Patent Application
20230200222
The present disclosure relates to a compound, a material for organic electroluminescent devices, an organic electroluminescent device, and an electronic device including the organic luminescent device.
In general, an organic electroluminescent device (which may be hereinafter referred to as an “organic EL device”) 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 the 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 providing a high-performance organic EL device.
PTLs 1 to 13 describe compounds used for a material for organic electroluminescent devices.
Various compounds for organic EL devices have been reported, but a compound that further enhances the capability of an organic EL device has been still demanded.
The present disclosure has been made for solving the problem, and an object thereof is to provide a compound that further improves the capability of an organic EL device, an organic EL device having a further improved device capability, and an electronic device including the organic EL device.
As a result of the continued investigations by the present inventors on the capabilities of organic EL devices containing the compounds described in the above-mentioned patent publications and another compounds, it has been found that a monoamine represented by the following formula (1) can provide an organic EL device having a further improved capability.
In one embodiment, the present disclosure relates to the following [1] to [25].
[1] A compound represented by the following formula (1):
wherein
Ar1 and Ar2 each independently represent a group represented by any of the following formulae (10) to (14):
wherein
R11 to R15, R21 to R26, R41 to R48, R51 to R62 and R71 to R78 each independently represent a hydrogen atom, 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, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms,
R31 to R35 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, unsubstituted cycloalkyl group having 3 to 6 ring carbon atoms, a halogen atom, a cyano group, a nitro group, an unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms,
X represents an oxygen atom, a sulfur atom, or NR81,
R81 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms,
provided that,
one selected from R11 to R15 is a single bond bonding to *c,
one selected from R21 to R26 is a single bond bonding to *d, the other one selected from R21 to R26 is a single bond bonding to *e,
one selected from R45 to R48 is a single bond bonding to *f,
one selected from R59 to R62 is a single bond bonding to *g,
one selected from R75 to R78 and R81 is a single bond bonding to *i,
*h bonds to one selected from the carbon atoms *4 to *8,
** represents a bonding position to the central nitrogen atom,
m is 0 or 1, n is 0 or 1,
in the formulae (10) to (12) and the formula (14), when m is 0 and n is 0, *e bonds to the central nitrogen atom, when m is 0 and n is 1, *c bonds to the central nitrogen atom, and when m is 1 and n is 0, *e bonds to one selected from R11 to R15,
in the formula (13), when m is 0 and n is 1, *c bonds to the central nitrogen atom, when m is 1 and n is 0, *e bonds to one selected from R11 to R15, a case where m is 0 and n is 0 is excluded,
in the formula (14), when m is 0 and n is 1, and when m is 1 and n is 0, one selected from R75 to R78 is a single bond bonding to *i,
adjacent two selected from R11 to R15 that are not a single bond, adjacent two selected from R21 to R26 and adjacent two selected from R31 to R35 that are not a single bond, adjacent two selected from R41 to R48 that are not a single bond, adjacent two selected from R51 to R62 that are not a single bond, and adjacent two selected from R71 to R78 that are not a single bond do not bond to each other and therefore do not form a cyclic structure,
the benzene ring A and the benzene ring B, the benzene ring A and the benzene ring C, the benzene ring B and the benzene ring C, the benzene ring A and the naphthalene ring, and the benzene ring B and the naphthalene ring do not crosslink,
*a bonds to one selected from the carbon atoms *1 to *3,
R1 to R4 each independently represent a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
provided that,
one selected from R1 to R4 is a single bond bonding to *b,
adjacent two selected from R1 to R4 that are not a single bond bonding to *b do not bond to each other and therefore do not form a cyclic structure,
R5 to R9 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted phenyl group,
provided that,
adjacent two selected from R5 to R9 each independently may bond to each other to form a substituted or unsubstituted cyclic structure, or may not bond to each other and therefore may not form a cyclic structure.
[2] The compound of [1], wherein Ar1 and Ar2 each are independently a group represented by any of the formulae (20) to (24):
wherein
R11 to R15, R21, R22, R24, R25, R31 to R35, R41 to R48, R51 to R62, R71 to R78, *f, *g, *h, *i, X, **, m, n, the benzene ring A, the benzene ring B and the benzene ring C are as defined in the formula (1).
[3] The compound of [1] or [2], wherein
R45 or R46 is a single bond bonding to *f,
R60 or R61 is a single bond bonding to *g, and
*h bonds to the carbon atom *8.
[4] The compound of any one of [1] to [3], wherein in the formulae (10) to (12) and the formula (14). m is 0 and n is 0.
[5] The compound of any one of [1] to [3], wherein m is 1 and n is 1.
[6] The compound of any one of [1] to [3], wherein m is 0 and n is 1.
[7] The compound of any one of [1] to [6], wherein Ar1 and Ar2 each are independently a group represented by any of the formulae (10), (11) and (14).
[8] The compound of any one of [1] to [7], wherein at least one of Ar1 and Ar2 is a group represented by the formula (11).
[9] The compound of any one of [1] to [8], wherein X is an oxygen atom.
[10] The compound of any one of [1] to [9], wherein R45 is a single bond bonding to *f.
[11] The compound of any one of [1] to [10], wherein R75 is a single bond bonding to *i.
[12] The compound of any one of [1] to [11], wherein *a bonds to the carbon atom *3.
[13] The compound of any one of [1] to [12], wherein R2 or R3 is a single bond bonding to *b.
[14] The compound of any one of [1] to [13], wherein R1 to R4 that are not a single bond bonding to *b are all hydrogen atoms.
[15] The compound of any one of [1] to [14], wherein R5 to R9 are all hydrogen atoms.
[16] The compound of any one of [1] to [15], wherein the compound contains at least one deuterium.
[17] A material for an organic electroluminescent device containing the compound of any one of [1] to [16].
[18] An organic electroluminescent device comprising an anode, a cathode, and organic layers intervening between the anode and the cathode, the organic layers including a light emitting layer, at least one layer of the organic layers containing the compound of any one of [1] to [16].
[19] The organic electroluminescent device of [18], wherein the organic layer includes a hole transporting zone between the anode and the light emitting layer, and the hole transporting zone contains the compound.
[20] The organic electroluminescent device of [19], wherein the hole transporting zone includes a first hole transporting layer on the anode side and a second hole transporting layer on the cathode side, and the first hole transporting layer or the second hole transporting layer or both the two contain the compound.
[21] The organic electroluminescent device of [20], wherein the second hole transporting layer contains the compound.
[22] The organic electroluminescent device of [20] or [21], wherein the second hole transporting layer is adjacent to the light emitting layer.
[23] The organic electroluminescent device of any one of [18] to [22], wherein the light emitting layer contains a fluorescent dopant.
[24] The organic electroluminescent device of any one of [18] to [22], wherein the light emitting layer contains a phosphorescent dopant.
[25] An electronic device comprising the organic electroluminescent device of any one of [18] to [24].
In one embodiment, the present disclosure provides a compound represented by the following formula (1):
wherein
In another embodiment, Ar1 is a group represented by the formula (10) or (11), and Ar2 is a group represented by any of the formulae (10) to (14):
wherein
R11 to R15, R21 to R26, R41 to R48, R51 to R62 and R71 to R78 each independently represent a hydrogen atom, 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, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms,
R31 to R35 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, unsubstituted cycloalkyl group having 3 to 6 ring carbon atoms, a halogen atom, a cyano group, a nitro group, an unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms,
X represents an oxygen atom, a sulfur atom, or NR81,
R81 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms,
provided that,
one selected from R11 to R15 is a single bond bonding to *c,
one selected from R21 to R26 is a single bond bonding to *d, the other one selected from R21 to R26 is a single bond bonding to *e,
one selected from R45 to R48 is a single bond bonding to *f,
one selected from R59 to R62 is a single bond bonding to *g,
one selected from R75 to R78 and R81 is a single bond bonding to *i,
*h bonds to one selected from the carbon atoms *4 to *8,
** represents a bonding position to the central nitrogen atom,
m is 0 or 1, n is 0 or 1,
in the formulae (10) to (12) and the formula (14), when m is 0 and n is 0, *e bonds to the central nitrogen atom, when m is 0 and n is 1, *c bonds to the central nitrogen atom, and when m is 1 and n is 0, *e bonds to one selected from R11 to R15,
in the formula (13), when m is 0 and n is 1, *c bonds to the central nitrogen atom, when m is 1 and n is 0, *e bonds to one selected from R11 to R15, a case where m is 0 and n is 0 is excluded,
in the formula (14), when m is 0 and n is 1, and when m is 1 and n is 0, one selected from R75 to R78 is a single bond bonding to *i,
adjacent two selected from R11 to R15 that are not a single bond, adjacent two selected from R21 to R26 and adjacent two selected from R31 to R35 that are not a single bond, adjacent two selected from R41 to R48 that are not a single bond, adjacent two selected from R51 to R62 that are not a single bond, and adjacent two selected from R71 to R78 that are not a single bond do not bond to each other and therefore do not form a cyclic structure,
the benzene ring A and the benzene ring B, the benzene ring A and the benzene ring C, the benzene ring B and the benzene ring C, the benzene ring A and the naphthalene ring, and the benzene ring B and the naphthalene ring do not crosslink,
*a bonds to one selected from the carbon atoms *1 to *3,
R1 to R4 each independently represent a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
provided that,
one selected from R1 to R4 is a single bond bonding to *b,
adjacent two selected from R1 to R4 that are not a single bond bonding to *b do not bond to each other and therefore do not form a cyclic structure,
R5 to R9 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted phenyl group,
provided that,
adjacent two selected from R5 to R9 each independently may bond to each other to form a substituted or unsubstituted cyclic structure, or may not bond to each other and therefore may not form a cyclic structure.
