CN116829552B - Compound, material for organic electroluminescent element, and electronic device - Google Patents

Compound, material for organic electroluminescent element, and electronic device

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CN116829552B
CN116829552B CN202280012655.3A CN202280012655A CN116829552B CN 116829552 B CN116829552 B CN 116829552B CN 202280012655 A CN202280012655 A CN 202280012655A CN 116829552 B CN116829552 B CN 116829552B
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CN116829552A (en
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吉田圭
齐藤雅俊
中村雅人
水谷清香
三谷真人
青山嘉宪
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Idemitsu Kosan Co Ltd
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    • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
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    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
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    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
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Abstract

A compound represented by the following formula (1) or (2), an organic electroluminescent element comprising the compound, and an electronic device comprising such an organic electroluminescent element. The symbols in the formulae are as defined in the specification.

Description

Compound, material for organic electroluminescent element, and electronic device
Technical Field
The present invention relates to a compound, a material for an organic electroluminescent element, and an electronic device including the organic electroluminescent element.
Background
In general, an organic electroluminescent element (hereinafter, also referred to as an "organic EL element") is composed of an anode, a cathode, and an organic layer interposed between the anode and the cathode. When a voltage is applied between the electrodes, electrons are injected from the cathode side into the light-emitting region, holes are injected from the anode side into the light-emitting region, and the injected electrons and holes recombine in the light-emitting region to generate an excited state, and light is emitted when the excited state returns to the ground state. Therefore, it is important to develop a material that efficiently transports electrons or holes to a light-emitting region and allows electrons and holes to be easily recombined, in order to obtain a high-performance organic EL element.
Patent documents 1 to 7 disclose compounds used as materials for organic electroluminescent elements.
Prior art literature
Patent literature
Patent document 1 International publication No. 2013/077352
Patent document 2 Korean laid-open patent publication No. 10-2020-0068398
Patent document 3 Korean laid-open patent publication No. 10-2017-0096769
Patent document 4 International publication No. 2020/022769
Patent document 5 U.S. patent application publication No. 2020/227658 specification
Patent document 6 Chinese patent publication No. 111072637
Patent document 7 U.S. patent application publication No. 2019/363260 specification
Disclosure of Invention
Problems to be solved by the invention
A large number of compounds for organic EL elements have been reported in the past, but compounds for further improving the performance of organic EL elements have been still sought.
The present invention has been made to solve the above-described problems, and an object thereof is to provide a compound that further improves the performance of an organic EL element, an organic EL element that further improves the element performance, and an electronic device including such an organic EL element.
Means for solving the problems
The present inventors have conducted intensive studies on the performance of an organic EL element comprising the compound described in patent documents 1 to 7, and as a result, have found that the performance of an organic EL element comprising the compound represented by the following formula (1) and an organic EL element comprising the compound represented by the following formula (2) is further improved.
In one embodiment, the present invention provides a compound represented by the following formula (1).
[ Chemical formula 1]
(In the formula (1),
Ar 1～Ar3 is independently a substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 30 ring-forming carbon atoms.
L 1 is a substituted or unsubstituted arylene group having 6 to 30 ring-forming carbon atoms or a substituted or unsubstituted divalent heterocyclic group having 5 to 30 ring-forming carbon atoms, and Ar 2 and L 1 may be bonded to each other to form a substituted or unsubstituted ring.
L2 is a single bond or a 2+p-valent residue of a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 25 ring-forming carbon atoms.
P is 0 or1, where L 2 is a single bond, p is 0, and where L 2 is a 2+p residue of a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 25 ring-forming carbon atoms, p is 0 or 1.
R 1～R6 and R 11～R14 are each independently of the other
A hydrogen atom,
Halogen atom,
Cyano group,
Nitro group,
Substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
Substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms,
Substituted or unsubstituted alkynyl having 2 to 50 carbon atoms,
Substituted or unsubstituted cycloalkyl having 3 to 50 ring-forming carbon atoms,
A group represented by Si (R 901)(R902)(R903),
A group represented by-O- (R 904),
A group represented by S- (R 905),
A group represented by-N (R 906)(R907),
Substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or
A substituted or unsubstituted heterocyclic group having 5 to 50 ring members,
R 901～R907 are each independently
A hydrogen atom,
Substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
Substituted or unsubstituted cycloalkyl having 3 to 50 ring-forming carbon atoms,
Substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or
A substituted or unsubstituted heterocyclic group having 5 to 50 ring members,
In the case where R 901 is present in an amount of 2 or more, 2 or more R 901 are the same or different from each other,
In the case where R 902 is present in an amount of 2 or more, 2 or more R 902 are the same or different from each other,
In the case where R 903 is present in an amount of 2 or more, 2 or more R 903 are the same or different from each other,
In the case where R 904 is present in an amount of 2 or more, 2 or more R 904 are the same or different from each other,
In the case where R 905 is present in an amount of 2 or more, 2 or more R 905 are the same or different from each other,
In the case where R 906 is present in an amount of 2 or more, 2 or more R 906 are the same or different from each other,
In the case where R 907 is present in an amount of 2 or more, 2 or more R 907 are the same or different from each other,
R 1 and R 2 are not bonded to each other to form a ring,
In the group of 1 or more selected from R 3 and R 4、R4 and R 5、R5 and R 6、R11 and R 12、R12 and R 13 and R 13 and R 14, adjacent 2 may be bonded to each other to form a substituted or unsubstituted ring.
X 1 is an oxygen atom or a sulfur atom.
* D is bonded to one selected from carbon atoms a, b and c. )
In another embodiment, the present invention provides a compound represented by the following formula (2).
[ Chemical formula 2]
(In the formula (2),
Ar 11～Ar13 is independently a substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 30 ring-forming carbon atoms.
L 11 is a substituted or unsubstituted arylene group having 6 to 30 ring-forming carbon atoms or a substituted or unsubstituted divalent heterocyclic group having 5 to 30 ring-forming carbon atoms, and Ar 12 and L 12 may be bonded to each other to form a substituted or unsubstituted ring.
L 12 is a 2+q-valent residue of a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 25 ring-forming carbon atoms.
Q is 0 or 1.
R 41～R46 and R 51～R54 are each independently of the other
A hydrogen atom,
Halogen atom,
Cyano group,
Nitro group,
Substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
Substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms,
Substituted or unsubstituted alkynyl having 2 to 50 carbon atoms,
Substituted or unsubstituted cycloalkyl having 3 to 50 ring-forming carbon atoms,
A group represented by Si (R 901)(R902)(R903),
A group represented by-O- (R 904),
A group represented by S- (R 905),
A group represented by-N (R 906)(R907),
Substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or
A substituted or unsubstituted heterocyclic group having 5 to 50 ring members,
R 901～R907 are each independently
A hydrogen atom,
Substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
Substituted or unsubstituted cycloalkyl having 3 to 50 ring-forming carbon atoms,
Substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or
A substituted or unsubstituted heterocyclic group having 5 to 50 ring members,
In the case where R 901 is present in an amount of 2 or more, 2 or more R 901 are the same or different from each other,
In the case where R 902 is present in an amount of 2 or more, 2 or more R 902 are the same or different from each other,
In the case where R 903 is present in an amount of 2 or more, 2 or more R 903 are the same or different from each other,
In the case where R 904 is present in an amount of 2 or more, 2 or more R 904 are the same or different from each other,
In the case where R 905 is present in an amount of 2 or more, 2 or more R 905 are the same or different from each other,
In the case where R 906 is present in an amount of 2 or more, 2 or more R 906 are the same or different from each other,
In the case where R 907 is present in an amount of 2 or more, 2 or more R 907 are the same or different from each other,
R 41 and R 42 are not bonded to each other to form a ring,
In the group of 1 or more selected from R 43 and R 44、R44 and R 45、R45 and R 46、R51 and R 52、R52 and R 53, and R 53 and R 54, adjacent 2 may be bonded to each other to form a substituted or unsubstituted ring.
X 11 is an oxygen atom or a sulfur atom. )
In still another aspect, the present invention provides a material for an organic electroluminescent element, comprising at least 1 selected from the group consisting of the compounds represented by the above formula (1) and the compounds represented by the formula (2).
In still another aspect, the present invention provides an organic electroluminescent element having a cathode, an anode, and an organic layer between the cathode and the anode, the organic layer including a light-emitting layer, at least 1 layer of the organic layer including at least 1 selected from the group consisting of the compounds represented by the above formula (1) and the compounds represented by the above formula (2).
In still another aspect, the present invention provides an electronic device including the above-described organic electroluminescent element.
ADVANTAGEOUS EFFECTS OF INVENTION
The organic EL element containing the compound represented by the above formula (1) shows improved element performance. In addition, the organic EL element containing the compound represented by the above formula (2) shows improved element performance.
Drawings
Fig. 1 is a schematic diagram showing an example of a layer structure of an organic EL element according to an embodiment of the present invention.
Fig. 2 is a schematic diagram showing another example of the layer structure of the organic EL element according to the embodiment of the present invention.
Detailed Description
[ Definition ]
In the present specification, the hydrogen atom means to contain isotopes having different neutron numbers, namely protium (protium), deuterium (deuterium) and tritium (tritium).
In the present specification, in the chemical structural formula, the symbol such as "R" and the bondable position of "D" indicating deuterium atom are not explicitly shown, and are set to be bonded with hydrogen atom, i.e., protium atom, deuterium atom or tritium atom.
In the present specification, the number of ring-forming carbon refers to the number of carbon atoms among atoms constituting the ring itself of a compound having a structure in which atoms are bonded in a ring (for example, a monocyclic compound, a condensed cyclic compound, a bridged cyclic compound, a carbocyclic compound, and a heterocyclic compound). When the ring is substituted with a substituent, the carbon contained in the substituent is not included in the number of ring-forming carbons. The "number of ring-forming carbons" described below is set similarly unless otherwise indicated. For example, the number of ring-forming carbons of the benzene ring is 6, the number of ring-forming carbons of the naphthalene ring is 10, the number of ring-forming carbons of the pyridine ring is 5, and the number of ring-forming carbons of the furan ring is 4. In addition, for example, the ring-forming carbon number of 9, 9-diphenylfluorenyl is 13,9,9' -spirobifluorenyl and the ring-forming carbon number is 25.
In addition, when an alkyl group is substituted as a substituent on the benzene ring, for example, the carbon number of the alkyl group is not included in the ring-forming carbon number of the benzene ring. Therefore, the ring carbon number of the benzene ring substituted with the alkyl group is 6. In addition, when an alkyl group is substituted as a substituent on the naphthalene ring, the carbon number of the alkyl group is not included in the ring-forming carbon number of the naphthalene ring. Therefore, the number of ring-forming carbons of the naphthalene ring substituted with an alkyl group is 10.
In the present specification, the number of ring-forming atoms refers to the number of atoms constituting the ring itself of a compound (for example, a monocyclic compound, a condensed compound, a bridged compound, a carbocyclic compound, and a heterocyclic compound) having a structure in which atoms are bonded in a ring (for example, a single ring, a condensed ring, and a bridged ring). Atoms that do not constitute a ring (e.g., hydrogen atoms that terminate bonds to atoms that constitute a ring), and atoms that are contained in a substituent when the ring is substituted with a substituent are not included in the number of ring-forming atoms. The "number of ring-forming atoms" described below is set similarly unless otherwise indicated. For example, the number of ring-forming atoms of the pyridine ring is 6, the number of ring-forming atoms of the quinazoline ring is 10, and the number of ring-forming atoms of the furan ring is 5. For example, the number of hydrogen atoms bonded to the pyridine ring or atoms constituting the substituent is not included in the number of pyridine ring-forming atoms. Therefore, the number of ring-forming atoms of the pyridine ring to which the hydrogen atom or the substituent is bonded is 6. In addition, for example, a hydrogen atom bonded to a carbon atom of a quinazoline ring or an atom constituting a substituent is not included in the number of ring-forming atoms of the quinazoline ring. Accordingly, the number of ring-forming atoms of the quinazoline ring to which a hydrogen atom or a substituent is bonded is 10.
In the present specification, "carbon number XX to YY" in the expression of "a substituted or unsubstituted ZZ group having carbon number XX to YY" means the carbon number when the ZZ group is unsubstituted, and the carbon number of the substituent when the substituent is substituted is not included. Here, "YY" is larger than "XX", where "XX" means an integer of 1 or more, and "YY" means an integer of 2 or more.
In the present specification, "atomic numbers XX to YY" in the expression of "a ZZ group of atomic numbers XX to YY that are substituted or unsubstituted" means the number of atoms when the ZZ group is unsubstituted, and the number of atoms of substituents when substitution occurs is not included. Here, "YY" is larger than "XX", where "XX" means an integer of 1 or more, and "YY" means an integer of 2 or more.
In the present specification, an unsubstituted ZZ group means that "a substituted or unsubstituted ZZ group" is an "unsubstituted ZZ group", and a substituted ZZ group means that "a substituted or unsubstituted ZZ group" is a "substituted ZZ group".
In the present specification, "unsubstituted" when expressed as "substituted or unsubstituted ZZ group" means that the hydrogen atom in the ZZ group is not substituted with a substituent. The hydrogen atom in the "unsubstituted ZZ group" is a protium atom, deuterium atom or tritium atom.
In the present specification, "substitution" when referring to "substituted or unsubstituted ZZ group" means that 1 or more hydrogen atoms in the ZZ group are replaced with substituents. The term "substitution" when referring to "BB group substituted with AA group" means that 1 or more hydrogen atoms in BB group are replaced with AA group.
"Substituent described in the specification"
Substituents described in the present specification are described below. Unless otherwise indicated, each substituent described in the present specification is defined as follows.
The number of ring-forming carbon atoms of the "unsubstituted aryl group" described in the present specification is 6 to 50, preferably 6 to 30, more preferably 6 to 18, unless otherwise described in the present specification.
The number of ring-forming atoms of the "unsubstituted heterocyclic group" described in the present specification is 5 to 50, preferably 5 to 30, more preferably 5 to 18, unless otherwise described in the present specification.
The carbon number of the "unsubstituted alkyl group" described in the present specification is 1 to 50, preferably 1 to 20, more preferably 1 to 6, unless otherwise described in the present specification.
The carbon number of the "unsubstituted alkenyl group" described in the present specification is 2 to 50, preferably 2 to 20, more preferably 2 to 6, unless otherwise described in the present specification.
The carbon number of the "unsubstituted alkynyl" described in the present specification is 2 to 50, preferably 2 to 20, more preferably 2 to 6, unless otherwise described in the present specification.
The number of ring-forming carbon atoms of the "unsubstituted cycloalkyl group" described in the present specification is 3 to 50, preferably 3 to 20, more preferably 3 to 6, unless otherwise described in the present specification.
The number of ring-forming carbon atoms of the "unsubstituted arylene group" described in the present specification is 6 to 50, preferably 6 to 30, more preferably 6 to 18, unless otherwise described in the present specification.
The number of ring-forming atoms of the "unsubstituted divalent heterocyclic group" described in the present specification is 5 to 50, preferably 5 to 30, more preferably 5 to 18, unless otherwise described in the present specification.
The carbon number of the "unsubstituted alkylene group" described in the present specification is 1 to 50, preferably 1 to 20, more preferably 1 to 6, unless otherwise described in the present specification.
"Substituted or unsubstituted aryl"
Specific examples of the "substituted or unsubstituted aryl group" described in the present specification (specific example group G1) include the following unsubstituted aryl group (specific example group G1A) and substituted aryl group (specific example group G1B). (herein, unsubstituted aryl means that "substituted or unsubstituted aryl" is "unsubstituted aryl", and substituted aryl means that "substituted or unsubstituted aryl" is "substituted aryl"), and in this specification, only "aryl" is referred to, both "unsubstituted aryl" and "substituted aryl" are included.
"Substituted aryl" refers to a group in which 1 or more hydrogen atoms of an "unsubstituted aryl" are replaced with a substituent. Examples of the "substituted aryl" include a group obtained by replacing 1 or more hydrogen atoms of the "unsubstituted aryl" of the following specific example group G1A with substituents, and a substituted aryl of the following specific example group G1B. The examples of "unsubstituted aryl" and "substituted aryl" listed herein are only examples, and the "substituted aryl" described in the present specification also includes a group in which a hydrogen atom bonded to a carbon atom of an aryl group itself in the "substituted aryl" of the following specific example group G1B is further substituted with a substituent, and a group in which a hydrogen atom of a substituent in the "substituted aryl" of the following specific example group G1B is further substituted with a substituent.
Unsubstituted aryl (specific example group G1A):
Phenyl group,
P-biphenyl group,
M-biphenyl group,
O-biphenyl group,
P-terphenyl-4-yl,
Para-terphenyl-3-yl,
Para-terphenyl-2-yl,
M-terphenyl-4-yl,
M-terphenyl-3-yl,
M-terphenyl-2-yl,
M-terphenyl-3' -yl,
O-terphenyl-4-yl,
O-terphenyl-3-yl,
O-terphenyl-2-yl,
1-Naphthyl group,
2-Naphthyl group,
Anthracenyl group,
Benzoanthryl radical,
Phenanthryl group,
Benzophenanthryl radical phenalkenyl group,
Pyrenyl group,
A base group,
Benzo (E) benzo (EA base group,
Triphenylene group,
Benzotriphenylene radical,
And tetraphenyl group,
Pentacenyl,
Fluorenyl group,
9,9' -Spirobifluorenyl,
Benzofluorenyl group,
Dibenzofluorenyl group,
Fluorescent anthracyl group,
Benzofluoranthenyl group,
Perylene groups
Monovalent aromatic groups derived by removing 1 hydrogen atom from a ring structure represented by the following general formulae (TEMP-1) to (TEMP-15).
[ Chemical formula 3]
[ Chemical formula 4]
Substituted aryl (specific example group G1B):
O-tolyl group,
M-tolyl group,
P-tolyl group,
P-xylyl radical,
M-xylyl radical,
O-xylyl radical,
P-isopropylphenyl group,
M-isopropylphenyl group,
O-isopropylphenyl group,
P-tert-butylphenyl group,
M-tert-butylphenyl group,
O-tert-butylphenyl group,
3,4, 5-Trimethylphenyl group,
9, 9-Dimethylfluorenyl group,
9, 9-Diphenylfluorenyl
9, 9-Bis (4-methylphenyl) fluorenyl,
9, 9-Bis (4-isopropylphenyl) fluorenyl,
9, 9-Bis (4-t-butylphenyl) fluorenyl,
Cyanophenyl group,
Triphenylsilylphenyl radical,
Trimethylsilylphenyl group,
Phenyl naphthyl group,
Naphthyl phenyl
A monovalent group derived from a ring structure represented by the general formulae (TEMP-1) to (TEMP-15) wherein 1 or more hydrogen atoms and substituents are substituted.
"Substituted or unsubstituted heterocyclyl"
The "heterocyclic group" described in the present specification is a cyclic group containing at least 1 hetero atom in the ring-forming atom. Specific examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, a silicon atom, a phosphorus atom and a boron atom. The "heterocyclic group" described in this specification is a monocyclic group or a condensed ring group.
