Organic electroluminescent element and electronic device using the same
阅读说明：本技术 有机电致发光元件和使用其的电子设备 (Organic electroluminescent element and electronic device using the same ) 是由 糸井裕亮 中野裕基 田崎聪美 八卷太郎 增田哲也 于 2020-04-08 设计创作，主要内容包括：有机电致发光元件,其是包含阴极、阳极、和在前述阴极和前述阳极之间配置的有机层的有机电致发光元件,前述有机层包含发光层和第1层,前述第1层在前述阴极和前述发光层之间配置,前述发光层包含下述式(1A)所示的化合物和下述式(1B)所示的化合物中任一者或两者,前述第1层包含下述式(BE1)所示的化合物。(An organic electroluminescent element comprising a cathode, an anode, and an organic layer disposed between the cathode and the anode, wherein the organic layer comprises a light-emitting layer and a1 st layer, the 1 st layer is disposed between the cathode and the light-emitting layer, and the light-emitting layer comprises a compound represented by the following formula (1A) and a compound represented by the following formula (1B)The 1 st layer contains a compound represented by the following formula (BE 1).)
1. An organic electroluminescent element comprising a cathode,
An anode,
And an organic electroluminescent element having an organic layer disposed between the cathode and the anode,
the organic layer includes a light-emitting layer and a1 st layer,
the 1 st layer is disposed between the cathode and the light-emitting layer,
the light-emitting layer contains either or both of a compound represented by the following formula (1A) and a compound represented by the following formula (1B),
the aforementioned layer 1 contains a compound represented by the following formula (BE1),
[ solution 119]
In the formulae (1A) and (1B),
X1is an oxygen atom or a sulfur atom;
Ar1is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms;
L1is composed of
A single bond, a,
A substituted or unsubstituted arylene group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 2-valent heterocyclic group having 5 to 50 ring atoms;
R1~R8、R11A~R19Aand R11B~R19BEach independently is
A hydrogen atom, a halogen atom, a cyano group, a nitro group,
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
A substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms,
A substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901)(R902)(R903)、
-O-(R904)、
-S-(R905)、
-N(R906)(R907)、
A substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms;
R901~R907each independently is
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 1-valent heterocyclic group having 5 to 50 ring atoms; r901~R907When there are more than 2, more than 2R901~R907Each may be the same or different;
[ chemical formula 120]
In the formula (BE1), in the formula,
X31~X33more than 2 of them are nitrogen atoms, and the others other than nitrogen atoms are CR;
r is
A hydrogen atom,
A cyano group,
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901)(R902)(R903)、
-O-(R904)、
A substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms;
R901~R904as defined in the aforementioned formulae (1A) and (1B);
when there are plural R, the plural R may be the same or different from each other;
AE is substituted or unsubstituted aryl with 6-50 ring-forming carbon atoms or substituted or unsubstituted 1-valent heterocyclic group with 5-50 ring-forming carbon atoms;
BE is a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms or a substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring-forming carbon atoms;
LE is a single bond, a substituted or unsubstituted (nE + 1) valent aromatic hydrocarbon ring group having 6 to 50 ring-forming carbon atoms, or a substituted or unsubstituted (nE + 1) valent heterocyclic group having 5 to 50 ring-forming carbon atoms; the aromatic hydrocarbon ring group may have a structure in which 2 or more different aromatic hydrocarbon rings are bonded;
each CE is independently a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms or a substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring-forming carbon atoms;
nE is an integer of 1-3; when nE is 2 or more, LE is not a single bond.
2. The organic electroluminescent element according to claim 1, wherein the compound represented by the formula (BE1) is a compound represented by the following formula (BE 10);
[ solution 121]
In the formula (BE10), in the formula,
AE. BE, LE, CE and nE are as defined in the aforementioned formula (BE 1).
3. The organic electroluminescent element according to claim 1 or 2, wherein,
L1is composed of
A single bond, or
A substituted or unsubstituted arylene group having 6 to 14 ring-forming carbon atoms.
4. The organic electroluminescent element according to claim 1 or 2, wherein,
the compound represented by the formula (1A) and the compound represented by the formula (1B) are each a compound represented by the following formula (1A-1) and a compound represented by the following formula (1B-1);
[ chemical formula 122]
In the formulae (1A-1) and (1B-1), X1、Ar1、R1~R8、R11A~R19AAnd R11B~R19BAs defined in the aforementioned formula (1A) or (1B).
5. The organic electroluminescent element according to any one of claims 1 to 4, wherein,
Ar1is a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms.
6. The organic electroluminescent element according to any one of claims 1 to 5, wherein,
Ar1selected from the group consisting of groups represented by the following formulae (a1) - (a4),
[ solution 123]
In the formulas (a1) - (a4), the formula (a) represents a single bond bonded to a carbon atom of the anthracene skeleton;
R21is composed of
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
A substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms,
A substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms,
A substituted or unsubstituted cycloalkyl group 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,
A substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms;
R901~R907as defined in the aforementioned formulae (1A) and (1B);
m1 is an integer of 0-4;
m2 is an integer of 0-5;
m3 is an integer of 0-7;
when m 1-m 3 are each 2 or more, a plurality of R21May be the same or different from each other;
when m 1-m 3 are each 2 or more, a plurality of adjacent R21And are bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring, or to form no substituted or unsubstituted saturated or unsaturated ring.
7. The organic electroluminescent element according to claim 1, wherein,
R1~R8、R11A~R19Aand R11B~R19BIs a hydrogen atom, and is a hydrogen atom,
L1is a single bond, an unsubstituted arylene group having 6 to 50 ring-forming carbon atoms or an unsubstituted heterocyclic group having 2 valences having 5 to 50 ring-forming carbon atoms,
Ar1is unsubstitutedThe aryl group having 6 to 50 ring-forming carbon atoms or an unsubstituted 1-valent heterocyclic group having 5 to 50 ring-forming carbon atoms.
8. The organic electroluminescent element according to any one of claims 1 to 7, wherein,
X1is an oxygen atom.
9. The organic electroluminescent element according to any one of claims 2 to 8, wherein,
the compound represented by the formula (BE10) is a compound represented by the following formula (BE11) or formula (BE 12);
[ solution 124]
In the formula (BE11), in the formula,
AE. BE and CE are as defined in the aforementioned formula (BE 1);
when a plurality of R's are present, 1 or more groups of adjacent 2 or more of the plurality of R's are bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring, or to form no substituted or unsubstituted saturated or unsaturated ring;
the aforementioned R which does not form a substituted or unsubstituted saturated or unsaturated ring is
A cyano group,
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901)(R902)(R903)、
-O-(R904)、
A substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms;
R901~R904as defined in the aforementioned formulae (1A) and (1B);
nE1 is an integer of 0-4;
when there are plural R, the plural R may be the same or different from each other;
[ solution 125]
In the formula (BE12), in the formula,
AE and BE are as defined in the aforementioned formula (BE 1);
XE is CR51R52、NR53Oxygen atom or sulfur atom;
the aforementioned XE is CR51R52When the aforementioned R is51And the aforementioned R52Bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring, or not to form a substituted or unsubstituted saturated or unsaturated ring;
when a plurality of R's are present, 1 or more groups of adjacent 2 or more of the plurality of R's are bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring, or to form no substituted or unsubstituted saturated or unsaturated ring;
R53r, R which does not form a substituted or unsubstituted saturated or unsaturated ring51And R52Each independently is
A hydrogen atom,
A cyano group,
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901)(R902)(R903)、
-O-(R904)、
A substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms;
R901~R904as defined in the aforementioned formulae (1A) and (1B);
nE2 is an integer of 0-4, nE3 is an integer of 0-3;
when there are plural R, the plural R may be the same or different from each other.
10. The organic electroluminescent element according to claim 1, wherein,
the compound represented by the formula (BE1) is a compound represented by the following formula (BE 14);
[ solution 126]
In the formula (BE14), in the formula,
X31~X33AE, BE, LE and nE are as defined in the aforementioned formula (BE 1);
cz is a group represented by any one of the following formulae (Cz1), (Cz2) and (Cz 3);
[ solution 127]
In the formulae (Cz1), (Cz2) and (Cz3),
when a plurality of R's are present, 1 or more groups of adjacent 2 or more of the plurality of R's are bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring, or to form no substituted or unsubstituted saturated or unsaturated ring;
the aforementioned R which does not form a substituted or unsubstituted saturated or unsaturated ring is
A cyano group,
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901)(R902)(R903)、
-O-(R904)、
A substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms;
R901~R904as defined in the aforementioned formulae (1A) and (1B);
nE6 and nE7 are each independently integers of 0-4;
nE8 and nE11 are each independently integers of 0-4, and nE9 and nE10 are each independently integers of 0-3;
nE12, nE14 and nE15 are each independently an integer of 0-4, and nE13 is an integer of 0-3;
when a plurality of R's are present, the plurality of R's may be the same or different from each other;
and LE is bonded.
11. The organic electroluminescent element according to any one of claims 1 to 8 and 10, wherein,
LE is a single bond or a substituted or unsubstituted (nE + 1) -valent aromatic hydrocarbon ring group having 6 to 12 ring-forming carbon atoms.
12. The organic electroluminescent element according to any one of claims 1 to 11,
BE is a substituted or unsubstituted aryl group having 6 to 12 ring-forming carbon atoms.
13. The organic electroluminescent element according to any one of claims 1 to 12, wherein,
the 1 st layer is directly adjacent to the light-emitting layer.
14. The organic electroluminescent element according to any one of claims 1 to 13, wherein,
a2 nd layer is provided between the cathode and the 1 st layer.
15. The organic electroluminescent element according to claim 14, wherein,
the 2 nd layer contains a compound represented by the following formula (EB 1);
[ solution 128]
In the formula (EB1), the compound,
XEB1is O, S, or CR41R42；
R41And R42Each independently is
A hydrogen atom,
A cyano group,
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901)(R902)(R903)、
-O-(R904)、
A substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms;
R901~R904as defined in the aforementioned formulae (1A) and (1B);
YE1、YE2and YE3Each independently is CH or N;
wherein, YE1、YE2And YE3More than 2 of them are N;
ArE1、ArE3and Are5Each independently is
A single bond, a,
A substituted or unsubstituted phenylene group,
A substituted or unsubstituted naphthylene group,
Substituted or unsubstituted phenanthrylene, or
A substituted or unsubstituted anthracenylene group;
ArE2and Are4Each independently is
Substituted or unsubstituted phenyl,
Substituted or unsubstituted naphthyl,
Substituted or unsubstituted phenanthryl, or
Substituted or unsubstituted anthracenyl;
ArE1and ArE with Are2And ArE3And ArE with Are4Each independently bonded to each other to form a substituted or unsubstituted, saturated or unsaturated ring consisting of only 6-membered rings, or to form no ring.
16. The compound of claim 15, wherein,
the compound represented by the formula (EB1) is a compound represented by the following formula (EB 4);
[ solution 129]
In the formula (EB4), Are1~ArE4As defined in the aforementioned formula (EB 1).
17. The compound of claim 15, wherein,
the compound represented by the formula (EB1) is a compound represented by the following formula (EB 5);
[ solution 130]
In the formula (EB5), Are1~ArE4、R41And R42As defined in the aforementioned formula (EB 1).
18. The organic electroluminescent element according to any one of claims 1 to 17, wherein,
the aforementioned organic layer further comprises a3 rd layer,
the 3 rd layer is disposed between the anode and the light-emitting layer,
the 3 rd layer contains a compound represented by the following formula (B1),
[ solution 131]
In the formula (B1), in the formula,
LA、LBand LCEach independently is a single bond, a substituted or unsubstituted arylene group having 6 to 50 ring-forming carbon atoms, or a substituted or unsubstituted heterocyclic group having 2-valent of 5 to 50 ring-forming carbon atoms;
A. b and C are each independently
A substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms,
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms, or
-Si(R’901)(R’902)(R’903)；
R’901~R’903Each independently is a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms;
R’901~R’9032 or more R's when 1 or more of (A) are present in each of 2 or more'901~R’903Each may be the same or different.
19. The organic electroluminescent element according to any one of claims 1 to 18,
the substituents referred to above as "substituted or unsubstituted" are selected from
An unsubstituted alkyl group having 1 to 50 carbon atoms,
An unsubstituted alkenyl group having 2 to 50 carbon atoms,
An unsubstituted alkynyl group having 2 to 50 carbon atoms,
An unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901)(R902)(R903)、
-O-(R904)、
-S-(R905)、
-N(R906)(R907)
(in this case, the amount of the solvent in the reaction mixture,
R901~R907each independently is
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 1-valent heterocyclic group having 5 to 50 ring atoms; r901~R907When there are more than 2, more than 2R901~R907Each may be the same or different)
Halogen atom, cyano group, nitro group,
An unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, and
and a group of an unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms.
20. The organic electroluminescent element according to any one of claims 1 to 19,
when referred to as "substituted or unsubstituted" substituents are
An unsubstituted alkyl group having 1 to 50 carbon atoms,
An unsubstituted alkenyl group having 2 to 50 carbon atoms,
An unsubstituted alkynyl group having 2 to 50 carbon atoms,
An unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901a)(R902a)(R903a)、
-O-(R904a)、
-S-(R905a)、
-N(R906a)(R907a)、
Halogen atom, cyano group, nitro group,
An unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
An unsubstituted heterocyclic group having a ring-forming atom number of 5 to 50 and having a valence of 1 (wherein R is901a~R907aEach independently is
A hydrogen atom,
An unsubstituted alkyl group having 1 to 50 carbon atoms,
An unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
An unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms; r901a~R907aWhen there are more than 2, more than 2R901a~R907aEach may be the same or different.
21. The organic electroluminescent element according to any one of claims 1 to 20, wherein,
when referred to as "substituted or unsubstituted" substituents are
An unsubstituted alkyl group having 1 to 50 carbon atoms,
An unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
An unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms.
22. An electronic device comprising the organic electroluminescent element according to any one of claims 1 to 21.
Technical Field
The present invention relates to an organic electroluminescent element and an electronic device using the same.
Background
When a voltage is applied to the organic electroluminescent element, holes are injected from the anode and electrons are injected from the cathode into the light-emitting layer. Then, the injected holes and electrons are recombined in the light-emitting layer to form excitons.
The organic EL element includes a light-emitting layer between an anode and a cathode. In addition, a laminated structure including organic layers such as a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer may be provided.
Patent documents 1 to 5 disclose materials for organic electroluminescent elements formed from anthracene compounds.
Documents of the prior art
Patent document
[ patent document 1] WO2010/137285A1
[ patent document 2] WO2014/141725A1
[ patent document 3] US2016/0351817A1
[ patent document 4] US2017/0133600A1
[ patent document 5] US2018/0198077A 1.
Disclosure of Invention
An object of the present invention is to provide an organic electroluminescent element (hereinafter, also referred to as an organic EL element) having high luminous efficiency and an equivalent element life to that of the conventional organic electroluminescent element, and an electronic device using the organic electroluminescent element.
According to the present invention, the following organic electroluminescent element and electronic device can be provided.
1. An organic electroluminescent element comprising a cathode,
An anode,
And an organic electroluminescent element having an organic layer disposed between the cathode and the anode,
the organic layer includes a light-emitting layer and a1 st layer,
the 1 st layer is disposed between the cathode and the light-emitting layer,
the light-emitting layer contains either or both of a compound represented by the following formula (1A) and a compound represented by the following formula (1B),
the 1 st layer contains a compound represented by the following formula (BE 1).
[ solution 1]
(in the formulae (1A) and (1B),
X1is an oxygen atom or a sulfur atom.
Ar1Is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms.
L1Is composed of
A single bond, a,
A substituted or unsubstituted arylene group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 2-valent heterocyclic group having 5 to 50 ring atoms.
R1~R8、R11A~R19AAnd R11B~R19BEach independently is
A hydrogen atom, a halogen atom, a cyano group, a nitro group,
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
A substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms,
A substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901)(R902)(R903)、
-O-(R904)、
-S-(R905)、
-N(R906)(R907)、
A substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms.
R901~R907Each independently is
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 1-valent heterocyclic group having 5 to 50 ring atoms. R901~R907When there are more than 2, more than 2R901~R907Each may be the same or different. ).
[ solution 2]
(in the formula (BE1),
X31~X33wherein 2 or more of the nitrogen atoms are nitrogen atoms, and the others other than nitrogen atoms are CR.
R is
A hydrogen atom,
A cyano group,
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901)(R902)(R903)、
-O-(R904)、
A substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms.
R901~R904As defined in the aforementioned formulae (1A) and (1B).
When there are plural R, the plural R may be the same or different from each other.
AE is a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms or a substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring-forming carbon atoms.
BE is a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms or a substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring-forming carbon atoms.
LE is a single bond, a substituted or unsubstituted (nE + 1) valent aromatic hydrocarbon ring group having 6 to 50 ring-forming carbon atoms, or a substituted or unsubstituted (nE + 1) valent heterocyclic group having 5 to 50 ring-forming carbon atoms. The aromatic hydrocarbon ring group may have a structure in which 2 or more different aromatic hydrocarbon rings are bonded.
Each CE is independently a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms or a substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring-forming carbon atoms.
nE is an integer of 1-3. When nE is 2 or more, LE is not a single bond. ).
2. An electronic device comprising the organic electroluminescent element according to 1.
According to the present invention, an organic electroluminescent element having high luminous efficiency and an equivalent element life to that of a conventional organic electroluminescent element and an electronic device using the same can be provided.
Drawings
Fig. 1 is a diagram showing a schematic configuration of an embodiment of an organic EL element according to an embodiment of the present invention.
Fig. 2 is a diagram showing a schematic configuration of another embodiment of an organic EL device according to an embodiment of the present invention.
Detailed Description
[ definitions ]
In the present specification, hydrogen atoms include isotopes having different numbers of neutrons, i.e., protium (protium), deuterium (deuterium), and tritium (tritium).
In the chemical structural formula, a hydrogen atom, i.e., a protium atom, a deuterium atom, or a tritium atom is bonded to a position, not explicitly shown, of "D" representing a deuterium atom, such as "R".
In the present specification, the number of ring-forming carbon atoms represents the number of carbon atoms among atoms constituting a ring itself of a compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, and a heterocyclic compound) having a structure in which atoms are bonded to a ring. When the ring is substituted with a substituent, the carbon contained in the substituent is not included in the number of ring-forming carbon atoms. The "number of ring-forming carbon atoms" described below is the same unless otherwise specified. For example, the number of ring-forming carbon atoms of the benzene ring is 6, the number of ring-forming carbon atoms of the naphthalene ring is 10, the number of ring-forming carbon atoms of the pyridine ring is 5, and the number of ring-forming carbon atoms of the furan ring is 4. For example, the number of ring-forming carbon atoms of the 9, 9-diphenylfluorenyl group is 13, 9,9' -spirobifluorenyl group is 25.
When an alkyl group is substituted on the benzene ring as a substituent, the number of carbon atoms of the alkyl group is not included in the number of ring-forming carbon atoms of the benzene ring. Therefore, the number of ring-forming carbon atoms of the benzene ring substituted with an alkyl group is 6. When an alkyl group is substituted on the naphthalene ring as a substituent, the number of carbon atoms of the alkyl group is not included in the number of ring-forming carbon atoms of the naphthalene ring. Therefore, the number of ring-forming carbon atoms of the naphthalene ring substituted with an alkyl group is 10.
In the present specification, the number of ring-forming atoms represents the number of atoms constituting a ring itself of a compound (e.g., monocyclic compound, fused ring compound, crosslinked compound, carbocyclic compound and heterocyclic compound) having a structure in which atoms are bonded to a ring (e.g., monocyclic ring, fused ring and ring set). The number of ring-forming atoms is not included in atoms that do not form a ring (e.g., hydrogen atoms that terminate bonds of atoms that form a ring), and atoms contained in a substituent when the ring is substituted with a substituent. The "ring-forming number" described below is the same unless otherwise specified. For example, the number of ring formation atoms of the pyridine ring is 6, the number of ring formation atoms of the quinazoline ring is 10, and the number of ring formation atoms of the furan ring is 5. For example, the number of hydrogen atoms bonded to the pyridine ring or the number of atoms constituting the substituent is not included in the number of atoms forming the pyridine ring. Therefore, the number of ring-forming atoms of the pyridine ring to which a hydrogen atom or a substituent is bonded is 6. Further, 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 the ring-forming atoms of the quinazoline ring. Therefore, the number of ring atoms of the quinazoline ring to which a hydrogen atom or a substituent is bonded is 10.
In the present specification, "XX to YY carbon atoms" in the expression "ZZ group having XX to YY carbon atoms which is substituted or unsubstituted" means the number of carbon atoms when the ZZ group is unsubstituted, and does not include the number of carbon atoms of the substituent when the group is substituted. Here, "YY" is larger than "XX", "XX" represents an integer of 1 or more, and "YY" represents an integer of 2 or more.
In the present specification, "the number of atoms XX to YY" in the expression "ZZ group having the number of atoms XX to YY which is substituted or unsubstituted" represents the number of atoms when the ZZ group is unsubstituted, and does not include the number of atoms of the substituent when the group is substituted. Here, "YY" is larger than "XX", "XX" represents an integer of 1 or more, and "YY" represents an integer of 2 or more.
In the present specification, an unsubstituted ZZ group means a case where a "substituted or unsubstituted ZZ group" is an "unsubstituted ZZ group", and a substituted ZZ group means a case where a "substituted or unsubstituted ZZ group" is a "substituted ZZ group".
In the present specification, "unsubstituted" in the case of "substituted or unsubstituted ZZ group" means that the hydrogen atom of the ZZ group is not replaced by a substituent. The hydrogen atom in the "unsubstituted ZZ group" is a protium atom, a deuterium atom, or a tritium atom.
In addition, "substituted" in the case of "substituted or unsubstituted ZZ group" in the present specification means that 1 or more hydrogen atoms of the ZZ group are replaced with a substituent. "substituted" in the case of "BB group substituted with AA group" also means that 1 or more hydrogen atoms of BB group are replaced with AA group.
"substituents described in the specification"
The substituents described in the present specification will be described below.
Unless otherwise stated in the present specification, the "unsubstituted aryl" described in the present specification has 6 to 50, preferably 6 to 30, and more preferably 6 to 18 ring-forming carbon atoms.