In still another embodiment, the present disclosure provides a material for an organic EL device containing the compound represented by the formula (1).
In still another embodiment, the present disclosure provides an organic electroluminescent device including an anode, a cathode, and organic layers intervening between the anode and the cathode, 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 a further embodiment, the present disclosure provides an electronic device including the organic electroluminescent device.
An organic EL device containing the compound represented by the formula (1) shows an improved device capability.
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.
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 benzanthryl group,
a phenanthryl group,
a benzophenanthryl group,
a phenarenyl group,
a pyrenyl group,
a chrysenyl group,
a benzochrysenyl group,
a triphenylenyl group,
a benzotriphenylenyl group,
a tetracenyl group,
a pentacenyl group,
a fluorenyl group,
a 9,9′-spirobifluorenyl group,
a benzofluorenyl group,
a dibenzofluorenyl group,
a fluoranthenyl group,
a benzofluoranthenyl group,
a perylenyl group, and
monovalent aryl groups derived by removing one hydrogen atom from each of the ring structures represented by the following general formulae (TEMP-1) to (TEMP-15):
an o-tolyl group,
a m-tolyl group,
a p-tolyl group,
a p-xylyl group,
a m-xylyl group,
an o-xylyl group,
a p-isopropylphenyl group,
a m-isopropylphenyl group,
an o-isopropylphenyl group,
a p-t-butylphenyl group,
a m-t-butylphenyl group,
a o-t-butylphenyl group,
a 3,4,5-trimethylphenyl group,
a 9,9-dimethylfluorenyl group,
a 9,9-diphenylfluorenyl group,
a 9,9-bis(4-methylphenyl)fluorenyl group,
a 9,9-bis(4-isopropylphenyl)fluorenyl group,
a 9,9-bis(4-t-butylphenyl)fluorenyl group,
a cyanophenyl group,
a triphenylsilylphenyl group,
a trimethylsilylphenyl group,
a phenylnaphthyl group,
a naphthylphenyl group, and
groups formed by substituting one or more hydrogen atom of each of monovalent aryl groups derived from the ring structures represented by the general formulae (TEMP-1) to (TEMP-15) 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).
a pyrrolyl group,
an imidazolyl group,
a pyrazolyl group,
a triazolyl group,
a tetrazolyl group,
an oxazolyl group,
an isoxazolyl group,
an oxadiazolyl group,
a thiazolyl group,
an isothiazolyl group,
a thiadiazolyl group,
a pyridyl group,
a pyridazinyl group,
a pyrimidinyl group,
a pyrazinyl group,
a triazinyl group,
an indolyl group,
an isoindolyl group,
an indolizinyl group,
a quinolizinyl group,
a quinolyl group,
an isoquinolyl group,
a cinnolinyl group,
a phthalazinyl group,
a quinazolinyl group,
a quinoxalinyl group,
a benzimidazolyl group,
an indazolyl group,
a phenanthrolinyl group,
a phenanthridinyl group,
an acridinyl group,
a phenazinyl group,
a carbazolyl group,
a benzocarbazolyl group,
a morpholino group,
a phenoxazinyl group,
a phenothiazinyl group,
an azacarbazolyl group, and
a diazacarbazolyl group.
a furyl group,
an oxazolyl group,
an isoxazolyl group,
an oxadiazolyl group,
a xanthenyl group,
a benzofuranyl group,
an isobenzofuranyl group,
a dibenzofuranyl group,
a naphthobenzofuranyl group,
a benzoxazolyl group,
a benzisoxazolyl group,
a phenoxazinyl group,
a morpholino group,
a dinaphthofuranyl group,
an azadibenzofuranyl group,
a diazadibenzofuranyl group,
an azanaphthobenzofuranyl group, and
a diazanaphthobenzofuranyl group.
a thienyl group,
a thiazolyl group,
an isothiazolyl group,
a thiadiazolyl group,
a benzothiophenyl group (benzothienyl group),
an isobenzothiophenyl group (isobenzothienyl group),
a dibenzothiophenyl group (dibenzothienyl group),
a naphthobenzothiophenyl group (naphthobenzothienyl group),
a benzothiazolyl group,
a benzisothiazolyl group,
a phenothiazinyl group,
a dinaphthothiophenyl group (dinaphthothienyl group),
an azadibenzothiophenyl group (azadibenzothienyl group),
a diazadibenzothiophenyl group (diazadibenzothienyl group),
an azanaphthobenzothiophenyl group (azanaphthobenzothienyl group), and
a diazanaphthobenzothiophenyl group (diazanaphthobenzothienyl group).
Monovalent Heterocyclic Group Derived by Removing One Hydrogen Atom from Ring Structures Represented by General Formulae (TEMP-16) to (TEMP-33) (Set of Specific Examples G2A4)
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.
a (9-phenyl)carbazolyl group,
a (9-biphenylyl)carbazolyl group,
a (9-phenyl)phenylcarbazolyl group,
a (9-naphthyl)carbazolyl group,
a diphenylcarbazol-9-yl group,
a phenylcarbazol-9-yl group,
a methylbenzimidazolyl group,
an ethylbenzimidazolyl group,
a phenyltriazinyl group,
a biphenyltriazinyl group,
a diphenyltriazinyl group,
a phenylquinazolinyl group, and
a biphenylquinazolinyl group.
a phenyldibenzofuranyl group,
a methyldibenzofuranyl group,
a t-butyldibenzofuranyl group, and
a monovalent residual group of spiro[9H-xanthene-9,9′-[9H]fluorene].
a phenyldibenzothiophenyl group,
a methyldibenzothiophenyl group,
a t-butyldibenzothiophenyl group, and
a monovalent residual group of spiro[9H-thioxanthene-9,9′-[9H]fluorene].
Group Formed by Substituting One or More Hydrogen Atom of Monovalent Heterocyclic Group Derived from Ring Structures Represented by General Formulae (TEMP-16) to (TEMP-33) by Substituent (Set of Specific Examples G2B4)
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.
a methyl group,
an ethyl group,
a n-propyl group,
an isopropyl group,
a n-butyl group,
an isobutyl group,
a s-butyl group, and
a t-butyl group.
a heptafluoropropyl group (including isomers),
a pentafluoroethyl group,
a 2,2,2-trifluoroethyl group, and
a trifluoromethyl group.
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.
a vinyl group,
an allyl group,
a 1-butenyl group,
a 2-butenyl group, and
a 3-butenyl group.
a 1,3-butanedienyl group,
a 1-methylvinyl group,
a 1-methylallyl group,
a 1,1-dimethylallyl group,
a 2-methylallyl group, and
a 1,2-dimethylallyl group.
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.
an ethynyl group.
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.
a cyclopropyl group,
a cyclobutyl group,
a cyclopentyl group,
a cyclohexyl group,
a 1-adamantyl group,
a 2-adamantyl group,
a 1-norbornyl group, and
a 2-norbornyl group.
a 4-methylcyclohexyl group.
Group Represented by —Si(R901)(R902)(R903)
In the description herein, specific examples (set of specific examples G7) of the group represented by —Si(R901)(R902)(R903) include:
—Si(G1)(G1)(G1),
—Si(G1)(G2)(G2),
—Si(G1)(G1)(G2),
—Si(G2)(G2)(G2),
—Si(G3)(G3)(G3), and
—Si(G6)(G6)(G6).
Herein,
G1 represents the “substituted or unsubstituted aryl group” described in the set of specific examples G1,
G2 represents the “substituted or unsubstituted heterocyclic group” described in the set of specific examples G2,
G3 represents the “substituted or unsubstituted alkyl group” described in the set of specific examples G3, and
G6 represents the “substituted or unsubstituted cycloalkyl group” described in the set of specific examples G6.
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:
—O(G1),
—O(G2),
—O(G3), and
—O(G6).
Herein,
G1 represents the “substituted or unsubstituted aryl group” described in the set of specific examples G1,
G2 represents the “substituted or unsubstituted heterocyclic group” described in the set of specific examples G2,
G3 represents the “substituted or unsubstituted alkyl group” described in the set of specific examples G3, and
G6 represents the “substituted or unsubstituted cycloalkyl group” described in the set of specific examples G6.
In the description herein, specific examples (set of specific examples G9) of the group represented by —S—(R905) include:
—S(G1),
—S(G2),
—S(G3), and
—S(G6).
Herein,
G1 represents the “substituted or unsubstituted aryl group” described in the set of specific examples G1,
G2 represents the “substituted or unsubstituted heterocyclic group” described in the set of specific examples G2,
G3 represents the “substituted or unsubstituted alkyl group” described in the set of specific examples G3, and
G6 represents the “substituted or unsubstituted cycloalkyl group” described in the set of specific examples G6.
Group Represented by —N(R906)(R907)
In the description herein, specific examples (set of specific examples G10) of the group represented by —N(R906)(R907) include:
—N(G1)(G1),
—N(G2)(G2),
—N(G1)(G2),
—N(G3)(G3), and
—N(G6)(G6).
G1 represents the “substituted or unsubstituted aryl group” described in the set of specific examples G1,
G2 represents the “substituted or unsubstituted heterocyclic group” described in the set of specific examples G2,
G3 represents the “substituted or unsubstituted alkyl group” described in the set of specific examples G3, and
G6 represents the “substituted or unsubstituted cycloalkyl group” described in the set of specific examples G6.
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.
