Fused ring compound, its production method, and material for organic electroluminescence device

Abstract

The present invention provides a novel fused ring compound that exhibits excellent charge transport ability, a method for producing the same, and a material for an organic EL device that contains the same. A fused ring compound having a specific structure represented by formula (1). [C1]

Description

[Technical field]

[0001] The present invention relates to a fused ring compound, a process for producing the same, and a material for an organic electroluminescence device containing the same. [Background technology]

[0002] Dibenzo[g,p]chrysene compounds are sometimes used as materials for organic electroluminescence (also called organic EL) devices. However, there are few reports of dibenzo[g,p]chrysene compounds, and research on them has not been sufficient.

[0003] Non-Patent Document 1 discloses unsubstituted dibenzo[g,p]chrysene and dibenzo[g,p]chrysene derivatives substituted with an electron donating group or an electron withdrawing group. Furthermore, Patent Document 1 and Patent Document 2 disclose dibenzo[g,p]chrysene compounds substituted with an aromatic hydrocarbon group and a triazyl group, respectively. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent No. 5685832 [Patent Document 2] US Patent Application Publication No. 2015 / 0318486 [Non-patent literature]

[0005] [Non-Patent Document 1] Chemistry - An Asian Journal, 2014, 9, p.1623-1628 Summary of the Invention [Problem to be solved by the invention]

[0006] The present inventors have further studied the above dibenzo[g,p]chrysene compounds. As a result, it has been found that the dibenzo[g,p]chrysene compounds disclosed in Non-Patent Document 1 and Patent Documents 1 and 2 have room for further improvement as materials for organic EL devices in terms of the driving voltage of the organic EL device. Therefore, one aspect of the present invention is directed to providing a fused ring compound capable of reducing the driving voltage, and a method for producing the same. Another aspect of the present invention is directed to providing a material for an organic EL device capable of reducing the driving voltage. [Means for solving the problem]

[0007] A fused ring compound according to one embodiment of the present invention is a fused ring compound represented by formula (1): [ka]

[0008] During the ceremony, X 1 ~X 16 each independently represents a nitrogen atom which may be substituted with an oxygen atom, or a carbon atom which may have a charge transporting group; X 1 ~X 4 at least two of the carbon atoms may have a charge transporting group; X 5 ~X 8 at least two of the carbon atoms may have a charge transporting group; X 13 ~X 16 at least two of the carbon atoms may have a charge transporting group; X 9 and X 12 represents a carbon atom which may have a charge transporting group; X 1 ~X 16 Among the charge transporting groups contained in the compound, two adjacent charge transporting groups may be bonded to each other to form a ring; X 14 and X15 When at least one of the carbon atoms is a carbon atom having a charge transport group forming a ring, the atoms constituting the ring structure of the ring and X 13 ~X 16 at least one of which is a nitrogen atom optionally substituted with an oxygen atom; X 14 and X 15 are not carbon atoms having a charge transport group forming a ring, X 14 and X 15 at least one of which is a nitrogen atom optionally substituted with an oxygen atom; (i)X 1 and X 16 , (ii) X 4 and X 5 , (iii) X 8 and X 9 or (iv) X 12 and X 13 When are unsubstituted carbon atoms, the two unsubstituted carbon atoms may be bonded to each other to form a ring.

[0009] A method for producing a fused ring compound according to another embodiment of the present invention includes the steps of: A method for producing the above fused ring compound includes reacting a compound represented by formula (7) with a compound represented by formula (8): [ka]

[0010] During the ceremony, Y 1 ~Y 8 each independently represents a nitrogen atom or a carbon atom which may have a charge transporting group; Y 1 ~Y 4 at least two of the carbon atoms may have a charge transporting group; Y 5 ~Y 8 at least two of the carbon atoms may have a charge transporting group; C 1and C 2 each independently represents a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, a quinoline ring, or an isoquinoline ring, which may have a charge transporting group; Z 1 ~Z 2 each independently represents a chlorine atom, a bromine atom, or an iodine atom; Y 1 ~Y 8 are each independently a carbon atom which may have a charge transporting group, C 1 and C 2 at least one of which represents a pyridine ring, a pyrimidine ring, a pyrazine ring, a quinoline ring, or an isoquinoline ring which may have a charge transporting group; C 1 and C 2 are each independently a benzene ring or a naphthalene ring, each of which may have a charge transporting group, 1 ~Y 8 At least one of these is a nitrogen atom.

[0011] A method for producing a fused ring compound according to still another aspect of the present invention is a method for producing the above fused ring compound, comprising the steps of: The method includes reacting a compound represented by formula (9) with a compound represented by formula (10):

[0012] [ka]

[0013] During the ceremony, Y 1 ~Y 8 each independently represents a nitrogen atom or a carbon atom which may have a charge transporting group; Y 1 ~Y 4 at least two of the carbon atoms may have a charge transporting group; Y 5 ~Y 8 at least two of the carbon atoms may have a charge transporting group; D 1 represents a benzene ring or a naphthalene ring which may have a charge transporting group; D 2 represents a pyridine ring, a pyrimidine ring, a pyrazine ring, a quinoline ring, or an isoquinoline ring, which may have a charge transporting group; Z 3 ~Z 4 each independently represents a chlorine atom, a bromine atom, or an iodine atom.

[0014] A method for producing the fused ring compound according to still another embodiment of the present invention is a method for producing the fused ring compound, which comprises intramolecular cyclization of a compound represented by formula (12).

[0015] [ka]

[0016] During the ceremony, X 2 ~X 15 each independently represents a nitrogen atom which may be substituted with an oxygen atom, or a carbon atom which may have a charge transporting group; X 2 ~X 4 at least two of the carbon atoms may have a charge transporting group; X 5 ~X 8 at least two of the carbon atoms may have a charge transporting group; X 13 ~X 15 at least one of which is a carbon atom which may have a charge transporting group; X 9 and X 12 represents a carbon atom which may have a charge transporting group; X 2 ~X 15 Among the charge transporting groups contained in the compound, two adjacent charge transporting groups may be bonded to each other to form a ring; X 14 and X15 When at least one of the carbon atoms is a carbon atom having a charge transport group forming a ring, the atoms constituting the ring structure of the ring and X 13 ~X 15 at least one of which is a nitrogen atom optionally substituted with an oxygen atom; X 14 and X 15 are not carbon atoms having a charge transport group forming a ring, X 14 and X 15 at least one of which is a nitrogen atom optionally substituted with an oxygen atom; Z 5 each independently represents a chlorine atom, a bromine atom, or an iodine atom. A material for an organic electroluminescence device according to still another embodiment of the present invention contains the above fused ring compound. Effect of the Invention

[0017] According to one aspect of the present invention, a fused ring compound capable of reducing the driving voltage can be provided. According to another aspect of the present invention, a method for producing a fused ring compound capable of reducing the driving voltage can be provided. According to yet another aspect of the present invention, a material for an organic electroluminescence device capable of reducing the driving voltage can be provided. [Brief description of the drawings]

[0018] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of a layered structure of an organic EL element according to one embodiment of the present invention. [Diagram 2] FIG. 2 is a schematic cross-sectional view showing another example of a laminate structure (structure of Element Example 1) of an organic EL element according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] As a result of further research by the present inventors into Non-Patent Document 1 and Patent Documents 1 and 2, the following findings were obtained. The unsubstituted dibenzo[g,p]chrysene skeleton described in Non-Patent Document 1 is composed of only carbon atoms, and the skeleton itself has low electron-accepting properties. Therefore, when used in an organic EL device, particularly in an electron transport layer in an organic EL device, it was found that although the device exhibits sufficient performance in terms of lifetime, the driving voltage is high and therefore it is necessary to reduce the driving voltage. In order to reduce the driving voltage, it is necessary to introduce an electron-accepting substituent into the dibenzo[g,p]chrysene skeleton. However, the introduction of such an electron-accepting substituent is accompanied by an increase in molecular weight, which leads to a decrease in the thermal stability of the material during sublimation purification and deposition film formation.

[0020] As a result of further research aimed at overcoming the above-mentioned difficulties, the present inventors have found that a fused ring compound having a specific skeleton can solve these problems due to the specific skeleton. That is, the fused ring compound according to one embodiment of the present invention is a skeleton in which one or more carbon atoms constituting a dibenzo[g,p]chrysene skeleton or a skeleton similar thereto are replaced with nitrogen atoms. Since nitrogen has a higher electronegativity than carbon, an electron-withdrawing effect occurs to the entire skeleton. Therefore, the present inventors speculate that this skeleton has improved electron-accepting properties compared to a dibenzo[g,p]chrysene skeleton or a skeleton similar thereto, and can be applied to various materials such as electron-transporting materials and light-emitting materials without relying on electron-withdrawing substituents. That is, the fused ring compound according to one embodiment of the present invention has a specific skeleton, and is suitable as an organic EL material having an excellent effect of reducing the driving voltage due to this skeleton, and it is speculated that the fused ring compound according to one embodiment of the present invention, when used in an electron-transporting layer constituting an organic EL device, contributes to the reduction of the driving voltage required for the electron-transporting layer.

[0021] <Fused ring compounds> A fused ring compound according to one embodiment of the present invention is represented by formula (1).

[0022] [ka]

[0023] The definitions of each symbol in formula (1) are as follows: <X 1 ~X 16 About > X 1 ~X 16 each independently represents a nitrogen atom which may be substituted with an oxygen atom, or a carbon atom which may have a charge transporting group; X 1 ~X 4 At least two of X are carbon atoms which may have a charge transporting group; 5 ~X 8 At least two of X are carbon atoms which may have a charge transporting group; 13 ~X 16 At least two of X are carbon atoms which may have a charge transporting group; 9 and X 12 is a carbon atom which may have a charge transporting group; X 1 ~X 16 Among the charge transporting groups contained in X, two adjacent charge transporting groups may be bonded to each other to form a ring; 14 and X 15 When at least one of the carbon atoms is a carbon atom having a charge transport group forming a ring, the atoms constituting the ring structure of the ring and X 13 ~X 16 at least one of X is a nitrogen atom optionally substituted with an oxygen atom; 14 and X 15 are not carbon atoms having a charge transport group forming a ring, X 14 and X 15 at least one of X is a nitrogen atom which may be substituted with an oxygen atom; 1 and X 16 , (ii) X 4 and X 5 , (iii) X 8 and X 9 or (iv) X 12 and X 13When are unsubstituted carbon atoms, the two unsubstituted carbon atoms may be bonded to each other to form a ring.

[0024] The fused ring compound represented by formula (1) is preferably one represented by any one of formulas (1') and formulas (2) to (5).

[0025] [ka]

[0026] The definitions of each symbol in formula (1′) and formulas (2) to (5) are as follows. <X 1 ~X 116 About > X 1 ~X 116 each independently represents a nitrogen atom which may be substituted with an oxygen atom, or a carbon atom which may have a charge transporting group; X 1 ~X 4 at least two of the carbon atoms may have a charge transporting group; X 5 ~X 8 at least two of the carbon atoms may have a charge transporting group; X 13 ~X 15 at least one of which is a carbon atom which may have a charge transporting group; X 17 ~X 20 at least two of the carbon atoms may have a charge transporting group; X 25 ~X 28 at least two of the carbon atoms may have a charge transporting group; X 42 ~X 44 at least two of the carbon atoms may have a charge transporting group; X 52 ~X 54 at least two of the carbon atoms may have a charge transporting group; X 101 ~X 104 at least two of the carbon atoms may have a charge transporting group; X 105 ~X 108 at least two of the carbon atoms may have a charge transporting group; X 113 ~X 116 at least two of the carbon atoms may have a charge transporting group; X 9 , X 12 , X 109 and X 112 represents a carbon atom which may have a charge transporting group; In formula (1'), X 114 and X 115 at least one of which is a nitrogen atom optionally substituted with an oxygen atom; In formulas (2) to (5), X n In the group X constituting the skeleton of the fused ring compound represented by the above formula (1), at least one is a nitrogen atom which may be substituted with an oxygen atom.

[0027] In formula (1') and formulas (1) to (5), X n At least one of the X groups constituting the skeleton of the fused ring compound represented by the formula (I) is a nitrogen atom which may be substituted with an oxygen atom. n Of the X group constituting the skeleton of the fused ring compound represented by the formula (I), it is preferable that one to eight of them are nitrogen atoms which may be substituted with an oxygen atom, and it is more preferable that one to four of them are nitrogen atoms which may be substituted with an oxygen atom. In the fused ring compound represented by any one of formulas (1') and (1) to (5), the X group is X 1 ~X 116 It consists of X n(n is an integer of 1 to 116). In the case of a fused ring compound represented by formula (1), n ​​is 1 to 16, in the case of a fused ring compound represented by formula (1'), n is 101 to 116, in the case of a fused ring compound represented by formula (2), n is 1 to 12 or 17 to 22, in the case of a fused ring compound represented by formula (3), n is 1 to 12 or 23 to 28, in the case of a fused ring compound represented by formula (4), n is 5 to 15 or 42 to 44, and in the case of a fused ring compound represented by formula (5), n is 5 to 12, 17 to 21 or 52 to 54.

[0028] X 1 ~X 8 , X 42 ~X 44 , X 52 ~X 54 and X 101 ~ 108 It is preferable that all of the X groups in either one of the X groups consisting of the above and the other X groups are carbon atoms which may have a charge transporting group. 1 ~X 4 X group other than X 5 ~X 8 X group other than X 9 ~X 12 X group other than X 13 ~X 28 X group other than X 42 ~X 44 X group other than X 52 ~X 54 X group other than X 101 ~X 104 X group other than X 105 ~X 108 X group other than X 109 ~X 113 X groups other than X and X 105 ~X 108 and X groups other than the above, all of which are carbon atoms optionally having a charge transporting group are more preferably carbon atoms. X 1 ~X 8 , X 42 ~X 44 , X 52 ~X 54 and X 101 ~ 108and the other X group, when one of the X groups is a carbon atom which may have a charge transport group, and one or more of the other X groups is a nitrogen atom which may be substituted with an oxygen atom, X 1 ~X 8 , X 42 ~X 44 , X 52 ~X 54 and X 101 ~ 108 In comparison with the case where any one or more of the X groups in the above and any one or more of the other X groups are nitrogen atoms optionally substituted with an oxygen atom, this is preferred because the fused ring compound represented by formula (1') or any one of formulas (1) to (5) can be produced in good yield.

[0029] <Charge transport group> A charge transporting group is a substituent that has the function of transporting a charge, which can be a hole, an electron, or both. Examples of the charge transporting group include the following substituents (a-1) to (a-16). (a-1) a deuterium atom, (a-2) a fluorine atom, a bromine atom, an iodine atom, (a-3) a trifluoromethyl group, (a-4) a pentafluoroethyl group, (a-5) a cyano group, (a-6) a nitro group, (a-7) hydroxyl group, (a-8) a thiol group, (a-9) a monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent; (a-10) a monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms which may have a substituent; (a-11) a phosphine oxide group which may have a substituent, (a-12) a silyl group which may have a substituent, (a-13) a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms, (a-14) a linear or branched alkyl group having 1 to 18 carbon atoms, (a-15) a linear or branched alkoxy group having 1 to 18 carbon atoms, (a-16) a trifluoromethylsulfonyloxy group, or (a-17) A group represented by formula (6) or (6'):

[0030] [ka]

[0031] During the ceremony, R 1 ~R 3 are each independently (r-1) a hydrogen atom, (r-2) a deuterium atom, (r-3) a monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent; (r-4) a monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms which may have a substituent, or (r-5) represents a linear or branched alkyl group having 1 to 18 carbon atoms; L is independently a phenylene group which may be substituted with a methyl group or a phenyl group; a naphthylene group optionally substituted with a methyl group or a phenyl group; a biphenylene group which may be substituted by a methyl group or a phenyl group, or represents a single bond; n represents 1 or 2; When L is a single bond, n is 1; when L is not a single bond, n is 1 or 2; If n is 2, multiple R 1 ~R 2 may be the same or different.

[0032] <Regarding (a-9)> Examples of the monocyclic, linked or fused aromatic hydrocarbon group having 6 to 30 carbon atoms (a-9) include a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, a fluorenyl group, an anthryl group, a phenanthryl group, a benzofluorenyl group, a triphenylenyl group, a spirobifluorenyl group, a diphenylfluorenyl group, a dibenzo[g,p]chrysenyl group, etc. The monocyclic, linked or fused aromatic hydrocarbon group having 6 to 30 carbon atoms is preferably a monocyclic, linked or fused aromatic hydrocarbon group having 6 to 18 carbon atoms.

[0033] In addition, when the aromatic hydrocarbon group of (a-9) has a substituent, the substituent is preferably each independently a fluorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a phosphine oxide group which may have a substituent, a silyl group which may have a substituent, a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a trifluoromethylsulfonyloxy group. The phosphine oxide group may be an unsubstituted phosphine oxide group or a phosphine oxide group having a substituent. A phosphine oxide group having a substituent is preferred. The phosphine oxide group having a substituent is preferably a phosphine oxide group having a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 18 carbon atoms, or a condensed heteroaromatic group. Specific examples include groups substituted with two aryl groups, such as diphenylphosphine oxide.

[0034] The silyl group may be an unsubstituted silyl group or a substituted silyl group, and is preferably a substituted silyl group. The silyl group having a substituent is preferably a silyl group having a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 18 carbon atoms, or a fused heteroaromatic group. Specific examples include groups substituted with three aryl groups, such as a triphenylsilyl group. Examples of the boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms include a dihydroxyboryl group (-B(OH)2), a 4,4,5,5-tetramethyl-[1,3,2]-dioxaborolanyl group, and a 5,5-dimethyl-[1,3,2]-dioxaborinane group.

[0035] Examples of the linear or branched alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an n-hexyl group, a cyclohexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. Examples of the linear or branched alkoxy group having 1 to 18 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, an n-hexyloxy group, a cyclohexyloxy group, an octyloxy group, a decyloxy group, a dodecyloxy group, and an octadecyloxy group.