The "heterocyclic group" described in the present specification is an aromatic heterocyclic group or a non-aromatic heterocyclic group.
Specific examples of the "substituted or unsubstituted heterocyclic group" described in the present specification (specific example group G2) include the following unsubstituted heterocyclic group (specific example group G2A) and substituted heterocyclic group (specific example group G2B). (herein, the unsubstituted heterocyclic group means a case where the "substituted or unsubstituted heterocyclic group" is an "unsubstituted heterocyclic group", and the substituted heterocyclic group means a case where the "substituted or unsubstituted heterocyclic group" is a "substituted heterocyclic group"). In this specification, only the "heterocyclic group" is expressed to include both the "unsubstituted heterocyclic group" and the "substituted heterocyclic group".
"Substituted heterocyclic group" means a group in which 1 or more hydrogen atoms of an "unsubstituted heterocyclic group" are replaced with a substituent. Specific examples of the "substituted heterocyclic group" include a group in which a hydrogen atom of the "unsubstituted heterocyclic group" of the following specific example group G2A is substituted, and examples of the substituted heterocyclic group of the following specific example group G2B. Examples of the "unsubstituted heterocyclic group" and examples of the "substituted heterocyclic group" mentioned herein are only examples, and the "substituted heterocyclic group" described in the present specification includes a group in which a hydrogen atom bonded to a ring-forming atom of the heterocyclic group itself in the "substituted heterocyclic group" of the specific example group G2B is further substituted with a substituent, and a group in which a hydrogen atom of the substituent in the "substituted heterocyclic group" of the specific example group G2B is further substituted with a substituent.
Specific examples of the group G2A include, for example, the following unsubstituted heterocyclic group containing a nitrogen atom (example group G2A 1), an unsubstituted heterocyclic group containing an oxygen atom (example group G2A 2), an unsubstituted heterocyclic group containing a sulfur atom (example group G2A 3), and a monovalent heterocyclic group derived by removing 1 hydrogen atom from a ring structure represented by the following general formulae (TEMP-16) to (TEMP-33) (example group G2A 4).
Specific examples of the group G2B include, for example, the following substituted heterocyclic group containing a nitrogen atom (specific example group G2B 1), substituted heterocyclic group containing an oxygen atom (specific example group G2B 2), substituted heterocyclic group containing a sulfur atom (specific example group G2B 3), and a monovalent heterocyclic group derived from a ring structure represented by the following general formulae (TEMP-16) to (TEMP-33) in which 1 or more hydrogen atoms and substituents have been replaced (specific example group G2B 4).
Unsubstituted heterocyclyl containing a nitrogen atom (specific example group G2 A1):
Pyrrole group,
Imidazolyl group,
Pyrazolyl radical,
Triazolyl radical,
Tetrazolyl group,
Oxazolyl group,
Isoxazolyl radical,
Oxadiazolyl group,
Thiazolyl group,
Isothiazolyl group,
Thiadiazolyl group,
A pyridyl group,
Pyridazinyl group,
Pyrimidinyl group,
Pyrazinyl group,
Triazinyl group,
Indolyl group,
Isoindolyl group,
An indolizinyl group, a quinolizinyl group,
Quinolinyl radical,
Isoquinolinyl radical,
Cinnolinyl radical,
Phthalazinyl radical,
Quinazolinyl group,
Quinoxalinyl group,
Benzimidazolyl group,
Indazolyl group,
Phenanthroline group,
Phenanthridinyl group,
Acridinyl group,
Phenazinyl group,
Carbazolyl group,
Benzocarbazolyl group,
Morpholinyl group,
Phenoxazinyl group,
Phenothiazinyl group,
Azacarbazolyl group diazacarbazolyl.
Unsubstituted heterocyclyl containing an oxygen atom (specific example group G2 A2):
Furyl group,
Oxazolyl group,
Isoxazolyl radical,
Oxadiazolyl group,
Xanthenyl,
Benzofuranyl group,
Isobenzofuranyl group,
Dibenzofuranyl group,
Naphthobenzofuranyl group,
Benzoxazolyl group,
Benzisoxazolyl group,
Phenoxazinyl group,
Morpholinyl group,
Dinaphthofuranyl group,
Azadibenzofuranyl radical,
Diazadibenzofuranyl radical,
Azanaphthobenzofuranyl groups
Naphthyridobenzofuranyl.
Unsubstituted heterocyclyl containing a sulfur atom (specific example group G2 A3):
Thienyl group,
Thiazolyl group,
Isothiazolyl group,
Thiadiazolyl group,
Benzothienyl (benzothienyl),
Isobenzothiophene a base (isobenzothienyl),
Dibenzothiophenes a base (dibenzothienyl),
Naphthacene thienyl (naphthobenzothienyl),
Benzothiazolyl group,
Benzisothiazolyl group,
Phenothiazinyl group,
Dinaphthiophene radical (dinaphthothienyl),
Azadibenzo-p thienyl (azadibenzothienyl),
Diazadibenzo-based compounds thienyl (diazadibenzothienyl),
Azanaphthobenzo thienyl (azanaphthobenzothienyl) and
Naphthyridine benzofurans and thienyl (diazanaphthobenzothienyl).
Monovalent heterocyclic groups derived by removing 1 hydrogen atom from the ring structure represented by the following general formulae (TEMP-16) to (TEMP-33) (concrete example group G2A 4):
[ chemical formula 5]
[ Chemical formula 6]
In the above general formulae (TEMP-16) to (TEMP-33), X A and Y A are each independently an oxygen atom, a sulfur atom, NH or CH2. Wherein at least 1 of X A and Y A is an oxygen atom, a sulfur atom or NH.
In the general formulae (TEMP-16) to (TEMP-33), when at least one of X A and Y A is NH or CH2, the monovalent heterocyclic group derived from the ring structure represented by the general formulae (TEMP-16) to (TEMP-33) includes a monovalent group obtained by removing 1 hydrogen atom from the NH or CH 2.
Substituted heterocyclyl containing a nitrogen atom (specific example group G2B 1):
(9-phenyl) carbazolyl group,
(9-Biphenylyl) carbazolyl group,
(9-Phenyl) phenylcarbazolyl group,
(9-Naphthyl) carbazolyl group,
Diphenylcarbazol-9-yl,
Phenylcarbazol-9-yl,
Methyl benzimidazolyl group,
Ethylbenzimidazolyl group,
Phenyl triazinyl radical,
Biphenyl triazinyl radical,
Diphenyl triazinyl radical,
Phenyl quinazolinyl group biphenylquinazolinyl.
Substituted heterocyclyl containing an oxygen atom (specific example group G2B 2):
Phenyl dibenzofuranyl group,
Methyl dibenzofuranyl group,
Tert-butyldibenzofuranyl group
Monovalent residues of spiro [ 9H-xanthene-9, 9' - [9H ] fluorene ].
Substituted heterocyclyl containing a sulfur atom (specific example group G2B 3):
Phenyl dibenzothienyl,
Methyl dibenzothienyl,
Tert-butyldibenzothienyl and
Monovalent residues of spiro [ 9H-thioxanthene-9, 9' - [9H ] fluorene ].
A monovalent heterocyclic group derived from the ring structure represented by the general formulae (TEMP-16) to (TEMP-33) wherein 1 or more hydrogen atoms and substituents are substituted (concrete example group G2B 4):
The "1 or more hydrogen atoms of the monovalent heterocyclic group" means 1 or more hydrogen atoms selected from the group consisting of hydrogen atoms bonded to ring-forming carbon atoms of the monovalent heterocyclic group, hydrogen atoms bonded to nitrogen atoms when at least one of X A and Y A is NH, and hydrogen atoms of methylene groups when one of X A and Y A is CH 2.
"Substituted or unsubstituted alkyl"
Specific examples of the "substituted or unsubstituted alkyl group" described in the present specification (specific example group G3) include the following unsubstituted alkyl group (specific example group G3A) and substituted alkyl group (specific example group G3B). (herein, unsubstituted alkyl means that "substituted or unsubstituted alkyl" is "unsubstituted alkyl", and substituted alkyl means that "substituted or unsubstituted alkyl" is "substituted alkyl") hereinafter, when only "alkyl" is expressed, both "unsubstituted alkyl" and "substituted alkyl" are included.
"Substituted alkyl" refers to a group in which 1 or more hydrogen atoms in the "unsubstituted alkyl" are replaced with a substituent. Specific examples of the "substituted alkyl" include the following "unsubstituted alkyl" (specific example group G3A), a group in which 1 or more hydrogen atoms and substituents have been replaced, and a substituted alkyl (specific example group G3B). In the present specification, an alkyl group in "unsubstituted alkyl group" means a chain-like alkyl group. Thus, "unsubstituted alkyl" includes "unsubstituted alkyl" as a straight chain and "unsubstituted alkyl" as a branched chain. The examples of "unsubstituted alkyl" and "substituted alkyl" mentioned herein are only examples, and the "substituted alkyl" described in the present specification includes a group in which a hydrogen atom of an alkyl group itself in the "substituted alkyl" of the specific example group G3B is further substituted with a substituent, and a group in which a hydrogen atom of a substituent in the "substituted alkyl" of the specific example group G3B is further substituted with a substituent.
Unsubstituted alkyl (specific example group G3A):
Methyl group,
Ethyl group,
N-propyl group,
Isopropyl group,
N-butyl group,
Isobutyl group,
Sec-butyl, and
And (3) tert-butyl.
Substituted alkyl (specific example group G3B):
Heptafluoropropyl (including isomers),
Pentafluoroethyl group,
2, 2-Trifluoroethyl group, and
Trifluoromethyl.
"Substituted or unsubstituted alkenyl"
Specific examples of the "substituted or unsubstituted alkenyl group" described in the present specification (specific example group G4) include the following unsubstituted alkenyl group (specific example group G4A) and substituted alkenyl group (specific example group G4B). (herein, unsubstituted alkenyl means that "substituted or unsubstituted alkenyl" is "unsubstituted alkenyl", and "substituted alkenyl" means that "substituted or unsubstituted alkenyl" is "substituted alkenyl"), and in this specification, only expression of "alkenyl" includes both "unsubstituted alkenyl" and "substituted alkenyl".
"Substituted alkenyl" refers to a group in which 1 or more hydrogen atoms in the "unsubstituted alkenyl" are replaced with a substituent. Specific examples of the "substituted alkenyl group" include the following "unsubstituted alkenyl group" (specific example group G4A) having a substituent, and examples of the substituted alkenyl group (specific example group G4B). The examples of "unsubstituted alkenyl" and "substituted alkenyl" listed herein are only examples, and the "substituted alkenyl" described in this specification includes a group in which a hydrogen atom of an alkenyl group itself in the "substituted alkenyl" of the specific example group G4B is further substituted with a substituent, and a group in which a hydrogen atom of a substituent in the "substituted alkenyl" of the specific example group G4B is further substituted with a substituent.
Unsubstituted alkenyl (specific example group G4A):
Vinyl group,
Allyl group,
1-Butenyl,
2-Butenyl
3-Butenyl.
Substituted alkenyl (specific example group G4B):
1, 3-butadienyl,
1-Methyl vinyl group,
1-Methylallyl,
1, 1-Dimethylallyl group,
2-Methylallyl
1, 2-Dimethylallyl.
"Substituted or unsubstituted alkynyl"
Specific examples of the "substituted or unsubstituted alkynyl group" described in the present specification (specific example group G5) include the following unsubstituted alkynyl group (specific example group G5A) and the like. (herein, unsubstituted alkynyl refers to the case where "substituted or unsubstituted alkynyl" is "unsubstituted alkynyl"), and when only "alkynyl" is described below, both "unsubstituted alkynyl" and "substituted alkynyl" are included.
"Substituted alkynyl" refers to a group in which 1 or more hydrogen atoms in "unsubstituted alkynyl" are replaced with substituents. Specific examples of the "substituted alkynyl" include an "unsubstituted alkynyl" described below (specific examples group G5A) in which 1 or more hydrogen atoms and substituents are replaced.
Unsubstituted alkynyl (concrete example group G5A):
Ethynyl group
"Substituted or unsubstituted cycloalkyl"
Specific examples of the "substituted or unsubstituted cycloalkyl group" described in the present specification (specific example group G6) include an unsubstituted cycloalkyl group (specific example group G6A) and a substituted cycloalkyl group (specific example group G6B) described below. (herein, unsubstituted cycloalkyl means that "substituted or unsubstituted cycloalkyl" is "unsubstituted cycloalkyl", and substituted cycloalkyl means that "substituted or unsubstituted cycloalkyl" is "substituted cycloalkyl"). In this specification, only "cycloalkyl" is expressed, and both "unsubstituted cycloalkyl" and "substituted cycloalkyl" are included.
"Substituted cycloalkyl" refers to a group in which 1 or more hydrogen atoms in the "unsubstituted cycloalkyl" have been replaced with a substituent. Specific examples of the "substituted cycloalkyl group" include an "unsubstituted cycloalkyl group" (specific example group G6A) in which 1 or more hydrogen atoms and substituents are replaced, and a substituted cycloalkyl group (specific example group G6B) described below. The examples of "unsubstituted cycloalkyl" and "substituted cycloalkyl" mentioned herein are only examples, and the term "substituted cycloalkyl" as used herein includes a group in which 1 or more hydrogen atoms bonded to the carbon atom of the cycloalkyl group itself in the "substituted cycloalkyl" of the specific example group G6B are replaced with a substituent, and a group in which the hydrogen atom of the substituent in the "substituted cycloalkyl" of the specific example group G6B is further replaced with a substituent.
Unsubstituted cycloalkyl (specific example group G6A):
Cyclopropyl group,
Cyclobutyl group,
Cyclopentyl group,
Cyclohexyl group,
1-Adamantyl group,
2-Adamantyl group,
1-Norbornyl group
2-Norbornyl.
Substituted cycloalkyl (specific example group G6B):
4-methylcyclohexyl.
Radicals "shown in" -Si (R 901)(R902)(R903) "
Specific examples of the group represented by-Si (R 901)(R902)(R903) described in the present specification (group G7) 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)。
Here the number of the elements is the number,
G1 is "substituted or unsubstituted aryl" as described in the concrete example group G1.
G2 is a "substituted or unsubstituted heterocyclic group" as described in the concrete example group G2.
G3 is "substituted or unsubstituted alkyl group" described in the concrete example group G3.
G6 is "substituted or unsubstituted cycloalkyl" as described in the concrete example group G6.
-A plurality of G1 in Si (G1) being the same or different from each other.
-A plurality of G2 of Si (G1) (G2) being the same or different from each other.
-A plurality of G1 s of Si (G1) (G2) being the same or different from each other.
-A plurality of G2 in Si (G2) being the same or different from each other.
-A plurality of G3 in Si (G3) being the same or different from each other.
-A plurality of G6 of Si (G6) being the same or different from each other.
Radical "-O- (R 904)" as indicated "
Specific examples of the group represented by-O- (R 904) described in the present specification (group G8) include
-O(G1)、
-O(G2)、
-O (G3) and
-O(G6)。
Here the number of the elements is the number,
G1 is "substituted or unsubstituted aryl" as described in the concrete example group G1.
G2 is a "substituted or unsubstituted heterocyclic group" as described in the concrete example group G2.
G3 is "substituted or unsubstituted alkyl group" described in the concrete example group G3.
G6 is "substituted or unsubstituted cycloalkyl" as described in the concrete example group G6.
"Group represented by S- (R 905)":
Specific examples of the group represented by-S- (R 905) described in the present specification (group G9) include
-S(G1)、
-S(G2)、
-S (G3) and
-S(G6)。
Here the number of the elements is the number,
G1 is "substituted or unsubstituted aryl" as described in the concrete example group G1.
G2 is a "substituted or unsubstituted heterocyclic group" as described in the concrete example group G2.
G3 is "substituted or unsubstituted alkyl group" described in the concrete example group G3.
G6 is "substituted or unsubstituted cycloalkyl" as described in the concrete example group G6.
"Group represented by N (R 906)(R907)":
Specific examples of the group represented by-N (R 906)(R907) described in the present specification (group G10) include
-N(G1)(G1)、
-N(G2)(G2)、
-N(G1)(G2)、
-N (G3) (G3) and
-N(G6)(G6)。
Here the number of the elements is the number,
G1 is "substituted or unsubstituted aryl" as described in the concrete example group G1.
G2 is a "substituted or unsubstituted heterocyclic group" as described in the concrete example group G2.
G3 is "substituted or unsubstituted alkyl group" described in the concrete example group G3.
G6 is "substituted or unsubstituted cycloalkyl" as described in the concrete example group G6.
-A plurality of G1 in N (G1) being the same or different from each other.
-A plurality of G2 in N (G2) being the same or different from each other.
-A plurality of G3 in N (G3) are the same or different from each other.
-A plurality of G6 in N (G6) being the same or different from each other.
"Halogen atom"
Specific examples of the "halogen atom" described in the present specification (specific example group G11) include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
"Substituted or unsubstituted fluoroalkyl"
The term "substituted or unsubstituted fluoroalkyl" as used herein refers to a group in which at least 1 hydrogen atom bonded to a carbon atom constituting an alkyl group in the term "substituted or unsubstituted alkyl group" is replaced with a fluorine atom, and includes a group (perfluoro group) in which all hydrogen atoms bonded to a carbon atom constituting an alkyl group in the term "substituted or unsubstituted alkyl group" are replaced with a fluorine atom. The carbon number of the "unsubstituted fluoroalkyl" is 1 to 50, preferably 1 to 30, more preferably 1 to 18, unless otherwise stated in the specification. "substituted fluoroalkyl" refers to a radical obtained by replacing 1 or more hydrogen atoms of "fluoroalkyl" with substituents. The term "substituted fluoroalkyl" as used herein includes a group in which 1 or more hydrogen atoms bonded to a carbon atom of an alkyl chain in the term "substituted fluoroalkyl" are further substituted with a substituent, and a group in which 1 or more hydrogen atoms of a substituent in the term "substituted fluoroalkyl" are further substituted with a substituent. Specific examples of the "unsubstituted fluoroalkyl group" include those obtained by replacing 1 or more hydrogen atoms and fluorine atoms in the "alkyl group" (specific example group G3).
"Substituted or unsubstituted haloalkyl"
The term "substituted or unsubstituted haloalkyl" as used herein refers to a group in which at least 1 hydrogen atom bonded to a carbon atom constituting an alkyl group in the term "substituted or unsubstituted alkyl" is replaced with a halogen atom, and includes a group in which all hydrogen atoms bonded to a carbon atom constituting an alkyl group in the term "substituted or unsubstituted alkyl" are replaced with a halogen atom. The carbon number of the "unsubstituted haloalkyl" is 1 to 50, preferably 1 to 30, more preferably 1 to 18, unless otherwise stated in the specification. "substituted haloalkyl" refers to a radical obtained by substituting 1 or more hydrogen atoms of "haloalkyl" with substituents. The term "substituted haloalkyl" as used herein also includes a group in which 1 or more hydrogen atoms bonded to a carbon atom of an alkyl chain in the term "substituted haloalkyl" are further substituted with a substituent, and a group in which 1 or more hydrogen atoms of a substituent in the term "substituted haloalkyl" are further substituted with a substituent. Specific examples of the "unsubstituted haloalkyl group" include those wherein 1 or more hydrogen atoms and halogen atoms in the above-mentioned "alkyl group" (specific example group G3) have been replaced. Haloalkyl is sometimes referred to as haloalkyl.