Substituted or Unsubstituted Arylene Group 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 Q9 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 QBformed 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
an unsubstituted alkyl group having 1 to 50 carbon atoms,
an unsubstituted alkenyl group having 2 to 50 carbon atoms,
an unsubstituted alkynyl group having 2 to 50 carbon atoms,
an unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms,
—Si(R901)(R902)(R903),
—O—(R904)
—S—(R905),
—N(R906)((R907),
a halogen atom, a cyano group, a nitro group,
an unsubstituted aryl group having 6 to 50 ring carbon atoms, and
an unsubstituted heterocyclic group having 5 to 50 ring atoms,
wherein R901 to R907 each independently represent
a hydrogen atom,
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,
a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or
a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
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 the case where two or more groups each represented by R902 exist, the two or more groups each represented by R902 are the same as or different from each other,
in the case where two or more groups each represented by R903 exist, the two or more groups each represented by R903 are the same as or different from each other,
in the case where two or more groups each represented by R904 exist, the two or more groups each represented by R904 are the same as or different from each other,
in the case where two or more groups each represented by R905 exist, the two or more groups each represented by R905 are the same as or different from each other,
in the case where two or more groups each represented by R906 exist, the two or more groups each represented by R906 are the same as or different from each other, and
in the case where two or more groups each represented by R907 exist, the two or more groups each represented by R907 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
an alkyl group having 1 to 50 carbon atoms,
an aryl group having 6 to 50 ring carbon atoms, and
a heterocyclic group having 5 to 50 ring atoms.
In one embodiment, the substituent for the case of “substituted or unsubstituted” may be a group selected from the group consisting of
an alkyl group having 1 to 18 carbon atoms,
an aryl group having 6 to 18 ring carbon atoms, and
a heterocyclic group having 5 to 18 ring atoms.
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 disclosure will be described below.
The compound of the present disclosure is represented by the following formula (1). In the following description, the compounds of the present disclosure represented by the formula (1) and by other formulae to be described below each may be referred simply to as an “inventive compound”.
The symbols in the formula (1) and the formulae described later will be explained below. Unless otherwise specifically noted, the same symbols in the following formulae have the same meanings.
In one embodiment of the present disclosure, Ar1 and Ar2 each independently represent a group represented by any of the following formulae (10) to (14):
R11 to R15, R21 to R26, R41 to R48, R51 to R62 and R71 to R78 each independently represent a hydrogen atom, 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, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
R31 to R35 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 6 ring carbon atoms, a halogen atom, a cyano group, a nitro group, an unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
X represents an oxygen atom, a sulfur atom, or NR81, R81 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
X is preferably an oxygen atom.
R81 is preferably a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, more preferably a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, even more preferably a phenyl group.
However, one selected from R11 to R15 is a single bond bonding to *c, one selected from R21 to R26 is a single bond bonding to *d, the other one selected from R21 to R26 is a single bond bonding to *e, one selected from R45 to R48 is a single bond bonding to *f, one selected from R59 to R62 is a single bond bonding to *g, one selected from R75 to R78 and R81 is a single bond bonding to *i, *h bonds to one selected from the carbon atoms *4 to *8.
R45 or R46 is preferably a single bond bonding to *f, and more preferably R45 is a single bond bonding to *f.
R60 or R61 is preferably a single bond bonding to *g.
In one embodiment of the present disclosure, preferably, R75 to R78 are a single bond bonding to *i, and more preferably R75 is a single bond bonding to *i.
In another embodiment of the present disclosure where m is 0 and n is 0 or where m is 1 and n is 1, preferably, R81 is a single bond bonding to *i.
*h preferably bonds to the carbon atom *8.
adjacent two selected from R11 to R15 that are not a single bond, adjacent two selected from R21 to R26 and adjacent two selected from R31 to R35 that are not a single bond, adjacent two selected from R41 to R48 that are not a single bond, adjacent two selected from R51 to R62 that are not a single bond, and adjacent two selected from R71 to R78 that are not a single bond do not bond to each other and therefore do not form a cyclic structure.
R11 to R15 that are not a single bond can be all hydrogen atoms, R21 to R26 that are not a single bond can be all hydrogen atoms, R31 to R35 can be all hydrogen atoms, R41 to R48 that are not a single bond can be all hydrogen atoms, R51 to R62 that are not a single bond can be all hydrogen atoms, and R71 to R78 that are not a single bond can be all hydrogen atoms.
** represents a bonding position to the central nitrogen atom, m is 0 or 1, n is 0 or 1.
In the formulae (10) to (12) and the formula (14), when m is 0 and n is 0, *e bonds to the central nitrogen atom, when m is 0 and n is 1, *c bonds to the central nitrogen atom, and when m is 1 and n is 0, *e bonds to one selected from R11 to R15.
In the formula (13), when m is 0 and n is 1, *c bonds to the central nitrogen atom, when m is 1 and n is 0, *e bonds to one selected from R11 to R15, a case where m is 0 and n is 0 is excluded.
In the formula (14), when m is 0 and n is 1, and when m is 1 and n is 0, one selected from R75 to R78 is a single bond bonding to *i.
In one embodiment of the present disclosure, in the formulae (10) to (12) and the formula (14), m is 0 and n is 0. In another embodiment of the present disclosure, in the formulae (10) to (13) and (14), m is 1 and n is 1. In still another embodiment, in the formulae (10) to (13) and (14), m is 0 and n is 1. In still another embodiment, in the formulae (10) to (13), m is 0 and n is 1.
The benzene ring A and the benzene ring B, the benzene ring A and the benzene ring C, the benzene ring B and the benzene ring C, the benzene ring A and the naphthalene ring, and the benzene ring B and the naphthalene ring do not crosslink.
In another embodiment of the present disclosure, Ar1 is a group represented by the formula (10) or (11), and Ar2 is a group represented by any of the formulae (10) to (14).
The group represented by the formula (10) is preferably a substituted or unsubstituted group selected from the following formulae.
wherein arbitrary groups are omitted.
The group represented by the formula (11) is preferably a substituted or unsubstituted group selected from the following formulae.
wherein arbitrary groups are omitted.
The group represented by the formula (12) is preferably a substituted or unsubstituted group selected from the following formula.
wherein arbitrary groups are omitted.
The group represented by the formula (13) is preferably a substituted or unsubstituted group selected from the following formulae.
wherein arbitrary groups are omitted.
In one embodiment of the present disclosure, the group represented by the formula (14) is preferably a group represented by the following formula (14-1).
In another embodiment of the present disclosure, the group represented by the formula (14) is preferably a group represented by the following formula (14-2).
wherein
R11 to R15, R21 to R26, R71 to R78, *c, *d, *e, X, **, m, n, the benzene ring A and the benzene ring B are as defined in the formula (1),
one selected from R75 to R78 is a single bond bonding to *j.
In the formula (14-1), R75 is preferably a single bond bonding to *i.
In one embodiment of the present disclosure, the group represented by the formula (14) is preferably a group represented by the following formula (14-1-1).
wherein
R11 to R15, R71 to R78, *c, X, **, m and the benzene ring A are as defined in the formula (1),
one selected from R75 to R78 is a single bond bonding to *j.
In the formula (14-1-1), R75 is preferably a single bond bonding to *i.
The group represented by the formula (14) is preferably a substituted or unsubstituted group selected from the following formulae.
wherein arbitrary groups are omitted.
Preferably, Ar1 and Ar2 each are independently a group represented by any of the formulae (10), (11) and (14), and more preferably, at least one of Ar1 and Ar2 is a group represented by the formula (11).
In one embodiment of the present disclosure, in the formula (10), preferably, m is 0 and n is 0, and R31 to R35 are hydrogen atoms.
In another embodiment of the present disclosure, in the formula (10), preferably, m is 0 and n is 1, and R31 to R35 are hydrogen atoms.
In still another embodiment of the present disclosure, in the formula (10), preferably, m is 0 and n is 1, and R21 to R26 that are not a single bond each are a hydrogen atom or a phenyl group, and R31 to R35 are hydrogen atoms.
In still another embodiment of the present disclosure, in the formula (10), preferably, m is 1 and n is 0, and R31 to R35 are hydrogen atoms.
In still another embodiment of the present disclosure, in the formula (10), preferably, m is 1 and n is 0, and R11 to R15 that are not a single bond each are a hydrogen atom or a phenyl group, and R31 to R35 are hydrogen atoms.
In still another embodiment, in the formula (11), preferably, m is 0 and n is 0.
In still another embodiment, in the formula (11), preferably, m is 0 and n is 1.
In still another embodiment, in the formula (11), preferably, m is 1 and n is 0.
Preferably, Ar1 and Ar2 each are independently a group represented by any of the formulae (20) to (24).
wherein
R11 to R15, R21, R22, R24, R25, R31 to R35, R41 to R48, R51 to R62, R71 to R78, *f, *g, *h, *i, X, **, m, n, the benzene ring A, the benzene ring B and the benzene ring C are as defined in the formula (1).
More preferably, Ar1 and Ar2 each are independently a group represented by the formula (20) or (21).
wherein
R11 to R15, R21, R22, R24, R25, R31 to R35, R41 to R48, *, m, n, the benzene ring A, the benzene ring B and the benzene ring C are as defined in the formula (1).
In one embodiment of the present disclosure, in the formulae (20) to (22) and (24), m is 0 and n is 0. In another embodiment of the present disclosure, in the formulae (20) to (24), m is 1 and n is 1. In still another embodiment, in the formulae (20) to (24), m is 0 and n is 1.
In one embodiment of the present disclosure, the group represented by the formula (24) is preferably a group represented by the formula (24-1).
