Patent Application
20240268223
The present invention relates to a novel compound, a material for an organic electroluminescence device, an organic electroluminescence device, and an electronic apparatus.
When voltage is applied to an organic electroluminescence device (hereinafter, also referred to as an organic EL device), holes and electrons are injected into an emitting layer from an anode and a cathode, respectively. Then, thus injected holes and electrons are recombined in the emitting layer, and excitons are formed therein.
Conventional organic EL devices have not yet had sufficient device performance. Although materials used for the organic EL device are gradually improved to enhance the device performance, further performance enhancement is required.
Patent Documents 1 and 2 disclose a compound having the specific structure capable of being used for an electron-transporting region provided between an emitting layer and a cathode of an organic EL device.
It is an object of the present invention to provide a compound capable of achieving an organic EL device having higher performance.
As a result of extensive studies, the present inventors have found that an organic EL device having higher performance, especially having higher efficiency, or being able to be driven at lower voltage is capable of being achieved, when a compound having the specific structure is used, and has completed the present invention.
According to the present invention, the following compound and the like are provided.
1. A compound represented by the following formula (1):
wherein in the formula (1),
wherein in the formula (1-21),
According to the present invention, there can be provided a compound capable of achieving an organic EL device having higher performance.
In this specification, a hydrogen atom includes its isotopes different in the number of neutrons, namely, a protium, a deuterium and a tritium.
In this specification, at a bondable position in a chemical formula where a symbol such as “R”, or “D” representing a deuterium atom is not indicated, a hydrogen atom, that is, a protium atom, a deuterium atom or a tritium atom is bonded.
In this specification, the number of ring carbon atoms represents the number of carbon atoms forming a subject ring itself among the carbon atoms of a compound having a structure in which atoms are bonded in a ring form (for example, a monocyclic compound, a fused ring compound, a cross-linked compound, a carbocyclic compound, or a heterocyclic compound). When the subject ring is substituted by a substituent, the carbon contained in the substituent is not included in the number of ring carbon atoms. The same shall apply to “the number of ring carbon atoms” described below, unless otherwise specified. For example, a benzene ring has 6 ring carbon atoms, a naphthalene ring includes 10 ring carbon atoms, a pyridine ring includes 5 ring carbon atoms, and a furan ring includes 4 ring carbon atoms. Further, for example, a 9,9-diphenylfluorenyl group includes 13 ring carbon atoms, and a 9,9′-spirobifluorenyl group includes 25 ring carbon atoms.
When a benzene ring is substituted by, for example, an alkyl group as a substituent, the number of carbon atoms of the alkyl group is not included in the number of ring carbon atoms of the benzene ring. Therefore, the number of ring carbon atoms of the benzene ring substituted by the alkyl group is 6. When a naphthalene ring is substituted by, for example, an alkyl group as a substituent, the number of carbon atoms of the alkyl group is not included in the number of ring carbon atoms of the naphthalene ring. Therefore, the number of ring carbon atoms of the naphthalene ring substituted by the alkyl group is 10.
In this specification, the number of ring atoms represents the number of atoms forming a subject ring itself among the atoms of a compound having a structure in which atoms are bonded in a ring form (for example, the structure includes a monocyclic ring, a fused ring and a ring assembly) (for example, a monocyclic compound, a fused ring compound, a cross-linked compound, a carbocyclic compound and a heterocyclic compound). The number of ring atoms does not include atoms which do not form the ring (for example, a hydrogen atom which terminates a bond of the atoms forming the ring), or atoms contained in a substituent when the ring is substituted by the substituent. The same shall apply to “the number of ring atoms” described below, unless otherwise specified. For example, the number of atoms of a pyridine ring is 6, the number of atoms of a quinazoline ring is 10, and the number of a furan ring is 5. For example, hydrogen atoms bonded to a pyridine ring and atoms constituting a substituent substituted on the pyridine ring are not included in the number of ring atoms of the pyridine ring. Therefore, the number of ring atoms of a pyridine ring with which a hydrogen atom or a substituent is bonded is 6. For example, hydrogen atoms and atoms constituting a substituent which are bonded with a quinazoline ring is not included in the number of ring atoms of the quinazoline ring. Therefore, the number of ring atoms of a quinazoline ring with which a hydrogen atom or a substituent is bonded is 10.
In this specification, “XX to YY carbon atoms” in the expression “a substituted or unsubstituted ZZ group including XX to YY carbon atoms” represents the number of carbon atoms in the case where the ZZ group is unsubstituted by a substituent, and does not include the number of carbon atoms of a substituent in the case where the ZZ group is substituted by the substituent. Here, “YY” is larger than “XX”, and “XX” means an integer of 1 or more and “YY” means an integer of 2 or more.
In this specification, “XX to YY atoms” in the expression “a substituted or unsubstituted ZZ group including XX to YY atoms” represents the number of atoms in the case where the ZZ group is unsubstituted by a substituent, and does not include the number of atoms of a substituent in the case where the ZZ group is substituted by the substituent. Here, “YY” is larger than “XX”, and “XX” means an integer of 1 or more and “YY” means an integer of 2 or more.
In this specification, the unsubstituted ZZ group represents the case where the “substituted or unsubstituted ZZ group” is a “ZZ group unsubstituted by a substituent”, and the substituted ZZ group represents the case where the “substituted or unsubstituted ZZ group” is a “ZZ group substituted by a substituent”
In this specification, a term “unsubstituted” in the case of “a substituted or unsubstituted ZZ group” means that hydrogen atoms in the ZZ group are not substituted by a substituent. Hydrogen atoms in a term “unsubstituted ZZ group” are a protium atom, a deuterium atom, or a tritium atom.
In this specification, a term “substituted” in the case of “a substituted or unsubstituted ZZ group” means that one or more hydrogen atoms in the ZZ group are substituted by a substituent. Similarly, a term “substituted” in the case of “a BB group substituted by an AA group” means that one or more hydrogen atoms in the BB group are substituted by the AA group.
“Substituent as Described in this Specification”
Hereinafter, the substituent described in this specification will be explained.
The number of ring carbon atoms of the “unsubstituted aryl group” described in this specification is 6 to 50, preferably 6 to 30, and more preferably 6 to 18, unless otherwise specified.
The number of ring atoms of the “unsubstituted heterocyclic group” described in this specification is 5 to 50, preferably 5 to 30, and more preferably 5 to 18, unless otherwise specified.
The number of carbon atoms of the “unsubstituted alkyl group” described in this specification is 1 to 50, preferably 1 to 20, and more preferably 1 to 6, unless otherwise specified.
The number of carbon atoms of the “unsubstituted alkenyl group” described in this specification is 2 to 50, preferably 2 to 20, and more preferably 2 to 6, unless otherwise specified.
The number of carbon atoms of the “unsubstituted alkynyl group” described in this specification is 2 to 50, preferably 2 to 20, and more preferably 2 to 6, unless otherwise specified.
The number of ring carbon atoms of the “unsubstituted cycloalkyl group” described in this specification is 3 to 50, preferably 3 to 20, and more preferably 3 to 6, unless otherwise specified.
The number of ring carbon atoms of the “unsubstituted arylene group” described in this specification is 6 to 50, preferably 6 to 30, and more preferably 6 to 18, unless otherwise specified.
The number of ring atoms of the “unsubstituted divalent heterocyclic group” described in this specification is 5 to 50, preferably 5 to 30, and more preferably 5 to 18, unless otherwise specified.
The number of carbon atoms of the “unsubstituted alkylene group” described in this specification is 1 to 50, preferably 1 to 20, and more preferably 1 to 6, unless otherwise specified.
Specific examples of the “substituted or unsubstituted aryl group” described in this specification (specific example group G1) include the following unsubstituted aryl groups (specific example group G1A), substituted aryl groups (specific example group G1B), and the like. (Here, the unsubstituted aryl group refers to the case where the “substituted or unsubstituted aryl group” is an “aryl group unsubstituted by a substituent”, and the substituted aryl group refers to the case where the “substituted or unsubstituted aryl group” is an “aryl group substituted by a substituent”.). In this specification, in the case where simply referred as an “aryl group”, it includes both a “unsubstituted aryl group” and a “substituted aryl group.”
The “substituted aryl group” means a group in which one or more hydrogen atoms of the “unsubstituted aryl group” are substituted by a substituent. Specific examples of the “substituted aryl group” include, for example, groups in which one or more hydrogen atoms of the “unsubstituted aryl group” of the following specific example group G1A are substituted by a substituent, the substituted aryl groups of the following specific example group G1B, and the like. It should be noted that the examples of the “unsubstituted aryl group” and the examples of the “substituted aryl group” enumerated in this specification are mere examples, and the “substituted aryl group” described in this specification also includes a group in which a hydrogen atom bonded with a carbon atom of the aryl group itself in the “substituted aryl group” of the following specific group G1B is further substituted by a substituent, and a group in which a hydrogen atom of a substituent in the “substituted aryl group” of the following specific group G1B is further substituted by a substituent.
Unsubstituted aryl group (specific example group G1A):
Substituted aryl group (specific example group G1B):
The “heterocyclic group” described in this specification is a ring group having at least one hetero atom in the ring atom. Specific examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, a silicon atom, a phosphorus atom, and a boron atom.
The “heterocyclic group” in this specification is a monocyclic group or a fused ring group.
The “heterocyclic group” in this specification is an aromatic heterocyclic group or a non-aromatic heterocyclic group.
Specific examples of the “substituted or unsubstituted heterocyclic group” (specific example group G2) described in this specification include the following unsubstituted heterocyclic group (specific example group G2A), the following substituted heterocyclic group (specific example group G2B), and the like. (Here, the unsubstituted heterocyclic group refers to the case where the “substituted or unsubstituted heterocyclic group” is a “heterocyclic group unsubstituted by a substituent”, and the substituted heterocyclic group refers to the case where the “substituted or unsubstituted heterocyclic group” is a “heterocyclic group substituted by a substituent”.). In this specification, in the case where simply referred as a “heterocyclic group”, it includes both the “unsubstituted heterocyclic group” and the “substituted heterocyclic group.”
