JP4316841B2 - Method for synthesizing perylene derivative, perylene derivative, and organic EL device - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an organic EL (electroluminescence) device, and more particularly to a compound used in a device that emits light by applying an electric field to a thin film made of an organic compound.
[0002]
[Prior art]
The organic EL element has a configuration in which a thin film containing a fluorescent organic compound is sandwiched between an electron injection electrode and a hole injection electrode, and excitons (excitons) are obtained by injecting electrons and holes into the thin film and recombining them. This is a device that emits light by utilizing light emission (fluorescence / phosphorescence) when the exciton is deactivated.
[0003]
The characteristics of the organic EL element are several hundred to several tens of thousand cd / m at a voltage of about 10V. ² It is possible to emit surface light with extremely high luminance, and to emit light from blue to red by selecting the type of fluorescent material.
[0004]
There is a doping method as a method for obtaining an arbitrary emission color of an organic EL element, and a report was made that the emission color was changed from blue to green by doping a small amount of tetracene in an anthracene crystal (Jpn. J. Appl. Phys ., 10,527 (1971)). In addition, in an organic thin film EL element having a laminated structure, a light emitting layer is formed by mixing a small amount of a fluorescent dye that emits light emitted from a host material having a light emitting function in response to the light emission as a dopant. Has been reported (Japanese Patent Laid-Open No. 63-264692) in which the emission color is changed from orange to red.
[0005]
Regarding long-wavelength emission of yellow to red, as a light-emitting material or a dopant material, a laser dye (EPO281381) that emits red light, a compound that exhibits exciplex light emission (JP-A-2-255788), and a coumarin compound (JP-A-3) -792), dicyanomethylene compounds (JP-A-3-162488), thioxanthene compounds (JP-A-3-177486), a mixture of a conjugated polymer and an electron transport compound (JP-A-6-73374). ), Squarylium compounds (JP-A-6-93257), oxadiazole compounds (JP-A-6-136359), oxynate derivatives (JP-A-6-145146), pyrene compounds (JP-A-6-6). -240246).
[0006]
Also, the fact that benzofluoranthene derivatives have a very high fluorescence quantum yield is described in J. Am. Chem. Soc 1996, 118, 2374-2379. In JP-A-10-330295 and JP-A-11-233261, dibenzo [f, f ′] derived from benzofluoranthene in various host materials. An organic EL device is disclosed in which a light-emitting layer is formed by doping a diindeno [1,2,3-cd: 1 ′, 2 ′, 3′-lm] perylene derivative.
[0007]
By the way, when synthesizing a perylene derivative including such a benzofluoranthene derivative, a method of synthesizing using a starting material and a catalyst as shown in the following formulas (A), (B), and (C) is generally used. Met.
[0008]
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[0009]
However, such a conventional synthesis method has a problem that the yield of the target product is 20% or less at most and the efficiency is very low. In addition, with such a conventional synthesis method, a target object having symmetry can be synthesized relatively easily, but it is difficult to directly synthesize itself when trying to obtain a target object having no symmetry. For this reason, the target product has to be separated from various products, and the production efficiency is extremely poor, and the degree of freedom in designing the compound is limited.
[0010]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing a perylene derivative having a sufficient yield and excellent production efficiency, a perylene derivative obtained by this production method, and an organic EL device using the perylene derivative.
[0011]
[Means for Solving the Problems]
The above object is achieved by the following configuration.
(1) In obtaining the perylene derivative, the starting material is halogenated and the halogenated site is coupled, or the halogenated starting material and the boronated starting material are used to determine the halogenated and boronated sites. A method for synthesizing perylene derivatives using Suzuki coupling or a combination thereof.
(2) coupling a 1,8-dihalogenated naphthalene derivative represented by the following formula (1):
[0012]
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[0013]
[In the above formula (1), R 1 to R 4, R 11 and R 12 are a hydrogen atom, a linear chain optionally having substituent (s), a branched or cyclic alkyl group, a linear chain optionally having substituent (s), Branched or cyclic alkoxy group, optionally having a straight chain, branched or cyclic alkylthio group, optionally having a straight chain, branched or cyclic alkenyl group, having a substituent Linear, branched or cyclic alkenyloxy group which may be substituted, linear, branched or cyclic alkenylthio group which may be substituted, substituted or unsubstituted aralkyl group, substituted or unsubstituted aralkyloxy group Group, substituted or unsubstituted aralkylthio group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted arylthio group, substituted or unsubstituted amino group, cyano group , Hydroxyl group, -COOM1 group (wherein M1 is a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent, a linear, branched or cyclic group which may have a substituent) An alkenyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group), a -COM2 group (wherein M2 is a hydrogen atom, an optionally substituted linear, branched or cyclic group) An alkyl group, an optionally substituted linear, branched or cyclic alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or an amino group), or -OCOM3 ( In the group, M3 is a linear, branched or cyclic alkyl group which may have a substituent, a linear, branched or cyclic alkenyl group which may have a substituent, a substituted or unsubstituted aralkyl group. , Or two or more adjacent groups selected from R1 to R4, R11 and R12 are bonded or condensed to each other together with a substituted carbon atom, and a substituted or unsubstituted aryl group. A substituted or unsubstituted carbocyclic aliphatic ring, aromatic ring, or condensed aromatic ring may be formed. When these carbocyclic aliphatic rings, aromatic rings or condensed aromatic rings have a substituent, the substituents are the same as those for R1 to R4, R11 and R12. ]
A method for synthesizing a perylene derivative of the above (1), which synthesizes a perylene derivative represented by the following formula (2).
[0014]
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[0015]
[In the above formula (2), R1 'to R4', R11 'and R12' have the same meanings as R1 to R4, R11 and R12 in formula (1). R1 to R4, R11 and R12 and R1 'to R4', R11 'and R12' may be the same or different. ]
(3) coupling a 3,4-dihalogenated fluoranthene derivative represented by the following formula (3);
[0016]
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[0017]
[In the above formula (3), R1 to R6, R21 and R22 are a hydrogen atom, a linear chain optionally having substituent (s), a branched or cyclic alkyl group, a linear chain optionally having substituent (s), Branched or cyclic alkoxy group, optionally having a straight chain, branched or cyclic alkylthio group, optionally having a straight chain, branched or cyclic alkenyl group, having a substituent Linear, branched or cyclic alkenyloxy group which may be substituted, linear, branched or cyclic alkenylthio group which may be substituted, substituted or unsubstituted aralkyl group, substituted or unsubstituted aralkyloxy group Group, substituted or unsubstituted aralkylthio group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted arylthio group, substituted or unsubstituted amino group, cyano group , Hydroxyl group, -COOM1 group (wherein M1 is a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent, a linear, branched or cyclic group which may have a substituent) An alkenyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group), a -COM2 group (wherein M2 is a hydrogen atom, an optionally substituted linear, branched or cyclic group) An alkyl group, an optionally substituted linear, branched or cyclic alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or an amino group), or -OCOM3 ( In the group, M3 is a linear, branched or cyclic alkyl group which may have a substituent, a linear, branched or cyclic alkenyl group which may have a substituent, a substituted or unsubstituted aralkyl group. , Or two or more adjacent groups selected from R1 to R6, R21 and R22 are bonded or condensed to each other together with a substituted carbon atom, and a substituted or unsubstituted aryl group. A substituted or unsubstituted carbocyclic aliphatic ring, aromatic ring, or condensed aromatic ring may be formed. ]
A method for synthesizing a perylene derivative of the above (1), wherein a perylene derivative represented by the following formula (4) is synthesized.
[0018]
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[0019]
[In the above formula (4), R1 'to R6', R21 'and R22' have the same meanings as R1 to R6, R21 and R22 in formula (3). R1 to R6, R21 and R22 and R1 'to R6', R21 'and R22' may be the same or different. ]
(4) coupling a 3,4-dihalogenated benzofluoranthene derivative represented by the following formula (5);
[0020]
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[0021]
[In the above formula (5), R1 to R8, R31 and R32 are each a hydrogen atom, a linear chain optionally having a substituent, a branched or cyclic alkyl group, a linear chain optionally having a substituent, Branched or cyclic alkoxy group, optionally having a straight chain, branched or cyclic alkylthio group, optionally having a straight chain, branched or cyclic alkenyl group, having a substituent Linear, branched or cyclic alkenyloxy group which may be substituted, linear, branched or cyclic alkenylthio group which may be substituted, substituted or unsubstituted aralkyl group, substituted or unsubstituted aralkyloxy group Group, substituted or unsubstituted aralkylthio group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted arylthio group, substituted or unsubstituted amino group, cyano group , Hydroxyl group, -COOM1 group (wherein M1 is a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent, a linear, branched or cyclic group which may have a substituent) An alkenyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group), a -COM2 group (wherein M2 is a hydrogen atom, an optionally substituted linear, branched or cyclic group) An alkyl group, an optionally substituted linear, branched or cyclic alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or an amino group), or -OCOM3 ( In the group, M3 is a linear, branched or cyclic alkyl group which may have a substituent, a linear, branched or cyclic alkenyl group which may have a substituent, a substituted or unsubstituted aralkyl group. , Or two or more adjacent groups selected from R1 to R8, R31 and R32 are bonded or condensed to each other together with a substituted carbon atom, and a substituted or unsubstituted aryl group. A substituted or unsubstituted carbocyclic aliphatic ring, aromatic ring, or condensed aromatic ring may be formed. ]
A method for synthesizing a perylene derivative of (1) above, wherein a perylene derivative represented by the following formula (6) is synthesized.
[0022]
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[0023]
[In the above formula (6), R1 'to R8', R31 'and R32' have the same meanings as R1 to R8, R31 and R32 in formula (5). R1 to R8, R31 and R32 and R1 'to R8', R31 'and R32' may be the same or different. ]
(5) The method for synthesizing the perylene derivative according to any one of (1) to (4), wherein the coupling reaction is homo- or hetero-coupled using a catalyst.
(6) The catalyst has at least one of group VIII or group IB elements of Ni, Pd, Pt, Fe, Co, Ru, and Rh, or two or more of these elements and Cu A method for synthesizing a perylene derivative according to the above (5), which is a metal catalyst, a metal complex catalyst, or a metal compound having the above element.
(7) The catalyst is NiCl ₂ (dppe) or NiCl ₂ (dppp) or Ni (COD) ₂ A method for synthesizing the perylene derivative of (5) or (6) above.
(8) Using a 1,8-dihalogenated naphthalene derivative represented by the formula (1) of the above (2) and a naphthyl-1,8-diboronic acid derivative represented by the following formula (7),
[0024]
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[0025]
[In the above formula (7), R1 to R4, R11 and R12 have the same meaning as in formula (1). ]
A method for synthesizing a perylene derivative of (1) above, wherein the perylene derivative of formula (2) is synthesized by Suzuki coupling.