In another embodiment of the present disclosure, the group represented by the formula (24) is preferably a group represented by the formula (24-2).
wherein
R11, R12, R14, R15, R21, R22, R24, R25, R71 to R78, X, *, m, n, the benzene ring A and the benzene ring B are as defined in the formula (1),
one selected from R75 to R78 is a single bond bonding to *j.
In the formula (24-1), R75 is preferably a single bond bonding to *i.
In one embodiment of the present disclosure, the group represented by the formula (24) is preferably a group represented by the formula (24-1-1).
wherein
R11, R12, R14, R15, R71 to R78, X, **, m, and the benzene ring A are as defined in the formula (1),
one selected from R75 to R78 is a single bond bonding to *j.
*a bonds to one selected from the carbon atoms *1 to *3.
*a preferably bonds to the carbon atom *2 or *3, and more preferably bond so *3.
R1 to R4 each independently represent a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms.
However, one selected from R1 to R4, preferably R2 and R3 are a single bond bonding to *b.
Adjacent two selected from R1 to R4 that are not a single bond bonding to *b do not bond to each other and therefore do not form a cyclic structure.
R1 to R4 not a single bond bonding to *b can be all hydrogen atoms.
R5 to R9 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted phenyl group.
However, adjacent two selected from R5 to R9 each independently may bond to each other to form a substituted or unsubstituted cyclic structure, or may not bond to each other and therefore may not form a cyclic structure.
In the case where two selected from R5 to R9 each independently bond to each other to form a substituted or unsubstituted cyclic structure, the following formulae are preferred.
R5 to R9 can be all hydrogen atoms.
Preferably, Ar1 and Ar2 each are independently a substituted or unsubstituted group represented by the following formulae.
wherein arbitrary groups are omitted.
Details of the substituted or unsubstituted alkyl group having 1 to 50 carbon atoms that are described for the definition of the formulae mentioned above are as described in the section of “Substituents in Description” described above.
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, a t-butyl group, or an n-pentyl group, more preferably a methyl group, an ethyl group, an isopropyl group, or a t-butyl group, even more preferably a methyl group or a t-butyl group.
Details of the substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms that are described for the definition of the formulae mentioned above are as described in the section of “Substituents in Description” described above.
The substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms is preferably selected from a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a p-biphenyl group, an 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, an m-terphenyl-4-yl group, an m-terphenyl-3-yl group, an m-terphenyl-2-yl group, an m-terphenyl-3′-yl group, an o-terphenyl-4-yl group, an o-terphenyl-3-yl group and an o-terphenyl-2-yl group.
Details of the arbitrary substituted or unsubstituted cyclic structure that adjacent two form, as described for the definition of the formulae mentioned above, are as described in the section of “Substituents in Description” described above, and is selected from a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aliphatic hydrocarbon ring, a substituted or unsubstituted aromatic hetero ring, and a substituted or unsubstituted nonaromatic hetero ring.
Examples of the aromatic hydrocarbon ring include a benzene ring, a biphenylene ring, a naphthalene ring, and a fluorene ring, and a naphthalene ring and a fluorene ring are preferred.
Examples of the aliphatic hydrocarbon ring include a cyclopentene ring, a cyclopentadiene ring, a cyclohexene ring, a cyclohexadiene ring, and a hydrocarbon ring formed by partially hydrogenating the above-mentioned aromatic hydrocarbon ring.
Examples of the aromatic hetero ring include a pyrrole ring, a furan ring, a thiophene ring, a pyridine ring, an imidazole ring, a pyrazole ring, an indole ring, an isoindole ring, a benzofuran ring, an isobenzofuran ring, a benzothiophene ring, a benzimidazole ring, an indazole ring, a dibenzofuran ring, a naphthobenzofuran ring, a dibenzothiophene ring, a naphthobenzothiophene ring, a carbazole ring, and a benzocarbazole ring, and a dibenzofuran ring, a dibenzothiophene ring and a carbazole ring are preferred.
Examples of the nonaromatic heterocyclic group include a hetero ring formed by partially hydrogenating the above-mentioned aromatic hetero ring.
In the case where the group in the definition of the formulae mentioned above has an arbitrary substituent, details of the arbitrary substituent expressed by “substituted or unsubstituted” are as described for those of the “substituent in the case of ‘substituted or unsubstituted’”. The arbitrary substituent is preferably an alkyl group having 1 to 50 carbon atoms or an aryl group having 6 to 50 ring carbon atoms, and details of the alkyl group and the aryl group are as described above.
The compound represented by the formula (1) is preferably any one selected from the group of the following compounds.
As described above, the “hydrogen atom” referred in the description herein encompasses a protium atom, a deuterium atom, and tritium atom. Accordingly, the inventive compound may contain a naturally-derived deuterium atom.
A deuterium atom may be intentionally introduced into the inventive compound by using a deuterated compound as a art or the whole of the raw material. Accordingly, in one embodiment of the present disclosure, 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:
a hydrogen atom that any of R1 to R4 represents; a hydrogen atom that the substituted or unsubstituted alkyl group of any of R1 to R4 has;
a hydrogen atom that any of R5 to R9 represents; a hydrogen atom that the substituted or unsubstituted alkyl group or the substituted or unsubstituted phenyl group of any of R5 to R9 has;
a hydrogen atom that any of R11 to R15, R21 to R26, R31 to R35, R41 to R48, R51 to R62 and R71 to R78 represents; a hydrogen atom that the substituted or unsubstituted alkyl group, the substituted or unsubstituted cycloalkyl group, the substituted or unsubstituted aryl group or the substituted or unsubstituted heterocyclic group of any of R11 to R15, R21 to R26, R31 to R35, R41 to R48, R51 to R62 and R71 to R78 has;
a hydrogen atom that R81 represents; a hydrogen atom that the substituted or unsubstituted alkyl group, the substituted or unsubstituted aryl group or the substituted or unsubstituted heterocyclic group of R81 has;
a hydrogen atom that the phenylene group bonding to the central nitrogen atom specified on the formula (1) has (that is, a hydrogen atom that the ring D in the following formula (1D) has); and
a hydrogen atom that an unsubstituted phenylene group not bonding to the central nitrogen atom specified on the formula (1) has (that is, a hydrogen atom that the ring E in the following formula (1D) has).
In the formula (1D), Ar1, Ar2, R1 to R9, *a, *b and *1 to *3 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 when a raw material having a predetermined deuteration rate is used, a naturally-derived protium isotope can be contained in a certain ratio. Accordingly, an embodiment of the deuteration rate of the inventive compound shown below includes the proportion for which a minor amount of a naturally-derived isotope is taken into consideration, relative to the proportion determined by counting the number of the deuterium atoms merely represented by a chemical formula.
The deuteration rate of the inventive compound is preferably 1% or more, more preferably 3% or more, even more preferably 5% or more, further more preferably 10% or more, further more preferably 50% or more.
The inventive compound may be a mixture of 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, even more preferably 5% or more, further more preferably 10% or more, further more preferably 50% or more, and is less than 100%.
The proportion of the number of the deuterium atoms to the number of all the hydrogen atoms in the inventive compound is preferably 1% or more, more preferably 3% or more, even more preferably 5% or more, further more preferably 10% or more, and is 100% or less.
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, but the inventive compound is not limited to the following example compounds.
The material for organic EL devices of the present invention contains the inventive compound. The content of the inventive compound in the material for organic EL devices may be 1% by mass or more (including 100%), and is preferably 10% by mass or more (including 100%), more preferably 50% by mass or more (including 100%), further preferably 80% by mass or more (including 100%), still further preferably 90% by mass or more (including 100%). The material for organic EL devices of the present invention is useful for the production of an organic EL device.
The organic EL device of the present invention includes an anode, a cathode, 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 device, more preferably as a material for the hole transporting zone, further 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 device of the present invention may be a fluorescent or phosphorescent light emission-type monochromatic light emitting device or a fluorescent/phosphorescent hybrid-type white light emitting device, and may be a simple type having a single light emitting unit or a tandem type having a plurality of light emitting units. Above all, the fluorescent light emission-type device is preferred. 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 device configuration of the simple type organic EL device, the following device 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 configurations of the simple type light emitting unit are described below. Layers in parentheses are optional.