The “substituted heterocyclic group” means a group in which one or more hydrogen atom of the “unsubstituted heterocyclic group” are substituted by a substituent. Specific examples of the “substituted heterocyclic group” include a group in which a hydrogen atom of “unsubstituted heterocyclic group” of the following specific example group G2A is substituted by a substituent, the substituted heterocyclic groups of the following specific example group G2B, and the like. It should be noted that the examples of the “unsubstituted heterocyclic group” and the examples of the “substituted heterocyclic group” enumerated in this specification are mere examples, and the “substituted heterocyclic group” described in this specification includes groups in which hydrogen atom bonded with a ring atom of the heterocyclic group itself in the “substituted heterocyclic group” of the specific example group G2B is further substituted by a substituent, and a group in which hydrogen atom of a substituent in the “substituted heterocyclic group” of the specific example group G2B is further substituted by a substituent.
Specific example group G2A includes, for example, the following unsubstituted heterocyclic group containing a nitrogen atom (specific example group G2A1), the following unsubstituted heterocyclic group containing an oxygen atom (specific example group G2A2), the following unsubstituted heterocyclic group containing a sulfur atom (specific example group G2A3), and the monovalent heterocyclic group derived by removing one hydrogen atom from the ring structures represented by any of the following general formulas (TEMP-16) to (TEMP-33) (specific example group G2A4).
Specific example group G2B includes, for example, the following substituted heterocyclic group containing a nitrogen atom (specific example group G2B1), the following substituted heterocyclic group containing an oxygen atom (specific example group G2B2), the following substituted heterocyclic group containing a sulfur atom (specific example group G2B3), and the following group in which one or more hydrogen atoms of the monovalent heterocyclic group derived from the ring structures represented by any of the following general formulas (TEMP-16) to (TEMP-33) are substituted by a substituent (specific example group G2B4).
Unsubstituted heterocyclic group containing a nitrogen atom (specific example group G2A1):
Unsubstituted heterocyclic group containing an oxygen atom (specific example group G2A2):
Unsubstituted heterocyclic group containing a sulfur atom (specific example group G2A3):
Monovalent heterocyclic group derived by removing one hydrogen atom from the ring structures represented by any of the following general formulas (TEMP-16) to (TEMP-33) (specific example group G2A4):
In the general formulas (TEMP-16) to (TEMP-33), XA and YA are independently an oxygen atom, a sulfur atom, NH, or CH2. Provided that at least one of XA and YA is an oxygen atom, a sulfur atom, or NH.
In the general formulas (TEMP-16) to (TEMP-33), when at least one of XA and YA is NH or CH2, the monovalent heterocyclic group derived from the ring structures represented by any of the general formulas (TEMP-16) to (TEMP-33) includes a monovalent group derived by removing one hydrogen atom from these NH or CH2.
Substituted heterocyclic group containing a nitrogen atom (specific example group G2B1):
Substituted heterocyclic group containing an oxygen atom (specific example group G2B2):
Substituted heterocyclic group containing a sulfur atom (specific example group G2B3):
Group in which one or more hydrogen atoms of the monovalent heterocyclic group derived from the ring structures represented by any of the following general formulas (TEMP-16) to (TEMP-33) are substituted by a substituent (specific example group G2B4):
The “one or more hydrogen atoms of the monovalent heterocyclic group” means one or more hydrogen atoms selected from hydrogen atoms bonded with ring carbon atoms of the monovalent heterocyclic group, a hydrogen atom bonded with a nitrogen atom when at least one of XA and YA is NH, and hydrogen atoms of a methylene group when one of XA and YA is CH2.
Specific examples of the “substituted or unsubstituted alkyl group” (specific example group G3) described in this specification include the following unsubstituted alkyl groups (specific example group G3A) and the following substituted alkyl groups (specific example group G3B). (Here, the unsubstituted alkyl group refers to the case where the “substituted or unsubstituted alkyl group” is an “alkyl group unsubstituted by a substituent”, and the substituted alkyl group refers to the case where the “substituted or unsubstituted alkyl group” is an “alkyl group substituted by a substituent”.). In this specification, in the case where simply referred as an “alkyl group” includes both the “unsubstituted alkyl group” and the “substituted alkyl group.”
The “substituted alkyl group” means a group in which one or more hydrogen atoms in the “unsubstituted alkyl group” are substituted by a substituent. Specific examples of the “substituted alkyl group” include groups in which one or more hydrogen atoms in the following “unsubstituted alkyl group” (specific example group G3A) are substituted by a substituent, the following substituted alkyl group (specific example group G3B), and the like. In this specification, the alkyl group in the “unsubstituted alkyl group” means a linear alkyl group. Thus, the “unsubstituted alkyl group” includes a straight-chain “unsubstituted alkyl group” and a branched-chain “unsubstituted alkyl group”. It should be noted that the examples of the “unsubstituted alkyl group” and the examples of the “substituted alkyl group” enumerated in this specification are mere examples, and the “substituted alkyl group” described in this specification includes a group in which hydrogen atom of the alkyl group itself in the “substituted alkyl group” of the specific example group G3B is further substituted by a substituent, and a group in which hydrogen atom of a substituent in the “substituted alkyl group” of the specific example group G3B is further substituted by a substituent.
Unsubstituted alkyl group (specific example group G3A):
Substituted alkyl group (specific example group G3B):
Specific examples of the “substituted or unsubstituted alkenyl group” described in this specification (specific example group G4) include the following unsubstituted alkenyl group (specific example group G4A), the following substituted alkenyl group (specific example group G4B), and the like. (Here, the unsubstituted alkenyl group refers to the case where the “substituted or unsubstituted alkenyl group” is a “alkenyl group unsubstituted by a substituent”, and the “substituted alkenyl group” refers to the case where the “substituted or unsubstituted alkenyl group” is a “alkenyl group substituted by a substituent.”). In this specification, in the case where simply referred as an “alkenyl group” includes both the “unsubstituted alkenyl group” and the “substituted alkenyl group.”
The “substituted alkenyl group” means a group in which one or more hydrogen atoms in the “unsubstituted alkenyl group” are substituted by a substituent. Specific examples of the “substituted alkenyl group” include a group in which the following “unsubstituted alkenyl group” (specific example group G4A) has a substituent, the following substituted alkenyl group (specific example group G4B), and the like. It should be noted that the examples of the “unsubstituted alkenyl group” and the examples of the “substituted alkenyl group” enumerated in this specification are mere examples, and the “substituted alkenyl group” described in this specification includes a group in which a hydrogen atom of the alkenyl group itself in the “substituted alkenyl group” of the specific example group G4B is further substituted by a substituent, and a group in which a hydrogen atom of a substituent in the “substituted alkenyl group” of the specific example group G4B is further substituted by a substituent.
Unsubstituted alkenyl group (specific example group G4A):
Substituted alkenyl group (specific example group G4B):
Specific examples of the “substituted or unsubstituted alkynyl group” described in this specification (specific example group G5) include the following unsubstituted alkynyl group (specific example group G5A) and the like. (Here, the unsubstituted alkynyl group refers to the case where the “substituted or unsubstituted alkynyl group” is an “alkynyl group unsubstituted by a substituent”.). In this specification, in the case where simply referred as an “alkynyl group” includes both the “unsubstituted alkynyl group” and the “substituted alkynyl group.”
The “substituted alkynyl group” means a group in which one or more hydrogen atoms in the “unsubstituted alkynyl group” are substituted by a substituent. Specific examples of the “substituted alkynyl group” include a group in which one or more hydrogen atoms in the following “unsubstituted alkynyl group” (specific example group G5A) are substituted by a substituent, and the like.
Unsubstituted alkynyl group (specific example group G5A):
Specific examples of the “substituted or unsubstituted cycloalkyl group” described in this specification (specific example group G6) include the following unsubstituted cycloalkyl group (specific example group G6A), the following substituted cycloalkyl group (specific example group G6B), and the like. (Here, the unsubstituted cycloalkyl group refers to the case where the “substituted or unsubstituted cycloalkyl group” is a “cycloalkyl group unsubstituted by a substituent”, and the substituted cycloalkyl group refers to the case where the “substituted or unsubstituted cycloalkyl group” is a “cycloalkyl group substituted by a substituent”.). In this specification, in the case where simply referred as a “cycloalkyl group” includes both the “unsubstituted cycloalkyl group” and the “substituted cycloalkyl group.”
The “substituted cycloalkyl group” means a group in which one or more hydrogen atoms in the “unsubstituted cycloalkyl group” are substituted by a substituent. Specific examples of the “substituted cycloalkyl group” include a group in which one or more hydrogen atoms in the following “unsubstituted cycloalkyl group” (specific example group G6A) are substituted by a substituent, and examples of the following substituted cycloalkyl group (specific example group G6B), and the like. It should be noted that the examples of the “unsubstituted cycloalkyl group” and the examples of the “substituted cycloalkyl group” enumerated in this specification are mere examples, and the “substituted cycloalkyl group” in this specification includes a group in which one or more hydrogen atoms bonded with the carbon atom of the cycloalkyl group itself in the “substituted cycloalkyl group” of the specific example group G6B are substituted by a substituent, and a group in which a hydrogen atom of a substituent in the “substituted cycloalkyl group” of specific example group G6B is further substituted by a substituent.
Unsubstituted cycloalkyl group (specific example group G6A):
Substituted cycloalkyl group (specific example group G6B):
Specific examples of the group represented by —Si(R901)(R902)(R903) described in this specification (specific example group G7) include:
Specific examples of the group represented by —O—(R904) in this specification (specific example group G8) include:
Specific examples of the group represented by —S—(R905) in this specification (specific example group G9) include:
Specific examples of the group represented by —N(R906)(R907) in this specification (specific example group G10) include:
Specific examples of the “halogen atom” described in this specification (specific example group G11) include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
The “substituted or unsubstituted fluoroalkyl group” described in this specification is a group in which at least one hydrogen atom bonded with a carbon atom constituting the alkyl group in the “substituted or unsubstituted alkyl group” is substituted by a fluorine atom, and includes a group in which all hydrogen atoms bonded with a carbon atom constituting the alkyl group in the “substituted or unsubstituted alkyl group” are substituted by a fluorine atom (a perfluoro group). The number of carbon atoms of the “unsubstituted fluoroalkyl group” is 1 to 50, preferably 1 to 30, more preferably 1 to 18, unless otherwise specified in this specification. The “substituted fluoroalkyl group” means a group in which one or more hydrogen atoms of the “fluoroalkyl group” are substituted by a substituent. The “substituted fluoroalkyl group” described in this specification also includes a group in which one or more hydrogen atoms bonded with a carbon atom of the alkyl chains in the “substituted fluoroalkyl group” are further substituted by a substituent, and a group in which one or more hydrogen atom of a substituent in the “substituted fluoroalkyl group” are further substituted by a substituent. Specific examples of the “unsubstituted fluoroalkyl group” include a group in which one or more hydrogen atoms in the “alkyl group” (specific group G3) are substituted by a fluorine atom, and the like.
