Method for producing hydrogenated fused ring compound, hydrogenated fused ring compound, organic thin film, and photoelectric conversion element

Abstract

The present invention provides a method for producing a hydrogenated fused ring compound that is hydrogenated and reduced in a short time without using hydrogen gas, a hydrogenated fused ring compound obtained by the method, and an organic thin film and a photoelectric conversion element that use the hydrogenated fused ring compound. [Solution] A method for producing a hydrogenated fused ring compound is used, which includes the steps of mixing a fused ring compound (p-14) containing a benzene ring, represented by the following formula, with a rhodium metal complex and diboron using a grinder, and then hydrogenating the benzene ring through a mechanochemical reaction. TIFF2026041157000033.tif41134

Description

[Technical Field]

[0001] The present invention relates to a method for producing a hydrogenated fused ring compound, a hydrogenated fused ring compound, an organic thin film, and a photoelectric conversion element. [Background technology]

[0002] In recent years, fused ring compounds have been actively studied and applied to materials for photoelectric conversion devices. As a method for synthesizing a hydrogenated fused ring compound obtained by hydrogenation reduction of a fused ring compound, for example, Non-Patent Document 1 discloses a method for hydrogenation reduction of perylene using a Pd / Rh catalyst. [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] R.Abu-Reziq et al.,Journal of Molecular Catalysis A:Chemical,185(2002),179-185 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the method disclosed in Non-Patent Document 1 requires the use of high-pressure hydrogen and has production problems such as a long reaction time.

[0005] The present invention has been made in view of the above-mentioned problems, and aims to provide a method for producing a hydrogenated fused ring compound that is hydrogenated and reduced in a short time without using hydrogen gas, a hydrogenated fused ring compound obtained by the method, and an organic thin film and a photoelectric conversion element that use the hydrogenated fused ring compound. [Means for solving the problem]

[0006] The present inventors have found that the above problems can be solved by using a specific mechanochemical reaction, and have completed the present invention.

[0007] Aspects of the present disclosure relate to the following method for producing a hydrogenated fused ring compound, a hydrogenated fused ring compound, an organic thin film, and a photoelectric conversion element.

[0008] [1] A method for producing a hydrogenated fused ring compound, comprising the steps of: mixing a fused ring compound containing a benzene ring with a rhodium metal complex and diboron using a grinder; and hydrogenating the benzene ring by a mechanochemical reaction. [2] The production method according to [1], wherein the fused ring compound containing a benzene ring is a compound represented by any one of the following formulas (a-1) to (a-7): [ka] In the above formulas (a-1) to (a-7), Rings I to V represent a structure represented by the following formula (B) or (C): R 11 ~R 18 , R 19 ~R 28 , R 29 ~R 40 , R 41 ~R 52 , R 53 ~R 56 , R 57 ~R 64 , and R 65 ~R 74 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR 75 R 76 , or -OR 77 represents R 75 ~R 77each independently represents an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or an optionally substituted heteroaromatic group having 3 to 30 carbon atoms; R 11 ~R 18 , R 19 ~R 28 , R 29 ~R 40 , R 41 ~R 52 , R 53 ~R 56 , R 57 ~R 64 , and R 65 ~R 74 Two adjacent groups may be bonded to each other to form a ring; [ka] In formulas (B) and (C), * represents a bond; R a ~R d and R e ~R l are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR 78 R 79 , or -OR 80 represents; R 78 ~R 80 each independently represents an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or an optionally substituted heteroaromatic group having 3 to 30 carbon atoms; R a ~R d Among these, two adjacent groups may be bonded to each other to form a ring. [3] In the above formulas (a-1) to (a-7), R 11 ~R 18 , R 19 ~R 28 , R 29 ~R 40 , R 41 ~R 52 , R 53 ~R 56 , R 57 ~R 64 , and R 65 ~R 74 The method according to [2], wherein two adjacent groups are not bonded to each other to form a ring. [4] In the above formulas (a-1) to (a-7), R 11 ~R 18 , R 19 ~R 28 , R 29 ~R 40 , R 41 ~R 52 , R 53 ~R 56 , R 57 ~R 64 , and R 65 ~R 74 each independently represents a hydrogen atom, 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 n-octyl group, an n-decyl group, an n-dodecyl group, an n-octadecyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, -NR 78 R 79 , and -OR80 is at least one group selected from the group consisting of R 78 ~R 80 are each independently at least one group selected from the group consisting of a hydrogen atom, a benzyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, and an optionally substituted dibenzothienyl group. [5] In the above formulas (a-1) to (a-7), R a ~R d and R e ~R l The method according to any one of [2] to [4], wherein all of are hydrogen atoms. [6] The method according to any one of [1] to [5], wherein the pulverizer is at least one selected from the group consisting of a ball mill, a bead mill, a rod mill, a jet mill, and a rocking mill. [7] The method according to any one of [1] to [6], wherein the rhodium metal complex is at least one selected from the group consisting of Rh(PPh3)3Cl, [Rh(COD)Cl]2, [Rh(C2H4)Cl]2, [Rh(COD)OH]2, and Rh(COD)2BF4. [8] The manufacturing method according to any one of [1] to [7], wherein the diboron is at least one selected from the group consisting of B2(OH)4, B2(pin)2, B2(cat)2, and B2(neop)2. [9] The production method according to any one of [1] to [8], wherein the mechanochemical reaction is carried out by further adding a solvent-based additive.

