yield 65%, MS: [ M+H ] ] + ＝573)
Synthesis example 63
Sub63 (15 g,43.8 mmol) and sub2-10 (19.2 g,45.9 mmol) were added to 300ml of THF, stirred and refluxed. Then, potassium carbonate (18.1 g,131.3 mmol) was dissolved in 100ml of water and the mixture was stirred well, and bis (tri-t-butylphosphine) palladium (0) (0.2 g,0.4 mmol) was added thereto. After 4 hours of reaction, 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 19.1g of compound 63 was produced. (yield 73%, MS: [ M+H)] + ＝599)
If the production formula described in the examples of the present specification and the above intermediate are appropriately combined based on common technical knowledge, all the compounds of the above chemical formula 1 described in the present specification can be produced.
Experimental example
Experimental example 1-1
ITO (indium tin oxide) toThe glass substrate coated to have a thin film thickness is put into distilled water in which a detergent is dissolved, and washed with ultrasonic waves. 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. Washing ITO 30 After the minute, 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 usedIs formed, and the following a-1 compound is 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, as a hole transport auxiliary layer, compound EB-1 was added with +.>Is subjected to thermal vacuum evaporation. Next, as a light-emitting layer, compounds represented by the following chemical formulas BH and BD were used in a weight ratio of 25:1 and in +.>Vacuum evaporation was performed on the thickness of (c). Next, as a hole blocking layer, compound 1 synthesized by the present invention was prepared by +.>Vacuum evaporation was performed on the thickness of (c). Next, as an electron injection and transport layer, a compound represented by the following chemical formula ET-1 and a compound represented by the following LiQ were added in a weight ratio of 1:1 and +. >Is subjected to thermal vacuum evaporation. 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, thereby manufacturing an organic light-emitting device. />
Experimental examples 1-2 to 1-63
Organic light-emitting devices of experimental examples 1-2 to 1-63 were manufactured by the same method as that of the above experimental example 1-1, except that the compound described in table 1 below was used instead of the compound 1.
Comparative examples 1-1 to 1-6
Organic light emitting devices of comparative examples 1-1 to 1-6 were manufactured by the same method as in example 1-1 except that the following compounds B-1 to B-6 were used instead of compound 1.
10mA/cm was applied to the organic light emitting devices manufactured in experimental examples 1-1 to 1-63 and comparative experimental examples 1-1 to 1-6 2 The voltage and efficiency were measured, and the results are shown in table 1 below. Lifetime T95 refers to the time required for the luminance to decrease from the initial luminance (1000 nits) to 95%.
TABLE 1
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As shown in the above experimental examples, the compound of the present invention is used as a hole blocking layer of a blue light emitting layer. When compared with the compound of the comparative experimental example, it was confirmed that the organic light emitting device using the compound of the present invention showed an improvement effect in terms of driving voltage, efficiency and lifetime.
It can be seen that the compounds of the present invention contribute more to the ability to act as hole blocking layers within the device than the compounds of the comparative examples. It can be seen that efficiency or lifetime is improved by good transfer of electrons from the electron transport layer to the light emitting layer, thereby affecting the balanced charge flow within the device.
Comparative examples 1-1 and 1-2 used compounds in which benzofuran was bonded to the 8 and 9 positions of fluoranthene.
Comparative experimental examples 1-3 to 1-6 used compounds in which benzofuran was bonded to positions 2 and 3 of fluoranthene and substituted with carbazole; or a compound in which benzofuran is bonded to positions 7 and 8 of fluoranthene and substituted with a tricyclic or pentacyclic heteroaryl group including N.

Claims (15)