"Substituted or unsubstituted alkoxy"
Specific examples of the "substituted or unsubstituted alkoxy group" described in the present specification are groups represented by-O (G3), and G3 is a "substituted or unsubstituted alkyl group" described in the specific example group G3. The carbon number of the "unsubstituted alkoxy group" is 1 to 50, preferably 1 to 30, more preferably 1 to 18, unless otherwise stated in the present specification.
"Substituted or unsubstituted alkylthio"
Specific examples of the "substituted or unsubstituted alkylthio group" described in the present specification are groups represented by-S (G3), and G3 is a "substituted or unsubstituted alkyl group" described in the specific example group G3. The carbon number of the "unsubstituted alkylthio group" is 1 to 50, preferably 1 to 30, more preferably 1 to 18, unless otherwise stated in the specification.
"Substituted or unsubstituted aryloxy"
Specific examples of the "substituted or unsubstituted aryloxy group" described in the present specification are groups represented by-O (G1), and G1 is a "substituted or unsubstituted aryl group" described in the specific example group G1. The number of ring-forming carbon atoms of the "unsubstituted aryloxy group" is 6 to 50, preferably 6 to 30, more preferably 6 to 18, unless otherwise described in the specification.
"Substituted or unsubstituted arylthio"
Specific examples of the "substituted or unsubstituted arylthio group" described in the present specification are groups represented by-S (G1), and G1 is a "substituted or unsubstituted aryl group" described in the specific example group G1. The number of ring-forming carbon atoms of the "unsubstituted arylthio group" is 6 to 50, preferably 6 to 30, more preferably 6 to 18, unless otherwise stated in the specification.
"Substituted or unsubstituted trialkylsilyl"
Specific examples of the "trialkylsilyl group" described in the present specification are groups represented by-Si (G3) (G3) (G3), where G3 is a "substituted or unsubstituted alkyl group" described in the specific example group G3. -a plurality of G3 in Si (G3) being the same or different from each other. The carbon number of each alkyl group of the "trialkylsilyl" is 1 to 50, preferably 1 to 20, more preferably 1 to 6, unless otherwise stated in the specification.
"Substituted or unsubstituted aralkyl"
Specific examples of the "substituted or unsubstituted aralkyl group" described in the present specification are groups represented by- (G3) to (G1), where G3 is a "substituted or unsubstituted alkyl group" described in the specific example group G3, and G1 is a "substituted or unsubstituted aryl group" described in the specific example group G1. Accordingly, the "aralkyl" is a group obtained by replacing a hydrogen atom of the "alkyl" with the "aryl" as a substituent, and is one embodiment of the "substituted alkyl". The "unsubstituted aralkyl group" is an "unsubstituted alkyl group substituted with an" unsubstituted aryl group ", and the carbon number of the" unsubstituted aralkyl group "is 7 to 50, preferably 7 to 30, and more preferably 7 to 18, unless otherwise described in the present specification.
Specific examples of the "substituted or unsubstituted aralkyl group" include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyltert-butyl, α -naphthylmethyl, 1- α -naphthylethyl, 2- α -naphthylethyl, 1- α -naphthylisopropyl, 2- α -naphthylisopropyl, β -naphthylmethyl, 1- β -naphthylethyl, 2- β -naphthylethyl, 1- β -naphthylisopropyl, and 2- β -naphthylisopropyl.
The substituted or unsubstituted aryl group described in the present specification is preferably phenyl, p-biphenyl, m-biphenyl, o-biphenyl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-terphenyl-4-yl, o-terphenyl-3-yl, o-terphenyl-2-yl, 1-naphthyl, 2-naphthyl, anthracenyl, phenanthryl, pyrenyl,Phenyl, triphenylenyl, fluorenyl, 9' -spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, and the like.
The substituted or unsubstituted heterocyclic group described in the present specification is preferably pyridyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, benzimidazolyl, phenanthrolinyl, carbazolyl (1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl or 9-carbazolyl), benzocarbazolyl, azacarbazolyl, diazacarbazolyl, dibenzofuranyl, naphthobenzofuranyl, azadibenzofuranyl, diazadibenzofuranyl, dibenzothienyl, naphthobenzothienyl, azadibenzothienyl, (9-phenyl) carbazolyl ((9-phenyl) carbazol-1-yl, (9-phenyl) carbazol-2-yl, (9-phenyl) carbazol-3-yl or (9-phenyl) carbazol-4-yl), (9-phenyl) phenylcarbazolyl, diphenylcarbazolyl, phenylcarbazolyl, phenyltriazinyl, dibenzotriazinyl, dibenzofuranyl, etc., unless otherwise specified.
In the present specification, the carbazolyl group is specifically any of the following groups unless otherwise specified in the present specification.
[ Chemical formula 7]
In the present specification, (9-phenyl) carbazolyl is specifically any of the following unless otherwise specified in the present specification.
[ Chemical formula 8]
In the general formulas (TEMP-Cz 1) - (TEMP-Cz 9), the bonding position is represented by x.
In the present specification, dibenzofuranyl and dibenzothiophenyl are specifically any of the following unless otherwise specified in the present specification.
[ Chemical formula 9]
In the general formulae (TEMP-34) - (TEMP-41), the bonding position is represented.
The substituted or unsubstituted alkyl group described in the present specification is preferably methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or the like unless otherwise specified in the present specification.
"Substituted or unsubstituted arylene"
The "substituted or unsubstituted arylene group" described in the present specification is a divalent group derived from the "substituted or unsubstituted aryl group" by removing 1 hydrogen atom from the aryl ring unless otherwise specified. Specific examples of the "substituted or unsubstituted arylene group" (concrete example group G12) include a divalent group derived from the "substituted or unsubstituted aryl group" described in concrete example group G1 by removing 1 hydrogen atom from the aryl ring.
"Substituted or unsubstituted divalent heterocyclic radical"
The "substituted or unsubstituted divalent heterocyclic group" described in the present specification is a divalent group derived from the above-mentioned "substituted or unsubstituted heterocyclic group" by removing 1 hydrogen atom from the heterocyclic ring unless otherwise specified. Specific examples of the "substituted or unsubstituted divalent heterocyclic group" (concrete example group G13) include a divalent group derived from the "substituted or unsubstituted heterocyclic group" described in concrete example group G2 by removing 1 hydrogen atom from the heterocycle.
"Substituted or unsubstituted alkylene"
The "substituted or unsubstituted alkylene group" described in the present specification is a divalent group derived by removing 1 hydrogen atom on the alkyl chain from the "substituted or unsubstituted alkyl group" unless otherwise specified. Specific examples of the "substituted or unsubstituted alkylene group" (concrete example group G14) include a divalent group derived from the "substituted or unsubstituted alkyl group" described in concrete example group G3 by removing 1 hydrogen atom from the alkyl chain.
The substituted or unsubstituted arylene group described in the present specification is preferably any one of the following general formulae (TEMP-42) to (TEMP-68) unless otherwise described in the present specification.
[ Chemical formula 10]
[ Chemical formula 11]
In the general formulae (TEMP-42) to (TEMP-52), Q 1～Q10 is independently a hydrogen atom or a substituent.
In the general formulae (TEMP-42) - (TEMP-52), the bonding position is represented.
[ Chemical formula 12]
In the general formulae (TEMP-53) to (TEMP-62), Q 1～Q10 is independently a hydrogen atom or a substituent.
Formulas Q 9 and Q 10 may be bonded to each other via a single bond to form a ring.
In the general formulae (TEMP-53) - (TEMP-62), the bonding position is represented.
[ Chemical formula 13]
In the general formulae (TEMP-63) to (TEMP-68), Q 1～Q8 is independently a hydrogen atom or a substituent.
In the general formulae (TEMP-63) - (TEMP-68), the bonding position is represented.
The substituted or unsubstituted divalent heterocyclic group described in the present specification is preferably any one of the following general formulae (TEMP-69) to (TEMP-102) unless otherwise described in the present specification.
[ Chemical formula 14]
[ Chemical formula 15]
[ Chemical formula 16]
In the general formulae (TEMP-69) - (TEMP-82), Q 1～Q9 each independently represents a hydrogen atom or a substituent.
[ Chemical formula 17]
[ Chemical formula 18]
[ Chemical formula 19]
[ Chemical formula 20]
In the general formulae (TEMP-83) - (TEMP-102), Q 1～Q8 are each independently a hydrogen atom or a substituent.
The above is a description of "substituents described in the present specification".
"Case of bonding to form a Ring"
In this specification, the expression "a case where 1 or more groups of 2 or more adjacent groups are bonded to each other to form a substituted or unsubstituted single ring, or are bonded to each other to form a substituted or unsubstituted condensed ring, or are not bonded to each other" refers to a case where 1 or more groups of 2 or more adjacent groups are bonded to each other to form a substituted or unsubstituted single ring, "a case where 1 or more groups of 2 or more adjacent groups are bonded to each other to form a substituted or unsubstituted condensed ring," and a case where 1 or more groups of 2 or more adjacent groups are not bonded to each other.
Hereinafter, a description will be given of a case where 1 or more groups of 2 or more adjacent groups are bonded to each other to form a substituted or unsubstituted single ring and a case where 1 or more groups of 2 or more adjacent groups are bonded to each other to form a substituted or unsubstituted condensed ring (hereinafter, these cases are sometimes referred to as "a case where bonding forms a ring"). The case of an anthracene compound represented by the following general formula (TEMP-103) having a parent skeleton as an anthracene ring will be described as an example.
[ Chemical formula 21]
For example, in the case where 1 or more groups of "adjacent 2 or more groups among R 921～R930 are bonded to each other to form a ring", the group of adjacent 2 groups of 1 means that the group of R 921 and R 922, the group of R 922 and R 923, A group of R 923 and R 924, a group of R 924 and R 930, a group of R 930 and R 925, A group of R 925 and R 926, a group of R 926 and R 927, a group of R 927 and R 928, A group of R 928 and R 929, and a group of R 929 and R 921.
The "1 or more groups" means that 2 or more groups of the adjacent 2 or more groups can simultaneously form a ring. For example, when R 921 and R 922 are bonded to each other to form a ring Q A and simultaneously R 925 and R 926 are bonded to each other to form a ring Q B, the anthracene compound represented by the above general formula (TEMP-103) is represented by the following general formula (TEMP-104).
[ Chemical formula 22]
The case where "a group of 2 or more adjacent groups" forms a ring includes not only the case where a group of 2 or more adjacent groups is bonded as in the foregoing example, but also the case where a group of 3 or more adjacent groups is bonded. For example, R 921 and R 922 are bonded to each other to form a ring Q A, and R 922 and R 923 are bonded to each other to form a ring Q C, and 3 groups (R 921、R922 and R 923) adjacent to each other are bonded to each other to form a ring and condensed on an anthracene skeleton, and in this case, an 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), R 922 is shared by the ring Q A and the ring Q C.
[ Chemical formula 23]
In the "single ring" or "condensed ring" formed, the ring formed may have a saturated ring or an unsaturated ring as a structure of the ring itself. Even in the case where "1 group of adjacent 2 groups" forms a "single ring" or "condensed ring", the "single ring" or "condensed ring" may form a saturated ring or an unsaturated ring. For example, the ring Q A and the ring Q B formed in the above general formula (TEMP-104) are each a "single ring" or a "condensed ring". In addition, the ring Q A and the ring Q c formed in the above general formula (TEMP-105) are "condensed rings". The rings Q A and Q C of the general formula (TEMP-105) are fused to form a fused ring by the ring Q A and the ring Q C. If ring Q A of the above general formula (TMEP-104) is a benzene ring, ring Q A is a single ring. If the ring Q A of the above general formula (TMEP-104) is a naphthalene ring, the ring Q A is a condensed ring.
"Unsaturated ring" refers to an aromatic hydrocarbon ring or an aromatic heterocycle. "saturated ring" refers to an aliphatic hydrocarbon ring or a non-aromatic heterocyclic ring.
Specific examples of the aromatic hydrocarbon ring include a structure in which a group specifically exemplified as group G1 is blocked with a hydrogen atom.
Specific examples of the aromatic heterocyclic ring include a structure in which an aromatic heterocyclic group specifically exemplified as group G2 is blocked with a hydrogen atom.
Specific examples of the aliphatic hydrocarbon ring include structures in which a group specifically exemplified as group G6 is blocked with a hydrogen atom.
"Forming a ring" means forming a ring from only multiple atoms of the parent skeleton or from multiple atoms of the parent skeleton with 1 or more additional optional elements. For example, the ring Q A formed by bonding R 921 and R 922 shown by the general formula (TEMP-104) refers to a ring formed by the carbon atom of the anthracene skeleton bonded by R 921 and the carbon atom of the anthracene skeleton bonded by R 922 and 1 or more optional elements. Specifically, in the case where R 921 and R 922 form a ring Q A, when a monocyclic unsaturated ring is formed by a carbon atom of an anthracene skeleton to which R 921 is bonded, a carbon atom of an anthracene skeleton to which R 922 is bonded, and 4 carbon atoms, the ring formed by R 921 and R 922 is a benzene ring.
Here, the "optional element" is preferably at least 1 element selected from the group consisting of a carbon element, a nitrogen element, an oxygen element, and a sulfur element unless otherwise described in the present specification. In the optional element (for example, in the case of a carbon element or a nitrogen element), the bond which does not form a ring may be blocked by a hydrogen atom or the like, or may be substituted by an "optional substituent" described later. When an optional element other than carbon is included, the ring formed is a heterocyclic ring.
If not otherwise described in the present specification, "1 or more optional elements" constituting a single ring or a condensed ring are preferably 2 or more and 15 or less, more preferably 3 or more and 12 or less, and still more preferably 3 or more and 5 or less.
In the present specification, unless otherwise stated, the term "monocyclic ring" and the term "condensed ring" are preferably "monocyclic ring".
In the present specification, unless otherwise stated, the "saturated ring" and the "unsaturated ring" are preferably "unsaturated ring".
In the present specification, unless otherwise stated, the "monocyclic ring" is preferably a benzene ring.
In the present specification, unless otherwise stated, the "unsaturated ring" is preferably a benzene ring.
In the case where "1 or more groups of 2 or more adjacent groups" are bonded to each other to form a substituted or unsubstituted single ring "or" are bonded to each other to form a substituted or unsubstituted condensed ring "unless otherwise described in the present specification, it is preferable that 1 or more groups of 2 or more adjacent groups are bonded to each other to form a substituted or unsubstituted" unsaturated ring "formed of a plurality of atoms of a parent skeleton and 1 or more and 15 or less elements selected from at least 1 element selected from the group consisting of carbon element, nitrogen element, oxygen element and sulfur element.
The substituent when the "single ring" or "condensed ring" has a substituent is, for example, an "optional substituent" described later. Specific examples of the substituent when the "single ring" or "condensed ring" has a substituent are the substituents described in the above item of "substituent described in the present specification".
The substituent when the "saturated ring" or "unsaturated ring" has a substituent is, for example, an "optional substituent" described later. Specific examples of the substituent when the "single ring" or "condensed ring" has a substituent are the substituents described in the above item of "substituent described in the present specification".
The above description is for the case of "a substituted or unsubstituted single ring is formed by bonding 1 or more groups of 2 or more adjacent groups" and the case of "a substituted or unsubstituted condensed ring is formed by bonding 1 or more groups of 2 or more adjacent groups" (the case of "a ring is formed by bonding").
Substituents when expressed as "substituted or unsubstituted
In one embodiment of the present specification, the substituent when expressed as "substituted or unsubstituted" (in the present specification, sometimes referred to as "optional substituent") is, for example, a substituent selected from the group consisting of
Unsubstituted alkyl group having 1 to 50 carbon atoms,
Unsubstituted alkenyl group having 2 to 50 carbon atoms,
Unsubstituted alkynyl with 2-50 carbon atoms,
Unsubstituted cycloalkyl having 3 to 50 ring-forming carbon atoms,
-Si(R901)(R902)(R903)、
-O-(R904)、
-S-(R905)、
-N(R906)(R907)、
Halogen atom, cyano group, nitro group,
Unsubstituted aryl groups having 6 to 50 ring carbon atoms and
Unsubstituted heterocyclic group having 5 to 50 ring members
A group in the group consisting of, and the like,
Here, R 901～R907 are each independently
A hydrogen atom,
Substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
Substituted or unsubstituted cycloalkyl having 3 to 50 ring-forming carbon atoms,
Substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or
A substituted or unsubstituted heterocyclic group having 5 to 50 ring members.
In the case where R 901 is present in an amount of 2 or more, 2 or more R 901 are the same or different from each other,
In the case where R 902 is present in an amount of 2 or more, 2 or more R 902 are the same or different from each other,
In the case where R 903 is present in an amount of 2 or more, 2 or more R 903 are the same or different from each other,
In the case where R 904 is present in an amount of 2 or more, 2 or more R 904 are the same or different from each other,
In the case where R 905 is present in an amount of 2 or more, 2 or more R 905 are the same or different from each other,
In the case where R 906 is present in an amount of 2 or more, 2 or more R 906 are the same or different from each other,
When there are 2 or more R 907, 2 or more R 907 are the same or different from each other.
In one embodiment, the substituents described above as "substituted or unsubstituted" are selected from the group consisting of
An alkyl group having 1 to 50 carbon atoms,
Aryl with ring-forming carbon number of 6-50
Heterocyclic group with ring-forming atom number of 5-50
Groups in the group consisting of.
In one embodiment, the substituents described above as "substituted or unsubstituted" are selected from the group consisting of
An alkyl group having 1 to 18 carbon atoms,
Aryl with ring-forming carbon number of 6-18
Heterocyclic group with 5-18 ring atoms
Groups in the group consisting of.
Specific examples of the groups of the above-mentioned optional substituents are specific examples of the substituents described in the item of "substituents described in the present specification" above.
Unless otherwise indicated herein, adjacent optional substituents may form a "saturated ring" or an "unsaturated ring", and preferably form a substituted or unsubstituted saturated five-membered ring, a substituted or unsubstituted saturated six-membered ring, a substituted or unsubstituted unsaturated five-membered ring, or a substituted or unsubstituted unsaturated six-membered ring, and more preferably form a benzene ring.
The optional substituent may further have a substituent unless otherwise stated in the specification. The substituent further included as an optional substituent is the same as the above optional substituent.
