Patent Grant
9947879
The invention relates to an anthracene derivative, an organic electroluminescence device using the same and an electronic appliance comprising the same.
An organic electroluminescence (EL) device is regarded as a promising solid-emitting large-area full color display device, and various developments have been conducted so far. In general, an organic EL device comprises an emitting layer and a pair of opposing electrodes that sandwich the emitting layer. When an electrical field is applied between the both electrodes, electrons are injected from the cathode and holes are injected from the anode. Further, these electrons are re-combined with the holes in the emitting layer, create an excited state, and energy is emitted as light when the excited state is returned to the ground state.
Conventional organic EL devices had a high driving voltage as compared with inorganic emitting diodes, and hence, the luminance and the luminous efficiency were low. In addition, conventional organic EL devices suffered significant deterioration in properties, and hence, practical application thereof has not been realized yet. Although gradual improvements have been attained in recent organic EL devices, there is an increasing demand for further improvements in luminous efficiency or the like.
With improvements in organic EL emitting materials, performance of an organic EL device has been gradually improved. Improvement in luminous efficiency in an organic EL device is an important subject that leads to lowering in consumption power or improvement in durability of a display. Although improvements have been attained by various researches so far, further improvements have been required.
In order to solve these problems, Patent Documents 1 to 6 disclose an organic EL device in which an anthracene derivative having dibenzofuran as a substituent is used as an emitting material.
Further, Patent Documents 4, 7 to 11 disclose an emitting material having a naphthobenzofuran structure or a naphthobenzothiophene structure. Although use of these materials leads to improvement in luminous efficiency, further improvement in efficiency has been required.
Patent Document 1: JP-A-H11-111460
Patent Document 2: JP-A-2005-314239
Patent Document 3: JP-A-2007-63501
Patent Document 4: WO06/128800
Patent Document 5: WO05/113531
Patent Document 6: WO08/143229
Patent Document 7: WO07/140847
Patent Document 8: WO08/6449
Patent Document 9: WO10/137285
Patent Document 10: JP-T-2012-503027
Patent Document 11: Korean Patent Publication No. 2012-0104067
An object of the invention is to provide a material capable of producing a low-voltage and high-efficient organic electroluminescence device.
According to one aspect of the invention, an anthracene derivative represented by the following formula (1) is provided.
wherein in the formula (1), R1 to R8 are independently selected from a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkyl group including 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group including 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group including 6 to 30 carbon atoms that form a ring (hereinafter referred to as “ring carbon atoms”), a substituted or unsubstituted arylthio group including 6 to 30 ring carbon atoms, a substituted or unsubstituted alkylsilyl group including 3 to 60 carbon atoms, a substituted or unsubstituted arylsilyl group including 8 to 60 carbon atoms, a substituted or unsubstituted aryl group including 6 to 30 ring carbon atoms and a substituted or unsubstituted heterocyclic group including 5 to 30 atoms that form a ring (hereinafter referred to as “ring atoms”).
L1 is selected from a single bond and a linking group, and the linking group is selected from a divalent arylene group, a divalent heterocyclic group and a group formed by linking of 2 to 4 divalent arylene groups and/or divalent heterocyclic groups.
Ar1 is selected from the following formulas (2) and (3).
In the formulas (2) and (3), X is selected form an oxygen atom and a sulfur atom.
In the formula (2), any one of R11 to R14 is used for bonding to L1. R11 to R14 that are not used for bonding to L1 and R15 to R20 are the same as R1 to R8.
In the formula (3), any one of R21 to R24 is used for bonding to L1. R21 to R24 that are not used for bonding to L1 and R25 to R30 are the same as R1 to R8.
Ar2 is selected from a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms and a substituted or unsubstituted heterocyclic group including 5 to 50 ring atoms.
Among R1 to R8, R11 to R20, R21 to R30, L1 and Ar2, adjacent groups may be bonded with each other to form a ring.
According to the invention, a material capable of producing a low-voltage and high-efficient organic electroluminescence device can be provided.
The anthracene derivative according to one aspect of the invention is represented by the following formula (1).
wherein in the formula (1), R1 to R8 are independently selected from a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkyl group including 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group including 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group including 6 to 30 ring carbon atoms, a substituted or unsubstituted arylthio group including 6 to 30 ring carbon atoms, a substituted or unsubstituted alkylsilyl group including 3 to 60 carbon atoms, a substituted or unsubstituted arylsilyl group including 8 to 60 carbon atoms, a substituted or unsubstituted aryl group including 6 to 30 ring carbon atoms and a substituted or unsubstituted heterocyclic group including 5 to 30 ring atoms.
L1 is selected from a single bond and a linking group, and the linking group is selected from a divalent arylene group, a divalent heterocyclic group and a group formed by linking of 2 to 4 divalent arylene groups and/or divalent heterocyclic groups.
Ar1 is selected from the following formulas (2) and (3).
In the formulas (2) and (3), X is selected form an oxygen atom and a sulfur atom.
In the formula (2), any one of R11 to R14 is used for bonding to L1. R11 to R14 that are not used for bonding to L1 and R15 to R20 are the same as R1 to R8.
In the formula (3), any one of R21 to R24 is used for bonding to L1. R21 to R24 that are not used for bonding to L1 and R25 to R30 are the same as R1 to R8.
Ar2 is selected from a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms and a substituted or unsubstituted heterocyclic group including 5 to 50 ring atoms.
Among R1 to R8, R11 to R20, R21 to R30, L1 and Ar2, adjacent groups may be bonded with each other to form a ring.
As stated in Patent Document 9, the substituents represented by the formulas (2) and (3) are substituents contributing to an increase in efficiency of an organic EL device. The invention has been completed based on a finding that, an organic EL device that can exhibit a luminous efficiency that is equivalent to or larger than that of Patent Document 9 can be driven at a lower voltage by specifying these substituents and the bonding position on the anthracene skeleton.
In the above-mentioned compound, by the bonding of the group represented by the formula (2) or (3) and an anthracene derivative at a specific position, intermolecular packing is improved due to the widening of the planarity of molecules, whereby electron-injecting/transporting performance is improved. Accordingly, when used in an organic EL device or the like, it can lower the driving voltage or improve the efficiency.
As the substituent represented by the formula (3), a substituent represented by the following formula (3′) or the like can be given,
wherein in the formula (3′), any one of R31 to R34 is used for bonding to L1. R31 to R34 that are not used for bonding to L1 and R35 to R42 are the same as R1 to R8.
In the formula (2), R12 or R13 among R11 to R14 is preferably used for bonding to L1. In the formula (3), R22 or R23 among R21 to R24 is preferably used for bonding to L1.
That is, the above-mentioned anthracene derivative is preferably represented by any of the following formulas (4) to (7).
wherein in the formulas (4) to (7), R1 to R8, L1, X, R11 to R20, R21 to R30 and Ar2 are as defined in the formula (1).
In the formula (3′), R32 or R33 among R31 to R34 is preferably used for bonding to L1. That is, the above-mentioned anthracene derivative is preferably represented by any of the following formula (6′) or (7′).
wherein in the formulas (6′) and (7′), R1 to R8, L1, X, R31 to R42 and Ar2 are as defined in the formula (1).
In the formula (1), Ar2 is preferably a substituted or unsubstituted aryl group.
R1 to R8 are preferably a hydrogen atom.
L1 is preferably a single bond or a substituted or unsubstituted divalent arylene group.
In formulas (2), (3) and (3′), X is preferably an oxygen atom.
In the formula (2), R11 to R14 that are not used for bonding to L1 and R15 to R20 are preferably independently a hydrogen atom.
In the formula (3), R21 to R24 that are not used for bonding to L1 and R25 to R30 are preferably independently a hydrogen atom.
In the formula (3′), R31 to R34 that are not used for bonding to L1 and R35 to R42 are preferably independently a hydrogen atom.
The above-mentioned anthracene derivative is preferably represented by any of the following formulas (8) to (11).
wherein in the formulas (8) to (11), R1 to R8, X, R11 to R20, R21 to R30 and Ar2 are as defined in the formula (1).
The above-mentioned anthracene derivative is preferably represented by any of the following formulas (12) to (15).
wherein in the formulas (12) to (15), R1 to R3, X, R11 to R20, R21 to R30 and Ar2 are as defined in the formula (1).
The above-mentioned anthracene derivative is preferably represented by any of the following formulas (10′), (11′), (14′) and (15′).
wherein in the formulas (10′), (11′), (14′) and (15′), R, to R2, X, R31 to R42, and Ar2 are as defined in the formula (1).