1. A compound of the following chemical formula 1:
[ chemical formula 1]
Ar-LL-Z
In the chemical formula 1 described above, a compound having the formula,
l is a direct bond; a substituted or unsubstituted arylene group; substituted or unsubstituted monocyclic, bicyclic, or tetracyclic heteroarylene; substituted or unsubstituted 2-valent benzothienopyrimidinyl; substituted or unsubstituted 2-valent benzofuropyrimidinyl; substituted or unsubstituted phenanthrene of valence 2An azole group; substituted or unsubstituted phenanthrothiazolyl of valence 2; substituted or unsubstituted phenanthroline group of 2 valence; or substituted or unsubstituted naphtho ∈2-valent >An azole group, an azole group and an azole group,
z is represented by the following chemical formula 2 or 3,
[ chemical formula 2]
[ chemical formula 3]
The chemical formula 2 or 3 is substituted or unsubstituted with deuterium, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group except for the site to which L is bonded,
ar is hydrogen; deuterium; substituted or unsubstituted alkyl; substituted or unsubstituted alkoxy; substituted or unsubstituted aryl; substituted or unsubstituted monocyclic, bicyclic, or tetracyclic heteroaryl groups; substituted or unsubstituted benzothienopyrimidinyl; substituted or unsubstituted benzofuropyrimidinyl; substituted or unsubstituted phenanthreneAn azole group; substituted or unsubstituted phenanthrothiazolyl; a substituted or unsubstituted phenanthroline group; substituted or unsubstituted naphtho->An azole group; a substituted or unsubstituted amine group; or a substituted or unsubstituted phosphine oxide group,
when L is a direct bond, ar is not hydrogen or deuterium.
2. The compound of claim 1, wherein the chemical formula 2 or 3 is substituted or unsubstituted with deuterium except for a site to which L is bound.
3. The compound according to claim 1, wherein the chemical formula 1 is any one of structures of the following chemical formulas 1-1 to 1-4:
In the chemical formulas 1-1 to 1-4, the Ar and L are as defined in the chemical formula 1.
4. The compound according to claim 1, wherein the chemical formula 1 is any one of the following chemical formulas 1-5 to 1-8:
in the chemical formulas 1-5 to 1-8, the Ar and L are as defined in the chemical formula 1.
5. The compound according to claim 1, wherein the chemical formula 1 is any one of the following chemical formulas 1-1-1 to 1-1-12:
in the chemical formulas 1-1-1 to 1-1-12, the L and Ar are as defined in the chemical formula 1.
6. The compound according to claim 1, wherein the chemical formula 1 is any one of the following chemical formulas 2-1-1 to 2-1-12:
in the chemical formulas 2-1-1 to 2-1-12, the L and Ar are as defined in the chemical formula 1.
7. The compound of claim 1, wherein L is a direct bond; arylene groups; monocyclic, bicyclic, or tetracyclic heteroarylene; benzothiophenopyrimidinyl of valence 2; benzofuropyrimidinyl of valence 2, phenanthro of valence 2An azole group; phenanthrothiazolyl of valence 2; phenanthroline group of 2 valence; or 2-valent naphtho->An azole group, an azole group and an azole group,
the substituent is substituted or unsubstituted with one or more groups selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 3 to 30 carbon atoms.
8. The compound according to claim 1, wherein Ar is a substituted or unsubstituted aryl group having 6 to 15 carbon atoms; substituted or unsubstituted monocyclic, bicyclic or tetracyclic heteroaryl groups having 3 to 15 carbon atoms; substituted or unsubstituted benzothienopyrimidinyl; substituted or unsubstituted benzofuropyrimidinyl; substituted or unsubstituted phenanthreneAn azole group; substituted or unsubstituted phenanthrothiazolyl; a substituted or unsubstituted phenanthroline group; substituted or unsubstituted naphtho->An azole group; or a substituted or unsubstituted phosphine oxide group.
9. The compound of claim 1, wherein the chemical formula 1 is any one of the following structural formulas:
/>
10. an organic light emitting device, comprising: a first electrode, a second electrode provided opposite to the first electrode, and 1 or more organic layers provided between the first electrode and the second electrode, wherein 1 or more of the organic layers contains the compound according to any one of claims 1 to 9.
11. The organic light-emitting device according to claim 10, wherein the first electrode is an anode and the second electrode is a cathode, the organic layer comprises a light-emitting layer, and an organic layer containing the compound is provided between the cathode and the light-emitting layer.
12. The organic light-emitting device of claim 10, wherein the organic layer comprises a light-emitting layer, the compound being contained between the light-emitting layer and a cathode.
13. The organic light-emitting device of claim 10, wherein the organic layer comprises a hole blocking layer comprising the compound.
14. An organic light-emitting device according to claim 13 wherein an electron injection layer, an electron transport layer, or an electron injection and transport layer is included between the hole blocking layer and the second electrode.
15. An organic light-emitting device according to claim 14 wherein the hole blocking layer and the electron injection and transport layer meet each other.
CN202280045827.7A 2021-12-17 2022-12-19 Compound and organic light emitting device comprising the same Pending CN117580837A (en)

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