Patent Application
20230413664
The present invention relates to a compound, a material for organic electroluminescent elements, an organic electroluminescent element, and an electronic device including the organic electroluminescent element.
In general, an organic electroluminescent element (which may be hereinafter referred to as an “organic EL element”) is constituted by an anode, a cathode, and an organic layer intervening between the anode and the cathode. In application of a voltage between both the electrodes, electrons from the cathode side and holes from the anode side are injected into a light emitting region, and the injected electrons and holes are recombined in the light emitting region to generate an excited state, which then returns to a ground state to emit light. Accordingly, development of a material that efficiently transports electrons or holes into the light emitting region, and promotes recombination of the electrons and holes is important for obtaining a high-performance organic EL element.
PTLs 1 to 8 describe compounds used as materials for organic electroluminescent elements.
Conventionally, various compounds for organic EL elements have been reported. However, a compound that further enhances the performance of an organic EL element has been still demanded.
The present invention has been made for solving the aforementioned problem, and an object thereof is to provide a compound that further improves the performance of an organic EL element, an organic EL element that has further improved element performance, and an electronic device that includes the organic EL element.
As a result of intensive research by the present inventors on the performance of organic EL elements containing compounds for organic EL elements, the present inventors have found that an organic EL element having further improved element performance can be provided by a monoamine in which a partial structure to which a 1-dibenzofuranyl group or a 2-dibenzofuranyl group is bonded via an m-phenylene group, a partial structure to which a 1-naphthyl group or 2-naphthyl group is bonded via a p-phenylene group, and the remaining partial structure which has a specific ring structure are bonded to a central nitrogen atom.
In an aspect, the present invention provides a compound represented by the following formula (1).
In the formula (1),
In another aspect, the present invention provides a material for organic electroluminescent elements, containing the compound represented by the formula (1).
In yet another aspect, the present invention provides an organic electroluminescent element including a cathode, an anode, and organic layers intervening between the cathode and the anode, the organic layers including a light emitting layer, at least one layer of the organic layers containing the compound represented by the formula (1).
In further another aspect, the present invention provides an electronic device including the organic electroluminescent element.
An organic EL element containing the compound represented by the formula (1) shows improved element performance.
In the description herein, the hydrogen atom encompasses isotopes thereof having different numbers of neutrons, i.e., a light hydrogen atom (protium), a heavy hydrogen atom (deuterium), and tritium.
In the description herein, the bonding site where the symbol, such as “R”, or “D” representing a deuterium atom is not shown is assumed to have a hydrogen atom, i.e., a protium atom, a deuterium atom, or a tritium atom, bonded thereto.
In the description herein, the number of ring carbon atoms shows the number of carbon atoms among the atoms constituting the ring itself of a compound having a structure including atoms bonded to form a ring (such as a monocyclic compound, a condensed ring compound, a bridged compound, a carbocyclic compound, and a heterocyclic compound). In the case where the ring is substituted by a substituent, the carbon atom contained in the substituent is not included in the number of ring carbon atoms. The same definition is applied to the “number of ring carbon atoms” described hereinafter unless otherwise indicated. For example, a benzene ring has 6 ring carbon atoms, a naphthalene ring has 10 ring carbon atoms, a pyridine ring has 5 ring carbon atoms, and a furan ring has 4 ring carbon atoms. For example, 9,9-diphenylfluorenyl group has 13 ring carbon atoms, and 9,9′-spirobifluorenyl group has 25 ring carbon atoms.
In the case where a benzene ring has, for example, an alkyl group substituted thereon 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. Accordingly, a benzene ring having an alkyl group substituted thereon has 6 ring carbon atoms. In the case where a naphthalene ring has, for example, an alkyl group substituted thereon 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. Accordingly, a naphthalene ring having an alkyl group substituted thereon has 10 ring carbon atoms.
In the description herein, the number of ring atoms shows the number of atoms constituting the ring itself of a compound having a structure including atoms bonded to form a ring (such as a monocyclic ring, a condensed ring, and a set of rings) (such as a monocyclic compound, a condensed ring compound, a bridged compound, a carbocyclic compound, and a heterocyclic compound). The atom that does not constitute the ring (such as a hydrogen atom terminating the bond of the atom constituting the ring) and, in the case where the ring is substituted by a substituent, the atom contained in the substituent are not included in the number of ring atoms. The same definition is applied to the “number of ring atoms” described hereinafter unless otherwise indicated. For example, a pyridine ring has 6 ring atoms, a quinazoline ring has 10 ring atoms, and a furan ring has 5 ring atoms. For example, the number of hydrogen atoms bonded to a pyridine ring or atoms constituting a substituent is not included in the number of ring atoms of the pyridine ring. Accordingly, a pyridine ring having a hydrogen atom or a substituent bonded thereto has 6 ring atoms. For example, the number of hydrogen atoms bonded to carbon atoms of a quinazoline ring or atoms constituting a substituent is not included in the number of ring atoms of the quinazoline ring. Accordingly, a quinazoline ring having a hydrogen atom or a substituent bonded thereto has 10 ring atoms.
In the description herein, the expression “having XX to YY carbon atoms” in the expression “substituted or unsubstituted ZZ group having XX to YY carbon atoms” means the number of carbon atoms of the unsubstituted ZZ group, and, in the case where the ZZ group is substituted, the number of carbon atoms of the substituent is not included. Herein, “YY” is larger than “XX”, “XX” represents an integer of 1 or more, and “YY” represents an integer of 2 or more.
In the description herein, the expression “having XX to YY atoms” in the expression “substituted or unsubstituted ZZ group having XX to YY atoms” means the number of atoms of the unsubstituted ZZ group, and, in the case where the ZZ group is substituted, the number of atoms of the substituent is not included. Herein, “YY” is larger than “XX”, “XX” represents an integer of 1 or more, and “YY” represents an integer of 2 or more.
In the description herein, an unsubstituted ZZ group means the case where the “substituted or unsubstituted ZZ group” is an “unsubstituted ZZ group”, and a substituted ZZ group means the case where the “substituted or unsubstituted ZZ group” is a “substituted ZZ group”.
In the description herein, the expression “unsubstituted” in the expression “substituted or unsubstituted ZZ group” means that hydrogen atoms in the ZZ group are not substituted by a substituent. The hydrogen atoms in the “unsubstituted ZZ group” each are a protium atom, a deuterium atom, or a tritium atom.
In the description herein, the expression “substituted” in the expression “substituted or unsubstituted ZZ group” means that one or more hydrogen atom in the ZZ group is substituted by a substituent. The expression “substituted” in the expression “BB group substituted by an AA group” similarly means that one or more hydrogen atom in the BB group is substituted by the AA group.
The substituents described in the description herein will be explained.
In the description herein, the number of ring carbon atoms of the “unsubstituted aryl group” is 6 to 50, preferably 6 to 30, and more preferably 6 to 18, unless otherwise indicated in the description.
In the description herein, the number of ring atoms of the “unsubstituted heterocyclic group” is 5 to 50, preferably 5 to 30, and more preferably 5 to 18, unless otherwise indicated in the description.
In the description herein, the number of carbon atoms of the “unsubstituted alkyl group” is 1 to 50, preferably 1 to 20, and more preferably 1 to 6, unless otherwise indicated in the description.
In the description herein, the number of carbon atoms of the “unsubstituted alkenyl group” is 2 to 50, preferably 2 to 20, and more preferably 2 to 6, unless otherwise indicated in the description.
In the description herein, the number of carbon atoms of the “unsubstituted alkynyl group” is 2 to 50, preferably 2 to 20, and more preferably 2 to 6, unless otherwise indicated in the description.
In the description herein, the number of ring carbon atoms of the “unsubstituted cycloalkyl group” is 3 to 50, preferably 3 to 20, and more preferably 3 to 6, unless otherwise indicated in the description.
In the description herein, the number of ring carbon atoms of the “unsubstituted arylene group” is 6 to 50, preferably 6 to 30, and more preferably 6 to 18, unless otherwise indicated in the description.
In the description herein, the number of ring atoms of the “unsubstituted divalent heterocyclic group” is 5 to 50, preferably 5 to 30, and more preferably 5 to 18, unless otherwise indicated in the description.
In the description herein, the number of carbon atoms of the “unsubstituted alkylene group” is 1 to 50, preferably 1 to 20, and more preferably 1 to 6, unless otherwise indicated in the description.
In the description herein, specific examples (set of specific examples G1) of the “substituted or unsubstituted aryl group” include the unsubstituted aryl groups (set of specific examples G1A) and the substituted aryl groups (set of specific examples G1B) shown below. (Herein, the unsubstituted aryl group means the case where the “substituted or unsubstituted aryl group” is an “unsubstituted aryl group”, and the substituted aryl group means the case where the “substituted or unsubstituted aryl group” is a “substituted aryl group”.) In the description herein, the simple expression “aryl group” encompasses both the “unsubstituted aryl group” and the “substituted aryl group”.
The “substituted aryl group” means a group formed by substituting one or more hydrogen atom of the “unsubstituted aryl group” by a substituent. Examples of the “substituted aryl group” include groups formed by one or more hydrogen atom of each of the “unsubstituted aryl groups” in the set of specific examples G1A by a substituent, and the examples of the substituted aryl groups in the set of specific examples G1B. The examples of the “unsubstituted aryl group” and the examples of the “substituted aryl group” enumerated herein are mere examples, and the “substituted aryl group” in the description herein encompasses groups formed by substituting a hydrogen atom bonded to the carbon atom of the aryl group itself of each of the “substituted aryl groups” in the set of specific examples G1B by a substituent, and groups formed by substituting a hydrogen atom of the substituent of each of the “substituted aryl groups” in the set of specific examples G1B by a substituent.
In the description herein, the “heterocyclic group” means a cyclic group containing at least one hetero atom in the ring atoms. 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.
In the description herein, the “heterocyclic group” is a monocyclic group or a condensed ring group.
In the description herein, the “heterocyclic group” is an aromatic heterocyclic group or a non-aromatic heterocyclic group.
In the description herein, specific examples (set of specific examples G2) of the “substituted or unsubstituted heterocyclic group” include the unsubstituted heterocyclic groups (set of specific examples G2A) and the substituted heterocyclic groups (set of specific examples G2B) shown below. (Herein, the unsubstituted heterocyclic group means the case where the “substituted or unsubstituted heterocyclic group” is an “unsubstituted heterocyclic group”, and the substituted heterocyclic group means the case where the “substituted or unsubstituted heterocyclic group” is a “substituted heterocyclic group”.) In the description herein, the simple expression “heterocyclic group” encompasses both the “unsubstituted heterocyclic group” and the “substituted heterocyclic group”.
The “substituted heterocyclic group” means a group formed by substituting one or more hydrogen atom of the “unsubstituted heterocyclic group” by a substituent. Specific examples of the “substituted heterocyclic group” include groups formed by substituting a hydrogen atom of each of the “unsubstituted heterocyclic groups” in the set of specific examples G2A by a substituent, and the examples of the substituted heterocyclic groups in the set of specific examples G2B. The examples of the “unsubstituted heterocyclic group” and the examples of the “substituted heterocyclic group” enumerated herein are mere examples, and the “substituted heterocyclic group” in the description herein encompasses groups formed by substituting a hydrogen atom bonded to the ring atom of the heterocyclic group itself of each of the “substituted heterocyclic groups” in the set of specific examples G2B by a substituent, and groups formed by substituting a hydrogen atom of the substituent of each of the “substituted heterocyclic groups” in the set of specific examples G2B by a substituent.
The set of specific examples G2A includes, for example, the unsubstituted heterocyclic group containing a nitrogen atom (set of specific examples G2A1), the unsubstituted heterocyclic group containing an oxygen atom (set of specific examples G2A2), the unsubstituted heterocyclic group containing a sulfur atom (set of specific examples G2A3), and monovalent heterocyclic groups derived by removing one hydrogen atom from each of the ring structures represented by the following general formulae (TEMP-16) to (TEMP-33) (set of specific examples G2A4).
The set of specific examples G2B includes, for example, the substituted heterocyclic groups containing a nitrogen atom (set of specific examples G2B1), the substituted heterocyclic groups containing an oxygen atom (set of specific examples G2B2), the substituted heterocyclic groups containing a sulfur atom (set of specific examples G2B3), and groups formed by substituting one or more hydrogen atom of each of monovalent heterocyclic groups derived from the ring structures represented by the following general formulae (TEMP-16) to (TEMP-33) by a substituent (set of specific examples G2B4).