In this specification, the “ring carbon atoms” means carbon atoms that constitute a saturated ring, an unsaturated ring or an aromatic ring. The “ring atoms” means carbon atoms and hetero atoms that constitute a hetero ring (including a saturated ring, an unsaturated ring and an aromatic ring).
In this specification, the “a to b carbon atoms” in the “substituted or unsubstituted XX group including a to b carbon atoms” mean the number of carbon atoms when the XX group is unsubstituted, and does not include the number of carbon atoms of the substituent when the XX group is substituted.
As the substituent of the “substituted or unsubstituted”, unless otherwise indicated, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, a silyl group, a substituted silyl group, an alkoxy group, an aryloxy group, an arylthio group, an aryl group, a heterocyclic group, a halogenated alkyl group, a hydroxyl group, a nitro group, a carboxy group, an aralkyl group, or the like (mentioned later), can be given.
The “unsubstituted” in the “substituted or unsubstituted” means that the group is not substituted by the above-mentioned substituent and a hydrogen atom is bonded.
In the invention, the hydrogen atom includes isomers differing in the number of neutrons, i.e. protium, deuterium and tritium.
As for R1 to R3, L1, R11 to R20, R21 to R30, R31 to R42, Ar2 and each substituent in the “substituted or unsubstituted”, a detailed explanation will be given below.
As the halogen atom, fluorine, chlorine, bromine, iodine or the like can be given, and fluorine is preferable. As the halogenated alkyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a trifluoromethyl group or the like can be given.
As the amino group, one represented by —NHRw or —N(Rw)2 can be given. As examples of the Rw, an aryl group including 6 to 30 ring carbon atoms (mentioned later) can be mentioned. In particular, a phenylamino group is preferable.
As the alkyl group including 1 to 20 (preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 4) carbon atoms, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group or the like can be mentioned. Further, the alkyl group may be an alkyl group substituted by an aryl group mentioned later, that is, a substituent obtained by combining an alkylene group and an aryl group (for example, a phenylmethyl group, a 2-phenylisopropyl group or the like).
The number of carbon atoms is preferably 1 to 10, with 1 to 6 being further preferable. Among these alkyl groups, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group and an n-hexyl group are preferable.
As the cycloalkyl group, a cycloalkyl group including 3 to 20 (preferably 3 to 10, more preferably 3 to 8) ring carbon atoms can be given. For example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, an adamantyl group, a norbornyl group or the like can be given.
The alkoxy group including 1 to 20 (preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 4) carbon atoms is a group represented by —OY. As examples of Y, examples of the above-mentioned alkyl group can be given. The alkoxy group is a methoxy group or an ethoxy group, for example.
As the aryl group including 6 to 50 (preferably 6 to 30, more preferably 6 to 20, and particularly preferably 6 to 12) ring carbon atoms, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, a 9-phenanthryl group, a 1-naphthacenyl group, a 2-naphthacenyl group, a 9-naphthacenyl group, a 1-pyrenyl group, a 2-pyrenyl group, a 4-pyrenyl group, a 6-chrycenyl group, a 1-benzo[c]phenanthryl group, a 2-benzo[c]phenanthryl group, a 3-benzo[c]phenanthryl group, a 4-benzo[c]phenanthryl group, a 5-benzo[c]phenanthryl group, a 6-benzo[c]phenanthryl group, a 1-benzo[g]chrycenyl group, a 2-benzo[g]chrycenyl group, a 3-benzo[g]chrycenyl group, a 4-benzo[g]chrycenyl group, a 5-benzo[g]chrycenyl group, a 6-benzo[g]chrycenyl group, a 7-benzo[g]chrycenyl group, a 8-benzo[g]chrycenyl group, a 9-benzo[g]chrycenyl group, a 10-benzo[g]chrycenyl group, a 11-benzo[g]chrycenyl group, a 12-benzo[g]chrycenyl group, a 13-benzo[g]chrycenyl group, a 14-benzo[g]chrycenyl group, a 1-benzo[a]anthryl group, a 2-benzo[a]anthryl group, a 3-benzo[a]anthryl group, a 4-benzo[a]anthryl group, a 5-benzo[a]anthryl group, a 6-benzo[a]anthryl group, a 7-benzo[a]anthryl group, a 8-benzo[a]anthryl group, a 9-benzo[a]anthryl group, a 10-benzo[a]anthryl group, a 11-benzo[a]anthryl group, a 12-benzo[a]anthryl group, a 13-benzo[a]anthryl group, a 14-benzo[a]anthryl group, a 1-triphenyl group, a 2-triphenyl group, a 1-fluorenyl group, a 2-fluorenyl group, a 3-fluorenyl group, a 4-fluorenyl group, a benzofluorenyl group, a dibenzofluorenyl group, a 2-biphenylyl group, a 3-biphenylyl group, a 4-biphenylyl group, a p-terphenyl-4-yl group, a p-terphenyl-3-yl group, a p-terphenyl-2-yl group, a m-terphenyl-4-yl group, a m-terphenyl-3-yl group, a m-terphenyl-2-yl group, or the like can be given.
A phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, a 9-phenanthryl group, a 1-fluorenyl group, a 2-fluorenyl group, a 3-fluorenyl group, a 4-fluorenyl group, a 5-benzo[c]phenanthryl group, a 4-benzo[a]anthryl group, a 7-benzo[a]anthryl group, a 1-triphenyl group and a 2-triphenyl group are preferable.
As for the 1-fluorenyl group, the 2-fluorenyl group, the 3-fluorenyl group and the 4-fluorenyl group, it is preferred that the carbon atom at the 9th position be substituted by the substituted or unsubstituted alkyl group including 1 to 20 carbon atoms or the substituted or unsubstituted aryl group including 6 to 18 carbon atoms.
In the specification, the aryl group (aromatic hydrocarbon) is a hydrocarbon composed of an aromatic single ring (non-fused aryl group) or a plurality of rings (fused aryl group).
The fused aryl group is, among the above-mentioned aryl groups, a group obtained by fusing of two or more ring structures. The non-fused aryl group is a group, among the above-mentioned aryl groups, other than the fused aryl groups.
As the fused aryl group, a fused aryl group including 10 to 50 (preferably 10 to 30, more preferably 10 to 20) ring carbon atoms can be given. Among the specific examples of the above-mentioned aryl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, a 9-phenanthryl group, a 1-naphthacenyl group, a 2-naphthacenyl group, a 9-naphthacenyl group, a 1-pyrenyl group, a 2-pyrenyl group, a 4-pyrenyl group, a 6-chrysenyl group, a 5-benzo[c]phenanthryl group, a 4-benzo[a]anthryl group, a 7-benzo[a]anthryl group, a 1-triphenyl group, a 2-triphenyl group or the like can be given, for example.
Among these, a 1-naphthyl group, a 2-naphthyl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, a 9-phenanthryl group, a 5-benzo[c]phenanthryl group, a 4-benzo[a]anthryl group, a 7-benzo[a]anthryl group, a 1-triphenyl group and a 2-triphenyl group are preferable.
As the divalent arylene group, a group obtained by removing two hydrogen atoms from the above-mentioned aryl group can be mentioned.
The aryloxy group including 6 to 30 (preferably 6 to 20, more preferably 6 to 12) ring carbon atoms is a group represented by —OAr. As examples of Ar, the same aryl groups as those mentioned above can be given. The aryloxy group is a phenoxy group, for example.
The arylthio group including 6 to 30 (preferably 6 to 20, more preferably 6 to 12) ring carbon atoms is a group represented by —SAr. As examples of Ar, the same aryl groups as those mentioned above can be given.