(9) Using a 3,4-dihalogenated fluoranthene derivative represented by the formula (3) of the above (3) and a fluorantheno-1,8-diboronic acid derivative represented by the following formula (8),
[0026]
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[0027]
[In the above formula (8), R1 to R6, R21 and R22 have the same meaning as in formula (3). ]
A method for synthesizing a perylene derivative of (1) above, wherein the perylene derivative of formula (4) is synthesized by Suzuki coupling.
(10) A 3,4-dihalogenated benzofluoranthene derivative represented by the formula (5) in the above (4) and a dibenzofluorantheno-1,8-diboronic acid derivative represented by the following formula (9) Use
[0028]
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[0029]
[In the above formula (9), R1 to R8, R31 and R32 have the same meaning as in formula (5). ]
A method for synthesizing a perylene derivative of (1) above, wherein the perylene derivative of formula (6) is synthesized by Suzuki coupling.
(11) Using a naphthalene derivative represented by the following formula (13),
[0030]
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[0031]
[In the above formula (13), R1 to R4, R11 and R12 have the same meaning as in formula (1). ]
The method for synthesizing a perylene derivative according to the above (1), wherein the perylene derivative is synthesized by Suzuki coupling.
(12) Using a fluoranthene derivative represented by the following formula (14),
[0032]
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[0033]
[In the above formula (14), R1 to R6, R21 and R22 have the same meaning as in formula (3). ]
A method for synthesizing a perylene derivative by synthesizing a perylene derivative by Suzuki coupling.
(13) Using a benzofluoranthene derivative represented by the following formula (15),
[0034]
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[0035]
[In the above formula (15), R1 to R8, R31 and R32 have the same meaning as in formula (5). ]
A method for synthesizing a perylene derivative by synthesizing a perylene derivative by Suzuki coupling.
(14) 1,8-dihalogenated naphthalene derivative represented by the formula (1) of the above (2) to (4), 3,4-dihalogenated fluoranthene derivative represented by the formula (3), represented by the formula (5) A perylene derivative synthesis method for obtaining an asymmetric compound using any one or two of 3,4-dihalogenated benzofluoranthene derivatives.
(15) The method for synthesizing a perylene derivative according to the above (14), wherein the asymmetric compound is a compound represented by the following formula (10).
[0036]
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[0037]
[In the above formula (10), R51 to R55, R61 to R65, R111 ' and R121 ' Is synonymous with R1 to R4, R11 and R12 in formula (1). ]
(16) The method for synthesizing a perylene derivative according to the above (1), wherein the perylene derivative is a compound represented by the following formula (11).
[0038]
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[0039]
[In the above formula (11), R111, R121, R111 'and R121' have the same meanings as R1 to R4, R11 and R12 in formula (1). ]
(17) The method for synthesizing a perylene derivative according to the above (1), wherein the perylene derivative is a compound represented by the following formula (12).
[0040]
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[0041]
[In the above formula (12), R111, R121, R111 ′ and R121 ′ have the same meanings as R1 to R4, R11 and R12 in the formula (1). ]
(18) The method for synthesizing a perylene derivative according to any one of the above (4) to (7), wherein at least R5 and R6 and / or R5 'and R6' are different.
(19) coupling a bisnaphthalene derivative represented by the following formula (16):
[0042]
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[0043]
[In the above formula (16), R1 to R4, R11 and R12 are a hydrogen atom, a linear chain which may have a substituent, a branched or cyclic alkyl group, a linear chain which may have a substituent, Branched or cyclic alkoxy group, optionally having a straight chain, branched or cyclic alkylthio group, optionally having a straight chain, branched or cyclic alkenyl group, having a substituent Linear, branched or cyclic alkenyloxy group which may be substituted, linear, branched or cyclic alkenylthio group which may be substituted, substituted or unsubstituted aralkyl group, substituted or unsubstituted aralkyloxy group Group, substituted or unsubstituted aralkylthio group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted arylthio group, substituted or unsubstituted amino group, Ano group, hydroxyl group, —COOM1 group (in which M1 is a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent, a linear chain which may have a substituent, branched or A cyclic alkenyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group), a -COM2 group (wherein M2 is a hydrogen atom, a linear or branched chain optionally having a substituent) Or a cyclic alkyl group, an optionally substituted linear, branched or cyclic alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or an amino group), or- OCOM3 (In the group, M3 is a linear, branched or cyclic alkyl group which may have a substituent, a linear, branched or cyclic alkenyl group which may have a substituent, substituted or unsubstituted. A An alkyl group, or a substituted or unsubstituted aryl group), and two or more adjacent groups selected from R1 to R4, R11 and R12 are bonded to each other or condensed to form a substituted carbon atom. In addition, a substituted or unsubstituted carbocyclic aliphatic ring, aromatic ring, or condensed aromatic ring may be formed. When these carbocyclic aliphatic rings, aromatic rings, or condensed aromatic rings have a substituent, the substituents are the same as R1 to R4, R11, and R12.
R1 ′ to R4 ′, R11 ′ and R12 ′ have the same meanings as R1 to R4, R11 and R12 in Formula (1). R1 to R4, R11 and R12 and R1 ′ to R4 ′, R11 ′ and R12 ′ may be the same or different. ]
A method for synthesizing a perylene derivative of the above (1), which synthesizes a perylene derivative represented by the following formula (2).
[0044]
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[0045]
[In the above formula (2), R1 'to R4', R11 'and R12' have the same meanings as R1 to R4, R11 and R12 in formula (1). R1 to R4, R11 and R12 and R1 'to R4', R11 'and R12' may be the same or different. ]
(20) An organic EL device containing a perylene derivative obtained by any one of the methods (1) to (19).
(21) The organic EL device according to (20), wherein the perylene derivative is contained in a light emitting layer.
(22) A perylene derivative having a structure represented by the following formula (10).
[0046]
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[0047]
[In the above formula (10), R51 to R55, R61 to R65, R111 ' and R121 ' Is synonymous with R1 to R4, R11 and R12 in formula (1). ]
[0048]
DETAILED DESCRIPTION OF THE INVENTION
In the synthesis method of the present invention, in order to obtain a perylene derivative, a starting material is halogenated and coupled, or a halogenated starting material and a boronated starting material are used, and these are Suzuki-coupled, or these are used in combination. To do.
[0049]
By using such a synthesis method, the target perylene derivative can be synthesized very efficiently, and the yield can reach 90% or more. In addition, a target object having no symmetry can be synthesized relatively easily by any one of the above synthesis methods or a combination thereof, and the use of asymmetric compounds that have not been used so far has been expanded. To do.
[0050]
Hereinafter, the synthesis method of the present invention will be described in detail for each embodiment.
[0051]
[First embodiment: coupling by halogenation]
In the synthesis method according to the first aspect of the present invention, a 1,8-dihalogenated naphthalene derivative represented by the following formula (1) is halogenated and coupled to synthesize a perylene derivative represented by the following formula (2). It is.
[0052]
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[0053]
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[0054]
The formula (1) will be explained. In the formula (1), R1 to R4, R11 and R12 each have a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent, and a substituent. Linear, branched or cyclic alkoxy group which may have, linear, branched or cyclic alkylthio group which may have a substituent, linear, branched or cyclic alkenyl which may have a substituent A linear, branched or cyclic alkenyloxy group which may have a substituent, a linear, branched or cyclic alkenylthio group which may have a substituent, a substituted or unsubstituted aralkyl group, Substituted or unsubstituted aralkyloxy group, substituted or unsubstituted aralkylthio group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted arylthio group, substituted or Unsubstituted amino group, cyano group, hydroxyl group, —COOM1 group (in which M1 is a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent, or a substituent. A linear, branched or cyclic alkenyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group), a -COM2 group (wherein M2 has a hydrogen atom or a substituent) May be a linear, branched or cyclic alkyl group, an optionally substituted linear, branched or cyclic alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or an amino group -OCOM3 (wherein M3 is a linear, branched or cyclic alkyl group which may have a substituent, a linear, branched or cyclic alkenyl group which may have a substituent) , Replace Represents an unsubstituted aralkyl group or a substituted or unsubstituted aryl group), and two or more adjacent groups selected from R1 to R4, R11 and R12 are bonded or condensed to each other to be substituted. A substituted or unsubstituted carbocyclic aliphatic ring, aromatic ring, or condensed aromatic ring may be formed together with the carbon atom. When these carbocyclic aliphatic rings, aromatic rings or condensed aromatic rings have a substituent, the substituents are the same as those for R1 to R4, R11 and R12.
[0055]
The aryl group represents a carbocyclic aromatic group such as a phenyl group or a naphthyl group, for example, a heterocyclic aromatic group such as a furyl group, a thienyl group, or a pyridyl group.
[0056]
In the formula (1), R1 to R4, R11 and R12 are linear, branched or cyclic alkyl groups, linear, branched or cyclic alkoxy groups, linear, branched or cyclic alkylthio groups, linear and branched. Alternatively, the cyclic alkenyl group, the linear, branched or cyclic alkenyloxy group, and the linear, branched or cyclic alkenylthio group may have a substituent, for example, a halogen atom, a carbon number of 4 to 20 Aryl group, alkoxy group having 1 to 20 carbon atoms, alkoxy alkoxy group having 2 to 20 carbon atoms, alkenyloxy group having 2 to 20 carbon atoms, aralkyloxy group having 4 to 20 carbon atoms, aralkyloxy having 5 to 20 carbon atoms Alkoxy group, aryloxy group having 3 to 20 carbon atoms, aryloxyalkoxy group having 4 to 20 carbon atoms, arylalkenyl group having 5 to 20 carbon atoms, carbon An aralkylalkenyl group having 6 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkoxyalkylthio group having 2 to 20 carbon atoms, an alkylthioalkylthio group having 2 to 20 carbon atoms, an alkenylthio group having 2 to 20 carbon atoms, and a carbon number An aralkylthio group having 4 to 20 carbon atoms, an aralkyloxyalkylthio group having 5 to 20 carbon atoms, an aralkylthioalkylthio group having 5 to 20 carbon atoms, an arylthio group having 3 to 20 carbon atoms, an aryloxyalkylthio group having 4 to 20 carbon atoms, The arylthioalkylthio group having 4 to 20 carbon atoms, the cyclic alkyl group having 4 to 20 carbon atoms, or a halogen atom may be mono- or polysubstituted. Furthermore, the aryl group contained in these substituents further includes an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 3 to 10 carbon atoms, an aralkyl group having 4 to 10 carbon atoms, and the like. May be substituted.