Unless otherwise stated in the present specification, the "unsubstituted heterocyclic group" described in the present specification has 5 to 50 ring-forming atoms, preferably 5 to 30 ring-forming atoms, and more preferably 5 to 18 ring-forming atoms.
Unless otherwise stated in the present specification, the "unsubstituted alkyl group" described in the present specification has 1 to 50 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 1 to 6 carbon atoms.
Unless otherwise stated in the present specification, the "unsubstituted alkenyl" as described in the present specification has 2 to 50 carbon atoms, preferably 2 to 20 carbon atoms, and more preferably 2 to 6 carbon atoms.
Unless otherwise stated in the present specification, the "unsubstituted alkynyl" as described in the present specification has 2 to 50 carbon atoms, preferably 2 to 20 carbon atoms, and more preferably 2 to 6 carbon atoms.
Unless otherwise stated in the present specification, the "unsubstituted cycloalkyl" described in the present specification has 3 to 50, preferably 3 to 20, and more preferably 3 to 6 ring-forming carbon atoms.
Unless otherwise stated in the present specification, the "unsubstituted arylene" described in the present specification has 6 to 50, preferably 6 to 30, and more preferably 6 to 18 ring-forming carbon atoms.
Unless otherwise stated in the present specification, the "unsubstituted 2-valent heterocyclic group" described in the present specification has 5 to 50 ring-forming atoms, preferably 5 to 30 ring-forming atoms, and more preferably 5 to 18 ring-forming atoms.
Unless otherwise stated in the present specification, the "unsubstituted alkylene group" described in the present specification has 1 to 50 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 1 to 6 carbon atoms.
Harvesting "substituted or unsubstituted aryl radicals"
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). (As used herein, unsubstituted aryl means that "substituted or unsubstituted aryl" is "unsubstituted aryl" and substituted aryl means that "substituted or unsubstituted aryl" is "substituted aryl.) in this specification, a single reference to" aryl "includes both" unsubstituted aryl "and" substituted aryl ".
"substituted aryl" refers to a group in which 1 or more hydrogen atoms of an "unsubstituted aryl" group are replaced with a substituent. Examples of the "substituted aryl group" include a group in which 1 or more hydrogen atoms of the "unsubstituted aryl group" of the following specific group G1A are replaced with a substituent, a substituted aryl group of the following specific group G1B, and the like. Further, the "unsubstituted aryl" and the "substituted aryl" mentioned herein are merely examples, and the "substituted aryl" mentioned in the present specification 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 replaced 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 replaced with a substituent.
Seeded and unsubstituted aryl (specific group G1A):
phenyl, phenyl,
P-biphenyl,
M-biphenyl group,
Ortho-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 group,
2-naphthyl group,
Anthracene base,
Benzanthracene group,
Phenanthryl,
Benzophenanthryl,
A phenalkenyl group,
Pyrenyl group,
chrysene radical,
Benzo chrysene radical,
A triphenylene group,
A benzotriphenylene group,
Tetracenyl,
A pentacenyl group,
A fluorenyl group,
9,9' -spirobifluorenyl group,
A benzofluorenyl group,
Dibenzofluorenyl group,
Fluoranthenyl,
A benzofluoranthenyl group,
Perylene groups, and
a 1-valent aryl group derived by removing 1 hydrogen atom from a ring structure represented by the following general formulae (TEMP-1) to (TEMP-15).
[ solution 3]
[ solution 4]
Seeded substituted aryl (specific group G1B):
o-tolyl radical,
M-tolyl radical,
P-tolyl radical,
P-xylyl group,
M-xylyl group,
O-xylyl group,
P-isopropylphenyl,
M-isopropylphenyl group,
O-isopropylphenyl,
P-tert-butylphenyl,
M-tert-butylphenyl,
O-tert-butylphenyl group,
3,4, 5-trimethylphenyl,
9, 9-dimethylfluorenyl group,
9, 9-diphenylfluorenyl group,
9, 9-bis (4-methylphenyl) fluorenyl group,
9, 9-bis (4-isopropylphenyl) fluorenyl group,
9, 9-bis (4-tert-butylphenyl) fluorenyl group,
A cyanophenyl group,
Triphenylsilylphenyl group,
A trimethylsilylphenyl group,
Phenyl naphthyl,
Naphthyl phenyl, and
the group in which 1 or more hydrogen atoms of a 1-valent group derived from a ring structure represented by the general formulae (TEMP-1) to (TEMP-15) are replaced with a substituent.
Harvesting "substituted or unsubstituted heterocyclic radicals"
The "heterocyclic group" described in the present specification is a cyclic group containing at least 1 hetero atom in ring-forming atoms. Specific examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, a silicon atom, a phosphorus atom and a boron atom.
The "heterocyclic group" described in the present specification is a monocyclic group or a condensed ring group.
The term "heterocyclic group" as used herein refers to 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). (As used herein, the term "unsubstituted heterocyclic group" means the case where "substituted or unsubstituted heterocyclic group" is "unsubstituted heterocyclic group", and the term "substituted heterocyclic group" means the case where "substituted or unsubstituted heterocyclic group" is "substituted heterocyclic group").
"substituted heterocyclic group" means a group in which 1 or more hydrogen atoms of "unsubstituted heterocyclic group" are replaced with a substituent. Specific examples of the "substituted heterocyclic group" include a group obtained by replacing a hydrogen atom of the "unsubstituted heterocyclic group" of the following specific example group G2A, and a substituted heterocyclic group of the following specific example group G2B. Further, the "unsubstituted heterocyclic group" and the "substituted heterocyclic group" recited herein are merely examples, and the "substituted heterocyclic group" described in the present specification also includes a group in which a hydrogen atom bonded to a ring-forming atom of the heterocyclic group itself in the "substituted heterocyclic group" in the specific group G2B is further replaced by a substituent, and a group in which a hydrogen atom of a substituent in the "substituted heterocyclic group" in the specific group G2B is further replaced by a substituent.
Specific example group G2A includes, for example, the following unsubstituted heterocyclic group containing a nitrogen atom (specific example group G2a1), an unsubstituted heterocyclic group containing an oxygen atom (specific example group G2a2), an unsubstituted heterocyclic group containing a sulfur atom (specific example group G2A3), and a 1-valent heterocyclic group derived by removing 1 hydrogen atom from a ring structure represented by the following general formulae (TEMP-16) to (TEMP-33) (specific example group G2a 4).
Specific example group G2B includes, for example, the following substituted heterocyclic group containing a nitrogen atom (specific example group G2B1), the following substituted heterocyclic group containing an oxygen atom (specific example group G2B2), the following substituted heterocyclic group containing a sulfur atom (specific example group G2B3), and a group in which 1 or more hydrogen atoms of a 1-valent heterocyclic group derived from a ring structure represented by the following general formulae (TEMP-16) to (TEMP-33) are replaced with a substituent (specific example group G2B 4).
Ziziprashige of unsubstituted heterocyclic group containing nitrogen atom (specific group G2A 1):
a pyrrole group,
Imidazolyl group,
Pyrazolyl, pyrazolyl,
A triazolyl group,
Tetrazolyl group,
An oxazolyl group,
Isoxazolyl group,
An oxadiazolyl group,
Thiazolyl,
Isothiazolyl group,
A thiadiazolyl group,
A pyridyl group,
A pyridazinyl group,
Pyrimidinyl,
A pyrazinyl group,
A triazine group,
Indolyl, a,
Isoindolyl group,
Indolizinyl radical,
A quinolizinyl group,
Quinolyl group,
Isoquinolinyl group,
Cinnolinyl group, cinnolinyl group and cinnolinyl group,
Phthalazinyl radical,
A quinazoline group,
A quinoxalinyl group,
A benzimidazolyl group,
Indazolyl group,
Phenanthroline radical,
Phenanthridinyl,
Acridinyl group,
Phenazine group,
Carbazolyl group,
A benzocarbazolyl group,
A morpholino group,
A phenoxazinyl group,
Phenothiazinyl group,
Azacarbazolyl group, and
diazacarbazolyl.
Ziziprashige of unsubstituted heterocyclic group containing oxygen atom (specific group G2A 2):
furyl, furyl,
An oxazolyl group,
Isoxazolyl group,
An oxadiazolyl group,
Xanthenyl group,
A benzofuranyl group,
Isobenzofuranyl radical,
Dibenzofuranyl radical,
Naphthobenzofuranyl, naphthofuranyl, and furanyl,
Benzoxazolyl group,
A benzisoxazolyl group,
A phenoxazinyl group,
A morpholino group,
A dinaphthofuranyl group,
An aza-dibenzofuranyl group,
Diaza dibenzofuranyl group,
An azabenzofuranyl group, and
naphthyridobenzofuranyl.
Seeding of unsubstituted heterocyclic group containing sulfur atom (specific example group G2a 3):
a thienyl group,
Thiazolyl,
Isothiazolyl group,
A thiadiazolyl group,
Benzothienyl groups,
Isobenzothienyl (isobenzothienyl group),
Dibenzothienyl (dibenzothienyl group),
Naphthobenzothienyl group,
A benzothiazolyl group,
Benzisothiazolyl,
Phenothiazinyl group,
Dinaphthhtothienyl group,
Azadibenzothiophenyl group,
Diaza-dibenzothienyl group,
Azanaphthobenzothienyl (azanaphthothienyl group), and
diazanaphnobenzothienyl (diazanaphnobenzothienyl group).
Seeding 1-valent heterocyclic group derived by removing 1 hydrogen atom from a ring structure represented by the following general formulae (TEMP-16) to (TEMP-33) (specific example group G2a 4):
[ solution 5]
[ solution 6]
In the general formulae (TEMP-16) - (TEMP-33), XAAnd YAEach independently is an oxygen atom, a sulfur atom, NH, or CH2. Wherein, XAAnd YAAt least 1 of them is an oxygen atom, a sulfur atom, or NH.
In the general formulae (TEMP-16) - (TEMP-33), XAAnd YAAt least one of (A) and (B) is NH or CH2When the 1-valent heterocyclic group derived from the ring structure represented by the general formulae (TEMP-16) to (TEMP-33) includes NH or CH2A 1-valent group obtained by removing 1 hydrogen atom.
Seeding substituted heterocyclic group containing nitrogen atom (specific group G2B 1):
(9-phenyl) carbazolyl,
(9-biphenylyl) carbazolyl group,
(9-phenyl) phenylcarbazolyl,
(9-naphthyl) carbazolyl,
Diphenylcarbazol-9-yl,
Phenylcarbazol-9-yl,
A methylbenzimidazolyl group,
An ethyl benzimidazolyl group,
A phenyl triazinyl group,
A biphenyltriazinyl group,
Diphenyltriazinyl group,
Phenylquinazolinyl, and
a biphenyl quinazolinyl group.
Seeding substituted heterocyclic group containing oxygen atom (specific group G2B 2):
phenyl dibenzofuranyl radical,
Methyl dibenzofuranyl radical,
Tert-butyl dibenzofuranyl, and
spiro [ 9H-xanthene-9, 9' - [ 9H ] fluorene ] residue with valence of 1.
Seeding substituted heterocyclic group containing sulfur atom (specific example group G2B 3):
phenyl dibenzothienyl, phenyl dibenzothienyl,
Methyl dibenzothienyl, methyl dibenzothienyl,
Tert-butyl dibenzothienyl, and
spiro [ 9H-thioxanthene-9, 9' - [ 9H ] fluorene ] residue having a valence of 1.
Seeding of the above-mentioned group in which 1 or more hydrogen atoms of the 1-valent heterocyclic group derived from the ring structure represented by the general formulae (TEMP-16) to (TEMP-33) are replaced with a substituent (specific example group G2B 4):
the phrase "1 or more hydrogen atoms of a 1-valent heterocyclic group" means that the hydrogen atom bonded to a ring-forming carbon atom of the 1-valent heterocyclic group, the hydrogen atom bonded to a nitrogen atom when at least one of XA and YA is NH, and one of XA and YA is CH2At least 1 hydrogen atom out of the hydrogen atoms of methylene group.
Zijing "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). (As used herein, unsubstituted alkyl means that where "substituted or unsubstituted alkyl" is "unsubstituted alkyl" and substituted alkyl means that "substituted or unsubstituted alkyl" is "substituted alkyl"), the following, when referring to "alkyl" alone, includes both "unsubstituted alkyl" and "substituted alkyl".
"substituted alkyl" refers to a group in which 1 or more hydrogen atoms in an "unsubstituted alkyl" group are replaced with a substituent. Specific examples of the "substituted alkyl group" include a group in which 1 or more hydrogen atoms in the "unsubstituted alkyl group" (specific example group G3A) are replaced with a substituent, a substituted alkyl group (specific example group G3B), and the like. In the present specification, the alkyl group in the "unsubstituted alkyl group" refers to a chain alkyl group. Thus, "unsubstituted alkyl" includes both straight-chain "unsubstituted alkyl" and branched-chain "unsubstituted alkyl". Further, the "unsubstituted alkyl group" and the "substituted alkyl group" mentioned herein are merely examples, and the "substituted alkyl group" mentioned in the present specification includes a group in which a hydrogen atom of an alkyl group itself in the "substituted alkyl group" of the specific group G3B is further replaced with a substituent, and a group in which a hydrogen atom of a substituent in the "substituted alkyl group" of the specific group G3B is further replaced with a substituent.
Seeded and unsubstituted alkyl (specific group G3A):
methyl, methyl,
Ethyl group, ethyl group,
N-propyl group,
An isopropyl group,
N-butyl,
Isobutyl, and,
Sec-butyl, and
a tertiary butyl group.
Seeded substituted alkyl (specific group G3B):
heptafluoropropyl (including isomers),
Pentafluoroethyl group,
2,2, 2-trifluoroethyl, and
a trifluoromethyl group.
Zijing "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 the case where "substituted or unsubstituted alkenyl" is "unsubstituted alkenyl", and "substituted alkenyl" means the case where "substituted or unsubstituted alkenyl" is "substituted alkenyl.) in the present specification, a single reference to" alkenyl "includes both" unsubstituted alkenyl "and" substituted alkenyl ".
"substituted alkenyl" refers to a group in which 1 or more hydrogen atoms in an "unsubstituted alkenyl" are replaced with a substituent. Specific examples of the "substituted alkenyl group" include a group having a substituent in the following "unsubstituted alkenyl group" (specific example group G4A), and a substituted alkenyl group (specific example group G4B). In addition, examples of "unsubstituted alkenyl group" and "substituted alkenyl group" cited herein are only examples, and "substituted alkenyl group" as used herein includes also groups in which a hydrogen atom of an alkenyl group itself in the "substituted alkenyl group" of the specific group G4B is further replaced with a substituent, and groups in which a hydrogen atom of a substituent in the "substituted alkenyl group" of the specific group G4B is further replaced with a substituent.
Seeded unsubstituted alkenyl (specific group G4A):
vinyl group,
Allyl group,
1-butenyl radical,
2-butenyl, and
3-butenyl.
Seeded substituted alkenyl groups (specific group G4B):
1, 3-butadienyl,
1-methylvinyl group,
1-methylallyl group,
1, 1-dimethylallyl,
2-methylallyl, and
1, 2-dimethylallyl.
Zijing "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 groups (specific example group G5A). (As used herein, unsubstituted alkynyl means that "substituted or unsubstituted alkynyl" is "unsubstituted alkynyl") hereinafter, a single reference to "alkynyl" includes both "unsubstituted alkynyl" and "substituted alkynyl".
"substituted alkynyl" refers to a group in which 1 or more hydrogen atoms in an "unsubstituted alkynyl" group are replaced with a substituent. Specific examples of the "substituted alkynyl group" include groups in which 1 or more hydrogen atoms in the "unsubstituted alkynyl group" (specific example group G5A) described below are replaced with a substituent, and the like.
Seeded unsubstituted alkynyl (specific group G5A):
and an ethynyl group.
Zizania seed "substituted or unsubstituted cycloalkyl"
Specific examples of the "substituted or unsubstituted cycloalkyl group" described in the present specification (specific example group G6) include the following unsubstituted cycloalkyl group (specific example group G6A) and substituted cycloalkyl group (specific example group G6B). (As used herein, unsubstituted cycloalkyl means the case where "substituted or unsubstituted cycloalkyl" is "unsubstituted cycloalkyl" and substituted cycloalkyl means the case where "substituted or unsubstituted cycloalkyl" is "substituted cycloalkyl.) in this specification, a single reference to" cycloalkyl "includes both" unsubstituted cycloalkyl "and" substituted cycloalkyl ".
"substituted cycloalkyl" refers to a group in which 1 or more hydrogen atoms in an "unsubstituted cycloalkyl" group are replaced with a substituent. Specific examples of the "substituted cycloalkyl group" include a group in which 1 or more hydrogen atoms in the "unsubstituted cycloalkyl group" (specific example group G6A) are replaced with a substituent, a substituted cycloalkyl group (specific example group G6B), and the like. Further, the "unsubstituted cycloalkyl" and the "substituted cycloalkyl" mentioned herein are merely examples, and the "substituted cycloalkyl" mentioned in the present specification includes a group in which 1 or more hydrogen atoms bonded to carbon atoms of the cycloalkyl group itself in the "substituted cycloalkyl" of specific group G6B are replaced by a substituent, and a group in which hydrogen atoms of the substituent in the "substituted cycloalkyl" of specific group G6B are further replaced by a substituent.
Seeded and unsubstituted cycloalkyl (specific group G6A):
a cyclopropyl group,
A cyclobutyl group,
A cyclopentyl group,
Cyclohexyl,
1-adamantyl group,
2-adamantyl group,
1-norbornyl, and
2-norbornyl.
Seeded substituted cycloalkyl (specific group G6B):
4-methylcyclohexyl group.
・“-Si(R901)(R902)(R903) Group shown "
Si (R) as described in the present specification901)(R902)(R903) Specific examples of the groups shown (specific example 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). In this case, the amount of the solvent to be used,
g1 is a "substituted or unsubstituted aryl" group as described in specific example group G1.
G2 is the "substituted or unsubstituted heterocyclic group" described in specific group G2.
G3 is a "substituted or unsubstituted alkyl" group as described in specific group G3.
G6 is a "substituted or unsubstituted cycloalkyl" as described in specific example group G6.
The plurality of G1 in-Si (G1) (G1) (G1) may be the same as or different from each other.
The plurality of G2 in-Si (G1) (G2) (G2) may be the same as or different from each other.
The plurality of G1 in-Si (G1) (G1) (G2) may be the same as or different from each other.
The plurality of G2 in-Si (G2) (G2) (G2) may be the same as or different from each other.
The plurality of G3 in-Si (G3) (G3) (G3) may be the same as or different from each other.
The plurality of G6 in-Si (G6) (G6) (G6) may be the same as or different from each other.
・“-O-(R904) Group shown "
O- (R) as described in the present specification904) Specific examples of the groups shown (specific example group G8) include
-O(G1)、
-O(G2)、
-O (G3), and
-O(G6)。
in this case, the amount of the solvent to be used,
g1 is a "substituted or unsubstituted aryl" group as described in specific example group G1.
G2 is the "substituted or unsubstituted heterocyclic group" described in specific group G2.
G3 is a "substituted or unsubstituted alkyl" group as described in specific group G3.
G6 is a "substituted or unsubstituted cycloalkyl" as described in specific example group G6.
・“-S-(R905) Group shown "
As described in the present specification, -S- (R)905) Specific examples of the groups shown (specific example group G9) include
-S(G1)、
-S(G2)、
-S (G3), and
-S(G6)。
in this case, the amount of the solvent to be used,
g1 is a "substituted or unsubstituted aryl" group as described in specific example group G1.
G2 is the "substituted or unsubstituted heterocyclic group" described in specific group G2.
G3 is a "substituted or unsubstituted alkyl" group as described in specific group G3.
G6 is a "substituted or unsubstituted cycloalkyl" as described in specific example group G6.
・“-N(R906)(R907) Group shown "
As described in this specification, -N (R)906)(R907) Specific examples of the groups shown (specific example group G10) include
-N(G1)(G1)、
-N(G2)(G2)、
-N(G1)(G2)、
-N (G3) (G3), and
-N(G6)(G6)。
in this case, the amount of the solvent to be used,
g1 is a "substituted or unsubstituted aryl" group as described in specific example group G1.
G2 is the "substituted or unsubstituted heterocyclic group" described in specific group G2.
G3 is a "substituted or unsubstituted alkyl" group as described in specific group G3.
G6 is a "substituted or unsubstituted cycloalkyl" as described in specific example group G6.
The plurality of G1 in-N (G1) (G1) may be the same as or different from each other.
The plurality of G2 in-N (G2) (G2) may be the same as or different from each other.
The plurality of G3 in-N (G3) (G3) may be the same as or different from each other.
A plurality of G6 of-N (G6) (G6) may be the same as or different from each other
Harvesting or treating "halogen atoms"
Specific examples of the "halogen atom" described herein (specific example group G11) include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Novel substituted or unsubstituted fluoroalkyl groups "
The "substituted or unsubstituted fluoroalkyl group" as used herein means a group in which at least 1 hydrogen atom bonded to a carbon atom constituting an alkyl group in the "substituted or unsubstituted alkyl group" is replaced with a fluorine atom, and also includes a group (perfluoro group) in which all hydrogen atoms bonded to carbon atoms constituting an alkyl group in the "substituted or unsubstituted alkyl group" are replaced with fluorine atoms. The "unsubstituted fluoroalkyl group" has 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms, and more preferably 1 to 18 carbon atoms, unless otherwise stated in the specification. "substituted fluoroalkyl" refers to a "fluoroalkyl" group in which 1 or more hydrogen atoms have been replaced with a substituent. In addition, the "substituted fluoroalkyl group" described in the present specification also includes a group in which 1 or more hydrogen atoms bonded to carbon atoms of an alkyl chain in the "substituted fluoroalkyl group" are further replaced with a substituent, and a group in which 1 or more hydrogen atoms of a substituent in the "substituted fluoroalkyl group" are further replaced with a substituent. Specific examples of the "unsubstituted fluoroalkyl group" include groups in which 1 or more hydrogen atoms in the "alkyl group" (specific example group G3) are replaced with fluorine atoms.