As the heterocyclic group including 5 to 50 (preferably 5 to 30, more preferably 5 to 30, and particularly preferably 5 to 12) ring atoms, a 1-pyrrolyl group, a 2-pyrrolyl group, a 3-pyrrolyl group, a pyrazinyl group, a 2-pyridinyl group, a 3-pyridinyl group, a 4-pyridinyl group, a 1-indolyl group, a 2-indolyl group, a 3-indolyl group, a 4-indolyl group, a 5-indolyl group, a 6-indolyl group, a 7-indolyl group, a 1-isoindolyl group, a 2-isoindolyl group, a 3-isoindolyl group, a 4-isoindolyl group, a 5-isoindolyl group, a 6-isoindolyl group, a 7-isoindoly group, a 2-furyl group, a 3-furyl group, a 2-benzofuranyl group, a 3-benzofuranyl group, a 4-benzofuranyl group, a 5-benzofuranyl group, a 6-benzofuranyl group, a 7-benzofuranyl group, a 1-isobenzofuranyl group, a 3-isobenzofuranyl group, a 4-isobenzofuranyl group, a 5-isobenzofuranyl group, a 6-isobenzofuranyl group, a 7-isobenzofuranyl group, a 1-dibenzoisofuranyl group, a 2-dibenzofuranyl group, a 3-dibenzofuranyl group, a 4-dibenzofuranyl group, a 1-dibenzothiophenyl group, a 2-dibenzothiophenyl group, a 3-dibenzothiophenyl group, a 4-dibenzothiophenyl group, a quinolyl group, a 3-quinolyl group, a 4-quinolyl group, a 5-quinolyl group, a 6-quinolyl group, a 7-quinolyl group, a 8-quinolyl group, a 1-isoquinolyl group, a 3-isoquinolyl group, a 4-isoquinolyl group, a 5-isoquinolyl group, a 6-isoquinolyl group, a 7-isoquinolyl group, a 8-isoquinolyl group, a 2-quinoxalynyl group, a 5-quinoxalynyl group, a 6-quinoxalynyl group, a 1-carbazolyl group, a 2-carbazolyl group, a 3-carbazolyl group, a 4-carbazolyl group, a 9-carbazolyl group, a 1-phenanthridinyl group, a 2-phenanthridinyl group, a 3-phenanthridinyl group, a 4-phenanthridinyl group, a 6-phenanthridinyl group, a 7-phenanthridinyl group, a 8-phenanthridinyl group, a 9-phenanthridinyl group, a 10-phenanthridinyl group, a 1-acridinyl group, a 2-acridinyl group, a 3-acridinyl group, a 4-acridinyl group, a 9-acridinyl group, a 1,7-phenanthrolin-2-yl group, a 1,7-phenanthrolin-3-yl group, a 1,7-phenanthrolin-4-yl group, a 1,7-phenanthrolin-5-yl group, a 1,7-phenanthrolin-6-yl group, a 1,7-phenanthrolin-8-yl group, a 1,7-phenathrolin-9-yl group, a 1,7-phenanthrolin-10-yl group, a 1,8-phenanthrolin-2-yl group, a 1,8-phenanthrolin-3-yl group, a 1,8-phenanthrolin-4-yl group, a 1,8-phenanthrolin-5-yl group, a 1,8-phenanthrolin-6-yl group, a 1,8-phenanthrolin-7-yl group, a 1,8-phenanthrolin-9-yl group, a 1,8-phenanthrolin-10-yl group, a 1,9-phenanthrolin-2-yl group, a 1,9-phenathrolin-3-yl group, a 1,9-phenanthrolin-4-yl group, a 1,9-phenanthrolin-5-yl group, a 1,9-phenanthrolin-6-yl group, a 1,9-phenanthrolin-7-yl group, a 1,9-phenanthrolin-8-yl group, a 1,9-phenanthrolin-10-yl group, 1,10-phenanthrolin-2-yl group, a 1,10-phenanthrolin-3-yl group, a 1,10-phenanthrolin-4-yl group, a 1,10-phenanthrolin-5-yl group, a 2,9-phenanthrolin-1-yl group, a 2,9-phenanthrolin-3-yl group, a 2,9-phenanthrolin-4-yl group, a 2,9-phenanthrolin-5-yl group, a 2,9-phenanthrolin-6-yl group, a 2,9-phenanthrolin-7-yl group, a 2,9-phenanthrolin-8-yl group, a 2,9-phenanthrolin-10-yl group, a 2,8-phenanthrolin-1-yl group, a 2,8-phenanthrolin-3-yl group, a 2,8-phenanthoroin-4-yl group, a 2,8-phenanthrolin-5-yl group, a 2,8-phenanthrolin-6-yl group, a 2,8-phenanthrolin-7-yl group, a 2,8-phenanthrolin-9-yl group, a 2,8-phenanthrolin-10-yl group, a 2,7-phenanthrolin-1-yl group, a 2,7-phenanthrolin-3-yl group, a 2,7-phenanthrolin-4-yl group, a 2,7-phenanthrolin-5-yl group, a 2,7-phenanthrolin-6-yl group, a 2,7-phenanthrolin-8-yl group, a 2,7-phenanthrolin-9-yl group, a 2,7-phenanthrolin-10-yl group, a 1-phenazinyl group, a 2-phenazinyl group, a 1-phenothiazinyl group, a 2-phenothiazinyl group, a 3-phenothiazinyl group, a 4-phenothiazinyl group, a 10-phenothiazinyl group, a 1-phenoxazinyl group, a 2-phenoxazinyl group, a 3-phenoxazinyl group, a 4-phenoxazinyl group, a 10-phenoxazinyl group, a 2-oxazolyl group, a 4-oxazolyl group, a 5-oxazolyl group, a 2-oxadiazolyl group, a 5-oxadiazolyl group, a 3-furazanyl group, a 2-thienyl group, a 3-thienyl group, a 2-methylpyrrole-1-yl group, a 2-methylpyrrole-3-yl group, a 2-methylpyrrole-4-yl group, a 2-methylpyrrole-5-yl group, a 3-methylpyrrole-1-yl group, a 3-methylpyrrole-2-yl group, a 3-methylpyrrole-4-yl group, a 3-methylpyrrole-5-yl group, a 2-t-butylpyrrole-4-yl group, a 3-(2-phenylpropyl)pyrrole-1-yl group, a 2-methyl-1-indolyl group, a 4-methyl-1-indolyl group, a 2-methyl-3-indoyl group, a 4-methyl-3-indolyl group, a 2-t-butyl-1-indolyl group, a 4-t-butyl-1-indolyl group, a 2-t-butyl-3-indolyl group, a 4-t-butyl-3-indolyl group, a 1-benzimidazolyl group, a 2-benzimidazolyl group, a 4-benzimidazolyl group, a 5-benzimidazolyl group, a 6-benzimidazolyl group, a 7-benzimidazolyl group, a 2-imidazo[1,2-a]pyridinyl group, a 3-imidazo[1,2-a]pyridinyl group, a 5-imidazo[1,2-a]pyridinyl group, a 6-imidazo[1,2-a]pyridinyl group, a 7-imidazo[1,2-a]pyridinyl group, a 8-imidazo[1,2-a]pyridinyl group, a benzimidazol-2-one-1-yl group, a benzimidazol-2-one-3-yl group, a benzimidazol-2-one-4-yl group, a benzimidazol-2-one-5-yl group, a benzimidazol-2-one-6-yl group, a benzimidazol-2-one-7-yl group or the like can be given.
Among these, a 1-dibenzofuranyl group, a 2-dibenzofuranyl group, a 3-dibenzofuranyl group, a 4-dibenzofuranyl group, a 1-dibenzothiophenyl group, a 2-dibenzothiophenyl group, a 3-dibenzothiophenyl group, a 4-dibenzothiophenyl group, a 1-carbazolyl group, a 2-carbazolyl group, a 3-carbazolyl group, a 4-carbazolyl group, a 9-carbazolyl group, a 1-benzimidazolyl group, a 2-benzimidazolyl group, a 4-benzimidazolyl group, a 5-benzimidazolyl group, a 6-benzimidazolyl group, a 7-benzimidazolyl group, a 2-imidazo[1,2-a]pyridinyl group, a 3-imidazo[1,2-a]pyridinyl group, a 5-imidazo[1,2-a]pyridinyl group, a 6-imidazo[1,2-a]pyridinyl group, a 7-imidazo[1,2-a]pyridinyl group, a 8-imidazo[1,2-a]pyridinyl group, a 2-pyridinyl group, a 3-pyridinyl group, a 4-pyridinyl group, a 1,10-phenanthrolin-2-yl group, a 1,10-phenanthrolin-3-yl group, a 1,10-phenanthrolin-4-yl group, a 1,10-phenanthrolin-5-yl group, a benzoimidazol-2-one-1-yl group, a benzimidazol-2-one-3-yl group, a benzimidazol-2-one-4-yl group, a benzimidazol-2-one-5-yl group, a benzimidazol-2-one-6-yl group, a benzimidazol-2-one-7-yl group are preferable. A 1-dibenzofuranyl group, a 2-dibenzofuranyl group, a 3-dibenzofuranyl group, a 4-dibenzofuranyl group, a 1-dibenzothiophenyl group, a 2-dibenzothiophenyl group, a 3-dibenzothiophenyl group, a 4-dibenzothiophenyl group, a 1-carbazolyl group, a 2-carbazolyl group, a 3-carbazolyl group, a 4-carbazolyl group and a 9-carbazolyl group are particularly preferable.