In the present specification, the numerical range indicated by "AA to BB" means a range including the numerical value AA described in front of "AA to BB" as a lower limit value and the numerical value BB described in rear of "AA to BB" as an upper limit value.
The compounds of the present invention will be described below.
The compound according to one embodiment of the present invention is represented by the following formula (1).
Among them, the compounds of the present invention represented by the formula (1) and the formula (1) described below are sometimes referred to as "inventive compound (1)". The compound according to another embodiment of the present invention is represented by formula (2) described below. Hereinafter, the compound of the present invention represented by the formula (2) and the formula (2) described below will be referred to simply as "inventive compound (2)". In addition, in the case where both of the "invention compound (1)" and the "invention compound (2)" are meant, they are sometimes referred to as "invention compound" only.
[ Chemical formula 24]
The following description will be given of the formula (1) and symbols included in the formula (1) described later. Note that the same symbols have the same meaning.
In the formula (1), the components are as follows,
Ar 1～Ar3 is independently a substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 30 ring-forming carbon atoms.
The details of the substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms represented by Ar 1～Ar3 are the same as those described in the above description of the substituent group described in the present specification.
The unsubstituted aryl group represented by Ar 1～Ar3 is preferably phenyl, biphenyl, naphthyl, or fluorenyl.
The details of the substituted or unsubstituted heterocyclic group having 5 to 30 ring members represented by Ar 1～Ar3 are the same as those described in the above description of the "substituent group described in the present specification".
The above unsubstituted heterocyclic group represented by Ar 1～Ar3 is preferably pyridyl, quinazolinyl, dibenzofuranyl, or dibenzothienyl.
Ar 1 is preferably a substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms, more preferably a phenyl group, a biphenyl group, or a naphthyl group, and still more preferably a phenyl group.
In one embodiment, ar 2 is preferably a substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms, more preferably a phenyl group, a biphenyl group, a naphthyl group, or a fluorenyl group, and still more preferably a phenyl group, a biphenyl group, or a naphthyl group.
In another embodiment, ar 2 is preferably a substituted or unsubstituted heterocyclic group having 5 to 30 ring members, more preferably a pyridyl group, a quinazolinyl group, a dibenzofuranyl group, or a dibenzothienyl group.
Ar 3 is preferably phenyl, pyridyl, dibenzofuranyl, or dibenzothienyl, more preferably dibenzofuranyl.
L 1 is a substituted or unsubstituted arylene group having 6 to 30 ring-forming carbon atoms or a substituted or unsubstituted divalent heterocyclic group having 5 to 30 ring-forming carbon atoms, and Ar 2 and L 1 may be bonded to each other to form a substituted or unsubstituted ring.
L 1 is preferably a substituted or unsubstituted arylene group having 6 to 30 ring-forming carbon atoms.
The details of the substituted or unsubstituted arylene group having 6 to 30 ring-forming carbon atoms represented by L 1 are the same as those described in the above description of the "substituent group described in the present specification".
The unsubstituted arylene group having 6 to 30 ring-forming carbon atoms represented by L 1 is preferably phenylene, biphenylene, or naphthylene, and more preferably phenylene.
The details of the substituted or unsubstituted divalent heterocyclic group having 5 to 30 ring members represented by L 1 are the same as those described in the above description of the "substituent described in the present specification".
The details of the optionally substituted or unsubstituted ring formed by bonding Ar 2 and L 1 to each other are the same as those described in the description of the substituent described in the description of the present invention, and are selected from a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aliphatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocyclic ring, and a substituted or unsubstituted non-aromatic heterocyclic ring.
The aromatic hydrocarbon ring is, for example, a benzene ring, a biphenylene ring, a naphthalene ring, or a fluorene ring, and preferably a naphthalene ring or a fluorene ring.
The aliphatic hydrocarbon ring is, for example, a cyclopentene ring, a cyclopentadiene ring, a cyclohexene ring, a cyclohexadiene ring, or a hydrocarbon ring obtained by partially hydrogenating the aromatic hydrocarbon ring.
The aromatic heterocyclic ring is, for example, 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, or a benzocarbazole ring, and preferably a dibenzofuran ring or a dibenzothiophene ring.
The non-aromatic heterocycle is, for example, a heterocycle obtained by partially hydrogenating the aromatic heterocycle.
L2 is a single bond or a 2+p-valent residue of a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 25 ring-forming carbon atoms.
In one embodiment of the invention, L2 is preferably a single bond. In another embodiment, L2 is preferably a 2+p-valent residue of a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 25 ring-forming carbon atoms.
Examples of the 2+p-valent residue of the substituted or unsubstituted aromatic hydrocarbon ring having 6 to 25 ring-forming carbon atoms represented by L2 include phenylene, biphenylene, terphenylene, naphthylene, anthrylene, benzanthracene, phenanthrylene, benzophenanthrylene, phenalenylene, picene, pentylenene, pyrenylene, andBenzo (a) base, a phenyleneA group, a triphenylene group, a fluoranthene group, a fluorenylene group, or the like.
The 2+p-valent residue of the unsubstituted aromatic hydrocarbon ring having 6 to 25 ring-forming carbon atoms represented by L 2 is preferably phenylene, biphenylene, or naphthylene, more preferably phenylene.
P is 0 or1, where L 2 is a single bond, p is 0, and where L 2 is a 2+p residue of a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 25 ring-forming carbon atoms, p is 0 or 1.
P is preferably 0.
R 1～R6 and R 11～R14 are each independently of the other
A hydrogen atom,
Halogen atom,
Cyano group,
Nitro group,
Substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
Substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms,
Substituted or unsubstituted alkynyl having 2 to 50 carbon atoms,
Substituted or unsubstituted cycloalkyl having 3 to 50 ring-forming carbon atoms,
A group represented by Si (R 901)(R902)(R903),
A group represented by-O- (R 904),
A group represented by S- (R 905),
A group represented by-N (R 906)(R907),
Substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or
A substituted or unsubstituted heterocyclic group having 5 to 50 ring members,
R 901～R907 are each independently
A hydrogen atom,
Substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
Substituted or unsubstituted cycloalkyl having 3 to 50 ring-forming carbon atoms,
Substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or
A substituted or unsubstituted heterocyclic group having 5 to 50 ring members,
In the case where R 901 is present in an amount of 2 or more, 2 or more R 901 are the same or different from each other,
In the case where R 902 is present in an amount of 2 or more, 2 or more R 902 are the same or different from each other,
In the case where R 903 is present in an amount of 2 or more, 2 or more R 903 are the same or different from each other,
In the case where R 904 is present in an amount of 2 or more, 2 or more R 904 are the same or different from each other,
In the case where R 905 is present in an amount of 2 or more, 2 or more R 905 are the same or different from each other,
In the case where R 906 is present in an amount of 2 or more, 2 or more R 906 are the same or different from each other,
In the case where R 907 is present in an amount of 2 or more, 2 or more R 907 are the same or different from each other,
R 1 and R 2 are not bonded to each other to form a ring,
In the group of 1 or more selected from R 3 and R 4、R4 and R 5、R5 and R 6、R11 and R 12、R12 and R 13 and R 13 and R 14, adjacent 2 may be bonded to each other to form a substituted or unsubstituted ring.
R 1～R6 and R 11～R14 are each independently preferably 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-forming carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring-forming carbon atoms, more preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, still more preferably a hydrogen atom.
The details of the halogen atom represented by R 1～R6 and R 11～R14 are the same as those described in the above description of the substituent "described in the present specification, and a fluorine atom is preferable.
The details of the substituted or unsubstituted alkyl group having 1 to 50 carbon atoms represented by R 1～R6 and R 11～R14 are the same as those described in the "substituents described in the present specification" above.
The unsubstituted alkyl group represented by R 1～R6 and R 11～R14 is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl, more preferably methyl, ethyl, isopropyl, or tert-butyl, and still more preferably methyl or tert-butyl.
The details of the substituted or unsubstituted alkenyl group having 2 to 50 ring-forming carbon atoms represented by R 1～R6 and R 11～R14 are the same as those described in the above description of the "substituent described in the present specification".
The details of the above-mentioned substituted or unsubstituted alkynyl group having 2 to 50 ring-forming carbon atoms represented by R 1～R6 and R 11～R14 are the same as those described in the above-mentioned "substituents described in the present specification".
The details of the substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms represented by R 1～R6 and R 11～R14 are the same as those described in the above description of the "substituent described in the present specification".
The unsubstituted cycloalkyl group represented by R 1～R6 and R 11～R14 is preferably cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, or 2-norbornyl, more preferably cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl, still more preferably cyclopentyl or cyclohexyl.
R 1～R6 and R 11～R14 are the above-mentioned-Si (R 901)(R902)(R903), the above-mentioned-O- (R 904) group, -S- (R 905) group and the details of the group represented by-N (R 906)(R907) are the same as those described in the "substituents described in the present specification".
The details of the substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms represented by R 1～R6 and R 11～R14 are the same as those described in the "substituents described in the present specification".
The unsubstituted aryl group represented by R 1～R6 and R 11～R14 is preferably phenyl, biphenyl, naphthyl, or phenanthryl, more preferably phenyl, biphenyl, or naphthyl, and still more preferably phenyl.
The details of the above-mentioned substituted or unsubstituted heterocyclic group having 5 to 50 ring members represented by R 1～R6 and R 11～R14 are the same as those described in "substituents described in the present specification".
The unsubstituted heterocyclic group is preferably dibenzofuranyl or dibenzothienyl.
In the group of 1 or more selected from R 3 and R 4、R4 and R 5、R5 and R 6、R11 and R 12、R12 and R 13 and R 13 and R 14, details of the optionally substituted or unsubstituted ring formed by bonding adjacent 2 groups to each other are the same as those described for the optionally substituted or unsubstituted ring formed by bonding Ar 2 and L 1 to each other.
In the present invention, in the group of 1 or more selected from R 3 and R 4、R4 and R 5、R5 and R 6、R11 and R 12、R12 and R 13 and R 13 and R 14, adjacent 2 may not be bonded to each other to form a substituted or unsubstituted ring.
X 1 is an oxygen atom or a sulfur atom.
In one embodiment of the invention, X 1 is preferably an oxygen atom. In another embodiment, X 1 is preferably a sulfur atom.
* D is bonded to one selected from carbon atoms a, b and c.
In one embodiment of the invention, d is preferably bonded to carbon atom a. In another embodiment, d is preferably bonded to carbon atom b. In yet another embodiment, d is preferably bonded to carbon atom c.
The inventive compound (1) represented by the formula (1) is preferably represented by any one of the following formulas (1A) to (1C).
[ Chemical formula 25]
In the steps (1A) - (1C),
R 21～R25 and R 31～R38 are each independently of the other
A hydrogen atom,
Halogen atom,
Cyano group,
Nitro group,
Substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
Substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms,
Substituted or unsubstituted alkynyl having 2 to 50 carbon atoms,
Substituted or unsubstituted cycloalkyl having 3 to 50 ring-forming carbon atoms,
A group represented by Si (R 901)(R902)(R903),
A group represented by-O- (R 904),
A group represented by S- (R 905),
A group represented by-N (R 906)(R907),
Substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or
A substituted or unsubstituted heterocyclic group having 5 to 50 ring members.
Wherein, the
In the formula (1A), the amino acid sequence,
In the case where p is 0, 1 selected from R 21～R25 is a single bond to f,
In the case where p is 1,1 selected from R 21～R25 is a single bond to e, the other 1 selected from R 21～R25 is a single bond to f,
In the formula (1B), the amino acid sequence,
In the case where p is 0, 1 selected from R 31～R38 is a single bond to g, the other 1 selected from R 31～R38 is a single bond to i,
In the case where p is 1, 1 selected from R 31～R38 is a single bond to g, another 1 selected from R 31～R38 is a single bond to h, and yet another 1 selected from R 31～R38 is a single bond to i.
Ar1～Ar3、L1、p、R1～R6、R11～R14、X1、＊a、＊b、＊c、＊d And R 901～R907 is as defined in formula (1).
R 21～R25 and R 31～R38 are each independently preferably 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-forming carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring-forming carbon atoms, more preferably 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-forming carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring-forming carbon atoms, still more preferably a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, and still more preferably a hydrogen atom.
The details of each group represented by R 21～R25 and R 31～R38 are the same as those of the corresponding group described for R 1～R6 and R 11～R14, and preferably the groups and the like are the same.
In the formula (1A), the amino acid sequence,
In the case where p is 0, preferably 1 selected from R 22～R24 is a single bond to f.
In the case where p is 1, it is preferable that 1 selected from R 22 and R 23 is a single bond to be bonded to e, and 1 selected from R 24 and R 23 is a single bond to be bonded to f.
The inventive compound (1) represented by the formula (1) is preferably represented by the following formula (1A-1) or (1B-1).
[ Chemical formula 26]
In the formulae (1A-1) and (1B-1),
Ar 1、Ar2、L1、R1～R6、R11～R14、X1, a, B, c and d are as defined in formula (1), R 21～R26 and f are as defined in formula (1A), and R 31～R38, g and i are as defined in formula (1B).
The inventive compound (1) represented by the formula (1) is preferably represented by the following formula (1A-1A) or (1A-1 b).
[ Chemical formula 27]
In the formulae (1A-1A) and (1A-1 b),
Ar 1、Ar2、L1、R1～R6、R11～R14、X1, a, b, c and d are as defined in formula (1), and R 21～R25 is as defined in formula (1A).
The inventive compound (1) represented by the formula (1) is preferably represented by the following formulas (1A-1 c).
[ Chemical formula 28]
In the formula (1A-1 c),
Ar 1、Ar2、L1、R1～R6、R11～R14, and X 1 are as defined in formula (1), and R 21～R25 and f are as defined in formula (1A).
The inventive compound (1) represented by the formula (1) is preferably represented by the following formula (1C-1 a).
[ Chemical formula 29]
In the formula (1C-1 a),
Ar 1、Ar2、L1、R1～R6、R11～R14 and X 1 are as defined in formula (1).
As an aspect of the present invention,
(1-1) R 1～R6 may be a hydrogen atom,
(1-2) R 11～R14 may be a hydrogen atom,
(1-3) In formula (1A), R 21～R25, which is not a single bond bonded to f and e, may each be a hydrogen atom,
(1-4) In formula (1B), R 31～R38, which is not a single bond to g, h and i, may be a hydrogen atom,
(1-5) In formula (1A-1), R 21～R25, which is not a single bond to f, may be a hydrogen atom,
(1-6) In formula (1B-1), R 31～R38 which is not a single bond to g and i may each be a hydrogen atom,
(1-7) In the formula (1A-1A), R 21、R22、R24 and R 25 may each be a hydrogen atom,
(1-8) In the formula (1A-1 b), R 21 and R 23～R25 may each be a hydrogen atom,
(1-9) In formula (1A-1 c), R 21～R25, which is not a single bond to f, may be a hydrogen atom.
The compound according to another embodiment of the present invention is represented by the following formula (2).
[ Chemical formula 30]
The following describes the symbols in the formulas (2) and (2) described below. Note that the same symbols have the same meaning.
In the formula (2), the amino acid sequence of the compound,
Ar 11～Ar13 is independently a substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 30 ring-forming carbon atoms.
The details of the substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms represented by Ar 11～Ar13 are the same as those described in the above description of the substituent group described in the present specification.
The unsubstituted aryl group represented by Ar 11～Ar13 is preferably phenyl, biphenyl, naphthyl, or fluorenyl.
The details of the substituted or unsubstituted heterocyclic group having 5 to 30 ring members represented by Ar 11～Ar13 are the same as those described in the above description of the "substituent group described in the present specification".
The above unsubstituted heterocyclic group represented by Ar 11～Ar13 is preferably pyridyl, quinazolinyl, dibenzofuranyl, or dibenzothienyl.
Ar 11 is preferably a substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms, more preferably a phenyl group, a biphenyl group, or a naphthyl group, and still more preferably a phenyl group.
In one embodiment, ar 12 is preferably a substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms, more preferably a phenyl group, a biphenyl group, a naphthyl group, or a fluorenyl group, and still more preferably a phenyl group, a biphenyl group, or a naphthyl group.
In another embodiment, ar 12 is preferably a substituted or unsubstituted heterocyclic group having 5 to 30 ring members, more preferably a pyridyl group, a quinazolinyl group, a dibenzofuranyl group, or a dibenzothienyl group.
Ar 23 is preferably phenyl, pyridyl, dibenzofuranyl, or dibenzothienyl, more preferably dibenzofuranyl.
L 11 is a substituted or unsubstituted arylene group having 6 to 30 ring-forming carbon atoms or a substituted or unsubstituted divalent heterocyclic group having 5 to 30 ring-forming carbon atoms, and Ar 12 and L 11 may be bonded to each other to form a substituted or unsubstituted ring.
L 11 is preferably a substituted or unsubstituted arylene group having 6 to 30 ring-forming carbon atoms.
The details of the substituted or unsubstituted arylene group having 6 to 30 ring-forming carbon atoms represented by L 11 are the same as those described in the above description of the "substituent group described in the present specification".
The unsubstituted arylene group having 6 to 30 ring-forming carbon atoms represented by L 11 is preferably phenylene, biphenylene, or naphthylene, and more preferably phenylene.
The details of the substituted or unsubstituted divalent heterocyclic group having 5 to 30 ring members represented by L 11 are the same as those described in the above description of the "substituent described in the present specification".
The details of the optionally substituted or unsubstituted ring formed by bonding Ar 12 and L 11 to each other are the same as those described in the description of the substituent described in the description of the present invention, and are selected from a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aliphatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocyclic ring, and a substituted or unsubstituted non-aromatic heterocyclic ring. The details of the substituted or unsubstituted aromatic hydrocarbon ring, the substituted or unsubstituted aliphatic hydrocarbon ring, the substituted or unsubstituted aromatic heterocyclic ring, and the substituted or unsubstituted non-aromatic heterocyclic ring are the same as those of the case where Ar 2 and L 1 of formula (1) are bonded to each other to form a substituted or unsubstituted ring.
L 12 is a 2+q-valent residue of a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 25 ring-forming carbon atoms.
Examples of the 2+q-valent residue of the substituted or unsubstituted aromatic hydrocarbon ring having 6 to 25 ring-forming carbon atoms represented by L 12 include phenylene, biphenylene, terphenylene, naphthylene, anthrylene, benzanthracene, phenanthrylene, benzophenanthrylene, phenalenylene, picenylene, pentylenene, pyrenylene, andBenzo (a) base, a phenyleneA group, a triphenylene group, a fluoranthene group, a fluorenylene group, or the like.
The 2+q-valent residue of the unsubstituted aromatic hydrocarbon ring having 6 to 25 ring-forming carbon atoms represented by L 12 is preferably phenylene, biphenylene, or naphthylene, more preferably phenylene.
Q is 0 or 1.
Q is preferably 0.