Zizania seed "substituted or unsubstituted haloalkyl"
The "substituted or unsubstituted haloalkyl group" as used herein means a group in which at least 1 hydrogen atom bonded to a carbon atom constituting an alkyl group in the "substituted or unsubstituted alkyl group" is replaced with a halogen atom, and also includes a group in which all hydrogen atoms bonded to carbon atoms constituting an alkyl group in the "substituted or unsubstituted alkyl group" are replaced with halogen atoms. Unless otherwise stated in the specification, the "unsubstituted haloalkyl" has 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms, and more preferably 1 to 18 carbon atoms. "substituted haloalkyl" refers to a "haloalkyl" wherein 1 or more hydrogen atoms have been replaced with a substituent. Further, the "substituted haloalkyl" as referred to in the present specification also includes a group in which 1 or more hydrogen atoms bonded to carbon atoms of an alkyl chain in the "substituted haloalkyl" are further replaced with a substituent, and a group in which 1 or more hydrogen atoms of a substituent in the "substituted haloalkyl" are further replaced with a substituent. Specific examples of the "unsubstituted haloalkyl group" include groups in which 1 or more hydrogen atoms in the "alkyl group" (specific example group G3) are replaced with halogen atoms. Haloalkyl is sometimes referred to as halogenated alkyl.
Zip "substituted or unsubstituted alkoxy"
Specific examples of the "substituted or unsubstituted alkoxy" described in the present specification include a group represented by — O (G3), and here, G3 is a "substituted or unsubstituted alkyl" described in specific example group G3. Unless otherwise stated in the specification, the "unsubstituted alkoxy group" has 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms, and more preferably 1 to 18 carbon atoms.
Zijing "substituted or unsubstituted alkylthio"
Specific examples of the "substituted or unsubstituted alkylthio" described in the present specification include a group represented by-S (G3), and G3 is a "substituted or unsubstituted alkyl" described in specific example group G3. Unless otherwise stated in the specification, the "unsubstituted alkylthio group" has 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms, and more preferably 1 to 18 carbon atoms.
Zizania seed "substituted or unsubstituted aryloxy"
Specific examples of the "substituted or unsubstituted aryloxy" described in the present specification include a group represented by — O (G1), and here, G1 is the "substituted or unsubstituted aryl" described in specific example group G1. As long as the description does not otherwise describe, the number of ring-forming carbon atoms of the "unsubstituted aryloxy group" is 6 to 50, preferably 6 to 30, and more preferably 6 to 18.
Zip "substituted or unsubstituted arylthio"
Specific examples of the "substituted or unsubstituted arylthio" described in the present specification include a group represented by the formula-S (G1), and G1 represents a "substituted or unsubstituted aryl" described in specific example group G1. The number of ring-forming carbon atoms of the "unsubstituted arylthio group" is 6 to 50, preferably 6 to 30, and more preferably 6 to 18, unless otherwise stated in the specification.
Novel seed "substituted or unsubstituted trialkylsilyl"
Specific examples of the "trialkylsilyl group" described herein include groups represented by-Si (G3) (G3) (G3), and G3 is a "substituted or unsubstituted alkyl group" described in specific example group G3. The plurality of G3 in-Si (G3) (G3) (G3) may be the same as or different from each other. Unless otherwise stated in the specification, each alkyl group of the "trialkylsilyl group" has 1 to 50 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 1 to 6 carbon atoms.
Novel "substituted or unsubstituted aralkyl group"
Specific examples of the "substituted or unsubstituted aralkyl" described in the present specification are groups represented by- (G3) to- (G1), where G3 is a "substituted or unsubstituted alkyl" described in specific example group G3, and G1 is a "substituted or unsubstituted aryl" described in specific example group G1. Thus, "aralkyl" is a group in which a hydrogen atom of "alkyl" is replaced with "aryl" as a substituent, and is an embodiment of "substituted alkyl". The "unsubstituted aralkyl group" is an "unsubstituted alkyl group" substituted with an "unsubstituted aryl group", and the number of carbon atoms of the "unsubstituted aralkyl group" is 7 to 50, preferably 7 to 30, and more preferably 7 to 18, unless otherwise stated in the specification.
Specific examples of the "substituted or unsubstituted aralkyl group" include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl-tert-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 a phenyl group, a p-biphenylyl group, an m-biphenylyl group, an o-biphenylyl group, a p-terphenyl-4-yl group, a p-terphenyl-3-yl group, a p-terphenyl-2-yl group, an m-terphenyl-4-yl group, an m-terphenyl-3-yl group, an m-terphenyl-2-yl group, an o-terphenyl-4-yl group, an o-terphenyl-3-yl group, an o-terphenyl-2-yl group, a 1-naphthyl group, a 2-naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, an chrysene -yl group, a triphenylene group, a fluorenyl group, a 9,9' -spirobifluorenyl group, a 9, 9-dimethyl fluorenyl group, a 9, 9-diphenyl fluorenyl group, or the like, as long as not described otherwise in the present specification.
The substituted or unsubstituted heterocyclic group described in the present specification is preferably a pyridyl group, a pyrimidyl group, a triazinyl group, a quinolyl group, an isoquinolyl group, a quinazolinyl group, a benzimidazolyl group, a phenanthrolinyl group, a carbazolyl group (1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, or 9-carbazolyl group), a benzocarbazolyl group, an azacarbazolyl group, a diazacarbozolyl group, a dibenzofuranyl group, a naphthobenzofuranyl group, an azabicyclobenzofuranyl group, a diazebenzofuranyl group, a dibenzothiophenyl group, a naphthobenzothiophenyl group, an azabenzothiophenyl group, a diazebenzothiophenyl group, (9-phenyl) carbazolyl group ((9-phenyl) carbazol-1-yl group, (9-phenyl) carbazol-2-yl group, (9-phenyl) carbazol-3-yl group, a quinophthalo-1-yl group, a benzofuranyl group, or a 9-phenyl group, as long as the heterocyclic group is not otherwise described in the present specification, Or (9-phenyl) carbazol-4-yl, (9-biphenyl) carbazolyl, (9-phenyl) phenylcarbazolyl, diphenylcarbazol-9-yl, phenylcarbazol-9-yl, phenyltriazinyl, biphenyltriazinyl, diphenyltriazinyl, phenyldibenzofuranyl, phenyldibenzothiophenyl, and the like.
In the present specification, the carbazolyl group is specifically any one of the following groups unless otherwise stated in the present specification.
[ solution 7]
In the present specification, unless otherwise stated, the (9-phenyl) carbazolyl group is specifically any one of the following groups.
[ solution 8]
In the general formulae (TEMP-Cz1) - (TEMP-Cz9), the bonding position is represented.
In the present specification, unless otherwise stated, the dibenzofuranyl group and the dibenzothiophenyl group are specifically any of the following groups.
[ solution 9]
In the general formulae (TEMP-34) to (TEMP-41), the bonding position is represented.
The substituted or unsubstituted alkyl group described in the present specification is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, or the like, as long as it is not described in the present specification.
Harvesting "substituted or unsubstituted arylenes"
Unless otherwise stated, the "substituted or unsubstituted arylene" referred to herein is a 2-valent group derived by removing 1 hydrogen atom on an aryl ring from the "substituted or unsubstituted aryl" described above. Specific examples of the "substituted or unsubstituted arylene group" (specific example group G12) include a 2-valent group derived by removing 1 hydrogen atom from an aryl ring by the "substituted or unsubstituted aryl group" described in specific example group G1, and the like.
Zizania seed "substituted or unsubstituted 2-valent heterocyclic group"
Unless otherwise stated, a "substituted or unsubstituted 2-valent heterocyclic group" as used herein is a 2-valent group derived by removing 1 hydrogen atom from a heterocyclic ring by the "substituted or unsubstituted heterocyclic group". Specific examples of the "substituted or unsubstituted 2-valent heterocyclic group" (specific example group G13) include a 2-valent group derived by removing 1 hydrogen atom from a heterocyclic ring by the "substituted or unsubstituted heterocyclic group" described in specific example group G2, and the like.
Zijing "substituted or unsubstituted alkylene"
Unless otherwise stated, "substituted or unsubstituted alkylene" in the present specification is a 2-valent group derived by removing 1 hydrogen atom on an alkyl chain from the above "substituted or unsubstituted alkyl group". Specific examples of the "substituted or unsubstituted alkylene group" (specific example group G14) include a 2-valent group derived by removing 1 hydrogen atom from an alkyl chain by the "substituted or unsubstituted alkyl group" described in specific example group G3, and the like.
The substituted or unsubstituted arylene group described in the present specification is preferably any of the groups represented by the following general formulae (TEMP-42) to (TEMP-68), unless otherwise specified in the present specification.
[ solution 10]
[ solution 11]
In the general formulae (TEMP-42) - (TEMP-52), Q1~Q10Each independently is a hydrogen atom, or a substituent.
In the general formulae (TEMP-42) to (TEMP-52), the bonding position is represented.
[ solution 12]
In the general formulae (TEMP-53) - (TEMP-62), Q1~Q10Each independently is a hydrogen atom, or a substituent.
Formula Q9And Q10The rings may be bonded to each other by a single bond to form a ring.
In the general formulae (TEMP-53) to (TEMP-62), the bonding position is represented.
[ solution 13]
The aforementioned tubeIn the formulae (TEMP-63) - (TEMP-68), Q1~Q8Each independently is a hydrogen atom, or a substituent.
In the general formulae (TEMP-63) to (TEMP-68), the bonding position is represented.
The substituted or unsubstituted 2-valent heterocyclic group described in the present specification is preferably any of the following general formulae (TEMP-69) to (TEMP-102) unless otherwise stated in the specification.
[ solution 14]
[ solution 15]
[ solution 16]
In the general formulae (TEMP-69) to (TEMP-82), Q1~Q9Each independently is a hydrogen atom, or a substituent.
[ solution 17]
[ solution 18]
[ solution 19]
[ solution 20]
In the general formulae (TEMP-83) to (TEMP-102), Q1~Q8Each independently is a hydrogen atom, or a substituent.
The above description is of "substituents described in the present specification".
Seed "case of bonding to form Ring"
In the present specification, the case "1 or more groups out of a group consisting of 2 or more adjacent groups are bonded to each other to form a substituted or unsubstituted monocyclic ring, or bonded to each other to form a substituted or unsubstituted condensed ring, or not bonded to each other" means a case "1 or more groups out of a group consisting of 2 or more adjacent groups are bonded to each other to form a substituted or unsubstituted monocyclic ring", "1 or more groups out of a group consisting of 2 or more adjacent groups are bonded to each other to form a substituted or unsubstituted condensed ring", and "1 or more groups out of a group consisting of 2 or more adjacent groups are not bonded to each other".
In the present specification, "a substituted or unsubstituted single ring is formed by bonding 1 or more groups of adjacent 2 or more groups to each other" and "a substituted or unsubstituted condensed ring is formed by bonding 1 or more groups of adjacent 2 or more groups to each other" (hereinafter, such cases may be collectively referred to as "a ring is formed by bonding"). An anthracene compound represented by the following general formula (TEMP-103) wherein the parent skeleton is an anthracene ring will be described as an example.
[ solution 21]
。
For example, R921~R930In the case of "1 or more groups of 2 or more adjacent groups are bonded to each other to form a ring", the group of 2 or more adjacent groups which becomes the 1 group is R921And R922Group (1), R922And R923Group (1), R923And R924Group (1), R924And R930Group (1), R930And R925Group (1), R925And R926Group (1), R926And R927Group (1), R927And R928Group (1), R928And R929Group of (1), and R929And R921The group (2).
The above-mentioned "1 group or more" means that 2 or more groups out of the above-mentioned groups of adjacent 2 or more may form a ring at the same time. For example, R921And R922Are bonded to each other to form a ring QAWhile R is925And R926Are bonded to each other to form a ring QBIn the case, the anthracene compound represented by the general formula (TEMP-103) is represented by the following general formula (TEMP-104).
[ solution 22]
。
The case where "a group consisting of 2 or more adjacent" forms a loop includes not only the case where a group consisting of "2" adjacent to each other is bonded as in the above-described example, but also the case where a group consisting of "3 or more" adjacent to each other is bonded. For example, it means: r921And R922Are bonded to each other to form a ring QAAnd R is922And R923Are bonded to each other to form a ring QCFrom 3 (R) adjacent to each other921、R922And R923) When the anthracene skeleton is condensed by bonding the constituent groups to each other to form a ring, the anthracene compound represented by the general formula (TEMP-103) is represented by the following general formula (TEMP-105). In the following general formula (TEMP-105), ring QAAnd ring QCHas a total of R922。
[ solution 23]
。
The "monocyclic ring" or the "condensed ring" to be formed is only a structure of the ring to be formed, and may be a saturated ring or an unsaturated ring. "1 group of groups consisting of adjacent 2"Even in the case of forming a "single ring" or a "condensed ring", the "single ring" or the "condensed ring" may form a saturated ring or an unsaturated ring. For example, ring Q formed in the aforementioned general formula (TEMP-104)AAnd ring QBAre "monocyclic" or "fused ring", respectively. Further, ring Q formed in the aforementioned general formula (TEMP-105)AAnd ring QCAre "fused rings". Ring Q of the aforementioned formula (TEMP-105)AAnd ring QCThrough ring QAAnd ring QCCondensed to form a condensed ring. If ring Q of the aforementioned formula (TMEP-104)AIs a benzene ring, then ring QAIs a single ring. If ring Q of the aforementioned formula (TMEP-104)AIs naphthalene ring, then ring QAAre fused rings.
"unsaturated ring" means an aromatic hydrocarbon ring, or an aromatic heterocyclic ring. "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 the group exemplified as a specific example in specific example group G1 is terminated with a hydrogen atom.
Specific examples of the aromatic heterocyclic group include those in which the aromatic heterocyclic group exemplified as specific examples in specific group G2 is terminated with a hydrogen atom.
Specific examples of the aliphatic hydrocarbon ring include a structure in which a group exemplified as a specific example in the specific group G6 is terminated with a hydrogen atom.
The term "form a ring" means that only a plurality of atoms of the parent skeleton or a plurality of atoms of the parent skeleton and 1 or more of any elements form a ring. For example, R represented by the aforementioned general formula (TEMP-104)921And R922Ring Q formed by bonding to each otherAIs represented by R921Carbon atom of bonded anthracene skeleton, R922A ring formed by a carbon atom of the bonded anthracene skeleton and any one of 1 or more elements. As a specific example, R921And R922Form a ring QAIn the case of (1), R921Carbon atom of bonded anthracene skeleton, R922When the carbon atom of the bonded anthracene skeleton and 4 carbon atoms form a monocyclic unsaturated ring, R represents921And R922The ring formed is a benzene ring.
Here, the "arbitrary element" is preferably at least 1 element selected from the group consisting of carbon, nitrogen, oxygen, and sulfur, as long as it is not otherwise described in the present specification. In any element (for example, in the case of a carbon element or a nitrogen element), a bond which does not form a ring may be terminated with a hydrogen atom or the like, or may be substituted with an "optional substituent" described later. When any element other than carbon is contained, the ring formed is a heterocyclic ring.
The "1 or more arbitrary elements" constituting a single ring or a condensed ring is preferably 2 or more and 15 or less, more preferably 3 or more and 12 or less, and further preferably 3 or more and 5 or less, unless otherwise described in the specification.
Of the "monocyclic ring" and the "condensed ring", the "monocyclic ring" is preferable as long as it is not described otherwise in the present specification.
Among the "saturated ring" and the "unsaturated ring", the "unsaturated ring" is preferable as long as it is not described in the specification.
The "monocyclic ring" is preferably a benzene ring as long as it is not otherwise described in the present specification.
The "unsaturated ring" is preferably a benzene ring unless otherwise stated in the present specification.
The "1 or more groups of adjacent 2 or more groups" are "bonded to each other to form a substituted or unsubstituted monocyclic ring" or "bonded to each other to form a substituted or unsubstituted condensed ring", and, unless otherwise stated in the present specification, a substituted or unsubstituted "unsaturated ring" in which 1 or more groups of adjacent 2 or more groups are bonded to each other to form a plurality of atoms including a parent skeleton and 1 or more and 15 or less elements of at least 1 element selected from a carbon element, a nitrogen element, an oxygen element, and a sulfur element is preferable.
The substituent in the case where the "single ring" or the "condensed ring" has a substituent is, for example, "optional substituent" described later. Specific examples of the substituent in the case where the "single ring" or "condensed ring" has a substituent are the substituents described in the above "substituent described in the present specification".
The substituent for the case where the "saturated ring" or the "unsaturated ring" has a substituent is, for example, "an optional substituent" described below. Specific examples of the substituent in the case where the "single ring" or "condensed ring" has a substituent are the substituents described in the above "substituent described in the present specification".
The above description has been made of a case where "1 or more groups of adjacent 2 or more groups are bonded to each other to form a substituted or unsubstituted monocyclic ring" and a case where "1 or more groups of adjacent 2 or more groups are bonded to each other to form a substituted or unsubstituted fused ring" (a case where a ring is formed by bonding ").
Substituents when seeded or otherwise referred to as "substituted or unsubstituted
In one embodiment of the present specification, the substituent referred to as "substituted or unsubstituted" (in the present specification, it may be referred to as "optional substituent") is selected from, for example
An unsubstituted alkyl group having 1 to 50 carbon atoms,
An unsubstituted alkenyl group having 2 to 50 carbon atoms,
An unsubstituted alkynyl group having 2 to 50 carbon atoms,
An unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901)(R902)(R903)、
-O-(R904)、
-S-(R905)、
-N(R906)(R907)、
Halogen atom, cyano group, nitro group,
An unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, and
a group of an unsubstituted heterocyclic group having 5 to 50 ring atoms,
herein, R is901~R907Each independently is
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 atoms.
R901When there are more than 2, more than 2R901Are the same as or different from each other,
R902when there are more than 2, more than 2R902Are the same as or different from each other,
R903when there are more than 2, more than 2R903Are the same as or different from each other,
R904when there are more than 2, more than 2R904Are the same as or different from each other,
R905when there are more than 2, more than 2R905Are the same as or different from each other,
R906when there are more than 2, more than 2R906Are the same as or different from each other,
R907when there are more than 2, more than 2R907The same or different from each other.
In one embodiment, the aforementioned substituents when referred to as "substituted or unsubstituted" are selected from
An alkyl group having 1 to 50 carbon atoms,
An aryl group having 6 to 50 ring-forming carbon atoms, and
a heterocyclic group having 5 to 50 ring atoms.
In one embodiment, the aforementioned substituents when referred to as "substituted or unsubstituted" are selected from
An alkyl group having 1 to 18 carbon atoms,
An aryl group having 6 to 18 ring-forming carbon atoms, and
a heterocyclic group having 5 to 18 ring-forming atoms.
Specific examples of the respective groups of the above-mentioned optional substituents are the specific examples of the substituents described in the above-mentioned "substituents described in the present specification".
Unless otherwise stated in the present specification, a "saturated ring" or an "unsaturated ring" may be formed between adjacent arbitrary substituents, and a substituted or unsubstituted saturated 5-membered ring, a substituted or unsubstituted saturated 6-membered ring, a substituted or unsubstituted unsaturated 5-membered ring, or a substituted or unsubstituted unsaturated 6-membered ring may be preferably formed, and a benzene ring may be more preferably formed.
Any substituent may further have a substituent unless otherwise described in the present specification. The optional substituent further has the same substituent as the optional substituent described above.
In the present specification, the numerical range represented by "AA to BB" means a range including the numerical value AA described before "AA to BB" as a lower limit value and the numerical value BB described after "AA to BB" as an upper limit value.
[ organic electroluminescent element ]
An organic electroluminescent element according to one embodiment of the present invention comprises
A cathode, a cathode,
An anode, and
an organic electroluminescent element having an organic layer disposed between the cathode and the anode,
the organic layer includes a light-emitting layer and a1 st layer,
the 1 st layer is disposed between the cathode and the light-emitting layer,
the light-emitting layer contains either or both of a compound represented by the following formula (1A) and a compound represented by the following formula (1B),
the 1 st layer contains a compound represented by the following formula (BE 1).
[ solution 24]
[ solution 25]
The definitions of the substituents and the like in the above-mentioned formulae (1A), (1B) and (BE1) are described in detail in the description of the respective compounds to BE described later, and therefore, are omitted here.
The light-emitting layer contains either or both of the compound represented by the formula (1A) and the compound represented by the formula (1B), and the 1 st layer disposed between the cathode and the light-emitting layer contains the compound represented by the formula (BE1), whereby an organic EL element having high light-emitting efficiency and having an equivalent element life to that of the conventional one can BE obtained.
Fig. 1 is a schematic configuration of an organic EL device according to an embodiment of the present invention.
The organic EL element 1 includes a light-transmissive 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 is configured by stacking a hole injection layer 6, a hole transport layer 7, a light-emitting layer 5, an electron transport layer 8, and an electron injection layer 9 in this order from the anode 3 side. The organic EL element 1 is a bottom emission type organic EL element in which light is emitted from the substrate 2 side.
The organic EL element according to one embodiment of the present invention may be a bottom emission type (fig. 1) in which light is emitted from the substrate side, or a top emission type (fig. 2) in which light is emitted from the cathode side.
In the case of the top emission type, a light-emitting unit portion (light-emitting unit 10 in fig. 1) sandwiched between an anode and a cathode may have the same configuration as the bottom emission type.
< Compound represented by formula (1A) and Compound represented by formula (1B) >
The light-emitting layer of the organic EL element according to one embodiment of the present invention contains either one or both of a compound represented by formula (1A) and a compound represented by formula (1B).
[ solution 26]
(in the formulae (1A) and (1B),
X1is an oxygen atom or a sulfur atom.
Ar1Is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms.
L1Is composed of
A single bond, a,
A substituted or unsubstituted arylene group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 2-valent heterocyclic group having 5 to 50 ring atoms.
R1~R8、R11A~R19AAnd R11B~R19BEach independently is
A hydrogen atom, a halogen atom, a cyano group, a nitro group,
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
A substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms,
A substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901)(R902)(R903)、
-O-(R904)、
-S-(R905)、
-N(R906)(R907)、
A substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms.
R901~R907Each independently is
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 1-valent heterocyclic group having 5 to 50 ring atoms. R901~R907When there are more than 2, more than 2R901~R907Each may be the same or different. )
In one embodiment, the compound represented by the formula (1A) and the compound represented by the formula (1B) are a compound represented by the following formula (1A-1) and a compound represented by the following formula (1B-1), respectively.
[ solution 27]
(in the formulae (1A-1) and (1B-1), X1、Ar1、R1~R8、R11A~R19AAnd R11B~R19BAs defined in the aforementioned formula (1A) or (1B). ).