(a) (hole injecting layer/) hole transporting layer/fluorescent light emitting layer/electron transporting layer (/electron injecting layer)
(b) (hole injecting layer/) hole transporting layer/phosphorescent light emitting layer/electron transporting layer (/electron injecting layer)
(c) (hole injecting layer/) hole transporting layer/first fluorescent light emitting layer/second fluorescent light emitting layer/electron transporting layer (/electron injecting layer)
(d) (hole injecting layer/) hole transporting layer/first phosphorescent light emitting layer/second phosphorescent light emitting layer/electron transporting layer (/electron injecting layer)
(e) (hole injecting layer/) hole transporting layer/phosphorescent light emitting layer/space layer/fluorescent light emitting layer/electron transporting layer (/electron injecting layer)
(f) (hole injecting layer/) hole transporting layer/first phosphorescent light emitting layer/second phosphorescent light emitting layer/space layer/fluorescent light emitting layer/electron transporting layer (/electron injecting layer)
(g) (hole injecting layer/) hole transporting layer/first phosphorescent light emitting layer/space layer/second phosphorescent light emitting layer/space layer/fluorescent light emitting layer/electron transporting layer (/electron injecting layer)
(h) (hole injecting layer/) hole transporting layer/phosphorescent light emitting layer/space layer/first fluorescent light emitting layer/second fluorescent light emitting layer/electron transporting layer (/electron injecting layer)
(i) (hole injecting layer/) hole transporting layer/electron blocking layer/fluorescent light emitting layer/electron transporting layer (/electron injecting layer)
(j) (hole injecting layer/) hole transporting layer/electron blocking layer/phosphorescent light emitting layer/electron transporting layer (/electron injecting layer)
(k) (hole injecting layer/) hole transporting layer/exciton blocking layer/fluorescent light emitting layer/electron transporting layer (/electron injecting layer)
(l) (hole injecting layer/) hole transporting layer/exciton blocking layer/phosphorescent light emitting layer/electron transporting layer (/electron injecting layer)
(m) (hole injecting layer/) first hole transporting layer/second hole transporting layer/fluorescent light emitting layer/electron transporting layer (/electron injecting layer)
(n) (hole injecting layer/) first hole transporting layer/second hole transporting layer/phosphorescent light emitting layer/electron transporting layer (/electron injecting layer)
(o) (hole injecting layer/) first hole transporting layer/second hole transporting layer/fluorescent light emitting layer/first electron transporting layer/second electron transporting layer (/electron injecting layer)
(p) (hole injecting layer/) first hole transporting layer/second hole transporting layer/phosphorescent light emitting layer/first electron transporting layer/second electron transporting layer (/electron injecting layer)
(q) (hole injecting layer/) hole transporting layer/fluorescent light emitting layer/hole blocking layer/electron transporting layer (/electron injecting layer)
(r) (hole injecting layer/) hole transporting layer/phosphorescent light emitting layer/hole blocking layer/electron transporting layer (/electron injecting layer)
(s) (hole injecting layer/) hole transporting layer/fluorescent light emitting layer/exciton blocking layer/electron transporting layer (/electron injecting layer)
(t) (hole injecting layer/) hole transporting layer/phosphorescent light emitting layer/exciton blocking layer/electron transporting layer (/electron injecting layer)
The phosphorescent and fluorescent light emitting layers may emit emission colors different from each other, respectively. Specifically, in the light emitting unit (f), a layer configuration, 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. 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 to improve 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.
As a representative device configuration of the tandem type organic EL device, the following device configuration may be exemplified.
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 can be used, in which electrons are supplied to the first light emitting unit, and holes are supplied to the second light emitting unit.
In the present invention, a host combined with a fluorescent dopant (a fluorescent 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. Specifically, the phosphorescent host means a material that forms a phosphorescent light emitting layer containing a phosphorescent dopant, but 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 device. 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 polycarbonate, polyarylate, polyether sulfone, polypropylene, polyester, polyvinyl fluoride, or polyvinyl chloride. In addition, an inorganic vapor deposition film can be used.
It is preferred that a metal, an alloy, an electrically conductive compound, or 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. Besides, 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), or 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 wt % 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 wt % of tungsten oxide and 0.1 to 1 wt % of zinc oxide with respect to indium oxide. Besides, the manufacturing 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, or mixtures thereof, elements belonging to Group 1 or 2 of the periodic table of the elements). It is also possible to use elements belonging to Group 1 or 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), and 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 except 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, and manganese oxide 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 is added, such as poly(3,4-ethylenedioxythiophene)/poly (styrene sulfonic acid) (PEDOT/PSS), and polyaniline/poly (styrenesulfonic acid) (PAni/PSS), can also be used.
Furthermore, it is also preferred to use an acceptor material, such as a hexaazatriphenylene (HAT) compound represented by formula (K).
In the aforementioned formula, R21 to R26 each independently represent a cyano group, —CONH2, a carboxy group, or —COOR27 (R27 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 R21 and R22, R23 and R24, and R25 and R26 may be bonded to each other to form a group represented by —CO—O—CO—.
Examples of R27 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 can be used as the hole transporting layer either singly or as combined with the compound mentioned below.
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, and an electron blocking layer described later 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 of a two-layer structure, the inventive compound may be in the first hole transporting layer or the second hole transporting layer, or may be in the two.
In one embodiment of the present invention, the inventive compound is preferably contained in the first hole transporting layer alone, and in another embodiment, the inventive compound is preferably contained in the second hole transporting layer alone, and in still 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 protium compound from the viewpoint of production cost.
The protium compound is the inventive compound where all hydrogen atoms are protium atoms.
Accordingly, the present invention includes an organic EL device where one or both of the first hole transporting layer and the second hole transporting layer contain the inventive compound of substantially a protium compound alone. The “inventive compound of substantially a protium compound alone” means that the content ratio of a protium compound relative 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 inclusive of 100%).
As the hole transporting material except the inventive compound, for example, an aromatic amine compound, a carbazole derivative, and an anthracene derivative can be used.
Examples of the aromatic amine compound include 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB) or 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-dimethylfluoren-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′-bifluoren-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 so 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 emitting material or a phosphorescent emitting material can be used as the dopant material. The fluorescent emitting material is a compound that emits light from a singlet excited state, and the phosphorescent emitting material is a compound that emits light from a triplet excited state.
Examples of a blue-based fluorescent 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 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 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 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 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 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).
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 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:
(1) a metal complex, such as an aluminum complex, a beryllium complex, and a zinc complex,
(2) a heterocyclic compound, such as an oxadiazole derivative, a benzimidazole derivative, and a phenanthroline derivative,
(3) a fused aromatic compound, such as a carbazole derivative, an anthracene derivative, a phenanthrene derivative, a pyrene derivative, and a chrysene derivative, or
(4) an aromatic amine compound, such as a triarylamine derivative and a fused polycycic aromatic amine derivative.
For example,
metal complexes, such as tris(8-quinolinolato)aluminum(III) (abbreviation: Alq), tris(4-methyl-8-quinolinolato)aluminum(III) (abbreviation: Almq3), bis(10-hydroxybenzo[h]quinolinato)beryllium(II) (abbreviation: BeBq2), bis(2-methyl-8-quinolinolato)(4-phenylphenolato)aluminum(III) (abbreviation: BAlq), bis(8-quinolinolato)zinc(II) (abbreviation: Zng), bis[2-(2-benzoxazolyl)phenolato]zinc(II) (abbreviation: ZnPBO), and bis[2-(2-benzothiazolyl)phenolato]zinc(II) (abbreviation: ZnBTZ);
heterocyclic compounds, such as 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-biphenylyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole (abbreviation: TAZ), 2,2′,2″-(1,3,5-benzenetriyl)tris(1-phenyl-1H-benzimidazole) (abbreviation: TPBI), bathophenanthroline (abbreviation: BPhen), and bathocuproine (abbreviation: BCP);
fused aromatic compounds, such as 9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (abbreviation: CzPA), 3,6-diphenyl-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (abbreviation: DPCzPA), 9,10-bis(3,5-diphenylphenyl)anthracene (abbreviation: DPPA), 9,10-di(2-naphthyl)anthracene (abbreviation: DNA), 2-tert-butyl-9,10-di(2-naphthyl)anthracene (abbreviation: t-BuDNA), 9,9′-bianthryl(abbreviation: BANT), 9,9′-(stilbene-3,3′-diyl)diphenanthrene (abbreviation: DPNS), 9,9′-(stilbene-4,4′-diyl)diphenanthrene (abbreviation: DPNS2), 3,3′,3″-(benzene-1,3,5-triyl)tripyrene (abbreviation: TPB3), 9,10-diphenylanthracene (abbreviation: DPAnth), and 6,12-dimethoxy-5,11-diphenylchrysene; and
aromatic amine compounds, such as N,N-diphenyl-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole-3-amine (abbreviation: CzA1PA), 4-(10-phenyl-9-anthryl)triphenylamine (abbreviation: DPhPA), N,9-diphenyl-N-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole-3-amine (abbreviation: PCAPA), N,9-diphenyl-N-{4-[4-(10-phenyl-9-anthryl)phenyl]phenyl}-9H-carbazole-3-amine (abbreviation: PCAPBA), N-(9,10-diphenyl-2-anthryl)-N,9-diphenyl-9H-carbazole-3-amine (abbreviation: 2PCAPA), 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB or α-NPD), N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (abbreviation: TPD), 4,4′-bis[N-(9,9-dimethylfluoren-2-yl)-N-phenylamino]biphenyl (abbreviation: DFLDPBi), and 4,4′-bis[N-(spiro-9,9′-bifluoren-2-yl)-N-phenylamino]biphenyl (abbreviation: BSPB) can be used. A plurality of host materials may be used.
In particular, in the case of a blue fluorescent device, it is preferred 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, and a hole blocking layer described later 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.
As the electron transporting layer, for example,
(1) a metal complex, such as an aluminum complex, a beryllium complex, and a zinc complex;
(2) a heteroaromatic compound, such as an imidazole derivative, a benzimidazole derivative, an azine derivative, a carbazole derivative, and a phenanthroline derivative; and
(3) a high-molecular weight compound can be used.
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: BeBq2), 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), and bis[2-(2-benzothiazolyl)phenolato]zinc(II) (abbreviation: ZnBTZ).
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 so 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. As the electron injecting layer, 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. 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. 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, examples thereof include a material constituting the aforementioned electron transporting layer (such as a metal complex and a heteroaromatic compound). 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 preferred that a metal, an alloy, an electrically conductive compound, or 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 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), and alloys containing these (such as MgAg, and AlLi), and 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 adopted. In addition, when a silver paste or the like is used, a coating method, an inkjet method, or the like can be adopted.
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. Such a conductive material can be deposited by using a sputtering method, an inkjet method, a spin coating method, or the like.
The organic EL device 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 this, 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 stacked. The space layer can also be provided among the 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 preferred. Also, one having a triplet energy of 2.6 eV or more is preferred in order to prevent triplet energy diffusion in the adjacent phosphorescent light emitting layer. Examples of the material used for the space layer include the same as those used for the hole transporting layer as described above.