The “substituted or unsubstituted haloalkyl group” described in this specification is a group in which at least one hydrogen atom bonded with a carbon atom constituting the alkyl group in the “substituted or unsubstituted alkyl group” is substituted by a halogen atom, and also includes a group in which all hydrogen atoms bonded with a carbon atom constituting the alkyl group in the “substituted or unsubstituted alkyl group” are substituted by a halogen atom. The number of carbon atoms of the “unsubstituted haloalkyl group” is 1 to 50, preferably 1 to 30, more preferably 1 to 18, unless otherwise specified in this specification. The “substituted haloalkyl group” means a group in which one or more hydrogen atoms of the “haloalkyl group” are substituted by a substituent. The “substituted haloalkyl group” described in this specification also includes a group in which one or more hydrogen atoms bonded with a carbon atom of the alkyl chain in the “substituted haloalkyl group” are further substituted by a substituent, and a group in which one or more hydrogen atoms of a substituent in the “substituted haloalkyl group” are further substituted by a substituent. Specific examples of the “unsubstituted haloalkyl group” include a group in which one or more hydrogen atoms in the “alkyl group” (specific example group G3) are substituted by a halogen atom, and the like. A haloalkyl group is sometimes referred to as an alkyl halide group.
Specific examples of the “substituted or unsubstituted alkoxy group” described in this specification include a group represented by —O(G3), wherein G3 is the “substituted or unsubstituted alkyl group” described in the specific example group G3. The number of carbon atoms of the “unsubstituted alkoxy group” is 1 to 50, preferably 1 to 30, more preferably 1 to 18, unless otherwise specified in this specification.
Specific examples of the “substituted or unsubstituted alkylthio group” described in this specification include a group represented by —S(G3), wherein G3 is the “substituted or unsubstituted alkyl group” described in the specific example group G3. The number of carbon atoms of the “unsubstituted alkylthio group” is 1 to 50, preferably 1 to 30, more preferably 1 to 18, unless otherwise specified in this specification.
Specific examples of the “substituted or unsubstituted aryloxy group” described in this specification include a group represented by —O(G1), wherein G1 is the “substituted or unsubstituted aryl group” described in the specific example group G1. The number of ring carbon atoms of the “unsubstituted aryloxy group” is 6 to 50, preferably 6 to 30, more preferably 6 to 18, unless otherwise specified in this specification.
Specific examples of the “substituted or unsubstituted arylthio group” described in this specification include a group represented by —S(G1), wherein G1 is a “substituted or unsubstituted aryl group” described in the specific example group G1. The number of ring carbon atoms of the “unsubstituted arylthio group” is 6 to 50, preferably 6 to 30, more preferably 6 to 18, unless otherwise specified in this specification.
Specific examples of the “trialkylsilyl group” described in this specification include a group represented by —Si(G3)(G3)(G3), where G3 is the “substituted or unsubstituted alkyl group” described in the specific example group G3. Plural G3's in —Si(G3)(G3)(G3) are the same or different. The number of carbon atoms in each alkyl group of the “trialkylsilyl group” is 1 to 50, preferably 1 to 20, more preferably 1 to 6, unless otherwise specified in this specification.
Specific examples of the “substituted or unsubstituted aralkyl group” described in this specification is a group represented by -(G3)-(G1), wherein G3 is the “substituted or unsubstituted alkyl group” described in the specific example group G3, and G1 is the “substituted or unsubstituted aryl group” described in the specific example group G1. Therefore, the “aralkyl group” is a group in which a hydrogen atom of the “alkyl group” is substituted by an “aryl group” as a substituent, and is one form of the “substituted alkyl group.” The “unsubstituted aralkyl group” is the “unsubstituted alkyl group” substituted by the “unsubstituted aryl group”, and the number of carbon atoms of the “unsubstituted aralkyl group” is 7 to 50, preferably 7 to 30, more preferably 7 to 18, unless otherwise specified in this specification.
Specific examples of the “substituted or unsubstituted aralkyl group” include a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 1-phenylisopropyl group, a 2-phenylisopropyl group, a phenyl-t-butyl group, an α-naphthylmethyl group, a 1-α-naphthylethyl group, a 2-α-naphthylethyl group, a 1-α-naphthylisopropyl group, a 2-α-naphthylisopropyl group, a ß-naphthylmethyl group, a 1-β-naphthylethyl group, a 2-β-naphthylethyl group, a 1-β-naphthylisopropyl group, a 2-β-naphthylisopropyl group, and the like.
Unless otherwise specified in this specification, examples of the substituted or unsubstituted aryl group described in this specification preferably include a phenyl group, a p-biphenyl group, a m-biphenyl group, an o-biphenyl group, a p-terphenyl-4-yl group, a p-terphenyl-3-yl group, a p-terphenyl-2-yl group, a m-terphenyl-4-yl group, a m-terphenyl-3-yl group, a m-terphenyl-2-yl group, an o-terphenyl-4-yl group, an o-terphenyl-3-yl group, an o-terphenyl-2-yl group, a 1-naphthyl group, a 2-naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a chrysenyl group, a triphenylenyl group, a fluorenyl group, a 9,9′-spirobifluorenyl group, 9,9-dimethylfluorenyl group, 9,9-diphenylfluorenyl group, and the like.
Unless otherwise specified in this specification, examples of the substituted or unsubstituted heterocyclic groups described in this specification preferably include a pyridyl group, a pyrimidinyl group, a triazinyl group, a quinolyl group, an isoquinolyl group, a quinazolinyl group, a benzimidazolyl group, a phenanthrolinyl group, a carbazolyl group (a 1-carbazolyl group, a 2-carbazolyl group, a 3-carbazolyl group, a 4-carbazolyl group, or a 9-carbazolyl group), a benzocarbazolyl group, an azacarbazolyl group, a diazacarbazolyl group, a dibenzofuranyl group, a naphthobenzofuranyl group, an azadibenzofuranyl group, a diazadibenzofuranyl group, a dibenzothiophenyl group, a naphthobenzothiophenyl group, an azadibenzothiophenyl group, a diazadibenzothiophenyl group, a (9-phenyl)carbazolyl group (a (9-phenyl)carbazol-1-yl group, a (9-phenyl)carbazol-2-yl group, a (9-phenyl)carbazol-3-yl group, or a (9-phenyl)carbazol-4-yl group), a (9-biphenylyl)carbazolyl group, a (9-phenyl)phenylcarbazolyl group, a diphenylcarbazol-9-yl group, a phenylcarbazol-9-yl group, a phenyltriazinyl group, a biphenylyltriazinyl group, a diphenyltriazinyl group, a phenyldibenzofuranyl group, a phenyldibenzothiophenyl group, and the like.
In this specification, the carbazolyl group is specifically any of the following groups, unless otherwise specified in this specification.
In this specification, the (9-phenyl)carbazolyl group is specifically any of the following groups, unless otherwise specified in this specification.
In the general formulas (TEMP-Cz1) to (TEMP-Cz9), * represents a bonding site.
In this specification, the dibenzofuranyl group and the dibenzothiophenyl group are specifically any of the following groups, unless otherwise specified in this specification.
In the general formulas (TEMP-34) to (TEMP-41), * represents a bonding site.
The substituted or unsubstituted alkyl group described in this specification is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a t-butyl group, or the like, unless otherwise specified in this specification.
The “substituted or unsubstituted arylene group” described in this specification is a divalent group derived by removing one hydrogen atom on the aryl ring of the “substituted or unsubstituted aryl group”, unless otherwise specified. Specific examples of the “substituted or unsubstituted arylene group” (specific example group G12) include a divalent group derived by removing one hydrogen atom on the aryl ring of the “substituted or unsubstituted aryl group” described in the specific example group G1, and the like.
The “substituted or unsubstituted divalent heterocyclic group” described in this specification is a divalent group derived by removing one hydrogen atom on the heterocycle of the “substituted or unsubstituted heterocyclic group”, unless otherwise specified. Specific examples of the “substituted or unsubstituted divalent heterocyclic group” (specific example group G13) include a divalent group derived by removing one hydrogen atom on the heterocycle of the “substituted or unsubstituted heterocyclic group” described in the specific example group G2, and the like.
The “substituted or unsubstituted alkylene group” described in this specification is a divalent group derived by removing one hydrogen atom on the alkyl chain of the “substituted or unsubstituted alkyl group”, unless otherwise specified. Specific examples of the “substituted or unsubstituted alkylene group” (specific example group G14) include a divalent group derived by removing one hydrogen atom on the alkyl chain of the “substituted or unsubstituted alkyl group” described in the specific example group G3, and the like.
The substituted or unsubstituted arylene group described in this specification is preferably any group of the following general formulas (TEMP-42) to (TEMP-68), unless otherwise specified in this specification.
In the general formulas (TEMP-42) to (TEMP-52), Q1 to Q10 are independently a hydrogen atom or a substituent.
In the general formulas (TEMP-42) to (TEMP-52), * represents a bonding site.
In the general formulas (TEMP-53) to (TEMP-62), Q1 to Q10 are independently a hydrogen atom or a substituent.
Q9 and Q10 may be bonded with each other via a single bond to form a ring.
In the general formulas (TEMP-53) to (TEMP-62), * represents a bonding site.
In the general formulas (TEMP-63) to (TEMP-68), Q1 to Q8 are independently a hydrogen atom or a substituent.