[0036] <About (a-10)> The (a-10) monocyclic, linked or fused heteroaromatic group having 3 to 36 carbon atoms is a monocyclic, linked or fused heteroaromatic group having 3 to 36 carbon atoms and containing at least one atom selected from the group consisting of oxygen, nitrogen and sulfur atoms on the aromatic ring. Examples of the heteroaromatic group include a pyrrolyl group, a thienyl group, a furyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a pyridyl group, a phenylpyridyl group, a pyridylphenyl group, a pyrimidyl group, a pyrazyl group, a 1,3,5-triazyl group, a 1,3,5-triazylphenyl group, a 1,3,5-triazylbiphenylyl group, a 4,6-diphenyl-1,3,5-triazyl group, an indolyl group, a benzothienyl group, a benzofuranyl group, a benzimidazolyl group, a benzophenyl ... Examples of such groups include an indazolyl group, a benzothiazolyl group, a benzoisothiazolyl group, a 2,1,3-benzothiadiazolyl group, a benzoxazolyl group, a benzoisoxazolyl group, a 2,1,3-benzoxadiazolyl group, a quinolyl group, an isoquinolyl group, a quinoxalyl group, a quinazolyl group, a carbazolyl group, a 9-phenylcarbazolyl group, a 9-(4-biphenylyl)carbazolyl group, a dibenzothienyl group, a dibenzofuranyl group, a phenoxazinyl group, a phenothiazinyl group, a phenazine group, and a thianthrenyl group.

[0037] In addition, when the heteroaromatic group of (a-10) has a substituent, the substituent is preferably each independently a cyano group, a fluorine atom, a trifluoromethyl group, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a trifluoromethylsulfonyloxy group. Examples of the linear or branched alkyl group having 1 to 18 carbon atoms include the same as the linear or branched alkyl group having 1 to 18 carbon atoms exemplified in (a-9) above. Examples of the linear or branched alkoxy group having 1 to 18 carbon atoms include the same as the linear or branched alkoxy group having 1 to 18 carbon atoms exemplified in (a-9) above.

[0038] <About (a-11)> The phosphine oxide group (a-11) may be an unsubstituted phosphine oxide group or a phosphine oxide group having a substituent. A phosphine oxide group having a substituent is preferred. Examples of the phosphine oxide group having a substituent include the same phosphine oxide groups as exemplified in (a-9) above. <Regarding (a-12)> The silyl group (a-12) may be an unsubstituted silyl group or a silyl group having a substituent. A silyl group having a substituent is preferred. Examples of the silyl group having a substituent include the same silyl groups as those exemplified in (a-9) above.

[0039] <About (a-13)> Examples of the (a-13) boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms and the boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms include the same boronyl groups as exemplified in the above-mentioned (a-9).

[0040] (a-14): A straight or branched alkyl group having 1 to 18 carbon atoms. Examples of the linear alkyl group having 1 to 18 carbon atoms include the same linear or branched alkyl groups having 1 to 18 carbon atoms as exemplified in the above-mentioned (a-9).

[0041] (a-15): A straight-chain or branched alkoxy group having 1 to 18 carbon atoms Examples of the linear or branched alkoxy group having 1 to 18 carbon atoms include the same linear or branched alkoxy groups having 1 to 18 carbon atoms exemplified in the above-mentioned (a-9).

[0042] (a-17): Groups represented by formulas (6) and (6') As described above, the charge transport group may be a group represented by the above formula (6) or (6'). In formulas (6) and (6'), L, R 1 ~R 3, n is defined as follows:

[0043] <Regarding formulas (6) and (6')> In formulas (6) and (6'), R 1 ~R 3 each independently represents: (r-1) a hydrogen atom; (r-2) a deuterium atom; (r-3) an optionally substituted monocyclic, linked or fused aromatic hydrocarbon group having 6 to 30 carbon atoms; (r-4) an optionally substituted monocyclic, linked or fused aromatic heteroaromatic group having 3 to 36 carbon atoms; or (r-5) a linear or branched alkyl group having 1 to 18 carbon atoms. R 1 ~R 3 When R has a substituent, 1 ~R 3 may be substituted with one substituent or with two or more substituents.

[0044] The definition of the monocyclic, linked or fused aromatic hydrocarbon group having 6 to 30 carbon atoms in (r-3) above is the same as the definition of the monocyclic, linked or fused aromatic hydrocarbon group having 6 to 30 carbon atoms described in (a-9) above, except for the definition of the substituent. In addition, when the aromatic hydrocarbon group of (r-3) has a substituent, the substituent is preferably a deuterium atom, a fluorine atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, a 9-carbazolyl group, a dibenzothienyl group, a dibenzofuranyl group, an N,N-diphenylamino group, or an N,N-bis(4-biphenylyl)-amino group.

[0045] Examples of the linear or branched alkyl group having 1 to 18 carbon atoms include the same linear alkyl groups having 1 to 18 carbon atoms as exemplified in (a-9) above. Examples of the linear or branched alkoxy group having 1 to 18 carbon atoms include the same linear or branched alkoxy groups having 1 to 18 carbon atoms as exemplified in the above-mentioned (a-9).

[0046] The definition of the monocyclic, linked or fused heteroaromatic group having 3 to 36 carbon atoms in the above (r-4) is the same as that of the monocyclic, linked or fused heteroaromatic group having 3 to 36 carbon atoms exemplified in the above (a-10), except for the definition of the substituent. A monocyclic, linked or fused heteroaromatic group having 3 to 20 carbon atoms is more preferable. In addition, when the heteroaromatic group of (r-4) has a substituent, the substituent is preferably a deuterium atom, a fluorine atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, a 9-carbazolyl group, a dibenzothienyl group, a dibenzofuranyl group, an N,N-diphenylamino group, or an N,N-bis(4-biphenylyl)-amino group. These substituents are, for example, defined in the same way as the substituent of (r-3) described above. The definition of the linear or branched alkyl group having 1 to 18 carbon atoms in the above (r-5) is the same as that shown in the above (a-9).

[0047] In formulas (6) and (6'), L represents a phenylene group which may be substituted with a methyl group or a phenyl group; a naphthylene group which may be substituted with a methyl group or a phenyl group; a biphenylene group which may be substituted with a methyl group or a phenyl group; or a single bond. Examples of the phenylene group include a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group. Examples of the naphthylene group include a naphthalene-1,2-diyl group, a naphthalene-1,4-diyl group, a naphthalene-1,8-diyl group, and a naphthalene-2,3-diyl group. Examples of the biphenylene group include a biphenyl-4,4'-diyl group, a biphenyl-4,3'-diyl group, a biphenyl-4,2'-diyl group, a biphenyl-3,3'-diyl group, a biphenyl-3,2'-diyl group, and a biphenyl-2,2'-diyl group.

[0048] In formulas (6) and (6'), n represents an integer of 1 or 2. When L is a single bond, n is an integer of 1. When L is not a single bond, n is an integer of 1 or 2. Note that when n is 2, R 1 and R 2 There are two of each, and they may be the same or different.

[0049] <Preferable fused ring compounds> The fused ring compound represented by formula (1) is more preferably any one selected from the group consisting of formulae (1B), (1C), (1E), (1F), (1J), (1K), (2A) to (2F), (3A) to (3F), (4B), (4J), and (5B).

[0050] [ka]

[0051] [ka]

[0052] In formulas (1B) to (5B), X 0 represents a nitrogen atom which may be substituted with an oxygen atom; A 1 ~A 8 each independently represents a charge transport group; k1 to k3 and k6 each independently represent an integer of 0 or more and 4 or less; k4 is an integer between 0 and 3; k5 and k8 are integers between 0 and 2; k7 is an integer between 0 and 1; If the sum of k1 to k8 is an integer equal to or greater than 2, multiple A 1 ~A 7 may be the same or different.

[0053] <k1~k8について> k1 to k3 and k6 are each independently an integer of 0 or more and 4 or less. k4 is an integer of 0 or more and 3 or less. k5 and k8 are integers of 0 or more and 2 or less. k7 is an integer of 0 or more and 1 or less. In addition, if the sum of k1 to k8 is 2 or more, A 1 ~A 8 There are multiple A's, but there are multiple A's 1 ~A 8 may be the same as or different from each other. The sum of k1 to k8 (k1+k2+k3+k4+k5+k6+k7+k8) is preferably 3 or less, more preferably 2 or less, and particularly preferably 0 or 1. When the sum of k1 to k8 is 3 or less, the molecular weight becomes smaller compared to a compound in which the sum of k1 to k8 is 4 or more. As a result, the sublimation temperature of the compound becomes lower, and the heat resistance stability during sublimation is improved, which is preferable.

[0054] In order to realize excellent charge transport in the organic EL device, k1 and k2 are preferably 0 or 1, and more preferably 0. From the viewpoint of realizing excellent charge transport in an organic EL device, k3 to k8 are preferably 0, 1 or 2, and more preferably 0 or 1. With regard to the fused ring compound represented by any one selected from the group consisting of the above formulae (1B), (1C), (1E), (1F), (1J), (1K), (2A) to (2F), (3A) to (3F), (4B), (4J), and (5B), from the viewpoint of realizing excellent charge transport in an organic EL device, it is particularly preferable that k1 and k2 are 0 and any one of k3 to k8 is 1.

[0055] 1 ~A 8 About > A 1 ~A 8 The charge transporting group represented by the following formula has the same definition as the charge transporting group in formula (1') and formulas (2) to (5), and the preferred range is also the same. A 1 ~A 8 ​When A has a substituent, 1 ~A 8 may be substituted with one substituent or with two or more substituents. A 1 ~A 8 When is an aromatic hydrocarbon group having a substituent, or a heteroaromatic group having a substituent, the substituents are each independently the same as those exemplified in (a-9) above.

[0056] A 1 ~A 8 Preferred specific examples of the group include the groups (1) to (24) shown below. (1): Methyl group, ethyl group, fluorine atom, bromine atom, iodine atom, cyano group, nitro group, hydroxyl group, thiol group, deuterium atom, methoxy group, trifluoromethylsulfonyloxy group

[0057] (2): phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 4-hydroxyphenyl group, 3-hydroxy group, 2-hydroxyphenyl group, 3,5-dihydroxyphenyl group, 3,4-dihydroxyphenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 3,5-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 4-trifluoromethylsulfonyloxyphenyl group, 3-trifluoromethylsulfonyloxyphenyl group, 2-trifluoromethylsulfonyloxyphenyl group, 3,5-bis(trifluoromethylsulfonyloxy)phenyl group, 3,4-bis(trifluoromethylsulfonyloxy)phenyl group,

[0058] (3): 4-biphenyl group, 3-biphenyl group, 2-biphenyl group, 2-methyl-1,1'-biphenyl-4-yl group, 3-methyl-1,1'-biphenyl-4-yl group, 2'-methyl-1,1'-biphenyl-4-yl group, 3'-methyl-1,1'-biphenyl-4-yl group, 4'-methyl-1,1'-biphenyl-4-yl group, 2,6-dimethyl-1,1'-biphenyl-4-yl group, 2,2'-dimethyl-1,1'-biphenyl-4-yl group, 2,3'-dimethyl dimethyl-1,1'-biphenyl-4-yl group, 2,4'-dimethyl-1,1'-biphenyl-4-yl group, 3,2'-dimethyl-1,1'-biphenyl-4-yl group, 2',3'-dimethyl-1,1'-biphenyl-4-yl group, 2',4'-dimethyl-1,1'-biphenyl-4-yl group, 2',5'-dimethyl-1,1'-biphenyl-4-yl group, 2',6'-dimethyl-1,1'-biphenyl-4-yl group, 4-phenylbiphenyl group, 2-phenylbiphenyl group

[0059] (4): 1-naphthyl group, 2-naphthyl group, 2-methylnaphthalen-1-yl group, 4-methylnaphthalen-1-yl group, 6-methylnaphthalen-2-yl group, 4-(1-naphthyl)phenyl group, 4-(2-naphthyl)phenyl group, 3-(1-naphthyl)phenyl group, 3-(2-naphthyl)phenyl group, 3-methyl-4-(1-naphthyl)phenyl group, 3-methyl-4-(2-naphthyl)phenyl group, 4-(2-methylnaphthalen-1-yl)phenyl group, 3-( 2-methylnaphthalen-1-yl)phenyl group, 4-phenylnaphthalen-1-yl group, 4-(2-methylphenyl)naphthalen-1-yl group, 4-(3-methylphenyl)naphthalen-1-yl group, 4-(4-methylphenyl)naphthalen-1-yl group, 6-phenylnaphthalen-2-yl group, 4-(2-methylphenyl)naphthalen-2-yl group, 4-(3-methylphenyl)naphthalen-2-yl group, 4-(4-methylphenyl)naphthalen-2-yl group

[0060] (5): 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, 9,9'-spirobifluorenyl group, 9-phenanthryl group, 2-phenanthryl group, 11,11'-dimethylbenzo[a]fluoren-9-yl group, 11,11'-dimethylbenzo[a]fluoren-3-yl group, 11,11'-dimethylbenzo[b]fluoren-9-yl group, 11,11'-dimethylbenzo[b]fluoren-3-yl group, 11,11'-dimethylbenzo[c]fluoren-9-yl group, 11,11'-dimethylbenzo[c]fluoren-2-yl group, 3-fluoranthenyl group, 8-fluoranthenyl group

[0061] (6): 1-imidazolyl group, 2-phenyl-1-imidazolyl group, 2-phenyl-3,4-dimethyl-1-imidazolyl group, 2,3,4-triphenyl-1-imidazolyl group, 2-(2-naphthyl)-3,4-dimethyl-1-imidazolyl group, 2-(2-naphthyl)-3,4-diphenyl-1-imidazolyl group, 1-methyl-2-imidazolyl group, 1-ethyl-2-imidazolyl group , 1-phenyl-2-imidazolyl group, 1-methyl-4-phenyl-2-imidazolyl group, 1-methyl-4,5-dimethyl-2-imidazolyl group, 1-methyl-4,5-diphenyl-2-imidazolyl group, 1-phenyl-4,5-dimethyl-2-imidazolyl group, 1-phenyl-4,5-diphenyl-2-imidazolyl group, 1-phenyl-4,5-dibiphenylyl-2-imidazolyl group

[0062] (7): 1-methyl-3-pyrazolyl group, 1-phenyl-3-pyrazolyl group, 1-methyl-4-pyrazolyl group, 1-phenyl-4-pyrazolyl group, 1-methyl-5-pyrazolyl group, 1-phenyl-5-pyrazolyl group (8): 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group (9): 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 3-isoxazolyl group, 4-isoxazolyl group, 5-isoxazolyl group

[0063] (10): 2-pyridyl group, 3-methyl-2-pyridyl group, 4-methyl-2-pyridyl group, 5-methyl-2-pyridyl group, 6-methyl-2-pyridyl group, 3-pyridyl group, 4-methyl-3-pyridyl group, 4-pyridyl group, 2-pyrimidyl group, 2,2'-bipyridin-3-yl group, 2,2'-bipyridin-4-yl group, 2,2'-bipyridin-5-yl group, 2,3'-bipyridin-3-yl group, 2,3'-bipyridin-4-yl group, 2,3'-bipyridin-5-yl group, 5-pyrimidyl group, pyrazyl group, 1,3,5-triazyl group, 4,6-diphenyl-1,3,5-triazin-2-yl group

[0064] (11): 1-benzimidazolyl group, 2-methyl-1-benzimidazolyl group, 2-phenyl-1-benzimidazolyl group, 1-methyl-2-benzimidazolyl group, 1-phenyl-2-benzimidazolyl group, 1-methyl-5-benzimidazolyl group, 1,2-dimethyl-5-benzimidazolyl group, 1-methyl-2-phenyl-5-benzimidazolyl group, 1-phenyl-5-benzimidazolyl group, 1,2-diphenyl-5-benzimidazolyl group, 1-methyl-6-benzimidazolyl group, 1,2-dimethyl-6-benzimidazolyl group, 1-methyl-2-phenyl-6-benzimidazolyl group, 1-phenyl-6-benzimidazolyl group, 1,2-diphenyl-6-benzimidazolyl group, 1-methyl-3-indazolyl group, 1-phenyl-3-indazolyl group

[0065] (12): 2-benzothiazolyl group, 4-benzothiazolyl group, 5-benzothiazolyl group, 6-benzothiazolyl group, 7-benzothiazolyl group, 3-benzoisothiazolyl group, 4-benzoisothiazolyl group, 5-benzoisothiazolyl group, 6-benzoisothiazolyl group, 7-benzoisothiazolyl group, 2,1,3-benzothiadiazol-4-yl group, 2,1,3-benzothiadiazol-5-yl group

[0066] (13): 2-benzoxazolyl group, 4-benzoxazolyl group, 5-benzoxazolyl group, 6-benzoxazolyl group, 7-benzoxazolyl group, 3-benzoisoxazolyl group, 4-benzoisoxazolyl group, 5-benzoisoxazolyl group, 6-benzoisoxazolyl group, 7-benzoisoxazolyl group, 2,1,3-benzoxadiazolyl-4-yl group, 2,1,3-benzoxadiazolyl-5-yl group

[0067] (14): 2-quinolyl group, 3-quinolyl group, 5-quinolyl group, 6-quinolyl group, 1-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 2-quinoxalyl group, 3-phenyl-2-quinoxalyl group, 6-quinoxalyl group, 2,3-dimethyl-6-quinoxalyl group, 2,3-diphenyl-6-quinoxalyl group, 2-quinazolyl group, 4-quinazolyl group, 2-acridinyl group, 9-acridinyl group, 1,10-phenanthroline-3-yl group, 1,10-phenanthroline-5-yl group

[0068] (15): 2-thienyl group, 3-thienyl group, 2-benzothienyl group, 3-benzothienyl group, 2-dibenzothienyl group, 4-dibenzothienyl group (16): 2-furanyl group, 3-furanyl group, 2-benzofuranyl group, 3-benzofuranyl group, 2-dibenzofuranyl group, 4-dibenzofuranyl group

[0069] (17): 9-methylcarbazol-2-yl group, 9-methylcarbazol-3-yl group, 9-methylcarbazol-4-yl group, 9-phenylcarbazol-2-yl group, 9-phenylcarbazol-3-yl group, 9-phenylcarbazol-4-yl group, 9-biphenylcarbazol-2-yl group, 9-biphenylcarbazol-3-yl group, 9-biphenylcarbazol-4-yl group

[0070] (18): 2-thianthryl group, 10-phenylphenothiazin-3-yl group, 10-phenylphenothiazin-2-yl group, 10-phenylphenoxazin-3-yl group, 10-phenylphenoxazin-2-yl group (19): 1-methylindol-2-yl group, 1-phenylindol-2-yl group, 9-phenylcarbazol-4-yl group