[0057]
In the formula (1), the aryl group in R1 to R4, R11 and R12 may have a substituent in the aralkyl group, aralkyloxy group, aralkylthio group, aryl group, aryloxy group and arylthio group. For example, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 4 to 20 carbon atoms, an aryl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 2 carbon atoms -20 alkoxyalkyl group, C2-C20 alkoxyalkyloxy group, C2-C20 alkenyloxy group, C3-C20 alkenyloxyalkyl group, C3-C20 alkenyloxyalkyloxy group , An aralkyloxy group having 4 to 20 carbon atoms, an aralkyloxyalkyl group having 5 to 20 carbon atoms, and an aralkyloxy group having 5 to 20 carbon atoms An alkyloxy group, an aryloxy group having 3 to 20 carbon atoms, an aryloxyalkyl group having 4 to 20 carbon atoms, an aryloxyalkyloxy group having 4 to 20 carbon atoms, an alkylcarbonyl group having 2 to 20 carbon atoms, and 3 carbon atoms -20 alkenylcarbonyl group, C5-20 aralkylcarbonyl group, C4-20 arylcarbonyl group, C2-20 alkoxycarbonyl group, C3-20 alkenyloxycarbonyl group, carbon number An aralkyloxycarbonyl group having 5 to 20 carbon atoms, an aryloxycarbonyl group having 4 to 20 carbon atoms, an alkylcarbonyloxy group having 2 to 20 carbon atoms, an alkenylcarbonyloxy group having 3 to 20 carbon atoms, and 5 to 20 carbon atoms Aralkylcarbonyloxy group, C4-20 arylcarbonyloxy group, C1-2 Alkylthio group, aralkylthio group having 4 to 20 carbon atoms, arylthio group having 3 to 20 carbon atoms, nitro group, cyano group, formyl group, halogen atom, halogenated alkyl group, hydroxyl group, amino group, 1 to 20 carbon atoms May be mono- or poly-substituted with a substituent such as an N-monosubstituted amino group or an N, N-disubstituted amino group having 2 to 40 carbon atoms.
[0058]
Furthermore, the aryl group contained in these substituents further includes an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, and the like. May be substituted.
[0059]
In the formula (1), the amino groups of R1 to R4, R11 and R12 may have a substituent, for example, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 4 to 20 carbon atoms, or a carbon number It may be monosubstituted or disubstituted with 3 to 20 aryl groups.
[0060]
Further, adjacent groups selected from R1 to R4, R11 and R12 are bonded or condensed to each other, and together with the substituted carbon atom, a substituted or unsubstituted carbocyclic aliphatic ring, aromatic ring, or condensed aromatic An aromatic ring may be formed.
[0061]
In the formula (1), a halogen element X is bonded to the 1 and 8 positions of the naphthalene derivative to be halogenated. The halogen element X used for halogenation may be any of Cl, Br, and I, and among these, Br is particularly preferable. The two halogen elements X may be the same or different, but are usually the same.
[0062]
The compound represented by the formula (1) is coupled with the halogen element and then coupled. For the coupling, various known methods can be used. In the present invention, a method in which a homo- or hetero-coupling reaction is performed using a catalyst is particularly preferable.
[0063]
The catalyst used in the reaction is not particularly limited as long as the coupling reaction can be performed, and various catalysts can be used. Specifically, it has any one or more of group VIII or IB elements excluding Cu, such as Ni, Pd, Pt, Fe, Co, Ru, and Rh, or these elements and Cu A metal catalyst having two or more elements, a metal complex catalyst, a metal compound, or the like can be given.
[0064]
Among these catalysts, a nickel catalyst is preferable, and various catalysts can be used as the Ni catalyst. Specifically, the Ni catalyst is [1,2-bis (diphenylphosphino) ethane]. Dichloronickel (II) [hereinafter: NiCl ₂ (dppe)], [1,3-bis (diphenylphosphino) propane] dichloronickel (II) [hereinafter: NiCl ₂ (dppp)], tetrakis (triphenylphosphine) nickel, or nickel-bis- (1.5-cyclooctadiene) [hereinafter: Ni (COD) ₂ And the like. In this case, NiCl ₂ (dppe) or NiCl ₂ Using (dppp) results in Grignard coupling.
[0065]
The coupling reaction conditions vary depending on the material and catalyst used, but Ni (COD) ₂ As an example, a halogenated naphthalene derivative is dissolved preferably in an amount of 0.01 to 10 mol / l, particularly 0.05 to 1 mol / l in a solvent such as DMF, and nickel is added thereto. Catalyst [Ni (COD) ₂ Etc.]. At this time, the amount of the catalyst to be used may be usually an equimolar amount, but considering that a part of the catalyst may lose its activity, it is preferably equimolar to 1.5 times, especially equimolar to 1. About 2 times the amount is good. Further, if necessary, cyclooctadiene (COD) is added 2 to 10 times mol of halogenated naphthalene and 0.5 to 5 times mol of pyridine is added to the halogenated derivative, and 50 to 100 ° C., particularly 60 to 90 ° C. The reaction is carried out at 0.degree. C. for 0.5-12 hours, especially about 1-5 hours. After the reaction, an aqueous hydrochloric acid solution, methanol, or the like may be added to precipitate and recover the target product.
[0066]
A compound represented by the formula (2) is obtained by a coupling reaction of such a halogenated naphthalene, preferably using a catalyst.
[0067]
In the formula (2), R1 ′ to R4 ′, R11 ′ and R12 ′ have the same meanings as R1 to R4, R11 and R12 in the formula (1). R1 to R4, R11 and R12 and R1 'to R4', R11 'and R12' may be the same or different, but are preferably different.
[0068]
The 3,4-dihalogenated fluoranthene derivative represented by the following formula (3) is coupled by the coupling reaction of the halogenated naphthalene according to the first aspect of the present invention, preferably using a catalyst, to obtain the following formula (4): It is also possible to synthesize perylene derivatives represented by
[0069]
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[0070]
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[0071]
In the above formula (3), R1 to R6, R21 and R22 are the same as R1 to R4, R11 and R12 in the formula (1), and the preferred ranges are also the same.
[0072]
That is, in the formula (3), R1 to R6, R21 and R22 are a hydrogen atom, a linear chain which may have a substituent, a branched or cyclic alkyl group, a linear chain which may have a substituent, Branched or cyclic alkoxy group, optionally having a straight chain, branched or cyclic alkylthio group, optionally having a straight chain, branched or cyclic alkenyl group, having a substituent Linear, branched or cyclic alkenyloxy group which may be substituted, linear, branched or cyclic alkenylthio group which may be substituted, substituted or unsubstituted aralkyl group, substituted or unsubstituted aralkyloxy group Group, substituted or unsubstituted aralkylthio group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted arylthio group, substituted or unsubstituted amino group, Group, hydroxyl group, -COOM1 group (in which M1 is a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent, a linear group which may have a substituent, branched or A cyclic alkenyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group), a -COM2 group (wherein M2 is a hydrogen atom, a linear or branched group optionally having a substituent) Or a cyclic alkyl group, an optionally substituted linear, branched or cyclic alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or an amino group), or- OCOM3 (wherein M3 is a linear, branched or cyclic alkyl group which may have a substituent, a linear, branched or cyclic alkenyl group which may have a substituent, substituted or unsubstituted Aralkyl Or a substituted or unsubstituted aryl group), and two or more adjacent groups selected from R1 to R6, R21 and R22 are bonded or condensed to each other, together with the substituted carbon atom, A substituted or unsubstituted carbocyclic aliphatic ring, aromatic ring, or condensed aromatic ring may be formed.
[0073]
In the formula (4), R1 ′ to R6 ′, R21 ′ and R22 ′ have the same meanings as R1 to R6, R21 and R22 in the formula (3). R1 to R6, R21 and R22 and R1 'to R6', R21 'and R22' may be the same or different.
[0074]
A 3,4-dihalogenated benzofluoranthene derivative represented by the following formula (5) is coupled by a coupling reaction of the halogenated naphthalene according to the first aspect of the present invention, preferably using a catalyst, A perylene derivative represented by the formula (6) can also be synthesized.
[0075]
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[0076]
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[0077]
In the above formula (5), R1 to R8, R31 and R32 are the same as R1 to R4, R11 and R12 in the formula (1), and the preferred ranges are also the same.
[0078]
That is, in the above formula (5), R1 to R8, R31 and R32 are each a hydrogen atom, a linear chain which may have a substituent, a branched or cyclic alkyl group, and a linear chain which may have a substituent. A branched or cyclic alkoxy group, a linear, branched or cyclic alkylthio group which may have a substituent, a linear, branched or cyclic alkenyl group which may have a substituent, and a substituent. Linear, branched or cyclic alkenyloxy group which may be substituted, linear, branched or cyclic alkenylthio group which may be substituted, substituted or unsubstituted aralkyl group, substituted or unsubstituted aralkyl An oxy group, a substituted or unsubstituted aralkylthio group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted amino group, A cyano group, a hydroxyl group, a -COOM1 group (wherein M1 is a hydrogen atom, an optionally substituted straight chain, branched or cyclic alkyl group, an optionally substituted straight chain, branched or A cyclic alkenyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group), a -COM2 group (wherein M2 is a hydrogen atom, a linear or branched group optionally having a substituent) Or a cyclic alkyl group, an optionally substituted linear, branched or cyclic alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or an amino group), or- OCOM3 (wherein M3 is a linear, branched or cyclic alkyl group which may have a substituent, a linear, branched or cyclic alkenyl group which may have a substituent, substituted or unsubstituted Aral Or a substituted or unsubstituted aryl group), and two or more adjacent groups selected from R1 to R8, R31 and R32 are bonded to or condensed with each other to form a substituted carbon atom In addition, a substituted or unsubstituted carbocyclic aliphatic ring, aromatic ring, or condensed aromatic ring may be formed.
[0079]
In the above formula (6), R1 'to R8', R31 'and R32' have the same meanings as R1 to R8, R31 and R32 in formula (5). R1 to R8, R31 and R32 and R1 'to R8', R31 'and R32' may be the same or different.
[0080]
In the above formula (6), at least R5 and R6 and / or R5 'and R6' are preferably different. By having such an asymmetric structure, an orange to red light emitting material, or an electron or hole transport material can be obtained as an organic EL material.
[0081]
Further, the dissolution can be improved, the material can be easily purified, the decomposability during the sublimation purification can be suppressed, and the fluorescence is also improved. Furthermore, the interaction with the same or different molecules can be reduced, the fluorescence luminance of the EL element is improved, and the concentration quenching is suppressed, so that the margin as an EL dopant is improved and the degree of freedom in design is improved.
[0082]
Further, a 1,8-dihalogenated naphthalene derivative represented by the above formula (1), a 3,4-dihalogenated fluoranthene derivative represented by the formula (3), and a 3,4-dihalogenated compound represented by the formula (5) It is also possible to obtain an asymmetric compound by heterocoupling using any one or two of benzofluoranthene derivatives.
[0083]
Thus, by using the method of the present invention, an asymmetric compound can be easily produced freely, and the yield of the target compound is also dramatically improved.
[0084]
Such an asymmetric compound is not particularly limited as long as it is obtained by a combination of formulas (1), (3), and (5), but in the present invention, in particular, the following formula (10) The compounds represented are preferred.
[0085]
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[0086]
In the above formula (10), R51 to R55, R61 to R65, R111 'and R121' have the same meanings as R1 to R4, R11 and R12 in the formula (1). R1 to R4, R1 'to R4' R31 and R32 are the same as those in the formula (1).