R 41～R46 and R 51～R54 are each independently of the other
A hydrogen atom,
Halogen atom,
Cyano group,
Nitro group,
Substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
Substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms,
Substituted or unsubstituted alkynyl having 2 to 50 carbon atoms,
Substituted or unsubstituted cycloalkyl having 3 to 50 ring-forming carbon atoms,
A group represented by Si (R 901)(R902)(R903),
A group represented by-O- (R 904),
A group represented by S- (R 905),
A group represented by-N (R 906)(R907),
Substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or
A substituted or unsubstituted heterocyclic group having 5 to 50 ring members,
R 901～R907 are each independently
A hydrogen atom,
Substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
Substituted or unsubstituted cycloalkyl having 3 to 50 ring-forming carbon atoms,
Substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or
A substituted or unsubstituted heterocyclic group having 5 to 50 ring members,
In the case where R 901 is present in an amount of 2 or more, 2 or more R 901 are the same or different from each other,
In the case where R 902 is present in an amount of 2 or more, 2 or more R 902 are the same or different from each other,
In the case where R 903 is present in an amount of 2 or more, 2 or more R 903 are the same or different from each other,
In the case where R 904 is present in an amount of 2 or more, 2 or more R 904 are the same or different from each other,
In the case where R 905 is present in an amount of 2 or more, 2 or more R 905 are the same or different from each other,
In the case where R 906 is present in an amount of 2 or more, 2 or more R 906 are the same or different from each other,
In the case where R 907 is present in an amount of 2 or more, R 907 are the same or different from each other, R 41 and R 42 are not bonded to each other to form a ring,
In the group of 1 or more selected from R 43 and R 44、R44 and R 45、R45 and R 46、R51 and R 52、R52 and R 53, and R 53 and R 54, adjacent 2 may be bonded to each other to form a substituted or unsubstituted ring.
The details of each group represented by R 41～R46 and R 51～R54 are the same as those of the corresponding group described for R 1～R6 and R 11～R14, and preferably the groups and the like are the same.
In the group of 1 or more selected from R 43 and R 44、R44 and R 45、R45 and R 46、R51 and R 52、R52 and R 53, and R 53 and R 54, details of the optionally substituted or unsubstituted ring formed by bonding 2 adjacent groups to each other are the same as those described in the substituent described in the description above and are selected from a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aliphatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocyclic ring, and a substituted or unsubstituted non-aromatic heterocyclic ring. The details of the substituted or unsubstituted aromatic hydrocarbon ring, the substituted or unsubstituted aliphatic hydrocarbon ring, the substituted or unsubstituted aromatic heterocyclic ring, and the substituted or unsubstituted non-aromatic heterocyclic ring are the same as those of the case where Ar 2 and L 1 of formula (1) are bonded to each other to form a substituted or unsubstituted ring.
In the present invention, in the group of 1 or more selected from R 43 and R 44、R44 and R 45、R45 and R 46、R51 and R 52、R52 and R 53, and R 53 and R 54, adjacent 2 may not be bonded to each other to form a substituted or unsubstituted ring.
X 11 is an oxygen atom or a sulfur atom.
In one embodiment of the invention, X 11 is preferably an oxygen atom. In another embodiment, X 11 is preferably a sulfur atom.
The inventive compound (2) represented by the formula (2) is preferably represented by the following formula (2A) or (2B).
[ Chemical formula 31]
In the formulas (2A) and (2B),
R 61～R65 and R 71～R78 are each independently of the other
A hydrogen atom,
Halogen atom,
Cyano group,
Nitro group,
Substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
Substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms,
Substituted or unsubstituted alkynyl having 2 to 50 carbon atoms,
Substituted or unsubstituted cycloalkyl having 3 to 50 ring-forming carbon atoms,
A group represented by Si (R 901)(R902)(R903),
A group represented by-O- (R 904),
A group represented by S- (R 905),
A group represented by-N (R 906)(R907),
Substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or
A substituted or unsubstituted heterocyclic group having 5 to 50 ring members.
Wherein, the
In the formula (2A), the amino acid sequence of the formula (2A),
In the case where q is 0, the other 1 selected from R 61～R65 is a single bond to k,
In the case where q is 1,1 selected from R 61～R65 is a single bond to j, the other 1 selected from R 61～R65 is a single bond to k,
In the formula (2B), the amino acid sequence,
In the case where q is 0, 1 selected from R 71～R78 is a single bond to l, the other 1 selected from R 71～R78 is a single bond to m,
In the case where q is 1, 1 selected from R 71～R78 is a single bond to l, another 1 selected from R 71～R78 is a single bond to j, and yet another 1 selected from R 71～R78 is a single bond to m.
Ar 11～Ar13、L11、q、R41～R46、R51～R54、X11 and R 901～R907 are as defined for formula (2).
R 61～R65 and R 71～R78 are each independently preferably 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-forming carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring-forming carbon atoms, more preferably 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-forming carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring-forming carbon atoms, still more preferably a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, and still more preferably a hydrogen atom.
The details of each group represented by R 61～R65 and R 71～R78 are the same as those of the corresponding group described for R 1～R6 and R 11～R14, and preferably the groups and the like are the same.
In the formula (2A), the amino acid sequence of the formula (2A),
In the case where q is 0, preferably 1 selected from R 62～R64 is a single bond to k.
In the case where q is 1, it is preferable that 1 selected from R 62 and R 63 is a single bond to k, and 1 selected from R 64 and R 65 is a single bond to j.
The inventive compound (2) represented by the formula (2) is preferably represented by the following formula (2A-1) or (2B-1).
[ Chemical formula 32]
In the formulae (2A-1) and (2B-1),
Ar 11 and Ar 12、L11、R41～R46、R51～R54, and X 11 are as defined in formula (2), R 61～R65 and k are as defined in formula (2A), and R 71～R78, l and n are as defined in formula (2B).
The inventive compound (2) represented by the formula (2) is preferably represented by the following formula (2A-1 a) or (2B-1B).
[ Chemical formula 33]
In the formulae (2A-1 a) and (2B-1B),
Ar 11 and Ar 13、L11、R41～R46、R51～R54, and X 11 are as defined in formula (2), and R 61～R66 is as defined in formula (2A).
As an aspect of the present invention,
(2-1) R 41～R46 may be a hydrogen atom,
(2-2) R 51～R54 may each be a hydrogen atom,
(2-3) In formula (2A), R 61～R65, which is not a single bond to j and k, may each be a hydrogen atom,
(2-4) In formula (2B), R 71～R78, which is not a single bond to l, m, and n, may be a hydrogen atom,
(2-5) In formula (2A-1), R 61～R65, which are not single bonds to j, may each be a hydrogen atom,
(2-6) In formula (2B-1), R 71～R78 other than the single bond to k and l may each be a hydrogen atom,
(2-7) In the formula (2A-1 a), R 61、R62、R64 and R 65 may each be a hydrogen atom,
(2-8) In the formula (2A-1 b), R 61 and R 63～R65 may each be a hydrogen atom.
As described above, the term "hydrogen atom" used in the present specification includes protium atom, deuterium atom, and tritium atom. Thus, the inventive compounds may also contain deuterium atoms of natural origin.
In addition, deuterium atoms can be intentionally introduced into the inventive compound by using a deuterated compound as part or all of the starting compound. Thus, in one embodiment of the invention, the inventive compounds contain at least 1 deuterium atom. That is, the inventive compound (1) may be a compound represented by the formula (1), at least one of the hydrogen atoms contained in the compound is a deuterium atom, and the inventive compound (2) may be a compound represented by the formula (2), at least one of the hydrogen atoms contained in the compound is a deuterium atom.
Of the compounds represented by the formula (1), those selected from
A hydrogen atom of a substituted or unsubstituted aryl group or a heterocyclic group represented by any one of Ar 1～Ar3;
A substituted or unsubstituted arylene group having 6 to 30 ring-forming carbon atoms represented by L 1, and a hydrogen atom of a divalent heterocyclic group;
a hydrogen atom of a 2+p-valent residue of a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 25 ring-forming carbon atoms represented by L 2;
A hydrogen atom represented by any one of R 1～R6 and R 11～R14; a hydrogen atom of a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, or heterocyclic group represented by any one of R 1～R6 and R 11～R14; a group represented by-Si (R 901)(R902)(R903) represented by any one of R 1～R6 and R 11～R14, a group represented by-O- (R 904) -a group represented by S- (R 905), -a hydrogen atom of a group represented by N (R 906)(R907);
A hydrogen atom represented by any one of R 901～R907, a hydrogen atom represented by any one of R 901～R907, a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, or heterocyclic group;
A hydrogen atom constituting a pyrimidine ring of formula (1);
A hydrogen atom other than R 11～R14 contained in the structure represented by the following formula (1-x) constituting formula (1);
at least one hydrogen atom of (c) may be a deuterium atom.
[ Chemical formula 34]
Wherein, in the formula (1-x), the bonding position with L 2, R 11～R14、X1, a, b, c and d are defined as in the formula (1).
Of the compounds represented by the formula (2), those selected from
A hydrogen atom of a substituted or unsubstituted aryl group or a heterocyclic group represented by any one of Ar 11～Ar13;
A substituted or unsubstituted arylene group having 6 to 30 ring-forming carbon atoms represented by L 11, and a hydrogen atom of a divalent heterocyclic group;
a hydrogen atom of a 2+q-valent residue of a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 25 ring-forming carbon atoms represented by L 12;
a hydrogen atom represented by any one of R 41～R46 and R 51～R54; a hydrogen atom of a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, or heterocyclic group represented by any one of R 41～R46 and R 51～R54; a group represented by-Si (R 901)(R902)(R903) represented by any one of R 41～R46 and R 51～R54, a group represented by-O- (R 904) -a group represented by S- (R 905), -a hydrogen atom of a group represented by N (R 906)(R907);
A hydrogen atom represented by any one of R 901～R907, a hydrogen atom represented by any one of R 901～R907, a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, or heterocyclic group;
A hydrogen atom constituting a pyrimidine ring of formula (2);
a hydrogen atom other than R 51～R54 contained in the structure represented by the following formula (2-x) constituting formula (2);
at least one hydrogen atom of (c) may be a deuterium atom.
[ Chemical formula 35]
Wherein, in the formula (2-X), the bonding position with L 12, R 51～R54 and X 12 are defined as in the formula (2).
The deuteration rate of the inventive compounds depends on the deuteration rate of the starting compounds used. Even if a raw material having a predetermined deuteration rate is used, the protium isotope may be contained in a constant ratio from a natural source. Accordingly, the following schemes of deuteration rates of the inventive compounds include ratios in which the natural-derived trace isotopes are considered, relative to ratios obtained by counting only the number of deuterium atoms represented by the chemical formula.
The deuteration ratio of the compound of the present invention is preferably 1% or more, more preferably 3% or more, further preferably 5% or more, still more preferably 10% or more, and still more preferably 50% or more.
The inventive compound may be a mixture comprising a deuterated compound and a non-deuterated compound, a mixture of more than 2 compounds having different deuteration rates. The deuteration rate of such a mixture is preferably 1% or more, more preferably 3% or more, further preferably 5% or more, still more preferably 10% or more, still more preferably 50% or more, and less than 100%.
The ratio of the number of deuterium atoms to the total number of hydrogen atoms in the compound of the present invention is preferably 1% or more, more preferably 3% or more, still more preferably 5% or more, still more preferably 10% or more, and 100% or less.
The details of the substituent (optional substituent) when expressed as "substituted or unsubstituted" included in the above-mentioned definition of each of the formulae are the same as those described in "substituent when expressed as" substituted or unsubstituted ".
The compounds of the present invention can be easily produced by those skilled in the art with reference to the synthesis examples described below and known synthesis methods.
Specific examples of the compounds of the present invention are shown below, and are not limited to the following exemplary compounds.
In the following specific examples, D represents a deuterium atom.
[ Chemical formula 36]
[ Chemical formula 37]
[ Chemical formula 38]
[ Chemical formula 39]
[ Chemical formula 40]
[ Chemical formula 41]
[ Chemical formula 42]
[ Chemical formula 43]
[ Chemical formula 44]
[ Chemical formula 45]
[ Chemical formula 46]
[ Chemical formula 47]
[ Chemical formula 48]
[ Chemical formula 49]
[ Chemical formula 50]
[ Chemical formula 51]
[ Chemical formula 52]
[ Chemical formula 53]
[ Chemical formula 54]
[ Chemical formula 55]
[ Chemical formula 56]
[ Chemical formula 57]
[ Chemical formula 58]
[ Chemical formula 59]
[ Chemical formula 60]
[ Chemical formula 61]
[ Chemical formula 62]
[ Chemical formula 63]
[ Chemical formula 64]
[ Chemical formula 65]
[ Chemical formula 66]
[ Chemical formula 67]
[ Chemical formula 68]
[ Chemical formula 69]
[ Chemical formula 70]
[ Chemical formula 71]
[ Chemical formula 72]
[ Chemical formula 73]
[ Chemical formula 74]
[ Chemical formula 75]
[ Chemical formula 76]
[ Chemical formula 77]
[ Chemical formula 78]
[ Chemical formula 79]
[ Chemical formula 80]
[ Chemical formula 81]
[ Chemical formula 82]
[ Chemical formula 83]
[ Chemical formula 84]
[ Chemical formula 85]
[ Chemical formula 86]
[ Chemical formula 87]
[ Chemical formula 88]
[ Chemical formula 89]
[ Chemical formula 90]
[ Chemical formula 91]
[ Chemical formula 92]
[ Chemical formula 93]
[ Chemical formula 94]
[ Chemical formula 95]
[ Chemical formula 96]
[ Chemical formula 97]
Material for organic EL element
The material for an organic EL element of the present invention contains the compound of the present invention. The content of the inventive compound in the material for an organic EL element is 1% by mass or more (including 100%), preferably 10% by mass or more (including 100%), more preferably 50% by mass or more (including 100%), still more preferably 80% by mass or more (including 100%), and particularly preferably 90% by mass or more (including 100%). The material for an organic EL element of the present invention is useful for the production of an organic EL element.
Organic EL element
The organic EL element of the present invention comprises an anode, a cathode, and an organic layer disposed between the anode and the cathode. The organic layer comprises a light emitting layer, at least one layer of the organic layer comprising an inventive compound.
Examples of the organic layer containing the compound of the present invention include, but are not limited to, a hole transport region (a hole injection layer, a hole transport layer, an electron blocking layer, an exciton blocking layer, etc.) provided between the anode and the light-emitting layer, a spacer layer, an electron transport region (an electron injection layer, an electron transport layer, a hole blocking layer, etc.) provided between the cathode and the light-emitting layer, and the like. The inventive compound is preferably used as a material for an electron transport region of a fluorescent or phosphorescent EL element, more preferably as a material for an electron transport layer or a hole blocking layer, particularly preferably as a material for an 1 st electron transport layer, a2 nd electron transport layer or a hole blocking layer.
The organic EL element of the present invention may be a fluorescent or phosphorescent single-color light-emitting element, a fluorescent/phosphorescent hybrid white light-emitting element, a simple type having a single light-emitting unit, or a tandem type having a plurality of light-emitting units, and among these, a fluorescent light-emitting element is preferable. Here, the "light emitting unit" means a unit including an organic layer, at least one of which is a light emitting layer, and which emits light by recombination of injected holes and electrons.
For example, the following element configuration is typical of a simple organic EL element.
(1) Anode/light emitting unit/cathode
In addition, the light-emitting unit may be a multilayer structure having a plurality of phosphorescent light-emitting layers and fluorescent light-emitting layers, and in this case, a spacer layer may be provided between the light-emitting layers for the purpose of preventing excitons generated in the phosphorescent light-emitting layers from diffusing into the fluorescent light-emitting layers. A typical layer configuration of the simple light emitting unit is shown below. The layers in brackets are optional.
(A) (hole injection layer /) hole transport layer/fluorescent light emitting layer/electron transport layer (/ electron injection layer)
(B) (hole injection layer /) hole transport layer/phosphorescent light emitting layer/electron transport layer (/ electron injection layer)
(C) (hole injection layer /) hole transport layer/1 st fluorescent light-emitting layer/2 nd fluorescent light-emitting layer/electron transport layer (/ electron injection layer)
(D) (hole injection layer /) hole transport layer/1 st phosphorescent light emitting layer/2 nd phosphorescent light emitting layer/electron transport layer (/ electron injection layer)
(E) (hole injection layer /) hole transport layer/phosphorescent light emitting layer/spacer layer/fluorescent light emitting layer/electron transport layer (/ electron injection layer)
(F) (hole injection layer /) hole transport layer/1 st phosphorescent light emitting layer/2 nd phosphorescent light emitting layer/spacer layer/fluorescent light emitting layer/electron transport layer (/ electron injection layer)
(G) (hole injection layer /) hole transport layer/1 st phosphorescent light emitting layer/spacer layer/2 nd phosphorescent light emitting layer/spacer layer/fluorescent light emitting layer/electron transport layer (/ electron injection layer)
(H) (hole injection layer /) hole transport layer/phosphorescent light emitting layer/spacer layer/1 st fluorescent light emitting layer/2 nd fluorescent light emitting layer/electron transport layer (/ electron injection layer)
(I) (hole injection layer /) hole transport layer/electron blocking layer/fluorescent light emitting layer/electron transport layer (/ electron injection layer)
(J) (hole injection layer /) hole transport layer/electron blocking layer/phosphorescent light emitting layer/electron transport layer (/ electron injection layer)
(K) (hole injection layer /) hole transport layer/exciton blocking layer/fluorescent light emitting layer/electron transport layer (/ electron injection layer)
(L) (hole injection layer /) hole transport layer/exciton blocking layer/phosphorescent light emitting layer/electron transport layer (/ electron injection layer)
(M) (hole injection layer /) 1 st hole transport layer/2 nd hole transport layer/fluorescent light-emitting layer/electron transport layer (/ electron injection layer)
(N) (hole injection layer /) 1 st hole transport layer/2 nd hole transport layer/phosphorescent light emitting layer/electron transport layer (/ electron injection layer)
(O) (hole injection layer /) 1 st hole transport layer/2 nd hole transport layer/fluorescent light-emitting layer/1 st electron transport layer/2 nd electron transport layer (/ electron injection layer)
(P) (hole injection layer /) 1 st hole transport layer/2 nd hole transport layer/phosphorescent light emitting layer/1 st electron transport layer/2 nd electron transport layer (/ electron injection layer)
(Q) (hole injection layer /) hole transport layer/fluorescent light-emitting layer/hole blocking layer/electron transport layer (/ electron injection layer)
(R) (hole injection layer /) hole transport layer/phosphorescent light emitting layer/hole blocking layer/electron transport layer (/ electron injection layer)
(S) (hole injection layer /) hole transport layer/fluorescent light emitting layer/exciton blocking layer/electron transport layer (/ electron injection layer)
(T) (hole injection layer /) hole transport layer/phosphorescent light emitting layer/exciton blocking layer/electron transport layer (/ electron injection layer)
The phosphorescent or fluorescent light-emitting layers may be light-emitting layers each of which exhibits a different light-emitting color. Specifically, the light-emitting unit (f) includes a layer structure such as a hole transport layer (hole injection layer /) a1 st phosphorescent light-emitting layer (red light emission)/a 2 nd phosphorescent light-emitting layer (green light emission)/a spacer layer/a fluorescent light-emitting layer (blue light emission)/an electron transport layer.