In one embodiment, the compound represented by the formula (1A) and the compound represented by the formula (1B) are each a compound represented by the following formula (1A-2) or a compound represented by the following formula (1B-2).
[ solution 28]
(in the formulae (1A-2) and (1B-2), X1、Ar1、R1~R8、R11A~R19AAnd R11B~R19BAs defined in the aforementioned formula (1A) or (1B). ).
In one embodiment, L1Is composed of
A single bond, or a substituted or unsubstituted arylene group having 6 to 14 ring-forming carbon atoms.
In one embodiment, Ar1Is a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms.
In one embodiment, Ar1Selected from the group consisting of the groups represented by the following formulae (a1) - (a 4).
[ solution 29]
In the formulae (a1) to (a4), perylene is bonded to a carbon atom of an anthracene skeleton.
R21Is composed of
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
A substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms,
A substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms,
A substituted or unsubstituted cycloalkyl group 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,
A substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms.
R901~R907As defined in the aforementioned formulae (1A) and (1B).
m1 is an integer of 0 to 4.
m2 is an integer of 0 to 5.
m3 is an integer of 0 to 7.
When m 1-m 3 are each 2 or more, a plurality of R21May be the same or different from each other.
When m 1-m 3 are each 2 or more, a plurality of adjacent R21And are bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring, or to form no substituted or unsubstituted saturated or unsaturated ring. )
In one embodiment, Ar1Is selected from
Substituted or unsubstituted carbazolyl group,
Substituted or unsubstituted dibenzothienyl,
Substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzofuranyl,
Substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzofuranyl,
Substituted or unsubstituted naphthobenzothienyl, and
substituted or unsubstituted naphthobenzofuranyl.
In one embodiment, R1~R8、R11A~R19AAnd R11B~R19BIs a hydrogen atom, and is a hydrogen atom,
L1is a single bond, unsubstitutedAn arylene group having 6 to 50 ring-forming carbon atoms or an unsubstituted 2-valent heterocyclic group having 5 to 50 ring-forming carbon atoms,
Ar1the heterocyclic group is an unsubstituted aryl group having 6 to 50 ring-forming carbon atoms or an unsubstituted heterocyclic group having 1-valent of 5 to 50 ring-forming carbon atoms.
In one embodiment, X1Is an oxygen atom.
Specific examples of the compound represented by the formula (1A) and the compound represented by the formula (1B) are described below, but the compound is not limited to these specific examples. In the following specific examples, D represents a deuterium atom.
(Compound represented by the formula (1))
Among the compounds represented by the formula (1B), the compounds represented by the following formula (1) are novel compounds.
[ solution 51]
(in the formula (1),
X1is an oxygen atom.
Ar1Is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted phenanthryl group.
L1Is composed of
A single bond, a,
Substituted or unsubstituted phenylene, or
Substituted or unsubstituted naphthylene.
Wherein Ar is1When it is a substituted or unsubstituted phenyl group, L1Is a substituted or unsubstituted naphthylene group.
R1~R8And R11B~R19BEach independently is
A hydrogen atom, a halogen atom, a cyano group, a nitro group,
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
A substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms,
A substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901)(R902)(R903)、
-O-(R904)、
-S-(R905)、
-N(R906)(R907)、
A substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms.
R901~R907Each independently is
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 1-valent heterocyclic group having 5 to 50 ring atoms. R901~R907When there are more than 2, more than 2R901~R907Each may be the same or different. )
In one embodiment, Ar in the above formula (1)1Unsubstituted phenyl, unsubstituted naphthyl, or unsubstituted phenanthryl.
In one embodiment, Ar in the above formula (1)1Is a group selected from the following group.
[ solution 52]
(wherein, r represents a single bond bonded to the anthracene skeleton).
In one embodiment, L in the above formula (1)1Is a single bond, unsubstituted phenylene, or unsubstituted naphthylene.
In one embodiment, L in the above formula (1)1Is unsubstituted phenylene, is 1, 2-phenylene, 1, 3-phenylene, or 1, 4-phenylene.
In one embodiment, L in the above formula (1)1Is unsubstituted naphthylene and is represented by the formula (L)a)~(Lj) Either one of themThe 2-valent radical shown.
[ Hua 53]
(formula (L)a)~(Lj) In the (2) perylene, one is bonded to an anthracene skeleton and the other is bonded to a naphthobenzofuran skeleton. ).
In one embodiment, L in the above formula (1)1Selected from the group consisting of a single bond, 1, 3-phenylene, 1, 4-phenylene, 1, 2-naphthylene (formula (L) above)a) A group shown in the formula), 1, 3-naphthylene group (the above formula (L)b) A group shown in the formula), 1, 4-naphthylene group (the above formula (L)c) A group shown in the formula), 1, 5-naphthylene group (the above formula (L)d) A group shown in the formula), 1, 6-naphthylene group (the above formula (L)e) A group shown in the formula), 1, 7-naphthylene group (the above formula (L)f) A group shown in the above), and 2, 6-naphthylene (the above formula (L)i) The indicated groups).
In one embodiment, the compound represented by the formula (1) is a compound selected from the following groups.
[ solution 54]
The compound represented by the formula (1A), the compound represented by the formula (1B), and the compound represented by the formula (1) can be synthesized by the synthesis method described in the synthesis example using known substitution reactions and starting materials corresponding to the target compounds.
< Compound represented by the formula (BE1) >
The 1 st layer of the organic EL element according to one embodiment of the present invention contains a compound represented by the following formula (BE 1).
[ solution 55]
(in the formula (BE1),
X31~X33wherein 2 or more of the nitrogen atoms are nitrogen atoms, and the others other than nitrogen atoms are CR.
R is
A hydrogen atom,
A cyano group,
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901)(R902)(R903)、
-O-(R904)、
A substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms.
R901~R904As defined in the aforementioned formulae (1A) and (1B).
When there are plural R, the plural R may be the same or different from each other.
AE is a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms or a substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring-forming carbon atoms.
BE is a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms or a substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring-forming carbon atoms.
LE is a single bond, a substituted or unsubstituted (nE + 1) valent aromatic hydrocarbon ring group having 6 to 50 ring-forming carbon atoms, or a substituted or unsubstituted (nE + 1) valent heterocyclic group having 5 to 50 ring-forming carbon atoms. The aromatic hydrocarbon ring group may have a structure in which 2 or more different aromatic hydrocarbon rings are bonded.
Each CE is independently a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms or a substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring-forming carbon atoms.
nE is an integer of 1-3. When nE is 2 or more, LE is not a single bond. )
In one embodiment, LE in the formula (BE1) is a 2-valent group having a structure in which 1 or more substituted or unsubstituted phenylene groups and 1 or more substituted or unsubstituted naphthylene groups are bonded to each other.
In one embodiment, LE in the formula (BE1) is a 2-valent group having a structure in which a substituted or unsubstituted phenylene group-substituted or unsubstituted naphthylene group-substituted or unsubstituted phenylene group is bonded.
In one embodiment, LE in the aforementioned formula (BE1) is a 2-valent aromatic hydrocarbon group having the following structure.
[ solution 56]
。
In one embodiment, the compound represented by the formula (BE1) is a compound represented by the following formula (BE 10).
[ solution 57]
(in the formula (BE10),
AE. BE, LE, CE and nE are as defined in the aforementioned formula (BE 1). ).
In one embodiment, the compound represented by the formula (BE10) is a compound represented by the following formula (BE11) or formula (BE 12).
[ solution 58]
(in the formula (BE11),
AE. BE and CE are as defined in the aforementioned formula (BE 1).
When a plurality of R's are present, 1 or more groups of adjacent 2 or more of the plurality of R's are bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring, or to form no substituted or unsubstituted saturated or unsaturated ring.
The aforementioned R which does not form a substituted or unsubstituted saturated or unsaturated ring is
A cyano group,
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901)(R902)(R903)、
-O-(R904)、
A substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms.
R901~R904As defined in (1A) and (1B) above.
nE1 is an integer of 0 to 4.
When there are plural R, the plural R may be the same or different from each other. ).
[ chemical 59]
(in the formula (BE12),
AE and BE are as defined in the aforementioned formula (BE 1).
XE is CR51R52、NR53Oxygen atom or sulfur atom.
The aforementioned XE is CR51R52When the aforementioned R is51And the aforementioned R52And are bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring, or to form no substituted or unsubstituted saturated or unsaturated ring.
When a plurality of R's are present, 1 or more groups of adjacent 2 or more of the plurality of R's are bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring, or to form no substituted or unsubstituted saturated or unsaturated ring.
R53R, R not forming a substituted or unsubstituted saturated or unsaturated ring with the preceding51And R52Each independently is
A hydrogen atom,
A cyano group,
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901)(R902)(R903)、
-O-(R904)、
A substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms.
R901~R904As defined in (1A) and (1B) above.
nE2 is an integer of 0 to 4, and nE3 is an integer of 0 to 3.
When there are plural R, the plural R may be the same or different from each other. )
In one embodiment, the compound represented by the formula (BE12) is a compound represented by the following formula (BE 12-1).
[ solution 60]
(in the formula (BE12-1),
AE. BE, XE, R, nE2 and nE3 are as defined in the aforementioned formula (BE 12). )
In one embodiment, the compound represented by the formula (BE10) is a compound represented by the following formula (BE 13).
[ solution 61]
(in the formula (BE13),
AE. BE and CE are as defined in the aforementioned formula (BE 1).
When a plurality of R's are present, 1 or more groups of adjacent 2 or more of the plurality of R's are bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring, or to form no substituted or unsubstituted saturated or unsaturated ring.
The aforementioned R which does not form a substituted or unsubstituted saturated or unsaturated ring is
A cyano group,
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901)(R902)(R903)、
-O-(R904)、
A substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms.
R901~R904As defined in (1A) and (1B) above.
nE4 and nE5 are each independently integers of 0 to 4.
When there are plural R, the plural R may be the same or different from each other. )
In one embodiment, CE is a substituted or unsubstituted aryl group having 14 to 24 ring-forming carbon atoms or a substituted or unsubstituted 1-valent heterocyclic group having 13 to 35 ring-forming carbon atoms.
In one embodiment, the compound represented by the formula (BE1) is a compound represented by the following formula (BE 14).
[ solution 62]
(in the formula (BE14),
X31~X33AE, BE, LE and nE are as defined in the aforementioned formula (BE 1).
Cz is a group represented by any one of the following formulae (Cz1), (Cz2), and (Cz 3). ).
[ solution 63]
(in the formulae (Cz1), (Cz2) and (Cz3),
when a plurality of R's are present, 1 or more groups of adjacent 2 or more of the plurality of R's are bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring, or to form no substituted or unsubstituted saturated or unsaturated ring.
The aforementioned R which does not form a substituted or unsubstituted saturated or unsaturated ring is
A cyano group,
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901)(R902)(R903)、
-O-(R904)、
A substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms.
R901~R904As defined in (1A) and (1B) above.
nE6 and nE7 are each independently integers of 0 to 4.
nE8 and nE11 are each independently integers of 0-4, and nE9 and nE10 are each independently integers of 0-3.
nE12, nE14 and nE15 are each independently an integer of 0 to 4, and nE13 is an integer of 0 to 3.
When a plurality of R's are present, the plurality of R's may be the same as or different from each other.
And LE is bonded. )
In one embodiment, the compound represented by the formula (BE10) is a compound represented by the following formula (BE 15).
[ solution 64]
(in the formula (BE15),
AE and BE are as defined in the aforementioned formula (BE 1).
LaThe aromatic hydrocarbon ring is a single bond, a substituted or unsubstituted 2-valent aromatic hydrocarbon ring group having 6 to 18 ring-forming carbon atoms, or a substituted or unsubstituted 2-valent heterocyclic group having 5 to 13 ring-forming carbon atoms. The aromatic hydrocarbon ring group may have a structure in which 2 or more different aromatic hydrocarbon rings are bonded.
Ac is a group represented by any one of the following formulae (Ac1), (Ac2), and (Ac 3). ).
[ solution 65]
(in the formula (Ac1),
XE1~XE61 to 5 of the groups are nitrogen atoms, and the others other than nitrogen atoms are CR, any one of R and LaAnd (4) bonding.
Not in contact with LaBonded R is
A hydrogen atom,
A cyano group,
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901)(R902)(R903)、
-O-(R904)、
A substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms.
R901~R904As defined in (1A) and (1B) above.
When there are plural R, the plural R may be the same or different from each other. )
(in the formula (Ac2),
XE21~XE281 to 7 of the groups are nitrogen atoms, and the others other than nitrogen atoms are CR, any one of R and LaAnd (4) bonding.
When a plurality of R's are present, 1 or more groups of adjacent 2 or more of the plurality of R's are bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring, or to form no substituted or unsubstituted saturated or unsaturated ring.
Not in contact with LaR bonded to the ring not forming the aforementioned substituted or unsubstituted saturated or unsaturated ring is
A hydrogen atom,
A cyano group,
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901)(R902)(R903)、
-O-(R904)、
A substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms.
R901~R904As defined in (1A) and (1B) above.
When there are plural R, the plural R may be the same or different from each other. )
(in the formula (Ac3),
d is an aryl group having 6 to 18 ring-forming carbon atoms substituted with 16 n cyano groups, or a 1-valent heterocyclic group having 5 to 13 ring-forming carbon atoms substituted with 16 n cyano groups. Wherein D may have a substituent other than a cyano group.
nE16 represents the number of cyano groups substituted on D, and is an integer of 1 to 9.
H and LaAnd (4) bonding. )
In one embodiment, the compound represented by the formula (BE15) is a compound represented by the following formula (BE 16).
[ solution 66]
(in the formula (BE16),
AE. BE and Ac are as defined in the aforementioned formula (BE 15).
nE17 is an integer of 0 to 4.
R31When there are plural, plural R31Wherein adjacent 2 or more groups 1 or more are bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring, or to form no substituted or unsubstituted saturated or unsaturated ring.
R is not a ring31Is composed of
A cyano group,
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901)(R902)(R903)、
-O-(R904)、
A substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms.
R901~R904As defined in (1A) and (1B) above.
When there are plural R, the plural R may be the same or different from each other. )
In one embodiment, LE or LaAn aromatic hydrocarbon ring group represented by any one of the following formulae (L1) to (L4).
[ solution 67]
(in the formulae (L1) ~ (L4), any one of 2 is bonded to a nitrogen-containing 6-membered ring, and the other is bonded to (C)nE、(Cz)nEOr an Ac bond. And (C)nEOr (Cz)nEWhen nE is an integer of 1 to 3,1 to 3 of the bonded elements are present. ).
In one embodiment, LE or LaIs an aromatic hydrocarbon ring group represented by the following formula (L5).
[ solution 68]
(in the formula (L5), any one of 2 members is bonded to a nitrogen-containing 6-membered ring, and the other is bonded to (C)nE、(Cz)nEOr an Ac bond. And (C)nEOr (Cz)nEWhen nE is an integer of 1 to 3,1 to 3 of the bonded elements are present. ).
In one embodiment, LE is a single bond or a substituted or unsubstituted (nE + 1) valent aromatic hydrocarbon ring group having 6 to 12 ring-forming carbon atoms.
In one embodiment, LE or LaIs a single bond.
In one embodiment, AE is a substituted or unsubstituted aryl group having 6 to 12 ring-forming carbon atoms.
In one embodiment, AE is substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, or substituted or unsubstituted naphthyl.
In one embodiment, AE is unsubstituted phenyl, unsubstituted biphenyl, or unsubstituted naphthyl.
In one embodiment, BE is a substituted or unsubstituted aryl group having 6 to 12 ring-forming carbon atoms.
In one embodiment, the BE is a substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, or substituted or unsubstituted naphthyl.
In one embodiment, BE is an unsubstituted phenyl, unsubstituted biphenyl, or unsubstituted naphthyl.
In one embodiment, the 1 st layer is directly adjacent to the light-emitting layer.
Specific examples of the compound represented by the formula (BE1) are described below, but the compound is not limited to these specific examples.
In one embodiment, a2 nd layer is provided between the cathode and the 1 st layer.
That is, the organic EL device of the present embodiment has a layer structure of at least cathode/2 nd layer/1 st layer/light-emitting layer/anode. The 2 nd layer may or may not contain the compound represented by the formula (BE 1).
< Compound represented by the formula (EB1) >
In one embodiment, the 2 nd layer contains a compound represented by the following formula (EB 1).
[ solution 97]
(in the formula (EB1),
XEB1is O, S, or CR41R42。
R41And R42Each independently is
A hydrogen atom,
A cyano group,
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901)(R902)(R903)、
-O-(R904)、
A substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms.
R901~R904As defined in (1A) and (1B) above.
YE1、YE2And YE3Each independently is CH or N.
Wherein, YE1、YE2And YE3More than 2 of the groups are N.
ArE1、ArE3And Are5Each independently is
A single bond, a,
A substituted or unsubstituted phenylene group,
A substituted or unsubstituted naphthylene group,
Substituted or unsubstituted phenanthrylene, or
Substituted or unsubstituted anthracenylene.
ArE2And Are4Each independently is
Substituted or unsubstituted phenyl,
Substituted or unsubstituted naphthyl,
Substituted or unsubstituted phenanthryl, or
Substituted or unsubstituted anthracenyl.
ArE1And ArE with Are2And ArE3And ArE with Are4Each independently bonded to each other to form a substituted or unsubstituted, saturated or unsaturated ring consisting of only 6-membered rings, or to form no ring. )
In one embodiment, the compound represented by the formula (EB1) is a compound represented by the following formula (EB 2).
[ solution 98]
(in the formula (EB2), YE1~YE3、ArE1~ArE4And XEB1As defined in the aforementioned formula (EB 1). ).
In one embodiment, the compound represented by the formula (EB1) is a compound represented by the following formula (EB 4).
[ solution 99]
(in the formula (EB4), Are1~ArE4As defined in the aforementioned formula (EB 1). ).
In one embodiment, ArE1And ArE with Are2And ArE3And ArE with Are4Each independently of the otherBut are bonded to each other without forming a ring.
In one embodiment, ArE2And Are4Each independently is
Unsubstituted phenyl group,
Unsubstituted naphthyl,
Unsubstituted anthracenyl, or
Unsubstituted phenanthryl.
In one embodiment, the compound represented by the formula (EB1) is a compound represented by the following formula (EB 5).
[ solution 100]
(in the formula (EB5), Are1~ArE4、R41And R42As defined in the aforementioned formula (EB 1). ).
In one embodiment, ArE1And Are3Each independently is
A single bond, a,
Unsubstituted p-phenylene, or
Unsubstituted 1, 4-naphthylene.
Specific examples of the compound represented by the formula (EB1) are described below, but the compound is not limited to these specific examples.
[ solution 101]
In one embodiment, the organic layer further comprises a layer 3,
the 3 rd layer is disposed between the anode and the light-emitting layer,
the 3 rd layer contains a compound represented by the following formula (B1).
That is, the organic EL device of the present embodiment has at least a layer structure of cathode/1 st layer/light-emitting layer/3 rd layer/anode.
< Compound represented by the formula (B1) >
[ solution 102]
(in the formula (B1),
LA、LBand LCEach independently represents a single bond, a substituted or unsubstituted arylene group having 6 to 50 ring-forming carbon atoms, or a substituted or unsubstituted heterocyclic group having 2-valent of 5 to 50 ring-forming carbon atoms.
A. B and C are each independently
A substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms,
A substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms, or
-Si(R’901)(R’902)(R’903)。
R’901~R’903Each independently represents a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms.
R’901~R’9032 or more R's when 1 or more of (A) are present in each of 2 or more'901~R’903Each may be the same or different. ).
In one embodiment, the 3 rd layer contains a compound represented by the formula (B1).
In one embodiment, LA、LBAnd LCEach independently represents a single bond or a substituted or unsubstituted arylene group having 6 to 12 ring-forming carbon atoms.
In one embodiment, LCIs phenylene.
In one embodiment, A is a substituted or unsubstituted aryl group having 6 to 12 ring-forming carbon atoms.
In one embodiment, A is
Substituted or unsubstituted phenyl,
Substituted or unsubstituted biphenyl, or
Substituted or unsubstituted naphthyl.
In one embodiment, A is
Unsubstituted phenyl group,
Unsubstituted biphenyl, or
Unsubstituted naphthyl.
In one embodiment, B is a substituted or unsubstituted aryl group having 6 to 12 ring-forming carbon atoms.
In one embodiment, B is
Substituted or unsubstituted phenyl,
Substituted or unsubstituted biphenyl, or
Substituted or unsubstituted naphthyl.
In one embodiment, B is
Unsubstituted phenyl group,
Unsubstituted biphenyl, or
Unsubstituted naphthyl.
Specific examples of the compound represented by the formula (B1) are described below, but the compound is not limited to these specific examples.
[ solution 103]
In one embodiment, the substituent referred to as "substituted or unsubstituted" in each of the above formulae is selected from an unsubstituted alkyl group having 1 to 50 carbon atoms,
An unsubstituted alkenyl group having 2 to 50 carbon atoms,
An unsubstituted alkynyl group having 2 to 50 carbon atoms,
An unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901)(R902)(R903)、
-O-(R904)、
-S-(R905)、
-N(R906)(R907)
(in this case, the amount of the solvent in the reaction mixture,
R901~R907each independently is
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 1-valent heterocyclic group having 5 to 50 ring atoms. R901~R907When there are more than 2, more than 2R901~R907Each may be the same or different. ) A
Halogen atom, cyano group, nitro group,
An unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, and
and a group of an unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms.
In one embodiment, the substituent referred to as "substituted or unsubstituted" in the above formulae is an unsubstituted alkyl group having 1 to 50 carbon atoms,
An unsubstituted alkenyl group having 2 to 50 carbon atoms,
An unsubstituted alkynyl group having 2 to 50 carbon atoms,
An unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms,
-Si(R901a)(R902a)(R903a)、
-O-(R904a)、
-S-(R905a)、
-N(R906a)(R907a)、
Halogen atom, cyano group, nitro group,
An unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
An unsubstituted heterocyclic group having a ring-forming atom number of 5 to 50 and having a valence of 1 (wherein R is901a~R907aEach independently is
A hydrogen atom,
An unsubstituted alkyl group having 1 to 50 carbon atoms,
An unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
An unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms. R901a~R907aWhen there are more than 2, more than 2R901a~R907aEach may be the same or different. ).