[0087]
With such a structure, an orange to green light emitting material, or an electron or hole transport material can be obtained as the organic EL material.
[0088]
Further, the perylene derivative represented by the formula (2) is preferably a compound represented by the following formula (11).
[0089]
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[0090]
In the above formula (11), R111, R121, R111 ′ and R121 ′ have the same meanings as R1 to R4, R11 and R12 in the formula (1).
[0091]
Alternatively, the perylene derivative represented by the above formula (2) may be a compound represented by the following formula (12).
[0092]
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[0093]
In the above formula (12), R111, R121, R111 ′ and R121 ′ have the same meanings as R1 to R4, R11 and R12 in the formula (1).
[0094]
The compound represented by the formula (11) and the compound represented by the formula (12) are not clearly distinguished from each other, and become a compound represented by the formula (11) depending on the state of conjugated electrons. Or a compound represented by Formula (12). However, in the present invention, the state of the compound represented by the formula (12) is more preferable.
[0095]
The synthesis scheme of these synthesis methods is shown below.
[0096]
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[0097]
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[0098]
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[0099]
[Second aspect: Suzuki coupling with boronic acid derivative]
The synthesis method according to the second aspect of the present invention uses a 1,8-dihalogenated naphthalene derivative represented by the formula (1) and a naphthyl-1,8-diboronic acid derivative represented by the following formula (7). This is a method for synthesizing a perylene derivative by synthesizing a perylene derivative of the formula (2) by Suzuki coupling.
[0100]
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[0101]
In the above formula (7), R1 to R4, R11 and R12 have the same meanings as R1 to R4, R11 and R12 in the formula (1). The boronic acid derivative represented by Z is usually B (OH) ₂ A boronic acid represented by the formula is used, but derivatives having the same action are also included.
[0102]
The Suzuki coupling reaction is carried out, for example, by treating the compounds of the formulas (1) and (7) in a reaction inert solvent in the presence of a base and a palladium catalyst at a temperature of room temperature to 125 ° C. for 10 minutes to 24 hours. A reaction product is obtained.
[0103]
The solvent to be used is not particularly limited. For example, aromatic hydrocarbons (eg, benzene, toluene, etc.), ethers (eg, tetrahydrofuran, dioxane, etc.), amides (eg, dimethylformamide, dimethylacetamide, etc.), esters Examples include a system (for example, ethyl acetate), an alcohol system (for example, methanol), a ketone system (for example, acetone, cyclohexanone, and the like).
[0104]
Further, a perylene derivative of the formula (4) is obtained by Suzuki coupling using a 3,4-dihalogenated fluoranthene derivative represented by the formula (3) and a fluorantheno-1,8-diboronic acid derivative represented by the following formula (8). Can also be synthesized.
[0105]
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[0106]
In the above formula (8), R1 to R6 and R21 and R22 have the same meanings as R1 to R6 and R21 and R22 in the formula (3).
[0107]
Furthermore, using a 3,4-dihalogenated benzofluoranthene derivative represented by the formula (5) and a dibenzofluorantheno-1,8-diboronic acid derivative represented by the following formula (9), the compound was obtained by Suzuki coupling. The perylene derivative (6) can also be synthesized.
[0108]
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[0109]
The synthesis scheme of these synthesis methods is shown below.
[0110]
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[0111]
[Third Aspect: Coupling by Combined Use of Halogenation and Boron Derivative]
In the third aspect of the present invention, the coupling by halogenation according to the first aspect and the coupling by a boron derivative according to the second aspect are used in combination. That is, using a naphthalene derivative represented by the following formula (13),
[0112]
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[0113]
This is a method for synthesizing a perylene derivative by synthesizing a perylene derivative by Suzuki coupling.
[0114]
In the above formula (13), R1 to R4, R11 and R12 have the same meaning as in formula (1). X and Z are the same as those in the first and second aspects, and the preferable ones are also the same (the same applies to the following formulas 14 and 15).
[0115]
Further, using a fluoranthene derivative represented by the following formula (14),
[0116]
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[0117]
Perylene derivatives can also be synthesized by Suzuki coupling.
[0118]
In the above formula (14), R1 to R6, R21 and R22 have the same meaning as in the formula (3).
[0119]
Furthermore, using a benzofluoranthene derivative represented by the following formula (15),
[0120]
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[0121]
Perylene derivatives can also be synthesized by Suzuki coupling.
[0122]
In the above formula (15), R1 to R8, R31 and R32 have the same meaning as in formula (5).
[0123]
[Fourth Embodiment: Synthesis from Bishalogenated Naphthalene]
The method of the present invention is characterized in that a coupling treatment is carried out using a modification site by halogenation or a modification site by a boronic acid derivative. The two binding sites may be bonded at the same time or may be bonded one by one over time, the modified sites may be modified at two sites simultaneously, or may be modified one by one over time. .
[0124]
Therefore, in the method of the present invention, a bisnaphthalene derivative represented by the following formula (16) is used as a starting material or an intermediate, and this is coupled.
[0125]
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[0126]
A method of synthesizing a perylene derivative represented by the following formula (2) is also included in the present invention.
[0127]
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[0128]
In the above formula (16), R1 to R4, R11 and R12 have the same meanings as R1 to R4, R11 and R12 in the formula (1). In the above formula (2), R1 ′ to R4 ′, R11 ′ and R12 ′ have the same meanings as R1 to R4, R11 and R12 in the formula (1). R1 to R4, R11 and R12 and R1 'to R4', R11 'and R12' may be the same or different. X represents a halogen element, the details of which are the same as in the description of the above formula (1). In some cases, one may be a boronic acid derivative represented by Z.
[0129]
The method of the present invention is particularly effective as a method for synthesizing the compound represented by the formula (6). In the formula (6), R1 to R8 and R31, R32, R1 'to R8' and R31 'and R32' are any of substituted or unsubstituted aryl groups, alkyl groups, alkenyl groups, alkoxy groups and aryloxy groups. It is preferable that
[0130]
Furthermore, in the compound represented by the formula (6), it is preferable that any one or more of R1 to R8 and R31, R32, R1 'to R8' and R31 'and R32' is an ortho-substituted phenyl group. By using the method of the present invention, a compound having a substituent at a specific position such as ortho-position substitution can be easily obtained. In addition, a vertically and horizontally asymmetric compound can be easily obtained.
[0131]
In particular, in the compound represented by the formula (6), either or both of R5 and R6, R5 'and R6' or both (left and right) or both (up and down) may be an ortho-substituted phenyl group. preferable.
[0132]
Thus, by introducing a substituent at the ortho position, the decomposability during sublimation purification can be suppressed. In addition, fluorescence is improved by introducing a substituent at the ortho position.
[0133]
By using such an ortho-substituted compound, the fluorescence brightness of the EL element is improved and the concentration quenching property is suppressed, so that the margin as an EL dopant is improved and the degree of freedom in design is improved.
[0134]
That is, by introducing an ortho-substituted phenyl group, the associative property of the perylene skeleton can be controlled by the steric hindrance, the solubility in a solvent is improved, and the purification can be performed with high purity. For the same reason, sublimation purification can be performed at a lower temperature, decomposition during sublimation purification hardly occurs, and this point is also effective for obtaining a high-purity material. When an element is manufactured, exciton is hardly deactivated by impurities, and high light emission efficiency can be obtained.
[0135]
Another reason why high luminous efficiency can be obtained is to suppress concentration quenching by suppressing association between the same molecules or different molecules in the light emitting layer.
[0136]
Preferred specific examples of the compounds represented by formulas (2), (4) and (6) are shown below.
[0137]
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[0138]
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[0139]
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[0140]
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[0141]
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[0142]
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[0143]
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[0144]
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[0145]
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[0146]
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[0147]
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[0148]
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[0149]
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[0150]
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[0151]
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[0152]
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[0153]
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[0154]
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[0155]
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[0156]
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[0157]
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[0158]
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[0159]
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[0160]
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[0161]
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[0162]
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[0163]
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[0164]
[Chemical Formula 86]
[0165]
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[0166]
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[0167]
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[0168]
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[0169]
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[0170]
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[0171]
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[0172]
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[0173]
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[0174]
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[0175]
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[0176]
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[0177]
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[0178]
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[0179]
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[0180]
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[0181]
More preferred are the compounds exemplified below.
[0182]
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[0183]
The diindeno [1,2,3-cd: 1 ′, 2 ′, 3′-lm] perylene derivative represented by the above formula (6) has a vibration structure in both the excitation spectrum and the emission spectrum. preferable. Such a vibration structure can be confirmed from the fact that two or more peaks appear in each spectrum.
[0184]
More preferably, the host material used when the indenoperylene derivative is doped is also preferred to have such a vibration structure.
[0185]
By having the vibration structure, an organic EL element having excellent temperature characteristics can be obtained.
[0186]
The decrease in EL luminous efficiency due to temperature is considered to be due to thermal relaxation accompanied by a change in conformation in the excited state. When the conformation changes in the excited state, the overlap of the molecular orbital functions of the ground state and the excited state changes, so that the emission spectrum is not a mirror image of the absorption spectrum. Further, although the emission spectrum of the excited state can take many conformations, the emission spectrum is a sum of various vibration structures, so that it appears to be a broad spectrum having no vibration structure.
[0187]
Therefore, an organic compound having a vibration structure in the emission spectrum, and a compound whose vibration structure is a mirror image of the absorption spectrum has little conformational change in an excited state, and when used as a light-emitting material of an organic EL element, It is possible to provide an element having excellent temperature characteristics with little decrease in EL luminous efficiency due to temperature.
[0188]
For the same reason, a compound having a Stokes shift of 0.1 eV or less, particularly 0.05 eV or less is preferred. The lower limit is not particularly limited, but is usually about 0.01 eV.
[0189]
Another factor that affects the temperature characteristics of the organic EL element is thermal excitation of carriers from the trap order. In particular, in the doped light-emitting layer, the dopant forms a trap order, so when the temperature changes, the carrier hopping probability due to thermal excitation changes, and as a result, the carrier balance in the light-emitting layer changes, and the efficiency May have large temperature-dependent characteristics. In the element of the present invention, such a change in the trapping property of the light emitting layer due to heat is small, and an element having low temperature dependency of efficiency can be obtained.
[0190]
It is desirable that the electron affinity of any one of the host materials contained in the light-emitting layer, particularly at least one of the organic compounds represented by the following formula (I), is larger than the electron affinity of the electron transport layer and / or the hole transport layer. When the electron affinity of the host material contained in the light emitting layer is larger than the electron affinity of the electron transport layer and / or the hole transport layer, the efficiency of injecting electrons into the light emitting layer is improved, and electrons are injected at the interface of the hole transport layer. Since it is blocked, the light emission efficiency is improved and the device life is also improved.
[0191]
One of the compounds serving as a preferred host material of the present invention has a basic skeleton represented by the following formula (I).