The heterocyclic group includes a monocyclic heteroaromatic ring group, a heterofused aromatic ring group obtained by fusing of a plurality of heteroaromatic rings and a heterofused aromatic ring group obtained by fusing of an aromatic hydrocarbon ring and a heteroaromatic ring.
As the fused heterocyclic ring group including 8 to 30 (preferable 8 to 20) ring atoms, among the specific examples of the heterocyclic group given above, a dibenzofuranyl group, a dibenzothiophenyl group and a carbazolyl group can be mentioned, for example.
As the divalent heterocyclic group, a group obtained by removing two hydrogen atoms from the above-mentioned heterocyclic groups can be given.
The divalent arylene group and the divalent heterocyclic group forming the group formed by linking of 2 to 4 divalent arylene groups and/or divalent heterocyclic groups are respectively the same as those mentioned above. The arylene group is preferably selected from a substituted or unsubstituted phenylenyl group, a substituted or unsubstituted naphthalenyleny group, a substituted or unsubstituted phenanthrenylenyl group, a substituted or unsubstituted anthrylenyl group, a substituted or unsubstituted pyrenylenyl group and a substituted or unsubstituted fluorenylenyl group. The heterocyclic group is preferably selected from a substituted or unsubstituted pyridinylenyl group, a substituted or unsubstituted pyrimidinylenyl group, a substituted or unsubstituted pyrazinylenyl group, a substituted or unsubstituted pyridazinyleneyl group, a substituted or unsubstituted triazinylenyl group, a substituted or unsubstituted dibenzofuranylenyl group, a substituted or unsubstituted dibenzothiophenylenyl group, and a substituted or unsubstituted carbazolylenyl group.
The following structures are more preferable.
As for the preferable structure of the anthracene derivative formed by linking of 2 to 4 divalent arylene groups and/or divalent heterocyclic groups, the following can be given, for example.
As the alkylsilyl group including 3 to 60 carbon atoms, a trialkylsilyl group including one of the alkyl groups given above as the examples of the alkyl group can be mentioned. Specific examples thereof include a trimethylsilyl group, a triethylsilyl group, a tri-n-butylsilyl group, a tri-n-octylsilyl group, a triisobutylsilyl group, a dimethylethylsilyl group, a dimethylisopropylsilyl group, a dimethyl-n-propylsilyl group, a dimethyl-n-butylsilyl group, a dimethyl-t-butylsilyl group, a diethylisopropylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triisopropylsilyl group or the like can be given. The three alkyl groups may be the same or different.
As the arylsilyl group including 8 to 60 carbon atoms, an arylsilyl group, an alkylarylsilyl group, a dialkylarylsilyl group, a diarylsilyl group, an alkyldiarylsilyl group and a triarylsilyl group can be given. The plural aryl groups or the plural alkyl groups may be the same or different.
As the dialkylarylsilyl group, a dialkylarylsilyl group including two of the alkyl groups given above as the examples of the alkyl group and one of the aryl groups mentioned above can be mentioned, for example. It is preferred that the number of carbon atoms of the dialkylarylsilyl group be 8 to 30. The two alkyl groups may be the same or different.
As the alkyldiarylsilyl group, an alkyldiarylsilyl group including one of the alkyl groups given above as the examples of the alkyl group and two of the aryl groups mentioned above can be given, for example. It is preferred that the number of carbon atoms of the alkyldiarylsilyl group be 13 to 30. The two aryl groups may be the same or different.
As the triarylsilyl group, a triarylsilyl group including three of the aryl groups mentioned above can be given. It is preferred that the number of carbon atoms of the triarylsilyl group be 18 to 30. The three aryl groups may be the same or different.
As the arylsilyl group, a phenyldimethylsilyl group, a diphenylmethylsilyl group, a diphenyl-t-butylsilyl group and a triphenylsilyl group can be given, for example.
The aralkyl group is represented by —Y—Z. As examples of Y, the examples of alkylene corresponding to the examples of the alkyl can be given. As examples of Z, the examples of the aryl can be given. The aralkyl group is preferably an aralkyl group including 7 to 50 (the aryl part includes 6 to 49 (preferably 6 to 30, more preferably 6 to 20, particularly preferably 6 to 12) and the alkyl part includes 1 to 44 (preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 10, and particularly preferably 1 to 6)) carbon atoms. The aralkyl group is preferably a benzyl group, a phenylethyl group and a 2-phenylpropane-2-yl group, for example.
The anthracene derivatives according to one aspect of the invention are exemplified below. The invention is not limited to these.
The *s in the table respectively show the bonding position to the anthracene ring.
The *s in the table respectively show the bonding position to the anthracene ring.
The anthracene derivative mentioned above can be used as the material for an organic EL device or an emitting material for an organic EL device.
The organic electroluminescence (EL) device according to one aspect of the invention includes one or more organic thin film layers including an emitting layer between a cathode and an anode, and at least one layer of the organic thin film layers include the anthracene derivative as a single component or a mixture component.
In the above-mentioned organic EL device, the emitting layer preferably comprise the anthracene derivative mentioned above. It is preferred that the anthracene derivative be a host material of the emitting layer.
As the organic EL device including a plurality of organic thin film layers, one having a configuration in which layers are stacked as follows can be given: (anode/hole-injecting layer/emitting layer/cathode), (anode/emitting layer/electron-injecting layer/cathode), (anode/hole-injecting layer/emitting layer/electron-injecting layer/cathode), (anode/hole-injecting layer/hole-transporting layer/emitting layer/electron-injecting layer/cathode), etc.
In the above-mentioned organic EL device, the anthracene derivative can be used in any of the above-mentioned organic layers. It is preferred that the anthracene derivative be contained in an emission zone. It is particularly preferred that the anthracene derivative be contained in the emitting layer. The content is normally 30 to 100 mol %.
In the organic EL device, by providing a plurality of the above-mentioned organic thin film layers, it is possible to prevent lowering in luminance or life caused by quenching. If necessary, an emitting material, a doping material, a hole-injecting material or an electron-injecting material can be used in combination. Further, by the use of a doping material, the luminance or the luminous efficiency may be improved. The hole-injecting layer, the emitting layer and the electron-injecting layer may respectively be formed into a stacked layer structure composed of two or more layers. In such a layer configuration, in the case of the hole-injecting layer, a layer to which holes are injected from the electrode is referred to as the hole-injecting layer, and a layer for receiving holes from the hole-injecting layer and transporting the holes to the emitting layer is referred to as the hole-transporting layer. Similarly, in the case of the electron-injecting layer, a layer to which electrons are injected from the electrode is referred to as the electron-injecting layer, and a layer for receiving electrons from the electron-injecting layer and transporting the electrons to the emitting layer is referred to as the electron-transporting layer. Each of these layers is selected according to factors such as the energy level of the materials, heat resistance, adhesiveness to the organic layer or the metal electrode.
As the material that can be used together with the above-mentioned anthracene derivative, for example, a fused polycyclic aromatic compound such as naphthalene, phenanthrene, rubrene, anthracene, tetracene, pyrene, perylene, chrysene, decacyclene, coronene, tetraphenyl cyclopentadiene, pentaphenylcyclopentadiene, fluorene, spirofluorene, or the like and a derivative thereof; organic metal complex such as tris(8-quinolinolate)aluminum; a triarylamine derivative; a styrylamine derivative; a stilbene derivative; a cumarine derivative; a pyrane derivative; an oxazone derivative; an benzothiozole derivative; a benzoxazole derivative; a benzimidazole derivative; a pyrazine derivative; a cinnamic acid ester derivative; a diketo-pyrrolo-pyrrole derivative; an acrylidone derivative; a quinacridone derivative or the like can be given. The materials are not limited to those mentioned above.
In the above-mentioned organic EL device, if desired, in addition to the above-mentioned emitting materials, an emitting dopant (phosphorescent dopant and/or fluorescent dopant) may be contained in the emitting layer. An emitting layer that comprises these dopants may be stacked on the emitting layer that comprises the above-mentioned compounds.
A fluorescent dopant is a compound that can emit light from a singlet exciton. A fluorescent dopant is preferably a compound selected from an amine-based compound, an aromatic compound, a chelate complex such as tris(8-quinolinolato)aluminum complex, a coumarin derivative, a tetraphenylbutadiene derivative, a bistyrylarylene derivative and an oxadiazole derivative according to the required emission color. A styrylamine compound, a styryldiamine compound, an arylamine compound and an aryldiamine compound are more preferable, with a fused polycyclic amine derivative being further preferable. These fluorescent dopants may be used singly or in combination of two or more.