Unsubstituted Heterocyclic Group containing Nitrogen Atom (Set of Specific Examples G2A1):
In the general formulae (TEMP-16) to (TEMP-33), XA and YA each independently represent an oxygen atom, a sulfur atom, NH, or CH2, provided that at least one of XA and YA represents an oxygen atom, a sulfur atom, or NH.
In the general formulae (TEMP-16) to (TEMP-33), in the case where at least one of XA and YA represents NH or CH2, the monovalent heterocyclic groups derived from the ring structures represented by the general formulae (TEMP-16) to (TEMP-33) include monovalent groups formed by removing one hydrogen atom from the NH or CH2.
The “one or more hydrogen atom of the monovalent heterocyclic group” means one or more hydrogen atom selected from the hydrogen atom bonded to the ring carbon atom of the monovalent heterocyclic group, the hydrogen atom bonded to the nitrogen atom in the case where at least one of XA and YA represents NH, and the hydrogen atom of the methylene group in the case where one of XA and YA represents CH2.
In the description herein, specific examples (set of specific examples G3) of the “substituted or unsubstituted alkyl group” include the unsubstituted alkyl groups (set of specific examples G3A) and the substituted alkyl groups (set of specific examples G3B) shown below. (Herein, the unsubstituted alkyl group means the case where the “substituted or unsubstituted alkyl group” is an “unsubstituted alkyl group”, and the substituted alkyl group means the case where the “substituted or unsubstituted alkyl group” is a “substituted alkyl group”.) In the description herein, the simple expression “alkyl group” encompasses both the “unsubstituted alkyl group” and the “substituted alkyl group”.
The “substituted alkyl group” means a group formed by substituting one or more hydrogen atom of the “unsubstituted alkyl group” by a substituent. Specific examples of the “substituted alkyl group” include groups formed by substituting one or more hydrogen atom of each of the “unsubstituted alkyl groups” (set of specific examples G3A) by a substituent, and the examples of the substituted alkyl groups (set of specific examples G3B). In the description herein, the alkyl group in the “unsubstituted alkyl group” means a chain-like alkyl group. Accordingly, the “unsubstituted alkyl group” encompasses an “unsubstituted linear alkyl group” and an “unsubstituted branched alkyl group”. The examples of the “unsubstituted alkyl group” and the examples of the “substituted alkyl group” enumerated herein are mere examples, and the “substituted alkyl group” in the description herein encompasses groups formed by substituting a hydrogen atom of the alkyl group itself of each of the “substituted alkyl groups” in the set of specific examples G3B by a substituent, and groups formed by substituting a hydrogen atom of the substituent of each of the “substituted alkyl groups” in the set of specific examples G3B by a substituent.
In the description herein, specific examples (set of specific examples G4) of the “substituted or unsubstituted alkenyl group” include the unsubstituted alkenyl groups (set of specific examples G4A) and the substituted alkenyl groups (set of specific examples G4B) shown below. (Herein, the unsubstituted alkenyl group means the case where the “substituted or unsubstituted alkenyl group” is an “unsubstituted alkenyl group”, and the substituted alkenyl group means the case where the “substituted or unsubstituted alkenyl group” is a “substituted alkenyl group”.) In the description herein, the simple expression “alkenyl group” encompasses both the “unsubstituted alkenyl group” and the “substituted alkenyl group”.
The “substituted alkenyl group” means a group formed by substituting one or more hydrogen atom of the “unsubstituted alkenyl group” by a substituent. Specific examples of the “substituted alkenyl group” include the “unsubstituted alkenyl groups” (set of specific examples G4A) that each have a substituent, and the examples of the substituted alkenyl groups (set of specific examples G4B). The examples of the “unsubstituted alkenyl group” and the examples of the “substituted alkenyl group” enumerated herein are mere examples, and the “substituted alkenyl group” in the description herein encompasses groups formed by substituting a hydrogen atom of the alkenyl group itself of each of the “substituted alkenyl groups” in the set of specific examples G4B by a substituent, and groups formed by substituting a hydrogen atom of the substituent of each of the “substituted alkenyl groups” in the set of specific examples G4B by a substituent.
In the description herein, specific examples (set of specific examples G5) of the “substituted or unsubstituted alkynyl group” include the unsubstituted alkynyl group (set of specific examples G5A) shown below. (Herein, the unsubstituted alkynyl group means the case where the “substituted or unsubstituted alkynyl group” is an “unsubstituted alkynyl group”.) In the description herein, the simple expression “alkynyl group” encompasses both the “unsubstituted alkynyl group” and the “substituted alkynyl group”.
The “substituted alkynyl group” means a group formed by substituting one or more hydrogen atom of the “unsubstituted alkynyl group” by a substituent. Specific examples of the “substituted alkenyl group” include groups formed by substituting one or more hydrogen atom of the “unsubstituted alkynyl group” (set of specific examples G5A) by a substituent.
In the description herein, specific examples (set of specific examples G6) of the “substituted or unsubstituted cycloalkyl group” include the unsubstituted cycloalkyl groups (set of specific examples G6A) and the substituted cycloalkyl group (set of specific examples G6B) shown below. (Herein, the unsubstituted cycloalkyl group means the case where the “substituted or unsubstituted cycloalkyl group” is an “unsubstituted cycloalkyl group”, and the substituted cycloalkyl group means the case where the “substituted or unsubstituted cycloalkyl group” is a “substituted cycloalkyl group”.) In the description herein, the simple expression “cycloalkyl group” encompasses both the “unsubstituted cycloalkyl group” and the “substituted cycloalkyl group”.
The “substituted cycloalkyl group” means a group formed by substituting one or more hydrogen atom of the “unsubstituted cycloalkyl group” by a substituent. Specific examples of the “substituted cycloalkyl group” include groups formed by substituting one or more hydrogen atom of each of the “unsubstituted cycloalkyl groups” (set of specific examples G6A) by a substituent, and the example of the substituted cycloalkyl group (set of specific examples G6B). The examples of the “unsubstituted cycloalkyl group” and the examples of the “substituted cycloalkyl group” enumerated herein are mere examples, and the “substituted cycloalkyl group” in the description herein encompasses groups formed by substituting one or more hydrogen atom bonded to the carbon atoms of the cycloalkyl group itself of the “substituted cycloalkyl group” in the set of specific examples G6B by a substituent, and groups formed by substituting a hydrogen atom of the substituent of the “substituted cycloalkyl group” in the set of specific examples G6B by a substituent.
In the description herein, specific examples (set of specific examples G7) of the group represented by —Si(R901)(R902)(R903) include:
Herein,
Plural groups represented by G1 in —Si(G1)(G1)(G1) are the same as or different from each other.
Plural groups represented by G2 in —Si(G1)(G2)(G2) are the same as or different from each other.
Plural groups represented by G1 in —Si(G1)(G1)(G2) are the same as or different from each other.
Plural groups represented by G2 in —Si(G2)(G2)(G2) are the same as or different from each other.
Plural groups represented by G3 in —Si(G3)(G3)(G3) are the same as or different from each other.
Plural groups represented by G6 in —Si(G6)(G6)(G6) are the same as or different from each other.
In the description herein, specific examples (set of specific examples G8) of the group represented by —O—(R904) include:
Herein,
Herein,
In the description herein, specific examples (set of specific examples G10) of the group represented by —N(R906)(R907) include:
Plural groups represented by G1 in —N(G1)(G1) are the same as or different from each other.
Plural groups represented by G2 in —N(G2)(G2) are the same as or different from each other.
Plural groups represented by G3 in —N(G3)(G3) are the same as or different from each other.
Plural groups represented by G6 in —N(G6)(G6) are the same as or different from each other.
In the description herein, specific examples (set of specific examples G11) of the “halogen atom” include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In the description herein, the “substituted or unsubstituted fluoroalkyl group” means a group formed by substituting at least one hydrogen atom bonded to the carbon atom constituting the alkyl group in the “substituted or unsubstituted alkyl group” by a fluorine atom, and encompasses a group formed by substituting all the hydrogen atoms bonded to the carbon atoms constituting the alkyl group in the “substituted or unsubstituted alkyl group” by fluorine atoms (i.e., a perfluoroalkyl group). The number of carbon atoms of the “unsubstituted fluoroalkyl group” is 1 to 50, preferably 1 to 30, and more preferably 1 to 18, unless otherwise indicated in the description. The “substituted fluoroalkyl group” means a group formed by substituting one or more hydrogen atom of the “fluoroalkyl group” by a substituent. In the description herein, the “substituted fluoroalkyl group” encompasses a group formed by substituting one or more hydrogen atom bonded to the carbon atom of the alkyl chain in the “substituted fluoroalkyl group” by a substituent, and a group formed by substituting one or more hydrogen atom of the substituent in the “substituted fluoroalkyl group” by a substituent. Specific examples of the “unsubstituted fluoroalkyl group” include examples of groups formed by substituting one or more hydrogen atom in each of the “alkyl group” (set of specific examples G3) by a fluorine atom.
In the description herein, the “substituted or unsubstituted haloalkyl group” means a group formed by substituting at least one hydrogen atom bonded to the carbon atom constituting the alkyl group in the “substituted or unsubstituted alkyl group” by a halogen atom, and encompasses a group formed by substituting all the hydrogen atoms bonded to the carbon atoms constituting the alkyl group in the “substituted or unsubstituted alkyl group” by halogen atoms. The number of carbon atoms of the “unsubstituted haloalkyl group” is 1 to 50, preferably 1 to 30, and more preferably 1 to 18, unless otherwise indicated in the description. The “substituted haloalkyl group” means a group formed by substituting one or more hydrogen atom of the “haloalkyl group” by a substituent. In the description herein, the “substituted haloalkyl group” encompasses a group formed by substituting one or more hydrogen atom bonded to the carbon atom of the alkyl chain in the “substituted haloalkyl group” by a substituent, and a group formed by substituting one or more hydrogen atom of the substituent in the “substituted haloalkyl group” by a substituent. Specific examples of the “unsubstituted haloalkyl group” include examples of groups formed by substituting one or more hydrogen atom in each of the “alkyl group” (set of specific examples G3) by a halogen atom. A haloalkyl group may be referred to as a halogenated alkyl group in some cases.
In the description herein, specific examples of the “substituted or unsubstituted alkoxy group” include a group represented by —O(G3), wherein G3 represents the “substituted or unsubstituted alkyl group” described in the set of specific examples G3. The number of carbon atoms of the “unsubstituted alkoxy group” is 1 to 50, preferably 1 to 30, and more preferably 1 to 18, unless otherwise indicated in the description.
In the description herein, specific examples of the “substituted or unsubstituted alkylthio group” include a group represented by —S(G3), wherein G3 represents the “substituted or unsubstituted alkyl group” described in the set of specific examples G3. The number of carbon atoms of the “unsubstituted alkylthio group” is 1 to 50, preferably 1 to 30, and more preferably 1 to 18, unless otherwise indicated in the description.
In the description herein, specific examples of the “substituted or unsubstituted aryloxy group” include a group represented by —O(G1), wherein G1 represents the “substituted or unsubstituted aryl group” described in the set of specific examples G1. The number of ring carbon atoms of the “unsubstituted aryloxy group” is 6 to 50, preferably 6 to 30, and more preferably 6 to 18, unless otherwise indicated in the description.
In the description herein, specific examples of the “substituted or unsubstituted arylthio group” include a group represented by —S(G1), wherein G1 represents the “substituted or unsubstituted aryl group” described in the set of specific examples G1. The number of ring carbon atoms of the “unsubstituted arylthio group” is 6 to 50, preferably 6 to 30, and more preferably 6 to 18, unless otherwise indicated in the description.
In the description herein, specific examples of the “trialkylsilyl group” include a group represented by —Si(G3)(G3)(G3), wherein G3 represents the “substituted or unsubstituted alkyl group” described in the set of specific examples G3. Plural groups represented by G3 in —Si(G3)(G3)(G3) are the same as or different from each other. The number of carbon atoms of each of alkyl groups of the “substituted or unsubstituted trialkylsilyl group” is 1 to 50, preferably 1 to 20, and more preferably 1 to 6, unless otherwise indicated in the description.