[0192]
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[0193]
In the device of the present invention, a naphthacene derivative is preferably used as a host material, whereby strong light emission from a dopant can be obtained.
[0194]
A naphthacene derivative is a particularly preferable organic material as a host material in the above organic material group. For example, a film obtained by doping 1% by mass of a dibenzo [f, f ′] diindeno [1,2,3-cd: 1 ′, 2 ′, 3′-lm] perylene derivative as a dopant into a naphthacene derivative as a host material When the fluorescence intensity by photoexcitation of is measured, the fluorescence intensity is about three times that of the case where another organic substance (for example, Alq3) is used as a host.
[0195]
The reason why such strong fluorescence can be obtained is that the naphthacene derivative and the dopant substance have an ideal combination that does not cause an interaction such as the formation of an exciplex, and further, due to the dipolar interaction between both molecules. It is conceivable that the fluorescence intensity is maintained high.
[0196]
In addition, when the dopant is red, the energy gap is relatively close to that of the dopant, so that in addition to the energy transfer due to electron exchange, an energy transfer phenomenon due to light emission reabsorption also occurs, and such a high fluorescence luminance can be obtained. it is conceivable that.
[0197]
Furthermore, the fact that the concentration quenching property of the dopant can be kept very small by the combination with the host material also contributes to such strong fluorescence intensity.
[0198]
Further, when an organic EL element having the above doped film as a light emitting layer is prepared, 10 mA / cm ² 600 cd / m at the maximum current density ² The above luminance is obtained, and the driving voltage at this time is as low as about 6V. 600mA / cm ² At a current density of about 20000 cd / m ² The above luminance can be obtained stably. Compared to the case where another organic substance (for example, Alq3) is used as a host, this is about 4 times the luminous efficiency in terms of current efficiency and can be driven at a lower voltage, so the power efficiency is about 5 times as efficient. is there. Further, when the red dopant as in the above example is doped, the energy transfer efficiency from the host to the dopant is good, so that light emission from the host is hardly seen, and only the dopant has high color purity. An element is obtained.
[0199]
Such a very good light emission efficiency when an organic EL device is produced is not only the above-mentioned mechanism for obtaining a strong fluorescence intensity, but also an improvement in the carrier recombination probability in the light emitting layer, and further a naphthacene triplet. This is considered to be due to effects such as generation of a singlet excited state of the dopant by energy transfer from the excited state.
[0200]
Further, in a general organic EL element, the drive voltage becomes high due to carrier trapping by a dopant, whereas the drive voltage of the organic EL element using the light emitting layer is very low in the element of the present invention. This is because the order of dopant carrier traps is small, and high-efficiency light emission is realized by the mechanism described above. Furthermore, it is conceivable that carriers can be easily injected into the light emitting layer.
[0201]
In addition, since a naphthacene derivative is very stable and has high durability against carrier injection, an element formed using a combination of the host and the dopant has a very long lifetime. For example, in a device having a light emitting layer in which a specific naphthacene derivative is doped with 1% by mass of dibenzo [f, f ′] diindeno [1,2,3-cd: 1 ′, 2 ′, 3′-lm] perylene, 50mA / cm ² When driven at 2400cd / m ² It is also possible to obtain a highly durable element in which the above luminance lasts for 1000 hours or more with only attenuation of about 1% or less.
[0202]
In the organic EL element as described above, the doping concentration that keeps the color purity of the element and maximizes the efficiency is about 1% by mass, but even about 2 to 3% by mass, it is sufficient to reduce only about 10% or less. Thus, an element that can withstand practical use can be obtained.
[0203]
In formula (I), Q ¹ ~ Q ^Four Each represents hydrogen or an unsubstituted or substituted alkyl group, aryl group, amino group, heterocyclic group or alkenyl group. Moreover, it is preferably any of an aryl group, an amino group, a heterocyclic group, and an alkenyl group. Q ¹ , Q ^Four Is hydrogen and Q ² , Q ^Three Those in which is the above substituent are also preferred.
[0204]
Q ¹ ~ Q ^Four The aryl group represented by can be monocyclic or polycyclic, and includes condensed rings and ring assemblies. The total carbon number is preferably 6 to 30, and may have a substituent.
[0205]
Q ¹ ~ Q ^Four As the aryl group represented by, preferably a phenyl group, (o-, m-, p-) tolyl group, pyrenyl group, perylenyl group, coronenyl group, (1- and 2-) naphthyl group, anthryl group, (O-, m-, p-) biphenylyl group, terphenyl group, phenanthryl group and the like.
[0206]
Q ¹ ~ Q ^Four The amino group represented by may be any of alkylamino group, arylamino group, aralkylamino group and the like. These preferably have an aliphatic group having 1 to 6 carbon atoms in total and / or an aromatic carbocyclic ring having 1 to 4 rings. Specific examples include a dimethylamino group, a diethylamino group, a dibutylamino group, a diphenylamino group, a ditolylamino group, a bisdiphenylylamino group, and a bisnaphthylamino group.
[0207]
Q ¹ ~ Q ^Four Examples of the heterocyclic group represented by the formula include a 5-membered or 6-membered aromatic heterocyclic group containing O, N, S as a hetero atom, and a condensed polycyclic aromatic heterocyclic group having 2 to 20 carbon atoms. Can be mentioned.
[0208]
Q ¹ ~ Q ^Four Are represented by (1- and 2-) phenylalkenyl groups, (1,2-, and 2,2-) diphenylalkenyl groups having a phenyl group as at least one substituent, (1 , 2,2-) triphenylalkenyl group and the like are preferable, but may be unsubstituted.
[0209]
Examples of the aromatic heterocyclic group and the condensed polycyclic aromatic heterocyclic group include a thienyl group, a furyl group, a pyrrolyl group, a pyridyl group, a quinolyl group, and a quinoxalyl group.
[0210]
Q ¹ ~ Q ^Four When has a substituent, at least two of these substituents are preferably any of an aryl group, an amino group, a heterocyclic group, an alkenyl group, and an aryloxy group. For the aryl group, amino group, heterocyclic group and alkenyl group, the above Q ¹ ~ Q ^Four It is the same.
[0211]
Q ¹ ~ Q ^Four As the aryloxy group serving as a substituent, a group having an aryl group having 6 to 18 carbon atoms is preferable, and specifically, an (o-, m-, p-) phenoxy group or the like.
[0212]
Two or more of these substituents may form a condensed ring. Further, it may be further substituted, and preferred substituents in that case are the same as described above.
[0213]
Q ¹ ~ Q ^Four When has a substituent, it is preferable that at least two or more thereof have the above-described substituent. The substitution position is not particularly limited, and may be any of meta, para, and ortho positions. Q ¹ And Q ^Four , Q ² And Q ^Three Are preferably the same, but may be different.
[0214]
Q ^Five , Q ⁶ , Q ⁷ And Q ⁸ Each represents hydrogen or an alkyl group, aryl group, amino group, alkenyl group and heterocyclic group which may have a substituent.
[0215]
Q ^Five , Q ⁶ , Q ⁷ And Q ⁸ As the alkyl group represented by formula (1), those having 1 to 6 carbon atoms are preferable, which may be linear or branched. Preferable specific examples of the alkyl group include methyl group, ethyl group, (n, i) propyl group, (n, i, sec, tert) -butyl group, (n, i, neo, tert) -pentyl group and the like. Can be mentioned.
[0216]
Q ^Five , Q ⁶ , Q ⁷ And Q ⁸ As the aryl group, amino group and alkenyl group represented by ¹ ~ Q ^Four It is the same as the case of. Q ^Five And Q ⁶ , Q ⁷ And Q ⁸ Are preferably the same, but they may be different.
[0217]
Q ¹ ~ Q ^Four Are all phenyl groups and Q ^Five , Q ⁶ , Q ⁷ And Q ⁸ It is preferable not to contain rubrene in which is hydrogen.
[0218]
The light-emitting layer containing the host material and the dopant has a hole and electron injection function, a transport function thereof, and a function of generating excitons by recombination of holes and electrons. In the light emitting layer, in addition to the compound of the present invention, a relatively electronically neutral compound can be used to inject and transport electrons and holes easily and in a balanced manner.
[0219]
The above host materials may be used alone or in combination of two or more. The mixing ratio in the case of using a mixture of two or more is arbitrary. The host material is preferably contained in the light emitting layer in an amount of 80 to 99.9% by mass, particularly 90 to 99.9% by mass, and more preferably 95.0 to 99.5% by mass. .
[0220]
Further, the thickness of the light emitting layer is preferably less than the thickness of the organic compound layer from the thickness corresponding to one molecular layer, specifically 1 to 85 nm, more preferably 5 to 60 nm, In particular, the thickness is preferably 5 to 50 nm.
[0221]
In addition, as a method for forming the mixed layer, co-evaporation is preferably performed by evaporating from different evaporation sources, but when the vapor pressure (evaporation temperature) is the same or very close, the mixture is previously mixed in the same evaporation board, It can also be deposited. In the mixed layer, it is preferable that the compounds are uniformly mixed, but in some cases, the compounds may be present in an island shape. In general, the light emitting layer is formed to have a predetermined thickness by depositing an organic fluorescent material or coating the light emitting layer by dispersing it in a resin binder.
[0222]
As a structural example of the organic EL light emitting device manufactured using the compound of the present invention, for example, a hole injection electrode, a hole injection / transport layer, a light emission and electron injection transport layer, and an electron injection electrode are sequentially provided on a substrate. Moreover, you may have a protective electrode, an auxiliary electrode, and a sealing layer on the electron injection electrode as needed.
[0223]
The organic EL device of the present invention is not limited to the above example, and can have various configurations. For example, a light emitting layer is provided alone, and an electron injection / transport layer is interposed between the light emitting layer and the electron injection electrode. It can also be a structure. If necessary, the hole injection / transport layer and the light emitting layer may be mixed.
[0224]
The thickness of the light emitting layer, the thickness of the hole injecting and transporting layer, and the thickness of the electron injecting and transporting layer are not particularly limited and vary depending on the forming method, but are usually about 5 to 500 nm, particularly preferably 10 to 300 nm. .
[0225]
The thickness of the hole injecting and transporting layer and the thickness of the electron injecting and transporting layer may be about the same as the thickness of the light emitting layer or about 1/10 to 10 times depending on the design of the recombination / light emitting region. When the injection layer and the transport layer for holes or electrons are separated, the injection layer is preferably 1 nm or more, and the transport layer is preferably 1 nm or more. In this case, the upper limit of the thickness of the injection layer and the transport layer is usually about 500 nm for the injection layer and about 500 nm for the transport layer. Such a film thickness is the same when two injection transport layers are provided.
[0226]
The hole injecting and transporting layer has the function of facilitating the injection of holes from the hole injecting electrode, the function of stably transporting holes, and the function of blocking electrons, and the electron injecting and transporting layer is the injection of electrons from the electron injecting electrode. These layers have the function of easily transporting electrons, the function of transporting electrons stably, and the function of blocking holes. These layers increase and confine holes and electrons injected into the light-emitting layer and optimize the recombination region. And improve luminous efficiency.