[0071] (20): 4-(2-pyridyl)phenyl group, 4-(3-pyridyl)phenyl group, 4-(4-pyridyl)phenyl group, 3-(2-pyridyl)phenyl group, 3-(3-pyridyl)phenyl group, 3-(4-pyridyl)phenyl group

[0072] (21): 4-(2-phenylimidazol-1-yl)phenyl group, 4-(1-phenylimidazol-2-yl)phenyl group, 4-(2,3,4-triphenylimidazol-1-yl)phenyl group, 4-(1-methyl-4,5-diphenylimidazol-2-yl)phenyl group, 4-(2-methylbenzimidazol-1-yl)phenyl group, 4-(2-phenylbenzimidazol-1-yl)phenyl group, 4-(1-methylbenzimidazol-2-yl)phenyl group, 4-(2-phenylbenzimidazol-1-yl)phenyl group, 3-(2-methylbenzimidazol-1-yl)phenyl group, 3-(2-phenylbenzimidazol-1-yl)phenyl group, 3-(1-methylbenzimidazol-2-yl)phenyl group, 3-(1-phenylbenzimidazol-1-yl)phenyl group

[0073] (22): 4-(3,5-diphenyltriazin-1-yl)phenyl group, 4-(2-thienyl)phenyl group, 4-(2-furanyl)phenyl group, 5-phenylthiophen-2-yl group, 5-phenylfuran-2-yl group, 4-(5-phenylthiophen-2-yl)phenyl group, 4-(5-phenylfuran-2-yl)phenyl group, 3-(5-phenylthiophen-2-yl)phenyl group, 3-(5-phenylfuran-2-yl)phenyl group, 4-(2-benzothienyl)phenyl group, 4-(3-benzothienyl)phenyl group, 3-(2-benzothienyl)phenyl group, 3-(3 -benzothienyl)phenyl group, 4-(2-dibenzothienyl)phenyl group, 4-(4-dibenzothienyl)phenyl group, 3-(2-dibenzothienyl)phenyl group, 3-(4-dibenzothienyl)phenyl group, 4-(2-dibenzofuranyl)phenyl group, 4-(4-dibenzofuranyl)phenyl group, 3-(2-dibenzofuranyl)phenyl group, 3-(4-dibenzofuranyl)phenyl group, 5-phenylpyridin-2-yl group, 4-phenylpyridin-2-yl group, 5-phenylpyridin-3-yl group, 4-(9-carbazolyl)phenyl group, 3-(9-carbazolyl)phenyl group

[0074] (23): 2-dibenzo[g,p]chrysenyl group, 3-dibenzo[g,p]chrysenyl group, 2-(7-phenyl)dibenzo[g,p]chrysenyl group, 3-(7-phenyl)dibenzo[g,p]chrysenyl group

[0075] (24): N,N-diphenylamino group, N,N-bis(4-biphenylyl)-amino group, N,N-bis(3-biphenylyl)-amino group, N-phenyl-4-biphenylamino group, N-phenyl-3-biphenylamino group, N-(4-biphenyl)-4-p-terphenylamino group, N-[4-(carbazol-9-yl)phenyl]-4-biphenylamino group, N 3 -[1,1'-biphenyl]-4-yl-N 1 ,N 1-Diphenyl-1,3-benzenediamino group, 4-triphenylamino group, 3-triphenylamino group, 4-(4',4''-diphenyl)triphenylamino group, 3-(4',4''-diphenyl)triphenylamino group, N 1 ,N 1 ,N 3 ,N 3 -Tetraphenyl-1,3-benzenediamino group, 4-(phenylamino)triphenylamino group

[0076] In the fused ring compounds represented by formulae (1B) to (5B), A 1 ~A 8 are independently ranked in terms of ease of obtaining raw materials. a phenyl group, a biphenylyl group, a pyridylphenyl group, a terphenylyl group, a naphthyl group, a phenanthryl group, a pyrenyl group, a 9,9-spirobi[9H-fluorenyl] group, a triphenylenyl group, a dibenzothienyl group, a dibenzofuranyl group, a pyridyl group, a pyrimidyl group, or any of these groups substituted with a cyano group, a nitro group, a hydroxyl group, a thiol group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, a methoxy group, or a trifluoromethylsulfonyloxy group; a fluorenyl group, a benzofluorenyl group, an anthryl group, a dibenzo[g,p]chrysenyl group, a carbazolyl group, or any of these groups substituted with a cyano group, a nitro group, a hydroxyl group, a thiol group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, a methoxy group, or a phenyl group; 4,6-diphenyl-1,3,5-triazin-2-yl group, (4,6-diphenyl-1,3,5-triazin-2-yl)phenyl group, 4,6-bis(4-biphenylyl)-1,3,5-triazin-2-yl group, 4,6-bis(3-biphenylyl)-1,3,5-triazin-2-yl group, cyano group, nitro group, hydroxyl group, thiol group, fluorine atom, chlorine atom, bromine atom, iodine atom, diphenylphosphine oxide, triphenylsilyl group, dihydroxyboryl group (-B(OH)2), 4,4,5,5-tetramethyl-[1,3,2]-dioxaborolane group, 5,5-dimethyl-[1,3,2]-dioxaborinane group, methyl group, N,N-diphenylamino group, N,N-bis(4-biphenylyl)amino group, N 3 -[1,1'-biphenyl]-4-yl-N 1 ,N 1 -Diphenyl-1,3-benzenediamino group, N-phenyl-3-biphenylylamino group, 4-triphenylamino group, 3-triphenylamino group, 4-(4',4''-diphenyl)triphenylamino group, 3-(4',4''-diphenyl)triphenylamino group, N 1 ,N 1 ,N 3 ,N 3 -tetraphenyl-1,3-benzenediamino group, or 4-(phenylamino)triphenylamino group.

[0077] <Preferred specific examples of fused ring compounds> Preferable specific examples of the fused ring compound represented by any one of formulas (1') to (5B) are shown below, but the invention is not limited thereto. Tables B-1 to B-7 show compounds (N-1) to (N-275) having skeletons (1Ba) to (5Ba) and (1ba) to (5ba) shown in Tables A-1 and A-2, and the substituent A of the skeleton is a group shown in Tables B-1 to B-7. Here, N represents any symbol of 1Ba to 5ba. Therefore, for example, in the case of a compound (N-3), when N=1Ba, it shows a compound (1Ba-3) having a skeleton of (1Ba) and a substituent A of the skeleton is an F atom. In addition, N=1Bb, 1Bc, 1Cb, 1Eb, 1Fb, 1Jb, 1Kb, 2Bb, 2Cb, 2Db, 2Eb, 3Cb, 3Db, 3Eb, 1bb, 1bc, 1cb, 1eb, 1fb, 1j For b, 1kb, 2bb, 2cb, 2db, 2eb, 3cb, 3db, 3eb, (1Bc-1), (1Cb-1), (1Eb-1), (1Fb-1), (1Jb-1), (1Kb-1 ), (2Bb-1), (2Cb-1), (2Db-1), (2Eb-1), (3C-1), (3Db-1), (3Eb-1), (1bc-1), (1cb-1), (1eb-1), (1fb-1), (1jb-1), (1kb-1), (2bb-1), (2cb-1), (2db-1), (2eb-1), (3c-1), (3db-1), and (3eb-1) do not exist.

[0078] [Table A-1] [Table A-2]

[0079] [Table B-1]

[0080] [Table B-2]

[0081] [Table B-3]

[0082] [Table B-4]

[0083] [Table B-5]

[0084] [Table B-6]

[0085] [Table B-7]

[0086] <Method for producing fused ring compound> From the viewpoint of yield and purity during production, the fused ring compound represented by any one of formulas (1'), (2), and (3) (hereinafter also referred to as the fused ring compound represented by any one of formulas (1') to (3)) is preferably produced by any one of a production method using a compound represented by formula (7) and a compound represented by formula (8) as starting materials, which will be described later, and a production method using a compound represented by formula (9) and a compound represented by formula (10) as starting materials. That is, a method for producing a fused ring compound according to one embodiment of the present invention includes a method of reacting a compound represented by formula (5) with a compound represented by formula (8), or a method of reacting a compound represented by formula (9) with a compound represented by formula (10).

[0087] [ka]

[0088] <Y 1 ~Y 8 About > Y 1 ~Y 8each independently represents a nitrogen atom or a carbon atom which may have a charge transporting group; Y 1 ~Y 4 At least two of the carbon atoms may have a charge transporting group; Y 5 ~Y 8 At least two of these are carbon atoms which may have a charge transporting group. Y 1 ~Y 8 Preferably, no more than four of Y are nitrogen atoms; 1 ~Y 8 More preferably, no more than two of Y are nitrogen atoms. 1 ~Y 8 It is further preferred that not more than one of

[0089] <C 1 and C 2 About > C 1 and C 2 each independently represents a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, a quinoline ring, or an isoquinoline ring, which may have a charge transport group. Y 1 ~Y 8 are each independently a carbon atom which may have a charge transporting group, C 1 and C 2 At least one of these rings is a pyridine ring, a pyrimidine ring, a pyrazine ring, a quinoline ring, or an isoquinoline ring which may have a charge transporting group. C 1 and C 2 are each independently a benzene ring or a naphthalene ring which may have a charge transporting group, 1 ~Y 8 At least one of these is a nitrogen atom.

[0090] <Z 1 and Z 2 About > Z in formula (7), formula (8) and formula (11) 1 and Z 2each independently represents a chlorine atom, a bromine atom, or an iodine atom. Z 1 From the viewpoint of yield, Z is preferably a bromine atom or an iodine atom, and more preferably an iodine atom. 2 From the viewpoint of yield, is preferably a chlorine atom, a bromine atom, or an iodine atom, and more preferably a bromine atom or an iodine atom.

[0091] Here, Y 1 ~Y 8 is preferably a carbon atom which may have a charge transporting group. 1 ~Y 8 is a carbon atom which may have a charge transporting group, and C 1 is a benzene ring or a naphthalene ring which may have a charge transport group, and C 2 It is particularly preferable that the ring is a pyridine ring, a pyrimidine ring, a pyrazine ring, a quinoline ring, or an isoquinoline ring, which may have a charge transporting group. Y 1 ~Y 8 is a carbon atom which may have a charge transporting group, Y 1 ~Y 8 In comparison with the case where any one or more of the above are nitrogen atoms, this is preferable since the fused ring compound represented by any one of the formulae (1') to (3) can be produced in good yield. The definition of the charge transporting group is the same as that of the charge transporting group in the fused ring compound described above.

[0092] [ka]

[0093] In formula (9), Y 1 ~Y 8 The definitions of Y in formula (7), including preferred embodiments thereof, are as follows: 1 ~Y 8 The definition is the same as that of Z. 3 ~Z 4 each independently represents a chlorine atom, a bromine atom, or an iodine atom.

[0094] <D 1 and D. 2 About > D 1 represents a benzene ring or a naphthalene ring which may have a charge transporting group, and is preferably a benzene ring which may have a charge transporting group. 2 represents a pyridine ring, pyrimidine ring, pyrazine ring, quinoline ring, or isoquinoline ring which may have a charge transporting group, more preferably a pyridine ring, pyrimidine ring, or pyrazine ring which may have a charge transporting group, and particularly preferably a pyrazine ring which may have a charge transporting group.

[0095] <Z 3 and Z 4 About > Z in Equation (9) 3 and Z 4 From the viewpoint of yield, each of the groups independently is preferably a bromine atom or an iodine atom, and more preferably an iodine atom. Here, Y 1 ~Y 8 is preferably a carbon atom which may have a charge transporting group. 1 ~Y 8 is a carbon atom which may have a charge transporting group, and D 1 is a benzene ring which may have a charge transport group, and D 2 is more preferably a pyridine ring, a pyrimidine ring, or a pyrazine ring which may have a charge transporting group. Y 1 ~Y 8 is a carbon atom which may have a charge transporting group, Y 1 ~Y 8 In comparison with the case where any one or more of the above are nitrogen atoms, this is preferable since it allows production of any one of the fused ring compounds represented by formulae (1') to (3) in good yield. The definition of the charge transporting group is the same as that of the charge transporting group in the fused ring compound described above.

[0096] The method for producing a fused ring compound according to one embodiment of the present invention is preferably a method for producing the above-mentioned preferred fused ring compound among the fused ring compounds represented by any one of formulas (1') to (3). Therefore, the preferred range of the compounds represented by formulas (7) to (10) is similar to the preferred range of the fused ring compounds represented by any one of formulas (1') to (3).

[0097] <Reaction of a compound represented by formula (7) and a compound represented by formula (8)> A compound represented by formula (7) and a compound represented by formula (8) can be reacted in the presence of a catalyst and a base to give a fused ring compound represented by any one of formulas (1') to (3) directly via a phenanthrene compound represented by formula (11). The starting compound represented by formula (7) or formula (8) can be synthesized based on known methods, or a commercially available compound can be used.

[0098] From the viewpoint of yield, the catalyst is preferably a palladium-based catalyst. Examples of the palladium catalyst include palladium(II) acetate, palladium(II) chloride, palladium(II) pivalate, palladium trifluoroacetate, bis(triphenylphosphine)palladium(II) dichloride, tetrakis(acetonitrile)palladium(II) bis(tetrafluoroborate), tris(benzylideneacetone)palladium(0), tetrakis(triphenylphosphine)palladium(0), etc. Among these, palladium(II) acetate is preferred from the viewpoint of yield.

[0099] When using the above palladium catalyst, a compound that serves as a ligand may be used as necessary. Examples of the ligand include tricyclohexylphosphine (PCy3), tritertiary butylphosphine (P t Bu3), di-tertiary butyl methyl phosphine (P tBu2Me), tricyclohexylphosphonium tetrafluoroborate (PCy3·HBF4), tri-tertiary butylphosphonium tetrafluoroborate (P t Bu3·HBF4), tri-tertiary butyl phosphonium tetraphenylborate (P t Bu3·HBPh4), di-tertiary butyl methyl phosphonium tetrafluoroborate (P t Bu2Me·HBF4), 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride (IPR·HCl), 1,2-bis(diphenylphosphino)ethane (dppe), 1,2-bis(dicyclohexylphosphino)ethane, tridamantylphosphine, etc. Among them, tricyclohexylphosphine (PCy3), tritertiary butylphosphine (P t Bu3), di-tertiary butyl methyl phosphine (P t Bu2Me), tricyclohexylphosphonium tetrafluoroborate (PCy3·HBF4), tritertiary butylphosphonium tetraphenylborate (P t Bu3·HBPh4), di-tertiary butyl methyl phosphonium tetrafluoroborate (P t Bu2Me·HBF4)(P t Bu2Me·HBF4), or 1,2-bis(diphenylphosphino)ethane (dppe), are preferred. Tricyclohexylphosphine (PCy3), tritertiary butylphosphine (P t Bu3), di-tertiary butyl methyl phosphine (P t Bu2Me), tricyclohexylphosphonium tetrafluoroborate (PCy3·HBF4), tritertiary butylphosphonium tetraphenylborate (P t Bu3·HBPh4), or di-tertiary butyl methyl phosphonium tetrafluoroborate (P t Bu2Me·HBF4) is more preferred.

[0100] Examples of the base include sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, sodium acetate, potassium acetate, potassium t-butoxide, potassium pivalate, and cesium pivalate. Among these, from the viewpoint of yield, potassium carbonate, sodium acetate, potassium acetate, or cesium pivalate is preferred, and potassium acetate or sodium acetate is more preferred.

[0101] Examples of the solvent include dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone. Among them, dimethylformamide or dimethylacetamide is preferred from the viewpoint of yield.

[0102] From the viewpoint of yield, the reaction temperature is preferably from room temperature to 200° C., more preferably from 110° C. to 200° C., and particularly preferably from 130° C. to 200° C. Here, room temperature means from 10° C. to 30° C. From the viewpoint of maintaining the catalytic activity, the reaction atmosphere is preferably a dry nitrogen or dry argon atmosphere.

[0103] <Reaction of a compound represented by formula (9) and a compound represented by formula (10)> A compound represented by formula (9) and a compound represented by formula (10) can be reacted in the presence of a base to directly obtain a fused ring compound represented by any one of formulas (1') to (3). The compound represented by formula (9) or formula (10) can be produced based on known methods, or a commercially available compound can be used.

[0104] Examples of the base include potassium t-butoxide, sodium t-butoxide, and lithium t-butoxide. In addition to the above bases, t-butyl hydroperoxide may be used. Among them, potassium t-butoxide is preferable from the viewpoint of yield. When the above base is used, a compound that acts as a ligand may be used as necessary. Examples of the ligand include dimethylethylenediamine (DMEDA), 1,10-phenanthroline, bathophenanthroline, 4,7-dimethyl-1,10-phenanthroline, and 2,9-diphenyl-1,10-phenanthroline.

[0105] When the compound represented by formula (10) is liquid, the solvent may not be used. When the compound represented by formula (10) is solid, it may be melted by heating before use. When the compound represented by formula (10) is difficult to melt, a solvent may be used as necessary. Examples of the solvent include dimethylformamide and dimethylsulfoxide. Among them, from the viewpoint of yield, it is preferable that the compound represented by formula (10) is liquid, and it is more preferable to carry out the reaction without a solvent.

[0106] From the viewpoint of yield, the reaction temperature is preferably from room temperature to 200° C., more preferably from 110° C. to 200° C. If necessary, a microwave irradiation device may be used. When a microwave irradiation device is used, the reaction temperature is preferably from room temperature to 110° C. From the viewpoint of yield, the reaction atmosphere is preferably a dry nitrogen or dry argon atmosphere.

[0107] When the compound represented by any one of the formulas (1') to (3) obtained by the above route has a halogen atom (fluorine, chlorine, bromine, or iodine) or a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms, an additional coupling reaction may be carried out as necessary.

[0108] Examples of the boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms include the same as the boronyl groups which may have a saturated hydrocarbon group having 2 to 10 carbon atoms exemplified in (a-9) above.

[0109] From the viewpoint of yield and purity during production, the fused ring compound represented by any one of formulas (4) and (5) is preferably produced by a production method using a compound represented by formula (12) as a starting material. That is, a method for producing a fused ring compound according to one embodiment of the present invention includes a method of reacting a compound represented by formula (12) in the presence of a catalyst and a base to obtain a fused ring compound represented by any one of formulas (4) and (5) by intramolecular cyclization reaction.