In the description herein, specific examples of the “substituted or unsubstituted aralkyl group” include a group represented by -(G3)-(G1), wherein G3 represents the “substituted or unsubstituted alkyl group” described in the set of specific examples G3, and G1 represents the “substituted or unsubstituted aryl group” described in the set of specific examples G1. Accordingly, the “aralkyl group” is a group formed by substituting a hydrogen atom of an “alkyl group” by an “aryl group” as a substituent, and is one embodiment of the “substituted alkyl group”. The “unsubstituted aralkyl group” is an “unsubstituted alkyl group” that is substituted by an “unsubstituted aryl group”, and the number of carbon atoms of the “unsubstituted aralkyl group” is 7 to 50, preferably 7 to 30, and more preferably 7 to 18, unless otherwise indicated in the description.
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 β-naphthylmethyl group, a 1-β-naphthylethyl group, a 2-β-naphthylethyl group, a 1-β-naphthylisopropyl group, and a 2-β-naphthylisopropyl group.
In the description herein, the substituted or unsubstituted aryl group is preferably 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, a 9,9-dimethylfluorenyl group, a 9,9-diphenylfluorenyl group, and the like, unless otherwise indicated in the description.
In the description herein, the substituted or unsubstituted heterocyclic group is preferably 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 (e.g., 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 naphthobenzofuranly group, an azadibenzofuranyl group, a diazadibenzofuranyl group, a dibenzothiophenyl group, a naphthobenzothiophenyl group, an azadibenzothiophenyl group, a diazadibenzothiophenyl group, a (9-phenyl)carbazolyl group (e.g., 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, unless otherwise indicated in the description.
In the description herein, the carbazolyl group is specifically any one of the following groups unless otherwise indicated in the description.
In the description herein, the (9-phenyl)carbazolyl group is specifically any one of the following groups unless otherwise indicated in the description.
In the general formulae (TEMP-Cz1) to (TEMP-Cz9), * represents a bonding site.
In the description herein, the dibenzofuranyl group and the dibenzothiophenyl group are specifically any one of the following groups unless otherwise indicated in the description.
In the general formulae (TEMP-34) to (TEMP-41), represents a bonding site.
In the description herein, the substituted or unsubstituted alkyl group 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 indicated in the description.
In the description herein, the “substituted or unsubstituted arylene group” is a divalent group derived by removing one hydrogen atom on the aryl ring from the “substituted or unsubstituted aryl group” described above unless otherwise indicated in the description. Specific examples (set of specific examples G12) of the “substituted or unsubstituted arylene group” include divalent groups derived by removing one hydrogen atom on the aryl ring from the “substituted or unsubstituted aryl groups” described in the set of specific examples G1.
In the description herein, the “substituted or unsubstituted divalent heterocyclic group” is a divalent group derived by removing one hydrogen atom on the heterocyclic ring from the “substituted or unsubstituted heterocyclic group” described above unless otherwise indicated in the description. Specific examples (set of specific examples G13) of the “substituted or unsubstituted divalent heterocyclic group” include divalent groups derived by removing one hydrogen atom on the heterocyclic ring from the “substituted or unsubstituted heterocyclic groups” described in the set of specific examples G2.
In the description herein, the “substituted or unsubstituted alkylene group” is a divalent group derived by removing one hydrogen atom on the alkyl chain from the “substituted or unsubstituted alkyl group” described above unless otherwise indicated in the description. Specific examples (set of specific examples G14) of the “substituted or unsubstituted alkylene group” include divalent groups derived by removing one hydrogen atom on the alkyl chain from the “substituted or unsubstituted alkyl groups” described in the set of specific examples G3.
In the description herein, the substituted or unsubstituted arylene group is preferably any one of the groups represented by the following general formulae (TEMP-42) to (TEMP-68) unless otherwise indicated in the description.
In the general formulae (TEMP-42) to (TEMP-52), Q1 to Q10 each independently represent a hydrogen atom or a substituent.
In the general formulae (TEMP-42) to (TEMP-52), * represents a bonding site.
In the general formulae (TEMP-53) to (TEMP-62), Q1 to Q10 each independently represent a hydrogen atom or a substituent.
The formulae Qs and Q10 may be bonded to each other to form a ring via a single bond.
In the general formulae (TEMP-53) to (TEMP-62), * represents a bonding site.
In the general formulae (TEMP-63) to (TEMP-68), Q1 to Q8 each independently represent a hydrogen atom or a substituent.
In the general formulae (TEMP-63) to (TEMP-68), * represents a bonding site.
In the description herein, the substituted or unsubstituted divalent heterocyclic group is preferably the groups represented by the following general formulae (TEMP-69) to (TEMP-102) unless otherwise indicated in the description.
In the general formulae (TEMP-69) to (TEMP-82), Q1 to Q9 each independently represent a hydrogen atom or a substituent.
In the general formulae (TEMP-83) to (TEMP-102) Q1 to Q8 each independently represent a hydrogen atom or a substituent.
The above are the explanation of the “substituents in the description herein”.
In the description herein, the case where “one or more combinations of combinations each including adjacent two or more each are bonded to each other to form a substituted or unsubstituted monocyclic ring, or each are bonded to each other to form a substituted or unsubstituted condensed ring, or each are not bonded to each other” means a case where “one or more combinations of combinations each including adjacent two or more each are bonded to each other to form a substituted or unsubstituted monocyclic ring”, a case where “one or more combinations of combinations each including adjacent two or more each are bonded to each other to form a substituted or unsubstituted condensed ring”, and a case where “one or more combinations of combinations each including adjacent two or more each are not bonded to each other”.
In the description herein, the case where “one or more combinations of combinations each including adjacent two or more each are bonded to each other to form a substituted or unsubstituted monocyclic ring” and the case where “one or more combinations of combinations each including adjacent two or more each are bonded to each other to form a substituted or unsubstituted condensed ring” (which may be hereinafter collectively referred to as a “case forming a ring by bonding”) will be explained below. The cases will be explained for the anthracene compound represented by the following general formula (TEMP-103) having an anthracene core skeleton as an example.
For example, in the case where “one or more combinations of combinations each including adjacent two or more each are bonded to each other to form a ring” among R921 to R930, the combinations each including adjacent two as one combination include a combination of R921 and R922, a combination of R922 and R923, a combination of R923 and R924, a combination of R924 and R930, a combination of R930 and R925, a combination of R925 and R926, a combination of R926 and R927, a combination of R927 and R928, a combination of R928 and R929, and a combination of R929 and R921.
The “one or more combinations” mean that two or more combinations each including adjacent two or more may form rings simultaneously. For example, in the case where R921 and R922 are bonded to each other to form a ring QA, and simultaneously R925 and R926 are bonded to each other to form a ring QB, the anthracene compound represented by the general formula (TEMP-103) is represented by the following general formula (TEMP-104).
The case where the “combination including adjacent two or more forms rings” encompasses not only the case where adjacent two included in the combination are bonded as in the aforementioned example, but also the case where adjacent three or more included in the combination are bonded. For example, this case means that R921 and R922 are bonded to each other to form a ring QA, R922 and R923 are bonded to each other to form a ring Qc, and adjacent three (R921, R922, and R923) included in the combination are bonded to each other to form rings, which are condensed to the anthracene core skeleton, and 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 formed “monocyclic ring” or “condensed ring” may be a saturated ring or an unsaturated ring in terms of structure of the formed ring itself. In the case where the “one combination including adjacent two” forms a “monocyclic ring” or a “condensed ring”, the “monocyclic ring” or the “condensed 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) each are a “monocyclic ring” or a “condensed ring”. The ring QA and the ring Qc formed in the general formula (TEMP-105) each are a “condensed ring”. The ring QA and the ring Qc in the general formula (TEMP-105) form a condensed ring through condensation of the ring QA and the ring Qc. In the case where the ring QA in the general formula (TMEP-104) is a benzene ring, the ring QA is a monocyclic ring. In the case where the ring QA in the general formula (TMEP-104) is a naphthalene ring, the ring QA is a condensed ring.
The “unsaturated ring” means an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The “saturated ring” means an aliphatic hydrocarbon ring or a non-aromatic heterocyclic ring.
Specific examples of the aromatic hydrocarbon ring include the structures formed by terminating the groups exemplified as the specific examples in the set of specific examples G1 with a hydrogen atom.
Specific examples of the aromatic heterocyclic ring include the structures formed by terminating the aromatic heterocyclic groups exemplified as the specific examples in the set of specific examples G2 with a hydrogen atom.
Specific examples of the aliphatic hydrocarbon ring include the structures formed by terminating the groups exemplified as the specific examples in the set of specific examples G6 with a hydrogen atom.
The expression “to form a ring” means that the ring is formed only with the plural atoms of the core structure or with the plural atoms of the core structure and one or more arbitrary element. For example, the ring QA formed by bonding R921 and R922 each other shown in the general formula (TEMP-104) means a ring formed with the carbon atom of the anthracene skeleton bonded to R921, the carbon atom of the anthracene skeleton bonded to R922, and one or more arbitrary element. As a specific example, in the case where the ring QA is formed with R921 and R922, and in the case where a monocyclic unsaturated ring is formed with the carbon atom of the anthracene skeleton bonded to R921, the carbon atom of the anthracene skeleton bonded to R922, and four carbon atoms, the ring formed with R921 and R922 is a benzene ring.
Herein, the “arbitrary element” is preferably at least one kind of an element selected from the group consisting of a carbon element, a nitrogen element, an oxygen element, and a sulfur element, unless otherwise indicated in the description. For the arbitrary element (for example, for a carbon element or a nitrogen element), a bond that does not form a ring may be terminated with a hydrogen atom or the like, and may be substituted by an “arbitrary substituent” described later. In the case where an arbitrary element other than a carbon element is contained, the formed ring is a heterocyclic ring.
The number of the “one or more arbitrary element” constituting the monocyclic ring or the condensed ring is preferably 2 or more and 15 or less, more preferably 3 or more and 12 or less, and further preferably 3 or more and 5 or less, unless otherwise indicated in the description.
What is preferred between the “monocyclic ring” and the “condensed ring” is the “monocyclic ring” unless otherwise indicated in the description.
What is preferred between the “saturated ring” and the “unsaturated ring” is the “unsaturated ring” unless otherwise indicated in the description.
The “monocyclic ring” is preferably a benzene ring unless otherwise indicated in the description.
The “unsaturated ring” is preferably a benzene ring unless otherwise indicated in the description.
In the case where the “one or more combinations of combinations each including adjacent two or more” each are “bonded to each other to form a substituted or unsubstituted monocyclic ring”, or each are “bonded to each other to form a substituted or unsubstituted condensed ring”, it is preferred that the one or more combinations of combinations each including adjacent two or more each are bonded to each other to form a substituted or unsubstituted “unsaturated ring” containing the plural atoms of the core skeleton and 1 or more and 15 or less at least one kind of an element selected from the group consisting of a carbon element, a nitrogen element, an oxygen element, and a sulfur element, unless otherwise indicated in the description.
In the case where the “monocyclic ring” or the “condensed ring” has a substituent, the substituent is, for example, an “arbitrary substituent” described later. In the case where the “monocyclic ring” or the “condensed ring” has a substituent, specific examples of the substituent include the substituents explained in the section “Substituents in Description” described above.
In the case where the “saturated ring” or the “unsaturated ring” has a substituent, the substituent is, for example, an “arbitrary substituent” described later. In the case where the “monocyclic ring” or the “condensed ring” has a substituent, specific examples of the substituent include the substituents explained in the section “Substituents in Description” described above.
The above are the explanation of the case where “one or more combinations of combinations each including adjacent two or more” each are “bonded to each other to form a substituted or unsubstituted monocyclic ring”, and the case where “one or more combinations of combinations each including adjacent two or more” each are “bonded to each other to form a substituted or unsubstituted condensed ring” (i.e., the “case forming a ring by bonding”).
In one embodiment in the description herein, the substituent for the case of “substituted or unsubstituted” (which may be hereinafter referred to as an “arbitrary substituent”) is, for example, a group selected from the group consisting of
In the case where two or more groups each represented by R901 exist, the two or more groups each represented by R901 are the same as or different from each other,
In one embodiment, the substituent for the case of “substituted or unsubstituted” may be a group selected from the group consisting of
In one embodiment, the substituent for the case of “substituted or unsubstituted” may be a group selected from the group consisting of
The specific examples of the groups for the arbitrary substituent described above are the specific examples of the substituent described in the section “Substituents in Description” described above.