The blocking layer such as the electron blocking layer, the hole blocking layer, or 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 device may be formed by a conventionally known vapor deposition method, a coating method, or the like. For example, formation can be performed by a known method using a vapor deposition method such as a vacuum vapor deposition method, or a molecular beam vapor deposition method (MBE method), or a coating method using a solution of a compound for 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 device can be used for electronic devices, such as display components of an organic EL panel module, display devices of a television, a mobile phone and a personal computer, and light emitting devices of lightings and vehicular lamps.
The present disclosure is hereunder described in more detail by reference to Examples, but it should be construed that the present disclosure 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 HI1 were vapor co-deposited on the 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 to Compound HI1 (HT1/HI1) was 97/3.
Subsequently, on this hole injecting layer, Compound HT1 was vapor deposited to form a first hole transporting layer with a film thickness of 80 nm.
Subsequently, on this first hole transporting layer, Compound Inv-2 was vapor deposited to form a second hole transporting layer with a film thickness of 10 nm.
Subsequently, on this 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 to Compound BD (BH/BD) was 96/4.
Subsequently, on this light emitting layer, Compound ET1 was vapor deposited to form a first electron transporting layer with a film thickness of 10 nm.
Subsequently, on this first electron transporting layer, Compound ET2 and Liq were vapor co-deposited to form a second electron transporting layer with a film thickness of 15 nm. The mass ratio of Compound ET2 to Liq (Compound ET2/Liq) was 50/50.
Subsequently, on this second electron transporting layer, LiF was vapor deposited to form an electron injecting electrode with a film thickness of 1 nm.
Then, on this electron injecting electrode, metal Al was vapor deposited to form a metal cathode with a film thickness of 80 nm.
The layer configuration of the organic EL device of Example 1 thus obtained was as follows.
ITO (130)/(HT1/HI1=97/3) (10)/HT1 (80)/Compound Inv-2 (10)/(BH/BD=96/4) (25)/ET1 (10)/(ET2/Liq=50/50) (15)/LiF (1)/Al (80)
In the layer configuration, the numeral in parentheses indicates the film thickness (nm), and the ratio is a mass ratio.
An organic EL device was produced in the same manner as in Example 1 except that Comparative Compound Ref-1 was used in place of Compound Inv-2.
Organic EL Devices of Examples 2 to 22 and Comparative Examples 2 to 4 were produced in the same manner as in Example 1, except that Compounds Inv-1, 3 to 22 and Comparative Compounds Ref-2 to 4, respectively, were used in place of Compound Inv-2 and that HT2 was used in place of Compound HT1 in the hole injecting layer and Compound HT1 in the first hole transporting layer.
The resulting organic EL device was emitted by driving at room temperature with DC direct current at a current density of 50 mA/cm2, and the period of time until the luminance was reduced to 90% of the initial luminance was measured, and was defined as 90% lifetime (LT90). The results are shown in Tables 1 and 2.
The resulting organic EL device was driven at room temperature with DC direct current at a current density of 10 mA/cm2. Using a luminance meter (spectral radiance meter CS-1000 by Konica Minolta, Inc.), the luminance of the device was measured, and from the found data, the external quantum efficiency (%) was derived. The results are shown in Table 1.
From the results in Tables 1 and 2, it is known that the organic EL devices containing Inventive Compound (Compound Inv-1 to 22) have a longer lifetime than the organic EL devices containing Reference Compound (Ref-1 to 4), Also from the results in Table 1, it is known that the organic EL device containing Inventive Compound (Compound Inv-2) has a higher light emission efficiency than the organic EL device containing Comparative Compound (Ref-1).
In an argon atmosphere, 85.0 g of 3,4-dibromoaniline, 99.0 g of phenylboronic acid, 7.83 g of tetrakis(triphenylphosphine)palladium(0), 813 ml of an aqueous solution of 2 M sodium carbonate, and 800 ml of 1,2-dimethoxyethane were mixed and stirred at 80° C. for 3 hours. Subsequently, this was extracted with ethyl acetate. The organic layer was dried with anhydrous magnesium sulfate, and then concentrated, and the residue was purified through silica gel column chromatography to give 78.5 g of [1,1′:2′,1″-terphenyl]-4′-amine (Intermediate A). The yield was 94%.
In an argon atmosphere, 25.0 g of (1,1′:2′,1″-terphenyl)-4′-amine and 360 mL of acetonitrile were put in a flask and completely dissolved. To this, 58.2 g of p-toluenesulfonic acid was added, and then set at 0° C. To the mixture, 180 mL of an aqueous solution of 42.3 g of potassium iodide and 14.1 g of sodium nitrite was dropwise added taking 30 minutes. With cooling with ice, this was stirred for 30 minutes, then 600 mL of water was added, and while restoring to room temperature, this was stirred for further 2 hours. Subsequently, the resulting solid was taken out through filtration, and this was dissolved in 500 mL of toluene, and further an aqueous solution of sodium sulfate was added for extraction. The organic layer was dried with anhydrous magnesium sulfate, then concentrated, and washed with hexane to give 29.0 g of 4′-iodo-1,1′:2′,1″-terphenyl (Intermediate B). The yield was 80%.
In an argon atmosphere, 22.5 g of Intermediate B, 9.88 g of 4-chlorophenylboronic acid, 1.34 g of dichlorobis[di-tert-butyl(4-dimethylaminophenyl)phosphine]palladium(II), 60 mL of an aqueous solution of 2 M sodium carbonate, and 240 mL of 1,2-dimethoxyethane were mixed, and stirred at 80° C. for 1.5 hours. Subsequently, water was added, and the precipitated solid was taken out through filtration. The solid was recrystallized with a mixed solvent of toluene and hexane to give 18.3 g of 4′-(4-chlorophenyl)-1,1′:2′1″-terphenyl (Intermediate C). The yield was 85%.
In an argon atmosphere, 3.18 g of N-([1,1′-biphenyl]-4-yl)naphthalene-1-amine, 3.50 g of Intermediate C, 0.188 g of tris(dibenzylideneacetone)dipalladium(0), 0.238 g of tri-t-butylphosphonium tetrafluoroborate, 1.48 g of sodium-t-butoxide and 50 mL of toluene were mixed, and stirred at 110° C. for 5 hours. The reaction mixture was cooled at room temperature, and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography and recrystallization with a mixed solvent of toluene and hexane to give 3.36 g of a white solid. The yield was 55%.
The resulting product was Compound Inv-1 as a result of mass spectrometry (m/e=600 relative to molecular weight 599.78).
In an argon atmosphere, 3.75 g of N-(4-(dibenzo[b,d]furan-4-yl)phenyl)naphthalene-1-amine, 3.25 g of Intermediate C, 0.175 g of tris(dibenzylideneacetone)dipalladium(0), 0.221 g of tri-t-butylphosphonium tetrafluoroborate, 1.38 g of sodium-t-butoxide, and 53 mL of toluene were mixed, and stirred at 110° C. for 4 hours. The reaction mixture was cooled at room temperature, and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography and recrystallization with a mixed solvent of toluene and hexane to give 4.23 g of a white solid. The yield was 64%.
The resulting product was Compound Inv-2 as a result of mass spectrometry (m/e=690 relative to molecular weight 689.86).
In an argon atmosphere, 3.75 g of 1-naphthalene-2,3,4,5,6,7,8-d7-amine, 3.25 g of bromobenzene d5, 0.175 g of tris(dibenzylideneacetone)dipalladium(0), 0.221 g of tri-t-butylphosphonium tetrafluoroborate, 5.24 g of sodium-t-butoxide, and 53 mL of toluene were mixed, and stirred at 110° C. for 4 hours. The reaction mixture was cooled at room temperature, and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography and recrystallization with a mixed solvent of toluene and hexane to give 8.75 g of a white solid, Intermediate D. The yield was 77%.
In an argon atmosphere, 4.99 g of Intermediate D, 6.45 g of N-bromosuccinimide, and 180 mL of dichloromethane (dewatered) were mixed, and stirred at room temperature for 4 hours. Subsequently, 100 mL of water was added, and this was stirred at room temperature for 1 hour. Subsequently, this was extracted with dichloromethane. The organic layer was dried with anhydrous magnesium sulfate, then concentrated, and the residue was purified through silica gel column chromatography and recrystallization with a mixed solvent of toluene and hexane to give 6.78 g of a yellow solid, Intermediate E. The yield was 80%.
In an argon atmosphere, 4.42 g of Intermediate E, 5.39 g of bis(pinacolato)diboron, 0.064 g of palladium(II) acetate, 0.270 g of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (XPhos), 7.55 g of potassium acetate, and 80 ml of 1.4-dioxane (dewatered) were mixed, and stirred at 100° C. for 4 hours. Subsequently, 50 mL of water was added, and this was stirred at room temperature for 1 hour. Subsequently, this was extracted with dichloromethane. The organic layer was dried with anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography to give 6.44 g of a white solid, Intermediate F. The yield was 81%.
In an argon atmosphere, 3.99 g of Intermediate F, 0.74 mL of bromobenzene, 0.164 g of tetrakis(triphenylphosphine)palladium(0), 40 mL of an aqueous solution of 2 M sodium carbonate, and 100 mL of 1,2-dimethoxyethane were mixed, and stirred at 80° C. for 3 hours. Subsequently, this was extracted with toluene. The organic layer was dried with anhydrous magnesium sulfate, then concentrated, and the residue was purified through silica gel column chromatography to give 2.26 g of Intermediate G. The yield was 62%.