An electron blocking layer may be provided between each light emitting layer and the hole transport layer or the spacer layer as appropriate. In addition, a hole blocking layer may be provided between each light emitting layer and the electron transport layer as appropriate. By providing the electron blocking layer and the hole blocking layer, electrons or holes can be enclosed in the light emitting layer, and the recombination probability of charges in the light emitting layer can be improved, thereby improving the light emitting efficiency.
Typical element configurations of the tandem organic EL element include the following.
(2) Anode/1 st light-emitting unit/intermediate layer/2 nd light-emitting unit/cathode
Here, the 1 st light-emitting unit and the 2 nd light-emitting unit may be, for example, each independently selected from the light-emitting units described above.
The intermediate layer is also generally referred to as an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron extraction layer, a connection layer, or an intermediate insulating layer, and may be formed using a known material that supplies electrons to the 1 st light-emitting cell and holes to the 2 nd light-emitting cell.
Fig. 1 is a schematic diagram showing an example of the structure of an organic EL element of the present invention. The organic EL element 1 includes a substrate 2, an anode 3, a cathode 4, and a light-emitting unit 10 disposed between the anode 3 and the cathode 4. The light emitting unit 10 has a light emitting layer 5. A hole transport region 6 (hole injection layer, hole transport layer, etc.) is provided between the light-emitting layer 5 and the anode 3, and an electron transport region 7 (electron injection layer, electron transport layer, etc.) is provided between the light-emitting layer 5 and the cathode 4. An electron blocking layer (not shown) may be provided on the anode 3 side of the light-emitting layer 5, and a hole blocking layer (not shown) may be provided on the cathode 4 side of the light-emitting layer 5. This can further improve the efficiency of generating excitons in the light-emitting layer 5 by blocking electrons and holes in the light-emitting layer 5.
Fig. 2 is a schematic diagram showing another configuration of the organic EL element of the present invention. The organic EL element 11 includes a substrate 2, an anode 3, a cathode 4, and a light-emitting unit 20 disposed between the anode 3 and the cathode 4. The light emitting unit 20 has a light emitting layer 5. The hole transport region disposed between the anode 3 and the light-emitting layer 5 is formed of a hole injection layer 6a, a1 st hole transport layer 6b, and a2 nd hole transport layer 6c. The electron transport region disposed between the light-emitting layer 5 and the cathode 4 is formed by the 1 st electron transport layer 7a and the 2 nd electron transport layer 7 b.
In the present invention, a host combined with a fluorescent dopant material (fluorescent light-emitting material) is referred to as a fluorescent host, and a host combined with a phosphorescent dopant material is referred to as a phosphorescent host. Fluorescent and phosphorescent hosts are not distinguished solely by molecular structure. That is, the phosphorescent host means a material forming a phosphorescent light emitting layer containing a phosphorescent dopant, and does not mean that the material cannot be used as a material forming a fluorescent light emitting layer. The same applies to the fluorescent body.
Substrate board
The substrate serves as a support for the organic EL element. As the substrate, for example, a plate of glass, quartz, plastic, or the like can be used. In addition, a flexible substrate may be used. Examples of the flexible substrate include plastic substrates made of polycarbonate, polyarylate, polyethersulfone, polypropylene, polyester, polyvinyl fluoride, and polyvinyl chloride. In addition, an inorganic vapor deposition film may be used.
Anode
The anode formed on the substrate is preferably made of a metal, an alloy, a conductive compound, or a mixture thereof having a large work function (specifically, 4.0eV or more). Specifically, examples thereof include Indium Tin Oxide (ITO), indium Tin Oxide containing silicon or silicon Oxide, indium zinc Oxide, indium Oxide containing tungsten Oxide and zinc Oxide, and graphene. Examples of the metal include gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), titanium (Ti), and nitrides thereof (for example, titanium nitride).
These materials are typically formed into films by sputtering. For example, indium oxide-zinc oxide can be formed by sputtering using a target in which zinc oxide is added in an amount of 1 to 10wt% to indium oxide, and indium oxide containing tungsten oxide and zinc oxide can be formed by sputtering using a target in which tungsten oxide is added in an amount of 0.5 to 5wt% and zinc oxide is added in an amount of 0.1 to 1wt% to indium oxide. The composition may be produced by vacuum vapor deposition, coating, ink jet, spin coating, or the like.
The hole injection layer formed adjacent to the anode is formed using a material that is easily subjected to hole injection regardless of the work function of the anode, and therefore, a material that is generally used as an electrode material (for example, a metal, an alloy, a conductive compound, and a mixture thereof, an element belonging to the first group or the second group of the periodic table) can be used.
An alkali metal such as lithium (Li) and cesium (Cs), an alkaline earth metal such as magnesium (Mg), calcium (Ca) and strontium (Sr), an alloy containing the same (for example, mgAg, alLi), a rare earth metal such as europium (Eu) and ytterbium (Yb), an alloy containing the same, and the like can be used as the material having a small work function. In the case of forming the anode using an alkali metal, an alkaline earth metal, or an alloy containing them, a vacuum vapor deposition method or a sputtering method may be used. In addition, when silver paste or the like is used, a coating method, an inkjet method, or the like may be used.
Hole injection layer
The hole injection layer is a layer containing a material having high hole injection property (hole injection material), and is formed between the anode and the light-emitting layer, or between the hole transport layer and the anode in the presence of the hole transport layer.
As the hole injecting material other than the inventive compound, molybdenum oxide, titanium oxide, vanadium oxide, rhenium oxide, ruthenium oxide, chromium oxide, zirconium oxide, hafnium oxide, tantalum oxide, silver oxide, tungsten oxide, manganese oxide, or the like can be used.
Examples of the hole injection layer material include aromatic amines such as 4,4',4″ -tris (N, N-diphenylamino) triphenylamine (abbreviated as TDATA), 4',4″ -tris [ N- (3-methylphenyl) -N-phenylamino ] triphenylamine (abbreviated as MTDATA), 4 '-bis [ N- (4-diphenylaminophenyl) -N-phenylamino ] biphenyl (abbreviated as DPAB), 4' -bis (N- {4- [ N '- (3-methylphenyl) -N' -phenylamino ] phenyl } -N-phenylamino) biphenyl (abbreviated as DNTPD), 1,3, 5-tris [ N- (4-diphenylaminophenyl) -N-phenylamino ] benzene (abbreviated as DPA 3B), 3- [ N- (9-phenylcarbazole-3-yl) -N-phenylamino ] -9-phenylcarbazole (abbreviated as pczpczpcz 1), 3, 6-bis [ N- (9-phenylcarbazole-3-yl) -N-phenylamino ] -9-phenylcarbazole (abbreviated as pczpcz 2), and 3- [ N- (4-diphenylaminophenyl) -N-phenylamino ] -9-phenylcarbazole (abbreviated as pcz 1).
Polymer compounds (oligomers, dendrimers, polymers, etc.) may also be used. Examples thereof include polymer compounds such as Poly (N-vinylcarbazole) (abbreviated as PVK), poly (4-vinyltriphenylamine) (abbreviated as PVTPA), poly [ N- (4- { N '- [4- (4-diphenylamino) phenyl ] phenyl-N' -phenylamino } phenyl) methacrylamide ] (abbreviated as PTPDMA), and Poly [ N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine ] (abbreviated as Poly-TPD). In addition, acid-added polymer compounds such as poly (3, 4-ethylenedioxythiophene)/poly (styrenesulfonic acid) (PEDOT/PSS) and polyaniline/poly (styrenesulfonic acid) (PAni/PSS) may be used.
In addition, an acceptor material such as a Hexaazatriphenylene (HAT) compound represented by the following formula (K) is also preferably used.
[ Chemical formula 98]
(In the above formula, R 21～R26 independently represents cyano, -CONH 2, carboxyl, or-COOR 27(R27 represents alkyl group having 1 to 20 carbon atoms or cycloalkyl group having 3 to 20 carbon atoms). In addition, adjacent 2 selected from R 21 and R 22、R23 and R 24, and R 25 and R 26 may be bonded to each other to form a group represented by-CO-O-CO-. )
Examples of R 27 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl and the like.
Hole transport layer
The hole-transporting layer is a layer containing a material having high hole-transporting property (hole-transporting material), and is formed between the anode and the light-emitting layer, or between the hole-injecting layer and the light-emitting layer in the presence of the hole-injecting layer.
The hole transport layer may have a single-layer structure or a multilayer structure including 2 or more layers. For example, the hole transport layer may be a 2-layer structure including a1 st hole transport layer (anode side) and a 2 nd hole transport layer (cathode side). In one embodiment of the present invention, the hole transport layer of the single-layer structure is preferably adjacent to the light-emitting layer, and the hole transport layer closest to the cathode in the multi-layer structure, for example, the 2 nd hole transport layer of the 2 nd layer structure is preferably adjacent to the light-emitting layer. In another embodiment of the present invention, an electron blocking layer or the like described below may be interposed between the hole transporting layer and the light emitting layer having the single-layer structure or between the hole transporting layer and the light emitting layer closest to the light emitting layer in the multilayer structure.
As the hole transport layer material, for example, an aromatic amine compound, a carbazole derivative, an anthracene derivative, or the like can be used.
Examples of the aromatic amine compound include: 4,4' -bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl (abbreviation: NPB), N ' -bis (3-methylphenyl) -N, N ' -diphenyl- [1,1' -biphenyl ] -4,4' -diamine (abbreviated as TPD), 4-phenyl-4 ' - (9-phenylfluoren-9-yl) triphenylamine (abbreviated as BAFLP), 4' -bis [ N- (9, 9-dimethylfluoren-2-yl) -N-phenylamino ] biphenyl (abbreviated as DFLDPBi), 4',4 "-tris (N, N-diphenylamino) triphenylamine (abbreviated as TDATA), 4',4" -tris [ N- (3-methylphenyl) -N-phenylamino ] triphenylamine (abbreviated as MTDATA), and 4,4' -bis [ N- (spiro-9, 9' -bifluor-2-yl) -N-phenylamino ] biphenyl (abbreviated as BSPB). The compound has hole mobility of more than 10 -6cm2/Vs.
Examples of carbazole derivatives include 4,4' -bis (9-carbazolyl) biphenyl (abbreviated as CBP), 9- [4- (9-carbazolyl) phenyl ] -10-phenylanthracene (abbreviated as CzPA), and 9-phenyl-3- [4- (10-phenyl-9-anthryl) phenyl ] -9H-carbazole (abbreviated as PCzPA).
Examples of the anthracene derivative include 2-t-butyl-9, 10-bis (2-naphthyl) anthracene (abbreviated as t-BuDNA), 9, 10-bis (2-naphthyl) anthracene (abbreviated as DNA), and 9, 10-diphenylanthracene (abbreviated as DPAnth).
Polymer compounds such as poly (N-vinylcarbazole) (PVK) and poly (4-vinyltriphenylamine) (PVTPA) may be used.
Among them, compounds other than the above compounds may be used as long as they have a higher hole-transporting property than electron-transporting property.
Dopant material of light emitting layer
The light-emitting layer is a layer containing a material having high light-emitting properties (dopant material), and various materials can be used. For example, a fluorescent light-emitting material, a phosphorescent light-emitting material may be used as the dopant material. The fluorescent light-emitting material is a compound that emits light in a singlet excited state, and the phosphorescent light-emitting material is a compound that emits light in a triplet excited state.
As a blue-based fluorescent light-emitting material which can be used for the light-emitting layer, a pyrene derivative, a styrylamine derivative, a,Derivatives, fluoranthene derivatives, fluorene derivatives, diamine derivatives, triarylamine derivatives, and the like. Specifically, N ' -bis [4- (9H-carbazol-9-yl) phenyl ] -N, N ' -diphenylstilbene-4, 4' -diamine (abbreviated as YGA 2S), 4- (9H-carbazol-9-yl) -4' - (10-phenyl-9-anthryl) triphenylamine (abbreviated as YGAPA), 4- (10-phenyl-9-anthryl) -4' - (9-phenyl-9H-carbazol-3-yl) triphenylamine (abbreviated as PCBAPA) and the like can be mentioned.
As a green-based fluorescent light-emitting material that can be used for the light-emitting layer, an aromatic amine derivative or the like can be used. Specifically, N- (9, 10-diphenyl-2-anthryl) -N, 9-diphenyl-9H-carbazol-3-amine (abbreviated as: 2 PCAPA), N- [9, 10-bis (1, 1' -biphenyl-2-yl) -2-anthryl ] -N, 9-diphenyl-9H-carbazol-3-amine (abbreviated as: 2 PCABPhA), N- (9, 10-diphenyl-2-anthryl) -N, N ', N ' -triphenyl-1, 4-phenylenediamine (abbreviated as: 2 DPAPA), N- [9, 10-bis (1, 1' -biphenyl-2-yl) -2-anthryl ] -N, N ', N ' -triphenyl-1, 4-phenylenediamine (abbreviated as: 2 DPABPhA), N- [9, 10-bis (1, 1' -biphenyl-2-yl) ] -N- [4- (9H-carbazol-9-yl) phenyl ] -N-phenylanthracene-2-amine (abbreviated as: 2 YGABPhA), N, 9-triphenylanthracene-9-amine (abbreviated as: 34) and the like can be cited.
As a red-based fluorescent light-emitting material that can be used for the light-emitting layer, a naphthacene derivative, a diamine derivative, or the like can be used. Specifically, N, N, N ', N' -tetrakis (4-methylphenyl) naphthacene-5, 11-diamine (abbreviated as p-mPhTD), 7, 14-diphenyl-N, N, N ', N' -tetrakis (4-methylphenyl) acenaphtho [1,2-a ] fluoranthene-3, 10-diamine (abbreviated as p-mPhAFD), and the like are exemplified.
In one embodiment of the invention, the light-emitting layer preferably comprises a fluorescent light-emitting material (fluorescent dopant material).
As a blue-based phosphorescent light-emitting material that can be used for the light-emitting layer, a metal complex such as an iridium complex, an osmium complex, or a platinum complex can be used. Specifically, bis [2- (4 ',6' -difluorophenyl) pyridine-N, C2'] iridium (III) tetrakis (1-pyrazolyl) borate (abbreviated as Fir 6), bis [2- (4', 6 '-difluorophenyl) pyridine-N, C2' ] iridium (III) pyridine formate (abbreviated as FIrpic), bis [2- (3 ',5' -bistrifluoromethylphenyl) pyridine-N, C2'] iridium (III) pyridine formate (abbreviated as Ir (CF 3 ppy) 2 (pic)), bis [2- (4', 6 '-difluorophenyl) pyridine-N, C2' ] iridium (III) acetylacetonate (abbreviated as FIracac) and the like can be cited.
As a green-based phosphorescent light-emitting material that can be used for the light-emitting layer, iridium complex or the like can be used. Examples thereof include tris (2-phenylpyridine-N, C2 ') iridium (III) (abbreviated as Ir (ppy) 3), bis (2-phenylpyridine-N, C2') iridium (III) acetylacetonate (abbreviated as Ir (ppy) 2 (acac)), bis (1, 2-diphenyl-1H-benzimidazole) iridium (III) acetylacetonate (abbreviated as Ir (pbi) 2 (acac)), and bis (benzo [ H ] quinoline) iridium (III) acetylacetonate (abbreviated as Ir (bzq) 2 (acac)).
As a red-based phosphorescent material that can be used for the light-emitting layer, a metal complex such as iridium complex, platinum complex, terbium complex, or europium complex can be used. Specifically, there may be mentioned organometallic complexes such as bis [2- (2 ' -benzo [4,5- α ] thienyl) pyridine-N, C3' ] iridium (III) acetylacetonate (abbreviated as Ir (btp) 2 (acac)), bis (1-phenylisoquinoline-N, C2 ') iridium (III) acetylacetonate (abbreviated as Ir (piq) 2 (acac)), (acetylacetonate) bis [2, 3-bis (4-fluorophenyl) quinoxaline ] iridium (III) (abbreviated as Ir (Fdpq) 2 (acac)), and 2,3,7,8,12,13,17, 18-octaethyl-21H, 23H-porphyrin platinum (II) (abbreviated as PtOEP).
In addition, rare earth metal complexes such as tris (acetylacetonato) (Shan Feige in) terbium (III) (abbreviated as Tb (acac) 3 (Phen)), tris (1, 3-diphenyl-1, 3-acetonyl) (Shan Feige in) europium (III) (abbreviated as Eu (DBM) 3 (Phen)), tris [1- (2-thenoyl) -3, 3-trifluoroacetonyl ] (Shan Feige in) europium (III) (abbreviated as Eu (TTA) 3 (Phen)) are useful as phosphorescent materials because they are luminescent (electron transitions between different multiple degrees) from rare earth metal ions.
In one aspect of the invention, the light emitting layer preferably comprises a phosphorescent light emitting material (phosphorescent dopant material).
Host material for light-emitting layer
The light-emitting layer may be formed by dispersing the dopant material in another material (host material). Preferably, a material is used that has a lowest unoccupied orbital level (LUMO level) higher than the dopant material and a highest occupied orbital level (HOMO level) lower than the dopant material.
As the host material, for example, use is made of
(1) Metal complexes such as aluminum complexes, beryllium complexes, and zinc complexes,
(2) Heterocyclic compounds such as oxadiazole derivatives, benzimidazole derivatives, or phenanthroline derivatives,
(3) Carbazole derivative, anthracene derivative, phenanthrene derivative, pyrene derivative, orCondensed aromatic compounds such as derivatives,
(4) Aromatic amine compounds such as triarylamine derivatives and condensed polycyclic aromatic amine derivatives.