[0110] [ka]

[0111] <X 2 ~X 15 About > X 2 ~X 15 each independently represents a nitrogen atom which may be substituted with an oxygen atom, or a carbon atom which may have a charge transporting group; X 2 ~X 4 at least two of the carbon atoms may have a charge transporting group; X 5 ~X 8 at least two of the carbon atoms may have a charge transporting group; X 13 ~X 15 at least one of which is a carbon atom which may have a charge transporting group; X 9 and X 12 represents a carbon atom which may have a charge transporting group; X 2 ~X 15 Among the charge transporting groups contained in the compound, two adjacent charge transporting groups may be bonded to each other to form a ring; X 14 and X 15 When at least one of the carbon atoms is a carbon atom having a charge transport group forming a ring, the atoms constituting the ring structure of the ring and X 13 ~X 15at least one of which is a nitrogen atom optionally substituted with an oxygen atom; X 14 and X 15 are not carbon atoms having a charge transport group forming a ring, X 14 and X 15 At least one of these is a nitrogen atom which may be substituted with an oxygen atom. The definition of the charge transporting group is the same as that of the charge transporting group in the fused ring compound described above.

[0112] <Z 5 About > Z in Equation (12) 5 represents a chlorine atom, a bromine atom, or an iodine atom. 5 From the viewpoint of easy availability of raw materials, is preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom. The method for producing a fused ring compound according to one embodiment of the present invention is preferably a method for producing the above-mentioned preferred fused ring compound among the fused ring compounds represented by any one of formulas (4) and (5). Therefore, the preferred range of the compound represented by formula (12) is similar to the preferred range of the fused ring compound represented by any one of formulas (4) and (5).

[0113] From the viewpoint of yield, the catalyst is preferably a palladium-based catalyst. Examples of the palladium catalyst include palladium(II) acetate, palladium(II) chloride, palladium(II) pivalate, palladium trifluoroacetate, bis(triphenylphosphine)palladium(II) dichloride, tetrakis(acetonitrile)palladium(II) bis(tetrafluoroborate), tris(benzylideneacetone)palladium(0), tetrakis(triphenylphosphine)palladium(0), etc. Among these, palladium(II) acetate is preferred from the viewpoint of yield.

[0114] When using the above palladium catalyst, a compound that serves as a ligand may be used as necessary. Examples of the ligand include 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (Xphos), tricyclohexylphosphine (PCy3), tritertiary butylphosphine (P t Bu3), tricyclohexylphosphonium tetrafluoroborate (PCy3·HBF4), tritertiary butylphosphonium tetrafluoroborate (P t Bu3·HBF4), tri-tertiary butyl phosphonium tetraphenylborate (P t Bu3·HBPh4), 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride (IPR·HCl), 1,2-bis(diphenylphosphino)ethane (dppe), 1,2-bis(dicyclohexylphosphino)ethane, tridamantylphosphine, etc. Among them, from the viewpoint of yield, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (Xphos), tricyclohexylphosphine (PCy3), tricyclohexylphosphonium tetrafluoroborate (PCy3·HBF4), 1,2-bis(diphenylphosphino)ethane (dppe) are preferred, and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (Xphos) is particularly preferred.

[0115] Examples of the base include sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, sodium acetate, potassium acetate, potassium t-butoxide, potassium pivalate, and cesium pivalate. Among these, from the viewpoint of yield, potassium carbonate, potassium phosphate, potassium acetate, or sodium acetate is preferred, and potassium carbonate or potassium phosphate is more preferred. Examples of the solvent include tetrahydrofuran, toluene, dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone. Among them, tetrahydrofuran or toluene is preferable from the viewpoint of yield. From the viewpoint of yield, the reaction temperature is preferably from room temperature to 200° C., more preferably from room temperature to 150° C., and particularly preferably from room temperature to 100° C. The definition of room temperature is the same as that in the above-mentioned method for producing a fused ring compound. From the viewpoint of maintaining the catalytic activity, the reaction atmosphere is preferably a dry nitrogen or dry argon atmosphere.

[0116] <Materials for organic electroluminescence devices> The fused ring compound represented by formula (1) can be used as a material for an organic EL device. Therefore, the material for an organic EL device according to one embodiment of the present invention includes the fused ring compound represented by formula (1). In addition, the fused ring compound represented by formula (1) is preferably high purity in terms of charge transport properties and device life. Specifically, it is preferable that the fused ring compound has as little impurities as possible, such as halogen atoms and transition metal elements, and impurities such as manufacturing raw materials and by-products. The material for an organic EL device containing the fused ring compound represented by formula (1) can be used as a material for forming a light-emitting layer or an electron-transporting layer (each layer having electron transport properties between the cathode and the light-emitting layer, specifically, an electron injection layer, an electron transport layer, etc.). Among them, it is preferably used as a material for an electron-transporting layer, and particularly preferably used as a material for an electron transporting layer.

[0117] When the fused ring compound represented by formula (1) is used as a material for the light-emitting layer of an organic EL device, the fused ring compound may be used alone, or may be doped into a known light-emitting host material or a known light-emitting dopant. Such known materials will be described later.

[0118] As a method for forming an electron injection layer, an electron transport layer, or a light emitting layer containing a fused ring compound represented by formula (1), for example, a known method such as a vacuum deposition method, a spin coating method, a casting method, etc. can be used. The material for organic EL devices used in coating methods such as spin coating and casting contains an organic solvent in addition to the fused ring compound represented by formula (1). The organic solvent is not particularly limited, and examples thereof include monochlorobenzene and orthodichlorobenzene. The organic solvent may be a combination of two or more of these. It is preferable that the organic solvent is selected so as to exhibit the desired coating performance, and the viscosity and concentration of the material for organic EL devices are adjusted.

[0119] <Organic EL element> The organic EL device according to one embodiment of the present invention includes a layer containing the fused ring compound represented by the above formula (1). Fig. 1 is a schematic cross-sectional view showing an example of a layered structure of an organic EL element according to one embodiment of the present invention. Hereinafter, the organic EL element according to this embodiment will be described with reference to Fig. 1. Note that the organic EL element shown in Fig. 1 has a so-called bottom emission type element structure, but the organic EL element according to one embodiment of the present invention is not limited to a bottom emission type element structure. In other words, the organic EL element according to one embodiment of the present invention may have a top emission type element structure or other known element structure.

[0120] The basic structure of the organic EL device 100 includes a substrate 1, an anode 2, a hole injection layer 3, a charge generation layer 4, a hole transport layer 5, a light emitting layer 6, an electron transport layer 7, an electron injection layer 8, and a cathode 9 in this order. However, some of these layers may be omitted, or other layers may be added. For example, the charge generation layer 4 may be omitted, and the hole transport layer 5 may be provided directly on the hole injection layer 3, or a hole blocking layer may be provided between the light emitting layer 6 and the electron transport layer 7. Alternatively, a single layer having the functions of multiple layers, such as an electron injection / transport layer having the functions of both the electron injection layer and the electron transport layer in a single layer, may be provided instead of the multiple layers.

[0121] In the organic EL device according to this embodiment, at least one layer selected from the group consisting of the light-emitting layer, the electron-transporting layer, and the electron-injecting layer contains a fused ring compound represented by formula (1). Among the light-emitting layer, the electron transport layer, and the electron injection layer, the layer containing the fused ring compound represented by formula (1) may contain, together with the fused ring compound, any one or more selected from known materials. Also, among the light-emitting layer, the electron transport layer, and the electron injection layer, the layer not containing the fused ring compound represented by formula (1) preferably contains any one or more selected from known materials.

[0122] The anode 2 and the cathode 9 of the organic EL element 100 are connected to a power source via electrical conductors. By applying a voltage between the anode 2 and the cathode 9, the organic EL element 100 operates and emits light. Holes are injected into the organic EL element 100 at the anode 2 and electrons are injected into the organic EL element 100 at the cathode 9 . In the organic EL device 100 according to this embodiment, the anode 2 is provided in contact with the substrate 1. The electrode in contact with the substrate is conveniently called the lower electrode. However, this embodiment is not limited to this configuration, and a cathode may be provided in contact with the substrate instead of the anode to serve as the lower electrode, or the anode or cathode may not be in contact with the substrate, and the anode or cathode may be laminated on the substrate via another layer.

[0123] <Substrate 1> The light transmittance of the substrate may be appropriately selected according to the desired light emission direction (direction from which light is extracted) of the organic EL element. That is, the substrate may or may not have light transmittance (it may be opaque to light having a predetermined wavelength). Whether the substrate has light transmittance or not can be confirmed, for example, by whether or not a desired amount or more of light originating from the emission of the organic EL element is observed from the substrate. The substrate having optical transparency is generally a transparent glass plate or a plastic plate, but is not limited thereto. The substrate may be, for example, a composite structure including multiple material layers.

[0124] <Anode 2> An anode 2 is provided on a substrate 1. In the case of an organic EL element configured so that light emitted passes through the anode and is extracted, the anode is formed from a material that is transparent or substantially transparent to the emitted light. Examples of transparent materials used for the anode include indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide, aluminum-doped tin oxide, magnesium indium oxide, nickel tungsten oxide, and other metal oxides; metal nitrides such as gallium nitride; metal selenides such as zinc selenide; and metal sulfides such as zinc sulfide. The anode can be modified with a plasma deposited fluorocarbon. In the case of an organic EL element configured to extract light only from the cathode side, the transmission characteristics of the anode are not important, and any conductive material that is transparent, opaque, or reflective can be used as the anode material. Therefore, examples of materials that can be used for the anode in this case include gold, iridium, molybdenum, palladium, platinum, etc.

[0125] <Hole-transporting layer (hole injection layer 3, hole transport layer 5)> Between the anode 2 and the light-emitting layer 6, a hole-transporting layer is provided. The hole transport layer is a layer having hole transport properties provided between the anode and the light emitting layer, and is a hole injection layer, a hole transport layer, etc. A plurality of hole transport layers may be provided between the anode and the light emitting layer. The hole injection layer and the hole transport layer have a function of transmitting holes injected from the anode to the light emitting layer. By interposing these layers between the anode and the light emitting layer, holes are injected into the light emitting layer at a lower electric field. In the embodiment shown in Fig. 1, the hole transport layer is composed of a single layer, but may be composed of multiple layers, for example, a first hole transport layer on the anode side and a second hole transport layer on the cathode side. In the case of this two-layer hole transport layer, it is preferable that the first hole transport layer has a better hole transporting ability than the second hole transport layer, and the second hole transport layer has a better electron blocking ability than the first hole transport layer. The second hole transport layer is also generally referred to as an electron blocking layer.

[0126] Examples of known materials having hole transport properties (including hole injection materials, hole transport materials, electron blocking materials, etc.) include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline-based copolymers, conductive polymer oligomers, and in particular thiophene oligomers. Among these, porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds are preferred, and aromatic tertiary amine compounds are particularly preferred.

[0127] Representative examples of the aromatic tertiary amine compounds and styrylamine compounds include N,N,N',N'-tetraphenyl-4,4'-diaminophenyl, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine (TPD), 2,2-bis(4-di-p-tolylaminophenyl)propane, 1,1-bis(4-di-p-tolylaminophenyl)cyclohexane, N,N,N',N'-tetra-p-tolyl-4,4' -Diaminobiphenyl, 1,1-bis(4-di-p-tolylaminophenyl)-4-phenylcyclohexane, bis(4-dimethylamino-2-methylphenyl)phenylmethane, bis(4-di-p-tolylaminophenyl)phenylmethane, N,N'-diphenyl-N,N'-di(4-methoxyphenyl)-4,4'-diaminobiphenyl, N,N,N',N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis(diphenylamino)quartz N,N,N-tri(p-tolyl)amine, 4-(di-p-tolylamino)-4'-[4-(di-p-tolylamino)styryl]stilbene, 4-N,N-diphenylamino-(2-diphenylvinyl)benzene, 3-methoxy-4'-N,N-diphenylaminostilbene, N-phenylcarbazole, 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPD), 4,4',4''-tris[N-(3-methylphenyl) -N-phenylamino]triphenylamine (MTDATA), 3-[4-[1,1'-biphenyl-4-yl](9,9-dimethylfluoren-2-yl)amino]phenyl]-9-phenyl-9H-carbazole, and 4,4'-bis[N-phenyl-N-(9-phenylcarbazol-3-yl)amino]-1,1'-biphenyl], N,N-bis[4-(dibenzofuran-4-yl)phenyl]-N-(p-terphenyl-4-yl)amine, etc.

[0128] Furthermore, inorganic compounds such as p-type Si and p-type SiC can also be used as the hole injection material and hole transport material. The hole injection layer and the hole transport layer may have a single layer structure made of one or more materials selected from the above materials, or may have a laminate structure made of multiple layers of the same or different compositions.

[0129] <Charge generation layer 4> A charge generating layer may be provided between the hole injection layer 3 and the hole transport layer 5 . An example of the material for the charge generating layer is dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile (HAT-CN).

[0130] <Light-emitting layer 6> The light-emitting layer 6 is provided between the hole transport layer 5 and the electron transport layer 7 or a hole blocking layer described later. The light-emitting layer contains a phosphorescent, fluorescent, or thermally activated delayed fluorescent material, and emits light as a result of recombination of electron-hole pairs in this region. Fluorescent materials primarily utilize the emission of fluorescence in the singlet state, while thermally activated delayed fluorescence, in addition to emitting fluorescence in the singlet state, also emits fluorescence by converting a triplet state back to the singlet state by heat.

[0131] The light-emitting layer may consist of a single material, including both small molecule and polymeric materials, but more commonly consists of a host material doped with a guest compound. Emission comes primarily from the dopant and can be of any color. Examples of the host material include compounds having a biphenyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group, a pyrenyl group, or an anthranyl group. More specifically, DPVBi (4,4'-bis(2,2-diphenylvinyl)-1,1'-biphenyl), BCzVBi (4,4'-bis(9-ethyl-3-carbazovinylene)1,1'-biphenyl), TBADN (2-tertiarybutyl-9,10-di(2-naphthyl)anthracene), ADN (9,10-di(2-naphthyl)anthracene), CBP (4,4'-bis(carbazol-9-yl)biphenyl), Examples of the fused ring compound represented by the formula (1) include 4,4'-bis(carbazol-9-yl)-2,2'-dimethylbiphenyl), 2-(9-phenylcarbazol-3-yl)-9-[4-(4-phenylphenylquinazolin-2-yl)carbazole, 9,10-bis(biphenyl)anthracene, 2-(10-phenyl-9-anthracenyl)benzo[b]naphtho[2,3-d]furan, and the like. The host material may be an electron-transporting material described below, a material having a hole-transporting property described above, another material that supports hole-electron recombination, or a combination of these materials.

[0132] Examples of the fluorescent dopant include anthracene, pyrene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine, quinacridone, dicyanomethylenepyran compound, thiopyran compound, polymethine compound, pyrylium, thiapyrylium compound, fluorene derivative, periflanthene derivative, indenoperylene derivative, bis(azinyl)amine boron compound, bis(azinyl)methane compound, carbostyril compound, condensed ring compound represented by any one of formulas (1) to (3), etc. The fluorescent dopant may be a combination of two or more selected from these. Phosphorescent dopants include, for example, organometallic complexes of transition metals such as iridium, platinum, palladium, and osmium. Examples of the thermally activated delayed fluorescent dopant include carbazole derivatives.

[0133] Specific examples of fluorescent dopants, phosphorescent dopants, and thermally activated delayed fluorescent dopants include Alq3 (tris(8-hydroxyquinoline)aluminum), DPAVBi (4,4'-bis[4-(di-p-tolylamino)styryl]biphenyl), perylene, bis[2-(4-n-hexylphenyl)quinoline](acetylacetonato)iridium(III), Ir(PPy)3 (tris(2-phenylpyridine)iridium(III)), and FIrPic (bis(3,5-difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl)iridium(III))), 1,6-pyrene diamine, N 1 ,N 6 -Bis([1,1'-biphenyl]-3-yl)-N 1 ,N 6 -bis(4-dibenzofuranyl)-, 1,2,4,5-tetrakis(carbazol-9-yl)-3,6-dicyanobenzene (4Cz-IPN), and the like. The light-emitting layer may have a single-layer structure or a laminate structure consisting of multiple layers of the same or different compositions.

[0134] <Electron Transporting Layer (Electron Transporting Layer 7, Electron Injecting Layer 8)> The electron transport layer 7 is provided between the electron injection layer 8 and the light emitting layer 6 . The electron transport layer has a function of transporting the electrons injected from the electron injection layer to the light emitting layer. By interposing the electron transport layer between the electron injection layer and the light emitting layer, the electrons are injected into the light emitting layer at a lower electric field. In the embodiment shown in FIG. 1, the electron transport layer is composed of a single layer, but may be composed of multiple layers, for example, a first electron transport layer on the anode side and a second electron transport layer on the cathode side. In the case of this two-layered electron transport layer, it is preferable that the second electron transport layer is a layer having a superior electron transporting ability compared to the first hole transport layer, and the first electron transport layer is a layer having a superior hole blocking ability compared to the second electron transport layer. The first electron transport layer is generally sometimes called a hole blocking layer. The hole blocking layer can improve the carrier balance. When the electron transport layer is composed of multiple layers, the fused ring compound represented by any one of the formulas (1') to (5) may be contained in any one layer, or in two or more layers. When the electron transport layer contains a fused ring compound represented by formula (1), the electron transport layer may consist only of the fused ring compound represented by formula (1), or may further contain a known electron transport material described later.

[0135] The electron transport layer includes an electron transporting material. Examples of the electron transporting material include 8-hydroxyquinolinato lithium (Liq), bis(8-hydroxyquinolinato) zinc, bis(8-hydroxyquinolinato) copper, bis(8-hydroxyquinolinato) manganese, tris(8-hydroxyquinolinato) aluminum, tris(2-methyl-8-hydroxyquinolinato) aluminum, tris(8-hydroxyquinolinato) gallium, bis(10-hydroxybenzo[h]quinolinato) beryllium, bis(10-hydroxybenzo[h]quinolinato) zinc, bis(2-methyl-8-quinolinato) chlorogallium, bis(2-methyl-8-quinolinato) (o-cresolate) gallium, bis(2-methyl-8-quinolinato)-1-naphtholato aluminum, or the like. or bis(2-methyl-8-quinolinato)-2-naphtholatogallium, 2-[3-(9-phenanthrenyl)-5-(3-pyridinyl)phenyl]-4,6-diphenyl-1,3,5-triazine, 2-(4,''-di-2-pyridinyl[1,1':3',1''-terphenyl]-5-yl)-4,6-diphenyl-1,3,5-triazine, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis(2-methyl-8-quinolinato)-4-(phenylphenolato)aluminum), bis(10-hydroxybenzo[h]quinolinato)beryllium), and the condensed ring compound represented by formula (1).