In the description herein, the arbitrary adjacent 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, and more preferably form a benzene ring, unless otherwise indicated.
In the description herein, the arbitrary substituent may further have a substituent unless otherwise indicated in the description. The definition of the substituent that the arbitrary substituent further has may be the same as the arbitrary substituent.
In the description herein, a numerical range shown by “AA to BB” means a range including the numerical value AA as the former of “AA to BB” as the lower limit value and the numerical value BB as the latter of “AA to BB” as the upper limit value.
The compound of the present invention will be described below.
A compound according to one aspect of the present invention is represented by the following formula (1).
However, hereinafter, the compounds represented by the formula (1), and formulas (1-1) to (1-4); formulas (1-1-1), (1-2-1), (1-1-2), (1-2-2), (1-3-1), (1-4-1), (1- 3-2), and (1-4-2); formulas (1-1a), (1-1b), (1-1c), (1-1d), (1-2a), (1-2b), (1-2c), and (1-2d); and formulas (1-3a), (1-3b), (1-3c), (1-3d), (1-4a), (1-4b), (1-4c), and (1-4b); etc. that are included in the formula (1) to be described later each may be simply referred to as “inventive compound”.
The symbols in the formula (1) and the formulas included in the formula (1) to be described later will be explained below. The same symbols have the same meaning.
In the formula (1),
L1 is a single bond or a phenylene group.
The phenylene group that L1 can be may be any of a para bond (p-phenylene group), a meta bond (m-phenylene group), and an ortho bond (o-phenylene group). Of these, an m-phenylene group bonded via a meta bond or a p-phenylene group bonded via a para bond is preferred, and a p-phenylene group bonded via a para bond is more preferred.
Ar is represented by any one of the following formulas (1-a) to (1-d).
In the formula (1-a),
When R2 is a single bond that is bonded to *a, and m1 and n1 are 1, specifically, for example, assuming that the single bond bonded to *d is R21 and the single bond bonded to *e is R26 located adjacent to R21 on the benzene ring, the formula (1-a) is represented by the following formula (1-a-1).
In the formula (1-a-1), **, *c, R11 to R15, R22 to R25 and R31 to R35 are as defined in the formula (1-a) above.
In one embodiment of the formula (1-a), m1 is 0 and n1 is 1, or m1 is 1 and n1 is 0. In another embodiment, m1 is 0 and n1 is 2. In still another embodiment, m1 is 1 and n1 is 1. In other embodiments, m1 is 1 and n1 is 2. Of these, it is preferable that m1 is 1 and n1 is 0.
R11 to R15, R21 to R26, and R31 to R35 each are independently preferably a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, more preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms.
The details of the halogen atom are as described above in “Substituents in Description”.
The details of the substituted or unsubstituted alkyl group having 1 to 50 carbon atoms are as described above in “Substituents in Description”.
The unsubstituted alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group or a t-butyl group, more preferably a methyl group, an ethyl group, an isopropyl group or a t-butyl group, and still more preferably a methyl group or a t-butyl group.
The details of the substituted or unsubstituted alkenyl group having 2 to 50 ring carbon atoms are as described above in “Substituents in Description”.
The details of the substituted or unsubstituted alknyl group having 2 to 50 ring carbon atoms are as described above in “Substituents in Description”.
The details of the substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms are as described above in “Substituents in Description”.
The unsubstituted cycloalkyl group is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, a 2-adamantyl group, a 1-norbornyl group, or a 2-norbornyl group, more preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and still more preferably a cyclopentyl group or a cyclohexyl group.
The details of the substituted or unsubstituted haloalkyl group having 1 to 50 carbon atoms are as described above in “Substituents in Description”, and the substituted or unsubstituted haloalkyl group having 1 to 50 carbon atoms is preferably a substituted or unsubstituted fluoroalkyl group having 1 to 50 carbon atoms.
The unsubstituted fluoroalkyl group is preferably a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group or a heptafluoropropyl group, and more preferably a trifluoromethyl group.
The details of the substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms are as described above in “Substituents in Description”.
The unsubstituted alkoxy group is preferably a methoxy group, an ethoxy group, a propoxy group, or a t-butoxy group.
The substituted or unsubstituted haloalkoxy group having 1 to 50 carbon atoms is a group represented by —O(G15), and G15 is the substituted or unsubstituted haloalkyl group.
The substituted or unsubstituted haloalkoxy group having 1 to 50 carbon atoms is preferably a substituted or unsubstituted fluoroalkoxy group having 1 to 50 carbon atoms.
The unsubstituted fluoroalkoxy group is preferably a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a pentafluoroethoxy group, or a heptafluoropropoxy group, more preferably a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group or a pentafluoroethoxy group, and still more preferably a trifluoromethoxy group.
The details of the substituted or unsubstituted alkylthio group having 1 to 50 ring carbon atoms are as described above in “Substituents in Description”.
The unsubstituted alkylthio group is preferably a methylthio group, an ethylthio group, a propylthio group, or a butylthio group.
The details of the substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms are as described above in “Substituents in Description”.
The unsubstituted aryl group is preferably a phenyl group, a biphenyl group, a naphthyl group, or a phenanthryl group, more preferably a phenyl group,
The details of the substituted or unsubstituted aryloxy group having 6 to 50 ring carbon atoms are as described above in “Substituents in Description”.
The unsubstituted aryloxy group is preferably a phenoxy group, a biphenyloxy group, or a terphenyloxy group, and more preferably a phenoxy group or a biphenyloxy group.
The details of the substituted or unsubstituted arylthio group having 6 to 50 ring carbon atoms are as described above in “Substituents in Description”.
The unsubstituted arylthio group is preferably a phenylthio group or a tolylthio group.
The details of the substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms are as described above in “Substituents in Description”.
The unsubstituted aralkyl group is preferably a benzyl group, a phenyl-t-butyl group, an α-naphthylmethyl group, a β-naphthylmethyl group, a 1-β-naphthylisopropyl group, or a 2-β-naphthylisopropyl group, and more preferably a benzyl group, a phenyl-t-butyl group, an α-naphthylmethyl group, or a β-naphthylmethyl group.
The details of the substituents of the mono-, di-, or tri-substituted silyl group are as described above in “Substituents in Description”.
The mono-, di- or tri-substituted silyl group is preferably a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a propyldimethylsilyl group, an isopropyldimethylsilyl group, a triphenylsilyl group, a phenyldimethylsilyl group, a t-butyldiphenylsilyl group, or a tritolylsilyl group, and more preferably a trimethylsilyl group or a triphenylsilyl group.
In the formula (1-b),
The details of each group represented by R41 to R48 are the same as the details of the corresponding groups described for R11 to R15, R21 to R26 and R31 to R35.
R41 to R48 each are independently preferably a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms, and more preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms.
As described above, when R2 is a single bond that is bonded to *a, in the substituted or unsubstituted biphenylene group represented by L2, (i) with respect to a bonding position to the central nitrogen atom N* on one benzene ring, the other benzene ring is bonded at an ortho position or a meta position, or (ii) with respect to a bonding position to the central nitrogen atom N* on one benzene ring, the other benzene ring is bonded at a para position, and with respect to the bonding position to the one benzene ring on the other benzene ring, one of R41 to R48 that are single bonds is bonded at the ortho position or the meta position.
In other words, in the case of (i) above, the formula (1-b) is represented by the following formula (1-b-1) or (1-b-2). Further, in the case of (ii) above, (1-b) is represented, for example, by the following formula (1-b-3) or (1-b-4).
In the formulas (1-b-1) to (1-b-4),
The details of each group represented by R71 to R75 and R81 to R85 are the same as the details of the corresponding groups described for R11 to R15, R21 to R26 and R31 to R35.
When L2 is a substituted phenylene group, a substituted biphenylene group, or a substituted naphthylene group, one or more substituents that L2 can be each are independently
The details of each substituent that L2 may have as a substituent are the same as the details of the corresponding groups described for R11 to R15, R21 to R26, and R31 to R35.
Each of the substituents that L2 may have as a substituent is preferably a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, more preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, and still more preferably a hydrogen atom.
L2 is preferably a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group, more preferably a single bond, an unsubstituted phenylene group, or an unsubstituted biphenylene group, and still more preferably a single bond or an unsubstituted phenylene group.
The unsubstituted phenylene group that L2 can be may be any of a para bond (p-phenylene group), a meta bond (m-phenylene group), and an ortho bond (o-phenylene group). Of these, an m-phenylene group bonded via a meta bond or a p-phenylene group bonded via a para bond is preferred.
In the formula (1-c),
The details of each group represented by R51 to R60 are the same as the details of the corresponding groups described for R11 to R15, R21 to R26, and R31 to R35.
R51 to R60 each are independently preferably a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms, and more preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms.
When L3 is a substituted phenylene group, a substituted biphenylene group, or a substituted naphthylene group, one or more substituents that L3 can be each are independently
The details of each substituent that L3 may have as a substituent are the same as the details of the corresponding groups described for R11 to R15, R21 to R26, and R31 to R35.
Each of the substituents that L3 may have as a substituent is preferably a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, more preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, and still more preferably a hydrogen atom.
L3 is preferably a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group, more preferably a single bond, an unsubstituted phenylene group, or an unsubstituted biphenylene group, and still more preferably a single bond or an unsubstituted phenylene group.
The unsubstituted phenylene group that L3 can be may be any of a para bond (p-phenylene group), a meta bond (m-phenylene group), and an ortho bond (o-phenylene group). Of these, an m-phenylene group bonded via a meta bond or a p-phenylene group bonded via a para bond is preferred.
In the formula (1-d),
The details of each group represented by R61 to R68 are the same as the details of the corresponding groups described for R11 to R15, R21 to R26 and R31 to R35.
The details of the substituted or unsubstituted alkyl group having 1 to 50 carbon atoms represented by Ra and Rb are the same as the details of the alkyl group described for R11 to R15, R21 to R26, and R31 to R35, and the substituted or unsubstituted alkyl group having 1 to 50 carbon atoms represented by Ra and Rb is more preferably a methyl group.
The details of the substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms represented by Ra and Rb are as described above in “Substituents in Description”.
The unsubstituted aryl groups having 6 to 50 ring carbon atoms represented by Ra and Rb each are independently preferably a phenyl group, a biphenyl group, a naphthyl group, or a phenanthryl group, and more preferably a phenyl group.
In an embodiment of the present invention, when X is CRaRb, preferably both Ra and Rb are substituted or unsubstituted phenyl groups, or both Ra and Rb are methyl groups, or both Ra and Rb are substituted or unsubstituted phenyl groups, and Ra and Rb form a ring together.
In addition, in an embodiment of the present invention, when X is CRaRb, Ra and Rb respectively may not bond to each other and therefore may not form a ring structure.
R61 to R68 each are independently preferably a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, and more preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms.
When L4 is a substituted phenylene group, a substituted biphenylene group, or a substituted naphthylene group, one or more substituents that L4 can be each are independently
The details of each substituent that L4 may have as a substituent are the same as the details of the corresponding groups described for R11 to R15, R21 to R26, and R31 to R35.
Each of the substituents that L4 may have as a substituent is preferably a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, more preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, and still more preferably a hydrogen atom.
L4 is preferably a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group, more preferably a single bond, an unsubstituted phenylene group, or an unsubstituted biphenylene group, and still more preferably a single bond or an unsubstituted phenylene group.
The unsubstituted phenylene group that L4 can be may be any of a para bond (p-phenylene group), a meta bond (m-phenylene group), and an ortho bond (o-phenylene group). Of these, an m-phenylene group bonded via a meta bond or a p-phenylene group bonded via a para bond is preferred.
The compound represented by the formula (1) is preferably represented by the following formula (1-1) or (1-2).
In the formulas (1-1) and (1-2), N*, L1, and Ar are as defined in the formula (1).
Moreover, the compound represented by the formula (1) is preferably represented by the following formula (1-3) or (1-4).
In the formulas (1-3) and (1-4), N*, L1, and Ar are as defined in the formula (1).
Further, the compound represented by the formula (1) is preferably represented by the following formula (1-1-1) or (1-2-1).
In the formulas (1-1-1) and (1-2-1), N* and Ar are as defined in the formula (1).
Moreover, the compound represented by the formula (1) is preferably represented by the following formula (1-1-2) or (1-2-2).
In the formulas (1-1-2) and (1-2-2), N*, L1 and Ar are as defined in the formula (1).