As the fused polycyclic amine derivative, those represented by the following formula (20) are preferable.
In the formula (20), Y is a substituted or unsubstituted fused aromatic hydrocarbon group including 10 to 50 ring carbon atoms.
Ar101 and Ar102 are independently a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms or a substituted or unsubstituted heterocyclic ring group including 5 to 50 ring atoms.
Specific examples of Y include the above-mentioned fused aryl group. Y is preferably a substituted or unsubstituted anthryl group, a substituted or unsubstituted pyrenyl group or a substituted or unsubstituted chrysenyl group.
n is an integer of 1 to 4. It is preferred that n be an integer of 1 to 2.
The above-mentioned formula (20) is preferably one represented by the following formulas (21) to (24).
In the formulas (21) to (24), Re, Rf and Rg are independently a substituted or unsubstituted alkyl group including 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group including 2 to 50 carbon atoms, a substituted or unsubstituted alkynyl group including 2 to 50 carbon atoms, a substituted or unsubstituted aralykyl group including 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group including 3 to 20 ring carbon atoms, a substituted or unsubstituted alkoxy group including 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group including 6 to 20 ring carbon atoms, a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms, a substituted or unsubstituted silyl group, a substituted or unsubstituted alkyl germanium group including 1 to 50 carbon atoms or a substituted or unsubstituted aryl germanium group including 6 to 50 ring carbon atoms. Re, Rf and Rg may independently be bonded to any of the bonding positions of the benzene rings that constitutes the fused polycyclic skeleton.
As preferable examples of Re, Rf and Rg, a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms can be given. More preferably, Re, Rf and Rg are a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or the like.
t is an integer of 0 to 10. u is an integer of 0 to 8. m is an integer of 0 to 10.
Ar201 to Ar218 are independently an aryl group including 6 to 50 ring carbon atoms or a substituted or unsubstituted heterocyclic group including 5 to 50 ring atoms.
Preferred examples of Ar201 to Ar218 include a substituted or unsubstituted phenyl group, a substituted or unsubstituted dibenzofuranyl group or the like. As preferable examples of the substituent of Ar201 to Ar218, an alkyl group, a cyano group and a substituted or unsubstituted silyl group can be given.
In the formulas (21) to (24), as examples of the alkyl group, the alkoxy group, the aryl group, the aryloxy group and the heterocyclic group, those exemplified above can be given.
As the alkenyl group including 2 to 50 (preferably 2 to 30, more preferably 2 to 20, and particularly preferably 2 to 10) carbon atoms, a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1,3-butanedienyl group, a 1-methylvinyl group, a styryl group, a 2,2-diphenylvinyl group, a 1,2-diphenylvinyl group, a 1-methylallyl group, a 1,1-dimethylallyl group, a 2-methylallyl group, a 1-phenylallyl group, a 2-phenylallyl group, a 3-phenylallyl group, a 3,3-diphenylallyl group, a 1,2-dimethylallyl group, a 1-phenyl-1-butenyl group, a 3-phenyl-1-butenyl group or the like can be given. Preferred are a styryl group, a 2,2-diphenylvinyl group, a 1,2-diphenylvinyl group or the like.
As the alkynyl group including 2 to 50 (preferably 2 to 30, more preferably 2 to 20, particularly preferably 2 to 10) carbon atoms, a propargyl group, a 3-pentynyl group or the like can be given.
As the alkyl germanium group, a methylhydrogermyl group, a trimethylgermyl group, a triethylgermyl group, a tripropylgermyl group, a dimethyl-t-butylgermyl group or the like can be given.
As the aryl germanium group, a phenyldihydrogermyl group, a diphenylhydrogermyl group, a triphenylgermyl group, a tritolylgermyl group, a trinaphthylgermyl group or the like can be given.
As the styrylamine compound and the styryldiamine compound, those represented by the following formulas (17) and (18) are preferable.
In the formula (17), Ar301 is a k-valent group; a k-valent group corresponding to a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a stilbene group, a styrylaryl group and a distyrylaryl group. Ar302 and Ar303 are independently an aryl group including 6 to 20 ring carbon atoms, and Ar301, Ar302 and Ar303 may be substituted.
k is an integer of 1 to 4, with an integer of 1 and 2 being preferable. Any one of Ar301 to Ar303 is a group including a styryl group. It is further preferred that at least one of Ar302 and Ar303 be substituted by a styryl group.
As for the aryl group including 6 to 20 ring carbon atoms, the above-mentioned aryl group can be specifically given. Preferable examples include a phenyl group, a naphthyl group, an anthranyl group, a phenanthryl group, a terphenyl group or the like.
In the formula (18), Ar304 to Ar306 are a v-valent substituted or unsubstituted aryl group including 6 to 40 ring carbon atoms. v is an integer of 1 to 4, with an integer of 1 and 2 being preferable.
Here, as the aryl group including 6 to 40 ring carbon atoms in the formula (18), the above-mentioned aryl group can be specifically given. A naphthyl group, an anthranyl group, a chrysenyl group, a pyrenyl group or an aryl group represented by the formula (20) is preferable.
As preferable substituents that substitute on the aryl group, an alkyl group including 1 to 6 carbon atoms, an alkoxy group including 1 to 6 carbon atoms, an aryl group including 6 to 40 ring carbon atoms, an amino group substituted by an aryl group including 6 to 40 ring carbon atoms, an ester group including an aryl group that includes 5 to 40 ring carbon atoms, an ester group including an alkyl group that includes 1 to 6 carbon atoms, a cyano group, a nitro group, a halogen atom or the like can be given.
As the hole-injecting material, preferable is a compound that has a hole-transporting capability, exhibits hole-injection effects from the anode, exhibits excellent hole-injection effects for the emitting layer or the emitting material, and has excellent thin-film forming capability. Specific examples thereof include a phthalocyanine derivative, a naphthalocyanine derivative, a porphyrin derivative, a benzidine-type triphenylamine, a diamine-type triphenylamine, hexacyanohexaazatriphenylene or the like, a derivative thereof, a polymeric material such as polyvinyl carbazole, polysilane and conductive polymers. The hole-injecting material is, however, not limited thereto.
Among the hole-injecting materials mentioned above that are usable in an organic EL device, a further effective hole-injecting material is a phthalocyanine derivative.
As the phthalocyanine (Pc) derivative, for example, phthalocyanine derivatives and naphthalocyanine derivatives such as H2Pc, CuPc, CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl2SiPc, (HO)AlPc, (HO)GaPc, VOPc, TiOPc, MoOPc, GaPc-O-GaPc can be given, but the phthalocyanine derivatives are not limited thereto.
Further, by adding to the hole-injection material an electron-acceptor material such as a TCNQ derivative, a carrier can be sensitized.
Preferable hole-transporting materials usable in the above-mentioned organic EL device are aromatic tertiary amine derivatives.
As examples of the aromatic tertiary amine derivatives, N,N′-diphenyl-N,N′-dinaphthyl-1,1′-biphenyl-4,4′-diamine, N,N,N′,N′-tetrabiphenyl-1,1′-biphenyl-4,4′-diamine or the like or an oligomer or a polymer having these aromatic tertiary amine skeleton can be given, for example, but the aromatic tertiary amine derivatives are not limited thereto.
As the electron-injecting material, preferable is a compound that has an electron-transporting capability, exhibits electron-injection effects from the anode, exhibits excellent electron-injection effects for the emitting layer or the emitting material, and has excellent thin-film forming capability.
In the above-mentioned organic EL device, a further effective electron-injecting material is a metal complex compound and a nitrogen-containing heterocyclic derivative.
As the metal complex compound, 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, tris(8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h]quinolinato)beryllium, bis(10-hydroxy-benzo[h]quinolinato)zinc or the like can be given, for example. The metal complex compound is not limited thereto.
As the nitrogen-containing heterocyclic derivative, oxazole, thiazole, oxadiazole, thiadiazole, triazole, pyridine, pyrimidine, triazine, phenanthroline, benzimidazole, imidazopyridine or the like can be given, for example. Among them, a benzimidazole derivative, a phenanthroline derivative and an imidazopyridine derivative are preferable.
As a preferable mode, a dopant is further contained in these electron-injecting materials, and in order to facilitate receiving of electrons from the cathode, it is more preferred that the vicinity of the cathode interface of the second organic layer be doped with a dopant represented by an alkali metal.