[0227]
Examples of the hole injecting and transporting layer include, for example, Japanese Patent Application Laid-Open No. 63-295695, Japanese Patent Application Laid-Open No. 2-191694, Japanese Patent Application Laid-Open No. Hei 3-792, Japanese Patent Application Laid-Open No. Hei 5-23481, and Japanese Patent Application Laid-Open No. 5-239455. Various organic compounds described in JP-A No. 5-299174, JP-A No. 7-126225, JP-A No. 7-126226, JP-A No. 8-100192, EP0650955A1, and the like can be used. For example, tetraarylbenzidine compounds (triaryldiamine or triphenyldiamine: TPD), aromatic tertiary amines, hydrazone derivatives, carbazole derivatives, triazole derivatives, imidazole derivatives, oxadiazole derivatives having amino groups, polythiophenes, etc. . Two or more of these compounds may be used in combination, and when used in combination, they may be laminated as separate layers or mixed.
[0228]
When the hole injecting and transporting layer is divided into the hole injecting layer and the hole transporting layer, a preferred combination can be selected from the compounds for the hole injecting and transporting layer. At this time, it is preferable to laminate in order of a compound layer having a small ionization potential from the hole injection electrode (ITO or the like) side. Further, it is preferable to use a compound having a good thin film property on the surface of the hole injection electrode. Such a stacking order is the same when two or more hole injecting and transporting layers are provided. By adopting such a stacking order, the drive voltage is lowered, and the occurrence of current leakage and the generation / growth of dark spots can be prevented. In addition, in the case of elementization, since vapor deposition is used, a thin film of about 1 to 10 nm can be made uniform and pinhole-free, so that the ion injection potential is small in the hole injection layer and the visible portion has absorption. Even if such a compound is used, it is possible to prevent a decrease in efficiency due to a change in color tone of light emission and reabsorption. The hole injecting and transporting layer can be formed by evaporating the above compound in the same manner as the light emitting layer and the like.
[0229]
In addition, the electron injecting and transporting layer includes a quinoline derivative such as an organometallic complex having an 8-quinolinol or its derivative such as tris (8-quinolinolato) aluminum (Alq3) as a ligand, an oxadiazole derivative, a perylene derivative, Pyridine derivatives, pyrimidine derivatives, quinoxaline derivatives, diphenylquinone derivatives, nitro-substituted fluorene derivatives, and the like can be used. The electron injecting and transporting layer may also serve as the light emitting layer. In such a case, it is preferable to use the light emitting layer of the present invention. The electron injecting and transporting layer may be formed by vapor deposition or the like as in the light emitting layer.
[0230]
When the electron injecting and transporting layer is divided into an electron injecting layer and an electron transporting layer, a preferred combination can be selected from the compounds for the electron injecting and transporting layer. At this time, it is preferable to laminate in the order of compounds having a large electron affinity value from the electron injection electrode side. Such a stacking order is the same when two or more electron injecting and transporting layers are provided.
[0231]
In forming the hole injecting and transporting layer, the light emitting layer, and the electron injecting and transporting layer, it is preferable to use a vacuum deposition method because a homogeneous thin film can be formed. When the vacuum deposition method is used, a homogeneous thin film having an amorphous state or a crystal grain size of 0.1 μm or less can be obtained. If the crystal grain size exceeds 0.1 μm, non-uniform light emission occurs, the drive voltage of the element must be increased, and the hole injection efficiency is significantly reduced.
[0232]
The conditions for vacuum deposition are not particularly limited, but 10 ^-Four It is preferable that the degree of vacuum is less than or equal to Pa, and the deposition rate is about 0.01 to 1 nm / sec. Moreover, it is preferable to form each layer continuously in a vacuum. If formed continuously in a vacuum, impurities can be prevented from adsorbing to the interface of each layer, so that high characteristics can be obtained. Further, the driving voltage of the element can be lowered, and the growth / generation of dark spots can be suppressed.
[0233]
In the case of using a vacuum deposition method for forming each of these layers, when a plurality of compounds are contained in one layer, it is preferable to co-deposit each boat containing the compounds by individually controlling the temperature.
[0234]
The electron injection electrode is preferably made of a metal, alloy or intermetallic compound having a work function of 4 eV or less. When the work function exceeds 4 eV, the electron injection efficiency decreases, and as a result, the light emission efficiency also decreases. Examples of the constituent metal of the electron injection electrode film having a work function of 4 eV or less include alkali metals such as Li, Na and K, alkaline earth metals such as Mg, Ca, Sr and Ba, rare earth metals such as La and Ce, Al, In, Ag, Sn, Zn, Zr, and the like. Examples of the constituent alloy of the film having a work function of 4 eV or less include Ag · Mg (Ag: 0.1 to 50 at%), Al·Li (Li: 0.01 to 12 at%), and In · Mg (Mg: 50). ˜80 at%), Al · Ca (Ca: 0.01 to 20 at%), and the like. These may be present singly or as a combination of two or more, and the mixing ratio when two or more of these are combined is arbitrary. Alternatively, an oxide or halide of an alkali metal, alkaline earth metal, or rare earth metal may be thinly formed, and a support electrode (auxiliary electrode, wiring electrode) such as aluminum may be used.
[0235]
This electron injection electrode can be formed by vapor deposition or sputtering.
[0236]
The thickness of such an electron injection electrode may be a certain thickness that can sufficiently perform electron injection, and may be 0.1 nm or more. Moreover, although there is no restriction | limiting in particular in the upper limit, Usually, a film thickness should just be about 0.1-500 nm.
[0237]
For the hole injection electrode, it is preferable to determine the material and thickness so that the transmittance of the emitted light is preferably 80% or more. Specifically, an oxide transparent conductive thin film is preferable, for example, tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), indium oxide (In ₂ O _Three ), Tin oxide (SnO) ₂ ) And zinc oxide (ZnO) are preferred. These oxides may deviate somewhat from their stoichiometric composition. In ₂ O _Three Against SnO ₂ The mixing ratio is preferably 1 to 20% by mass, more preferably 5 to 12% by mass. In ₂ O _Three On the other hand, the mixing ratio of ZnO is preferably 12 to 32% by mass.
[0238]
The hole injection electrode preferably has an emission wavelength band, usually 350 to 800 nm, and particularly has a light transmittance of 80% or more, particularly 90% or more for each emission light. Usually, since emitted light is extracted through the hole injection electrode, if the transmittance is lowered, the light emitted from the light emitting layer itself is attenuated, and there is a tendency that luminance necessary for the light emitting element cannot be obtained. However, it is sufficient that the side from which the emitted light is extracted is 80% or more.
[0239]
The thickness of the hole injection electrode is sufficient if it has a certain thickness that allows sufficient hole injection, and is preferably in the range of 50 to 500 nm, more preferably 50 to 300 nm. The upper limit is not particularly limited, but if it is too thick, there is a concern about peeling. If the thickness is too thin, there are problems in terms of film strength, hole transport capability, and resistance value during manufacture.
[0240]
A sputtering method is preferable for forming the hole injection electrode. As the sputtering method, a high-frequency sputtering method using an RF power source or the like is possible, but the DC sputtering method is used in consideration of easy control of film physical properties of the hole injection electrode to be formed, smoothness of the film formation surface, and the like. It is preferable.
[0241]
Moreover, you may form a protective film as needed. Protective film is SiO _X It can be formed using an inorganic material such as Teflon (registered trademark). The protective film may be transparent or opaque, and the thickness of the protective film is about 50 to 1200 nm. The protective film may be formed by a general sputtering method, vapor deposition method or the like in addition to the reactive sputtering method described above.
[0242]
Furthermore, it is preferable to provide a sealing layer on the element in order to prevent oxidation of the organic layer and electrode of the element. The sealing layer is an adhesive resin layer such as a commercially available low-hygroscopic photocurable adhesive, epoxy adhesive, silicone adhesive, cross-linked ethylene-vinyl acetate copolymer adhesive sheet, etc. in order to prevent moisture from entering. Is used to adhere and seal a sealing plate such as a glass plate. Besides a glass plate, a metal plate, a plastic plate, etc. can also be used.
[0243]
As the substrate material, a transparent or translucent material such as glass, quartz, resin, or the like is used in the case where the light emitted from the substrate side is extracted. Further, the emission color may be controlled by using a color filter film, a color conversion film containing a fluorescent substance, or a dielectric reflection film on the substrate. In the case of the reverse lamination, the substrate may be transparent or opaque, and if it is opaque, ceramics or the like may be used.
[0244]
For the color filter film, a color filter used in a liquid crystal display or the like may be used, but it is only necessary to adjust the characteristics of the color filter according to the light emitted from the organic EL to optimize the extraction efficiency and the color purity. .
[0245]
In addition, if a color filter that can cut off short-wavelength external light that is absorbed by the EL element material or the fluorescence conversion layer is used, the light resistance and display contrast of the element can be improved.
[0246]
Further, an optical thin film such as a dielectric multilayer film may be used instead of the color filter.
[0247]
For example, as shown in FIG. 1, the organic EL device of the present invention has a hole injection electrode (anode) 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron injection transport layer 6, an electron injection on a substrate 1. An electrode (cathode) 7 and, if necessary, a protective electrode 8 are sequentially laminated. Moreover, it is good also as a structure contrary to this lamination | stacking order, and the hole injection layer 3, the hole transport layer 4, and the electron injection transport layer 6 may be abbreviate | omitted, or you may make it combine with the light emitting layer 5. FIG. What is necessary is just to adjust these structural layers to an optimal thing by the function of the element etc. which are calculated | required.
[0248]
The organic EL element of the present invention is usually used as a direct current drive type or a pulse drive type EL element, but may be an alternating current drive. The applied voltage is usually about 2 to 30V.
[0249]
【Example】
Hereinafter, the present invention will be described in more detail by showing specific synthesis examples and examples of the present invention together with comparative examples.
[0250]
<Example 1>
Synthesis of 1-o-biphenylyl-3-phenylisobenzofuran
-30 ° C THF (tetrahydrofuran) 30cm under Ar ^Three 3.9 g (1.68E-2 mol) of o-bromobiphenyl was dissolved in the solution. NBuLi hexane solution (1.5mol / l) 10cm there ^Three Was added. Two hours later, 3 g (1.4E-2 mol) of 3-phenylphthalide was added while cooling at −50 ° C. After 2 hours, the temperature was returned to room temperature and 10% of a 35% hydrochloric acid aqueous solution. ^Three Was added. After 1 hour, toluene extraction was performed with a separatory funnel and washed thoroughly with distilled water. After concentrating the toluene solution, the target product was fractionated by silica gel chromatography (developing solvent: toluene: hexane = 1: 4). 4 g of yellow viscous material emitting blue-green fluorescence was obtained (80%).