Moreover, the compound represented by the formula (1) is preferably represented by the following formula (1-3-1) or (1-4-1).
In the formulas (1-3-1) and (1-4-1), N* and Ar are as defined in the formula (1).
Moreover, the compound represented by the formula (1) is preferably represented by the following formula (1-3-2) or (1-4-2).
In the formulas (1-3-2) and (1-4-2), N* and Ar are as defined in the formula (1).
Moreover, the compound represented by the formula (1) is preferably represented by the following formula (1-1a), (1-1b), (1-1c), or (1-1d).
In the formulas (1-1a), (1-1b), (1-1c) and (1-1d), N*, L1, L2, L3, L4, *c, *d, *e, *f, * g, *h, m1, n1, R11 to R15, R21 to R26, R31 to R35, R41 to R48, R51 to R60, R61 to R68, and X are as defined in the formula (1) above.
Moreover, the compound represented by the formula (1) is preferably represented by the following formula (1-2a), (1-2b), (1-2c), or (1-2d).
In the formulas (1-2a), (1-2b), (1-2c) and (1-2d), N*, L1, L2, L3, L4, *c, *d, *e, *f, * g, *h, m1, n1, R11 to R15, R21 to R26, R31 to R35, R41 to R48, R51 to R60, R61 to R68, and X are as defined in the formula (1) above.
Moreover, the compound represented by the formula (1) is preferably represented by the following formula (1-3a), (1-3b), (1-3c), or (1-3d).
In the formulas (1-3a), (1-3b), (1-3c) and (1-3d), N*, L1, L2, L3, L4, *c, *d, *e, *f, * g, *h, m1, n1, R11 to R15, R21 to R26, R31 to R35, R41 to R48, R51 to R60, R61 to R68, and X are as defined in the formula (1) above.
Moreover, the compound represented by the formula (1) is preferably represented by the following formula (1-4a), (1-4b), (1-4c), or (1-4d).
In the formulas (1-4a), (1-4b), (1-4c) and (1-4d), N*, L1, L2, L3, L4, *c, *d, *e, *f, * g, *h, m1, n1, R11 to R15, R21 to R26, R31 to R35, R41 to R48, R51 to R60, R61 to R68, and X are as defined in the formula (1) above.
As described above, when R2 is a single bond that is bonded to *a, and m1 and n1 are 1 in the above formula (1-a), the above formulas (1-3a) and (1-4a) are represented, for example, by the following formulas (1-3a-1) and (1-4a-1).
In the formulas (1-3a-1) and (1-4a-1), N*, L1, *c, R11 to R15, R22 to R25, and R31 to R35 and X are as defined in the formula (1) above.
In addition, in relation to the above formula (1-b), as described above, when R2 is a single bond that is bonded to *a, the above formula (1-3b) is represented, for example, by the following formulas (1-3b-1) to (1-3b-3), and the above formula (1-4b) is represented, for example, by the following formulas (1-4b-1) to (1-4b-3).
In the formulas (1-3b-1) to (1-3b-3) and (1-4b-1) to (1-4b-3), N*, L1, R41 to R48, and *f are as defined in the above formula (1).
R81 to R85 in the formulas (1-3b-1) to (1-3b-3) and (1-4b-1) to (1-4b-3) are as defined in the formulas (1-b-1) and (1-b-2).
R71 to R73 and R75 in the formulas (1-3b-1) and (1-4b-1), R71 to R74 in the formulas (1-3b-2) and (1-4b-2), and R71, R72, R74 and R75 in the formulas (1-3b-3) and (1-4b-3) are as defined in the formulas (1-b-1), (1-b-2) and (1-b-3), respectively.
In one embodiment of the present invention,
As described above, the “hydrogen atom” used in the description herein includes a protium atom, a deuterium atom, and a tritium atom. Accordingly, the inventive compound may contain a naturally-derived deuterium atom.
Further, a deuterium atom may be intentionally introduced into the inventive compound by using a deuterated compound as a part or all of the raw material compound. Accordingly, in one embodiment of the present invention, the inventive compound contains at least one deuterium atom. That is, the inventive compound may be a compound represented by the formula (1) in which at least one hydrogen atom contained in the compound is a deuterium atom.
At least one hydrogen atom selected from the following hydrogen atoms may be a deuterium atom:
In the formula (1A), N*, L1, Ar, R1, R2, R3, R4, *a, and *b are as defined in the formula (1).
The deuteration rate of the inventive compound depends on the deuteration rate of the raw material compound used. Even if a raw material with a given deuteration rate is used, it may still contain a certain proportion of naturally-derived proton isotopes. Therefore, the embodiment of the deuteration rate of the inventive compound shown below includes a ratio that takes naturally-derived trace isotopes into consideration with respect to a proportion obtained by simply counting the number of deuterium atoms represented by a chemical formula.
The deuteration rate of the inventive compound is preferably 1% or more, more preferably 3% or more, still more preferably 5% or more, even more preferably 10% or more, and further more preferably 50% or more.
The inventive compound may be a mixture containing a deuterated compound and a non-deuterated compound, or a mixture of two or more compounds having different deuteration rates from each other. The deuteration rate of the mixture is preferably 1% or more, more preferably 3% or more, still more preferably 5% or more, even more preferably 10% or more, and further more preferably 50% or more, and is less 100%.
Further, the proportion of the number of deuterium atoms to the total number of hydrogen atoms in the inventive compound is preferably 1% or more, more preferably 3% or more, still more preferably 5% or more, and even more preferably 10% or more, and is 100% or less.
The details of the substituent (arbitrary substituent) in the expression “substituted or unsubstituted” included in the definitions of the aforementioned formulas are as described in “Substituent for ‘Substituted or Unsubstituted’”.
However, when L2 to L4 are a substituted phenylene group, a substituted biphenylene group, or a substituted naphthylene group, the one or more substituents that can be taken each are independently as described above.
In addition, the arbitrary substituents included in the definitions of R11 to R15 that are not a single bond bonded to *c; and R61 to R68 that are not a single bond bonded to *h in each of the above formulas do not include an aryl group, a heterocyclic group, and a substituent represented by —N(R906)(R907) among the substituents described in “Substituent for ‘Substituted or Unsubstituted’”.
Moreover, the arbitrary substituents included in the definitions of R21 to R26 that are not a single bond bonded to *d and that are not a single bond bonded to *e; R31 to R35; R41 to R48 that are not a single bond bonded to *f; R51 to R60 that are not a single bond bonded to *g in each of the above formulas do not include an aryl group having more than 14 ring carbon atoms, a heterocyclic group, and a substituent represented by —N(R906)(R907) among the substituents described in “Substituent for ‘Substituted or Unsubstituted’”.
In addition, the arbitrary substituents included in the definitions of Ra to Rb in each of the above formulas do not include a heterocyclic group and a substituent represented by —N(R906)(R907) among the substituents described in “Substituent for ‘Substituted or Unsubstituted’”.
Further, the details of the substituents (arbitrary substituents) in the expression “substituted or unsubstituted” included in the definitions of one or more of the substituents that can be taken when L2 to L4 in the formula (1) are a substituted phenylene group, a substituted biphenylene group, or a substituted naphthylene group; R71 to R75 in the formulas (1-1) to (1-b-4); R81 to R85 in the formulas (1-1) and (1-b-2) that are not a single bond bonded to *i are as described in “Substituent for ‘Substituted or Unsubstituted’”. However, the arbitrary substituents do not include an aryl group, a heterocyclic group, and a substituent represented by —N(R906)(R907) among the substituents described in “Substituent for ‘Substituted or Unsubstituted’”.
The inventive compound can be readily produced by a person skilled in the art with reference to the following synthesis examples and the known synthesis methods.
Specific examples of the inventive compound will be described below; however, the inventive compound is not limited to the following example compounds.
In the following specific examples, D represents a deuterium atom.
The material for an organic EL element, which is one aspect of the present invention, contains the inventive compound. The content of the inventive compound in the material for organic EL elements is 1% by mass or more (including 100%), preferably 10% by mass or more (including 100%), more preferably 50% by mass or more (including 100%), still more preferably 80% by mass or more (including 100%), and particularly preferably 90% by mass or more (including 100%). The material for organic EL elements, which is one aspect of the present invention, is useful for the production of an organic EL element.
The organic EL element, which is one aspect of the present invention, includes a cathode, an anode, and organic layers intervening between the anode and the cathode. The organic layers include a light emitting layer, and at least one layer of the organic layers contains the inventive compound. Examples of the organic layer containing the inventive compound include a hole transporting zone (such as a hole injecting layer, a hole transporting layer, an electron blocking layer, and an exciton blocking layer) intervening between the anode and the light emitting layer, the light emitting layer, a space layer, and an electron transporting zone (such as an electron injecting layer, an electron transporting layer, and a hole blocking layer) intervening between the cathode and the light emitting layer, but are not limited thereto. The inventive compound is preferably used as a material for the hole transporting zone or the light emitting layer in a fluorescent or phosphorescent EL element, more preferably as a material for the hole transporting zone, still preferably as a material for the hole injecting layer, the hole transporting layer, the electron blocking layer, or the exciton blocking layer, and particularly preferably as a material for the hole injecting layer or the hole transporting layer.
The organic EL element, which is one aspect of the present invention, may be a fluorescent or phosphorescent light emission-type monochromatic light emitting element or a fluorescent/phosphorescent hybrid-type white light emitting element, and may be a simple type having a single light emitting unit or a tandem type having a plurality of light emitting units. Among them, the fluorescent light emission-type element is preferable. The “light emitting unit” referred to herein refers to a minimum unit that emits light through recombination of injected holes and electrons, which includes organic layers among which at least one layer is a light emitting layer.
For example, as a representative element configuration of the simple type organic EL element, the following element configuration may be exemplified.
The light emitting unit may be a multilayer type having a plurality of phosphorescent light emitting layers or fluorescent light emitting layers. In this case, a space layer may intervene between the light emitting layers for the purpose of preventing excitons generated in the phosphorescent light emitting layer from diffusing into the fluorescent light emitting layer. Representative layer structures of the simple type light emitting unit are described below. Layers in parentheses are optional.
The phosphorescent and fluorescent light emitting layers each can emit emission colors different from each other. Specifically, in the light emitting unit (f), a layer structure, such as (hole injecting layer/) hole transporting layer/first phosphorescent light emitting layer (red light emission)/second phosphorescent light emitting layer (green light emission)/space layer/fluorescent light emitting layer (blue light emission)/electron transporting layer, may be exemplified.
An electron blocking layer may be properly provided between each light emitting layer and the hole transporting layer or the space layer. Further, a hole blocking layer may be properly provided between each light emitting layer and the electron transporting layer. The employment of the electron blocking layer or the hole blocking layer allows improving the emission efficiency by trapping electrons or holes within the light emitting layer and increasing the probability of charge recombination in the light emitting layer.
Here, examples of a representative element configuration of the tandem type organic EL element include the following element configuration.
Here, for example, each of the first light emitting unit and the second light emitting unit may be independently selected from the above-described light emitting units.
The intermediate layer is also generally referred to as an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron withdrawing layer, a connecting layer, or an intermediate insulating layer, and a known material configuration, in which electrons are supplied to the first light emitting unit and holes are supplied to the second light emitting unit, can be used.
In the present invention, a host combined with a fluorescent dopant (a fluorescent light emitting material) is referred to as a fluorescent host, and a host combined with a phosphorescent dopant is referred to as a phosphorescent host. The fluorescent host and the phosphorescent host are not distinguished from each other merely by the molecular structures thereof. That is, the phosphorescent host means a material that forms a phosphorescent light emitting layer containing a phosphorescent dopant, and does not mean unavailability as a material that forms a fluorescent light emitting layer. The same also applies to the fluorescent host.
The substrate is used as a support of the organic EL element. Examples of the substrate include a plate of glass, quartz, and plastic. In addition, a flexible substrate may be used. Examples of the flexible substrate include a plastic substrate made of polyimide, polycarbonate, polyarylate, polyether sulfone, polypropylene, polyester, polyvinyl fluoride, or polyvinyl chloride. In addition, an inorganic vapor deposition film can be used.
It is preferable that a metal, an alloy, an electrically conductive compound, and a mixture thereof, which has a high work function (specifically 4.0 eV or more) is used for the anode formed on the substrate. 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, indium oxide containing tungsten oxide and zinc oxide, and graphene. In addition, examples thereof include gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), titanium (Ti), and nitrides of the metals (for example, titanium nitride).