As the dopant, a donar metal, a donar metal compound and a donar metal complex can be given. These reductive dopants can be used singly or in combination of two or more.
In the above-mentioned organic EL device, in the emitting layer, in addition to at least one selected from the anthracene derivatives represented by the formula (1), at least one of an emitting material, a doping material, a hole-injecting material, a hole-transporting material and an electron-injecting material may be contained in the same layer. In addition, in order to improve stability of the obtained organic EL device against temperature, moisture, atmosphere or the like, it is possible to provide a protective layer on the surface, or to protect the entire device by silicone oil, a resin or the like.
As the conductive material used in the anode of the above-mentioned organic EL device, one having a work function larger than 4 eV is suitable, and carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum, palladium, and an alloy thereof; an oxide metal such as tin oxide and indium oxide used in an ITO substrate or a NESA substrate, and an organic conductive resin such as polythiophene or polypyrrole or the like are used. As the conductive material used in the cathode, one having a work function smaller than 4 eV is suitable, and magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, aluminum, lithium fluoride and an alloy thereof are used, but the conductive material is not limited thereto. As the alloy, a magnesium/silver alloy, a magnesium/indium alloy, a lithium/aluminum alloy or the like can be given as representative examples, but the alloy is not limited thereto. The ratio of the alloy is controlled by the temperature of the deposition source, atmosphere, vacuum degree, etc. and an adequate ratio is selected. The cathode and the anode may be formed in a stacked layer structure of two or more layers, if necessary.
In the above-mentioned organic EL device, in order to realize efficient emission, it is desired that at least one surface be fully transparent in an emission wavelength region of the device. Further, it is desired that the substrate be transparent. The transparent electrode is set such that prescribed transparency can be ensured by using the above-mentioned electroconductive material and by a method such as deposition and sputtering. It is desired that the electrode on the emission surface have a light transmittance of 10% or more. Although no specific restrictions are imposed on the substrate, as long as it has a mechanical or thermal strength and has transparency, a glass substrate and a transparent resin film can be mentioned.
For forming each of the layers constituting the above-mentioned organic EL device, any of dry film-forming methods such as vacuum deposition, sputtering, plasma coating, ion plating or the like and wet film-forming methods such as spin coating, dip coating and flow coating can be applied. The film thickness is not particularly restricted, but is required to be set to an appropriate film thickness. If the film thickness is too large, a large voltage is required to be applied in order to obtain a specific optical output, resulting in poor efficiency. If the film thickness is too small, pin holes or the like are generated, and a sufficient luminance may not be obtained even when an electrical field is applied. Normally, the film thickness is suitably 5 nm to 10 μm, further preferably 10 nm to 0.2 μm.
In the case of the wet film-forming method, a thin film is formed by using a solution or dispersion in which materials constituting each layer is dissolved or dispersed in an adequate solvent such as ethanol, chloroform, tetrahydrofuran and dioxane. Any of these solvents may be used.
As the solution suited for the wet film-forming method, an organic EL device material-containing solution that contains, as an organic EL material, the above-mentioned anthracene derivative and a solvent can be used.
In any of the organic thin film layers, in order to improve film-forming properties, to prevent generation of pin holes or for other purposes, an adequate resin or an adequate additive may be used.
The above-mentioned organic EL devices can be used in various electric appliances. For example, it can be used for a planar emitting body such as a flat panel display of a wall-hanging television, a copier, a printer, a backlight of a liquid crystal display, or a light source in instruments or the like, a sign board, a signal light or the like. In addition, the compound of the invention can be used not only in an organic EL device, but also in the fields of an electrophotographic photoreceptor, a photoelectric conversion element, a solar cell and an image sensor.
In an argon atmosphere, 106 mL of water was added to 10 g of 5-bromo-2-fluoroaniline, and the mixture was stirred, followed by addition of 79.2 mL of concentrated hydrochloric acid. The resulting mixture was cooled in ice, and an aqueous solution of 4.36 g of sodium nitrate was added dropwise. While cooling in ice, the resultant was stirred for 30 minutes, and then an aqueous solution of 87.3 g of potassium iodide was added. After extraction with ethyl acetate, an organic layer was washed with an aqueous solution of a saturated sodium hydrogen carbonate and an aqueous solution of sodium sulfite and dried with magnesium sulfate. Then, the solvent was distilled off under reduced pressure. Residues were purified by silica gel column chromatography, whereby 11.5 g (yield: 73%) of 5-bromo-2-fluoroiodebenzene was obtained.
15.8 g of 2-methoxynaphthalene and 300 mL of tetrahydrofuran (dehydrated) were put in a flask, and cooled to −78° C. Then, 66 mL of n-BuLi (1.60M in hexane) was added, followed by stirring at room temperature for 4 hours. Then, the solution was again cooled to −78° C. 27.3 of B(OMe)3 was added, followed by stirring at −78° C. for 10 minutes. Then, the resultant was stirred at room temperature for 5 hours.
After completion of the reaction, 1N HCl aq. (200 mL) was added, and the reaction solution was stirred at room temperature for 1 hour. Then, the solution was transferred to a separating funnel, and extracted with ethyl acetate.
This solution was dried with MgSO4, concentrated and washed with hexane, whereby 14.3 g (yield: 71%) of white solids of 3-methoxynaphthalene-2-boronic acid were obtained.
In an argon atmosphere, 14.3 g of 3-methoxynaphthalene-2-boronic acid, 21.3 g of 5-bromo-2-fluoroiodobenzene, 1.64 g of tetrakistriphenylphosphine palladium (0), 220 mL of toluene and 110 mL of a 2M aqueous solution of sodium carbonate were put in a flask, and the mixture was stirred for 8 hours while heating under reflux. After cooling to room temperature, the reaction solution was extracted with toluene. After removing an aqueous layer, an organic layer was washed with saturated saline. After drying the organic layer with magnesium sulfate, the organic layer was concentrated, and the residues were purified by means of silica gel chromatography, whereby 17.6 g (yield: 75%) of 2-methoxy-3-(2-fluoro-5-bromophenyl)naphthalene was obtained.
15.8 g of 2-methoxy-3-(2-fluoro-5-bromophenyl)naphthalene and 200 mL of dichloromethane (dehydrated) were put in a flask, and the resultant was cooled to 0° C. Then, 18.0 g of BBr3 was added, and stirred at room temperature for 24 hours.
After completion of the reaction, the solution was cooled to −78° C., and deactivated carefully with methanol, and further deactivated with a sufficient amount of water. The solution was transferred to a separating funnel, extracted with dichloromethane, and dried with MgSO4. By passing through a silica gel short column, origin impurities were removed. The solution was concentrated, and the obtained sample was dried in vacuum at 60° C. for 5 hours, whereby 15.1 g of white solids of 2-hydroxy-3-(2-fluoro-5-bromophenyl)naphthalene were obtained.
15.1 g of 2-hydroxy-3-(2-fluoro-5-bromophenyl)naphthalene, 150 mL of N-methyl-2-hydrolidinone (dehydrated) and 13.2 g of K2CO3 were put in a flask. Thereafter, the resultant was stirred at 120° C. for 2 hours.
After completion of the reaction, the solution was cooled to room temperature. Toluene (200 mL) was added, and the solution was transferred to a separating funnel, and washed with water. After drying this solution with MgSO4, purification was conducted by means of a silica gel column chromatography, whereby 12.6 g (yield: 89%) of white solids of intermediate (A) were obtained.
12.6 g of intermediate (A) and 500 mL of tetrahydrofuran (dehydrated) were put in a flask, and the resultant was cooled to −78° C. 28 mL of n-BuLi (1.60M in hexane) was added, and stirring was conducted for 2 hours while elevating the temperature to 0° C. Then, the solution was again cooled to −78° C., and 11.6 g of B(OMe)3 was added. After stirring at 10 minutes at −78° C., stirring was further conducted for 5 hours while gradually elevating the temperature to room temperature.
After completion of the reaction, 1N HCl aq. (100 mL) was added, and the reaction solution was stirred at room temperature for 1 hour. Then, the solution was transferred to a separating funnel, and extracted with ethyl acetate.
This solution was dried with MgSO4, concentrated and washed with hexane, whereby 7.2 g (yield: 65%) of white solids of intermediate (B) were obtained.
Intermediates (C) and (D) were synthesized in the same manner as in the synthesis of intermediates (A) and (B) in accordance with the above-mentioned scheme, except that 1-methoxynaphthalene was used instead of 2-methoxynaphthalene as the starting material.