[0136] The electron injection layer can improve the electron injection property and improve the device characteristics (for example, light emitting efficiency, constant voltage driving, or high durability). Compounds other than the fused ring compound represented by formula (1) that are desirable as materials for the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthraquinodimethane, anthrone, etc. In addition, inorganic compounds such as the above-mentioned metal complexes, alkali metal oxides, alkaline earth oxides, rare earth oxides, alkali metal halides, alkaline earth halides, rare earth halides, various oxides, nitrides, or oxynitrides such as SiO2, AlO, SiN, SiON, AlON, GeO, LiO, LiON, TiO, TiON, TaO, TaON, TaN, and C can also be used.

[0137] <Cathode 9> A cathode 9 is provided on the electron injection layer 8 . In the case of an organic EL element in which only light emitted through the anode is extracted, the cathode can be made of any conductive material as described above. Preferred cathode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al2O3) mixture, indium, lithium / aluminum mixture, rare earth metals, etc.

[0138] In the organic EL device 100 according to one embodiment of the present invention described above, at least one selected from the group consisting of the light-emitting layer 6, the electron-transporting layer 5, and the electron-injecting layer 3 contains a fused ring compound represented by formula (1). The fused ring compound represented by formula (1) can provide an organic EL device with a reduced driving voltage when used in an organic EL device, particularly in a phosphorescent light-emitting layer, a fluorescent light-emitting layer, or an electron transport layer, compared to a case where a conventional dibenzo[g,p]chrysene is used. Therefore, by replacing the dibenzo[g,p]chrysene compound in a conventional organic EL device with the fused ring compound represented by formula (1), an organic EL device with a reduced driving voltage can be provided. In addition, the fused ring compound represented by formula (1) has a twisted structure and is therefore more amorphous than a highly planar compound such as that represented by formula (11). Therefore, the fused ring compound represented by formula (1) can provide an organic EL device that can withstand long-term use, from the viewpoint of forming an amorphous film that is stable over a long period of time.

[0139] The fused ring compound represented by formula (1) can be used as a material for an organic EL device, for example, a light-emitting layer material, an electron transport material, or an electron injection material. An organic EL device using the fused ring compound represented by formula (1) can reduce the driving voltage. Furthermore, the fused ring compound represented by formula (1) can be used not only in organic EL devices, but also in the field of organic photoconductive materials such as electrophotographic photoreceptors, photoelectric conversion elements, solar cells, and image sensors. EXAMPLES

[0140] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The analytical and measurement methods used are as follows.

[0141] [Material purity measurement (HPLC analysis)] Measuring device: Tosoh Multistation LC-8020 (product name) Measurement conditions: Column: Inertsil ODS-3V (4.6mmΦ×250mm) Detector: UV detection (wavelength 254 nm), Eluent: methanol / tetrahydrofuran = 9 / 1 (v / v ratio) [NMR measurement] NMR measurements were carried out using a JEOL JNM-ECA-600 (product name, manufactured by JEOL Ltd.).

[0142] [Mass spectrometry] Mass spectrometer: Hitachi M-80B (product name) Measurement method: FD-MS analysis [Single crystal X-ray structure analysis] Single crystal X-ray structure analysis was performed using a high brightness X-ray structure analyzer for microcrystals, XtaLAB P200 MM007HF-N (product name, manufactured by Rigaku Corporation).

[0143] [Glass transition temperature analysis] The glass transition temperature was measured using a DSC7020 (product name, manufactured by Hitachi High-Tech Science Corporation). The measurement conditions for the DSC were as follows. The measurement was performed in a nitrogen atmosphere (flow rate 50 ml / min). The measurement was performed in the order of first heating, first cooling, and second heating, and the glass transition temperature during the second heating was taken as the glass transition temperature of the sample. Sample size: 5-10mg Measurement conditions: <First Heating> Heating rate: 10℃ / min Measurement temperature range: 30℃~400℃ <First cooling> Rapid cooling with dry ice <Second heating> Heating rate: 5℃ / min Measurement temperature range: 30℃~350℃

[0144] [Light-emitting characteristics of organic EL elements] Measuring device: Topcon Technohouse LUMINANCE METER (BM-9)

[0145] [Synthesis Example 1] (Synthesis of 3-[(2-bromophenyl)ethynyl]pyridine) [ka]

[0146] Under a nitrogen stream, 1.99g (11.0mmol) of 1-bromo-2-ethynylbenzene, 2.05g (10.0mmol) of 3-iodopyridine, 211mg (0.30mmol) of dichlorobis(triphenylphosphine)palladium, 114mg (0.60mmol) of copper iodide, 50mL of tetrahydrofuran, and 50mL of triethylamine were added to a 300mL two-necked eggplant flask and stirred at room temperature for 2 hours. Then, 100mL of saturated aqueous ammonium chloride solution was added and stirred. Next, the aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. From the obtained concentrate, 2.40g (9.30mmol) of 3-[(2-bromophenyl)ethynyl]pyridine was isolated as a pale yellow liquid by column chromatography (hexane:ethyl acetate=10:1, v / v) (yield 93%). Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);8.79(dd,1H),8.55(dd,1H),7.84(dt,1H),7.61(dd,1H),7.55(dd,1H),7.29(td,1H),7.28(td,1H),7.20(td,1H)

[0147] [Synthesis Example 2] (Synthesis of 4-[(2-bromophenyl)ethynyl]pyridine) [ka]

[0148] In a 300mL two-necked eggplant flask, 1.80g (9.90mmol) of 1-bromo-2-ethynylbenzene, 1.85g (9.00mmol) of 4-iodopyridine, 190mg (0.27mmol) of dichlorobis(triphenylphosphine)palladium, 83.0mg (0.43mmol) of copper iodide, 45mL of tetrahydrofuran, and 45mL of triethylamine were added under a nitrogen stream and stirred at room temperature for 2 hours. Then, 100mL of saturated aqueous ammonium chloride solution was added and stirred. The aqueous layer and the organic layer were separated, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. 2.33g (9.00mmol) of 4-[(2-bromophenyl)ethynyl]pyridine was isolated as a brown liquid from the concentrate by column chromatography (hexane:ethyl acetate=10:1, v / v) (yield>99%). Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);8.60(dd,2H),7.62(dd,1H),7.56(dd,1H),7.41(dd,2H),7.31(td,1H),7.22(td,1H)

[0149] [Example 1] (Synthesis of compound (1Ba-1)) [ka]

[0150] Under a nitrogen stream, 2.27g (8.80mmol) of 3-[(2-bromophenyl)ethynyl]pyridine, 2.24g (8.00mmol) of 2-iodobiphenyl, 358.4mg (1.60mmol) of palladium acetate, 857mg (2.33mmol) of tricyclohexylphosphonium tetrafluoroborate, 2.35g (24.0mmol) of potassium acetate, and 80mL of N,N-dimethylformamide were added to a 300mL two-necked eggplant flask, and the mixture was stirred at 130°C for 12 hours. After cooling to room temperature, 50mL of dichloromethane was added for dilution. Insoluble matter was removed by filtration, and 80mL of pure water was added and stirred. The aqueous layer and the organic layer were then separated, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. A yellow crude product was separated from the concentrate by column chromatography (hexane:ethyl acetate=3:1, v / v). The crude product was recrystallized (hot ethanol) to isolate 1.22 g (3.72 mmol) of colorless powder of benzo[f]phenanthro[9,10-h]isoquinoline (yield 46.5%, HPLC purity 99.91%). The sublimation temperature of compound (1Ba-1) was 240°C, and it was confirmed that the sublimed compound (1Ba-1) was in powder form. Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);9.96(s,1H),8.79(d,1H),8.75-8.70(m,4H),8.68(d,1H),8.64(dd,1H),8.46(d,1H),7.76-7.67(m,5H),7.65(td,1H)

[0151] [Example 2] (Synthesis of compound (1Ba-7)) [ka]

[0152] Under a nitrogen stream, 369 mg (1.00 mmol) of 5-[(2-bromophenyl)ethynyl]-2-(4-chlorophenyl)pyridine, 281 mg (1.00 mmol) of 2-iodobiphenyl, 12.3 mg (0.05 mmol) of palladium acetate, 37.9 mg (0.10 mmol) of tricyclohexylphosphonium tetrafluoroborate, 296 mg (3.00 mmol) of potassium acetate, and 10 mL of N,N-dimethylformamide were added to a 100 mL two-necked flask and stirred at 150°C for 24 hours. After cooling to room temperature, 15 mL of pure water was added and stirred. The precipitated solid was collected by filtration and washed with hexane and ethyl acetate, and 153 mg (0.35 mmol) of powder of compound (1Ba-7) was isolated (yield 35%). Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);10.05(s,1H),8.89(s,1H),8.86-8.68(m,6H),8.29(t,1H),8.16(dt,1H),7.80-7.65(m,6H),7.53-7.44(m,2H)

[0153] [Example 3] (Synthesis of compound (1Ba-18)) [ka] #

[0154] Under a nitrogen stream, 2.30g (8.00mmol) of 5-[(2-bromophenyl)ethynyl]-2-methoxypyridine, 2.24g (8.00mmol) of 2-iodobiphenyl, 89.6mg (0.40mmol) of palladium acetate, 198.4mg (0.80mmol) of di-tert-butylmethylphosphonium tetrafluoroborate, 2.35g (24.0mmol) of potassium acetate, and 80mL of N,N-dimethylformamide were added to a 300mL two-necked flask and stirred at 130°C for 35 hours. After cooling to room temperature, 160mL of pure water was added and stirred. The resulting precipitate was then collected by filtration while being washed with 200mL of pure water. The obtained solid was dissolved in 100mL of dichloromethane, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to column chromatography (hexane:chloroform=1:1, v / v) to obtain a red crude product. The crude product was dissolved in a small amount of ethyl acetate and reprecipitated with ethanol. The resulting precipitate was collected by filtration while washing with ethanol, and 828 mg (2.30 mmol) of pale yellow powder of 2-methoxybenzo[h]phenanthro[9,10-f]isoquinoline was isolated (yield 29%). The compounds were identified by 1H-NMR measurement. 1 H-NMR(CDCl3);9.58(s,1),8.73(dd,1H),8.72(dd,1H),8.69-8.66(m,2H),8.64(dd,1H),8.60(dd,1H),7.84(s,1H),7.73-7.63(m,6H),4.15(s,3H)

[0155] [Example 4] (Synthesis of compound (1Ba-30)) [ka]

[0156] In a 100mL eggplant flask, 538.5mg (1.5mmol) of 2-methoxybenzo[h]phenanthro[9,10-f]isoquinoline, 14.3g (75mmol) of paratoluenesulfonic acid monohydrate, 3.18g (75mmol) of lithium chloride, and 15mL of N,N-dimethylformamide were added and stirred at 120°C for 4 hours. After cooling to room temperature, 40mL of 1.0M aqueous sodium hydroxide solution was added, and saturated aqueous sodium bicarbonate solution was added until the pH was around 7.0. The resulting yellow precipitate was collected by filtration while being washed with pure water, and the water was removed under reduced pressure. Under a nitrogen stream, the obtained yellow solid, 15 mL of dichloromethane, and 242 μL (3.0 mmol) of pyridine were added to a 100 mL two-necked eggplant flask and stirred at room temperature. After cooling to 0 degrees, 400 μL (2.38 mmol) of trifluoromethanesulfonic anhydride was added dropwise and stirred at room temperature for another hour. 15 mL of saturated aqueous sodium bicarbonate was added and stirred for 15 minutes. The aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was subjected to column chromatography (hexane:chloroform=1:1, v / v) to isolate 704.9 mg (1.48 mmol) of pale yellow solid benzo[h]phenanthro[9,10-f]isoquinolin-2-yl trifluoromethanesulfonate (yield 98%). Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);9.75(s,1H),8.77-8.74(m,3H),8.67(t,2H),8.56(d,1H),8.31(s,1H),7.84-7.67(m,6H)

[0157] [Example 5] (Synthesis of compound (1Ba-39)) [ka] Benzo[h]phenanthro[9,10-f]isoquinolin-2-yl trifluoromethanesulfonate 47.7mg (100μmol), 4-cyanophenylboronic acid 14.7mg (100μmol), tetrakistriphenylphosphinepalladium 11.5mg (10μmol), potassium carbonate 41.4mg (300μmmol), toluene 500μL, ethanol 300μL, and water 200μL were added to a screw-cap test tube under a nitrogen stream, sealed, and stirred at 110℃ for 10 hours. After cooling to room temperature, water 10mL and chloroform 20mL were added. The aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was subjected to column chromatography (hexane:chloroform=1:1, v / v) to isolate 41.1 mg (95.4 μmol) of a pale yellow solid of 4-(benzo[h]phenanthro[9,10-f]isoquinolin-2-yl)benzonitrile (yield 95%). The compounds were identified by 1H-NMR measurement. 1 H-NMR(CDCl3);10.05(s,1H),8.92(s,1H),8.82-8.81(m,1H),8.79-8.77(m,1H),8.76 (d,2H),8.71(dd,1H),8.66(dd,1H),8.39(d,2H),7.86-7.85(m,2H),7.81-7.67(m,6H)

[0158] [Example 6] (Synthesis of compound (1Ba-44)) [ka]

[0159] Under a nitrogen stream, 2.34g (7.00mmol) of 5-[(2-bromophenyl)ethynyl]-2-phenylpyridine, 1.40g (5.00mmol) of 2-iodobiphenyl, 313mg (1.40mmol) of palladium acetate, 750mg (2.04mmol) of tricyclohexylphosphonium tetrafluoroborate, 2.05g (21.0mmol) of potassium acetate, and 70mL of N,N-dimethylformamide were added to a 200mL two-necked eggplant flask, and the mixture was stirred at 130°C for 12 hours. After cooling to room temperature, 50mL of dichloromethane was added for dilution. After removing insoluble matter by filtration, 80mL of pure water was added and stirred. Next, the aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. A red crude product was separated from the concentrate by column chromatography (hexane:ethyl acetate=10:1, v / v). The crude product was purified again by column chromatography (100% chloroform). The yellow solid was recrystallized (hot toluene) to isolate 928 mg (2.29 mmol) of pale yellow powder of 2-phenylbenzo[h]phenanthro[9,10-f]isoquinoline (46% yield). The sublimation temperature of compound (1Ba-44) was 260°C, and it was confirmed that the sublimed compound (1Ba-44) was in powder form. Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);10.05(s,1H),8.91(s,1H),8.85-8.83(m,1H),8.78-8.75(m,3 H),8.71(ddd,2H),8.28(dd,2H),7.78-7.66(m,6H),7.59(t,2H),7.49(tt,1H)

[0160] [Example 7] (Synthesis of compound (1Ba-46)) [ka]

[0161] Under a nitrogen stream, 1.09g (2.66mmol) of 2-([1,1'-biphenyl]-3-yl)-5-((2-bromophenyl)ethynyl)pyridine, 0.75g (2.66mmol) of 2-iodobiphenyl, 36.3mg (0.16mmol) of palladium acetate, 120mg (0.32mmol) of tricyclohexylphosphonium tetrafluoroborate, 788mg (7.99mmol) of potassium acetate, and 30mL of N,N-dimethylformamide were added to a 100mL two-necked flask and stirred at 150°C for 24 hours. After cooling to room temperature, 100mL of pure water was added and stirred. The precipitated solid was collected by filtration and recrystallized with acetone to isolate 200mg (0.42mmol) of powder of compound (1Ba-46) (yield 16%, HPLC purity 99.4%). It was confirmed that the sublimation temperature of the compound (1Ba-46) was 270° C., and the sublimed compound (1Ba-46) was in a powder form. Compound identification 1 This was measured by H-NMR. 1 H-NMR(DMSO-d6);9.96(s,1H),9.41(s,1H),9.37-9.30(m,1H),8.93(d,2H),8.74- 8.64(m,4H),8.50(d,1H),7.90-7.74(m,9H),7.69(t,1H),7.55(t,2H),7.44(t,1H)

[0162] [Example 8] (Synthesis of compound (1Ba-47)) [ka] #

[0163] Under a nitrogen stream, 2.58 g (6.30 mmol) of 2-([1,1'-biphenyl]-2-yl)-5-((2-bromophenyl)ethynyl)pyridine, 1.76 g (6.30 mmol), 141 mg (0.63 mmol) of palladium acetate, 312 mg (1.26 mmol) of di-tert-butylmethylphosphonium tetrafluoroborate, 1.85 g (18.9 mmol) of potassium acetate, and 63 mL of N,N-dimethylformamide were added to a 200 mL two-necked eggplant flask, and the mixture was stirred at 130°C for 39 hours. After cooling to room temperature, 120 mL of pure water was added and stirred. The resulting precipitate was then collected by filtration while being washed with 100 mL of pure water. The obtained solid was dissolved in 100 mL of dichloromethane, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (hexane:chloroform = 1:1, v / v) to obtain a pale yellow crude product. The crude product was dissolved in a small amount of toluene and reprecipitated with diethyl ether to isolate 1.14 g (2.37 mmol) of white powder of 2-([1,1'-biphenyl]-2-yl)benzo[f]phenanthro[9,10-h]isoquinoline (yield 37%). Compound identification 1 This was measured by H-NMR. 1 H-NMR(CD2Cl2);9.90(s,1H),8.74(dd,2H),8.68-8.64(m,3H),8.11(s,1H),8.03-8.0 0(m,2H),7.75-7.63(m,5H),7.59-7.53(m,4H),7.33(d,2H),7.28(t,2H),7.22(t,1H)