These materials are usually deposited by a sputtering method. For example, through a sputtering method, it is possible to form indium oxide-zinc oxide by using a target in which 1 to 10% by weight of zinc oxide is added to indium oxide, and to form indium oxide containing tungsten oxide and zinc oxide by using a target containing 0.5 to 5% by weight of tungsten oxide and 0.1 to 1% by weight of zinc oxide with respect to indium oxide. In addition, the production may be performed by a vacuum vapor deposition method, a coating method, an inkjet method, a spin coating method, or the like.
The hole injecting layer formed in contact with the anode is formed by using a material that facilitates hole injection regardless of a work function of the anode, and thus it is possible to use materials generally used as an electrode material (for example, metals, alloys, electrically conductive compounds, and mixtures thereof, elements belonging to Group 1 or Group 2 of the periodic table of the elements).
It is also possible to use elements belonging to Group 1 or Group 2 of the periodic table of the elements, which are materials having low work functions, that is, alkali metals such as lithium (Li) and cesium (Cs), alkaline earth metals such as magnesium (Mg), calcium (Ca), and strontium (Sr), and alloys containing these (such as MgAg and AlLi), as well as rare earth metals such as europium (Eu) and ytterbium (Yb), and alloys containing these. When the anode is formed by using the alkali metals, the alkaline earth metals, and alloys containing these, a vacuum vapor deposition method or a sputtering method can be used. Further, when a silver paste or the like is used, a coating method, an inkjet method, or the like can be used.
The hole injecting layer is a layer containing a material having a high hole injection capability (a hole injecting material) and is provided between the anode and the light emitting layer, or between the hole transporting layer, if exists, and the anode.
As the hole injecting material other than the inventive compound, molybdenum oxide, titanium oxide, vanadium oxide, rhenium oxide, ruthenium oxide, chromium oxide, zirconium oxide, hafnium oxide, tantalum oxide, silver oxide, tungsten oxide, manganese oxide, and the like can be used.
Examples of the hole injecting layer material also include aromatic amine compounds as low-molecular weight organic compounds, such as 4,4′,4″-tris(N,N-diphenylamino)triphenylamine (abbreviation: TDATA), 4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine (abbreviation: MTDATA), 4,4′-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl (abbreviation: DPAB), 4,4′-bis(N-{4-[N′-(3-methylphenyl)-N′-phenylamino]phenyl}-N-phenylamino)biphenyl (abbreviation: DNTPD), 1,3,5-tris[N-(4-diphenylaminophenyl)-N-phenylamino]benzene (abbreviation: DPA3B), 3-[N-(9-phenylcarbazole-3-yl)-N-phenylamino]-9-phenylcarbazole (abbreviation: PCzPCA1), 3,6-bis[N-(9-phenylcarbazole-3-yl)-N-phenylamino]-9-phenylcarbazole (abbreviation: PCzPCA2), and 3-[N-(1-naphthyl)-N-(9-phenylcarbazole-3-yl)amino]-9-phenylcarbazole (abbreviation: PCzPCN1).
High-molecular weight compounds (such as oligomers, dendrimers, and polymers) may also be used. Examples thereof include high-molecular weight compounds, such as poly(N-vinylcarbazole) (abbreviation: PVK), poly(4-vinyltriphenylamine) (abbreviation: PVTPA), poly[N-(4-{N′-[4-(4-diphenylamino)phenyl]phenyl-N′-phenylamino}phenyl)methacrylamide](abbreviation: PTPDMA), and poly[N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)benzidine] (abbreviation: Poly-TPD). In addition, high-molecular weight compounds to which an acid, such as poly(3,4-ethylenedioxythiophene)/poly (styrene sulfonic acid) (PEDOT/PSS) and polyaniline/poly (styrenesulfonic acid) (PAni/PSS), is added, can also be used.
Furthermore, it is also preferable to use an acceptor material, such as a hexaazatriphenylene (HAT) compound represented by the following formula (K).
In the above formula, R201 to R206 each independently represent a cyano group, —CONH2, a carboxy group, or —COOR207 (R207 represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms). In addition, adjacent two selected from R201 and R202, R203 and R204, and R205 and R206 may be bonded to each other to form a group represented by —CO—O—CO—.
Examples of R207 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a cyclopentyl group, and a cyclohexyl group.
The hole transporting layer is a layer containing a material having a high hole transporting capability (a hole transporting material) and is provided between the anode and the light emitting layer, or between the hole injecting layer, if exists, and the light emitting layer. The inventive compound may be used in the hole transporting layer alone or in combination with the following compounds.
The hole transporting layer may have a single layer structure or a multilayer structure including two or more layers. For example, the hole transporting layer may have a two-layer structure including a first hole transporting layer (anode side) and a second hole transporting layer (cathode side). In one embodiment of the present invention, the hole transporting layer having a single layer structure is preferably disposed adjacent to the light emitting layer, and the hole transporting layer that is closest to the cathode in the multilayer structure, such as the second hole transporting layer in the two-layer structure, is preferably disposed adjacent to the light emitting layer. In another embodiment of the present invention, an electron blocking layer described later and the like may be disposed between the hole transporting layer having a single layer structure and the light emitting layer, or between the hole transporting layer that is closest to the light emitting layer in the multilayer structure and the light emitting layer.
In the hole transporting layer having a two-layer structure, the inventive compound may be contained in either the first hole transporting layer or the second hole transporting layer, or may be contained in both of the first hole transporting layer and the second hole transporting layer.
In one embodiment of the present invention, the inventive compound is preferably contained only in the first hole transporting layer. In another embodiment, the inventive compound is preferably contained only in the second hole transporting layer. In yet another embodiment, the inventive compound is preferably contained in the first hole transporting layer and the second hole transporting layer.
In one embodiment of the present invention, the inventive compound contained in one or both of the first hole transporting layer and the second hole transporting layer is preferably a light hydrogen body from the viewpoint of production cost.
The light hydrogen body refers to the inventive compound in which all hydrogen atoms in the inventive compound are protium atoms.
Therefore, the organic EL element according to one aspect of the present invention is preferably an organic EL element containing the inventive compound in which one or both of the first hole transporting layer and the second hole transporting layer are substantially composed of only a light hydrogen body. The “inventive compound substantially composed of only of a light hydrogen body” means that the content ratio of the light hydrogen body to the total amount of the inventive compound is 90 mol % or more, preferably 95 mol % or more, more preferably 99 mol % or more (each including 100%).
As the hole transporting layer material other than the inventive compound, for example, an aromatic amine compound, a carbazole derivative, an anthracene derivative, and the like can be used.
Examples of the aromatic amine compound include 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB), N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (abbreviation: TPD), 4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BAFLP), 4,4′-bis[N-(9,9-dimethylfluorene-2-yl)-N-phenylamino]biphenyl (abbreviation: DFLDPBi), 4,4′,4″-tris(N,N-diphenylamino)triphenylamine (abbreviation: TDATA), 4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine (abbreviation: MTDATA), and 4,4′-bis[N-(spiro-9,9′-bifluorene-2-yl)-N-phenylamino]biphenyl (abbreviation: BSPB). The aforementioned compounds have a hole mobility of 10−6 cm2/Vs or more.
Examples of the carbazole derivative include 4,4′-di(9-carbazolyl)biphenyl (abbreviation: CBP), 9-[4-(9-carbazolyl)phenyl]-10-phenylanthracene (abbreviation: CzPA), and 9-phenyl-3-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (abbreviation: PCzPA).
Examples of the anthracene derivative include 2-t-butyl-9,10-di(2-naphthyl)anthracene (abbreviation: t-BuDNA), 9,10-di(2-naphthyl)anthracene (abbreviation: DNA), and 9,10-diphenylanthracene (abbreviation: DPAnth).
High-molecular weight compounds, such as poly(N-vinylcarbazole) (abbreviation: PVK) and poly(4-vinyltriphenylamine) (abbreviation: PVTPA), can also be used.
However, compounds other than those as mentioned above can also be used as long as they are compounds high in the hole transporting capability rather than in the electron transporting capability.
The light emitting layer is a layer containing a material having a high light emitting property (a dopant material), and various materials can be used. For example, a fluorescent light emitting material or a phosphorescent light emitting material can be used as the dopant material. The fluorescent light emitting material is a compound that emits light from a singlet excited state, and the phosphorescent light emitting material is a compound that emits light from a triplet excited state.
Examples of a blue-based fluorescent light emitting material that can be used for the light emitting layer include a pyrene derivative, a styrylamine derivative, a chrysene derivative, a fluoranthene derivative, a fluorene derivative, a diamine derivative, and a triarylamine derivative. Specific examples thereof include N,N′-bis[4-(9H-carbazole-9-yl)phenyl]-N,N′-diphenylstilbene-4,4′-diamine (abbreviation: YGA2S), 4-(9H-carbazole-9-yl)-4′-(10-phenyl-9-anthryl)triphenylamine (abbreviation: YGAPA), and 4-(10-phenyl-9-anthryl)-4′-(9-phenyl-9H-carbazole-3-yl)triphenylamine (abbreviation: PCBAPA).
Examples of a green-based fluorescent light emitting material that can be used for the light emitting layer include an aromatic amine derivative. Specific examples thereof include N-(9,10-diphenyl-2-anthryl)-N,9-diphenyl-9H-carbazole-3-amine (abbreviation: 2PCAPA), N-[9,10-bis(1,1′-biphenyl-2-yl)-2-anthryl]-N,9-diphenyl-9H-carbazole-3-amine (abbreviation: 2PCABPhA), N-(9,10-diphenyl-2-anthryl)-N,N′,N′-triphenyl-1,4-phenylenediamine (abbreviation: 2DPAPA), N-[9,10-bis(1,1′-biphenyl-2-yl)-2-anthryl]-N,N′,N′-triphenyl-1,4-phenylenediamine (abbreviation: 2DPABPhA), N-[9,10-bis(1,1′-biphenyl-2-yl)]-N-[4-(9H-carbazole-9-yl)phenyl]-N-phenylanthracene-2-amine (abbreviation: 2YGABPhA), and N,N,9-triphenylanthracene-9-amine (abbreviation: DPhAPhA).
Examples of a red-based fluorescent light emitting material that can be used for the light emitting layer include a tetracene derivative and a diamine derivative. Specific examples thereof include N,N,N′,N′-tetrakis(4-methylphenyl)tetracene-5,11-diamine (abbreviation: p-mPhTD) and 7,14-diphenyl-N,N,N′,N′-tetrakis(4-methylphenyl)acenaphtho[1,2-a]fluoranthene-3,10-diamine (abbreviation: p-mPhAFD).
Examples of a blue-based phosphorescent light emitting material that can be used for the light emitting layer include a metal complex, such as an iridium complex, an osmium complex, and a platinum complex. Specific examples thereof include bis[2-(4′,6′-difluorophenyl)pyridinato-N,C2′]iridium(III)tetrakis(1-pyrazolyl)borate (abbreviation: FIr6), bis[2-(4′,6′-difluorophenyl)pyridinato-N,C2′]iridium(III)picolinate (abbreviation: FIrpic), bis[2-(3′,5′bistrifluoromethylphenyl)pyridinato-N,C2′]iridium(III)picolinate (abbreviation: Ir(CF3ppy)2(pic)), and bis[2-(4′,6′-difluorophenyl)pyridinato-N,C2′]iridium(III)acetylacetonate (abbreviation: FIracac).
Examples of a green-based phosphorescent light emitting material that can be used for the light emitting layer include an iridium complex. Examples thereof include tris(2-phenylpyridinato-N,C2′)iridium(III) (abbreviation: Ir(ppy)3), bis(2-phenylpyridinato-N,C2′)iridium(III)acetylacetonate (abbreviation: Ir(ppy)2(acac)), bis(1,2-diphenyl-1H-benzimidazolato)iridium(III)acetylacetonate (abbreviation: Ir(pbi)2(acac)), and bis(benzo[h]quinolinato)iridium(III)acetylacetonate (abbreviation: Ir(bzq)2(acac)).