In an atmosphere of argon, 2.88 g of the intermediate (B), 2.81 g of 4-bromoiodobenzene, 0.231 g of tetrakistriphenylphosphine palladium (0), 40 mL of toluene and 20 mL of a 2M aqueous sodium carbonate solution were put in a flask, and the resultant was stirred for 8 hours while heating under reflux. After cooling to room temperature, the reaction solution was extracted with toluene. After removing an aqueous layer, an organic layer was washed with saturated saline. After drying with magnesium sulfate, the organic layer was concentrated, and the residues were purified by means of silica gel column chromatography, whereby 3.16 g (yield: 85%) of intermediate (E) was obtained.
Intermediate (F) was synthesized in the same manner as in the synthesis of intermediate (E), except that 3-bromoiodobenzene was used instead of 4-bromoiodobenzene.
Intermediate (G) was synthesized in the same manner as in the synthesis of intermediate (E), except that intermediate (D) was used instead of intermediate (B).
Intermediate (H) was synthesized in the same manner as in the synthesis of intermediate (E), except that intermediate (D) was used instead of intermediate (B) and 3-bromoiodobenzene was used instead of 4-bromoiodobenzene.
Intermediates (I) and (J) were synthesized in the same manner as in the synthesis of intermediates (A) and (B) in accordance with the above-mentioned scheme, except that 2-fluoro-4-bromoiodobenzene was used instead of 2-fluoro-5-bromoiodobenzene.
Intermediates (K) and (L) were synthesized in the same manner as in the synthesis of intermediates (A) and (B) in accordance with the above-mentioned scheme, except that 1-methoxynaphthalene was used instead of 2-methoxynaphthalene and 2-fluoro-4-bromoiodobenzene was used instead of 2-fluoro-5-bromoiodobenzene.
Intermediate (M) was synthesized in the same manner as in the synthesis of intermediate (E), except that intermediate (J) was used instead of intermediate (B).
Intermediate (N) was synthesized in the same manner as in the synthesis of intermediate (E), except that intermediate (L) was used instead of intermediate (B).
In an argon atmosphere, 2.96 g of intermediate (A), 3.28 g of 10-phenylanthracene-9-boronic acid, that had been prepared by a known method, 0.231 g of tetrakis(triphenylphosphine)palladium (0), 20 mL of 1,2-dimethoxyethane, 20 mL of toluene and 20 mL of a 2M aqueous sodium carbonate solution were charged. The resultant was stirred under reflux for 8 hours. After cooling to room temperature, precipitated solids were separated by filtration. The obtained solids were washed with water and methanol, and re-crystallized from toluene, whereby 4.04 g of pale yellow solids of compound 1 were obtained. As a result of mass spectrometry, it was found that the obtained solids were an intended product, and had an m/e of 470 relative to a molecular weight of 470.17.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that 10-(1-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 2 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 520 relative to a molecular weight of 520.18.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that 10-(2-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 3 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 520 relative to a molecular weight of 520.18.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that 10-(4-biphenyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 4 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 546 relative to a molecular weight of 546.20.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that 10-(3-biphenyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 5 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 546 relative to a molecular weight of 546.20.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that 10-[4-(1-naphthyl)phenyl]anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 6 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 596 relative to a molecular weight of 596.21.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that 10-[3-(1-naphthyl)phenyl]anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 7 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 596 relative to a molecular weight of 596.21.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that 10-[4-(2-naphthyl)phenyl]anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 8 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 596 relative to a molecular weight of 596.21.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that 10-[3-(2-naphthyl)phenyl]anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 9 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 596 relative to a molecular weight of 596.21.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that 10-(2-dibenzofuranyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 10 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 560 relative to a molecular weight of 560.64.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that 10-[3-(9-phenyl)carbazolyl]anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 11 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 635 relative to a molecular weight of 635.22.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (E) was used instead of intermediate (A), whereby compound 12 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 546 relative to a molecular weight of 546.20.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (E) was used instead of intermediate (A), and 10-(1-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 13 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 596 relative to a molecular weight of 596.21.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (E) was used instead of intermediate (A), and 10-(2-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 14 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 596 relative to a molecular weight of 596.21.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (E) was used instead of intermediate (A), and 10-(4-biphenyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 15 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 622 relative to a molecular weight of 622.23.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (E) was used instead of intermediate (A), and 10-(3-biphenyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 16 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 622 relative to a molecular weight of 622.23.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (E) was used instead of intermediate (A), and 10-[4-(1-naphthyl)phenyl]anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 17 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 672 relative to a molecular weight of 672.25.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (E) was used instead of intermediate (A), and 10-[3-(1-naphthyl)phenyl]anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 18 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 672 relative to a molecular weight of 672.25.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (E) was used instead of intermediate (A), and 10-[4-(2-naphthyl)phenyl]anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 19 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 672 relative to a molecular weight of 672.25.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (E) was used instead of intermediate (A), and 10-[3-(2-naphthyl)phenyl]anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 20 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 672 relative to a molecular weight of 672.25.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (F) was used instead of intermediate (A), whereby compound 21 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 546 relative to a molecular weight of 546.20.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (F) was used instead of intermediate (A), and 10-(1-naphthyl)phenyl]anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 22 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 596 relative to a molecular weight of 596.21.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (F) was used instead of intermediate (A), and 10-(2-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 23 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 596 relative to a molecular weight of 596.21.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (F) was used instead of intermediate (A), and 10-(4-biphenyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 24 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 622 relative to a molecular weight of 622.23.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (F) was used instead of intermediate (A), and 10-(3-biphenyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 25 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 622 relative to a molecular weight of 622.23.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (F) was used instead of intermediate (A), and 10-[4-(1-naphthyl)phenyl]anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 26 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 672 relative to a molecular weight of 672.25.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (F) was used instead of intermediate (A), and 10-[3-(1-naphthyl)phenyl]anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 27 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 672 relative to a molecular weight of 672.25.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (F) was used instead of intermediate (A), and 10-[4-(2-naphthyl)phenyl]anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 28 was obtained. As a result of mass spectrometry, the compound was an intended product, and had an m/e of 672 relative to a molecular weight of 672.25.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (F) was used instead of intermediate (A), and 10-[3-(2-naphthyl)phenyl]anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 29 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 672 relative to a molecular weight of 672.25.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (C) was used instead of intermediate (A), whereby compound 30 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 470 relative to a molecular weight of 470.17.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (C) was used instead of intermediate (A), and 10-(1-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 31 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 520 relative to a molecular weight of 520.18.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (C) was used instead of intermediate (A), and 10-(2-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 32 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 520 relative to a molecular weight of 520.18.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (H) was used instead of intermediate (A), whereby compound 33 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 546 relative to a molecular weight of 546.20.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (H) was used instead of intermediate (A), and 10-(1-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 34 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 596 relative to a molecular weight of 596.21.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (H) was used instead of intermediate (A), and 10-(2-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 35 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 596 relative to a molecular weight of 596.21.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (G) was used instead of intermediate (A), whereby compound 36 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 546 relative to a molecular weight of 546.20.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (G) was used instead of intermediate (A), and 10-(1-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 37 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 596 relative to a molecular weight of 596.21.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (G) was used instead of intermediate (A), and 10-(2-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 38 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 596 relative to a molecular weight of 596.21.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (I) was used instead of intermediate (A), whereby compound 39 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 470 relative to a molecular weight of 470.17.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (I) was used instead of intermediate (A), and 10-(1-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 40 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 520 relative to a molecular weight of 520.62.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (I) was used instead of intermediate (A), and 10-(2-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 41 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 520 relative to a molecular weight of 520.62.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (M) was used instead of intermediate (A), whereby compound 42 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 546 relative to a molecular weight of 546.20.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (M) was used instead of intermediate (A), and 10-(1-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 43 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 596 relative to a molecular weight of 596.21.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (M) was used instead of intermediate (A), and 10-(2-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 44 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 596 relative to a molecular weight of 596.21.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (K) was used instead of intermediate (A), whereby compound 45 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 470 relative to a molecular weight of 470.17.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (K) was used instead of intermediate (A), and 10-(1-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 46 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 520 relative to a molecular weight of 520.18.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (K) was used instead of intermediate (A), and 10-(2-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 47 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 520 relative to a molecular weight of 520.18.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (N) was used instead of intermediate (A), whereby compound 48 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 546 relative to a molecular weight of 546.20.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (N) was used instead of intermediate (A), and 10-(1-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 49 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 596 relative to a molecular weight of 596.21.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (N) was used instead of intermediate (A), and 10-(2-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 50 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 596 relative to a molecular weight of 596.21.