In one embodiment, the substituent referred to as "substituted or unsubstituted" in the above formulae is an unsubstituted alkyl group having 1 to 50 carbon atoms,
An unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or
An unsubstituted 1-valent heterocyclic group having 5 to 50 ring atoms.
In one embodiment, the substituent referred to as "substituted or unsubstituted" in the above formulae is an unsubstituted alkyl group having 1 to 18 carbon atoms,
An unsubstituted aryl group having 6 to 18 ring-forming carbon atoms, or
An unsubstituted 1-valent heterocyclic group having 5 to 18 ring atoms.
In one embodiment, the substituent referred to as "substituted or unsubstituted" in each of the above formulae is an unsubstituted alkyl group having 1 to 5 carbon atoms.
The layer structure of the organic EL element according to one embodiment of the present invention will be described below.
An organic EL device according to one embodiment of the present invention includes an organic layer between 1 pair of electrodes including a cathode and an anode. The organic layer comprises at least 1 layer containing an organic compound. Alternatively, the organic layer may be a stack of a plurality of layers containing an organic compound. The organic layer may have a layer consisting of only 1 or more organic compounds. The organic layer may have a layer containing both an organic compound and an inorganic compound. The organic layer may have a layer consisting of only 1 or more inorganic compounds.
At least 1 of the layers included in the organic layer is a light-emitting layer. The organic layer may be formed as a 1-layer light-emitting layer, for example, and may contain other layers that can be used in the layer structure of the organic EL element. Examples of the layer that can be used in the layer structure of the organic EL element include, but are not particularly limited to, a hole transport band region (a hole transport layer, a hole injection layer, an electron blocking layer, an exciton blocking layer, and the like) provided between the anode and the light-emitting layer, a spacer layer, and an electron transport band region (an electron transport layer, an electron injection layer, a hole blocking layer, and the like) provided between the cathode and the light-emitting layer.
The organic EL element according to one embodiment of the present invention may be a fluorescent or phosphorescent single-color light-emitting element, or may be a fluorescent/phosphorescent mixed white light-emitting element. Further, the light emitting element may be a single type having a single light emitting element, or a tandem type having a plurality of light emitting elements.
The "light-emitting unit" refers to a minimum unit including organic layers, at least 1 of which is a light-emitting layer, and emitting light by recombination of injected holes and electrons.
In addition, the "light-emitting layer" described in this specification is an organic layer having a light-emitting function. The light-emitting layer may be, for example, a phosphorescent light-emitting layer, a fluorescent light-emitting layer, or the like, and may be1 layer or a plurality of layers.
The light-emitting unit may be a stacked type including a plurality of phosphorescent light-emitting layers and a fluorescent light-emitting layer, and in this case, for example, a spacer layer for preventing excitons generated in the phosphorescent light-emitting layer from diffusing into the fluorescent light-emitting layer may be provided between the light-emitting layers.
The single-type organic EL element includes, for example, an anode, a light-emitting unit, and a cathode.
Representative layer configurations of the light-emitting unit are shown below. The layers in parentheses 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/fluorescent emission layer No. 1/fluorescent emission layer No. 2 (/ electron transport layer/electron injection layer)
(d) (hole injection layer /) hole transport layer/1 st/2 nd phosphorescent emitting layer (/ electron transport layer/electron injection layer)
(e) (hole injection layer /) hole transport layer/phosphorescent emitting layer/spacer layer/fluorescent emitting layer (/ electron transport layer/electron injection layer)
(f) (hole injection layer /) hole transport layer/1 st phosphorescent emission layer/2 nd phosphorescent emission layer/spacer layer/fluorescent emission 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/fluorescent light emitting layer 1/fluorescent light emitting layer 2 (/ 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/fluorescent light emitting layer (/ 1 st electron transport layer/2 nd electron transport layer/electron injection layer)
(o) (hole injection layer /) 1 st hole transport layer/2 nd hole transport layer/phosphorescent light emitting layer (/ 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 layer structure of the organic EL element according to one embodiment of the present invention is not limited to these. For example, when the organic EL element has a hole injection layer and a hole transport layer, the hole injection layer is preferably provided between the hole transport layer and the anode. In addition, when the organic EL element has an electron injection layer and an electron transport layer, the electron injection layer is preferably provided between the electron transport layer and the cathode. The hole injection layer, the hole transport layer, the electron transport layer, and the electron injection layer may each be composed of 1 layer, or may be composed of a plurality of layers.
The plurality of phosphorescent light-emitting layers, and the phosphorescent light-emitting layer and the fluorescent light-emitting layer may be light-emitting layers of different colors from each other, respectively. For example, the light-emitting unit (f) may be a hole-transporting layer/1 st phosphorescent light-emitting layer (red light-emitting)/2 nd phosphorescent light-emitting layer (green light-emitting)/spacer layer/fluorescent light-emitting layer (blue light-emitting)/electron-transporting layer.
An electron blocking layer may be provided between each light-emitting layer and the hole transport layer or the spacer layer. Further, a hole blocking layer may be provided between each light emitting layer and the electron transport layer. By arranging the electron blocking layer and the hole blocking layer, electrons or holes are sealed in the light emitting layer, the recombination probability of charges in the light emitting layer is improved, and the light emitting efficiency can be improved.
A typical element configuration of the tandem organic EL element includes, for example, an anode, a1 st light-emitting unit, an intermediate layer, a2 nd light-emitting unit, and a cathode.
The 1 st light-emitting unit and the 2 nd light-emitting unit may be, for example, each independently selected from the above-described light-emitting units.
The intermediate layer is generally referred to as an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron removal layer, a connection layer (the body frame), a connection layer (コネクター) or an intermediate insulating layer. The intermediate layer is a layer that supplies electrons to the 1 st light-emitting cell and holes to the 2 nd light-emitting cell, and may be formed of a known material.
Only one of the 1 st light-emitting unit and the 2 nd light-emitting unit may be the light-emitting layer according to one embodiment of the present invention, or both may be the light-emitting layers according to one embodiment of the present invention.
The functions, materials, and the like of the respective layers of the organic EL element described in this specification will be described below.
(substrate)
The substrate serves as a support for the organic EL element. The substrate preferably has a transmittance of 50% or more in a visible light region having a wavelength of 400 to 700nm, and is preferably a smooth substrate. Examples of the material of the substrate include soda lime glass, aluminosilicate glass, quartz glass, and plastic. In addition, as the substrate, a flexible substrate can be used. The flexible substrate is a bendable (flexible) substrate, and examples thereof include a plastic substrate. Specific examples of the material for forming the plastic substrate include polycarbonate, polyarylate, polyethersulfone, polypropylene, polyester, polyvinyl fluoride, polyvinyl chloride, polyimide, polyethylene naphthalate, and the like. Further, an inorganic vapor deposited film may be used.
(Anode)
As the anode, for example, a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a large work function (specifically, 4.0eV or more) is preferably used. Specific examples of the material of the anode include Indium Tin Oxide (ITO), Indium Tin Oxide containing silicon or silicon Oxide, Indium zinc Oxide, Indium Oxide containing tungsten Oxide or zinc Oxide, and graphene. Further, gold, silver, platinum, nickel, tungsten, chromium, molybdenum, iron, cobalt, copper, palladium, titanium, and nitrides of these metals (e.g., titanium nitride) and the like can be given.
The anode is generally formed by forming a film of these materials on a substrate by a sputtering method. For example, indium oxide-zinc oxide can be formed by a sputtering method using a target material in which 1 to 10 mass% of zinc oxide is added to indium oxide. Further, for example, indium oxide containing tungsten oxide or zinc oxide can be formed by a sputtering method using a target material in which 0.5 to 5 mass% of tungsten oxide or 0.1 to 1 mass% of zinc oxide is added to indium oxide.
Examples of other methods for forming the anode include vacuum vapor deposition, coating, ink-jet, and spin coating. For example, a silver paste or the like is used, and a coating method, an ink jet method, or the like can be used.
The hole injection layer formed in contact with the anode can be formed using a material that easily injects holes regardless of the work function of the anode. Therefore, a general electrode material, for example, a metal, an alloy, a conductive compound, or a mixture thereof can be used for the anode. Specifically, an alkali metal such as lithium or cesium; magnesium; alkaline earth metals such as calcium and strontium; alloys containing these metals (e.g., magnesium-silver, aluminum-lithium); rare earth metals such as europium and ytterbium; materials having a small work function, such as alloys containing rare earth metals, are used for the anode.
(hole injection layer)
The hole injection layer is a layer containing a substance having a high hole injection property, and has a function of injecting holes from the anode into the organic layer. Examples of the substance having a high hole-injecting property include molybdenum oxide, titanium oxide, vanadium oxide, rhenium oxide, ruthenium oxide, chromium oxide, zirconium oxide, hafnium oxide, tantalum oxide, silver oxide, tungsten oxide, manganese oxide, aromatic amine compounds, electron-withdrawing (acceptor) compounds, and polymer compounds (oligomers, dendrimers, polymers, and the like). Among them, aromatic amine compounds and receptor compounds are preferable, and receptor compounds are more preferable.
Specific examples of the aromatic amine compound include 4,4 '-tris (N, N-diphenylamino) triphenylamine (abbreviated as TDATA), 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 DPA3B), 3- [ N- (9-phenylcarbazol-3-yl) -N-phenylamino ] -9-phenylcarbazole (abbreviated as PCzPCA1), 3, 6-bis [ N- (9-phenylcarbazol-3-yl) -N-phenylamino ] -9-phenylcarbazole (abbreviated as PCzPCA2), 3- [ N- (1-naphthyl) -N- (9-phenylcarbazol-3-yl) amino ] -9-phenylcarbazole (abbreviated as PCzPCN1), and the like.
The acceptor compound is preferably a heterocyclic derivative having an electron-withdrawing group, a quinone derivative having an electron-withdrawing group, an aryl borane derivative, a heteroaryl borane derivative, etc., and specific examples thereof include hexacyanohexanyltriphenylene, 2,3,5, 6-tetrafluoro-7, 7,8, 8-tetracyanoquinodimethane (abbreviated as F4TCNQ), 1,2, 3-tris [ (cyano) (4-cyano-2, 3,5, 6-tetrafluorophenyl) methylene ] cyclopropane, etc.
When a receptor compound is used, the hole injection layer preferably further contains a host material. As the host material, a known material which is a material for an organic EL element can be used, and for example, a compound having an electron donating property (donor) is preferably used.
(hole transport layer)
The hole transport layer is a layer containing a substance having a high hole transport property, and has a function of transporting holes from the anode to the organic layer.
The substance having a high hole-transporting property is preferably 10-6cm2Materials having hole mobility equal to or higher than V (seeds) include, for example, aromatic amine compounds, carbazole derivatives, anthracene derivatives, and polymer compounds, which can be used together with the compound represented by the formula (B1) used in one embodiment of the present invention.
Specific examples of the aromatic amine compound include 4,4' -bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl (abbreviated as 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' -tris (N, N-diphenylamino) triphenylamine (abbreviated as TDATA), 4', 4' -tris [ N- (3-methylphenyl) -N-phenylamino ] triphenylamine (abbreviated as MTDATA), 4' -bis [ N- (spiro-9, 9' -bifluoren-2-yl) -N-phenylamino ] biphenyl (abbreviated as BSPB), and the like.
Specific examples of the carbazole derivative 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-anthracenyl) phenyl ] -9H-carbazole (abbreviated as PCzPA).
Specific examples of the anthracene derivative include 2-tert-butyl-9, 10-di (2-naphthyl) anthracene (abbreviated as t-BuDNA), 9, 10-di (2-naphthyl) anthracene (abbreviated as DNA), 9, 10-diphenylanthracene (abbreviated as DPAnth), and the like.
Specific examples of the polymer compound include poly (N-vinylcarbazole) (abbreviated as PVK) and poly (4-vinyltriphenylamine) (abbreviated as PVTPA).
As long as the compound has a hole-transporting property higher than an electron-transporting property, a substance other than these compounds may be used for the hole-transporting layer.
The hole transport layer may be a single layer, or 2 or more layers may be stacked. In this case, it is preferable to dispose a layer containing a substance having a larger energy gap among substances having high hole-transporting properties on the side closer to the light-emitting layer.
(luminescent layer)
The light-emitting layer is a layer containing a substance (dopant material) having a high light-emitting property. As the dopant material, various materials can be used, and for example, a fluorescent light-emitting compound (fluorescent dopant), a phosphorescent light-emitting compound (phosphorescent dopant), or the like can be used. The fluorescent light-emitting compound is a compound capable of emitting light from a singlet excited state, and a light-emitting layer including the same is referred to as a fluorescent light-emitting layer. Further, a phosphorescent compound is a compound capable of emitting light from a triplet excited state, and a light-emitting layer including the compound is referred to as a phosphorescent light-emitting layer.
The light-emitting layer generally contains a dopant material and a host material for causing it to emit light with high efficiency. Note that the dopant material may be referred to as a guest material, an emitter (エミッター), or a light-emitting material according to the literature. In addition, the host material is also referred to as a matrix material according to the literature.
The 1 light emitting layer may include a plurality of dopant materials and a plurality of host materials therein. Further, the light-emitting layer may be plural.
In this specification, a host material combined with a fluorescent dopant is referred to as a "fluorescent host", and a host material combined with a phosphorescent dopant is referred to as a "phosphorescent host". Note that the fluorescent host and the phosphorescent host are not distinguished only by the molecular structure. The phosphorescent host is a material for forming a phosphorescent light-emitting layer containing a phosphorescent dopant, but does not mean that it cannot be used as a material for forming a fluorescent light-emitting layer. The same applies to the fluorescent host.
The content of the dopant material in the light-emitting layer is not particularly limited, and is, for example, preferably 0.1 to 70 mass%, more preferably 0.1 to 30 mass%, even more preferably 1 to 20 mass%, and particularly preferably 1 to 10 mass%, from the viewpoint of sufficient light emission and concentration extinction.
< fluorescent dopant >
Examples of the fluorescent dopant include a condensed polycyclic aromatic derivative, a styrylamine derivative, a condensed cyclic amine derivative, a boron-containing compound, a pyrrole derivative, an indole derivative, and a carbazole derivative. Among them, fused cyclic amine derivatives, boron-containing compounds, and carbazole derivatives are preferable.
Examples of the fused ring amine derivative include a diaminopyrene derivative, a diamino chrysene derivative, a diaminoanthracene derivative, a diaminofluorene derivative, and a diaminofluorene derivative obtained by ring-shrinking one or more benzofuran skeletons.
Examples of the boron-containing compound include a methylene pyrrole derivative and a triphenylborane derivative.
Examples of the blue fluorescent dopant include pyrene derivatives, styrylamine derivatives, chrysene derivatives, fluoranthene derivatives, fluorene derivatives, diamine derivatives, and triarylamine derivatives. Specific examples thereof include N, N ' -bis [4- (9H-carbazol-9-yl) phenyl ] -N, N ' -diphenylstilbene-4, 4' -diamine (abbreviated as YGA2S), 4- (9H-carbazol-9-yl) -4' - (10-phenyl-9-anthracenyl) triphenylamine (abbreviated as YGAPA), and 4- (10-phenyl-9-anthracenyl) -4' - (9-phenyl-9H-carbazol-3-yl) triphenylamine (abbreviated as PCBAPA).
Examples of the green fluorescent dopant include aromatic amine derivatives. Specific examples thereof include N- (9, 10-diphenyl-2-anthryl) -N, 9-diphenyl-9H-carbazol-3-amine (abbreviated as 2PCAPA), N- [9, 10-bis (1,1' -biphenyl-2-yl) -2-anthryl ] -N, 9-diphenyl-9H-carbazol-3-amine (abbreviated as 2PCABPhA), N- (9, 10-diphenyl-2-anthryl) -N, N ', N ' -triphenyl-1, 4-phenylenediamine (abbreviated as 2DPAPA), N- [9, 10-bis (1,1' -biphenyl-2-yl) -2-anthryl ] -N, N ', n '-triphenyl-1, 4-phenylenediamine (abbreviated as 2DPABPhA), N- [9, 10-bis (1,1' -biphenyl-2-yl) ] -N- [4- (9H-carbazol-9-yl) phenyl ] -N-phenylanthracene-2-amine (abbreviated as 2YGABPhA), N, 9-triphenylanthracene-9-amine (abbreviated as DPhAPHA), and the like.
Examples of the fluorescent dopant of red color include tetracene derivatives and diamine derivatives. Specific examples thereof include N, N, N ', N' -tetrakis (4-methylphenyl) naphthacene-5, 11-diamine (p-mPHTD), 7, 14-diphenyl-N, N, N ', N' -tetrakis (4-methylphenyl) acenaphtho [1,2-a ] fluoranthene-3, 10-diamine (p-mPHAFD), and the like.
< phosphorescent dopant >
Examples of the phosphorescent dopant include phosphorescent heavy metal complexes and phosphorescent rare earth metal complexes.
Examples of the heavy metal complex include iridium complexes, osmium complexes, and platinum complexes. The heavy metal complex is preferably an ortho-metalated complex of a metal selected from iridium, osmium, and platinum.
Examples of the rare earth metal complex include terbium complexes and europium complexes. Specific examples thereof include tris (acetylacetonate) (monophenanthroline) terbium (III) (abbreviated as Tb (acac)3(Phen)), tris (1, 3-diphenyl-1, 3-propanedionate) (monophenanthroline) europium (III) (abbreviated as Eu (DBM)3(Phen)), and tris [1- (2-thenoyl) -3,3, 3-trifluoroacetone ] (monophenanthroline) europium (III) (abbreviated as Eu (TTA)3 (Phen)). These rare earth metal complexes are preferably used as phosphorescent dopants because they emit light from rare earth metal ions by utilizing electron transfer between different multiple states.
Examples of the blue-based phosphorescent dopant include iridium complexes, osmium complexes, and platinum complexes. Specific examples thereof include iridium (III) bis [2- (4',6' -difluorophenyl) pyridinato-N, C2'] tetrakis (1-pyrazolyl) borate (abbreviated as FIr6), iridium (III) bis [2- (4',6 '-difluorophenyl) pyridinato-N, C2' ] picolinate (abbreviated as FIrpic), iridium (III) bis [2- (3',5' -bistrifluoromethylphenyl) pyridinato-N, C2'] picolinate (abbreviated as Ir (CF3ppy)2(pic)), iridium (III) bis [2- (4',6 '-difluorophenyl) pyridinato-N, C2' ] acetylacetonate (abbreviated as FIRacac).
Examples of the green-based phosphorescent dopant include iridium complexes. Specific examples thereof include tris (2-phenylpyridino-N, C2') iridium (III) (abbreviated as Ir (ppy)3), bis (2-phenylpyridino-N, C2') iridium (III) acetylacetonate (abbreviated as Ir (ppy)2(acac)), bis (1, 2-diphenyl-1H-benzimidazolo) iridium (III) acetylacetonate (abbreviated as Ir (pbi)2(acac)), and bis (benzo [ H ] quinolino) iridium (III) acetylacetonate (abbreviated as Ir (bzq)2 (acac)).
Examples of the red-based phosphorescent dopant include iridium complexes, platinum complexes, terbium complexes, europium complexes, and the like. Specific examples thereof include bis [2- (2' -benzo [4, 5-. alpha. -thienyl) pyridinato-N, C3' ] acetylacetonatoiridium (III) (abbreviated as Ir (btp)2(acac)), bis (1-phenylisoquinolinato-N, C2') acetylacetonatoiridium (III) (abbreviated as Ir (piq)2(acac)), (acetylacetonato) bis [2, 3-bis (4-fluorophenyl) quinoxalinato ] iridium (III) (abbreviated as Ir (Fdpq)2(acac)), and 2,3,7,8,12,13,17, 18-octaethyl-21H, 23H-porphyrinato platinum (II) (abbreviated as PtOEP).
< host Material >
Examples of the host material that can be used together with the host material used in one embodiment of the present invention include metal complexes such as aluminum complexes, beryllium complexes, and zinc complexes; heterocyclic compounds such as indole derivatives, pyridine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, isoquinoline derivatives, quinazoline derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, oxadiazole derivatives, benzimidazole derivatives, and phenanthroline derivatives; fused aromatic compounds such as naphthalene derivatives, triphenylene derivatives, carbazole derivatives, anthracene derivatives, phenanthrene derivatives, pyrene derivatives, chrysene derivatives, tetracene derivatives, and fluoranthene derivatives; and aromatic amine compounds such as triarylamine derivatives and fused polycyclic aromatic amine derivatives. The host material may be used in combination of plural kinds.
Specific examples of the metal complex include tris (8-quinolinolato) aluminum (III) (Alq), tris (4-methyl-8-quinolinolato) aluminum (III) (Almq 3), bis (10-hydroxybenzo [ h ] quinolinato) beryllium (II) (BeBq 2), bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum (III) (BALq), bis (8-quinolinolato) zinc (II) (Znq), bis [2- (2-benzoxazolyl) phenol ] zinc (II) (ZnPBO), bis [2- (2-benzothiazolyl) phenol ] zinc (II) (ZnBTZ), and the like.
Specific examples of the heterocyclic 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-biphenyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2, 4-triazole (abbreviated as TAZ), 2,2',2' ' - (1,3, 5-benzenetriyl) tris (1-phenyl-1H-benzimidazole) (TPBI), bathophenanthroline (BPhen), Bathocuproine (BCP), etc.
Specific examples of the fused aromatic compound include 9- [4- (10-phenyl-9-anthryl) phenyl ] -9H-carbazole (abbreviated as CzPA), 3, 6-diphenyl-9- [4- (10-phenyl-9-anthryl) phenyl ] -9H-carbazole (abbreviated as DPCzPA), 9, 10-bis (3, 5-diphenylphenyl) anthracene (abbreviated as DPPA), 9, 10-bis (2-naphthyl) anthracene (abbreviated as DNA), 2-tert-butyl-9, 10-bis (2-naphthyl) anthracene (abbreviated as t-BuDNA), 9' -bianthracene (abbreviated as BANT), 9' - (stilbene-3, 3' -diyl) phenanthrene (abbreviated as DPNS), 9,9' - (stilbene-4, 4' -diyl) phenanthrene (abbreviated as DPNS2), 3',3' ' - (benzene-1, 3, 5-triyl) tripyrene (abbreviated as TPB3), 9, 10-diphenylanthracene (abbreviated as DPAnth), 6, 12-dimethoxy-5, 11-diphenyl chrysene, and the like.