Examples of a red-based phosphorescent light emitting material that can be used for the light emitting layer include a metal complex, such as an iridium complex, a platinum complex, a terbium complex, and a europium complex. Specific examples thereof include organic metal complexes, such as bis[2-(2′-benzo[4,5-a]thienyl)pyridinato-N,C3′]iridium(III)acetylacetonate (abbreviation: Ir(btp)2(acac)), bis(1-phenylisoquinolinato-N,C2′)iridium(III)acetylacetonate (abbreviation: Ir(piq)2(acac)), (acetylacetonate)bis[2,3-bis(4-fluorophenyl)quinoxalinato]iridium(III) (abbreviation: Ir(Fdpq)2(acac)), and 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrinplatinum(II) (abbreviation: PtOEP).
In addition, rare earth metal complexes, such as tris(acetylacetonate) (monophenanthroline)terbium(III) (abbreviation: Tb(acac)3(Phen)), tris(1,3-diphenyl-1,3-propanedionate)(monophenanthroline)europium(III) (abbreviation: Eu(DBM)3(Phen)), and tris[1-(2-thenoyl)-3,3,3-trifluoroacetonate](monophenanthroline)europium(III) (abbreviation: Eu(TTA)3(Phen)), emit light from rare earth metal ions (electron transition between different multiplicities), and thus may be used as the phosphorescent light emitting material.
The light emitting layer may have a configuration in which the aforementioned dopant material is dispersed in another material (a host material). The host material is preferably a material that has a higher lowest unoccupied orbital level (LUMO level) and a lower highest occupied orbital level (HOMO level) than the dopant material.
Examples of the host material include:
For example,
In particular, in the case of a blue fluorescent element, it is preferable to use the following anthracene compounds as the host material.
The electron transporting layer is a layer containing a material having a high electron transporting capability (an electron transporting material) and is provided between the light emitting layer and the cathode, or between the electron injecting layer, if exists, and the light emitting layer.
The electron transporting layer may have a single layer structure or a multilayer structure including two or more layers. For example, the electron transporting layer may have a two-layer structure including a first electron transporting layer (anode side) and a second electron transporting layer (cathode side). In one embodiment of the present invention, the electron transporting layer having a single layer structure is preferably disposed adjacent to the light emitting layer, and the electron transporting layer that is closest to the anode in the multilayer structure, such as the first electron transporting layer in the two-layer structure, is preferably disposed adjacent to the light emitting layer. In another embodiment of the present invention, a hole blocking layer described later and the like may be disposed between the electron transporting layer having a single layer structure and the light emitting layer, or between the electron transporting layer that is closest to the light emitting layer in the multilayer structure and the light emitting layer.
For example,
Examples of the metal complex include tris(8-quinolinolato)aluminum(III) (abbreviation: Alq), tris(4-methyl-8-quinolinolato)aluminum (abbreviation: Almq3), bis(10-hydroxybenzo[h]quinolinato)beryllium (abbreviation: BeBq), bis(2-methyl-8-quinolinolato)(4-phenylphenolato)aluminum(III) (abbreviation: BAlq), bis(8-quinolinolato)zinc(II) (abbreviation: Znq), bis[2-(2-benzoxazolyl)phenolato]zinc(II) (abbreviation: ZnPBO), bis[2-(2-benzothiazolyl)phenolato]zinc(II) (abbreviation: ZnBTZ), and (8-quinolinolato) lithium (abbreviation: Liq).
Examples of the heteroaromatic compound include 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (abbreviation: PBD), 1,3-bis[5-(p-tert-butylphenyl)-1,3,4-oxadiazole-2-yl]benzene (abbreviation: OXD-7), 3-(4-tert-butylphenyl)-4-phenyl-5-(4-biphenylyl)-1,2,4-triazole (abbreviation: TAZ), 3-(4-tert-butylphenyl)-4-(4-ethylphenyl)-5-(4-biphenylyl)-1,2,4-triazole (abbreviation: p-EtTAZ), bathophenanthroline (abbreviation: BPhen), bathocuproine (abbreviation: BCP), and 4,4′-bis(5-methylbenzxazol-2-yl)stilbene (abbreviation: BzOs).
Examples of the high-molecular weight compound include poly[(9,9-dihexylfluorene-2,7-diyl)-co-(pyridine-3,5-diyl)] (abbreviation: PF-Py), and poly[(9,9-dioctylfluorene-2,7-diyl)-co-(2,2′-bipyridine-6,6′-diyl)] (abbreviation: PF-BPy).
The materials are materials having an electron mobility of 10−6 cm2/Vs or more. Materials other than those as mentioned above may also be used in the electron transporting layer as long as they are materials high in the electron transporting capability rather than in the hole transporting capability.
The electron injecting layer is a layer containing a material having a high electron injection capability. Alkali metals such as lithium (Li) and cesium (Cs), alkaline earth metals such as magnesium (Mg), calcium (Ca), and strontium (Sr), rare earth metals such as europium (Eu) and ytterbium (Yb), and compounds containing these metals can be used for the electron injecting layer. Examples of the compounds include an alkali metal oxide, an alkali metal halide, an alkali metal-containing organic complex, an alkaline earth metal oxide, an alkaline earth metal halide, an alkaline earth metal-containing organic complex, a rare earth metal oxide, a rare earth metal halide, and a rare earth metal-containing organic complex. Further, these compounds may be used as a mixture of a plurality thereof.
In addition, a material having an electron transporting capability, in which an alkali metal, an alkaline earth metal, or a compound thereof is contained, specifically Alq in which magnesium (Mg) is contained may be used. In this case, electron injection from the cathode can be more efficiently performed.
Otherwise, in the electron injecting layer, a composite material obtained by mixing an organic compound with an electron donor may be used. Such a composite material is excellent in the electron injection capability and the electron transporting capability because the organic compound receives electrons from the electron donor. In this case, the organic compound is preferably a material excellent in transporting received electrons, and specifically, for example, a material constituting the aforementioned electron transporting layer (such as a metal complex and a heteroaromatic compound) can be used. As the electron donor, a material having an electron donation property for the organic compound may be used. Specifically, alkali metals, alkaline earth metals, and rare earth metals are preferred, and examples thereof include lithium, cesium, magnesium, calcium, erbium, and ytterbium. In addition, an alkali metal oxide or an alkaline earth metal oxide is preferred, and examples thereof include lithium oxide, calcium oxide, and barium oxide. In addition, a Lewis base, such as magnesium oxide, can also be used. In addition, an organic compound, such as tetrathiafulvalene (abbreviation: TTF), can also be used.
It is preferable that a metal, an alloy, an electrically conductive compound, and a mixture thereof, which has a low work function (specifically 3.8 eV or less) is used for the cathode. Specific examples of such a cathode material include elements belonging to Group 1 or Group 2 of the periodic table of the elements, that is, alkali metals such as lithium (Li) and cesium (Cs), alkaline earth metals such as magnesium (Mg), calcium (Ca), and strontium (Sr), as well as alloys containing these (such as MgAg, and AlLi), rare earth metals such as europium (Eu), and ytterbium (Yb), and alloys containing these.
When the cathode is formed by using the alkali metals, the alkaline earth metals, and the alloys containing these, a vacuum vapor deposition method or a sputtering method can be used. In addition, when a silver paste or the like is used, a coating method, an inkjet method, or the like can be used.
By providing the electron injecting layer, the cathode can be formed using various conductive materials, such as Al, Ag, ITO, graphene, and indium oxide-tin oxide containing silicon or silicon oxide regardless of the magnitude of a work function. These conductive materials can be deposited by using a sputtering method, an inkjet method, a spin coating method, or the like.
The organic EL element applies an electric field to an ultrathin film, and thus pixel defects are likely to occur due to leaks or short-circuiting. In order to prevent it, an insulating layer formed of an insulating thin film layer may be inserted between a pair of electrodes.
Examples of the material used for the insulating layer include aluminum oxide, lithium fluoride, lithium oxide, cesium fluoride, cesium oxide, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, aluminum nitride, titanium oxide, silicon oxide, germanium oxide, silicon nitride, boron nitride, molybdenum oxide, ruthenium oxide, and vanadium oxide. A mixture or a laminate of these may also be used.
The space layer is, for example, a layer provided between a fluorescent light emitting layer and a phosphorescent light emitting layer for the purpose of preventing excitons generated in the phosphorescent light emitting layer from diffusing into the fluorescent light emitting layer, or adjusting a carrier balance, in the case where the fluorescent light emitting layers and the phosphorescent light emitting layers are laminated. In addition, the space layer can also be provided among a plurality of phosphorescent light emitting layers.
Since the space layer is provided between the light emitting layers, a material having both an electron transporting capability and a hole transporting capability is preferable. Also, one having a triplet energy of 2.6 eV or more is preferable in order to prevent triplet energy diffusion in an adjacent phosphorescent light emitting layer. Examples of the material used for the space layer include the same materials as those used for the hole transporting layer as described above.
The blocking layer, such as the electron blocking layer, the hole blocking layer, and the exciton blocking layer, may be provided adjacent to the light emitting layer. The electron blocking layer is a layer that prevents electrons from leaking from the light emitting layer to the hole transporting layer, and the hole blocking layer is a layer that prevents holes from leaking from the light emitting layer to the electron transporting layer. The exciton blocking layer has a function of preventing excitons generated in the light emitting layer from diffusing into the surrounding layers, and trapping the excitons within the light emitting layer.
Each layer of the organic EL element may be formed by a conventionally known vapor deposition method, a coating method, or the like. For example, each layer can be formed by a known method using a vapor deposition method such as a vacuum vapor deposition method and a molecular beam vapor deposition method (MBE method), or a coating method using a solution of a compound forming a layer, such as a dipping method, a spin-coating method, a casting method, a bar-coating method, and a roll-coating method.
The film thickness of each layer is not particularly limited, but is typically 5 nm to 10 μm, and more preferably 10 nm to 0.2 μm because in general, when the film thickness is too small, defects such as pinholes are likely to occur, and conversely, when the film thickness is too large, a high driving voltage is required and the efficiency decreases.
The organic EL element can be suitably used in electronic devices, such as display components of an organic EL panel module and the like, display devices of a television, a mobile phone, a personal computer, and the like, and light emitting devices of lightings and vehicular lamps.
Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following Examples.
A glass substrate of 25 mm×75 mm×1.1 mm provided with an ITO transparent electrode (anode) (manufactured by GEOMATEC Co., Ltd.) was ultrasonically cleaned in isopropyl alcohol for 5 minutes and then subjected to UV ozone cleaning for 30 minutes. The film thickness of the ITO was 130 nm. The cleaned glass substrate provided with the transparent electrode was mounted on a substrate holder of a vacuum vapor deposition apparatus, and firstly, Compound HT1 and Compound HA were vapor co-deposited on a surface having the transparent electrode formed thereon, so as to cover the transparent electrode, resulting in a hole injecting layer with a film thickness of 10 nm. The mass ratio of Compound HT1 and Compound HA (HT1:HA) was 97:3.
Subsequently, on the hole injecting layer, Compound HT1 was vapor deposited to form a first hole transporting layer with a film thickness of 80 nm.
Subsequently, on the first hole transporting layer, Compound 1 was vapor deposited to form a second hole transporting layer with a film thickness of 10 nm.
Subsequently, on the second hole transporting layer, Compound BH (host material) and Compound BD (dopant material) were vapor co-deposited to form a light emitting layer with a film thickness of 25 nm. The mass ratio of Compound BH and Compound BD (BH:BD) was 96:4.
Subsequently, on the light emitting layer, Compound ET3 was vapor deposited to form a first electron transporting layer with a film thickness of 5 nm.
Subsequently, on the first electron transporting layer, Compound ET2 and (8-quinolinolato)lithium (abbreviation: Liq) were vapor co-deposited to form a second electron transporting layer with a film thickness of 20 nm. The mass ratio of Compound ET2 and Liq (ET2:Liq) was 50:50.
Subsequently, on the second electron transporting layer, LiF was vapor deposited to form an electron injecting electrode with a film thickness of 1 nm.
Then, on the electron injecting electrode, metal Al was vapor deposited to form a metal cathode with a film thickness of 50 nm.
The layer structure of the organic EL element of Example 1 thus obtained is shown as follows.
Hereinafter, the above layer structure may be referred to as “layer structure 1”.
In the layer structure 1, layer structure 2 and layer structure 3 to be described later, the numeral in parentheses indicates the film thickness (nm), and the ratio is a mass ratio.
An organic EL element was produced in the same manner as in Example 1 except that the material for the second hole transporting layer was changed to Comparative Compound 1, as shown in Table 1 below.