In an argon atmosphere, 2.53 g of Intermediate G, 1.76 g of 4′-iodo-1,1′:2′,1″-terphenyl, 0.114 g of tetrakis(triphenylphosphine)palladium(0), 14 mL of an aqueous solution of 2 M sodium carbonate, and 40 mL of 1,2-dimethoxyethane were mixed, and stirred at 80° C. for 3 hours. Subsequently, this was extracted with toluene. The organic layer was dried with anhydrous magnesium sulfate, then concentrated, and the residue was purified through silica gel column chromatography to give 2.09 g of a white solid. The yield was 69%.
As a result of mass spectrometry (m/e=615 relative to molecular weight 614.87), the resulting product was Compound Inv-3.
In an argon atmosphere, 3.33 g of di-([1,1′-biphenyl]-4-yl)amine, 3.54 g of Intermediate C, 0.196 g of tris(dibenzylideneacetone)dipalladium(0), 0.240 g of tri-t-butylphosphonium tetrafluoroborate, 2.99 g of sodium-t-butoxide and 58 mL of toluene were mixed, and stirred at 110° C. for 4 hours. The reaction mixture was cooled at room temperature and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography and recrystallization with a mixed solvent of toluene and hexane to give 4.67 g of a white solid. The yield was 72%.
The resulting product was Compound Inv-4 as a result of mass spectrometry (m/e=626 relative to molecular weight 625.82).
In an argon atmosphere, 3.21 g of N-(4-(naphthalene-1-yl)phenyl)naphthalene-1-amine, 3.25 g of Intermediate C, 0.170 g of tris(dibenzylideneacetone)dipalladium(0), 0.216 g of tri-t-butylphosphonium tetrafluoroborate, 2.68 g of sodium-t-butoxide and 53 mL of toluene were mixed, and stirred at 110° C. for 4 hours. The reaction mixture was cooled at room temperature and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography and recrystallization with a mixed solvent of toluene and hexane to give 6.04 g of a white solid. The yield was 68%.
The resulting product was Compound Inv-5 as a result of mass spectrometry (m/e=650 relative to molecular weight 649.84).
In an argon atmosphere, 3.01 g of N-(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1′-biphenyl]-4-amine, 2.97 g of Intermediate C, 0.160 g of tris(dibenzylideneacetone)dipalladium(0), 0.202 g of tri-t-butylphosphonium tetrafluoroborate, 2.51 g of sodium-t-butoxide and 48 mL of toluene were mixed, and stirred at 110° C. for 4 hours. The reaction mixture was cooled at room temperature and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography and recrystallization with a mixed solvent of toluene and hexane to give 4.42 g of a white solid. The yield was 78%.
The resulting product was Compound Inv-6 as a result of mass spectrometry (m/e=650 relative to molecular weight 649.84).
In an argon atmosphere, 3.61 g of 4-(dibenzo[b,d]furan-4-yl)-N-phenylaniline, 3.67 g of Intermediate C, 0.197 g of tris(dibenzylideneacetone)dipalladium(0), 0.250 g of tri-t-butylphosphonium tetrafluoroborate, 3.10 g of sodium-t-butoxide and 60 mL of toluene were mixed, and stirred at 110° C. for 4 hours. The reaction mixture was cooled at room temperature and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography and recrystallization with a mixed solvent of toluene and hexane to give 5.58 g of a white solid. The yield was 81%.
The resulting product was Compound Inv-7 as a result of mass spectrometry (m/e=690 relative to molecular weight 689.86).
In an argon atmosphere, 2.85 g of N-([1,1′-biphenyl]-4-yl)dibenzo[b,d]furan-1-amine, 2.89 g of Intermediate C, 0.155 g of tris(dibenzylideneacetone)dipalladium(0), 0.201 g of tri-t-butylphosphonium tetrafluoroborate, 2.45 g of sodium-t-butoxide and 47 mL of toluene were mixed, and stirred at 110° C. for 4 hours. The reaction mixture was cooled at room temperature and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography and recrystallization with a mixed solvent of toluene and hexane to give 3.69 g of a white solid. The yield was 68%.
The resulting product was Compound Inv-8 as a result of mass spectrometry (m/e=639 relative to molecular weight 639.26).
In an argon atmosphere, 5.86 g of N-([1,1′-biphenyl]-4-yl)-9,9-biphenyl-9H-fluorene-4-amine, 4.10 g of Intermediate C, 0.220 g of tris(dibenzylideneacetone)dipalladium(0), 0.285 g of tri-t-butylphosphonium tetrafluoroborate, 3.48 g of sodium-t-butoxide and 67 mL of toluene were mixed, and stirred at 110° C. for 4 hours. The reaction mixture was cooled at room temperature and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography and recrystallization with a mixed solvent of toluene and hexane to give 5.23 g of a white solid. The yield was 55%.
The resulting product was Compound Inv-9 as a result of mass spectrometry (m/e=789 relative to molecular weight 789.34).
In an argon atmosphere, 2.73 g of 4-(naphthalen-1-yl)-N-[4-(naphthalen-1-yl)phenyl]aniline, 2.20 g of Intermediate C, 0.118 g of tris(dibenzylideneacetone)dipalladium(0), 0.153 g of tri-t-butylphosphonium tetrafluoroborate, 1.87 g of sodium-t-butoxide and 36 mL of toluene were mixed, and stirred at 110° C. for 4 hours. The reaction mixture was cooled at room temperature and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography and recrystallization with a mixed solvent of toluene and hexane to give 3.84 g of a white solid. The yield was 82%.
The resulting product was Compound Inv-10 as a result of mass spectrometry (m/e=725 relative to molecular weight 725.31).
In an argon atmosphere, 3.51 g of N-[4-(naphthalen-1-yl)phenyl][1,1′-biphenyl]-4-amine, 3.21 g of Intermediate C, 0.172 g of tris(dibenzylideneacetone)dipalladium(0), 0.223 g of tri-t-butylphosphonium tetrafluoroborate, 2.72 g of sodium-t-butoxide and 52 mL of toluene were mixed, and stirred at 110° C. for 4 hours. The reaction mixture was cooled at room temperature and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography and recrystallization with a mixed solvent of toluene and hexane to give 4.65 g of a white solid. The yield was 73%.
The resulting product was Compound Inv-11 as a result of mass spectrometry (m/e=675 relative to molecular weight 675.29).
In an argon atmosphere, 5.33 g of N-[4-(dibenzo[b,d]furan-1-yl)phenyl][1,1′-biphenyl]-4-amine, 4.40 g of Intermediate C, 0.236 g of tris(dibenzylideneacetone)dipalladium(0), 0.306 g of tri-t-butylphosphonium tetrafluoroborate, 3.73 g of sodium-t-butoxide and 72 mL of toluene were mixed, and stirred at 110° C. for 4 hours. The reaction mixture was cooled at room temperature and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography and recrystallization with a mixed solvent of toluene and hexane to give 6.93 g of a white solid. The yield was 75%.
The resulting product was Compound Inv-12 as a result of mass spectrometry (m/e=715 relative to molecular weight 715.29).
In an argon atmosphere, 4.14 g of 4-(naphthalen-2-yl)-N-[4-(naphthalen-2-yl)phenyl]aniline, 3.34 g of Intermediate C, 0.179 g of tris(dibenzylideneacetone)dipalladium(0), 0.232 g of tri-t-butylphosphonium tetrafluoroborate, 2.83 g of sodium-t-butoxide and 54 mL of toluene were mixed, and stirred at 110° C. for 4 hours. The reaction mixture was cooled at room temperature and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography and recrystallization with a mixed solvent of toluene and hexane to give 4.91 g of a white solid. The yield was 69%.
The resulting product was Compound Inv-13 as a result of mass spectrometry (m/e=725 relative to molecular weight 725.31).
In an argon atmosphere, 3.63 g of N-[4-(phenanthren-9-yl)phenyl]naphthalene-1-amine, 3.12 g of Intermediate C, 0.168 g of tris(dibenzylideneacetone)dipalladium(0), 0.217 g of tri-t-butylphosphonium tetrafluoroborate, 2.65 g of sodium-t-butoxide and 51 mL of toluene were mixed, and stirred at 110° C. for 4 hours. The reaction mixture was cooled at room temperature and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography and recrystallization with a mixed solvent of toluene and hexane to give 5.32 g of a white solid. The yield was 82%.
The resulting product was Compound Inv-14 as a result of mass spectrometry (m/e=699 relative to molecular weight 699.29).
In an argon atmosphere, 4.28 g of N-([1,1′-biphenyl]-4-yl)-3′-(9H-carbazol-9-yl)[1,1′-biphenyl]-4-amine, 2.99 g of Intermediate C, 0.161 g of tris(dibenzylideneacetone)dipalladium(0), 0.208 g of tri-t-butylphosphonium tetrafluoroborate, 2.54 g of sodium-t-butoxide and 48 mL of toluene were mixed, and stirred at 110° C. for 4 hours. The reaction mixture was cooled at room temperature and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography and recrystallization with a mixed solvent of toluene and hexane to give 5.90 g of a white solid. The yield was 85%.
The resulting product was Compound Inv-15 as a result of mass spectrometry (m/e=790 relative to molecular weight 790.33).
In an argon atmosphere, 3.96 g of N-([1,1′-biphenyl]-4-yl)-2′-(9H-carbazol-9-yl)[1,1′-biphenyl]-4-amine, 2.77 g of Intermediate C, 0.148 g of tris(dibenzylideneacetone)dipalladium(0), 0.192 g of tri-t-butylphosphonium tetrafluoroborate, 2.35 g of sodium-t-butoxide and 45 mL of toluene were mixed, and stirred at 110° C. for 4 hours. The reaction mixture was cooled at room temperature and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography and recrystallization with a mixed solvent of toluene and hexane to give 4.89 g of a white solid. The yield was 76%.