Specific examples of the aromatic amine compound include N, N-diphenyl-9- [4- (10-phenyl-9-anthryl) phenyl ] -9H-carbazol-3-amine (abbreviation: CzA1PA), 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: 2PCAPA), 4' -bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl (abbreviation: NPB or α -NPD), N '-bis (3-methylphenyl) -N, N' -diphenyl- [1,1 '-biphenyl ] -4,4' -diamine (abbreviation: TPD), 4' -bis [ N- (9, 9-dimethylfluoren-2-yl) -N-phenylamino ] biphenyl (abbreviation: DFLDPBi), 4 '-bis [ N- (spiro-9, 9' -bifluoren-2-yl) -N-phenylamino ] biphenyl (abbreviation: BSPB), and the like.
The fluorescent host is preferably a compound having a higher singlet level than the fluorescent dopant, and examples thereof include heterocyclic compounds and condensed aromatic compounds. The fused aromatic compound is preferably, for example, an anthracene derivative, a pyrene derivative, an chrysene derivative, a tetracene derivative, or the like.
The phosphorescent host is preferably a compound having a triplet energy level higher than that of the phosphorescent dopant, and examples thereof include a metal complex, a heterocyclic compound, a condensed aromatic compound, and the like. Among them, for example, indole derivatives, carbazole derivatives, pyridine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, isoquinoline derivatives, quinazoline derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, naphthalene derivatives, triphenylene derivatives, phenanthrene derivatives, fluoranthene derivatives, and the like are preferable.
(Electron transport layer)
The electron transport layer is a layer containing a substance having a high electron transport property. The material having a high electron-transporting property is preferably 10-6cm2Examples of the substance having an electron mobility equal to or higher than Vs include a metal complex, an aromatic heterocyclic compound, an aromatic hydrocarbon compound, and a polymer compound, which can BE used together with the compound represented by the formula (BE1) and/or the compound represented by the formula (EB1) used in one embodiment of the present invention.
Examples of the metal complex include an aluminum complex, a beryllium complex, and a zinc complex. Specific examples thereof include tris (8-quinolinolato) aluminum (III) (Alq), tris (4-methyl-8-quinolinolato) aluminum (Almq 3), bis (10-hydroxybenzo [ h ] quinolino) beryllium (BeBq 2), bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum (III) (BALq), bis (8-quinolinolato) zinc (II) (Znq), bis [2- (2-benzoxazolyl) phenol ] zinc (II) (ZnPBO), bis [2- (2-benzothiazolyl) phenol ] zinc (II) (ZnBTZ) and the like.
Examples of the aromatic heterocyclic compound include imidazole derivatives such as benzimidazole derivatives, imidazopyridine derivatives, and benzimidazolophenanthridine derivatives; oxazine derivatives such as pyrimidine derivatives and triazine derivatives; and compounds containing a nitrogen-containing six-membered ring structure (including compounds having a phosphine oxide substituent on the heterocyclic ring), such as quinoline derivatives, isoquinoline derivatives, and phenanthroline derivatives. Specifically, 2- (4-biphenylyl) -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-biphenylyl) -1,2, 4-triazole (abbreviated as TAZ), 3- (4-tert-butylphenyl) -4- (4-ethylphenyl) -5- (4-biphenylyl) -1,2, 4-triazole (abbreviated as p-EtTAZ), bathophenanthroline (abbreviated as BPhen), and mixtures thereof, Bathocuproine (BCP for short), 4' -bis (5-methylbenzoxazole-2-yl) stilbene (BzOs for short) and the like.
Examples of the aromatic hydrocarbon compound include anthracene derivatives and fluoranthene derivatives.
Specific examples of the polymer compound include poly [ (9, 9-dihexylfluorene-2, 7-diyl) -co- (pyridine-3, 5-diyl) ] (abbreviated as PF-Py), poly [ (9, 9-dioctylfluorene-2, 7-diyl) -co- (2,2 '-bipyridine-6, 6' -diyl) ] (abbreviated as PF-BPy), and the like.
As long as the compound has a higher electron-transport property than the hole-transport property, a substance other than these compounds may be used for the electron-transport layer.
The electron transport layer may be a single layer, or 2 or more layers may be stacked. In this case, it is preferable to dispose a layer containing a substance having a larger energy gap among substances having high electron-transporting properties on the side closer to the light-emitting layer.
The electron transport layer may contain a metal such as an alkali metal, magnesium, an alkaline earth metal, or an alloy containing 2 or more metals of these; alkali metal compounds such as lithium 8-quinolinolate (Liq), and metal compounds such as alkaline earth metal compounds. When a metal such as an alkali metal, magnesium, an alkaline earth metal, or an alloy containing 2 or more metals of these is contained in the electron transporting layer, the content is not particularly limited, but is preferably 0.1 to 50 mass%, more preferably 0.1 to 20 mass%, and further preferably 1 to 10 mass%.
When a metal compound of a metal compound such as an alkali metal compound or an alkaline earth metal compound is contained in the electron transporting layer, the content thereof is preferably 1 to 99% by mass, more preferably 10 to 90% by mass. When the electron transport layer is a multilayer, the layer located on the light-emitting layer side may be formed only of these metal compounds.
(Electron injection layer)
The electron injection layer is a layer containing a substance having a high electron injection property, and has a function of efficiently injecting electrons from the cathode into the light-emitting layer. Examples of the substance having a high electron-injecting property include alkali metals, magnesium, alkaline earth metals, and compounds thereof. Specific examples thereof include lithium, cesium, calcium, lithium fluoride, cesium fluoride, calcium fluoride, and lithium oxide. Other electron-transporting substances containing an alkali metal, magnesium, an alkaline earth metal, or a compound thereof, for example, Alq-containing magnesium, may be used.
In addition, a composite material including an organic compound and a donor compound may be used for the electron injection layer. Since the organic compound takes electrons from the donor compound, such a composite material is excellent in electron injection properties and electron transport properties.
The organic compound is preferably a substance having excellent electron transport properties, and for example, a metal complex, an aromatic heterocyclic compound, or the like, which is a substance having high electron transport properties, can be used.
The donor compound may be any compound as long as it can donate electrons to the organic compound, and examples thereof include alkali metals, magnesium, alkaline earth metals, rare earth metals, and the like. Specific examples thereof include lithium, cesium, magnesium, calcium, erbium, and ytterbium. Further, alkali metal oxides and alkaline earth metal oxides are preferable, and specific examples thereof include lithium oxide, calcium oxide, barium oxide, and the like. In addition, lewis bases such as magnesium oxide may also be used. Further, an organic compound such as tetrathiafulvalene (abbreviated as TTF) may be used.
(cathode)
As the cathode, a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a small work function (specifically, 3.8eV or less) is preferably used. Examples of the material of the cathode include alkali metals such as lithium and cesium; magnesium; alkaline earth metals such as calcium and strontium; alloys containing these metals (e.g., magnesium-silver, aluminum-lithium); rare earth metals such as europium and ytterbium; alloys containing rare earth metals, and the like.
The cathode is generally formed by a vacuum deposition method or a sputtering method. In addition, a coating method, an ink jet method, or the like can be used when silver paste or the like is used.
In addition, when the electron injection layer is provided, the cathode can be formed using various conductive materials such as aluminum, silver, ITO, graphene, indium oxide-tin oxide containing silicon or silicon oxide, and the like, regardless of the magnitude of the work function. These conductive materials can be formed by sputtering, ink-jet method, spin coating, or the like.
In addition, when the top emission type is adopted, a capping layer may be provided on the upper portion of the cathode. By arranging the capping layer, the peak intensity and the peak wavelength of light emission can be adjusted.
The compound that can be used for the capping layer is a compound whose molecular formula contains a carbon atom and a hydrogen atom as constituent elements, and may contain an oxygen atom, a nitrogen atom, a fluorine atom, a silicon atom, a chlorine atom, a bromine atom, an iodine atom, and may have a substituent.
Preferred materials include the following compounds.
(i) A compound whose molecular formula contains a carbon atom and a hydrogen atom as constituent elements, which is an aromatic hydrocarbon compound that may contain an oxygen atom, a nitrogen atom, a fluorine atom, a silicon atom, a chlorine atom, a bromine atom, an iodine atom, and may have a substituent
(ii) The compound whose molecular formula contains a carbon atom and a hydrogen atom as constituent elements is an aromatic heterocyclic compound which may contain an oxygen atom, a nitrogen atom, a fluorine atom, a silicon atom, a chlorine atom, a bromine atom, an iodine atom, and may have a substituent
(iii) The compound whose molecular formula contains carbon atoms and hydrogen atoms as constituent elements is an amine compound which may contain an oxygen atom, a nitrogen atom, a fluorine atom, a silicon atom, a chlorine atom, a bromine atom, an iodine atom, and may have a substituent.
The thickness of the capping layer is preferably 200nm or less, more preferably 20nm or more and 200nm or less, and still more preferably 40nm or more and 140nm or less.
Fig. 2 shows a schematic configuration of an example of an organic EL element provided with a capping layer.
The organic EL element 100 includes an anode 3, a light-emitting unit 10, a cathode 4, and a capping layer 20 in this order on a substrate 2, and emits light from the capping layer 20 side. The light emitting unit 10 is illustrated in fig. 1.
(insulating layer)
In the organic EL device, an electric field is applied to the thin film, and thus a pixel defect due to leakage or short circuit is likely to occur. To prevent this, a thin film insulating layer may be interposed between the pair of electrodes.
Specific examples of the substance 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, vanadium oxide, and the like. The insulating layer may be a mixture of these, or may be a laminate of a plurality of layers including these.
(spacer layer)
The spacer layer is provided between the fluorescent light-emitting layer and the phosphorescent light-emitting layer in order to prevent excitons generated in the phosphorescent light-emitting layer from diffusing into the fluorescent light-emitting layer or to adjust carrier balance, for example, when the fluorescent light-emitting layer and the phosphorescent light-emitting layer are stacked. The spacer layer may also be provided between a plurality of phosphorescent light emitting layers, or the like.
The spacer layer is preferably formed of a material having both electron-transporting property and hole-transporting property because it is provided between a plurality of light-emitting layers. In addition, from the viewpoint of preventing diffusion of triplet energy in adjacent phosphorescent light-emitting layers, it is preferable that the triplet energy be 2.6eV or more.
Examples of the material used for the spacer layer include the same materials as those used for the hole transport layer.
(Electron blocking layer, hole blocking layer, exciton blocking layer)
An electron blocking layer, a hole blocking layer, an exciton (triplet) blocking layer, or the like may be provided adjacent to the light-emitting layer.
The electron blocking layer refers to a layer having a function of blocking leakage of electrons from the light emitting layer to the hole transport layer. The hole blocking layer refers to a layer having a function of preventing holes from leaking from the light emitting layer to the electron transport layer. The exciton blocking layer is a layer having a function of blocking diffusion of excitons generated in the light emitting layer to the adjacent layer and confining the excitons in the light emitting layer.
(intermediate layer)
In the tandem type organic EL element, an intermediate layer may be provided.
(layer Forming method)
The method for forming each layer of the organic EL element is not particularly limited as long as it is not described separately. As the formation method, a known method such as a dry film formation method or a wet film formation method can be used. Specific examples of the dry film formation method include a vacuum deposition method, a sputtering method, a plasma method, an ion plating method, and the like. Specific examples of the wet film formation method include various coating methods such as a spin coating method, a dipping method, a casting method, and an ink jet method.
(film thickness)
The film thickness of each layer of the organic EL element is not particularly limited as long as it is not described otherwise. If the film thickness is too small, defects such as pinholes tend to occur, and sufficient light emission luminance cannot be obtained. On the other hand, if the film thickness is too large, a high driving voltage is required, and the efficiency is lowered. From this viewpoint, the film thickness is preferably 1nm to 10 μm, and more preferably 1nm to 0.2 μm.
[ electronic apparatus ]
An electronic device according to an embodiment of the present invention includes the organic EL element according to the above-described embodiment of the present invention. Specific examples of the electronic device include a display member such as an organic EL panel module; display devices such as televisions, mobile phones, smart phones, personal computers, and the like; lighting, lighting devices for vehicle lamps, and the like.
Examples
The present invention will be described in more detail below by way of examples and comparative examples, which should not be construed as limiting the scope of the present invention.
< Compound >
The compounds represented by the formula (1A) used for producing the organic EL devices of examples 1 to 62 are shown below.
[ solution 104]
The structures of comparative compounds used for producing the organic EL devices of comparative examples 1 to 33 are shown below.
[ solution 105]
The compounds represented by the formula (BE1) used for producing the organic EL elements of examples 1 to 62 are shown below.
[ solution 106]
The compounds represented by the formula (B1) used for producing the organic EL devices of examples 1 to 62 are shown below.
[ solution 107]
The structures of other compounds used for the production of the organic EL devices of examples 1 to 62 and comparative examples 1 to 33 are shown below.
[ solution 108]
[ solution 109]
< production of organic EL element >
Example 1
[ production of bottom emission organic EL element ]
A glass substrate (manufactured by ジオマティック Co.) having a thickness of 25mm × 75mm × 1.1mm and an ITO (indium Tin oxide) transparent electrode (anode) was ultrasonically washed in isopropyl alcohol for 5 minutes, and then subjected to UV ozone washing for 30 minutes. The film thickness of the ITO transparent electrode was 130 nm. The washed glass substrate with the transparent electrode line was mounted on a substrate holder of a vacuum evaporation apparatus, and first, a compound HI-1 was evaporated on the surface on the side where the transparent electrode line was formed so as to cover the transparent electrode, thereby forming a hole injection layer (HI) having a thickness of 5 nm. Compound HT-1 was deposited on the hole injection layer to form a1 st hole transport layer (HT) having a thickness of 90 nm. A compound EBL-1 was deposited on the 1 st hole transport layer by vapor deposition to form a2 nd hole transport layer (referred to as an Electron Barrier Layer) (EBL) having a thickness of 10 nm. A light-emitting layer having a film thickness of 20nm was formed on the 2 nd hole transport layer by co-depositing a compound BH-2 (host material (BH)) and a compound BD-1 (dopant material (BD)) so that the proportion of BD-1 became 4 mass%. Compound aET-1 was vapor-deposited on the light-emitting layer to form a1 st electron-transporting layer (also referred to as a Hole Barrier Layer) (HBL) having a thickness of 5 nm. Compound bET-2 was deposited on the 1 st electron transporting layer to form a2 nd electron transporting layer (ET) having a thickness of 20 nm. LiF was deposited on the 2 nd electron transport layer by evaporation to form an electron injection layer having a film thickness of 1 nm. A metal Al was deposited on the electron injection layer to form a cathode having a film thickness of 80 nm.
The element structure of the organic EL element of example 1 is shown in brief as follows.
ITO(130)/HI-1(5)/HT-1(90)/EBL-1(10)/BH-2：BD-1(20, 96%：4%)/aET-1(5)/bET-2(20)/LiF(1)/Al(80)。
The numbers in parentheses indicate the film thickness (unit: nm). In the same parentheses, the numerals in percentage represent the proportion (mass%) of the compound of the host material and the dopant material in the light-emitting layer.
< evaluation of organic EL element >
The current density is 10mA/cm2The organic EL element was applied with a voltage, and the EL emission spectrum was measured with a spectral radiance meter CS-2000 (manufactured by コニカミノルタ Co., Ltd.). The external quantum efficiency EQE (%) was calculated from the obtained spectral radiance spectrum. The results are shown in Table 1.
The current density is 50mA/cm2The voltage was applied to the obtained organic EL element, and the time (LT90 (unit: hour) until the luminance reached 90% of the initial luminance was measured)). The results are shown in Table 1.
Comparative example 1
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 1 were used. The results are shown in Table 1.
[ Table 1]
Example 2 and comparative example 2
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 2 were used. The results are shown in Table 2.
[ Table 2]
Example 3 and comparative example 3
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 3 were used. The results are shown in Table 3.
[ Table 3]
Example 4 and comparative example 4
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 4 were used. The results are shown in Table 4.
[ Table 4]
Example 5 and comparative example 5
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 5 were used. The results are shown in Table 5.
[ Table 5]
Example 6 and comparative example 6
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 6 were used. The results are shown in Table 6.
[ Table 6]
Example 7 and comparative example 7
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 7 were used. The results are shown in Table 7.
[ Table 7]
Example 8 and comparative example 8
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 8 were used. The results are shown in Table 8.
[ Table 8]
Example 9 and comparative example 9
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 9 were used. The results are shown in Table 9.
[ Table 9]
Example 10 and comparative example 10
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 10 were used. The results are shown in Table 10.
[ Table 10]
Example 11 and comparative example 11
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 11 were used. The results are shown in Table 11.
[ Table 11]
Comparative examples 12 to 14
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 12 were used. The results are shown in Table 12.
[ Table 12]
As is clear from the results in tables 1 to 11, the element life (LT90) was equivalent but the emission efficiency (EQE) was improved in the bottom emission type example as compared with the comparative example.
Furthermore, from the results in Table 12, it is clear that the devices of comparative examples 12 to 14 using BH-R4 in place of BH-2 have a shorter device life and equivalent light-emitting efficiency than the devices of comparative examples 1 to 11.
Example 12
[ production and evaluation of Top-emission organic EL element ]
A layer (reflection layer) of APC (Ag-Pd-Cu) (film thickness 100nm) which is a silver alloy and a layer (film thickness 10nm) of IZO (Indium zinc oxide) were formed in this order on a glass substrate by sputtering. Next, the conductive material layer is patterned by etching using a resist pattern as a mask using a general Lithography (lithograph) technique, thereby forming an anode. The substrate on which the lower electrode was formed was ultrasonically washed in isopropyl alcohol for 5 minutes, and then subjected to UV ozone washing for 30 minutes. Then, compound HI-2 was evaporated by vacuum evaporation to form a hole injection layer (HI) having a thickness of 5 nm. Compound HT-1 was deposited on the hole injection layer to form a1 st hole transport layer (HT) having a thickness of 130 nm. A compound EBL-3 was deposited on the 1 st hole transport layer by vapor deposition to form a2 nd hole transport layer (referred to as an Electron Barrier Layer) (EBL) having a thickness of 10 nm. A light-emitting layer having a film thickness of 20nm was formed on the 2 nd hole transport layer by co-depositing a compound BH-2 (host material (BH)) and a compound BD-3 (dopant material (BD)) so that the proportion of BD-3 became 4 mass%. Compound aET-1 was vapor-deposited on the light-emitting layer to form a1 st electron-transporting layer (also referred to as a Hole Barrier Layer) (HBL) having a thickness of 5 nm. Compound bET-2 was deposited on the 1 st electron transporting layer to form a2 nd electron transporting layer (ET) having a thickness of 20 nm. LiF was deposited on the 2 nd electron transport layer by evaporation to form an electron injection layer having a film thickness of 1 nm. And the electron injection layer is coated with a mixture of Mg and Ag, wherein the ratio of Mg to Ag is 1: the film thickness of 9 was larger than that of the film formed by vapor deposition, and a cathode having a film thickness of 15nm and made of a semipermeable MgAg alloy was formed. CAP-1 was formed on the cathode by vacuum deposition to form a capping layer having a thickness of 65 nm.
The element structure of the organic EL element of example 12 is shown in brief as follows.
APC(100)/IZO(10)/HI-2(5)/HT-1(130)/EBL-3(10)/BH-2：BD-3(20, 96%：4%)/aET-1(5)/bET-2(20)/LiF(1)/MgAg(15)/CAP-1(65)。
The numbers in parentheses indicate the film thickness (unit: nm). In the same parentheses, the numerals in percentage represent the proportion (mass%) of the compound of the host material and the dopant material in the light-emitting layer.
< evaluation of organic EL element >
The current density is 10mA/cm2The organic EL element was applied with a voltage, and the EL emission spectrum was measured with a spectral radiance meter CS-2000 (manufactured by コニカミノルタ Co.). The external quantum efficiency EQE (%) was calculated from the obtained spectral radiance spectrum. The results are shown in Table 13.
By the flow of electric currentThe density was 15mA/cm2The voltage was applied to the obtained organic EL element, and the time (LT90 (unit: hour)) until the luminance reached 90% of the initial luminance was measured. The results are shown in Table 13.
Comparative example 15
Organic EL devices were produced and evaluated in the same manner as in example 12, except that the compounds in table 13 were used. The results are shown in Table 13.
[ Table 13]
Example 13 and comparative example 16
Organic EL devices were produced and evaluated in the same manner as in example 12, except that the compounds in table 14 were used. The results are shown in Table 14.
[ Table 14]
Example 14 and comparative example 17
Organic EL devices were produced and evaluated in the same manner as in example 12, except that the compounds in table 15 were used. The results are shown in Table 15.
[ Table 15]
Example 15 and comparative example 18
Organic EL devices were produced and evaluated in the same manner as in example 12, except that the compounds in table 16 were used. The results are shown in Table 16.
[ Table 16]
From the results in tables 13 to 16, it is understood that the elements of the top emission type example have the same lifetime (LT90) but improved emission efficiency (EQE) as the elements of the comparative example.
Example 16 and comparative example 19
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 17 were used. The results are shown in Table 17.
[ Table 17]
Example 17 and comparative example 20
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 18 were used. The results are shown in Table 18.
[ Table 18]
Example 18 and comparative example 21
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 19 were used. The results are shown in Table 19.
[ Table 19]
Example 19 and comparative example 22
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 20 were used. The results are shown in Table 20.
[ Table 20]
Example 20 and comparative example 23
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 21 were used. The results are shown in Table 21.
[ Table 21]
Example 21
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 22 were used. The results are shown in Table 22. Table 22 shows comparative example 8 described above by way of comparison.
[ Table 22]
Example 22
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 23 were used. The results are shown in Table 22. Table 23 shows comparative example 9 described above.
[ Table 23]
Example 23
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 24 were used. The results are shown in Table 24. Table 24 shows comparative example 10 described above by way of comparison.
[ Table 24]
Example 24
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 25 were used. The results are shown in Table 25. Table 25 shows comparative example 11 described above by way of comparison.
[ Table 25]
Example 25
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 26 were used. The results are shown in Table 26. Table 26 shows comparative example 19 described above by way of comparison.
[ Table 26]
Example 26
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 27 were used. The results are shown in Table 27. Table 27 shows comparative example 20 described above.