As shown in Table 1 below, an organic EL element was produced in the same manner as in Example 1 except that the material for the second hole transporting layer was changed to Compound 2 and the material for the first electron transporting layer was changed from ET3 to ET1.
The layer structure of the organic EL element of Example 2 thus obtained is shown as follows.
Hereinafter, the above layer structure may be referred to as “layer structure 2”.
An organic EL element having the layer structure 2 was produced in the same manner as in Example 2 except that the material for the second hole transporting layer was changed to Comparative Compound 1, as shown in Table 1 below.
Organic EL elements having the layer structure 2 were produced in the same manner as in Example 2 except that the material for the second hole transporting layer was changed to Compounds 1, 3 to 6 as shown in Table 2 below.
An organic EL element having the layer structure 2 was produced in the same manner as in Example 2 except that the material for the second hole transporting layer was changed to Comparative Compound 2, as shown in Table 2 below.
The obtained organic EL elements were driven at room temperature with a direct current constant current at a current density of 10 mA/cm2, and the luminance was measured using a spectral radiance meter “CS-1000” (manufactured by Konica Minolta, Inc.). An external quantum efficiency (%) was determined from the measurement results. The results are shown in Table 1 and Table 2.
As apparent from the results in Table 1, the monoamines meeting the requirements of the present invention (Compound 1 of Example 1 and Compound 2 of Example 2) exhibited significantly improved external quantum efficiency as compared with the monoamines not meeting the requirements of the present invention (Comparative Compound 1 of Comparative Examples 1 and 2).
In addition, as apparent from the results in Table 2, the monoamines meeting the requirements of the present invention (Compound 1 of Example 3, Compound 3 of Example 4, Compound 4 of Example 5, Compound 5 of Example 6, and Compound 6 of Example 7) exhibited significantly improved external quantum efficiency as compared with the monoamine not meeting the requirements of the present invention (Comparative Compound 2 of Comparative Example 3).
A glass substrate of 25 mm×75 mm×1.1 mm provided with an ITO transparent electrode (anode) (manufactured by GEOMATEC Co., Ltd.) was ultrasonically cleaned in isopropyl alcohol for 5 minutes and then subjected to UV ozone cleaning for 30 minutes. The film thickness of the ITO was 130 nm.
The cleaned glass substrate provided with the transparent electrode was mounted on a substrate holder of a vacuum vapor deposition apparatus, and firstly, Compound HT3 and Compound HA were vapor co-deposited on a surface having the transparent electrode formed thereon, so as to cover the transparent electrode, resulting in a hole injecting layer with a film thickness of 10 nm. The mass ratio of Compound HT3 and Compound HA (HT3:HA) was 97:3.
Subsequently, on the hole injecting layer, Compound HT3 was vapor deposited to form a first hole transporting layer with a film thickness of 80 nm.
Subsequently, on the first hole transporting layer, Compound 1 was vapor deposited to form a second hole transporting layer with a film thickness of 10 nm.
Subsequently, on the second hole transporting layer, Compound BH (host material) and Compound BD (dopant material) were vapor co-deposited to form a light emitting layer with a film thickness of 25 nm. The mass ratio of Compound BH and Compound BD (BH:BD) was 96:4.
Subsequently, on the light emitting layer, Compound ET1 was vapor deposited to form a first electron transporting layer with a film thickness of 5 nm.
Subsequently, on the first electron transporting layer, Compound ET2 and Liq were vapor co-deposited to form a second electron transporting layer with a film thickness of 20 nm. The mass ratio of Compound ET2 and Liq (ET2:Liq) was 50:50.
Subsequently, on the second electron transporting layer, LiF was vapor deposited to form an electron injecting electrode with a film thickness of 1 nm.
Then, on the electron injecting electrode, metal Al was vapor deposited to form a metal cathode with a film thickness of 50 nm.
The layer structure of the organic EL element of Example 8 thus obtained is shown as follows.
Hereinafter, the layer structure above may be referred to as “layer structure 3”.
As shown in Table 3 below, an organic EL element having the layer structure 3 was produced in the same manner as in Example 8 except that the material for the second hole transporting layer was changed to Compounds 7 and 8.
An organic EL element having the layer structure 3 was produced in the same manner as in Example 8 except that the material for the second hole transporting layer was changed to Comparative Compounds 3 and 4, as shown in Table 3 below.
The obtained organic EL element was driven at room temperature with a direct current constant current at a current density of 10 mA/cm2, and the luminance was measured using a spectral radiance meter “CS-1000” (manufactured by Konica Minolta, Inc.). An external quantum efficiency (%) was determined from the measurement results. The results are shown in Table 3.
As apparent from the results in Table 3, the monoamines meeting the requirements of the present invention (Compound 1 of Example 8, Compound 7 of Example 9, and Compound 8 of Example 10) exhibited significantly improved external quantum efficiency as compared with the monoamines not meeting the requirements of the present invention (Comparative Compound 3 of Comparative Example 4 and Comparative Compound 4 of Comparative Example 5).
7.41 g (30 mmol) of 1-bromodibenzofuran, 7.04 g (45 mmol) of 3-chlorophenylboronic acid, 693 mg (0.60 mmol) of tetrakis(triphenylphosphine) palladium (0), and 100 mL of DME were mixed, and an aqueous solution of 2M sodium hydrogen carbonate was added thereto. The mixture was heated with stirring at 80° C. for 12 hours. After allowing to cool, the mixture was extracted with toluene and the organic layer was dried. Then, the solvent was distilled off under a reduced pressure. The resulting residue was purified by column chromatography to obtain Intermediate B (8.25 g). Yield was 99%.
Under an argon atmosphere, aniline-2,3,4,5,6-d5 (2.19 g, 22.33 mmol), bromobenzene-d5 (3.29 g, 20.3 mmol), tris(dibenzylideneacetone) dipalladium (0) (372 mg, 0.41 mmol), BINAP (506 mg, 0.812 mmol), sodium-t-butoxide (2.15 g, 22.33 mmol) and toluene (200 ml) were added and heated with stirring at 100° C. for 3 hours. After allowing to cool, the residue obtained by filtration was purified by column chromatography to obtain Intermediate C1 (3.59 g). Yield was 99%.
Under an argon atmosphere, the Intermediate C1 (2.9 g, 16.18 mmol) and DMF (55 ml) were mixed and N-bromosuccinimide (5.76 g, 32.4 mmol) was added at 0° C. The organic layer obtained by adding water and ethyl acetate for extraction was distilled off under a reduced pressure to obtain Intermediate C2. The Intermediate C2 was subjected to the next reaction without purification.
Under an argon atmosphere, the Intermediate C2 (6.41 g, 19.12 mmol), 1-naphthylboronic acid (8.22 g, 47.8 mmol), bis(di-t-butyl(4-dimethylaminophenyl)phosphine) dichloropalladium (II) (406 mg, 0.574 mmol), and 1,4-dioxane (100 ml) were mixed, and an aqueous solution of potassium phosphate was added. After heating with stirring at 110° C. for 7 hours and allowing to cool, the mixture was filtered and purified by column chromatography and recrystallization to obtain Intermediate C3 (4.9 g). Yield was 71% (2 steps).
Under an argon atmosphere, a mixture of 6.46 g (20.0 mmol) of 2-(3-bromophenyl)dibenzofuran, 5.11 g (20.0 mmol) of 4-(1-naphthalenyl)benzenamine hydrochloride, 0.366 g (0.40 mmol) of tris(dibenzylideneacetone) dipalladium (0), 0.498 g (0.80 mmol) of BINAP, 4.81 g (50.0 mmol) of sodium-t-butoxide, and 100 mL of toluene was stirred at 100° C. for 7 hours. After the reaction solution was cooled to room temperature, the reaction solution was concentrated under a reduced pressure. The resulting residue was purified by silica gel column chromatography to obtain 5.80 g of white solid (Intermediate D). Yield was 63%.
Intermediate E was synthesized in the same manner as in the synthesis of the Intermediate D except that 4′-(1-naphthalenyl)[1,1′-biphenyl]4-amine was used instead of 4-(1-naphthalenyl)benzenamine hydrochloride and 1-iodonaphthalene was used instead of 2-(3-bromophenyl)dibenzofuran. Yield was 63%.
Intermediate F was synthesized in the same manner as in the synthesis of the Intermediate D except that 1,1′:4′,1″-terphenyl-4-amine was used instead of 4-(1-naphthalenyl)benzenamine hydrochloride. Yield was 69%.
Under an argon atmosphere, the commercially available Intermediate A (2-(3-bromophenyl)dibenzofuran) 3.23 g (10.0 mmol), 4-(naphthalen-1-yl)-N-[4-(naphthalen-1-yl)phenyl]aniline 4.22 g (10.01 mmol), tris(dibenzylideneacetone) dipalladium (0) 180 mg (0.197 mmol), tri-t-butylphosphonium tetrafluoroborate 230 mg (0.793 mmol), sodium-t-pentoside 4.2 mL (40% toluene solution), and toluene 100 mL were mixed and heated under reflux with stirring for 6 hours. After allowing to cool, the mixture was filtered. The solvent of the resulting residue was distilled off and the residue was purified by column chromatography to obtain a white solid (3.78 g). Yield was 57%.
The obtained compound was compound 1 as a result of mass spectrometry analysis (m/e=663 for a molecular weight of 663.26).
Compound 2 was synthesized in the same procedure as in the synthesis of the compound 1 except that the Intermediate B was used instead of the Intermediate A. Yield was 59%.
The obtained compound was compound 2 as a result of mass spectrometry analysis (m/e=663 for a molecular weight of 663.26).
Compound 3 was synthesized in the same procedure as in the synthesis of the compound 1 except that 4-(naphthalen-1-yl)-N-[4-(naphthalen-1-yl)phenyl]aniline was changed to the Intermediate C3. Yield was 60%. The obtained compound was compound 3 as a result of mass spectrometry analysis (m/e=671 for a molecular weight of 671.87).
Under an argon atmosphere, a mixture of 4.88 g (10.0 mmol) of the Intermediate F, 3.11 g (11.0 mmol) of 1-(4-bromophenyl)naphthalene, 0.183 g (0.20 mmol) of tris(dibenzylideneacetone) dipalladium (0), 0.232 g (0.80 mmol) of tri-t-butylphosphonium tetrafluoroborate, 1.44 g (15.0 mmol) of sodium-t-butoxide, and 100 mL of xylene was stirred at 110° C. for 7 hours. After the reaction solution was cooled to room temperature, the reaction solution was concentrated under a reduced pressure. The resulting residue was purified by silica gel column chromatography and recrystallization to obtain a white solid (3.13 g). Yield was 46%.
The obtained compound was compound 4 as a result of mass spectrometry analysis (m/e=689 for a molecular weight of 689.86).
Compound 5 was synthesized in the same manner as in the synthesis of the compound 4 except that the Intermediate D was used instead of the Intermediate F and 9-(4-bromophenyl)phenanthrene was used instead of 1-(4-bromophenyl)naphthalene. Yield was 78%.
The obtained compound was compound 5 as a result of mass spectrum analysis (m/e=713 for a molecular weight of 713.88).
Compound 6 was synthesized in the same manner as in the synthesis of the compound 4 except that 4-(4-dibenzofuranyl)-[4-(1-naphthalenyl)phenyl]benzenamine was used instead of the Intermediate F and the Intermediate B was used instead of 1-(4-bromophenyl)naphthalene. Yield was 43%.
The obtained compound was compound 6 as a result of mass spectrum analysis (m/e=703 for a molecular weight of 703.84).
Compound 7 was synthesized in the same manner as in the synthesis of the compound 4 except that the Intermediate E was used instead of the Intermediate F and the Intermediate B was used instead of 1-(4-bromophenyl)naphthalene. Yield was 59%.
The obtained compound was compound 7 as a result of mass spectrometry analysis (m/e=663 for molecular weight 663.82).
Compound 8 was synthesized in the same manner as in the synthesis of the compound 4 except that N-[1,1′-biphenyl]-4-yl-4′-(1-naphthalenyl)[1,1′-biphenyl]-4-amine was used instead of the Intermediate F and 2-(3-bromophenyl)dibenzofuran was used instead of 1-(4-bromophenyl)naphthalene. Yield was 37%.
The obtained compound was compound 8 as a result of mass spectrometry analysis (m/e=689 for a molecular weight of 689.86).
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-197450 | Nov 2020 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2021/043365 | 11/26/2021 | WO |