The resulting product was Compound Inv-16 as a result of mass spectrometry (m/e=790 relative to molecular weight 790.33).
In an argon atmosphere, 5.39 g of N-[4-(dibenzo[b,d]furan-4-yl)phenyl]dibenzo[b,d]furan-1-amine, 4.31 g of Intermediate C, 0.232 g of tris(dibenzylideneacetone)dipalladium(0), 0.299 g of tri-t-butylphosphonium tetrafluoroborate, 3.66 g of sodium-t-butoxide and 70 mL of toluene were mixed, and stirred at 110° C. for 4 hours. The reaction mixture was cooled at room temperature and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography and recrystallization with a mixed solvent of toluene and hexane to give 5.45 g of a white solid. The yield was 59%.
The resulting product was Compound Inv-17 as a result of mass spectrometry (m/e=729 relative to molecular weight 729.27).
In an argon atmosphere, 5.68 g (25.9 mmol) of 3-(naphthalen-1-yl)aniline, 6.58 g (25.9 mmol) of 1-iodo-naphthalene, 474 mg (0.51 mmol) of tris(dibenzylideneacetone)dipalladium(0), 645 mg (1.03 mmol) of BINAP, 2.74 g (28.5 mmol) of sodium-t-butoxide and 130 mL of toluene were mixed and stirred under heat at 110° C. for 7 hours. After left cooled, this was filtered and the resulting residue was purified through column chromatography to give 7.49 g of Intermediate H. The yield was 84%.
In an argon atmosphere, 3.2 g of Intermediate H, 3.27 g of Intermediate C, 0.176 g of tris(dibenzylideneacetone)dipalladium(0), 0.222 g of tri-t-butylphosphonium tetrafluoroborate, 2.70 g of sodium-t-butoxide and 54 mL of toluene were mixed, and stirred at 110° C. for 4 hours. The reaction mixture was cooled at room temperature and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography and recrystallization with a mixed solvent of toluene and hexane to give 6.05 g of a white solid. The yield was 68%.
The resulting product was Compound Inv-18 as a result of mass spectrometry (m/e=650 relative to molecular weight 649.84).
In an argon atmosphere, 2.19 g (22.33 mmol) of aniline-2,3,4,5,6-d5, 3.29 g (20.3 mmol) of bromobenzene-d5, 372 mg (0.41 mmol) of tris(dibenzylideneacetone)dipalladium(0), 506 mg (0.812 mmol) of BINAP, 2.15 g (22.33 mmol) of sodium-t-butoxide and 200 mL of toluene were mixed and stirred under heat at 100° C. for 3 hours. After left cooled, this was filtered and the resulting residue was purified through column chromatography to give 3.59 g of Intermediate I. The yield was 99%.
In an argon atmosphere, 2.9 g (16.18 mmol) of Intermediate I and 55 mL of DMF were mixed, and at 0° C., 5.76 g (32.4 mmol) of N-bromosuccinimide was added thereto. Water and ethyl acetate were added for extraction, and the resulting organic layer was distilled under reduced pressure to give Intermediate J. Intermediate J was subjected to the next reaction without purification.
In an argon atmosphere, 6.41 g (19.12 mmol) of Intermediate J, 5.83 g (47.8 mmol) of phenylboronic acid, 406 mg (0.574 mmol) of bis(di-t-butyl(4-dimethylaminophenyl)phosphine) dichloropalladium(II) and 1,4-dioxane (100 mL) were mixed, and an aqueous solution of potassium phosphate was added thereto. This was stirred under heat at 110° C. for 5 hours, then left cooled, and the mixture was filtered and purified by column chromatography and recrystallization to give 3.9 g of Intermediate K. The yield of Intermediate K produced via Intermediate J was 62% (2 steps).
In an argon atmosphere, 2.64 g of Intermediate J, 2.86 g of Intermediate C, 0.147 g of tris(dibenzylideneacetone)dipalladium(0), 0.186 g of tri-t-butylphosphonium tetrafluoroborate, 1.08 g of sodium-t-butoxide and 80 mL of toluene were mixed, and stirred at 110° C. for 7 hours. The reaction mixture was cooled at room temperature and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography and recrystallization with a mixed solvent of toluene and hexane to give 3.29 g of a white solid. The yield was 65%.
The resulting product was Compound Inv-19 as a result of mass spectrometry (m/e=633 relative to molecular weight 633.33).
In an argon atmosphere, 8.61 g (30 mmol) of 1-bromo-4-iodobenzene-2,3,5,6-d4, 8.63 g (31.5 mmol) of [1,1′:2′,1″-terphenyl]-4′-ylboronic acid, 1.39 g (1.2 mmol) of tetrakis(triphenylphosphine)palladium(0), 30 mL of an aqueous solution of 2 M tripotassium phosphate, and 150 mL of dioxane were mixed and stirred under heat at 80° C. for 7 hours. Water was added and the precipitated solid was extracted with dichloromethane and washed. The solvent was evaporated away, and the resulting residue was purified through column chromatography to give Intermediate L (7.3 g). The yield was 63%.
In an argon atmosphere, 2.64 g of Intermediate K, 3.27 g of Intermediate L, 0.147 g of tris(dibenzylideneacetone)dipalladium(0), 0.186 g of tri-t-butylphosphonium tetrafluoroborate, 1.08 g of sodium-t-butoxide and 80 mL of toluene were mixed, and stirred at 110° C. for 7 hours. The reaction mixture was cooled at room temperature and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography and recrystallization with a mixed solvent of toluene and hexane to give 4.11 g of a white solid. The yield was 80%.
The resulting product was Compound Inv-20 as a result of mass spectrometry (m/e=637 relative to molecular weight 637.35).
In an argon atmosphere, 6.0 g (15.41 mmol) of Intermediate L, 23.12 mL of a toluene solution of 1 M LiHMDS, 282 mg (0.31 mmol) of tris(dibenzylideneacetone)dipalladium(0), 179 mg (0.62 mmol) of tri-t-butylphosphonium tetrafluoroborate and 77 mL of toluene were mixed and stirred under heat at 110° C. for 7 hours. Hydrochloric acid was added and this was extracted with toluene, and the resulting residue was purified through column chromatography to give 3.45 g of Intermediate M. The yield was 69%.
In an argon atmosphere, 3.45 g (10.6 mmol) of Intermediate M, 2.69 g (10.6 mmol) of 1-iodonaphthalene, 194 mg (0.212 mmol) of tris(dibenzylideneacetone)dipalladium(0), 264 mg (0.424 mmol) of BINAP, 1.12 g (11.6 mmol) of sodium-t-butoxide and 53 mL of toluene were mixed and stirred under heat at 100° C. for 8 hours. The residue was purified through column chromatography to give 3.8 g of Intermediate N. The yield was 80%.
In an argon atmosphere, 2.87 g (10 mmol) of 1-bromo-4-iodobenzene-2,3,5,6-d4, 1.81 g (10.5 mmol) of 1-naphthaleneboronic acid, 462 mg (0.4 mmol) of tetrakis(triphenylphosphine)palladium(0), 10 mL of an aqueous solution of 2 M tripotassium phosphate, and 50 mL of dioxane were mixed and stirred under heat at 80° C. for 7 hours. The reaction liquid was purified through column chromatography to give Intermediate O (2.87 g). The yield was 99%.
In an argon atmosphere, 1.82 g of Intermediate N, 1.39 g of Intermediate O, 0.074 g of tris(dibenzylideneacetone)dipalladium(0), 0.094 g of tri-t-butylphosphonium tetrafluoroborate, 0.542 g of sodium-t-butoxide and 40 mL of toluene were mixed, and stirred at 110° C. for 7 hours. The reaction mixture was cooled at room temperature and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography and recrystallization with a mixed solvent of toluene and hexane to give 1.70 g of a white solid. The yield was 64%.
The resulting product was Compound Inv-21 as a result of mass spectrometry (m/e=657 relative to molecular weight 657.33).
According to the same operation as in synthesis of Intermediate O but changing 1-naphthaleneboronic acid to phenylboronic acid, Intermediate P was produced. The yield was 97%.
In an argon atmosphere, 2.03 g of Intermediate N, 1.28 g of Intermediate P, 0.082 g of tris(dibenzylideneacetone)dipalladium(0), 0.104 g of tri-t-butylphosphonium tetrafluoroborate, 0.61 g of sodium-t-butoxide and 45 mL of toluene were mixed and stirred at 110° C. for 7 hours. The reaction mixture was cooled at room temperature and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography and recrystallization with a mixed solvent of toluene and hexane to give 2.00 g of a white solid. The yield was 73%.
The resulting product was Compound Inv-22 as a result of mass spectrometry (m/e=607 relative to molecular weight 607.31).
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-064541 | Mar 2020 | JP | national |
| 2020-217191 | Dec 2020 | JP | national |
This application is a continuation application of U.S. application Ser. No. 17/704,646 filed Mar. 25, 2022, allowed, which is a continuation application of PCT/JP2021/013412 filed Mar. 29, 2021 and claims the benefit of JP 2020-217191 filed Dec. 25, 2020 and JP 2020-064541 filed Mar. 31, 2020.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 17704646 | Mar 2022 | US |
| Child | 18172622 | US | |
| Parent | PCT/JP21/12312 | Mar 2021 | US |
| Child | 17704646 | US |