[ Table 27]
Example 27
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 28 were used. The results are shown in Table 28. Table 28 shows comparative example 21 described above by way of comparison.
[ Table 28]
Example 28
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 29 were used. The results are shown in Table 29. Table 29 shows comparative example 22 described above by way of comparison.
[ Table 29]
Example 29
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 30 were used. The results are shown in Table 30. Table 30 shows comparative example 23 described above by way of comparison.
[ Table 30]
Example 30
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 31 were used. The results are shown in Table 31. Table 31 shows comparative example 8 described above by way of comparison.
[ Table 31]
Example 31
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 32 were used. The results are shown in Table 32. In addition, the comparison of the aforementioned comparative example 9 in table 32 shows.
[ Table 32]
Example 32
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 33 were used. The results are shown in Table 33. Table 33 shows comparative example 10 in comparison with the above.
[ Table 33]
Example 33
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 34 were used. The results are shown in Table 34. Table 34 shows comparative example 11 described above by way of comparison.
[ Table 34]
Example 34
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 35 were used. The results are shown in Table 35. Table 35 shows comparative example 19 described above by way of comparison.
[ Table 35]
Example 35
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 36 were used. The results are shown in Table 36. Table 36 shows comparative example 20 described above.
[ Table 36]
Example 36
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 37 were used. The results are shown in Table 37. Table 37 shows comparative example 21 described above by way of comparison.
[ Table 37]
Example 37
Organic EL devices were produced and evaluated in the same manner as in example 1, except that the compounds in table 38 were used. The results are shown in Table 38. Table 38 shows comparative example 22 described above by way of comparison.
[ Table 38]
From the results in tables 17 to 38, it is understood that the element of the bottom emission type example has the same element lifetime (LT90) but the emission efficiency (EQE) is improved as compared with the element of the comparative example.
Example 38
[ production of bottom emission organic EL element ]
A glass substrate (manufactured by ジオマティック Co.) having a thickness of 25mm × 75mm × 1.1mm and an ITO (indium Tin oxide) transparent electrode (anode) was ultrasonically washed in isopropyl alcohol for 5 minutes, and then subjected to UV ozone washing for 30 minutes. The film thickness of the ITO transparent electrode was 130 nm. The washed glass substrate with the transparent electrode line was mounted on a substrate holder of a vacuum evaporation apparatus, and first, a compound HI-1 was evaporated on the surface on the side where the transparent electrode line was formed so as to cover the transparent electrode, thereby forming a hole injection layer (HI) having a thickness of 5 nm. Compound HT-1 was deposited on the hole injection layer to form a1 st hole transport layer (HT) having a thickness of 80 nm. A compound EBL-5 was deposited on the 1 st hole transport layer by vapor deposition to form a2 nd hole transport layer (also referred to as an Electron Barrier Layer) (EBL) having a thickness of 10 nm. A light-emitting layer having a thickness of 25nm was formed on the 2 nd hole transport layer by co-depositing a compound BH-2 (host material (BH)) and a compound BD-14 (dopant material (BD)) so that the proportion of BD-14 became 4 mass%. Compound aET-3 was vapor-deposited on the light-emitting layer to form a1 st electron-transporting layer (also referred to as a Hole Barrier Layer) (HBL) having a thickness of 10 nm. Compound bET-5 was deposited on the 1 st electron transporting layer to form a2 nd electron transporting layer (ET) having a thickness of 15 nm. LiF was deposited on the 2 nd electron transport layer by evaporation to form an electron injection layer having a film thickness of 1 nm. A metal Al was deposited on the electron injection layer to form a cathode having a film thickness of 80 nm.
The element structure of the organic EL element of example 38 is shown in brief as follows.
ITO(130)/HI-1(5)/HT-1(80)/EBL-5(10)/BH-2：BD-14(25,96%：4%)/aET-3(10)/bET-5(15)/LiF(1)/Al(80)。
The numbers in parentheses indicate the film thickness (unit: nm). In the same parentheses, the numerals in percentage represent the proportion (mass%) of the compound of the host material and the dopant material in the light-emitting layer.
< evaluation of organic EL element >
The current density is 10mA/cm2The organic EL element was applied with a voltage, and the EL emission spectrum was measured with a spectral radiance meter CS-2000 (manufactured by コニカミノルタ Co.). The external quantum efficiency EQE (%) was calculated from the obtained spectral radiance spectrum. The results are shown in Table 39.
The current density is 50mA/cm2The voltage was applied to the obtained organic EL element, and the time (LT95 (unit: hour)) until the luminance reached 95% of the initial luminance was measured. The results are shown in Table 39.
Comparative example 24
Organic EL devices were produced and evaluated in the same manner as in example 38, except that the compounds in table 39 were used. The results are shown in Table 39.
[ Table 39]
Example 39 and comparative example 25
Organic EL devices were produced and evaluated in the same manner as in example 38, except that the compounds in table 40 were used. The results are shown in Table 40.
[ Table 40]
As is clear from the results in tables 39 and 40, the element life (LT95) was equivalent but the emission efficiency (EQE) was improved in the element of the bottom emission type example as compared with the element of the comparative example.
Example 40
[ production of bottom emission organic EL element ]
A glass substrate (manufactured by ジオマティック Co.) having a thickness of 25mm × 75mm × 1.1mm and an ITO (indium Tin oxide) transparent electrode (anode) was ultrasonically washed in isopropyl alcohol for 5 minutes, and then subjected to UV ozone washing for 30 minutes. The film thickness of the ITO transparent electrode was 130 nm. The washed glass substrate with the transparent electrode line was mounted on a substrate holder of a vacuum evaporation apparatus, and first, a compound HI-2 was evaporated on the surface on the side where the transparent electrode line was formed so as to cover the transparent electrode, thereby forming a hole injection layer (HI) having a thickness of 5 nm. Compound HT-2 was deposited on the hole injection layer to form a1 st hole transport layer (HT) having a thickness of 85 nm. A compound EBL-6 was deposited on the 1 st hole transport layer by vapor deposition to form a2 nd hole transport layer (also referred to as an Electron Barrier Layer) (EBL) having a thickness of 5 nm. A light-emitting layer having a thickness of 25nm was formed on the 2 nd hole transport layer by co-depositing a compound BH-2 (host material (BH)) and a compound BD-9 (dopant material (BD)) so that the proportion of BD-9 became 4 mass%. Compound aET-3 was vapor-deposited on the light-emitting layer to form a1 st electron-transporting layer (also referred to as a Hole Barrier Layer) (HBL) having a thickness of 10 nm. Compound bET-3 was deposited on the 1 st electron transporting layer to form a2 nd electron transporting layer (ET) having a thickness of 15 nm. LiF was deposited on the 2 nd electron transport layer by evaporation to form an electron injection layer having a film thickness of 1 nm. A metal Al was deposited on the electron injection layer to form a cathode having a film thickness of 80 nm.
The element structure of the organic EL element of example 1A is shown in brief as follows.
ITO(130)/HI-2(5)/HT-2(85)/EBL-6(5)/BH-2：BD-9(25,96%：4%)/aET-3(10)/bET-3(15)/LiF(1)/Al(80)。
The numbers in parentheses indicate the film thickness (unit: nm). In the same parentheses, the numerals in percentage represent the proportion (mass%) of the compound of the host material and the dopant material in the light-emitting layer.
< evaluation of organic EL element >
The current density is 10mA/cm2Applying electricity to the organic EL elementThe EL emission spectrum was measured by a spectral radiance meter CS-2000 (manufactured by コニカミノルタ Co., Ltd.). The external quantum efficiency EQE (%) was calculated from the obtained spectral radiance spectrum. The results are shown in Table 41.
The current density is 50mA/cm2The voltage was applied to the obtained organic EL element, and the time (LT90 (unit: hour)) until the luminance reached 95% of the initial luminance was measured. The results are shown in Table 41.
Comparative example 26
Organic EL devices were produced and evaluated in the same manner as in example 40, except that the compounds in table 41 were used and the thickness of each layer was changed as described in table 41. The results are shown in Table 41.
[ Table 41]
Example 41 and comparative examples 27 and 28
Organic EL devices were produced and evaluated in the same manner as in example 40, except that the compounds in table 42 were used and the thickness of each layer was changed as described in table 42. The results are shown in Table 42.
The element structure of the organic EL element of example 41 is shown in brief as follows.
ITO(130)/HI-2(5)/HT-4(110)/EBL-5(20)/BH-2：BD-2(25,96%：4%)/aET-3(5)/bET-3(20)/LiF(1)/Al(80)。
[ Table 42]
Example 42 and comparative example 29
Organic EL devices were produced and evaluated in the same manner as in example 40, except that the compounds in table 43 were used and the thickness of each layer was changed as described in table 43. The results are shown in Table 43.
The element structure of the organic EL element of example 42 is shown in brief as follows.
ITO(130)/HI-2(5)/HT-6(10)/EBL-3(5)/BH-2：BD-2(25,96%：4%)/aET-1(5)/bET-3(25)/LiF(1)/Al(80)
[ Table 43]
Example 43 and comparative example 30
Organic EL devices were produced and evaluated in the same manner as in example 40, except that the compounds in table 44 were used and the thickness of each layer was changed as described in table 44. The results are shown in Table 44.
The element structure of the organic EL element of example 43 is shown in brief as follows.
ITO(130)/HI-2(5)/HT-5(75)/EBL-8(15)/BH-4：BD-2(25,96%：4%)/aET-1(3)/bET-3(30)/LiF(1)/Al(80)
[ Table 44]
Example 44 and comparative example 31
Organic EL devices were produced and evaluated in the same manner as in example 40, except that the compounds in table 45 were used and the thickness of each layer was changed as described in table 45. The results are shown in Table 45.
The element structure of the organic EL element of example 44 is shown in brief as follows.
ITO(130)/HI-1(5)/HT-1(85)/EBL-1(5)/BH-2：BD-18(25,96%：4%)/aET-1(10)/bET-1(15)/LiF(1)/Al(80)
[ Table 45]
Examples 45 to 53 and comparative example 32
Organic EL devices were produced and evaluated in the same manner as in example 40, except that the compounds in table 46 were used and the thickness of each layer was changed as described in table 46. The results are shown in Table 46.
The element structure of the organic EL element of example 45 is shown in brief as follows.
ITO(130)/HI-1(5)/HT-1(85)/EBL-1(5)/BH-2：BD-19(25,96%：4%)/aET-1(10)/bET-1(15)/LiF(1)/Al(80)。
[ Table 46]
Examples 54 to 62 and comparative example 33
Organic EL devices were produced and evaluated in the same manner as in example 40, except that the compounds in table 47 were used and the thickness of each layer was changed as described in table 47. The results are shown in Table 47.
The element structure of the organic EL element of example 54 is shown in brief as follows.
ITO(130)/HI-1(5)/HT-1(85)/EBL-1(5)/BH-2：BD-19(25,96%：4%)/aET-6(10)/bET-6(15)/LiF(1)/Al(80)
[ Table 47]
From the results in tables 41 to 47, it is understood that the element life (LT90) is equivalent but the emission efficiency (EQE) is improved in the element of the bottom emission type example as compared with the element of the comparative example.
< Synthesis of Compound >
Synthesis example 1: synthesis of Compound BH-2
Compound BH-2 was synthesized according to the following synthetic route.
[ solution 110]
(1) Synthesis of (1-fluoronaphthalen-2-yl) boronic acid (intermediate 1)
Under an argon atmosphere, 7.2g of 2,2,6, 6-tetramethylpiperidine and 60mL of tetrahydrofuran (dehydrated) were put in a flask and cooled to-43 ℃. To this was added n-BuLi (1.55 in hexane)M)33mL, and then stirred at-40 ℃ for 30 minutes. Then cooling to-69 ℃, adding (A)iPrO)316.0mL of B was stirred at-78 ℃ for 5 minutes, 20mL of a THF solution containing 5.00g of 1-fluoronaphthalene dissolved therein was added dropwise thereto, and the mixture was stirred in an ice bath for 10 hours. After completion of the reaction, 1N HCl aq (100mL) was added, and the mixture was stirred at room temperature for 1 hour. Then transferred to a separatory funnel and extracted with ethyl acetate. The solution was dried over anhydrous magnesium sulfate, concentrated, and washed with hexane to obtain 6.13g (yield: 71%) of (1-fluoronaphthalen-2-yl) boronic acid (intermediate 1) as a white solid.
(2) Synthesis of 2- (2, 6-dimethoxyphenyl) -1-fluoronaphthalene (intermediate 2)
4.52g of (1-fluoronaphthalen-2-yl) boronic acid (intermediate 1), 4.30g of 2-bromo-1, 3-dimethoxybenzene, 0.91g of tris (dibenzylideneacetone) dipalladium (0), 0.81g of 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl (SPhos), 12.6g of tripotassium phosphate and 10mL of toluene (dehydrated) were added to a flask under an argon atmosphere, and heated under reflux with stirring for 7 hours. After cooling to room temperature, the reaction solution was extracted with toluene, the aqueous layer was removed, and the organic layer was washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate, concentrated, and the residue was purified by silica gel column chromatography to give 4.70g (yield 84%) of 2- (2, 6-dimethoxyphenyl) -1-fluoronaphthalene (intermediate 2).
(3) Synthesis of 2- (3-fluoronaphthalen-2-yl) benzene-1, 3-diol (intermediate 3)
Under an argon atmosphere, 4.70g of 2- (2, 6-dimethoxyphenyl) -1-fluoronaphthalene (intermediate 2) and 210mL of methylene chloride (dehydrated) were added to the flask and cooled to 0 ℃.41 mL of a 1.0mol/l boron tribromide-dichloromethane solution was added thereto, followed by stirring at room temperature for 4 hours. After the reaction was completed, the solution was cooled to-78 ℃ and carefully deactivated with methanol, and further deactivated with a sufficient amount of water. The solution was transferred to a separatory funnel, extracted with dichloromethane, dried over anhydrous sodium sulfate, passed through a short column of silica gel to remove the original impurities, the solution was concentrated, and the resulting sample was dried under vacuum at room temperature for 3 hours to give 4.00g (94%) of 2- (3-fluoronaphthalen-2-yl) benzene-1, 3-diol (intermediate 3) as a clear oil.
(4) Synthesis of naphtho [1,2-b ] benzofuran-7-ol (intermediate 4)
Under an argon atmosphere, 4.00g of 2- (3-fluoronaphthalen-2-yl) benzene-1, 3-diol (intermediate 3), 15mL of N-methyl-2-pyrrolidone (dehydrated), and K2CO33.26g was added to the flask, followed by stirring at 150 ℃ for 2 hours. After the reaction was completed, the solution was cooled to room temperature, ethyl acetate (200mL) was added, and the mixture was transferred to a separatory funnel and washed with water. The solution was dried over anhydrous sodium sulfate and purified by silica gel column chromatography to give naphtho [1,2-b ]]1.25g (yield 34%) of benzofuran-7-ol (intermediate 4) as a white solid.
(5) Synthesis of naphtho [1,2-b ] benzofuran-7-yl trifluoromethanesulfonate (intermediate 5)
1.25g of naphtho [1,2-b ] benzofuran-7-ol (intermediate 4), 65mg of N, N-dimethyl-4-aminopyridine, 1.08mL of trifluoromethanesulfonic anhydride and 27mL of methylene chloride (dehydrated) were added to a flask under an argon atmosphere, and cooled to 0 ℃. Pyridine (dehydrated) 10.6mL was added dropwise, followed by stirring at room temperature for 2 hours. After the reaction is completed, it is deactivated with a sufficient amount of water. The solution was transferred to a separatory funnel, extracted with dichloromethane, dried over anhydrous sodium sulfate, and then the origin impurity was removed by passing through a short column of silica gel, the solution was concentrated, and the resulting sample was dried under vacuum at room temperature for 3 hours to give 1.50g (77%) of naphtho [1,2-b ] benzofuran-7-yl trifluoromethanesulfonate (intermediate 5) as a white solid.
(5) Synthesis of Anthracene derivative (Compound BH-2)
4.09g of [1,2-b ] benzofuran-7-yl trifluoromethanesulfonate (intermediate 5), 4.09g of 10-phenylanthracene-9-boronic acid synthesized by a known method, 0.19g of tetrakis (triphenylphosphine) palladium (0), 0.87g of sodium carbonate, 30mL of 1, 4-dioxane, and 10mL of ion-exchanged water were added to the flask under an argon atmosphere, and stirred under reflux for 4 hours. After cooling to room temperature, the precipitated solid was collected by filtration. The obtained solid was washed with water, followed by acetone, and then recrystallized from a mixed solvent of acetonitrile and hexane to obtain 1.41g of a white solid. The mass spectrometry of this white solid resulted in compound BH-2, with m/e =470 relative to molecular weight 470.17.
Synthesis example 2: synthesis of Compound BH-4
Compound BH-4 was synthesized according to the following synthetic route.
[ solution 111]
A reaction was carried out in the same manner as in synthesis example 1 except that (4- (10-phenylanthracen-9-yl) phenyl) boronic acid synthesized by a known method was used instead of 10-phenylanthracene-9-boronic acid in the synthesis of compound BH-1 of synthesis example 1, thereby obtaining a white solid. The mass spectrometry of this white solid gave compound BH-4, with m/e =546, relative to molecular weight 546.20.
Synthesis example 3: synthesis of Compound BH-6
Compound BH-6 was synthesized according to the following synthetic route.
[ solution 112]
(1) Synthesis of triisopropyl (naphtho [1,2-b ] benzofuran-7-yloxy) silane (intermediate 6)
9.94g of naphtho [1,2-b ] benzofuran-7-ol (intermediate 4), 13.6mL of chlorotriisopropylsilane, 4.33g of imidazole, and 200mL of methylene chloride (dehydrated) were added to a flask under an argon atmosphere, and stirred at room temperature for 5 hours. The reaction solution was extracted with dichloromethane, the aqueous layer was removed, and the organic layer was washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate, concentrated, and the residue was purified by silica gel column chromatography to give 16.5g (yield 99%) of a transparent oil of triisopropyl (naphtho [1,2-b ] benzofuran-7-yloxy) silane (intermediate 6).
(2) Synthesis of ((10-bromonaphtho [1,2-b ] benzofuran-7-yl) oxy) triisopropylsilane (intermediate 7)
16.0g of triisopropyl (naphtho [1,2-b ] benzofuran-7-yloxy) silane (intermediate 6), 9.37g of 1, 3-dibromo-5, 5-Dimethylhydantoin (DBH), and 200mL of methylene chloride (dehydrated) were added to a flask under an argon atmosphere, and then stirred at room temperature for 4 hours. After the reaction is completed, it is deactivated with a sufficient amount of water. The solution was transferred to a separatory funnel, extracted with dichloromethane, and the organic layer was dried over anhydrous sodium sulfate, then concentrated, and the residue was purified by silica gel column chromatography, and the obtained sample was dried under vacuum at room temperature for 3 hours to obtain 19.2g (99%) of a clear oil of ((10-bromonaphtho [1,2-b ] benzofuran-7-yl) oxy) triisopropylsilane (intermediate 7).
(3) Synthesis of triisopropyl ((10-phenylnaphtho [1,2-b ] benzofuran-7-yl) oxy) silane (intermediate 8)
Will ((10-bromonaphtho [1, 2-b))]Benzofuran-7-yl) oxy) triisopropylsilane (intermediate 7)19.0g, phenylboronic acid (PhB (OH))2)6.41g, Palladium (II) acetate (Pd (OAc)2)0.27g of 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl (SPhos)1.00g, 17.2g of tripotassium phosphate, 380mL of toluene and 120mL of ion-exchanged water were put in a flask, and then the mixture was stirred under reflux for 6 hours. After the reaction was completed, the solution was cooled to room temperature and further deactivated with a sufficient amount of water. The solution was transferred to a separatory funnel, extracted with toluene, dried over anhydrous sodium sulfate, passed through a short column of silica gel to remove origin impurities, the solution was concentrated, and the obtained sample was dried under vacuum at room temperature for 3 hours to obtain triisopropyl ((10-phenylnaphtho [1,2-b ])]Benzofuran-7-yl) oxy) silane (intermediate 8) as a white solid 18.8g (98%).
(4) Synthesis of 10-phenylnaphtho [1,2-b ] benzofuran-7-ol (intermediate 9)
Triisopropyl ((10-phenylnaphtho [1,2-b ] benzofuran-7-yl) oxy) silane (intermediate 8)3.68g, cesium fluoride 4.60g, and dichloromethane (dehydrated) 32mL were added to the flask, followed by heating under reflux and stirring for 6 hours. After the reaction was completed, the solution was cooled to room temperature and further deactivated with a sufficient amount of water. The solution was transferred to a separatory funnel, extracted with toluene, dried over anhydrous sodium sulfate, and then the origin impurity was removed by passing through a short column of silica gel, the solution was concentrated, and the obtained sample was dried under vacuum at room temperature for 3 hours to obtain 1.92g (78%) of 10-phenylnaphtho [1,2-b ] benzofuran-7-ol (intermediate 9) as a white solid.
(5) Synthesis of 10-phenylnaphtho [1,2-b ] benzofuran-7-yl trifluoromethanesulfonate (intermediate 10)
Reacting 10-phenyl naphtho [1,2-b ]]Benzofuran-7-ols(intermediate 9)1.60g of trifluoromethanesulfonic anhydride (Tf)2O)1.75g, N-dimethyl-4-aminopyridine 0.06g, and methylene chloride (dehydrated) 26mL were added to the flask, and cooled to 0 ℃ under ice bath. Then, 10mL of pyridine was added dropwise from the dropping funnel, followed by stirring at room temperature for 3 hours. After the reaction was completed, the solution was cooled to 0 ℃ and further deactivated with a sufficient amount of water. Transferring the solution to a separating funnel, extracting with dichloromethane, drying with anhydrous sodium sulfate, concentrating, purifying the residue with silica gel column chromatography, and vacuum drying the obtained sample at room temperature for 3 hr to obtain 10-phenylnaphtho [1,2-b ]]1.89g (83%) of benzofuran-7-yl trifluoromethanesulfonate (intermediate 10) as a white solid.