In the general formulas (TEMP-63) to (TEMP-68), * represents a bonding site.
The substituted or unsubstituted divalent heterocyclic group described in this specification is preferably any group of the following general formulas (TEMP-69) to (TEMP-102), unless otherwise specified in this specification.
In the general formulas (TEMP-69) to (TEMP-82), Q1 to Q9 are independently a hydrogen atom or a substituent.
In the general formulas (TEMP-83) to (TEMP-102), Q1 to Q8 are independently a hydrogen atom or a substituent.
The above is the explanation of the “Substituent described in this specification.”
“The Case where Bonded with Each Other to Form a Ring”
In this specification, the case where “one or more sets of adjacent two or more form a substituted or unsubstituted monocycle by bonding with each other, form a substituted or unsubstituted fused ring by bonding with each other, or do not bond with each other” means the case where “one or more sets of adjacent two or more form a substituted or unsubstituted monocycle by bonding with each other”; the case where “one or more sets of adjacent two or more form a substituted or unsubstituted fused ring by bonding with each other”; and the case where “one or more sets of adjacent two or more do not bond with each other.”
The case where “one or more sets of adjacent two or more form a substituted or unsubstituted monocycle by bonding with each other” and the case where “one or more sets of adjacent two or more form a substituted or unsubstituted fused ring by bonding with each other” in this specification (these cases may be collectively referred to as “the case where forming a ring by bonding with each other”) will be described below. The case of an anthracene compound represented by the following general formula (TEMP-103) in which the mother skeleton is an anthracene ring will be described as an example.
For example, in the case where “one or more sets of adjacent two or more among R921 to R930 form a ring by bonding with each other”, the one set of adjacent two includes a pair of R921 and R922, a pair of R922 and R923, a pair of R923 and R924, a pair of R924 and R930, a pair of R930 and R925, a pair of R925 and R926, a pair of R926 and R927, a pair of R927 and R928, a pair of R928 and R929, and a pair of R929 and R921.
The “one or more sets” means that two or more sets of the adjacent two or more sets may form a ring at the same time. For example, R921 and R922 form a ring QA by bonding with each other, and at the same, time R925 and R926 form a ring QB by bonding with each other, the anthracene compound represented by the general formula (TEMP-103) is represented by the following general formula (TEMP-104).
The case where the “set of adjacent two or more” form a ring includes not only the case where the set (pair) of adjacent “two” is bonded with as in the above-mentioned examples, but also the case where the set of adjacent “three or more” are bonded with each other. For example, it means the case where R921 and R922 form a ring QA by bonding with each other, and R922 and R923 form a ring Qc by bonding with each other, and adjacent three (R921, R922 and R923) form rings by bonding with each other and together fused to the anthracene mother skeleton. In this case, the anthracene compound represented by the general formula (TEMP-103) is represented by the following general formula (TEMP-105). In the following general formula (TEMP-105), the ring QA and the ring Qc share R922.
The “monocycle” or “fused ring” formed may be a saturated ring or an unsaturated ring, as a structure of the formed ring alone. Even when the “one pair of adjacent two” forms a “monocycle” or a “fused ring”, the “monocycle” or the “fused ring” may form a saturated ring or an unsaturated ring. For example, the ring QA and the ring QB formed in the general formula (TEMP-104) are independently a “monocycle” or a “fused ring.” The ring QA and the ring Qc formed in the general formula (TEMP-105) are “fused ring.” The ring QA and ring Qc of the general formula (TEMP-105) are fused ring by fusing the ring QA and the ring Qc together. When the ring QA of the general formula (TMEP-104) is a benzene ring, the ring QA is a monocycle. When the ring QA of the general formula (TMEP-104) is a naphthalene ring, the ring QA is a fused ring.
The “unsaturated ring” includes, in addition to an aromatic hydrocarbon ring and an aromatic heterocycle, an aliphatic hydrocarbon ring with an unsaturated bond, i.e., double and/or triple bonds in the ring structure (e.g., cyclohexene, cyclohexadiene, etc.), and a non-aromatic heterocycle with an unsaturated bond (e.g., dihydropyran, imidazoline, pyrazoline, quinolizine, indoline, isoindoline, etc.). The “saturated ring” includes an aliphatic hydrocarbon ring without an unsaturated bond and a non-aromatic heterocycle without ab unsaturated bond.
Specific examples of the aromatic hydrocarbon ring include a structure in which the group listed as a specific example in the specific example group G1 is terminated by a hydrogen atom.
Specific examples of the aromatic heterocycle include a structure in which the aromatic heterocyclic group listed as a specific example in the example group G2 is terminated by a hydrogen atom. Specific examples of the aliphatic hydrocarbon ring include a structure in which the group listed as a specific example in the specific example group G6 is terminated by a hydrogen atom.
The term “to form a ring” means forming a ring only with plural atoms of the mother skeleton, or with plural atoms of the mother skeleton and one or more arbitrary atoms in addition. For example, the ring QA shown in the general formula (TEMP-104), which is formed by bonding R921 and R922 with each other, is a ring formed from the carbon atom of the anthracene skeleton with which R921 is bonded, the carbon atom of the anthracene skeleton with which R922 is bonded, and one or more arbitrary atoms. For example, in the case where the ring QA is formed with R921 and R922, when a monocyclic unsaturated ring is formed with the carbon atom of the anthracene skeleton with which R921 is bonded, the carbon atom of the anthracene skeleton with which R922 is bonded, and four carbon atoms, the ring formed with R921 and R922 is a benzene ring.
Here, the “arbitrary atom” is preferably at least one atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom, unless otherwise specified in this specification. In the arbitrary atom (for example, a carbon atom or a nitrogen atom), a bond which does not form a ring may be terminated with a hydrogen atom or the like, or may be substituted with “arbitrary substituent” described below. When an arbitrary atom other than a carbon atom is contained, the ring formed is a heterocycle.
The number of “one or more arbitrary atom(s)” constituting a monocycle or a fused ring is preferably 2 or more and 15 or less, more preferably 3 or more and 12 or less, and still more preferably 3 or more and 5 or less, unless otherwise specified in this specification.
The “monocycle” is preferable among the “monocycle” and the “fused ring”, unless otherwise specified in this specification.
The “unsaturated ring” is preferable among the “saturated ring” and the “unsaturated ring”, unless otherwise specified in this specification.
Unless otherwise specified in this specification, the “monocycle” is preferably a benzene ring. Unless otherwise specified in this specification, the “unsaturated ring” is preferably a benzene ring.
Unless otherwise specified in this specification, when “one or more sets of adjacent two or more” are “bonded with each other to form a substituted or unsubstituted monocycle” or “bonded with each other to form a substituted or unsubstituted fused ring”, this specification, one or more sets of adjacent two or more are preferably bonded with each other to form a substituted or unsubstituted “unsaturated ring” from plural atoms of the mother skeleton and one or more and 15 or less atoms which is at least one kind selected from a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom.
The substituent in the case where the above-mentioned “monocycle” or “fused ring” has a substituent is, for example, an “arbitrary substituent” described below. Specific examples of the substituent which the above-mentioned “monocycle” or “fused ring” has include the substituent described above in the “Substituent described in this specification” section.
The substituent in the case where the above-mentioned “saturated ring” or “unsaturated ring” has a substituent is, for example, an “arbitrary substituent” described below. Specific examples of the substituent which the above-mentioned “monocycle” or “fused ring” has include the substituent described above in the “Substituent described in this specification” section.
The foregoing describes the case where “one or more sets of adjacent two or more form a substituted or unsubstituted monocycle by bonding with each other” and the case where “one or more sets of adjacent two or more form a substituted or unsubstituted fused ring by bonding with each other” (the case where “forming a ring by bonding with each other”).
In one embodiment in this specification, the substituent (in this specification, sometimes referred to as an “arbitrary substituent”) in the case of “substituted or unsubstituted” is, for example, a group selected from the group consisting of:
When two or more R901's are present, the two or more R901's may be the same or different.
When two or more R902's are present, the two or more R902's may be the same or different.
When two or more R903's are present, the two or more Roos's may be the same or different.
When two or more R904's are present, the two or more R904's may be the same or different.
When two or more R905's are present, the two or more Roos's may be the same or different.
When two or more Roos's are present, the two or more R906's may be the same or different.
When two or more R907's are present, the two or more R907's may be the same or different.
In one embodiment, the substituent in the case of “substituted or unsubstituted” is a group selected from the group consisting of:
In one embodiment, the substituent in the case of “substituted or unsubstituted” is a group selected from the group consisting of:
Specific examples of each of the arbitrary substituents include specific examples of substituent described in the section “Substituent described in this specification” above.
Unless otherwise specified in this specification, adjacent arbitrary substituents may form a “saturated ring” or an “unsaturated ring”, preferably form a substituted or unsubstituted saturated 5-membered ring, a substituted or unsubstituted saturated 6-membered ring, a substituted or unsubstituted unsaturated 5-membered ring, or a substituted or unsubstituted unsaturated 6-membered ring, more preferably form a benzene ring.
Unless otherwise specified in this specification, the arbitrary substituent may further have a substituent. The substituent which the arbitrary substituent further has is the same as that of the above-mentioned arbitrary substituent.
In this specification, the numerical range represented by “AA to BB” means the range including the numerical value AA described on the front side of “AA to BB” as the lower limit and the numerical value BB described on the rear side of “AA to BB” as the upper limit.
A compound according to an aspect of the present invention is represented by the following formula (1):
wherein in the formula (1),
wherein in the formula (1-21),
When the compound according to an aspect of the present invention has the above structure, the compound is used in an organic EL device to be capable of enhancing the device performance thereof. Specifically, an organic EL device having higher efficiency, or being able to be driven at lower voltage can be achieved.
Any one of R1 to R12 represents a bond with L3. The expression “represents a bond” means that L3 is directly bonded with any one of the carbon atoms with which R1 to R12 are bonded in the benzanthracene ring. When n3 is 0, the carbon atom in the six-membered ring with which (L3)n3 is bonded, and the carbon atom with which R1 to R12 are bonded in the benzanthracene ring are directly bonded via a single bond.
In one embodiment, any one of R7 and R12 represents a bond with L3.