For example, metal complexes such as tris (8-hydroxyquinoline) aluminum (III) (abbreviated as Alq), tris (4-methyl-8-hydroxyquinoline) aluminum (III) (abbreviated as Almq 3), bis (10-hydroxybenzo [ h ] quinoline) beryllium (II) (abbreviated as BeBq 2), bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (abbreviated as BAlq), bis (8-hydroxyquinoline) zinc (II) (abbreviated as Znq), bis [2- (2-benzoxazolyl) phenol ] zinc (II) (abbreviated as ZnPBO), and bis [2- (2-benzothiazolyl) phenol ] zinc (II) (abbreviated as ZnBTZ) can be used;
Heterocyclic compounds such as 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole (abbreviated as PBD), 1, 3-bis [5- (p-tert-butylphenyl) -1,3, 4-oxadiazol-2-yl ] benzene (abbreviated as OXD-7), 3- (4-biphenyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2, 4-triazole (abbreviated as TAZ), 2' - (1, 3, 5-trimethoyl) tris (1-phenyl-1H-benzimidazole) (abbreviated as TPBI), bathophenanthroline (abbreviated as BPhen), bathocuproine (abbreviated as BCP);
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-bis (2-naphthyl) anthracene (abbreviated as DNA), 2-tert-butyl-9, 10-bis (2-naphthyl) anthracene (abbreviated as t-BuDNA), 9 '-dianthracene (abbreviated as BANT), 9' - (stilbene-3, 3 '-diyl) phenanthrene (abbreviated as DPNS), 9' - (stilbene-4, 4 '-diyl) phenanthrene (abbreviated as DPNS 2), 3' - (benzene-1, 3, 5-diyl) tripyrene (abbreviated as TPB 3), 9, 10-diphenylanthracene (abbreviated as DPAnth), 6, 12-dimethoxy-5, 11-diphenyl anthracene (abbreviated as DPAnth) And an isosdensed aromatic compound
N, N-diphenyl-9- [4- (10-phenyl-9-anthryl) phenyl ] -9H-carbazol-3-amine (abbreviation: czA PA), 4- (10-phenyl-9-anthryl) triphenylamine (abbreviation: DPhPA), N, 9-diphenyl-N- [4- (10-phenyl-9-anthryl) phenyl ] -9H-carbazol-3-amine (abbreviation: PCAPA), N, 9-diphenyl-N- {4- [4- (10-phenyl-9-anthryl) phenyl ] phenyl } -9H-carbazol-3-amine (abbreviation: PCAPBA), N- (9, 10-diphenyl-2-anthryl) -N, 9-diphenyl-9H-carbazol-3-amine (abbreviation: 2 PCAPA), 4 '-bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl (abbreviation: NPB or-NPD), N' -bis (3-methylphenyl) -N, N '-diphenyl- [1,1' -biphenyl ] -4,4 '-diamine (abbreviation: PCAPBA), N- (9, 10-diphenyl-2-anthryl) -N, 4' -bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl (abbreviation: NPD), 4 '-bis [4, 4' -dichloro-4-phenyl ] -2-diphenyl (LDi) -2-diphenyl (P-L-diphenyl (LDI) Aromatic amine compounds such as 4,4 '-bis [ N- (spiro-9, 9' -bifluorene-2-yl) -N-phenylamino ] biphenyl (BSPB). Two or more kinds of host materials may be used.
In particular, in the case of a blue fluorescent element, the anthracene compound described below is preferably used as a host material.
[ Chemical formula 99]
[ Chemical formula 100]
[ Chemical formula 101]
Electron transport layer
The electron transport layer is a layer containing a material having high electron transport properties (electron transport material), and is formed between the light-emitting layer and the cathode, or between the electron injection layer and the light-emitting layer in the presence of the electron injection layer. The inventive compound may be used for the electron transport layer alone or in combination with a compound described later.
The electron transport layer may have a single-layer structure or a multilayer structure including 2 or more layers. For example, the electron transport layer may be a 2-layer structure including a1 st electron transport layer (anode side) and a2 nd electron transport layer (cathode side). In one embodiment of the present invention, the electron transport layer of the single-layer structure is preferably adjacent to the light emitting layer, or the electron transport layer closest to the anode in the multi-layer structure, for example, the 1 st electron transport layer of the 2-layer structure is preferably adjacent to the light emitting layer. In another embodiment of the present invention, a hole blocking layer or the like described below may be interposed between the electron transport layer and the light emitting layer having the single-layer structure or between the electron transport layer and the light emitting layer closest to the light emitting layer in the multilayer structure.
In the electron transport layer having the above 2-layer structure, the inventive compound may be contained in one or both of the 1 st electron transport layer and the 2 nd electron transport layer.
In one embodiment of the present invention, the inventive compound is preferably contained in only the 1 st electron transport layer, in another embodiment, the inventive compound is preferably contained in only the 2 nd electron transport layer, and in yet another embodiment, the inventive compound is contained in both the 1 st electron transport layer and the 2 nd electron transport layer.
In one embodiment of the present invention, the inventive compound contained in one or both of the 1 st electron transport layer and the 2 nd electron transport layer is preferably protium from the viewpoint of manufacturing cost.
The protium is an inventive compound in which all hydrogen atoms in the inventive compound are protium atoms.
Accordingly, the present invention includes an organic EL element in which one or both of the above-mentioned 1 st electron transport layer and the above-mentioned 2 nd electron transport layer contain an inventive compound formed substantially only of protium. The term "an inventive compound formed substantially only of protium" means that the protium content is 90 mol% or more, preferably 95 mol% or more, and more preferably 99 mol% or more (each including 100%) based on the total amount of the inventive compound.
In the electron transport layer, for example, can be used
(1) Metal complexes such as aluminum complex, beryllium complex, zinc complex, etc,
(2) Heteroaromatic compounds such as imidazole derivatives, benzimidazole derivatives, azine derivatives, carbazole derivatives, phenanthroline derivatives, and the like,
(3) A polymer compound.
Examples of the metal complex include tris (8-hydroxyquinoline) aluminum (III) (abbreviated as Alq), tris (4-methyl-8-hydroxyquinoline) aluminum (abbreviated as Almq 3), bis (10-hydroxybenzo [ h ] quinoline) beryllium (abbreviated as BeBq 2), bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (abbreviated as BAlq), bis (8-hydroxyquinoline) zinc (II) (abbreviated as Znq), bis [2- (2-benzoxazolyl) phenol ] zinc (II) (abbreviated as ZnPBO), and bis [2- (2-benzothiazolyl) phenol ] zinc (II) (abbreviated as ZnBTZ).
Examples of the heteroaromatic compound include 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole (abbreviated as PBD), 1, 3-bis [5- (p-tert-butylphenyl) -1,3, 4-oxadiazol-2-yl ] benzene (abbreviated as OXD-7), 3- (4-tert-butylphenyl) -4-phenyl-5- (4-biphenyl) -1,2, 4-triazole (abbreviated as TAZ), 3- (4-tert-butylphenyl) -4- (4-ethylphenyl) -5- (4-biphenyl) -1,2, 4-triazole (abbreviated as p-ETAZ), bathophenanthroline (abbreviated as BPhen), bathocuproine (abbreviated as BCP), and 4,4' -bis (5-methylbenzoxazol-2-yl) stilbene (abbreviated as BzOs).
Examples of the polymer compound include poly [ (9, 9-dihexylfluorene-2, 7-diyl) -co- (pyridine-3, 5-diyl) ] (abbreviated as PF-Py), and poly [ (9, 9-dioctylfluorene-2, 7-diyl) -co- (2, 2 '-bipyridine-6, 6' -diyl) ] (abbreviated as PF-BPy).
The material has an electron mobility of 10 -6cm2/Vs or more. The electron transport layer may be made of a material other than the above materials as long as the electron transport property is higher than the hole transport property.
Electron injection layer
The electron injection layer is a layer containing a material having high electron injection properties. Examples of the electron injection layer include 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. Examples of such a compound include alkali metal oxides, alkali metal halides, alkali metal-containing organic complexes, alkaline earth metal oxides, alkaline earth metal halides, alkaline earth metal-containing organic complexes, rare earth metal oxides, rare earth metal halides, and rare earth metal-containing organic complexes. In addition, a plurality of these compounds may be used in combination.
In addition, a material containing an alkali metal, an alkaline earth metal, or a compound thereof in a material having electron-transporting property, specifically, a material containing magnesium (Mg) in Alq, or the like can be used. In this case, electron injection from the cathode can be performed more efficiently.
Alternatively, a composite material in which an organic compound and an electron donor (donor) are mixed may be used for the electron injection layer. Such a composite material is excellent in electron injection property and electron transport property because the organic compound accepts electrons from the electron donor. In this case, the organic compound is preferably a material excellent in the transport of the received electrons, and specifically, for example, the above-mentioned material (metal complex, heteroaromatic compound, or the like) constituting the electron transport layer can be used. The electron donor may be any material that exhibits electron donating properties to an organic compound. Specifically, alkali metals, alkaline earth metals, and rare earth metals are preferable, and examples thereof include lithium, cesium, magnesium, calcium, erbium, ytterbium, and the like. The alkali metal oxide and alkaline earth metal oxide are preferable, and examples thereof include lithium oxide, calcium oxide, and barium oxide. In addition, a Lewis base such as magnesium oxide may be used. In addition, an organic compound such as tetrathiafulvalene (abbreviated as TTF) may be used.
Cathode electrode
The cathode preferably uses a metal, an alloy, a conductive compound, a mixture thereof, or the like having a small work function (specifically, 3.8eV or less). Specific examples of such cathode materials include alkali metals such as lithium (Li) and cesium (Cs), alkaline earth metals such as magnesium (Mg), calcium (Ca) and strontium (Sr), alloys containing the same (for example, mgAg and AlLi), rare earth metals such as europium (Eu) and ytterbium (Yb), alloys containing the same, and the like, which belong to the first group or the second group of the periodic table.
When forming a cathode using an alkali metal, an alkaline earth metal, or an alloy containing these metals, a vacuum vapor deposition method or a sputtering method may be used. In addition, when silver paste or the like is used, a coating method, an inkjet method, or the like may be used.
By providing the electron injection layer, the cathode can be formed using Al, ag, ITO, graphene, indium oxide-tin oxide containing silicon or silicon oxide, or other various conductive materials, regardless of the magnitude of the work function. These conductive materials may be formed into films by sputtering, inkjet, spin coating, or the like.
Insulating layer
Since an electric field is applied to an ultrathin film, a pixel defect due to leakage or short circuit is likely to occur in an organic EL element. In order to prevent this, an insulating layer formed of an insulating thin film layer may be interposed between the pair of electrodes.
Examples of materials that can be used for the insulating layer include aluminum oxide, lithium fluoride, lithium oxide, cesium fluoride, cesium 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. It is to be noted that a mixture or a laminate of these may be used.
Spacer layer
For example, when the fluorescent light-emitting layer and the phosphorescent light-emitting layer are laminated, the spacer layer is a layer provided between the fluorescent light-emitting layer and the 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 carrier balance. In addition, a spacer layer may be disposed between the plurality of phosphorescent light emitting layers.
The spacer layer is preferably a material having both electron transport property and hole transport property because it is provided between the light emitting layers. In order to prevent diffusion of triplet energy in adjacent phosphorescent light emitting layers, the triplet energy is preferably 2.6eV or more. As a material for the spacer layer, the same materials as those described above for the hole transport layer can be mentioned.
Barrier layer
A blocking layer such as an electron blocking layer, a hole blocking layer, or an exciton blocking layer may be provided adjacent to the light emitting layer. The electron blocking layer refers to a layer that prevents electrons from leaking from the light emitting layer to the hole transporting layer, and the hole blocking layer refers to 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 to a peripheral layer to block the excitons in the light emitting layer.
In an embodiment of the present invention, it is preferable that the electron transport region comprises a hole blocking layer on the cathode side, the hole blocking layer comprising the inventive compound. In addition, the hole blocking layer is preferably adjacent to the light emitting layer.
The layers of the organic EL element can be formed by a conventionally known vapor deposition method, a coating method, or the like. For example, the film can be formed by a vapor deposition method such as a vacuum vapor deposition method or a molecular beam vapor deposition method (MBE method), or a known method using a solution of a compound forming a layer, such as a coating method such as a dip coating method, a spin coating method, a casting method, a bar coating method, or a roll coating method.
The film thickness of each layer is not particularly limited, and in general, if the film thickness is too small, defects such as pinholes tend to occur, whereas if it is too large, high driving voltage is required and efficiency is deteriorated, so that it is usually 5nm to 10 μm, more preferably 10nm to 0.2 μm.
The organic EL element can be used for electronic devices such as display members such as organic EL panel modules, display devices such as televisions, mobile phones, and personal computers, and light emitting devices for lighting and vehicle lighting.
Examples
The present invention will be described in further detail with reference to the following examples, which are not intended to limit the scope of the invention.
Inventive Compounds used in the production of organic EL elements (I) of examples 1 to 4
[ Chemical formula 102]
Comparative compounds used in the production of organic EL elements (I) of comparative examples 1 to 3
[ Chemical formula 103]
Other Compound used in the manufacture of organic EL element (I)
[ Chemical formula 104]
Production of organic EL element (I)
Example 1
A glass substrate (Geomatec Co., ltd.) having an ITO transparent electrode (anode) of 25 mm. Times.75 mm. Times.1.1 mm was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then to UV ozone cleaning for 30 minutes. The film thickness of ITO was 130nm.
The cleaned glass substrate with ITO transparent electrode was mounted on a substrate holder of a vacuum vapor deposition apparatus, and first, a hole injection layer having a film thickness of 10nm was formed by co-vapor deposition of a compound HT-1 and a compound HI-1 so as to cover the transparent electrode on the surface on which the transparent electrode was formed. The mass ratio of compound HT-1 to compound HI-1 (HT-1: HI-1) was 97:3.
Then, a1 st hole transport layer having a film thickness of 80nm was formed by vapor deposition of the compound HT-1 on the hole injection layer.
Subsequently, EBL-1 was deposited on the 1 st hole transport layer to form a 2 nd hole transport layer having a film thickness of 10 nm.
Then, a light-emitting layer having a film thickness of 25nm was formed by co-vapor deposition of compound BH-1 (host material) and compound BD-1 (dopant material) on the 2 nd hole transport layer. The mass ratio of the compound BH-1 to the compound BD-1 (BH-1: BD-1) was 96:4.
Next, compound 1 was deposited on the light-emitting layer to form a1 st electron transport layer having a film thickness of 10 nm.
Then, a compound ET-1 was deposited on the 1 st electron transport layer to form a 2 nd electron transport layer having a film thickness of 15 nm.
Next, liF was deposited on the 2 nd electron transport layer to form an electron injecting electrode having a film thickness of 1 nm.
Then, metal Al was deposited on the electron-injecting electrode to form a metal cathode having a film thickness of 50 nm.
The layer structure of the organic EL element (I) of example 1 thus obtained is shown below.
ITO (130)/HT-1:HI-1=97:3 (10)/HT-1 (80)/EBL-1 (10)/BH-1:BD-1=96:4 (25)/Compound 1 (10)/ET-1 (15)/LiF (1)/Al (50)
In the above layer structure, the numbers in brackets are film thickness (nm), and the ratio is the mass ratio.
Measurement of element Life (LT 90)
The obtained organic EL element (I) was dc-driven at room temperature at a current density of 50mA/cm 2, and the time (h) until the luminance was reduced to 90% of the initial luminance was measured and was taken as 90% lifetime (LT 90). The results are shown in Table 1.
Examples 2 to 4
An organic EL device (I) was produced in the same manner as in example 1 except that the material of the 1 st electron transport layer was changed to the compound shown in table 1 below, and LT90 was measured. The results are shown in Table 1.
Comparative examples 1 to 3
An organic EL device (I) was produced in the same manner as in example 1 except that the material of the 1 st electron transport layer was changed to the compound shown in table 1 below, and LT90 was measured. The results are shown in Table 1.
TABLE 1
TABLE 1
From the results of table 1, it can be seen that the compounds of the present invention provide organic EL elements having significantly improved element lifetime as compared to the comparative compounds.
Inventive Compounds used in the production of organic EL elements (II) of examples 5 to 8
[ Chemical formula 105]
Comparative compounds used in the production of organic EL elements (II) of comparative examples 4 to 6
[ Chemical formula 106]
Other Compound used in production of organic EL element (II)
[ Chemical formula 107]
Production of organic EL element (II)
Example 5
A glass substrate (Geomatec Co., ltd.) having an ITO transparent electrode (anode) of 25 mm. Times.75 mm. Times.1.1 mm was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then to UV ozone cleaning for 30 minutes. The film thickness of ITO was 130nm.
The cleaned glass substrate with ITO transparent electrode was mounted on a substrate holder of a vacuum vapor deposition apparatus, and first, a hole injection layer having a film thickness of 10nm was formed by co-vapor deposition of a compound HT-1 and a compound HI-1 so as to cover the transparent electrode on the surface on which the transparent electrode was formed. The mass ratio of compound HT-1 to compound HI-1 (HT-1: HI-1) was 97:3.
Then, a1 st hole transport layer having a film thickness of 80nm was formed by vapor deposition of the compound HT-1 on the hole injection layer.
Subsequently, EBL-1 was deposited on the 1 st hole transport layer to form a2 nd hole transport layer having a film thickness of 5 nm.
Then, a light-emitting layer having a film thickness of 25nm was formed by co-vapor deposition of compound BH-2 (host material) and compound BD-1 (dopant material) on the 2 nd hole transport layer. The mass ratio of the compound BH-2 to the compound BD-1 (BH-2: BD-1) was 96:4.
Next, compound 1 was deposited on the light-emitting layer to form a1 st electron transport layer having a film thickness of 5 nm.
Then, the 2 nd electron transport layer having a film thickness of 20nm was formed by co-depositing the compounds ET-2 and Liq on the 1 st electron transport layer. The mass ratio of the compound ET-2 to Liq (ET-2: liq) was 50:50.
Next, yb was deposited on the 2 nd electron transport layer to form an electron-injecting electrode having a film thickness of 1 nm.
Then, metal Al was deposited on the electron-injecting electrode to form a metal cathode having a film thickness of 50 nm.
The LT90 of the organic EL element (II) of example 5 thus obtained was measured in the same manner as in example 1. The results are shown in table 2, and the layer structure of the organic EL element (II) of example 5 is shown below.
ITO (130)/HT-1:HI-1=97:3 (10)/HT-1 (80)/EBL-1 (5)/BH-2:BD-1=96:4 (25)/Compound 1 (5)/ET-2:Liq=50:50 (20)/Yb (1)/Al (50)
In the above layer structure, the numbers in brackets are film thickness (nm), and the ratio is the mass ratio.
Examples 6 to 8
An organic EL element (II) was produced and LT90 was measured in the same manner as in example 5, except that the material of the 1 st electron transport layer was changed to the compound shown in table 2 below. The results are shown in Table 2.
Comparative examples 4 to 6
An organic EL element (II) was produced and LT90 was measured in the same manner as in example 5, except that the material of the 1 st electron transport layer was changed to the compound shown in table 2 below. The results are shown in Table 2.
TABLE 2
TABLE 2
From the results of table 2, it can be seen that the compounds of the present invention provide organic EL elements having significantly improved element lifetime as compared to the comparative compounds.
Inventive Compounds used in the production of organic EL elements (III) of examples 9 to 18
[ Chemical formula 108]
Other Compound used in production of organic EL element (III)
[ Chemical formula 109]
Fabrication of organic EL element (III)
Example 9
A glass substrate (Geomatec Co., ltd.) having an ITO transparent electrode (anode) of 25 mm. Times.75 mm. Times.1.1 mm was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then to UV ozone cleaning for 30 minutes. The film thickness of ITO was 130nm.
The cleaned glass substrate with ITO transparent electrode was mounted on a substrate holder of a vacuum vapor deposition apparatus, and first, a hole injection layer having a film thickness of 10nm was formed by co-vapor deposition of a compound HT-1 and a compound HI-1 so as to cover the transparent electrode on the surface on which the transparent electrode was formed. The mass ratio of compound HT-1 to compound HI-1 (HT-1: HI-1) was 97:3.