[0164] [Example 9] (Synthesis of compound (1Ba-83)) [ka] Benzo[h]phenanthro[9,10-f]isoquinolin-2-yl trifluoromethanesulfonate 47.7mg (100μmol), dibenzofuran-4-boronic acid 21.2mg (100μmol), tetrakistriphenylphosphine palladium 11.5mg (10μmol), potassium carbonate 41.4mg (300μmmol), toluene 500μL, ethanol 300μL, and water 200μL were added to a screw-cap test tube under a nitrogen stream, and the tube was sealed and stirred at 100℃ for 12 hours. After cooling to room temperature, water 10mL and chloroform 50mL were added. The aqueous layer and the organic layer were separated, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was subjected to column chromatography (100% chloroform) to obtain a white solid. The resulting solid was washed with ethanol containing a small amount of chloroform to isolate 40.1 mg (81.0 μmol) of a colorless solid of 2-(dibenzo[b,d]furan-4-yl)benzo[h]phenanthro[9,10-f]isoquinoline (yield 81%). Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);10.14(s,1H),9.69(s,1H),8.97(dd,1H),8.81(dd,1H),8.78-8.74(m,4H),8.55(d d,1H),8.09-8.07(m,2H),7.85-7.80(m,3H),7.77-7.72(m,3H),7.69(td,1H),7.60-7.55(m,2H), 7.45(t,1H)

[0165] [Example 10] (Synthesis of compound (1Ba-151)) [ka] Benzo[h]phenanthro[9,10-f]isoquinolin-2-yl trifluoromethanesulfonate 47.7mg (100μmol), 3-pyridylboronic acid 12.3mg (100μmol), tetrakistriphenylphosphinepalladium 11.5mg (10μmol), potassium carbonate 41.4mg (300μmmol), toluene 500μL, ethanol 300μL, and water 200μL were added to a screw-cap test tube under a nitrogen stream, and the tube was sealed and stirred at 100℃ for 12 hours. After cooling to room temperature, water 10mL and chloroform 20mL were added. The aqueous layer and the organic layer were separated, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was subjected to column chromatography (chloroform:methanol=10:1, v / v) to obtain a pale yellow solid. The obtained solid was washed with ethanol to isolate 22.1 mg (54.4 μmol) of a white solid of 2-(pyridin-3-yl)benzo[h]phenanthro[9,10-f]isoquinoline (yield 54%). The compounds were identified by 1H-NMR measurement. 1 H-NMR(CDCl3);10.06(s,1H),9.48(s,1H),8.92(s,1H),8.83-8.81(m,1H),8.79-8.77(m,1H),8.76(d,2H),8. 73-8.70(m,2H),8.68(d,1H),8.58(dt,1H),7.80-7.78(m,2H),7.77-7.66(m,3H),7.68(td,1H),7.51(ddd,1H)

[0166] [Example 11] (Synthesis of compound (1Bb-4)) [ka]

[0167] Under a nitrogen stream, 2.38g (6.45mmol) of 5-[(2-bromo-4-chlorophenyl)ethynyl]-2-phenylpyridine, 1.68g (6.00mmol) of 2-iodobiphenyl, 67.2mg (0.30mmol) of palladium acetate, 148.8mg (0.60mmol) of di-tert-butylmethylphosphonium tetrafluoroborate, 1.76g (18.0mmol) of potassium acetate, and 60mL of N,N-dimethylformamide were added to a 300mL two-necked flask and stirred at 130°C for 48 hours. After cooling to room temperature, 120mL of pure water was added and stirred. The resulting precipitate was then collected by filtration while being washed with 100mL of pure water. The obtained solid was dissolved in 100mL of dichloromethane, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was washed with diethyl ether to remove as much of the red impurity as possible. The resulting crude yellow product was purified by column chromatography (hexane:ethyl acetate=10:1, v / v) to isolate 606 mg (1.38 mmol) of pale yellow powder of 15-chloro-2-phenylbenzo[f]phenanthro[9,10-h]isoquinoline (yield 23%). Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);10.04(s,1H),8.79(s,1H),8.76-8.74(m,3H),8.68(d,2H) ,8.59(dd,1H),8.28(dd,2H),7.77-7.66(m,5H),7.60(t,2H),7.50(t,1H)

[0168] [Example 12] (Synthesis of compound (1ba-1)) [ka]

[0169] In a 50 ml eggplant flask, 329 mg (1.0 mmol) of benzo[f]phenanthro[9,10-h]isoquinoline and 10 mL of dichloromethane were added and stirred at room temperature for 5 minutes. 344 mg (1.4 mmol) of 3-chloroperbenzoic acid (containing about 30% water) was gradually added and stirred at room temperature overnight. 30 ml of dichloromethane and 20 mL of saturated aqueous sodium thiosulfate were added and stirred for 10 minutes, after which the aqueous layer and the organic layer were separated. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was subjected to column chromatography (chloroform:methanol=10:1, v / v) to isolate 329.8 mg (0.95 mol) of yellow solid benzo[f]phenanthro[9,10-h]isoquinoline 3-oxide (yield 95%). Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);9.63(s,1H),8.74-8.71(m,3H),8.68(d,1H),8.58-8.46(m,4H),7.78-7.73(m,4H),7.71-7.67(m,2H)

[0170] [Synthesis Example 3] (Synthesis of benzo[f]phenanthro[9,10-h]isoquinolin-4(3H)-one) [ka]

[0171] In a screw-top test tube, 34.5 mg (100 μmol) of benzo[f]phenanthro[9,10-h]isoquinoline 3-oxide and 1 mL of acetic anhydride were added, sealed, and stirred at 120°C for 14 hours. After cooling to room temperature, 5 mL of saturated aqueous sodium bicarbonate was added dropwise and stirred at room temperature for 3 hours. The resulting precipitate was collected by filtration and subjected to column chromatography (chloroform:cumethanol = 10:1, v / v) to isolate 26.1 mg (75.6 μmol) of pale yellow solid benzo[f]phenanthro[9,10-h]isoquinolin-4(3H)-one (yield 76%). Compound identification 1This was measured by H-NMR. 1 H-NMR(CDCl3); 8.79(dd,1H), 8.69(dd,1H), 8.63(dd,1H), 8.57(dd,1H), 8.53(dd,1H), 8.19(dd,1H), 7.74-7.71(m,1H), 7.70-7.66(m,2H), 7.64-7.61(m,2H), 7.56-7.53(m,1H), 7.47(d,1H), 7.45(d,1H); 1H of NH not observed

[0172] [Example 13] (Synthesis of compound (1Bc-30)) [ka]

[0173] Benzo[f]phenanthro[9,10-h]isoquinolin-4(3H)-one (69 mg, 200 μmol), dichloromethane (1 mL), and pyridine (32 μL, 398 μmol) were added to a 10 mL Schlenk tube under a nitrogen stream and stirred at room temperature. After cooling to 0 degrees, trifluoromethanesulfonic anhydride (40 μL, 243 μmol) was added dropwise and stirred at room temperature for another hour. Saturated aqueous sodium bicarbonate (1 mL) was added and stirred for 15 minutes. The aqueous layer and organic layer were separated, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was subjected to column chromatography (hexane:chloroform=1:1, v / v) to isolate 81.8 mg (171 μmol) of a yellow solid of benzo[h]phenanthro[9,10-f]isoquinolin-4-yl trifluoromethanesulfonate (yield 86%). Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);8.78(d,1H),8.74(d,1H),8.71(d,1H),8.67(d,1H),8.63(d,1H),8.5 7-8.55(m,2H),7.93(d,1H),7.81-7.73(m,3H),7.70(d,1H),7.68(d,1H),7.64(t,1H)

[0174] [Example 14] (Synthesis of compound (1Ca-1)) [ka]

[0175] Under a nitrogen stream, 2.27g (8.80mmol) of 4-[(2-bromophenyl)ethynyl]pyridine, 2.24g (8.00mmol) of 2-iodobiphenyl, 358.4mg (1.60mmol) of palladium acetate, 857mg (2.32mmol) of tricyclohexylphosphonium tetrafluoroborate, 2.35g (24.0mmol) of potassium acetate, and 80mL of N,N-dimethylformamide were added to a 300mL two-necked eggplant flask, and the mixture was stirred at 130°C for 12 hours. After cooling to room temperature, 50mL of dichloromethane was added for dilution. Insoluble matter was removed by filtration, and 80mL of pure water was added and stirred. The aqueous layer and the organic layer were then separated, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. A yellow crude product was separated from the concentrate by column chromatography (hexane:ethyl acetate=3:1, v / v). The crude product was recrystallized (hot ethanol) to isolate 1.31 g (3.98 mmol) of colorless powder of benzo[f]phenanthro[9,10-f]isoquinoline (yield 49.8%, HPLC purity 99.93%). The sublimation temperature of compound (1Ca-1) was 250°C, and it was confirmed that the sublimed compound (1Ca-1) was in powder form. Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);10.03(s,1H),8.81(d,1H),8.76(d,1H),8.72-8.69(m,4H),8.65(d,1H),8.50(d,1H),7.76-7.63(m,6H)

[0176] [Reference example-1] The reaction was carried out in the same manner as in Example 12, except that bis(1,5-cyclooctadiene)nickel(0) (Ni(COD)2) was used instead of palladium acetate and tricyclohexylphosphonium tetrafluoroborate used as catalysts in Example 12. However, the production of benzo[f]phenanthro[9,10-f]isoquinoline could not be confirmed.

[0177] [Examples 14-2 to 14-6, Reference Examples 2 to 7] In Example 14, instead of tricyclohexylphosphonium tetrafluoroborate (PCy3·HBF4) used as a ligand, tritertiary butylphosphonium tetraphenylborate (P t Bu3·HBPh4), di-tertiary butyl methyl phosphonium tetrafluoroborate (P t The same procedure as in Example 14 was carried out to produce benzo[f]phenanthro[9,10-f]isoquinoline, except that benzo[f]phenanthro[9,10-f]isoquinoline was produced by using 1,2-bis(diphenylphosphino)ethane (dppe), 1,2-bis(dicyclohexylphosphino)ethane (DPCYE), 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride (IPR·HCl), triphenylphosphine (PPh3), 3,4-bis(dicyclohexylphosphino)thiophene (DCYPT), 1,10-phenanthroline, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (Xphos), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos), or no ligand was used. 1 The yield was confirmed by H-NMR, and the results are shown in Table 1.

[0178] [Table 1]

[0179] [Examples 14-7 to 10] The same procedure as in Example 14 was carried out, except that dimethylacetamide (DMAc), potassium carbonate (K2CO3), potassium phosphate (K3PO4), and cesium pivalate (CsOPiV) were used in place of potassium acetate (KOAc) used as a base in Example 14, respectively, to produce benzo[f]phenanthro[9,10-f]isoquinoline. 1 The yield was confirmed by H-NMR, and the results are shown in Table 2.

[0180] [Table 2]

[0181] [Examples 14-11 to 12, Reference Examples 8 to 11] The same procedure as in Example 14 was carried out, except that N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), dimethylsulfoxide (DMSO), 1,4-dioxane, toluene, and 1,2-dichloroethane (ClCH2CH2Cl) were used in place of N,N-dimethylformamide (DMF) used as a solvent in Example 14, respectively, to produce benzo[f]phenanthro[9,10-f]isoquinoline. 1 The yield was confirmed by H-NMR, and the results are shown in Table 3.

[0182] [Table 3]

[0183] [Example 15] (Synthesis of compound (1Ea-1)) [ka]

[0184] Under a nitrogen stream, 1.00g (3.86mmol) of 5-[(2-bromophenyl)ethynyl]-pyrimidine, 777mg (2.78mmol) of 2-iodobiphenyl, 173mg (0.77mmol) of palladium acetate, 413mg (1.12mmol) of tricyclohexylphosphonium tetrafluoroborate, 1.13g (11.6mmol) of potassium acetate, and 40mL of N,N-dimethylformamide were added to a 200mL two-necked eggplant flask and stirred at 130°C for 12 hours. After cooling to room temperature, 50mL of dichloromethane was added for dilution. After removing insoluble matter by filtration, 80mL of pure water was added and stirred. Next, the aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. A red crude product was separated from the concentrate by column chromatography (chloroform:methanol = 10:1, v / v). The yellow solid was recrystallized (hot toluene) to isolate 671 mg (2.03 mmol) of colorless powder of benzo[h]phenanthro[9,10-f]quinazoline (73% yield). The sublimation temperature of compound (1Ea-1) was 250°C, and it was confirmed that the sublimed compound (1Ea-1) was in powder form. Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);10.05(s,1H),9.48(s,1H),9.40(dd,1H),8.78-8.75(m,4H),8 .52(dd,1H),7.87(ddd,1H),7.82(ddd,1H),7.78-7.72(m,3H),7.69(ddd,1H)

[0185] [Reference Example 16] (Synthesis of benzo[f]phenanthro[9,10-h]isoquinoxaline) [ka]

[0186] In a 100 mL Young-Schlenk flask, 2.60 g (5.13 mmol) of 9-iodo-10-(2-iodophenyl)phenanthrene, 41.0 g (51.3 mmol) of pyrazine, and 1.48 g (12.8 mmol) of potassium tert-butoxide were added under a nitrogen stream and stirred at 120°C for 2 hours. After cooling to room temperature, 20 mL of toluene was added and stirred. After filtering out the unnecessary substances, the mixture was concentrated under reduced pressure. From the concentrate, an orange crude product was separated by silica gel column chromatography (hexane:chloroform=1:1 (v / v)). The crude product was recrystallized (toluene / ethanol) to isolate 380 mg (1.16 mmol) of yellow crystals of benzo[f]phenanthro[9,10-h]isoquinoxaline (yield 22%, HPLC purity 99.79%).

[0187] Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);9.92-9.90(m,1H),9.31-9.29(m,1H),9.04(d,1H),8.93(d,1H),8.74-8.70(m,4H),7.79-7.70(m,5H),7.63(ddd,1H)

[0188] [Example 17] (Synthesis of compound (1Ja-1)) [ka]

[0189] Under a nitrogen stream, 2.46g (8.00mmol) of 3-[(1-bromonaphthalene-2-yl)ethynyl]-pyridine, 2.24g (8.00mmol) of 2-iodobiphenyl, 358mg (1.60mmol) of palladium acetate, 857mg (2.33mmol) of tricyclohexylphosphonium tetrafluoroborate, 2.35g (24.0mmol) of potassium acetate, and 80mL of N,N-dimethylformamide were added to a 200mL two-necked eggplant flask, and the mixture was stirred at 130°C for 18 hours. After cooling to room temperature, 80mL of dichloromethane was added for dilution. After removing insoluble matter by filtration, 150mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. A crude product was separated from the concentrate by column chromatography (chloroform:methanol = 50:1, v / v). The resulting crude product, a brown solid, was recrystallized (toluene) to isolate 958 mg (2.52 mmol) of naphtho[1,2-f]phenanthro[9,10-h]isoquinoline as a pale yellow powder (yield 32%, HPLC purity 99.63%). The sublimation temperature of compound (1Ja-1) was 260°C, and it was confirmed that the sublimed compound (1Ja-1) was in powder form. Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);10.05(s,1H),9.12(d,1H),8.83-8.79(m,3H),8.76-8.73(m,3H),8.70-8.69(m,1H),8.14(d,1H),8.07(d,1H),7.78-7.68(m,6H)

[0190] [Example 18] (Synthesis of compound (2Ba-1)) [ka]

[0191] Under a nitrogen stream, 2.16g (7.01mmol) of 3-[(2-bromophenyl)ethynyl]-quinoline, 1.96g (7.00mmol) of 2-iodobiphenyl, 313mg (1.40mmol) of palladium acetate, 750mg (2.04mmol) of tricyclohexylphosphonium tetrafluoroborate, 2.06g (21.0mmol) of potassium acetate, and 70mL of N,N-dimethylformamide were added to a 200mL two-necked eggplant flask and stirred at 130°C for 18 hours. After cooling to room temperature, 70mL of dichloromethane was added for dilution. Insoluble matter was removed by filtration, and 150mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. A crude product was separated from the concentrate by column chromatography (chloroform:methanol=10:1, v / v). The resulting brown solid crude product was recrystallized (hot toluene) to isolate 1.47 g (3.89 mmol) of colorless powder of benzo[k]phenanthro[9,10-i]phenanthridine (yield 55%). Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);10.21(s,1H),9.10(d,1H),9.04(dd,1H),8.81(dd,1H),8.75 -8.72(m,3H),8.68(dd,1H),8.32(dd,1H),7.84(ddd,1H),7.78-7.69(m,7H)

[0192] [Example 19] (Synthesis of compound (2Ba-7)) [ka]

[0193] Benzo[k]phenanthro[9,10-i]phenanthridine 6.07g (16.0mmol), rhodium(II) acetate dimer 356mg (0.80mmol), 1,3-dimesitylimidazolium chloride 548mg (1.60mmol), sodium tert-butoxide 3.86g (40.0mmol), 3-chloroiodobenzene 4.62g (19.2mmol), and toluene 160mL were added to a 300mL two-necked flask under a nitrogen stream, and the mixture was stirred at 110°C for 24 hours. After cooling to room temperature, hexane 160mL was added and stirred. The precipitate was collected by filtration and washed with pure water and ethanol to isolate 6.69g (13.77mmol) of pale yellow powder of compound (2Ba-7) (yield 85.4%, HPLC purity 95.3%). Compound identification 1 This was measured by HNMR. 1 H-NMR(DMSO-d6);10.03(s,1H),9.12(dd,1H),9.06(dd,1H),8.93(d,2H),8.80 (d,1H),8.75-8.69(m,2H),7.95-7.80(m,9H),7.70(dt,1H),7.58-7.50(m,2H)

[0194] [Example 20] (Synthesis of compound (2Ba-8)) [ka]

[0195] Benzo[k]phenanthro[9,10-i]phenanthridine 10.02g (26.4mmol), rhodium(II) acetate dimer 0.47g (1.06mmol), 1,3-dimesitylimidazolium chloride 0.73g (2.11mmol), sodium tert-butoxide 6.34g (66mmol), 4-chloroiodobenzene 7.60g (31.7mmol), and toluene 260mL were added to a 1L two-necked flask under a nitrogen stream, and the mixture was stirred at 110°C for 11 hours. After cooling to room temperature, hexane 200mL was added and stirred. The precipitate was collected by filtration, and 5.57g (11.37mmol) of pale yellow powder of compound (2Ba-8) was isolated by recrystallization (toluene) (yield 43.0%, HPLC purity 97.9%). Compound identification 1 This was measured by H-NMR. 1 H-NMR(DMSO-d6);10.20(s,1H),9.11(dd,1H),9.04(dd,1H),8.83(d,1H),8.76-8.73(m,3H),8.70(dd,1H),7.81-7.69(m,10H),7.53-7.50(m,2H)

[0196] [Example 21] (Synthesis of compound (2Ba-39)) [ka]