In one embodiment, R7 represents a bond with L3. In this case, R12 is a hydrogen atom or a substituent, and in one embodiment, R12 is a hydrogen atom.
In one embodiment, R12 represents a bond with L3. In this case, R7 is a hydrogen atom or a substituent, and in one embodiment, R7 is a substituent.
In one embodiment, n3 is 1.
In one embodiment, n3 is 0.
In one embodiment, L3 is a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted divalent heterocyclic group having 5 to 50 ring atoms and not containing a nitrogen atom.
The divalent heterocyclic group not containing a nitrogen atom in the expression “a substituted or unsubstituted divalent heterocyclic group having 5 to 50 ring atoms and not containing a nitrogen atom” is a divalent cyclic group containing one or more atoms selected from the group consisting of an oxygen atom, a sulfur atom, a silicon atom, a phosphorus atom, and a boron atom as a heteroatom. The heterocyclic group is the same as defined for the “a substituted or unsubstituted divalent heterocyclic group” in [Definition], except that it does not containing a nitrogen atom.
In one embodiment, L3 is a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms.
In one embodiment, L3 is a divalent group derived by removing one hydrogen atom on the aromatic hydrocarbon ring from a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted benzophenanthryl group, a substituted or unsubstituted phenalenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted benzochrysenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted benzotriphenylenyl group, a substituted or unsubstituted tetracenyl group, a substituted or unsubstituted pentacenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted 9,9′-spirobifluorenyl group, a substituted or unsubstituted benzofluorenyl group, a substituted or unsubstituted dibenzofluorenyl group, a substituted or unsubstituted fluoranthenyl group, a substituted or unsubstituted benzofluoranthenyl group, or a substituted or unsubstituted perylenyl group.
In one embodiment, L3 is a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthylene group.
Ar1 and Ar2 are independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted monovalent heterocyclic group having 5 to 50 ring atoms and not containing a nitrogen atom, a monovalent heterocyclic group represented by the following formula (1-21), or a monovalent heterocyclic group represented by the following formula (1-22).
The monovalent heterocyclic group not containing a nitrogen atom in the expression “a substituted or unsubstituted monovalent heterocyclic group having 5 to 50 ring atoms and not containing a nitrogen atom” is a monovalent cyclic group containing one or more atoms selected from the group consisting of an oxygen atom, a sulfur atom, a silicon atom, a phosphorus atom, and a boron atom as a heteroatom. The heterocyclic group is the same as defined for the “a substituted or unsubstituted heterocyclic group” in [Definition], except that it does not containing a nitrogen atom.
In one embodiment, Ar1 and Ar2 are independently
In one embodiment, Ar1 and Ar2 are independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In one embodiment, Ar1 and Ar2 are independently a monovalent group selected from the group consisting of
Ar1 and Ar2 may be the same as or different from each other. Further, -(L1)n1-Ar1 and -(L2)n2-Ar2 may be the same as or different from each other.
In one embodiment, Ar1 is a group selected from the group consisting of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted dibenzofuranyl group, and a substituted or unsubstituted carbazolyl group.
In one embodiment, Ar1 is a group selected from the group consisting of a substituted or unsubstituted phenyl group, and a substituted or unsubstituted biphenyl group.
In one embodiment, Ar1 is an unsubstituted group, or a group containing a cyano group as a substituent.
In one embodiment, Ar2 is a group selected from the group consisting of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted dibenzofuranyl group, and a substituted or unsubstituted carbazolyl group.
In one embodiment, Ar2 is a group selected from the group consisting of a substituted or unsubstituted phenyl group, and a substituted or unsubstituted biphenyl group.
In one embodiment, Ar2 is an unsubstituted group, or a group containing a cyano group as a substituent.
In one embodiment, the substituent in the case of “substituted or unsubstituted” for Ar1 and Ar2 is an unsubstituted group, R21 to R29 which are the substituent in the formula (1-21) are an unsubstituted group, and R31 to R37 which are the substituent in the formula (1-22) are an unsubstituted group.
The expression “the substituent in the case of “substituted or unsubstituted” for Ar1 and Ar2 is an unsubstituted group” means that all groups such as “a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms” exemplified as the substituent in the case of “substituted or unsubstituted” for Ar1 and Ar2 do not have the substituent, that is, they are “an unsubstituted alkyl group having 1 to 50 carbon atoms” and the like.
The expression “R21 to R29 which are the substituent in the formula (1-21) are an unsubstituted group” means that all groups such as “a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms” exemplified for R21 to R29 do not have the substituent, that is, they are “an unsubstituted alkyl group having 1 to 50 carbon atoms” and the like.
The expression “R31 to R37 which are the substituent in the formula (1-22) are an unsubstituted group” means that all groups such as “a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms” exemplified for R31 to R37 do not have the substituent, that is, they are “an unsubstituted alkyl group having 1 to 50 carbon atoms” and the like.
In one embodiment, in the formula (1-21), the adjacent two of R21 to R24 form a substituted or unsubstituted benzene ring by bonding with each other, the other two of R21 to R24 do not form the substituted or unsubstituted, saturated or unsaturated ring, and a set of the adjacent two or more of R25 to R28 do not form the substituted or unsubstituted, saturated or unsaturated ring.
In one embodiment, a set of the adjacent two or more of R21 to R28 in the formula (1-21) do not form the substituted or unsubstituted, saturated or unsaturated ring.
In one embodiment, a set of the adjacent two or more of R31 to R36 in the formula (1-22) do not form the substituted or unsubstituted, saturated or unsaturated ring.
In one embodiment, L1 and L2 are independently a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted divalent heterocyclic group having 5 to 50 ring atoms and not containing a nitrogen atom.
In one embodiment, L1 and L2 are independently a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms.
In one embodiment, L1 and L2 are independently a divalent group derived by removing one hydrogen atom on the aromatic hydrocarbon ring from a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted benzophenanthryl group, a substituted or unsubstituted phenalenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted benzochrysenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted benzotriphenylenyl group, a substituted or unsubstituted tetracenyl group, a substituted or unsubstituted pentacenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted 9,9′-spirobifluorenyl group, a substituted or unsubstituted benzofluorenyl group, a substituted or unsubstituted dibenzofluorenyl group, a substituted or unsubstituted fluoranthenyl group, a substituted or unsubstituted benzofluoranthenyl group, or a substituted or unsubstituted perylenyl group.
In one embodiment, n1 is 0.
In one embodiment, n2 is 0.
In one embodiment, the compound represented by the formula (1) does not include an anthracene structure.
The expression “it does not include an anthracene structure” means that the compound represented by the formula (1) does not include a monovalent or divalent or more group derived from an anthracene as a part thereof. Here, the term “anthracene structure” means a structure in which only three benzene rings are fused, and does not mean a fused ring structure derived from an anthracene such as a benzanthracene.
Further, in one embodiment, the compound represented by the formula (1) does not include a fused ring structure containing an anthracene other than the benzanthracene structure represented by one in parentheses of the formula (1) as a structure of a moiety.
The expression “it does not include a fused ring structure containing an anthracene as a structure of a moiety” means that the compound represented by the formula (1) does not include a monovalent or divalent or more group derived from a fused ring structure containing an anthracene as a structure of a moiety other than the benzanthracene structure represented by one in parentheses of the formula (1) as a part thereof. Here, the term “fused ring structure containing an anthracene as a structure of a moiety” represents a structure in which a substituted or unsubstituted, saturated or unsaturated ring is fused with one or more sets of the adjacent two or more of ten bonding positions in an anthracene structure, and examples thereof include a benzanthracene, a naphthacene, a benzopyrene and the like.
In one embodiment, the compound represented by the formula (1) does not comprise a nitrogen-containing six-membered ring structure, or a fused structure including a nitrogen-containing six-membered ring skeleton as a structure of a moiety, other than a pyrimidine skeleton with which L1, L2, and L3 are bonded.
The expression “it does not include a nitrogen-containing six-membered ring structure other than a pyrimidine skeleton with which L1, L2, and L3 are bonded” means that the compound represented by the formula (1) does not include a monovalent or divalent or more group derived from a nitrogen-containing six-membered ring (for example, a pyridine, a pyrimidine, a triazine or the like) other than a pyrimidine skeleton with which L1, L2, and L3 are bonded as a part thereof.
The expression “it does not include a fused structure including a nitrogen-containing six-membered ring skeleton as a structure of a moiety” means that the compound represented by the formula (1) does not include a monovalent or divalent or more group derived from a fused ring including a nitrogen-containing six-membered ring skeleton as a structure of a moiety (for example, a benzopyridine, a quinazoline or the like) as a part thereof.
In one embodiment, the compound represented by the formula (1) is a compound represented by the following formula (11):
wherein in the formula (11), Ar1, Ar2, L3, R1 to R6, and R& to R11 are the same as defined in the formula (1).
In one embodiment, the compound represented by the formula (1) is a compound represented by the following formula (21):
wherein in the formula (21), Ar1, Ar2, R1 to Re, and Re to Ru are the same as defined in the formula (1).
In one embodiment, the compound represented by the formula (1) is a compound represented by the following formula (31):
wherein in the formula (31), Ar1, Ar2, L2, L3, R1 to Re, and R8 to R11 are the same as defined in the formula (1).
In one embodiment, the compound represented by the formula (1) is a compound represented by the following formula (41):
wherein in the formula (41), Ar1, Ar2, L3, and R1 to R11 are the same as defined in the formula (1).
In one embodiment, R4 is a hydrogen atom.
In one embodiment, R1 to R6 and R8 to R11 are hydrogen atoms.
In one embodiment, the compound represented by the formula (1) is a compound represented by the following formula (12):
wherein in the formula (12), Ar1 and Ar2 are the same as defined in the formula (1).
In one embodiment, the compound represented by the formula (1) is a compound represented by the following formula (13):
wherein in the formula (13), Ar1 and Ar2 are the same as defined in the formula (1).
In one embodiment, the compound represented by the formula (1) is a compound represented by the following formula (14):
wherein in the formula (14), L2, Ar1 and Ar2 are the same as defined in the formula (1).