(6) Synthesis of Anthracene derivative (Compound BH-6)
Under argon atmosphere, adding 10-phenyl naphtho [1,2-b ]]4.00g of benzofuran-7-yl trifluoromethanesulfonate (intermediate 10), 2.70g of (10-phenylanthracen-9-yl) phenylboronic acid synthesized by a known method, and Palladium (II) acetate (Pd (OAc)2)0.04g of 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl (SPhos), 0.15g of tripotassium phosphate, 3.82g of toluene, 80mL of ion-exchanged water and 10mL of water were placed in a flask, and then the flask was heated under reflux and stirred for 6 hours. After the reaction was completed, the solution was cooled to room temperature and further deactivated with a sufficient amount of water. The solution was transferred to a separatory funnel, extracted with toluene, dried over anhydrous sodium sulfate, passed through a short column of silica gel to remove impurities at the origin, the solution was concentrated, and the obtained sample was vacuum-dried at room temperature for 3 hours, cooled to room temperature, and then filtered to collect the precipitated solid. The obtained solid was washed with water and acetone, and then recrystallized from a mixed solvent of toluene and hexane to obtain 2.90(60%) as a white solid. The mass spectrometry of this white solid gave compound BH-6, with m/e =547 relative to molecular weight 546.67.
Synthesis example 4: synthesis of Compound BH-7
Compound BH-7 was synthesized according to the following synthetic route.
[ solution 113]
。
(1) Synthesis of Anthracene derivative (Compound BH-7)
2.01g of naphtho [1,2-b ] benzofuran-7-yl trifluoromethanesulfonate (intermediate 5), 2.06g of (10- ([1, 1' -biphenyl ] -4-yl) anthracen-9-yl) boronic acid synthesized by a known method, 0.25g of tetrakis (triphenylphosphine) palladium (0), 1.75g of sodium carbonate, 28mL of 1, 4-dioxane, and 8mL of ion-exchanged water were added to a flask under an argon atmosphere, and stirred at reflux at 110 ℃ for 4 hours. After cooling to room temperature, the precipitated solid was collected by filtration. The obtained solid was washed with water, followed by acetone, and then reprecipitated with a mixed solvent of toluene and methanol to obtain 1.80g of a white solid. The mass spectrometry of this white solid gave compound BH-7, with m/e =547 relative to molecular weight 546.67.
Synthesis example 5: synthesis of Compound BH-8
Compound BH-8 was synthesized according to the following synthetic route.
[ chemical formula 114]
。
(1) Synthesis of Anthracene derivative (Compound BH-8)
1.83g of naphtho [1,2-b ] benzofuran-7-yl trifluoromethanesulfonate (intermediate 5), 2.25g of (10- [1,1' -biphenyl ] -2-yl-9-anthryl) boronic acid synthesized by a known method, 0.23g of tetrakis (triphenylphosphine) palladium (0), 1.59g of sodium carbonate, 50mL of 1, 4-dioxane, and 7mL of ion-exchanged water were added to a flask under an argon atmosphere, and stirred at 110 ℃ under reflux for 4 hours. After cooling to room temperature, the precipitated solid was collected by filtration. The obtained solid was washed with water, followed by acetone, and then reprecipitated with a mixed solvent of toluene and methanol to obtain 1.80g of a white solid. The mass spectrometry of this white solid gave compound BH-8, with m/e =547 relative to molecular weight 546.67.
Synthesis example 6: synthesis of Compound BH-17
Compound BH-17 was synthesized according to the following synthetic route.
[ solution 115]
(1) Synthesis of 9- ([1,1 ': 3', 1 "-terphenyl ] -3-yl) anthracene (intermediate 11)
Under an argon atmosphere, the ratio of 3-bromo-1, 1': 3', 1' -terphenyl 5.00g, anthracen-9-ylboronic acid synthesized by a known method 4.00g, tetrakis (triphenylphosphine) palladium (0)1.60g, sodium carbonate 3.90g, 1, 4-dioxane 135mL and ion-exchanged water 15mL were added to the flask, and stirred at 110 ℃ under reflux for 5 hours. After cooling to room temperature, the precipitated solid was collected by filtration. The obtained solid was washed with water, followed by acetone and reprecipitation from a mixed solvent of toluene and methanol to obtain 3.52g (yield 53%) of 9- ([1,1 ': 3', 1 "-terphenyl ] -3-yl) anthracene (intermediate 11).
(2) Synthesis of 9- ([1,1 ': 3', 1 "-terphenyl ] -3-yl) -10-bromoanthracene (intermediate 12)
Under an argon atmosphere, 0.67g of 9- ([1,1 ': 3', 1 "-terphenyl ] -3-yl) anthracene (intermediate 11) and 15mL of N, N-dimethylformamide were added to the flask. 0.60g of N-bromosuccinimide (NBS) was added thereto, followed by stirring at room temperature for 1 hour. After the reaction is completed, it is deactivated with a sufficient amount of water. The solution was transferred to a separatory funnel, and after the resulting solid was washed with water and methanol, the residue was purified by silica gel column chromatography, the solution was concentrated, and the resulting sample was dried under vacuum at room temperature for 3 hours to give 0.52g (64%) of a white solid of 9- ([1,1 ': 3', 1 "-terphenyl ] -3-yl) -10-bromoanthracene (intermediate 12).
(3) Synthesis of 2- (10- ([1,1 ': 3', 1 "-terphenyl ] -3-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan (intermediate 13)
Under argon atmosphere, 9- ([1,1 ': 3', 1' -terphenyl) is added]-3-yl) -10-bromoanthracene (intermediate 12)2.00g, bis (pinacolato) diboron 2.00g, [1,1' -bis (diphenylphosphino) ferrocene]Palladium (II) dichloride dichloromethane adduct (PdCl)2(dppf)4・CH2Cl2)0.30g, potassium acetate 0.80g, and 1, 4-dioxane (dehydrated) 40mL were added to the flask, and the mixture was heated and stirred at 100 ℃ for 4 hours. After cooling to room temperature, the mixture was transferred to a separatory funnel and extracted with ethyl acetate. Will be provided withThe solution was dried over anhydrous sodium sulfate and concentrated. Purifying the concentrated residue by silica gel column chromatography to obtain 2- (10- ([1,1 ': 3', 1' -terphenyl)]0.95g of (E) -3-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan (intermediate 13).
(4) Synthesis of Anthracene derivative (Compound BH-17)
Naphtho [1,2-b ] benzofuran-7-yl trifluoromethanesulfonate (intermediate 5)0.50g, 2- (10- ([1,1 ': 3', 1 "-terphenyl ] -3-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan (intermediate 13)0.80g, tetrakis (triphenylphosphine) palladium (0)0.07g, sodium carbonate 0.30g, 1, 4-dioxane 12mL and ion-exchanged water 1mL were added to a flask under an argon atmosphere, refluxed and stirred at 110 ℃ for 4 hours, cooled to room temperature, and then the precipitated solid was collected by filtration, washed with water, then with methanol, and washed with a mixed solvent of isopropanol and toluene to give a white solid 0.51g, which was mass-analyzed as compound BH-17, relative to molecular weight 546.67, m/e = 547.
Synthesis example 7: synthesis of Compound BH-18
Compound BH-18 was synthesized according to the following synthetic route.
[ solution 116]
(1) Synthesis of 1-fluoro-4-phenylnaphthalene (intermediate 14)
10.0g of 1-bromo-4-fluoronaphthalene, 5.70g of phenylboronic acid, 2.05g of tetrakis (triphenylphosphine) palladium (0), 9.50g of sodium carbonate, 360mL of 1, 4-dioxane, and 45mL of ion-exchanged water were charged into a flask under an argon atmosphere, and stirred at reflux at 110 ℃ for 6 hours. Then transferred to a separatory funnel and extracted with toluene. The solution was dried over anhydrous magnesium sulfate, concentrated, and the residue was purified by silica gel column chromatography to give 7.28g (yield 74%) of 1-fluoro-4-phenylnaphthalene (intermediate 14).
(2) Synthesis of (1-fluoro-4-phenylnaphthalen-2-yl) boronic acid (intermediate 15)
Under argon atmosphere, 4.99g of 2,2,6, 6-Tetramethylpiperidine (TMP) and 120mL of tetrahydrofuran (dehydrated) were put into a flask,cooled to-78 ℃. 16mL of n-BuLi (1.60M in hexane) was added thereto, followed by stirring at-78 ℃ for 30 minutes. Then cooling to-69 ℃, adding (A)iPrO)3B12.0 mL, at-78 degrees C stirring for 5 minutes, dropwise add dissolved 1-fluoro-4-phenyl naphthalene (intermediate 14)5.40g THF solution 50mL, in ice bath stirring for 4 hours. After completion of the reaction, 1N HCl aq (100mL) was added, and the mixture was stirred at room temperature for 1 hour. Then transferred to a separatory funnel and extracted with ethyl acetate. The solution was dried over anhydrous magnesium sulfate, concentrated, and washed with hexane to obtain 2.66g (1-fluoro-4-phenylnaphthalen-2-yl) boronic acid (intermediate 15) (yield 41%).
(3) Synthesis of 2- (2, 6-dimethoxyphenyl) -1-fluoro-4-phenylnaphthalene (intermediate 16)
3.91g of 1-bromo-2, 6-dimethoxybenzene, 2.66g of (1-fluoro-4-phenylnaphthalen-2-yl) boronic acid (intermediate 15), 0.46g of tetrakis (triphenylphosphine) palladium (0), 2.12g of sodium carbonate, 90mL of toluene and 10mL of water were added to a flask under an argon atmosphere, and the mixture was heated under reflux at 100 ℃ for 6 hours with stirring. After cooling to room temperature, the reaction solution was extracted with toluene, the aqueous layer was removed, and the organic layer was washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate, concentrated, and the residue was purified by silica gel column chromatography to give 2.44g (yield 68%) of 2- (2, 6-dimethoxyphenyl) -1-fluoro-4-phenylnaphthalene (intermediate 16).
(4) Synthesis of 2- (1-fluoro-4-phenylnaphthalen-2-yl) benzene-1, 3-diol (intermediate 17)
Under an argon atmosphere, 2.44g of 2- (2, 6-dimethoxyphenyl) -1-fluoro-4-phenylnaphthalene (intermediate 16) and 70mL of methylene chloride (dehydrated) were added to the flask, and cooled to 0 ℃. To this was added 1.0mol/L boron tribromide (BBr)3) The dichloromethane solution (14 mL) was stirred at room temperature for 4 hours. After the reaction was completed, the solution was cooled to-78 ℃ and carefully deactivated with methanol, and further deactivated with a sufficient amount of water. The solution was transferred to a separatory funnel, extracted with dichloromethane, dried over anhydrous sodium sulfate, and then the origin impurity was removed by passing through a short column of silica gel, the solution was concentrated, and the obtained sample was dried under vacuum at room temperature for 3 hours to obtain 1.62g (72%) of 2- (1-fluoro-4-phenylnaphthalen-2-yl) benzene-1, 3-diol (intermediate 17) as a white solid.
(5) Synthesis of 5-phenylnaphtho [1,2-b ] benzofuran-7-ol (intermediate 18)
2.00g of 2- (1-fluoro-4-phenylnaphthalen-2-yl) benzene-1, 3-diol (intermediate 17), 200mL of N-methyl-2-pyrrolidone (NMP) (dehydration), and K under an argon atmosphere2CO31.30g was added to the flask, followed by stirring at 150 ℃ for 2 hours. After the reaction was completed, the solution was cooled to room temperature, ethyl acetate (200mL) was added, and the mixture was transferred to a separatory funnel and washed with water. The organic phase was dried over anhydrous sodium sulfate and purified by silica gel column chromatography to give 5-phenylnaphtho [1,2-b ]]0.59g of benzofuran-7-ol (intermediate 18) as a white solid (yield 31%).
(6) Synthesis of 5-phenylnaphtho [1,2-b ] benzofuran-7-yl trifluoromethanesulfonate (intermediate 19)
Under an argon atmosphere, 1.06g of 5-phenylnaphtho [1,2-b ] benzofuran-7-ol (intermediate 18), 40mg of N, N-dimethyl-4-aminopyridine (DMAP), 0.70mL of trifluoromethanesulfonic anhydride and 30mL of dichloromethane (dehydrated) were added to a flask and cooled to 0 ℃. 3.0mL of pyridine (dehydrated) was added dropwise, followed by stirring at room temperature for 2 hours. After the reaction is completed, it is deactivated with a sufficient amount of water. The solution was transferred to a separatory funnel, extracted with dichloromethane, dried over anhydrous sodium sulfate, and then the origin impurity was removed by passing through a short column of silica gel, the solution was concentrated, and the resulting sample was dried under vacuum at room temperature for 3 hours to give 1.26g (83%) of 5-phenylnaphtho [1,2-b ] benzofuran-7-yl trifluoromethanesulfonate (intermediate 19) as a white solid.
(7) Synthesis of Anthracene derivative (Compound BH-18)
0.33g of 5-phenylnaphtho [1,2-b ] benzofuran-7-ol (intermediate 19), 0.34g of 10-phenylanthracene-9-boronic acid synthesized by a known method, 0.14g of tris (dibenzylideneacetone) dipalladium (0), 0.12g of 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl (SPhos), 0.17g of cesium fluoride, and 8mL of toluene (dehydrated) were added to a flask under an argon atmosphere, and stirred at 100 ℃ under reflux for 4 hours. After cooling to room temperature, the precipitated solid was collected by filtration. The obtained solid was washed with water, followed by acetone and reprecipitation from a mixed solvent of hexane and ethyl acetate to obtain 0.10g of a white solid. The mass spectrometry of this white solid gave compound BH-18, with m/e =547, relative to molecular weight of 546.67.
Synthesis example 8: synthesis of Compound BH-19
Compound BH-19 was synthesized according to the following synthetic route.
[ solution 117]
(1) Synthesis of 9- ([1,1 ': 2', 1 "-terphenyl ] -4' -yl) anthracene (intermediate 20)
Under an argon atmosphere, 4 '-iodo-1, 1': 7.12g of 2', 1' -terphenyl, 4.89g of 9-anthraceneboronic acid, 0.28g of dichlorobis [ di-tert-butyl (4-dimethylaminophenyl) phosphine ] palladium (II), 6.36g of sodium carbonate, 100mL of 1, 4-dioxane and 30mL of water were charged into a flask, and the mixture was heated under reflux and stirred at 110 ℃ for 7 hours. After cooling to room temperature, the reaction solution was extracted with toluene, the aqueous layer was removed, and the organic layer was washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate, concentrated, and the residue was purified by silica gel column chromatography to give 9- ([1,1 ': 2', 1 "-terphenyl ] -4' -yl) anthracene (intermediate 20)9.44g (yield 85%).
(2) Synthesis of 9- ([1,1 ': 2', 1 "-terphenyl ] -4' -yl) -10-bromoanthracene (intermediate 21)
Under an argon atmosphere, 3.00g of 9- ([1,1 ': 2', 1 "-terphenyl ] -4' -yl) anthracene (intermediate 20) and 37mL of methylene chloride were added to the flask. 1.25g of N-bromosuccinimide (NBS) was added thereto, followed by stirring at room temperature for 5 hours. The reaction solution was extracted with dichloromethane, the aqueous layer was removed, and the organic layer was washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate, concentrated, and the residue was purified by silica gel column chromatography, the solution was concentrated, and the obtained sample was dried under vacuum at room temperature for 3 hours to obtain 2.14g of 9- ([1,1 ': 2', 1 "-terphenyl ] -4' -yl) -10-bromoanthracene (intermediate 21) (yield 60%).
(3) Synthesis of 2- (10- ([1,1 ': 2', 1 "-terphenyl ] -4' -yl) anthracen-9-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan (intermediate 22)
Under an argon atmosphere, 2.43g of 9- ([1,1 ': 2', 1 "-terphenyl ] -4' -yl) -10-bromoanthracene (intermediate 21) and 75mL of tetrahydrofuran (dehydrated) were added to the flask, and cooled to-78 ℃. 3.8mL of n-BuLi (1.57M in hexane) was added thereto, followed by stirring at-78 ℃ for 4 minutes. Subsequently, 2.4mL of 2-methoxy-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborolane was added dropwise thereto, and the mixture was stirred at-78 ℃ for 4 hours. After completion of the reaction, 1N HCl aq (30mL) was added, and the mixture was stirred at room temperature for 1 hour. Then transferred to a separatory funnel and extracted with dichloromethane. The solution was dried over anhydrous sodium sulfate, concentrated, and the residue was purified by silica gel column chromatography, the solution was concentrated, and the obtained sample was dried under vacuum at room temperature for 3 hours to obtain 2.04g (yield 76%) of 2- (10- ([1,1 ': 2', 1 "-terphenyl ] -4' -yl) anthracen-9-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan (intermediate 22).
(4) Synthesis of Anthracene derivative (Compound BH-19)
4.01g of naphtho [1,2-b ] benzofuran-7-yl trifluoromethanesulfonate (intermediate 5), 5.34g of 2- (10- ([1,1 ': 2', 1 "-terphenyl ] -4' -yl) anthracen-9-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan (intermediate 22), 0.23g of tetrakis (triphenylphosphine) palladium (0), 1.38g of sodium carbonate, 150mL of 1, 4-dioxane, and 50mL of ion-exchange water were added to a flask under an argon atmosphere, and stirred at 110 ℃ under reflux for 4 hours. After cooling to room temperature, the precipitated solid was collected by filtration. The obtained solid was washed with water, followed by methanol and then with a mixed solvent of isopropanol and toluene, to obtain 2.49g of a white solid. The mass spectrometry of this white solid gave compound BH-19, with m/e =623, relative to molecular weight 622.77.
Synthesis example 9: synthesis of Compound BH-20
Compound BH-20 was synthesized according to the following synthetic route.
[ chemical formula 118]
(1) Synthesis of 1- (2, 6-dimethoxyphenyl) -2-methoxynaphthalene (intermediate 23)
20.0g of 2- (2-methoxynaphthalen-1-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan, 39.3g of 2-bromo-1, 3-dimethoxybenzene, 2.07g of palladium acetate, 13.2g of 2-dicyclohexylphosphino-2 ', 4',6' -triisopropylbiphenyl (XPhos), 58.7g of tripotassium phosphate and 90mL of tetrahydrofuran (dehydrated) were added to a flask under an argon atmosphere, and stirred under reflux for 5 hours. After cooling to room temperature, the reaction solution was extracted with toluene, the aqueous layer was removed, and the organic layer was washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate, concentrated, and the residue was purified by silica gel column chromatography to give 12.2g (yield: 45%) of 1- (2, 6-dimethoxyphenyl) -2-methoxynaphthalene (intermediate 23).
(2) Synthesis of 2- (1-hydroxynaphthalen-2-yl) benzene-1, 3-diol (intermediate 24)
12.1g of 1- (2, 6-dimethoxyphenyl) -2-methoxynaphthalene (intermediate 24) and 520mL of methylene chloride (dehydrated) were added to a flask under an argon atmosphere and cooled to 0 ℃. 156mL of a 1.0mol/l solution of boron tribromide in methylene chloride was added, followed by stirring at room temperature for 4 hours. After the reaction was completed, the solution was cooled to-78 ℃ and carefully deactivated with methanol, and further deactivated with a sufficient amount of water. The solution was transferred to a separatory funnel, extracted with dichloromethane, dried over anhydrous sodium sulfate, and then the origin impurity was removed by passing through a short column of silica gel, the solution was concentrated, and the obtained sample was dried under vacuum at room temperature for 3 hours to obtain 9.83g (95%) of 2- (1-hydroxynaphthalen-2-yl) benzene-1, 3-diol (intermediate 24) as a white solid.
(3) Synthesis of naphtho [2,1-b ] benzofuran-11-ol (intermediate 25)
4.47g of 2- (1-hydroxynaphthalen-2-yl) benzene-1, 3-diol (intermediate 24) and p-toluenesulfonic acid monohydrate (TsOH seed H)2O)6.20g and 350mL of toluene were put into the flask, and then heated under reflux at 100 ℃ for 8 hours with stirring. After the reaction was completed, the solution was cooled to room temperature and further deactivated with a sufficient amount of water. The solution was transferred to a separatory funnel, extracted with toluene, dried over anhydrous sodium sulfate, passed through a short column of silica gel to remove impurities at the origin, the solution was concentrated, and the resulting sample was dried under vacuum at room temperature for 3 hours to give naphtho [2,1-b ]]Benzofuran-11-ol (intermediate 25) as a white solid 2.41g (58%).
(4) Synthesis of naphtho [2,1-b ] benzofuran-11-yl trifluoromethanesulfonate (intermediate 26)
Under argon atmosphere, naphtho [2,1-b ] is added]Benzofuran-11-ol (intermediate 25)3.56g, N-dimethyl-4-aminopyridine 0.186g, trifluoromethanesulfonic anhydride (Tf)2O)3.07mL, and methylene chloride (dehydrated) 80mL were added to the flask, and cooled to 0 ℃. Pyridine (dehydrated) 30.4mL was added dropwise, followed by stirring at room temperature for 2 hours. After the reaction is completed, it is deactivated with a sufficient amount of water. The solution was transferred to a separatory funnel, extracted with dichloromethane, dried over anhydrous sodium sulfate, passed through a short column of silica gel to remove origin impurities, the solution was concentrated, and the resulting sample was dried under vacuum at room temperature for 3 hours to give naphtho [2,1-b ]]Benzofuran-11-yl trifluoromethanesulfonate (intermediate 26) as a white solid 2.88g (52%).
(5) Synthesis of Anthracene derivative (Compound BH-20)
1.05g of naphtho [2,1-b ] benzofuran-11-yl trifluoromethanesulfonate (intermediate 26), 1.22g of (3- (10- (naphthalen-1-yl) anthracen-9-yl) phenyl) boronic acid synthesized by a known method, 0.133g of tetrakis (triphenylphosphine) palladium (0), 0.609g of sodium carbonate, 22mL of 1, 4-dioxane, and 7mL of ion-exchanged water were charged into a flask under an argon atmosphere, and stirred under reflux at 110 ℃ for 4 hours. After cooling to room temperature, the precipitated solid was collected by filtration. The obtained solid was washed with water and acetone, and then recrystallized from a mixed solvent of toluene and hexane to obtain 1.41g of a white solid. The mass spectrometry of this white solid resulted in compound BH-20, with m/e =597 relative to molecular weight 596.73.
While several embodiments and/or examples of the present invention have been described in detail above, those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments and/or examples without materially departing from the novel teachings and effects of this invention. Accordingly, such further modifications are also included within the scope of the present invention.
The contents of the documents described in the present specification and the application based on the priority of the paris convention in the present application are incorporated herein by reference in their entirety.