[0197] Benzo[k]phenanthro[9,10-i]phenanthridine (190.0 mg, 0.50 mmol), rhodium(II) acetate dimer (6.6 mg, 0.015 mmol), 1,3-dimesitylimidazolium chloride (10.2 mg, 0.03 mmol), sodium tert-butoxide (120 mg, 1.25 mmol), 4-bromobenzonitrile (109.2 mg, 0.6 mmol), and toluene (5 mL) were added to a 50 mL two-necked flask under a nitrogen stream, and the flask was sealed and stirred at 110°C for 5 hours. After cooling to room temperature, hexane (5 mL) was added and stirred. The precipitate was collected by filtration and washed with pure water and ethanol. The washed powder was subjected to column chromatography (chloroform) to isolate 8.8 mg of yellow powder of compound (2Ba-39) (yield 3.6%). Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);10.22(s,1H),9.11(d,1H),9.05(d,1H),8.82(dd,1H),8.78-8.72(m,3H),8.70-8.68(m,1H),8.32(d,1H),7.93-7.59(m,11H)

[0198] [Example 22] (Synthesis of compound (2Ba-41)) [ka]

[0199] In a 100mL two-necked flask, 1.72g (3.50mmol) of compound (2Ba-8), 0.57g (3.85mmol) of 4-cyanophenylboronic acid, 16mg (0.07mmol) of palladium acetate, 67.6mg (0.14mmol) of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (Xphos), 35mL of tetrahydrofuran, and 12mL of 2M potassium carbonate aqueous solution were added under a nitrogen stream and stirred at 70°C for 4 hours. After cooling to room temperature, 50mL of hexane was added and stirred, and the precipitated solid was collected by filtration. By recrystallizing this solid (toluene), 1.41g (2.53mmol) of yellow powder of compound (2Ba-41) was isolated (yield 72.5%, HPLC purity 99.7%). Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);10.23(s,1H),9.13(dd,1H),9.06(dd,1H),8.83(dd,1H),8.77-8.72(m,3H),8.70(dd,1H),7.94-7.69(m,16H)

[0200] [Example 23] (Synthesis of compound (2Ba-44)) [ka]

[0201] Benzo[k]phenanthro[9,10-i]phenanthridine (37.9mg, 0.1mmol), rhodium(II) acetate dimer (1.32mg, 0.003mmol), 1,3-dimesitylimidazolium chloride (2.05mg, 0.006mmol), sodium tert-butoxide (24mg, 0.25mmol), bromobenzene (15.7mg), and toluene (0.5mL) were added to a dry test tube under a nitrogen stream, sealed, and stirred at 95°C for 24 hours. After cooling to room temperature, 4mL of dichloromethane was added for dilution. Insoluble matter was removed by filtration, and the mixture was concentrated under reduced pressure. 24.8mg (0.055mmol) of 11-phenylbenzo[k]phenanthro[9,10-i]phenanthridine was isolated as a white solid by column chromatography (chloroform) (yield 55%). Compound identification 1 This was measured by H-NMR. 1 H-NMR(CD2Cl2);10.11(s,1H),9.10(dd,1H),9.06(dd,1H),8.81(dd,1H),8. 77-8.74(m,3H),8.70(dd,1H),7.86-7.70(m,10H),7.53(t,2H),7.45(t,1H) [Example 24] (Synthesis of compound (2Ba-45)) [ka]

[0202] Benzo[k]phenanthro[9,10-i]phenanthridine 3.04g (8.00mmol), rhodium(II) acetate dimer 107mg (0.24mmol), 1,3-dimesitylimidazolium chloride 164mg (0.48mmol), sodium tert-butoxide 1.94g (20.0mmol), 4-iodobiphenyl 2.24g (8.00mmol), and toluene 80mL were added to a 300mL two-necked flask under a nitrogen stream, and the flask was sealed and stirred at 110°C for 24 hours. After cooling to room temperature, hexane 100mL was added and stirred. The precipitate was collected by filtration, and 1.68g (3.16mmol) of pale yellow powder of compound (2Ba-45) was isolated by recrystallization (toluene) (yield 39.5%, HPLC purity 98.1%). Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);10.24(s,1H),9.12(d,1H),9.06(d,1H),8.83(dd,1H),8.78-8.71(m,4 H),7.91-7.88(m,3),7.83(d,1H),7.80-7.68(m,10H),7.51-7.46(m,2H),7.37(tt,1H)

[0203] [Example 25] (Synthesis of compound (2Ba-46)) [ka]

[0204] In a 200mL two-necked flask, 3.04g (8.00mmol) of benzo[k]phenanthro[9,10-i]phenanthridine, 108mg (0.24mmol) of rhodium(II) acetate dimer, 165mg (0.48mmol) of 1,3-dimesitylimidazolium chloride, 1.93g (20.0mmol) of sodium tert-butoxide, 2.25g (8.00mmol) of 3-iodobiphenyl, and 80mL of toluene were added under a nitrogen stream, sealed, and stirred at 110°C for 24 hours. After cooling to room temperature, 80mL of hexane was added and stirred. The precipitate was collected by filtration, and 1.62g (3.05mmol) of pale yellow powder of compound (2Ba-46) was isolated by recrystallization (toluene) (yield 38.1%, HPLC purity 99.1%). Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);10.21(s,1H),9.11(dd,1H),9.07(dd,1H),8.82(dd,1H),8.77-8.70(m,4H ),7.99(t,1H),7.89(dd,1H),7.83-7.68(m,11H),7.63(t,1H),7.46(t,2H),7.35(tt,1H)

[0205] [Example 26] (Synthesis of compound (2Ba-59)) [ka]

[0206] Benzo[k]phenanthro[9,10-i]phenanthridine (1.90g, 5.00mmol), rhodium(II) acetate dimer (222mg, 0.50mmol), 1,3-dimesitylimidazolium chloride (341mg, 1.00mmol), sodium tert-butoxide (1.20g, 12.5mmol), 2-iodotriphenylene (1.77g, 5.00mmol), and toluene (50mL) were added to a 200mL two-neck flask under a nitrogen stream, and the mixture was stirred at 110°C for 13 hours. After cooling to room temperature, the precipitated solid was collected by filtration. The collected solid was recrystallized (o-xylene / hexane) to isolate 1.75g ​​(2.89mmol) of yellow powder of compound (2Ba-59) (yield 57.9%, HPLC purity 99.0%). Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);10.26(s,1H),9.18(dd,1H),9.14-9.10(m,1H),9.05(d,1H),8.86-8.83 (m,2H),8.80-8.70(m,8H),8.16(dd,1H),8.05(dd,1H),7.90(t,1H),7.81-7.63(m,10H)

[0207] [Example 27] (Synthesis of compound (2Ba-161)) [ka]

[0208] Benzo[k]phenanthro[9,10-i]phenanthridine (0.72g, 1.90mmol), rhodium(II) acetate dimer (25.7mg, 0.057mmol), 1,3-dimesitylimidazolium chloride (39.7mg, 0.114mmol), sodium tert-butoxide (0.46g, 4.75mmol), 4-bromo-2,6-diphenylpyridine (0.59g, 1.90mmol), and toluene (19mL) were added to a 100mL two-neck flask under a nitrogen stream, and the mixture was stirred at 110°C for 4 hours. After cooling to room temperature, the precipitated solid was collected by filtration. The recovered solid was recrystallized (toluene) to isolate 0.65 g (1.07 mmol) of a pale yellow powder of compound (2Ba-161) (yield 55.8%, HPLC purity 99.8%). Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);10.23(s,1H),9.20(dd,1H),9.07(dd,1H),8.83(dd,1H),8.77-8.68(m,4H),8.26- 8.23(m,4H),8.11(s,2H),7.95(dd,1H),7.87(t,1H),7.81-7.68(m,6H),7.51(t,4H),7.43(tt,2H)

[0209] [Example 28] (Synthesis of compound (2Ba-162)) [ka]

[0210] Benzo[k]phenanthro[9,10-i]phenanthridine (190mg, 0.50mmol), rhodium(II) acetate dimer (6.6mg, 0.015mmol), 1,3-dimesitylimidazolium chloride (10.3mg, 0.03mmol), sodium tert-butoxide (121mg, 1.25mmol), 4-(4-bromophenyl)-2,6-diphenylpyridine (233mg, 0.60mmol), and toluene (5mL) were added to a 50mL two-necked flask under a nitrogen stream, and the mixture was stirred at 110°C for 24 hours. After cooling to room temperature, the precipitated solid was collected by filtration. The collected solid was recrystallized (o-xylene / hexane) to obtain 353mg of powder containing compound (2Ba-162). Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);10.26(s,1H),9.14(d,1H),9.07(dd,1H),8.83(d,1H),8.78-8.71 (m,4H),8.24(d,4H),8.02(s,2H),7.99-7.68(m,12H),7.55(t,4H),7.47(td,2H)

[0211] [Example 29] (Synthesis of compound (2Ba-163)) [ka]

[0212] Benzo[k]phenanthro[9,10-i]phenanthridine (190mg, 0.50mmol), rhodium(II) acetate dimer (6.6mg, 0.015mmol), 1,3-dimesitylimidazolium chloride (10.3mg, 0.03mmol), sodium tert-butoxide (121mg, 1.25mmol), 4-(3-bromophenyl)-2,6-diphenylpyridine (233mg, 0.60mmol), and toluene (5mL) were added to a 50mL two-necked flask under a nitrogen stream, and the mixture was stirred at 110°C for 24 hours. After cooling to room temperature, the precipitated solid was collected by filtration. The collected solid was recrystallized (o-xylene / hexane) to obtain 384mg of powder containing compound (2Ba-163). Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);10.23(s,1H),9.15(dd,1H),9.07(dd,1H),8.84(d,1H),8.78-8.69(m,4H),8.21(dd,4H), 8.16(t,1H),8.02(s,2H),7.92(td,2H),7.87-7.83(m,2H),7.80-7.66(m,7H),7.50(td,4H),7.43(tt,2H)

[0213] [Example 30] (Synthesis of compound (2ba-1)) [ka]

[0214] Benzo[k]phenanthro[9,10-i]phenanthridine (19.0 g, 50.0 mmol), metachloroperbenzoic acid (17.3 g, 77% or less purity), and chloroform (500 mL) were added to a 1 L eggplant flask under a nitrogen stream, and the mixture was stirred at room temperature for 1 hour. After the reaction, an aqueous solution of sodium bicarbonate was added and stirred. The aqueous layer and the organic layer were separated, and an aqueous solution of sodium thiosulfate was added to the obtained organic layer and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The concentrate was washed with acetone to isolate 18.2 g (46.1 mmol) of yellow powder of compound (2ba-1) (yield 92.1%, HPLC purity 99.4%). Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);9.92(s,1H),9.11(dd,1H),9.06(dd,1H),8.88-8.86(m,1H) ,8.78-8.65(m,4H),8.61-8.59(m,1H),7.92-7.84(m,2H),7.78-7.68(m,6H)

[0215] [Example 31] (Synthesis of compound (2ba-44)) [ka]

[0216] Under a nitrogen stream, 10.9 g (24.0 mmol) of compound (2Ba-44), 8.30 g of metachloroperbenzoic acid with a purity of 77% or less, and 240 mL of chloroform were added to a 1 L eggplant flask and stirred at room temperature for 3 days. After the reaction, an aqueous solution of sodium hydrogen carbonate was added and stirred. The aqueous layer and the organic layer were separated, and an aqueous solution of sodium thiosulfate was added to the obtained organic layer and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The concentrate was washed with acetone to obtain 8.0 G of a powder containing compound (2ba-44). The obtained powder was used as it was in the next reaction.

[0217] [Example 32] (Synthesis of compound (2bb-14)) [ka]

[0218] Benzo[k]phenanthro[9,10-i]phenanthrolidine 10-oxide (39.5mg, 100μmol) and tetrahydrofuran (1mL) were added to a Schlenk flask under a nitrogen stream and stirred. After cooling to -78℃, 1.0M isopropylmagnesium chloride tetrahydrofuran solution (170μL, 170μmol) was added dropwise and stirred for 1 hour. After returning to room temperature, the mixture was stirred for another 1 hour. Iodine (42.8mg, 170μmol) was dissolved in 1mL of tetrahydrofuran and added dropwise, and the mixture was stirred for 1 hour. Saturated sodium thiosulfate aqueous solution (2mL) and chloroform (5mL) were added, and the aqueous layer and organic layer were separated. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. From the residue, 34.5 mg (78.8 μmol) of colorless powder of 9-isopropylbenzo[k]phenanthro[9,10-i]phenanthrolidine 10-oxide was isolated by column chromatography (chloroform) (yield 79%). The compounds were identified by 1H-NMR measurement and mass spectrometry (APCI). 1H-NMR(CDCl3);9.02(dd,1H),8.92(d,1H),8.90-8.88(m,2H),8.81(dd,1H),8.72(dd,1H),8.60(d,1H),8.02(dd,1H),7. 87(ddd,1H),7.82-7.77(m,2H),7.75-7.66(m,3H),7.63(ddd,1H),7.57(ddd,1H),3.85(sep,1H),1.84(d,3H),0.94(d,3H) MS(APCI);m / z calc. for C32H24NO[M+H] 438.5 found;438.2

[0219] [Example 33] (Synthesis of compound (2bb-44)) [ka]

[0220] Benzo[k]phenanthro[9,10-i]phenanthrolidine 10-oxide (39.5mg, 100μmol) and tetrahydrofuran (1mL) were added to a Schlenk flask under a nitrogen stream and stirred. After cooling to -78℃, 3.0M phenylmagnesium bromide tetrahydrofuran solution (57μL, 171μmol) was added dropwise and stirred for 1 hour. After returning to room temperature, the mixture was stirred for another 1 hour. Iodine (42.8mg, 170μmol) was dissolved in 1mL tetrahydrofuran and added dropwise, and the mixture was stirred at room temperature for 1 hour. Sodium thiosulfate aqueous solution (2mL) and chloroform (5mL) were added, and the aqueous layer and organic layer were separated. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. From the residue, 37.2 mg (78.9 μmol) of colorless powder of 9-phenylbenzo[k]phenanthro[9,10-i]phenanthrolidine 10-oxide was isolated by preparative thin layer chromatography (chloroform) (yield 79%). The compounds were identified by 1H-NMR measurement and mass spectrometry (APCI). 1H-NMR(CDCl3); 9.14(dd,1H), 9.12(d,1H), 8.93-8.92(m,1H), 8.81-8.80(m,1H), 8.78-8.76(m,1H), 8.59-8.56(m,1H), 8.23(d,1H), 7.92-7.87(m,2H), 7.78(d,1H), 7.56-7.70(m,4H), 7.27(t,1H), 7.10(t,1H), 6.96(t,1H); 4H not observed due to broadening MS(APCI);m / z calc. for C35H22NO[M+H] 472.5 found;472.1

[0221] [Example 34] (Synthesis of compound (2Bb-4)) [ka]

[0222] In a nitrogen stream, 18.2 g (46.0 mmol) of compound (2ba-1), 300 mL of toluene, and 150 mL of N,N-dimethylformamide were added to a 1 L eggplant flask and cooled to 0°C. Then, 18 mL of phosphoryl chloride (POCl3) was added and stirred for 10 minutes. After the reaction, an aqueous sodium bicarbonate solution was added and stirred. The aqueous layer and the organic layer were separated, and the resulting organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The concentrate was washed with ethyl acetate and hexane to obtain 18.1 g (43.7 mmol) of yellow powder of compound (2Bb-4) (yield 95.1%, HPLC purity 99.7%). Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);9.08(d,1H),9.02(d,1H),8.83(d,1H),8.72(t,2H),8.59(d,1H),8.26(d,1H),8.07(d,1H),7.86(t,1),7.79-7.63(m,6H),7.58( t,1H)

[0223] [Example 35] (Synthesis of compound (2Bc-4)) [ka]

[0224] Under a nitrogen stream, 7.12 g of powder containing the compound (2ba-44) obtained in Example 20, 140 mL of toluene, and 70 mL of N,N-dimethylformamide were added to a 1 L eggplant flask and cooled to 0°C. Then, 3 mL of phosphoryl chloride (POCl3) was added and stirred for 10 minutes. After the reaction, an aqueous sodium hydrogen carbonate solution was added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The concentrate was washed with ethyl acetate and hexane to obtain 5.11 G of a yellow powder containing the compound (2Bc-4). The obtained powder was used as it was in the next reaction. [Example 36] (Synthesis of compound (2Bb-44)) [ka]

[0225] In a 50mL two-necked flask, 706mg (1.70mmol) of compound (2Bb-4) and 17mL of tetrahydrofuran were added under a nitrogen stream, and 8.6mL of a 1.1M solution of phenyllithium, cyclohexane, and diethyl ether (Kanto Chemical Co., Ltd.) was added dropwise and stirred at room temperature for 15 minutes. After the reaction, 20mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the organic layer obtained was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The concentrate was recrystallized (toluene / hexane) to isolate 426mg (0.93mmol) of compound (2Bb-44) (yield 55.0%). It was confirmed that the sublimation temperature of compound (2Bb-44) was 250°C, and the sublimed compound (2Bb-44) was in powder form.

[0226] The compound was identified by single crystal X-ray structure analysis. X-ray crystal structure [ka]

[0227] Empirical formula;C35H21N Formula weight; 455.53 Temperature;293(2)K Wavelength; 0.71073 Å Crystal system; monoclinic Space group;P21 / n Unit cell dimensions;a=10.4468(6)Å,a=90°,b=10.9683(9)Å,b=92.890(6)°,c=19.4712(9)Å,g=90° Volume;2228.2(2)Å3 Z;4 Density(calculated);1.358Mg / m3 Absorption coefficient;0.078mm-1 F(000);952 Crystal Size: 0.1×0.1×0.1mm3 Theta range for data collection;2.09to25.00° Reflections collected;14871 Independent reflections;3873[R(int)=0.1325] parameters;325 Goodness-of-fit on F2; 0.957 Final R indices[I>2sigma(I)];R1=0.0580,wR2=0.1321 R indices(all data);R1=0.1195,wR2=0.1550

[0228] [Example 37] (Synthesis of compound (2Fa-1)) [ka]

[0229] Under a nitrogen stream, 1.49g (4.83mmol) of 8-bromo-7-(phenylethynyl)quinoline, 1.35g (4.83mmol) of 2-iodobiphenyl, 54mg (0.24mmol) of palladium acetate, 119mg (0.48mmol) of di-tert-butylmethylphosphonium tetrafluoroborate, 1.42g (14.5mmol) of potassium acetate, and 48mL of N,N-dimethylformamide were added to a 100mL two-necked eggplant flask and stirred at 130°C for 41 hours. After cooling to room temperature, 50mL of dichloromethane was added for dilution. Insoluble matter was removed by filtration, and 80mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. A red crude product was separated from the concentrate by column chromatography (hexane:chloroform=5:1, v / v). The crude product was purified again by column chromatography (hexane:ethyl acetate=20:1). The yellow solid was recrystallized (hot ethyl acetate) to isolate 407 mg (1.07 mmol) of pale yellow powder of benzo[11,12]chryseno[5,6-h]quinoline (yield 22%).