In one embodiment, the compound represented by the formula (1) is a compound represented by the following formula (15):
wherein in the formula (15), Ar1 and Ar2 are the same as defined in the formula (1).
As defined in the [Definition], the “hydrogen atom” used in the present specification includes a protium atom, a deuterium atom, and a tritium atom. Accordingly, the inventive compounds may contain naturally derived deuterium atoms.
In addition, deuterium atoms may be intentionally introduced into the inventive compound by using a deuterated compound as a part or all of raw material compounds. Accordingly, in one embodiment of the present invention, the compound represented by formula (1) includes at least one deuterium atom. That is, the compound of the present embodiment may be the compound represented by the formula (1), wherein at least one of hydrogen atoms contained in the compound is a deuterium atom.
In the compound represented by the formula (1), at least one hydrogen atom selected from hydrogen atoms possessed by the benzanthracene structure; hydrogen atoms possessed by L3; hydrogen atoms possessed by a pyrimidine skeleton with which L1, L2, and L3 are bonded; hydrogen atoms possessed by L1; hydrogen atoms possessed by L2; hydrogen atoms possessed by Ar1; and hydrogen atoms possessed by Ar2 may be a deuterium atom.
The deuteration rate of the compound depends on the deuteration rate of the raw material compounds used. Even if a raw material having a predetermined deuteration rate is used, a protium atom isotope may be included at a certain proportion derived naturally. Accordingly, an aspect of the deuteration rate includes a proportion in which a trace amount of naturally derived isotopes is considered, based on a proportion obtained by simply counting the number of deuterium atoms represented by the chemical formula.
In one embodiment, the deuteration rate of the compound is, for example, 1% or more, 3% or more, 5% or more, 10% or more, or 50% or more.
Specific examples of the compound represented by the formula (1) will be described below, but these are merely examples, and the compound represented by the formula (1) is not limited to the following specific examples.
The compound according to an aspect of the present invention is useful as a material for an organic EL device, and for example, is useful as an electron-transporting region for an organic EL device.
An organic EL device according to an aspect of the present invention will be described. The organic EL device according to an aspect of the present invention includes a cathode, an anode and one or two or more organic layers arranged between the cathode and the anode, wherein at least one layer of the organic layers includes the compound according to an aspect of the present invention.
The organic EL device according to an aspect of the present invention preferably includes an anode, an emitting layer, an electron-transporting region, and a cathode in this order, wherein the electron-transporting region includes the compound according to an aspect of the present invention.
As a representative device configuration of the organic EL device, structures in which structures of the following (1) to (4) and the like are stacked on a substrate can be given:
The electron-transporting region is generally composed of one or more layer selected from an electron-injecting layer and an electron-transporting layer. The hole-transporting region is generally composed of one or more layer selected from a hole-injecting layer and a hole-transporting layer.
A schematic configuration of the organic EL device according to an aspect of the present invention will be described with reference to
The organic EL device 1 according to an aspect of the present invention includes a substrate 2, an anode 3, an emitting layer 5, a cathode 10, a hole-transporting region 4 between the anode 3 and the emitting layer 5, and an electron-transporting region 6 between the emitting layer 5 and the cathode 10.
Members which can be used in the organic EL device according to an aspect of the present invention, materials for forming each layer, other than the above-mentioned compounds, and the like, will be described below.
The substrate is used as a support of an emitting device. As the substrate, glass, quartz, plastic or the like can be used, for example. Further, a flexible substrate may be used. The term “flexible substrate” means a bendable (flexible) substrate, and specific examples thereof include a plastic substrate formed of polycarbonate, polyvinyl chloride or the like.
For the anode formed on the substrate, metals, alloys, electrically conductive compounds, mixtures thereof, and the like, which have large work function (specifically 4.0 eV or more) are preferably used. Specific examples thereof include indium oxide-tin oxide (ITO: Indium Tin Oxide), indium oxide-tin oxide containing silicon or silicon oxide, indium oxide-zinc oxide, tungsten oxide, indium oxide containing zinc oxide, graphene, and the like. In addition thereto, specific examples thereof include gold (Au), platinum (Pt), a nitride of a metallic material (for example, titanium nitride), or the like.
The hole-injecting layer is a layer containing a substance having high hole-injecting property. As the substance having high hole-injecting property, molybdenum oxide, titanium oxide, vanadium oxide, rhenium oxide, ruthenium oxide, chromium oxide, zirconium oxide, hafnium oxide, tantalum oxide, silver oxide, tungsten oxide, manganese oxide, an aromatic amine compound, a polymer compound (oligomers, dendrimers, polymers, and the like), or the like can be given.
The hole-transporting layer is a layer containing a substance having high hole-transporting property. For the hole-transporting layer, an aromatic amine compound, a carbazole derivative, an anthracene derivative, or the like can be used. A polymer compound such as poly(N-vinylcarbazole) (abbreviation: PVK) and poly(4-vinyltriphenylamine) (abbreviation: PVTPA) can also be used. Provided that a substance other than the above-described substances may be used as long as the substance has higher hole-transporting property than electron-transporting property. The layer containing the substance having high hole-transporting property may be not only a single layer, but also layers in which two or more layers formed of the above-described substances are stacked.
The emitting layer is a layer containing a substance having high luminous property, and various materials can be used. For example, as the substance having high emitting property, a fluorescent compound which emits fluorescence or a phosphorescent compound which emits phosphorescence can be used. The fluorescent compound is a compound which can emit from a singlet excited state, and the phosphorescent compound is a compound which can emit from a triplet excited state.
As a blue fluorescent emitting material which can be used for the emitting layer, pyrene derivatives, styrylamine derivatives, chrysene derivatives, fluoranthene derivatives, fluorene derivatives, diamine derivatives, triarylamine derivatives, and the like can be used. As a green fluorescent emitting material which can be used for the emitting layer, aromatic amine derivatives and the like can be used. As a red fluorescent emitting material which can be used for the emitting layer, tetracene derivatives, diamine derivatives and the like can be used.
As a blue phosphorescent emitting material which can be used for the emitting layer, metal complexes such as iridium complexes, osmium complexes and platinum complexes are used. As a green phosphorescent emitting material which can be used for the emitting layer, iridium complexes and the like are used. As a red phosphorescent emitting material which can be used for the emitting layer, metal complexes such as iridium complexes, platinum complexes, terbium complexes and europium complexes are used.
The emitting layer may have a constitution in which the substance having high emitting property (guest material) is dispersed in another substance (host material). As a substance for dispersing the substance having high emitting property, a variety of substances can be used, and it is preferable to use a substance having a higher lowest unoccupied molecular orbital level (LUMO level) and a lower highest occupied molecular orbital level (HOMO level) than a substance having high emitting property.
As a substance (host material) for dispersing the substance having high emitting property, 1) a metal complex such as an aluminum complex, a beryllium complex, and a zinc complex, 2) a heterocyclic compound such as an oxadiazole derivative, a benzimidazole derivative, and a phenanthroline derivative, 3) a fused aromatic compound such as a carbazole derivative, an anthracene derivative, a phenanthrene derivative, a pyrene derivative, and a chrysene derivative, and 4) an aromatic amine compound such as a triarylamine derivative and a fused polycyclic aromatic amine derivative are used.
The electron-transporting layer is a layer containing a substance having high electron-transporting property. For the electron-transporting layer, 1) a metal complex such as an aluminum complex, a beryllium complex, and a zinc complex; 2) a heteroaromatic complex such as an imidazole derivative, a benzimidazole derivative, an azine derivative, carbazole derivative, and a phenanthroline derivative; and 3) a polymer compound can be used.
In one embodiment, the electron-transporting layer may include or may not include another substance described above in addition to the compound represented by the formula (1).
In one embodiment, the electron-transporting layer includes one or more compounds selected from the group consisting of a compound having an alkali metal, and a compound having a metal belonging to Group 13 of the Periodic Table of the Elements in addition to the compound represented by the formula (1). Examples of these compound include lithium fluoride, lithium oxide, 8-hydroxyquinolinolato-lithium (Liq), cesium fluoride, tris (8-quinolinolato) aluminum (Alq3), tris (4-methyl-8-quinolinolato) aluminum (Almq3), bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum (BAlq), and the like.
A ratio included therein (mass ratio) of the compound represented by the formula (1), and the compound having an alkali metal, and the compound having a metal belonging to Group 13 of the Periodic Table of the Elements is not particularly limited, and for example, is 10:90 to 90:10.
In the organic EL device according to an aspect of the present invention, the electron-transporting region includes a first layer (also referred to as “first electron-transporting layer” or “hole-barrier layer”) and a second layer (also referred to as “second electron-transporting layer”) in this order from the emitting layer side, and the second layer includes the compound represented by the formula (1). For example, the configuration of the electron-transporting layer described above can be applied as the first layer in this case. In the organic EL device according to another one aspect of the present invention, the first layer includes the compound represented by the formula (1). For example, the configuration of the electron-transporting layer described above can be applied as the second layer in this case.
The electron-injecting layer is a layer containing a substance having high electron-injecting property. For the electron-injecting layer, lithium (Li), ytterbium (Yb), lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF2), a metal complex compound such as 8-hydroxyquinolinolato-lithium (Liq), an alkali metal such as lithium oxide (LiOx), an alkaline earth metal, or a compound thereof can be used.
For the cathode, metals, alloys, electrically conductive compounds, mixtures thereof, and the like, which have small work function (specifically 3.8 eV or less) are preferably used. Specific examples of such a cathode material include an element belonging to Group 1 or Group 2 of the Periodic Table of the Elements, i.e., an alkali metal such as lithium (Li) and cesium (Cs), an alkaline earth metal such as magnesium (Mg), calcium (Ca) and strontium (Sr), and an alloy containing these (e.g., MgAg and AILi); a rare earth metal such as europium (Eu) and ytterbium (Yb), and an alloy containing these.
The cathode is usually formed by a vacuum deposition method or a sputtering method. Further, when silver paste or the like is used, it is possible to use the coating method, the inkjet method or the like.
When the electron-injecting layer is provided, the cathode can be formed using various conductive materials such as aluminum, silver, ITO, graphene, indium oxide-tin oxide containing silicon or silicon oxide, regardless of the work function value.