Then, a1 st hole transport layer having a film thickness of 80nm was formed by vapor deposition of the compound HT-1 on the hole injection layer.
Subsequently, EBL-1 was deposited on the 1 st hole transport layer to form a 2 nd hole transport layer having a film thickness of 10 nm.
Then, a light-emitting layer having a film thickness of 25nm was formed by co-vapor deposition of compound BH-1 (host material) and compound BD-1 (dopant material) on the 2 nd hole transport layer. The mass ratio of the compound BH-1 to the compound BD-1 (BH-1: BD-1) was 96:4.
Next, a1 st electron transport layer having a film thickness of 10nm was formed by vapor deposition of a compound 5 on the light-emitting layer.
Then, a compound ET-1 was deposited on the 1 st electron transport layer to form a 2 nd electron transport layer having a film thickness of 15 nm.
Next, liF was deposited on the 2 nd electron transport layer to form an electron injecting electrode having a film thickness of 1 nm.
Then, metal Al was deposited on the electron-injecting electrode to form a metal cathode having a film thickness of 50 nm.
The LT90 of the organic EL element (III) of example 5 thus obtained was measured in the same manner as in example 1. The results are shown in table 3, and the layer structure of the organic EL element (III) of example 9 is shown below.
ITO (130)/HT-1:HI-1=97:3 (10)/HT-1 (80)/EBL-1 (10)/BH-1:BD-1=96:4 (25)/Compound 5 (10)/ET-1 (15)/LiF (J)/Al (50)
In the above layer structure, the numbers in brackets are film thickness (nm), and the ratio is the mass ratio.
Examples 10 to 18
An organic EL element (III) was produced and LT90 was measured in the same manner as in example 9, except that the 1 st electron transport layer material was changed to the compound shown in table 3 below. The results are shown in Table 3.
TABLE 3
TABLE 3 Table 3
From the results of table 3, it can be seen that the compounds of the present invention provide organic EL elements having significantly improved element lifetime as compared to the comparative compounds.
Compounds synthesized in Synthesis examples 1 to 15
[ Chemical formula 110]
Synthesis of intermediate example 1 Synthesis of intermediate A
[ Chemical formula 111]
4-Bromo-1-naphthaldehyde (9.0 g), 4-acetylbiphenyl (7.5 g), sodium hydroxide (0.15 g) were added to 300mL of ethanol, and stirred at room temperature for 5 hours. Next, benzamidine hydrochloride (6.0 g), sodium hydroxide (1.8 g) were added and stirred at 70℃for 5 hours. After completion of the reaction, the precipitate was separated by filtration and purified by silica gel column chromatography (developing solvent: hexane/toluene) to obtain intermediate A (7.5 g, yield: 38%) as a white solid.
Intermediate Synthesis example 2 Synthesis of intermediate D
[ Chemical formula 112]
4-Bromo-1-naphthaldehyde (9.0 g), 3-acetylbiphenyl (7.5 g), sodium hydroxide (0.15 g) were added to 300mL of ethanol, and stirred at room temperature for 5 hours. Next, benzamidine hydrochloride (6.0 g), sodium hydroxide (1.8 g) were added and stirred at 70℃for 5 hours. After completion of the reaction, the precipitate was separated by filtration and purified by silica gel column chromatography (developing solvent: hexane/toluene) to obtain intermediate D (5.9 g, yield: 30%) as a white solid.
Intermediate Synthesis example 3 Synthesis of intermediate K
[ Chemical formula 113]
Under argon atmosphere, 5 '-chloro-1, 1':3',1 "-terphenyl-2, 2", 3", 4", 5", 6" -d10 (10.0 g, 36.4 mmol), dipinacolol diboron (10.2 g, 40.0 mmol), [1,1' -bis (diphenylphosphino) ferrocene ] palladium (II) dichloride (798 mg), potassium acetate (5.36 g, 54.6 mmol) were added dioxane (200 ml) and heated to 100℃for stirring for 12 hours. After completion of the reaction, the residue obtained by concentrating the solvent was purified by column chromatography to obtain a white solid (11.5 g, yield 86%). The resulting white solid was analyzed by mass spectrometry (m/e=366 relative to molecular weight 366.3) and was intermediate K.
Synthesis example 4 of intermediate L
[ Chemical formula 114]
To intermediate K (11.0 g, 30.0 mmol), 4, 6-dichloro-2-phenylpyrimidine (7.43 g, 33.0 mmol), tetrakis (triphenylphosphine) palladium (0) (1.73 g), potassium carbonate (8.30 g, 60.1 mmol) were added dimethoxyethane (200 m 1) and water (40 ml) under argon atmosphere, and the mixture was heated and stirred at 50℃for 12 hours. After completion of the reaction, extraction was performed with ethyl acetate, and a residue obtained by concentrating the organic layer was purified by column chromatography to obtain a white solid (6.2 g, yield 48%). The resulting white solid was subjected to mass spectrometry (m/e=429 with respect to molecular weight of 429.0) and was intermediate L.
Synthesis example 1 Synthesis of Compound 1
[ Chemical formula 115]
Intermediate A (4.7 g) and 4- (2-dibenzofuranyl) phenylboronic acid (3.4 g) were added to 1, 2-dimethoxyethane (90 mL) and the solution was purged with argon for 5 minutes. PdCl 2(Amphos)2 (0.26 g) and an aqueous sodium carbonate solution (2M, 12 mL) were added thereto, and the mixture was heated at 75℃for 17 hours while stirring under an argon atmosphere. The reaction solution was subjected to solvent distillation, and the obtained solid was purified by silica gel column chromatography (developing solvent: hexane/toluene), whereby a white solid (5.6 g, yield 90%) was obtained.
The result of mass spectrometry of the white solid obtained (m/e=676 with respect to molecular weight 676.82) is compound 1.
Synthesis example 2 Synthesis of Compound 2
[ Chemical formula 116]
The synthesis was performed in the same manner as in synthesis example 1 except for using intermediate a (2.5 g) and dibenzofuran-2-boronic acid (1.4 g) instead of 4- (2-dibenzofuranyl) phenylboronic acid, and a white solid was obtained (2.6 g, yield 88%).
The result of mass spectrometry of the white solid obtained (m/e=600 with respect to molecular weight 600.72) was compound 2.
Synthesis example 3 Synthesis of Compound 3
[ Chemistry 117]
The synthesis was performed in the same manner as in synthesis example 1 except for using intermediate a (5.0 g) and using 3- (2-dibenzofuranyl) phenylboronic acid (3.1 g) instead of 4- (2-dibenzofuranyl) phenylboronic acid, and a white solid was obtained (3.2 g, yield 48%).
The result of mass spectrometry of the resulting white solid (m/e=676 relative to molecular weight 676.82) was compound 3.
Synthesis example 4 Synthesis of Compound 4
[ Chemical formula 118]
The synthesis was performed in the same manner as in synthesis example 1 except for using intermediate a (5.0 g) and using 4- (4-dibenzofuranyl) phenylboronic acid (3.1 g) instead of 4- (2-dibenzofuranyl) phenylboronic acid, and a white solid was obtained (4.9 g, yield 74%).
The result of mass spectrometry of the resulting white solid (m/e=676 relative to molecular weight 676.82) was compound 4.
Synthesis example 5 Synthesis of Compound 5
[ Chemical formula 119]
Synthesis was performed in the same manner as in Synthesis example 1 except for using intermediate A (4.0 g) and intermediate B (2.4 g) synthesized in the same manner as in International publication No. 2010/137285 in place of 4- (2-dibenzofuranyl) phenylboronic acid, and a white solid (4.5 g, yield 88%) was obtained.
The result of mass spectrometry of the white solid obtained (m/e=650 with respect to molecular weight 650.78) is compound 5.
Synthesis example 6 Synthesis of Compound 6
[ Chemical formula 120]
Synthesis was performed in the same manner as in Synthesis example 1 except for using intermediate A (3.5 g) and intermediate C (2.1 g) synthesized in the same manner as in International publication No. 2010/137285 in place of 4- (2-dibenzofuranyl) phenylboronic acid, and a white solid (4.1 g, yield 92%) was obtained.
The result of mass spectrometry of the white solid obtained (m/e=650 with respect to molecular weight 650.78) was compound 6.
Synthesis example 7 Synthesis of Compound 7
[ Chemical formula 121]
The synthesis was performed in the same manner as in synthesis example 1 except for using intermediate D (2.5 g) instead of intermediate (a) and using dibenzofuran-2-boronic acid (1.4 g) instead of 4- (2-dibenzofuranyl) phenylboronic acid, and a white solid (2.1 g, yield 71%) was obtained.
The result of mass spectrometry of the white solid obtained (m/e=600 with respect to molecular weight 600.72) was compound 7.
Synthesis example 8 Synthesis of Compound 8
[ Chemical formula 122]
The synthesis was performed in the same manner as in synthesis example 1 except for using intermediate a (2.5 g) and dibenzothiophene-2-boronic acid (1.3 g) instead of 4- (2-dibenzofuranyl) phenylboronic acid, to obtain a white solid (2.0 g, 67%).
The result of mass spectrometry analysis of the resulting white solid (m/e=616 relative to molecular weight 616.78) was compound 8.
Synthesis example 9 Synthesis of Compound 9
[ Chemical formula 123]
The synthesis was performed in the same manner as in synthesis example 1 except that intermediate a (5.0 g) was used instead of 4- (2-dibenzofuranyl) phenylboronic acid and intermediate E (2.3 g) was used, to obtain a white solid (3.2 g, yield 55%).
The result of mass spectrometry analysis of the obtained white solid (m/e=601 relative to the molecular weight 600.7) was compound 9.
Synthesis example 10 Synthesis of Compound 10
[ Chemical formula 124]
The synthesis was performed in the same manner as in synthesis example 1 except that intermediate a (5.0 g) was used instead of 4- (2-dibenzofuranyl) phenylboronic acid and intermediate F (2.3 g) was used, to obtain a white solid (5.3 g, yield 91%).
The result of mass spectrometry analysis of the obtained white solid (m/e=601 relative to the molecular weight 600.7) was compound 10.
Synthesis example 11 Synthesis of Compound 11
[ Chemical formula 125]
The synthesis was performed in the same manner as in synthesis example 1 except that intermediate a (5.0G) was used instead of 4- (2-dibenzofuranyl) phenylboronic acid and intermediate G (2.2G) was used, to obtain a white solid (2.2G, yield 38%).
The result of mass spectrometry analysis of the obtained white solid (m/e=651 relative to molecular weight 650.7) was compound 11.
Synthesis example 12 Synthesis of Compound 12
[ Chemical formula 126]
The synthesis was performed in the same manner as in synthesis example 1 except that intermediate a (7.0 g) was used instead of 4- (2-dibenzofuranyl) phenylboronic acid and intermediate H (6.6 g) was used, to obtain a white solid (6.2 g, yield 73%).
The result of mass spectrometry analysis of the obtained white solid (m/e=691 relative to molecular weight 690.8) was compound 12.
Synthesis example 13 Synthesis of Compound 13
[ Chemical formula 127]
The synthesis was performed in the same manner as in synthesis example 1 except that intermediate a (5.0 g) was used instead of 4- (2-dibenzofuranyl) phenylboronic acid and intermediate I (4.5 g) was used, to obtain a white solid (5.7 g, yield 85%).
The result of mass spectrometry analysis of the obtained white solid (m/e=691 relative to molecular weight 690.8) was compound 13.
Synthesis example 14 Synthesis of Compound 14
[ Chemical formula 128]
The synthesis was performed in the same manner as in synthesis example 1 except that intermediate a (5.0 g) was used instead of 4- (2-dibenzofuranyl) phenylboronic acid and intermediate J (2.8 g) was used, to obtain a white solid (4.6 g, yield 73%).
The result of mass spectrometry analysis of the obtained white solid (m/e=651 relative to molecular weight 650.7) was compound 14.
Synthesis example 15 Synthesis of Compound 15
[ Chemical formula 129]
The synthesis was performed in the same manner as in synthesis example 1 except that intermediate L (5.0 g) was used instead of intermediate a (5.0 g) and intermediate M (5.4 g) was used instead of 4- (2-dibenzofuranyl) phenylboronic acid, to obtain a white solid (6.3 g, yield 79%).
The result of mass spectrometry analysis of the obtained white solid (m/e=687 with respect to molecular weight 686.9) was compound 15.
Symbol description
1. 11 Organic EL element
2. Substrate board
3. Anode
4. Cathode electrode
5. Light-emitting layer
6. Hole transport region (hole transport layer)
6A hole injection layer
6B 1 st hole transport layer
6C No. 2 hole transport layer
7. Electron transport region (electron transport layer)
7A 1 st electron transport layer
7B 2 nd electron transport layer
10. 20 Luminous unit

Claims (25)

1. A compound represented by the following formula (1),
In the formula (1), the components are as follows,
Ar 1 is phenyl, biphenyl or naphthyl,
Ar 3 is phenyl, pyridinyl, dibenzofuranyl, or dibenzothiophenyl,
Ar 2 is phenyl, biphenyl or naphthyl,
L 1 is phenylene, biphenylene or naphthylene,
L 2 is a single bond, phenylene, biphenylene or naphthylene,
P is 0 or 1, p is 0 in the case of L 2 being a single bond, p is 0 or 1 in the case of L 2 being phenylene, biphenylene or naphthylene,
R 1～R6 and R 11～R14 are each independently of the other
A hydrogen atom,
Substituted or unsubstituted alkyl group having 1 to 6 carbon atoms,
Substituted or unsubstituted cycloalkyl having 3 to 6 ring-forming carbon atoms,
Substituted or unsubstituted aryl group having 6 to 18 ring carbon atoms, or
A substituted or unsubstituted heterocyclic group having 5 to 18 ring members,
In the group of more than 1 selected from R 11 and R 12、R12 and R 13 and R 13 and R 14, adjacent 2 are optionally bonded to each other to form a substituted or unsubstituted benzene ring, naphthalene ring, benzofuran ring, or benzothiophene ring,
X 1 is an oxygen atom or a sulfur atom,
* D is bonded to one selected from the group consisting of carbon atoms a, b and c,
The substituent when expressed as "substituted or unsubstituted" is a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 ring-forming carbon atoms, and a heterocyclic group having 5 to 18 ring-forming atoms.
2. The compound according to claim 1, wherein,
R 1～R6 are each independently
A hydrogen atom,
Substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or
Substituted or unsubstituted aryl groups having 6 to 18 ring-forming carbon atoms.
3. The compound according to claim 1, wherein,
R 11～R14 are each independently
A hydrogen atom,
Substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or
Substituted or unsubstituted aryl groups having 6 to 18 ring-forming carbon atoms.
4. A compound according to any one of claims 1 to 3, represented by any one of the following formulas (1A) to (1C),
In the steps (1A) - (1C),
R 21～R25 and R 31～R38 are hydrogen atoms,
Wherein, the
In the formula (1A), the amino acid sequence,
In the case where p is 0, 1 selected from R 21～R25 is a single bond to f,
In the case where p is 1,1 selected from R 21～R25 is a single bond to e, the other 1 selected from R 21～R25 is a single bond to f,
In the formula (1B), the amino acid sequence,
In the case where p is 0, 1 selected from R 31～R38 is a single bond to g, the other 1 selected from R 31～R38 is a single bond to i,
In the case where p is 1, 1 selected from R 31～R38 is a single bond to g, another 1 selected from R 31～R38 is a single bond to h, yet another 1 selected from R 31～R38 is a single bond to i,
Ar1～Ar3、L1、p、R1～R6、R11～R14、X1、＊a、＊b、＊c D is as defined in formula (1).
5. The compound according to claim 4, which is represented by the following formula (1A-1) or (1B-1),
In the formulae (1A-1) and (1B-1),
Ar 1、Ar2、L1、R1～R6、R11～R14、X1, a, B, c and d are as defined in formula (1), R 21～R25 and f are as defined in formula (1A), and R 31～R38, g and i are as defined in formula (1B).
6. The compound according to claim 4, which is represented by the following formula (1A-1A) or (1A-1 b),
In the formulae (1A-1A) and (1A-1 b),
Ar 1、Ar2、L1、R1～R6、R11～R14、X1, a, b, c and d are as defined in formula (1), and R 21～R25 is as defined in formula (1A).
7. The compound according to claim 4, which is represented by the following formula (1A-1 c),
In the formula (1A-1 c),
Ar 1、Ar2、L1、R1～R6、R11～R14, and X 1 are as defined in formula (1), and R 21～R25 and f are as defined in formula (1A).
8. A compound according to any one of claims 1 to 3, represented by the following formula (1C-1 a),
In the formula (1C-1 a),
Ar 1、Ar2、L1、R1～R6、R11～R14 and X 1 are as defined in formula (1).
9. A compound according to any one of claim 1 to 3,
Ar 1 is phenyl.
10. A compound according to any one of claim 1 to 3,
Ar 2 is phenyl.
11. A compound according to any one of claim 1 to 3,
L 1 is phenylene.
12. A compound according to any one of claim 1 to 3,
L 1 is biphenylene.
13. A compound according to any one of claim 1 to 3,
R 1～R6 are hydrogen atoms.
14. A compound according to any one of claim 1 to 3,
R 11～R14 are hydrogen atoms.
15. A compound according to any one of claim 1 to 3,
The compound represented by the formula (1) contains at least 1 deuterium atom.
16. A compound which is any one of the following,
。
17. A material for an organic electroluminescent element, comprising the compound according to any one of claims 1 to 16.
18. An organic electroluminescent element having a cathode, an anode, and an organic layer between the cathode and the anode, the organic layer comprising a light-emitting layer, at least 1 layer of the organic layer comprising the compound of any one of claims 1 to 16.
19. The organic electroluminescent element according to claim 18, wherein,
The organic layer includes an electron transport region between the cathode and the light emitting layer, the electron transport region including the compound.
20. The organic electroluminescent element according to claim 19, wherein,
The electron transport region comprises a1 st electron transport layer on the anode side and a2 nd electron transport layer on the cathode side, the 1 st electron transport layer comprising the compound, or the 2 nd electron transport layer comprising the compound, or both the 1 st electron transport layer and the 2 nd electron transport layer comprising the compound.
21. The organic electroluminescent element according to claim 19, wherein,
The electron transport region further comprises a hole blocking layer on the cathode side, the hole blocking layer comprising the compound.
22. The organic electroluminescent element according to claim 21, wherein the hole blocking layer is adjacent to the light emitting layer.
23. The organic electroluminescent device as claimed in any one of claims 18 to 22, wherein,
The light emitting layer includes a fluorescent dopant material.
24. The organic electroluminescent device as claimed in any one of claims 18 to 22, wherein,
The light emitting layer includes a phosphorescent dopant material.
25. An electronic device comprising the organic electroluminescent element according to any one of claims 18 to 24.
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