Intermediates (O) and (P) were synthesized in the same manner as in the synthesis of intermediates (A) and (B) in accordance with the above-mentioned scheme, except that 9-methoxyphenathrene was used instead of 2-methoxynaphthalene as the starting material.
Intermediate (Q) was synthesized in the same manner as in the synthesis of intermediate (E), except that intermediate (P) was used instead of intermediate (B).
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (O) was used instead of intermediate (A), whereby compound 51 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 520 relative to a molecular weight of 520.18.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (O) was used instead of intermediate (A), and 10-(1-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 52 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 570 relative to a molecular weight of 570.20.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (O) was used instead of intermediate (A), and 10-(2-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 53 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 570 relative to a molecular weight of 570.20.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (O) was used instead of intermediate (A), and 10-(4-biphenyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 54 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 570 relative to a molecular weight of 596.21.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (Q) was used instead of intermediate (A), whereby compound 55 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 596 relative to a molecular weight of 596.21.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (Q) was used instead of intermediate (A), and 10-(1-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 56 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 646 relative to a molecular weight of 646.23.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (Q) was used instead of intermediate (A), and 10-(2-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 57 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 646 relative to a molecular weight of 646.23.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (Q) was used instead of intermediate (A), and 10-(4-biphenyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 58 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 672 relative to a molecular weight of 672.25.
Intermediates (R) and (S) were synthesized in the same manner as in the synthesis of intermediates (A) and (B) in accordance with the above-mentioned scheme, except that 9-methoxyphenanthrene was used instead of 2-methoxynaphthalene and 2-fluoro-4-bromoiodobenzene was used instead of 2-fluoro-5-bromoiodobenzene.
Synthesis was conducted in the same manner as in the synthesis of intermediate (E), except that intermediate (S) was used instead of the intermediate (B), whereby intermediate (T) was obtained.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (R) was used instead of intermediate (A), and 10-(1-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 59 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 570 relative to a molecular weight of 570.20.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (T) was used instead of intermediate (A), and 10-(1-naphthyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 60 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 646 relative to a molecular weight of 646.23.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (C) was used instead of intermediate (A), and 10-(4-biphenyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 61 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 546 relative to a molecular weight of 546.20.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (C) was used instead of intermediate (A), and 10-(3-biphenyl)anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 62 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 546 relative to a molecular weight of 546.20.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (C) was used instead of intermediate (A), and 10-[4-(1-naphthyl)phenyl]anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 63 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 596 relative to a molecular weight of 596.21.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (C) was used instead of intermediate (A), and 10-[4-(2-naphthyl)phenyl]anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 64 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 596 relative to a molecular weight of 596.21.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (C) was used instead of intermediate (A), and 10-[3-(1-naphthyl)phenyl]anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 65 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 596 relative to a molecular weight of 596.21.
Synthesis was conducted in the same manner as in the synthesis of compound 1 in Example 1, except that intermediate (C) was used instead of intermediate (A), and 10-[3-(2-naphthyl)phenyl]anthracene-9-boronic acid, that was synthesized by a known method, was used instead of 10-phenylanthracene-9-boronic acid, whereby compound 66 was obtained. As a result of mass spectrometry, it was found that the compound was an intended product, and had an m/e of 596 relative to a molecular weight of 596.21.
A glass substrate (25 mm×75 mm×1.1 mm) with ITO transparent electrode lines (manufactured by GEOMATEC Co., Ltd.) was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes and then UV ozone cleaning for 30 minutes. The cleaned glass substrate with ITO transparent electrode lines was mounted on a substrate holder in a vacuum deposition apparatus. First, on the surface of the side on which the ITO transparent electrode lines had been formed, compound HAT was deposited so as to cover the ITO transparent electrode lines to form a 5 nm-thick film. Subsequent to the formation of the HAT film, an 80 nm-thick HT1 film was formed on this HAT film. Subsequent to the formation of the HT1 film, a 15 nm-thick HT2 film was formed on this HT1 film.
On the HT2 film, BH1 (compound 4) produced in Example 4 and dopant BD1 were formed into films in a thickness ratio of 19:1, whereby a 25 nm-thick blue-emitting layer was formed.
On the emitting layer, ET1 was formed into a 20 nm-thick film by deposition as an electron-transporting layer. Subsequent to the formation of the ET1 film, ET2 was formed into a 5 nm-thick film on this ET1 film. Thereafter, LiF was formed into a 1 nm-thick film. Metal Al was deposited on this LiF film in a thickness of 80 nm to form a metal electrode, whereby an organic EL device was formed.
For the organic EL device fabricated above, the voltage and the external quantum efficiency (EQE) were measured. Specifically, they were measured by the following methods. The results are shown in Table 1.
Driving Voltage
A voltage (unit: V) when electric current was flown between the ITO transparent electrode and the metal Al cathode such that the current density became 10 mA/cm2 was measured.
External Quantum Yield Efficiency EQE
Assuming that Lambertian irradiation was conducted, an external quantum yield efficiency EQE (unit: %) was calculated from the spectral radiance.
An organic EL device was fabricated and evaluated in the same manner as in Example 67, except that BH2 was used instead of BH1 in the formation of the emitting layer. The results are shown in Table 1.
The compounds used in the Examples and the Comparative Examples are shown below.
From the above results, as compared with Comparative Example 1 in which compound BH2 was used, in Example 67 where the compound BH1 of the invention was used, by bonding of the group represented by the formula (2) with an anthracene skeleton at a specific position, the device could be driven at a low voltage and exhibited a high efficiency. The reason therefor is assumed that, intermolecular packing is increased due to the widening of the planarity of molecules, leading to an improvement in electron-injecting and transporting properties.
A glass substrate (25 mm×75 mm×1.1 mm) with ITO transparent electrode lines (manufactured by GEOMATEC Co., Ltd.) was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes and then UV ozone cleaning for 30 minutes. The cleaned glass substrate with ITO transparent electrode lines was mounted on a substrate holder in a vacuum deposition apparatus. First, on the surface of the side on which the ITO transparent electrode lines had been formed, compound HAT was deposited so as to cover the ITO electrode lines to form a 5 nm-thick film. Subsequent to the formation of the HAT film, an 80 nm-thick HT3 film was formed on this HAT film. Subsequent to the formation of the HT3 film, a 15 nm-thick HT4 film was formed on this HT3 film.
On the HT4 film, compound 1 produced in Example 1 and dopant BD1 were formed into films in a thickness ratio of 19:1, whereby a 25 nm-thick blue-emitting layer was formed.
On the emitting layer, ET1 was formed into a 20 nm-thick film by deposition as an electron-transporting layer. Subsequent to the formation of the ET1 film, ET3 was formed into a 5 nm-thick film on this ET-1 film. Thereafter, LiF was formed into a 1 nm-thick film. Metal Al was deposited on this LiF film in a thickness of 80 nm to form a metal electrode, whereby an organic EL device was fabricated.
The obtained organic EL device was evaluated in the same manner as in Example 67. The results are shown in Table 2.
Organic EL devices were fabricated and evaluated in the same manner as in Example 68, except that, in the formation of an emitting layer, compounds shown in Table 2 were used instead of compound 1. The results are shown in Table 2.
The compounds used in Examples and Comparative Examples are shown below.
It can be understood that the devices of Examples 68 to 88, in which the compounds of the invention were used, could be driven at a lower voltage and had a high efficiency as compared with the device of Comparative Example 2 in which compound BH3 was used. As mentioned above, the reason therefor is assumed that intermolecular packing is increased due to the widening of the planarity of molecules, leading to improvement in electron-injecting and transporting properties.
Further, the devices of Examples 68 to 88 could be driven at a lower voltage, and had a significantly high efficiency as compared with the device of Comparative Example 3 in which compound BH4 was used. The reason therefor is that the planarity of molecules is widened due to the specific bonding position on the anthracene skeleton, leading to improvement in electron-injecting and transporting properties, as mentioned above.
Although only some exemplary embodiments and/or examples of this invention have been described in detail above, those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments and/or examples without materially departing from the novel teachings and advantages of this invention. Accordingly, all such modifications are intended to be included within the scope of this invention.
The specification of a Japanese application on the basis of which the present application claims Paris Convention priority is incorporated herein by reference in its entirety.
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| PCT/JP2014/001481 | 3/14/2014 | WO | 00 |
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| WO2014/141725 | 9/18/2014 | WO | A |
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