In the organic EL device according to an aspect of the present invention, the thickness of each layer is not particularly limited, but is normally preferable several nm to 1 um generally in order to suppress defects such as pinholes, to suppress applied voltages to be low, and to improve luminous efficiency.
In the organic EL device according to an aspect of the present invention, the method for forming each layer is not particularly limited. A conventionally-known method for forming each layer such as a vacuum deposition process and a spin coating process can be used. Each layer such as the emitting layer can be formed by a known method such as a vacuum deposition process, a molecular beam deposition process (MBE process), or an application process such as a dipping process, a spin coating process, a casting process, a bar coating process and a roll coating process, using a solution prepared by dissolving the material in a solvent.
An electronic apparatus according to an aspect of the present invention is characterized by including the organic EL device according to an aspect of the present invention.
Specific examples of the electronic apparatus include display components such as an organic EL panel module; display devices for a television, a cellular phone and a personal computer; and emitting devices such as a light and a vehicular lamp; and the like.
Compounds represented by the formula (1) used in the fabrication of the organic EL devices of Examples are shown below.
Compound structures used in the fabrication of the organic EL devices of Comparative Examples are shown below.
Other compound structures used in the fabrication of the organic EL devices of Examples and Comparative Examples are shown below.
An organic EL device was fabricated as follows.
A 25 mm×75 mm×1.1 mm-thick glass substrate with an ITO transparent electrode (anode) (manufactured by GEOMATEC Co., Ltd.) was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then subjected to UV-ozone cleaning for 30 minutes. The ITO has the film thickness of 130 nm.
The glass substrate with the transparent electrode after being cleaned was mounted onto a substrate holder in a vacuum vapor deposition apparatus. First, compounds HT-1 and HI-1 were co-deposited on the surface on the side where the transparent electrode was formed so as to cover the transparent electrode to be 3% by mass in a proportion of the compound HI-1 to form a first hole-transporting layer having the thickness of 10 nm.
A compound HT-1 was deposited on the first hole-transporting layer to form a second hole-transporting layer having the thickness of 80 nm.
A compound EBL-1 was deposited on the second hole-transporting layer to form a third hole-transporting layer having the thickness of 5 nm.
A compound BH-1 (host material) and a compound BD-1 (dopant material) were co-deposited on the third hole-transporting layer to be 4% by mass in a proportion of the compound BD-1 to form an emitting layer having the thickness of 25 nm.
A compound HBL-1 was deposited on the emitting layer to form a first electron-transporting layer having the thickness of 5 nm.
A compound ET-1 and 8-hydroxyquinolinolato-lithium (Liq) were co-deposited on the first electron-transporting layer to be 50% by mass in a proportion of Liq to form a second electron-transporting layer having the thickness of 20 nm.
A metal Yb and LiF were co-deposited on the second electron-transporting layer to be 50% by mass in a proportion of Yb to form an electron-injecting layer having the thickness of 1 nm. A metal Al was deposited on the electron-injecting layer to form a cathode having the thickness of 50 nm.
The device configuration of the organic EL device of Example 1 is schematically shown as follows. ITO(130)/HT-1:HI-1(10:3%)/HT-1(80)/EBL-1(5)/BH-1:BD-1(25:4%)/HBL-1(5)/ET-1:Liq(20:50%)/LiF:Yb(1:50%)/AI(50)
The numerical values in parentheses indicate the film thickness (unit: nm). The numerical values represented by percent in parentheses indicate a proportion (% by mass) of the latter compound in the layer.
A voltage was applied to the organic EL device so that the current density became 1.0 mA/cm2, and the EL emission spectrum was measured by using Spectroradiometer CS—2000 (manufactured by KONICA MINOLTA, INC.). External quantum efficiency (EQE) (%) was calculated from the obtained spectral emission luminance spectrum. The results are shown in Table 1.
An organic EL device was fabricated and evaluated in the same manner as in Example 1, except that a compound described in Table 1 was used instead of the compound ET-1. The results are shown in Table 1.
An organic EL device was fabricated as follows.
A 25 mm×75 mm×1.1 mm-thick glass substrate with an ITO transparent electrode (anode) (manufactured by GEOMATEC Co., Ltd.) was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then subjected to UV-ozone cleaning for 30 minutes. The ITO has the film thickness of 130 nm.
The glass substrate with the transparent electrode after being cleaned was mounted onto a substrate holder in a vacuum vapor deposition apparatus. First, compounds HT-2 and HI-1 were co-deposited on the surface on the side where the transparent electrode was formed so as to cover the transparent electrode to be 3% by mass in a proportion of the compound HI-1 to form a first hole-transporting layer having the thickness of 10 nm.
A compound HT-2 was deposited on the first hole-transporting layer to form a second hole-transporting layer having the thickness of 80 nm.
A compound EBL-1 was deposited on the second hole-transporting layer to form a third hole-transporting layer having the thickness of 5 nm.
A compound BH-2 (host material) and a compound BD-1 (dopant material) were co-deposited on the third hole-transporting layer to be 4% by mass in a proportion of the compound BD-1 to form an emitting layer having the thickness of 25 nm.
A compound HBL-2 was deposited on the emitting layer to form a first electron-transporting layer having the thickness of 5 nm.
A compound ET-1 and Liq were co-deposited on the first electron-transporting layer to be 50% by mass in a proportion of Liq to form a second electron-transporting layer having the thickness of 20 nm.
A metal Yb was deposited on the second electron-transporting layer to form an electron-injecting layer having the thickness of 1 nm.
A metal Al was deposited on the electron-injecting layer to form a cathode having the thickness of 50 nm.
The device configuration of the organic EL device of Example 2 is schematically shown as follows. ITO(130)/HT-2:HI-1(10:3%)/HT-2(80)/EBL-1(5)/BH-2:BD-1(25:4%)/HBL-2(5)/ET-1:Liq(20:50%)/Yb(1)/AI(50)
The numerical values in parentheses indicate the film thickness (unit: nm). The numerical values represented by percent in parentheses indicate a proportion (% by mass) of the latter compound in the layer.
The initial property of the organic EL device was measured by driving it using DC (direct current) constant current of 50 mA/cm2 at room temperature. The results are shown in Table 2.
Organic EL devices were fabricated and evaluated in the same manner as in Example 2, except that compounds described in Table 2 were used instead of the compound ET-1. The results are shown in Table 2.
An organic EL device was fabricated and evaluated in the same manner as in Example 2, except that a compound described in Table 2 was used instead of the compound ET-1. The results are shown in Table 2.
An organic EL device was fabricated as follows.
A 25 mm×75 mm×1.1 mm-thick glass substrate with an ITO transparent electrode (anode) (manufactured by GEOMATEC Co., Ltd.) was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then subjected to UV-ozone cleaning for 30 minutes. The ITO has the film thickness of 130 nm.
The glass substrate with the transparent electrode after being cleaned was mounted onto a substrate holder in a vacuum vapor deposition apparatus. First, compounds HT-1 and HI-1 were co-deposited on the surface on the side where the transparent electrode was formed so as to cover the transparent electrode to be 3% by mass in a proportion of the compound HI-1 to form a first hole-transporting layer having the thickness of 10 nm.
A compound HT-1 was deposited on the first hole-transporting layer to form a second hole-transporting layer having the thickness of 80 nm.
A compound EBL-1 was deposited on the second hole-transporting layer to form a third hole-transporting layer having the thickness of 5 nm.
A compound BH-1 (host material) and a compound BD-1 (dopant material) were co-deposited on the third hole-transporting layer to be 4% by mass in a proportion of the compound BD-1 to form an emitting layer having the thickness of 25 nm.
A compound HBL-2 was deposited on the emitting layer to form a first electron-transporting layer having the thickness of 5 nm.
A compound ET-1 and Liq were co-deposited on the first electron-transporting layer to be 50% by mass in a proportion of Liq to form a second electron-transporting layer having the thickness of 20 nm. A metal Yb was deposited on the second electron-transporting layer to form an electron-injecting layer having the thickness of 1 nm.
A metal Al was deposited on the electron-injecting layer to form a cathode having the thickness of 50 nm.
The device configuration of the organic EL device of Example 6 is schematically shown as follows. ITO(130)/HT-1:HI-1(10:3%)/HT-1(80)/EBL-1(5)/BH-1:BD-1(25:4%)/HBL-2(5)/ET-1:Liq(20:50%)/Yb(1)/AI(50)
The numerical values in parentheses indicate the film thickness (unit: nm). The numerical values represented by percent in parentheses indicate a proportion (% by mass) of the latter compound in the layer.
A voltage was applied to the organic EL device so that the current density became 10 mA/cm2, and the EL emission spectrum was measured by using Spectroradiometer CS-2000 (manufactured by KONICA MINOLTA, INC.). External quantum efficiency (EQE) (%) was calculated from the obtained spectral emission luminance spectrum. The results are shown in Table 3.
Organic EL devices were fabricated and evaluated in the same manner as in Example 6, except that compounds described in Table 3 were used instead of the compound ET-1. The results are shown in Table 3.
The compound ET-1 was synthesized through the synthetic route described below.
4-([1,1′-biphenyl]-4-yl)-6-(4-bromophenyl)-2-phenylpyrimidine (4.00 g) and (Amphos)2PdCl2 (0.31 g) were added to a flask, it was replaced with argon gas, and then 1,4-dioxane (108 mL) and 2 M of aqueous solution of sodium carbonate (13.5 mL) were added thereto. A 1,4-dioxane solution (30 mL) of tetraphene-7-ylboronic acid (4.40 g) was added dropwise under reflux condition for three hours and 30 minutes, and further it was heated and stirred for 5 hours. The reaction solution was cooled, solvents were removed, and then it was filtered to collect solids precipitated by adding methanol therein. The obtained crude product was purified by silica gel chromatography, and then it was washed with ethyl acetate to obtain a compound ET-1 as a white solid (5.20 g, 79% yield).
The mass spectrum thereof was analyzed as m/e=611 for a molecular weight of 610.76, and it was identified as an intended product.
The compound ET-2 was synthesized through the synthetic route described below.