[0251]
Embedded image
[0252]
Synthesis of 3,4-dibromo- (7-o-biphenylyl 12-phenyl) benzo [k] fluoranthene
The previously synthesized 1-o-biphenylyl-3-phenylisobenzofuran (2.2 g, 6.45E-3 mol) and 5,6-dibromoacenaphthene (2.0 g, 6.45E-3 mol) were heated to reflux in toluene for 24 hours. After the reaction, the precipitate was collected to obtain an intermediate. 1.6g (41%)
[0253]
Intermediate 1.6g 150cm ^Three Overheated in acetic acid of 50% HBr aqueous solution 20cm ^Three And reacted at 120 ° C. for 30 minutes. After cooling, the target precipitate was collected. Separation was performed using silica gel chromatography (developing solvent: toluene: hexane = 1: 3). 1.0 g (70%) of a yellow powder was obtained.
[0254]
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[0255]
Synthesis of dibenzo-((bis-o-biphenylyl) (-diphenyl))-perifuranthene
The previously synthesized 3,4-dibromo- (7-o-biphenylyl 12-phenyl) benzo [k] fluoranthene (1.0 g, 1.57E-3 mol) was added to DMF 30 cm. ^Three Dissolved in. 0.52g Ni (COD) there ₂ (1.9E-3 mol), 1 ml of cyclooctadiene (COD) and 0.12 g (1.57E-3 mol) of bipyridine were added and reacted at 60 ° C. for 12 hours.
[0256]
After the reaction, 1N hydrochloric acid aqueous solution 30cm ^Three And 30cm ^Three The product was precipitated and recovered by adding methanol. Separation was performed using silica gel chromatography (developing solvent: toluene: hexane = 1: 3). 0.67 g (90%) of a violet solid was obtained.
[0257]
The fluorescence peak (EM) wavelengths in the dichloromethane solution were 602 and 652 nm. The fluorescence absorption peak (EX) wavelengths in the dichloromethane solution were 508, 547, and 593 nm.
[0258]
Mass spectrometry (M + 1) + = 957
Sublimation purification temperature 430 ° C
[0259]
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[0260]
<Example 2>
Synthesis of 3,4-dibromofluoranthene derivatives
Various 5,6-dibromofluoranthene derivatives can be obtained by Diels-Alder reaction of 5,6-dibromoacenaphthylene and butadiene derivatives followed by dehydrogenation with dichlorodicyanoquinone (DDQ).
[0261]
5,6-Dibromoacenaphthylene 5 g (1.6E-2 mol) and 2,3-diphenylbutadiene 3.3 g (1.6E-2 mol) were refluxed in xylene for 48 hours. 5.6 g (70%) of intermediate were obtained.
[0262]
This intermediate 5 g (9.6E-3 mol) and dichlorodicyanoquinone (DDQ) 2.2 g (9.6E-3 mol) were dissolved in toluene and reacted at 120 ° C. for 24 hours to give 3,4-dibromo-8,9 -3.0 g (60%) of diphenylfluoranthene were obtained.
[0263]
Embedded image
[0264]
Synthetic pathway reaction of dibenzotetraphenylperiflanten by Suzuki coupling (1)
Under Ar, 5.6 g (1.0E-2 mol) of 3,4-dibromo (7,12-diphenyl) benzo [k] fluoranthene was dried in 100 cm of THF. ^Three And cooled to −40 to −50 ° C. 1.57mol / l nBuLi hexane solution 14cm there ^Three (1.0E-2X2.2mol) was added slowly. After 1 h while maintaining the temperature at -40 to -50 ° C, 3.2 g (1.0E-2X2.2 mol) of triethyl borate was slowly added. 50cm after 2h ^Three Of distilled water was added. Thereafter, about 10% hydrochloric acid aqueous solution was added until the reaction solution became acidic until it became weakly acidic. The reaction is returned to room temperature and NaHCO 3 _Three After neutralization with aq, distilled water was added, the organic layer was distilled off under reduced pressure, and the precipitate was recovered.
[0265]
The recovered product was stirred and washed with a large amount of water and then filtered. The recovered material is then dissolved in acetone and MgSO. _Four And dried with hexane to cause precipitation.
Yield 4g (81%)
[0266]
Embedded image
[0267]
Reaction (2)
Under nitrogen, 4 g (8.1E-3 mol) of (7,12-diphenyl) benzo [k] fluoranthene-3,4-diboronic acid and 4.55 g (8.1E-3 mol) of 3,4-dibromobenzo [k] fluoranthene 150cm ^Three In a mixed solvent of toluene and ethanol (1: 1). Thereto was added 0.93 g (8.1E-3X2X0.05 mol) of tetrakistriphenylphosphinepalladium (0) (Pd (PPh3) 4), and the oil bath was heated at 85 ° C. Next, an aqueous solution of sodium carbonate (Na ₂ CO _Three 15g / 50cm distilled water ^Three ) And allowed to react overnight. After the reaction, the reaction mixture was extracted with chloroform and thoroughly washed with distilled water.
Silica gel was used for column purification.
Yield 5.2g (80%)
[0268]
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[0269]
<Example 3>
Synthesis of dibenzotetraphenyl perifuranthene
As shown in the following formula, 1.5 g (1.56E-3 mol) of 3,3′-dibromo-4,4′-bis ((7,12-diphenyl) benzo [k] fluoranthene) was added to 50 cm of DMF. ^Three Dissolved in. Thereto were added 0.52 g of Ni (COD) 2 (1.9E-3 mol), 1 ml of cyclooctane (COD) and 0.12 g (1.57E-3 mol) of bipyridine, and the mixture was reacted at 80 ° C. for 12 hours.
[0270]
Embedded image
[0271]
After reaction, 1N hydrochloric acid water monument 30cm ^Three And 30cm ^Three Of methanol was added to precipitate the desired product. Separation was performed using silica gel chromatography.
(Developing solvent is toluene: hexane = 1: 3)
1.1 g (90%) of a black solid was obtained.
The fluorescence peak (EM) wavelengths in the dichloromethane solution were 600 and 650 nm.
The fluorescence absorption peak (EX) wavelengths in the dichloromethane solution were 508, 546 and 591 nm.
Mass spectrometry (M + 1) + = 805
Sublimation purification temperature: 410 ° C
[0272]
<Comparative example>
Synthesis of dibenzotetraphenyl perifuranthene
(7,12-diphenyl) benzo [k] fluoranthene 2g (5E-3mol) and cobalt fluoride (CoF _Three ) 3 g (2.6E-2 mol) of the mixture was suspended in 100 ml in trifluoroacetic acid and heated to reflux for 40 hours. After the reaction, the reaction solution was poured into cold water and extracted with dichloromethane. After drying with magnesium sulfate, the organic solvent was removed to obtain a black solid. For purification, silica gel chromatography was used.
1 g (50%) of a black purple solid was obtained.
[0273]
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[0274]
Synthesis of dibenzotetra (β-naphthyl) periflanthene
(7,12-bis (β-naphthyl)) benzo [k] fluoranthene 2.52 g (5E-3 mol) and cobalt fluoride (CoF _Three ) 3 g (2.6E-2 mol) of the mixture was suspended in 100 ml of trifluoroacetic acid and heated to reflux for 40 hours. After the reaction, the reaction solution was poured into cold water and extracted with dichloromethane. After drying with magnesium sulfate, the organic solvent was removed to obtain a black solid. For purification, silica gel chromatography was used.
0.2 g (8%) of a black purple solid was obtained.
[0275]
Embedded image
[0276]
Synthesis of dibenzooctaphenyl perifuranthene
(7,9,10,12-tetraphenyl) benzo [k] fluoranthene 2.79 g (5E-3 mol) and cobalt fluoride (CoF _Three ) 3 g (2.6E-2 mol) of the mixture was suspended in 100 ml of trifluoroacetic acid and heated to reflux for 40 hours. After the reaction, the reaction solution was poured into cold water and extracted with dichloromethane. After drying with magnesium sulfate, the organic solvent was removed to obtain a black solid. For purification, silica gel chromatography was used.
0.42 g (15%) of a black purple solid was obtained.
[0277]
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[0278]
<Example 4>
An ITO transparent electrode thin film having a thickness of 100 nm was formed on a glass substrate by RF sputtering and patterned. This glass substrate with an ITO transparent electrode was subjected to ultrasonic cleaning using a neutral detergent, acetone and ethanol, and then pulled up from boiling ethanol and dried. Transparent electrode surface is UV / O _Three After cleaning, it is fixed to the substrate holder of the vacuum evaporation system and the inside of the tank is 1 × 10 ^-Five The pressure was reduced to Pa or lower.
[0279]
Then, while maintaining the reduced pressure state, N, N′-diphenyl-N, N′-bis [N- (4-methylphenyl) -N-phenyl- (4-aminophenyl)]-1,1 ′ having the following structure -Biphenyl-4,4'-diamine (ATP) (was deposited to a film thickness of 50 nm at a deposition rate of 0.1 nm / sec to form a hole injection layer.
[0280]
Embedded image
[0281]
Next, N, N, N ′, N′-tetrakis (m-biphenyl) -1,1′-biphenyl-4,4′-diamine (TPD) having the following structure was deposited to a thickness of 20 nm at a deposition rate of 0.1 nm / sec. Vapor deposition was performed to obtain a hole transport layer.
[0282]
Embedded image
[0283]
Further, while maintaining the reduced pressure, a host material having the following structure and a dopant mixture having the following structure were vapor-deposited to a thickness of 40 nm at a weight ratio of 99: 1 with an overall vapor deposition rate of 0.1 nm / sec. .
[0284]
Embedded image
[0285]
Embedded image
[0286]
Further, while maintaining the reduced pressure state, tris (8-quinolinolato) aluminum having the following structure was deposited to a thickness of 30 nm at a deposition rate of 0.1 nm / sec to form an electron transport layer.
[0287]
Embedded image
[0288]
Next, while maintaining the reduced pressure state, LiF was deposited at a deposition rate of 0.01 nm / sec to a thickness of 0.3 nm to form an electron injection electrode, and Al was deposited to a protective electrode of 150 nm to obtain an organic EL device.
[0289]
A DC voltage is applied to the organic EL element, and initially 10 mA / cm. ² At a current density of 630 cd / m with a driving voltage of 6.5 V ² The emission of was confirmed. The chromaticity coordinates at this time were (x, y) = (0.65, 0.35).
[0290]
【The invention's effect】
As described above, according to the present invention, a method for producing a perylene derivative having a sufficient yield and excellent production efficiency, a perylene derivative obtained by this production method, and an organic EL device using the perylene derivative are provided. Can do.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing a basic configuration of an organic EL element of the present invention.