[0230] Compound identification 1 This was confirmed by H-NMR measurements and single crystal X-ray structure analysis. 1 H-NMR(CDCl3);10.46(dd,1H),9.23(dd,1H),8.84(d,1H),8.76(dd,1H),8.74-8.72(m,3H) ,8.64(dd,1H),8.33(dd,1H),7.95(d,1H),7.80(ddd,1H),7.73-7.66(m,5H),7.58(dd,1H)

[0231] X-ray crystal structure [ka]

[0232] Empirical formula;C29H17N Formula weight;379.43 Temperature;123(2)K Wavelength;0.71073 Å Crystal system;Orthorhombic Space group;Pbca Unit cell dimensions;a=7.6965(2)Å,a=90°,b=18.3892(6)Å,b=90°,c=25.5080(8)Å,g=90° Volume;3610.21(19)Å3 Z;8 Density(calculated);1.396Mg / m3 Absorption coefficient;0.081mm-1 F(000);1584 Crystal Size;0.100×0.100×0.050mm3 Theta range for data collection;2.355to24.999° Index ranges;-9<=h<=9,-21<=k<=21,-30<=l<=29 Refrections collected;36884 Independent reflections;3177[R(int)=0.0349] Completeness to theta=24.999°,99.80% Refinement method; Full-matrix least-squares on F2 Data / restraints / parameters;3177 / 0 / 271 Goodness-of-fit on F2;1.061 Final R indices[I>2sigma(I)];R1=0.0329,wR2=0.0800 R indices(all data);R1=0.0398,wR2=0.0841 Extinction coefficient; n / a Largest diff. peak and hole;0.157and-0.151e·Å-3

[0233] [Example 38] (Synthesis of compound (3Fa-1)) [ka]

[0234] Under a nitrogen stream, 1.78g (5.80mmol) of 4-[(2-bromophenyl)ethynyl]-isoquinoline, 1.64g (5.80mmol) of 2-iodobiphenyl, 260mg (1.16mmol) of palladium acetate, 621mg (1.68mmol) of tricyclohexylphosphonium tetrafluoroborate, 1.70g (17.4mmol) of potassium acetate, and 58mL of N,N-dimethylformamide were added to a 200mL two-necked eggplant flask and stirred at 130°C for 18 hours. After cooling to room temperature, 60mL of dichloromethane was added for dilution. Insoluble matter was removed by filtration, and 100mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The concentrate was recrystallized (from toluene) to isolate 300 mg (0.79 mmol) of a colorless powder of benzo[c]phenanthro[9,10-a]phenanthrolidine (yield 14%).

[0235] Compound identification 1 This was confirmed by H-NMR measurements and single crystal X-ray structure analysis. 1 H-NMR(CDCl3);9.53-9.52(m,2H),8.81(dd,2H),8.75(d,1H),8.62(d,1H),8.27(d,1H),8.1 3(d,1H),8.05(d,1H),7.78-7.70(m,4H),7.61(d,1H),7.58(d,1H),7.46(t,1H),7.31(t,1H)

[0236] X-ray crystal structure [Chemical]

[0237] Empirical formula; C29H17N Formula weight; 379.43 Temperature; 123(2)K Wavelength; 0.71073 Å Crystal system; Monoclinic Space group; P21 / n Unit cell dimensions; a = 10.4701(3) Å, α = 90°, b = 8.8984(2) Å, β = 99.531(3)°, c = 19.6220(5) Å, γ = 90° Volume; 1802.89(8) Å3 Z; 4 Density (calculated); 1.398 Mg / m3 Absorption coefficient; 0.081 mm-1 F(000); 792 Crystal Size; 0.100×0.100×0.100 mm3 Theta range for data collection; 2.519 to 25.000° Index ranges; -12 <= h <= 12, -10 <= k <= 10, -23 <= l <= 23 Reflections collected; 19052 Independent reflections; 3183 [R(int) = 0.0286] Completeness to theta = 25.000°, 99.80% Refinement method; Full-matrix least-squares on F2 Data / restraints / parameters; 3183 / 0 / 271 Goodness-of-fit on F2; 1.049 Final R indices[I>2sigma(I)];R1=0.0321,wR2=0.0809 R indices(all data);R1=0.0382,wR2=0.0843 Extinction coefficient; n / a Largest diff. peak and hole;0.146and-0.182e·Å-3

[0238] [Example 39] (Synthesis of compound (5Ba-1)) [ka]

[0239] Under a nitrogen stream, 663 mg (1.60 mmol) of compound (2Bb-4), 19 mg (0.08 mmol) of palladium acetate, 78 mg (0.16 mmol) of Xphos, 15 mL of tetrahydrofuran, and 5 mL of 2 M potassium carbonate aqueous solution were added to a 50 mL Schlenk flask and stirred at 70°C for 24 hours. After the reaction, 20 mL of hexane was added and stirred. The precipitated solid was collected by filtration and recrystallized (o-xylene) to isolate 403 mg (1.07 mmol) of yellow powder of compound (5Ba-1) (yield 66.7%, HPLC purity 99.9%). Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);9.52(d,1H),9.45(d,1H),9.33(d,1H),9.26(d,1H),8.88(d,1H),8.55(t,2H),8.43(d,1H),7.95-7.81(m,7H)

[0240] [Example 40] (Synthesis of compound (5Ba-44)) [ka]

[0241] Under a nitrogen stream, 5.10 g of the powder containing the compound (2Bc-4) obtained in Example 22, 116 mg (0.52 mol) of palladium acetate, 496 mg (1.04 mmol) of Xphos, 100 mL of tetrahydrofuran, and 30 mL of a 2 M aqueous potassium carbonate solution were added to a 300 mL two-necked eggplant flask, and the mixture was stirred at 70° C. for 24 hours. After the reaction, the mixture was allowed to cool to room temperature, and the precipitated solid was collected by filtration and washed with toluene to isolate 2.41 g (5.31 mmol) of a yellow powder of the compound (5Ba-44) (HPLC purity 99.2%). Compound identification 1 This was measured by H-NMR. 1 H-NMR(CDCl3);9.54(dd,1H),9.47(dd,1H),9.34(dd,1H),9.28(dd,1H),8.87(dd ,1H),8.50(d,1H),8.28(d,1H),7.96-7.79(m,9H),7.58(t,2H),7.52-7.48(m,1H)

[0242] [Comparative Example 1] Dibenzo[g,p]chrysene represented by formula (X1) (a compound disclosed in Non-Patent Document 1) was synthesized. It was confirmed that the sublimation temperature of compound (X1) was 250° C., and that the sublimed compound (X1) was in a powder form. [ka]

[0243] [Comparative Example 2] 4-(10-phenyl-9-phenanthrenyl)pyridine (a compound disclosed in Synlett 2015, 26, p. 1991-1996) represented by formula (X2) was synthesized. The sublimation temperature of compound (X2) was 240°C, and it was confirmed that the sublimed compound (X2) was in powder form. [ka]

[0244] [Comparative Example 3] Benzo[f]phenanthro[9,10-h]isoquinoxaline represented by formula (X3) (the compound described in Example 5) was synthesized. The sublimation temperature of compound (X3) was 240° C., and it was confirmed that the sublimed product of compound (X3) was in powder form. [ka]

[0245] [Table 4]

[0246] Compared with dibenzo[g,p]chrysene (X1) described in Non-Patent Document 1, the fused ring compound according to one embodiment of the present invention is found to have a high glass transition temperature.

[0247] [Film formation example 1] The glass substrate was washed with isopropyl alcohol and then subjected to surface treatment by ozone ultraviolet cleaning. The washed glass substrate was introduced into a vacuum deposition chamber and 1.0×10 -4 The pressure was reduced to 100 Pa. A film of compound (1Ba-24) was formed on the substrate at a film formation rate of 0.15 nm / sec using a resistance heating method. The glass substrate after the film formation was then removed and stored in a nitrogen atmosphere. After 24 hours, the state of the film on the glass substrate was confirmed. The results are shown in Table 5.

[0248] [Film Formation Examples 2 to 4, Film Formation Comparative Examples 1 to 2] The evaluation was carried out in the same manner as in Film-forming Example 1, except that instead of Compound (1Ba-24), Compound (1Ca-1), Compound (1Ja-1), Compound (2B-1), Compound (X2), and Compound (X3) were used in that order. The measurement results are shown in Table 5.

[0249] [Table 5]

[0250] As can be seen from Table 1, the evaporated films made of the fused ring compounds according to the examples have high amorphous properties, and can provide organic EL devices that can withstand long-term use.

[0251] [Element Example 1] Next, using the compound (1Ba-1) obtained in Example-1, an organic EL element having a layered structure shown in Fig. 2 was produced. Fig. 2 is a schematic cross-sectional view showing another example of a layered structure of an EL element according to one embodiment of the present invention. The structural formulas and abbreviations of the compounds used in the production of the organic EL element are as follows.

[0252] [ka]

[0253] (Preparation of Substrate 1 and Anode 2) A glass substrate with an indium-tin oxide (ITO) transparent electrode, on which a 2 mm wide ITO film (thickness 110 nm) was patterned in stripes, was prepared as a substrate with an anode on its surface. The substrate was then washed with isopropyl alcohol and then subjected to surface treatment by ozone ultraviolet cleaning.

[0254] (Preparation for vacuum deposition) Each layer was deposited on the cleaned and surface-treated substrate by vacuum deposition. Each organic material and metal material was deposited by resistance heating. First, the glass substrate was placed in a vacuum deposition chamber and 1.0×10 -4 The pressure was reduced to 10 Pa. Then, each layer was formed according to the film formation conditions in the following order.

[0255] (Fabrication of Hole Injection Layer 3) The sublimated and purified HIL was deposited at a rate of 0.15 nm / sec to a thickness of 50 nm to prepare a hole injection layer. (Preparation of Charge Generation Layer 4) The sublimated and purified HAT was deposited at a rate of 0.05 nm / sec to form a 5 nm film to form a charge generating layer. (Preparation of First Hole Transport Layer 51) A 10 nm thick film of HTL-1 was formed at a rate of 0.15 nm / sec to form a first hole transport layer.

[0256] (Preparation of second hole transport layer 52) A 10 nm thick film of HTL-2 was formed at a rate of 0.15 nm / sec to prepare a second hole transport layer (electron blocking layer). This second hole transport layer also functions as an electron blocking layer that blocks the inflow of electrons. (Fabrication of Light Emitting Layer 6) The light-emitting layer was prepared by depositing a 25 nm film of EML-1 and EML-2 at a mass ratio of 5:95 at a deposition rate of 0.18 nm / sec.

[0257] (Fabrication of First Electron Transport Layer 71) ETL-1 was deposited at a rate of 0.15 nm / sec to a thickness of 5 nm to prepare a first electron transport layer (hole blocking layer). This first electron transport layer also functions as a hole blocking layer that blocks the inflow of holes. (Preparation of second electron transport layer 72) The compound (1Ba-1) and Liq were mixed in a ratio of 50:50 (mass ratio) to form a film of 25 nm, and the film formation rate was 0.15 nm / sec. (Fabrication of Electron Injection Layer 8) Liq was deposited at a rate of 0.01 nm / sec to a thickness of 1 nm to form an electron injection layer.

[0258] (Preparation of cathode 9) Finally, a metal mask was placed perpendicular to the ITO stripes on the substrate, and the cathode (cathode layer) was formed. The cathode had a two-layer structure, with silver / magnesium (mass ratio 1 / 10) and silver deposited in that order to thicknesses of 80 nm and 20 nm, respectively. The deposition rate of silver / magnesium was 0.5 nm / sec, and that of silver was 0.2 nm / sec.

[0259] As a result, a light-emitting area of ​​4 mm2 with a laminated structure as shown in FIG. 2 Organic EL devices were fabricated. The film thickness of each film was measured using a stylus film thickness gauge (DEKTAK manufactured by Bruker). The element was then sealed in a glove box with a nitrogen atmosphere having an oxygen concentration of 1 ppm or less and a moisture concentration of 1 ppm or less, by sealing the glass sealing cap and the film-formed substrate (element) with bisphenol F liquid epoxy resin (manufactured by Nagase ChemteX Corporation).

[0260] A direct current was applied to the organic EL device fabricated as described above, and the light-emitting characteristics were evaluated using a luminance meter (LUMINANCE METER BM-9 manufactured by TOPCON Corporation). 2 The voltage (V) and current efficiency (cd / A) when the current was passed were measured. The measurement results are shown in Table 6. The voltage and current efficiency are relative values, with the result in Comparative Example 1 of the element described below taken as the reference value (100).

[0261] [Element Examples 2 to 6, and Element Comparative Examples 1 and 2] In the device example 1, instead of the compound (1Ba-1), the compounds (1Ba-24), (1Ba-44), (1Ca-1), (1Ea-1), (1Ja-1), (2Ba-1), (2Ba-44), (2Ba-45), (2Ba-46), (2Bc-44), (5Ba-1), compound (X1), and compound (X2) were used, respectively, in order, and organic EL devices were prepared in the same manner as in the device example 1, and each was evaluated. The measurement results obtained are shown in Table 6.

[0262] [Table 6] [Explanation of symbols]

[0263] 1: substrate, 2: anode, 3: hole injection layer, 4: charge generation layer, 5: hole transport layer, 6: light emitting layer, 7: electron transport layer, 71: first electron transport layer, 71: second electron transport layer, 8: electron injection layer, 9: cathode, 51: first hole transport layer, 52: second hole transport layer, 10, 100: organic EL element

[0264] The entire contents of the specifications, claims, drawings, and abstracts of Japanese Patent Application No. 2018-222499 filed on November 28, 2018 and Japanese Patent Application No. 2018-064141 filed on March 28, 2019 are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims

1. A method for producing a fused ring compound represented by the following formula (1) in which two unsubstituted carbon atoms, X 1 and X 16 , are bonded to each other to form a ring, the method comprising intramolecularly cyclizing a compound represented by the following formula (12), and reacting a compound represented by the following formula (7) with a compound represented by the following formula (8): 【Chemistry 1】 In the above formula (1), X 1 and X 16 are unsubstituted carbon atoms; X2 to X ８ each independently represents a carbon atom which may have a charge transport group; X ９ to X15 each independently represent a nitrogen atom or a carbon atom which may have a charge transport group; X １３ At least two of X to X15 are carbon atoms which may have a charge transporting group; X ９ and X １２ represents a carbon atom which may have a charge transporting group; Among the charge transporting groups contained in X 2 to X 15, two adjacent charge transporting groups may be bonded to each other to form a ring; X １４ and X １５ When at least one of the carbon atoms is a carbon atom having a charge transport group forming a ring, the atoms constituting the ring structure of the ring and X １３ At least one of X to X 15 is a nitrogen atom; X １４ and X １５ are not carbon atoms having a charge transport group forming a ring, X １４ and X １５ At least one of these is a nitrogen atom. The charge transporting groups are each independently a deuterium atom; a fluorine atom, a bromine atom, an iodine atom; a trifluoromethyl group, a pentafluoroethyl group; a cyano group; a nitro group; a hydroxyl group; a thiol group; a monocyclic, linked or fused aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent; a monocyclic, linked or fused heteroaromatic group having 3 to 36 carbon atoms which may have a substituent; a phosphine oxide group which may have a substituent; a silyl group which may have a substituent; a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms; a linear or branched alkyl group having 1 to 18 carbon atoms; or a linear or branched alkoxy group having 1 to 18 carbon atoms. 【Chemistry 2】 In the above formula (7) and formula (8), X １ ~X １６ each independently represents an atom defined in formula (1). １ ~Z ２ each independently represents a chlorine atom, a bromine atom, or an iodine atom. 【Chemistry 3】 In the above formula (12), X 2 to X 14 each independently represent a carbon atom which may have a charge transport group defined in the above formula (1); X 15 represents a nitrogen atom; among the charge transport groups possessed by X 2 to X 14 , two adjacent charge transport groups may be bonded to each other to form a ring; and Z 5 represents a chlorine atom, a bromine atom, or an iodine atom.

2. The method according to claim 1, wherein the charge-transporting group is a chlorine atom, a cyano group, a monocyclic, linked or fused aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, a monocyclic, linked or fused aromatic heteroaromatic group having 3 to 36 carbon atoms which may have a substituent, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a trifluoromethylsulfonyloxy group.

3. A fused ring compound represented by any one selected from the group consisting of the following formulas (1Bα), (1Cα), (1Jα), (2Bα), (2Fα), (3Fα), and (5Bα). 【Chemistry 4】 In the above formula, X ０ represents a nitrogen atom; A ３ , A ４ , A ６ each independently represents a charge transporting group; k3 and k6 each independently represents an integer of 0 or more and 4 or less; k4 is an integer of 0 or more and 3 or less. The charge transporting groups are each independently a deuterium atom; a fluorine atom, a bromine atom, an iodine atom; a trifluoromethyl group, a pentafluoroethyl group; a cyano group; a nitro group; a hydroxyl group; a thiol group; a monocyclic, linked or fused aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent; a monocyclic, linked or fused heteroaromatic group having 3 to 36 carbon atoms which may have a substituent; a phosphine oxide group which may have a substituent; a silyl group which may have a substituent; a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms; a linear or branched alkyl group having 1 to 18 carbon atoms; or a linear or branched alkoxy group having 1 to 18 carbon atoms.

4. 4. The fused ring compound according to claim 3, wherein the charge-transporting group is a chlorine atom, a cyano group, a monocyclic, linked or fused aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, a monocyclic, linked or fused aromatic heteroaromatic group having 3 to 36 carbon atoms which may have a substituent, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a trifluoromethylsulfonyloxy group.

5. A material for an organic electroluminescence device, comprising the fused ring compound according to claim 3 or 4.

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