4-(4-bromophenyl)-2,6-diphenylpyrimidine (5.70 g) and (Amphos)2PdCl2 (0.42 g) were added to a flask, it was replaced with argon gas, and then 1,4-dioxane (98 mL) and 2 M of aqueous solution of sodium carbonate (18.4 mL) were added thereto. A 1,4-dioxane solution (49 mL) of tetraphene-7-ylboronic acid (6.01 g) was added dropwise under reflux condition for three hours and 30 minutes, and further it was heated and stirred for two hours. The reaction solution was cooled, solvents were removed, and then it was filtered to collect solids precipitated by adding methanol therein. The obtained crude product was purified by silica gel chromatography, and then it was washed with ethyl acetate to obtain a compound ET-2 as a white solid (6.26 g, 79% yield).
The mass spectrum thereof was analyzed as m/e=535 for a molecular weight of 534.66, and it was identified as an intended product.
The compound ET-3 was synthesized through the synthetic route described below.
(3-1) Intermediate A was synthesized through the synthetic route described below.
4-(3-bromophenyl)-6-(4-chlorophenyl)-2-phenylpyrimidine (5.53 g), (4-cyanophenyl)boronic acid (1.93 g), and Pd(PPh3)4 (0.30 g) were added to a flask, it was replaced with argon gas, DME (66 mL) and 2 M of aqueous solution of sodium carbonate (19.7 mL) were added thereto, and then it was heated and stirred for 5 hours under reflux condition. The reaction solution was cooled, and then it was filtered to collect solids precipitated by adding MeOH therein. The obtained crude product was washed with cyclohexane and toluene, and then it was purified by silica gel chromatography to obtain 3′-(6-(4-chlorophenyl)-2-phenylpyrimidine-4-yl)-[1,1′-biphenyl]-4-carbonitrile (Intermediate A) as a white solid (4.80 g, 82% yield).
The mass spectrum thereof was analyzed as m/e=444 for a molecular weight of 443.93, and it was identified as an intended product.
(3-2) The compound ET-3 was synthesized through the synthetic route described below.
3′-(6-(4-chlorophenyl)-2-phenylpyrimidine-4-yl)-[1,1′-biphenyl]-4-carbonitrile (4.30 g) obtained in (3-1) above, and tetraphene-7-ylboronic acid (3.95 g) were respectively used, and the conditions described in Synthesis Example 1 were used to obtain a compound ET-3 as a pale yellow solid 3.29 g, 53% yield). The mass spectrum thereof was analyzed as m/e=636 for a molecular weight of 635.77, and it was identified as an intended product.
The compound ET-4 was synthesized through the synthetic route described below.
4-([1,1′-biphenyl]-4-yl)-6-chloro-2-phenylpyrimidine (3.43 g), tetraphene-7-ylboronic acid (2.99 g), Pd2(dba)3 (0.18 g), SPhos (0.32 g), and K2CO3 (2.76 g) were added to a flask, it was replaced with argon gas, 1,4-dioxane (43 mL) and H2O (7.1 mL) were added thereto, and then it was heated and stirred for 6.5 hours under reflux condition. The reaction solution was cooled, and then the solid precipitated after adding MeOH therein was collected by filtration, followed by being washed with water and methanol. The obtained crude product was purified by silica gel chromatography, and then it was recrystallized using toluene to obtain a compound ET-4 as a pale yellow solid (4.51 g, 84% yield).
The mass spectrum thereof was analyzed as m/e=535 for a molecular weight of 534.66, and it was identified as an intended product.
The compound ET-5 was synthesized through the synthetic route described below.
(5-1) Intermediate B was synthesized through the synthetic route described below.
Fenclorim (7.94 g), tetraphene-7-ylboronic acid (8.00 g), and Pd(PPh3)4 (1.70 g) were added to a flask, it was replaced with argon gas, DME (147 mL) and 2 M of aqueous solution of sodium carbonate (29.4 mL) were added thereto, and then it was heated and stirred for 5.5 hours under reflux condition. The reaction solution was cooled, and then solvents were removed. The obtained crude product was purified by silica gel chromatography, and then it was washed with hexane to obtain 4-chloro-2-phenyl-6-(tetraphene-7-yl)pyrimidine (Intermediate B) as a white solid (6.07 g, 50% yield).
The mass spectrum thereof was analyzed as m/e=417 for a molecular weight of 416.91, and it was identified as an intended product.
(5-2) The compound ET-5 was synthesized through the synthetic route described below.
2-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)[1,1′-biphenyl]-3-yl]dibenzofuran (3.54 g), 4-chloro-2-phenyl-6-(tetraphene-7-yl)pyrimidine (3.15 g) obtained in (5-1) above, and (Amphos)2PdCl2 (0.21 g) were added to a flask, it was replaced with argon gas, DME (76 mL) and 2 M of aqueous solution of sodium carbonate (9.4 mL) were added thereto, and then it was heated and stirred for 6 hours under reflux condition. The reaction solution was cooled, and then solvents were removed. The obtained crude product was purified by silica gel chromatography, and then it was washed with ethyl acetate to obtain an ET-5 as a white solid (3.73 g, 70% yield).
The mass spectrum thereof was analyzed as m/e=701 for a molecular weight of 700.84, and it was identified as an intended product.
The compound ET-6 was synthesized through the synthetic route described below.
4-(4-bromophenyl)-6-(4-dibenzo[b,d]thiophene-4-yl)-2-phenylpyrimidine (4.50 g), and tetraphene-7-ylboronic acid (2.73 g) were respectively used, and the conditions described in Synthesis Example 4 were used to obtain a compound ET-6 as a pale yellow solid 4.27 g, 73% yield).
The mass spectrum thereof was analyzed as m/e=641 for a molecular weight of 640.80, and it was identified as an intended product.
The compound ET-7 was synthesized through the synthetic route described below.
4-(4-bromophenyl)-6-[4-(dibenzo[b,d]thiophene-4-yl)phenyl]-2-phenylpyrimidine (4.50), and tetraphene-7-ylboronic acid (2.36 g) were respectively used, and the conditions described in Synthesis Example 4 were used to obtain a compound ET-7 as a white solid (3.52 g, 62% yield).
The mass spectrum thereof was analyzed as m/e=717 for a molecular weight of 716.90, and it was identified as an intended product.
The compound ET-8 was synthesized through the synthetic route described below.
2-(4-bromophenyl)-6-(4-(dibenzo[b,d]furan-4-yl)phenyl)-2-phenylpyrimidine (5.00 g), and tetraphene-7-ylboronic acid (2.70 g) were respectively used, and the conditions described in Synthesis Example 4 were used to obtain a compound ET-8 as a white solid (4.94 g, 78% yield).
The mass spectrum thereof was analyzed as m/e=701 for a molecular weight of 700.81, and it was identified as an intended product.
The compound ET-9 was synthesized through the synthetic route described below.
4-([1,1′-biphenyl]-4-yl)-6-(4-bromonaphthalene-1-yl)-2-phenylpyrimidine (5.00 g), and tetraphene-7-ylboronic acid (2.91 g) were respectively used, and the conditions described in Synthesis Example 4 were used to obtain a compound ET-9 as a white solid (2.84 g, 44% yield).
The mass spectrum thereof was analyzed as m/e=661 for a molecular weight of 660.82, and it was identified as an intended product.
The compound ET-10 was synthesized through the synthetic route described below.
4-([1,1′-biphenyl]-4-yl)-2-phenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)phenyl)pyrimidine (3.50 g) and 12-bromo-7-phenyltetraphene (2.63 g) were respectively used, and the conditions described in Synthesis Example 4 were used to obtain a compound ET-10 as a white solid (2.47 g, 52% yield).
The mass spectrum thereof was analyzed as m/e=687 for a molecular weight of 686.86, and it was identified as an intended product.
The compound ET-11 was synthesized through the synthetic route described below.
2,4-diphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)phenyl)pyrimidine (4.00 g), and 12-bromo-7-phenyltetraphene (3.53 g) were respectively used, and the conditions described in Synthesis Example 4 were used to obtain a compound ET-10 as a white solid (2.36 g, 42% yield).
The mass spectrum thereof was analyzed as m/e=611 for a molecular weight of 610.76, and it was identified as an intended product.
The compound ET-12 was synthesized through the synthetic route described below.
(12-1) Intermediate C was synthesized through the synthetic route described below.
4-([1,1′-biphenyl]-4-yl-d9)-6-chloro-2-phenylpyrimidine (5.50 g), (4-chlorophenyl)boronic acid (3.67 g), and PdCl2(PPh3)2 (0.11 g) were added to a flask, it was replaced with argon gas, toluene (156 mL) and 2 M of aqueous solution of sodium carbonate (19.5 mL) were added thereto, and then it was heated and stirred at 60° ° C. for 16 hours. The reaction solution was cooled, and then the solid precipitated by adding water and MeOH was collected by filtration, followed by being washed with water and methanol. The obtained crude product was purified by silica gel chromatography and by recrystallizing using toluene to obtain 4-([1,1′-biphenyl]-4-yl-d9)-6-(4-chlorophenyl)-2-phenylpyrimidine (Intermediate C) as a white solid (4.82 g, 72% yield).
The mass spectrum thereof was analyzed as m/e=428 for a molecular weight of 427.98, and it was identified as an intended product.
(12-2) The compound ET-12 was synthesized through the synthetic route described below.
4-([1,1′-biphenyl]-4-yl-d9)-6-(4-chlorophenyl)-2-phenylpyrimidine (4.50 g) obtained in (12-1) above, and tetraphene-7-ylboronic acid (3.15 g) were respectively used, and the conditions described in Synthesis Example 4 were used to obtain a compound ET-12 as a white solid (4.30 g, 66% yield).
The mass spectrum thereof was analyzed as m/e=620 for a molecular weight of 619.82, and it was identified as an intended product.
Although only some exemplary embodiments and/or examples of this invention have been described in detail above, those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments and/or examples without materially departing from the novel teachings and advantages of this invention. Accordingly, all such modifications are intended to be included within the scope of this invention.
The documents described in the specification and the specification of Japanese application(s) on the basis of which the present application claims Paris convention priority are incorporated herein by reference in its entirety.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-101999 | Jun 2021 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2022/022487 | 6/2/2022 | WO |