[Explanation of symbols]
1 Substrate
2 hole injection electrode
3 Hole injection transport layer
4 Light emitting layer
5 Electron injection transport layer
6 Electron injection electrode
7 Protective electrode

Claims (11)

A 3,4-dihalogenated fluoranthene derivative represented by the following formula (3) is homo- or heterocoupled using a catalyst,
[In the above formula (3), R1 to R6, R21 and R22 are a hydrogen atom, a linear chain which may have a substituent, a branched or cyclic alkyl group, a linear chain which may have a substituent, Branched or cyclic alkoxy group, optionally having a straight chain, branched or cyclic alkylthio group, optionally having a straight chain, branched or cyclic alkenyl group, having a substituent Linear, branched or cyclic alkenyloxy group which may be substituted, linear, branched or cyclic alkenylthio group which may be substituted, substituted or unsubstituted aralkyl group, substituted or unsubstituted aralkyloxy group Group, substituted or unsubstituted aralkylthio group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted arylthio group, substituted or unsubstituted amino group, Group, hydroxyl group, —COOM1 group (wherein M1 is a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent, a linear group which may have a substituent, branched or A cyclic alkenyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group), a -COM2 group (wherein M2 is a hydrogen atom, a linear or branched chain optionally having a substituent) Or a cyclic alkyl group, an optionally substituted linear, branched or cyclic alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or an amino group), or- OCOM3 (In the group, M3 is a linear, branched or cyclic alkyl group which may have a substituent, a linear, branched or cyclic alkenyl group which may have a substituent, substituted or unsubstituted. Ara And represents a substituted or unsubstituted aryl group), and two or more adjacent groups selected from R1 to R6, R21 and R22 are bonded to each other or condensed to form a substituted carbon atom. In addition, a substituted or unsubstituted carbocyclic aliphatic ring, aromatic ring, or condensed aromatic ring may be formed. ]
A method for synthesizing a perylene derivative for synthesizing a perylene derivative represented by the following formula (4):
[In the above formula (4), R1 ′ to R6 ′, R21 ′ and R22 ′ have the same meanings as R1 to R6, R21 and R22 in the formula (3). R1 to R6, R21 and R22 and R1 ′ to R6 ′, R21 ′ and R22 ′ may be the same or different. ]
The catalyst has one or more of Group VIII or IB elements of Ni, Pd, Pt, Fe, Co, Ru and Rh, or contains two or more elements of these elements and Cu. A synthesis method comprising a metal catalyst, a metal complex catalyst, or a metal compound. A 3,4-dihalogenated benzofluoranthene derivative represented by the following formula (5) is homo- or heterocoupled using a catalyst,
[In the above formula (5), R1 to R8, R31 and R32 are a hydrogen atom, a linear chain which may have a substituent, a branched or cyclic alkyl group, a linear chain which may have a substituent, Branched or cyclic alkoxy group, optionally having a straight chain, branched or cyclic alkylthio group, optionally having a straight chain, branched or cyclic alkenyl group, having a substituent Linear, branched or cyclic alkenyloxy group which may be substituted, linear, branched or cyclic alkenylthio group which may be substituted, substituted or unsubstituted aralkyl group, substituted or unsubstituted aralkyloxy group Group, substituted or unsubstituted aralkylthio group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted arylthio group, substituted or unsubstituted amino group, Group, hydroxyl group, —COOM1 group (wherein M1 is a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent, a linear group which may have a substituent, branched or A cyclic alkenyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group), a -COM2 group (wherein M2 is a hydrogen atom, a linear or branched chain optionally having a substituent) Or a cyclic alkyl group, an optionally substituted linear, branched or cyclic alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or an amino group), or- OCOM3 (In the group, M3 is a linear, branched or cyclic alkyl group which may have a substituent, a linear, branched or cyclic alkenyl group which may have a substituent, substituted or unsubstituted. Ara And represents a substituted or unsubstituted aryl group), and two or more adjacent groups selected from R1 to R8, R31 and R32 are bonded to each other or condensed to form a substituted carbon atom. In addition, a substituted or unsubstituted carbocyclic aliphatic ring, aromatic ring, or condensed aromatic ring may be formed. ]
A method for synthesizing a perylene derivative for synthesizing a perylene derivative represented by the following formula (6):
[In the above formula (6), R1 ′ to R8 ′, R31 ′ and R32 ′ have the same meanings as R1 to R8, R31 and R32 in the formula (5). R1 to R8, R31 and R32 and R1 ′ to R8 ′, R31 ′ and R32 ′ may be the same or different. ]
The catalyst has one or more of Group VIII or IB elements of Ni, Pd, Pt, Fe, Co, Ru and Rh, or contains two or more elements of these elements and Cu. A synthesis method comprising a metal catalyst, a metal complex catalyst, or a metal compound.   The method for synthesizing a perylene derivative according to claim 1 or 2, wherein the catalyst is a nickel catalyst. The method for synthesizing a perylene derivative according to claim 1 or 2, wherein the catalyst is NiCl ₂ (dppe), NiCl ₂ (dppp), or Ni (COD) ₂ . A 1,8-dihalogenated naphthalene derivative represented by the following formula (1):
[In the above formula (1), R1 to R4, R11 and R12 are a hydrogen atom, a linear chain which may have a substituent, a branched or cyclic alkyl group, a linear chain which may have a substituent, Branched or cyclic alkoxy group, optionally having a straight chain, branched or cyclic alkylthio group, optionally having a straight chain, branched or cyclic alkenyl group, having a substituent Linear, branched or cyclic alkenyloxy group which may be substituted, linear, branched or cyclic alkenylthio group which may be substituted, substituted or unsubstituted aralkyl group, substituted or unsubstituted aralkyloxy group Group, substituted or unsubstituted aralkylthio group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted arylthio group, substituted or unsubstituted amino group, Group, hydroxyl group, —COOM1 group (wherein M1 is a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent, a linear group which may have a substituent, branched or A cyclic alkenyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group), a -COM2 group (wherein M2 is a hydrogen atom, a linear or branched chain optionally having a substituent) Or a cyclic alkyl group, an optionally substituted linear, branched or cyclic alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or an amino group), or- OCOM3 (In the group, M3 is a linear, branched or cyclic alkyl group which may have a substituent, a linear, branched or cyclic alkenyl group which may have a substituent, substituted or unsubstituted. Ara And a substituted or unsubstituted aryl group), and two or more adjacent groups selected from R1 to R4, R11 and R12 are bonded to each other or condensed to form a substituted carbon atom. In addition, a substituted or unsubstituted carbocyclic aliphatic ring, aromatic ring, or condensed aromatic ring may be formed. When these carbocyclic aliphatic rings, aromatic rings, or condensed aromatic rings have a substituent, the substituents are the same as R1 to R4, R11, and R12. ]
Using a naphthyl-1,8-diboronic acid derivative represented by the following formula (7),
[In said formula (7), R1-R4, R11, and R12 are synonymous with the thing of Formula (1). ]
A method for synthesizing a perylene derivative by synthesizing a perylene derivative represented by the following formula (2) by Suzuki coupling.
[In the formula (2), R1 ′ to R4 ′, R11 ′ and R12 ′ have the same meanings as R1 to R4, R11 and R12 in the formula (1). R1 to R4, R11 and R12 and R1 ′ to R4 ′, R11 ′ and R12 ′ may be the same or different. ] Using a 3,4-dihalogenated fluoranthene derivative represented by the formula (3) of claim 1 and a fluorantheno-1,8-diboronic acid derivative represented by the following formula (8):
[In said formula (8), R1-R6, R21, and R22 are synonymous with the thing of Formula (3). ]
A method for synthesizing a perylene derivative comprising synthesizing a perylene derivative represented by the formula (4) of claim 1 by Suzuki coupling. Using a 3,4-dihalogenated benzofluoranthene derivative represented by the formula (5) of claim 2 and a dibenzofluorantheno-1,8-diboronic acid derivative represented by the following formula (9):
[In the above formula (9), R1 to R8, R31 and R32 have the same meanings as those in formula (5). ]
A method for synthesizing a perylene derivative for synthesizing a perylene derivative represented by formula (6) of claim 2 by Suzuki coupling.   A 1,8-dihalogenated naphthalene derivative represented by formula (1) of claim 5, a 3,4-dihalogenated fluoranthene derivative represented by formula (3) of claim 1, and a formula (5) of claim 2 A perylene derivative synthesis method for obtaining an asymmetric compound using any one or two of 3,4-dihalogenated benzofluoranthene derivatives. The method for synthesizing a perylene derivative according to claim 8, wherein the asymmetric compound is a compound represented by the following formula (10).
[In the formula (10), R51 to R55, R61 to R65, R111 ′ and R121 ′ have the same meanings as R1 to R4, R11 and R12 in the formula (1) of claim 5. ]   The method for synthesizing a perylene derivative according to any one of claims 1 to 4, wherein at least R5 and R6 and / or R5 'and R6' are different. A bisnaphthalene derivative represented by the following formula (16) is coupled using NiCl ₂ (dppe), NiCl ₂ (dppp) or Ni (COD) ₂ as a catalyst ;
[In the above formula (16), R1 to R4, R11 and R12 are a hydrogen atom, a linear chain which may have a substituent, a branched or cyclic alkyl group, a linear chain which may have a substituent, Branched or cyclic alkoxy group, optionally having a straight chain, branched or cyclic alkylthio group, optionally having a straight chain, branched or cyclic alkenyl group, having a substituent Linear, branched or cyclic alkenyloxy group which may be substituted, linear, branched or cyclic alkenylthio group which may be substituted, substituted or unsubstituted aralkyl group, substituted or unsubstituted aralkyloxy group Group, substituted or unsubstituted aralkylthio group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted arylthio group, substituted or unsubstituted amino group, Ano group, hydroxyl group, —COOM1 group (in which M1 is a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent, a linear chain which may have a substituent, branched or A cyclic alkenyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group), a -COM2 group (wherein M2 is a hydrogen atom, a linear or branched chain optionally having a substituent) Or a cyclic alkyl group, an optionally substituted linear, branched or cyclic alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or an amino group), or- OCOM3 (In the group, M3 is a linear, branched or cyclic alkyl group which may have a substituent, a linear, branched or cyclic alkenyl group which may have a substituent, substituted or unsubstituted. A An alkyl group, or a substituted or unsubstituted aryl group), and two or more adjacent groups selected from R1 to R4, R11 and R12 are bonded to each other or condensed to form a substituted carbon atom. In addition, a substituted or unsubstituted carbocyclic aliphatic ring, aromatic ring, or condensed aromatic ring may be formed. When these carbocyclic aliphatic rings, aromatic rings, or condensed aromatic rings have a substituent, the substituents are the same as R1 to R4, R11, and R12.
R1 ′ to R4 ′, R11 ′ and R12 ′ have the same meanings as R1 to R4, R11 and R12 in Formula (1). R1 to R4, R11 and R12 and R1 ′ to R4 ′, R11 ′ and R12 ′ may be the same or different. ]
A method for synthesizing a perylene derivative for synthesizing a perylene derivative represented by the following formula (2).
[In the formula (2), R1 ′ to R4 ′, R11 ′ and R12 ′ have the same meanings as R1 to R4, R11 and R12 in the formula (1). R1 to R4, R11 and R12 and R1 ′ to R4 ′, R11 ′ and R12 ′ may be the same or different. ]