[10] The method according to [9], wherein the solvent-based additive is selected from the group consisting of methanol, ethanol, propanol, butanol, pentanol, and ethylene glycol.

[11] The production method according to any one of [1] to

[10] , wherein the reaction temperature in the mechanochemical reaction is 50°C or higher.

[12] The production method according to any one of [1] to

[10] , wherein the reaction temperature in the mechanochemical reaction is 90°C or higher.

[13] A hydrogenated fused ring compound represented by any one of the following formulas (D) to (F): [ka] In the above formulas (D) to (F), Rings I to V represent a structure represented by the following formula (G) or (H): R A1 ~R A4 , R A5 ~R A28 , and R A29 ~R A38 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR A39 R A40 , or -OR A41 represents R A39 ~R A41 each independently represents an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or an optionally substituted heteroaromatic group having 3 to 30 carbon atoms; R A1 ~R A4 , R A5 ~R A28 , and R A29 ~R A38 Two adjacent groups may be bonded to each other to form a ring; [ka] In formulas (G) and (H), * represents a bond; R Aa ~R Ad and R Ae ~R Al are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR A42 R A43 , or -OR A44 represents; R A42 ~R A44 each independently represents an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or an optionally substituted heteroaromatic group having 3 to 30 carbon atoms; R Aa ~R Ad Among these, two adjacent groups may be bonded to each other to form a ring.

[14] In the above formulas (D) to (F), R A1 ~R A4 , R A5 ~R A28 , and R A29 ~R A38

[13] The hydrogenated fused ring compound according to

[13] , wherein two adjacent groups are not bonded to each other to form a ring.

[15] In the above formulas (D) to (F), R A1 ~R A4 , R A5 ~R A28 , and R A29 ~R A38each independently represents a hydrogen atom, 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, an n-pentyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, an n-octadecyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, -NR A39 R A40 , and -OR A41 is at least one group selected from the group consisting of R A39 ~R A41are each independently at least one group selected from the group consisting of a hydrogen atom, a benzyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, an optionally substituted trimethylsilyl group, an optionally substituted phenyldimethylsilyl group, an optionally substituted diphenylmethylsilyl group, an optionally substituted acetyl group, and an optionally substituted benzoyl group.

[16] In the above formulas (D) to (F), R Aa ~R Ad and R Ae ~R Al The hydrogenated fused ring compound according to any one of

[13] to

[15] , wherein all of are hydrogen atoms.

[17] An organic thin film comprising a material for a photoelectric conversion device, which contains the hydrogenated fused ring compound according to any one of

[13] to

[16] .

[18] A photoelectric conversion element containing a material for a photoelectric conversion element, which contains the hydrogenated fused ring compound according to any one of

[13] to

[16] .

[19] A photoelectric conversion element for an imaging device, comprising a material for a photoelectric conversion element containing the hydrogenated fused ring compound according to any one of

[13] to

[16] . [Effects of the Invention]

[0009] According to one aspect of the present invention, it is possible to provide a method for producing a hydrogenated fused ring compound that is hydrogenated and reduced in a short time without using hydrogen gas, a hydrogenated fused ring compound obtained by the method, and an organic thin film and a photoelectric conversion element that use the hydrogenated fused ring compound. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, a method for producing a hydrogenated fused ring compound according to one embodiment of the present disclosure, the hydrogenated fused ring compound obtained by the method, and the like will be described in detail.

[0011] <Method for producing hydrogenated fused ring compound> The method for producing a hydrogenated fused ring compound includes the steps of mixing a fused ring compound containing a benzene ring with a rhodium metal complex and diboron using a grinder, and hydrogenating the benzene ring through a mechanochemical reaction. By using the above-mentioned specific mechanochemical reaction, it is possible to produce a hydrogenated fused ring compound that has been hydrogenated and reduced in a short period of time without using hydrogen gas.

[0012] <Fused ring compounds containing a benzene ring> The fused ring compound containing a benzene ring is preferably a compound represented by any one of the following formulas (a-1) to (a-7). [ka]

[0013] In the above formulas (a-1) to (a-7), Rings I to V represent a structure represented by the following formula (B) or (C): R 11 ~R 18 , R 19 ~R 28 , R 29 ~R 40 , R 41 ~R 52 , R 53 ~R 56 , R 57 ~R 64 , and R 65 ~R 74are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR 75 R 76 , or -OR 77 Represents. R 11 ~R 18 , R 19 ~R 28 , R 29 ~R 40 , R 41 ~R 52 , R 53 ~R 56 , R 57 ~R 64 , and R 65 ~R 74 Among these, two adjacent groups may be bonded to each other to form a ring. [ka] In formulas (B) and (C), * represents a bond; R a ~R d and R e ~R l are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR 78 R 79 , or -OR 80 Represents. R a ~R d Among these, two adjacent groups may be bonded to each other to form a ring.

[0014] Preferred embodiments of the definitions in the above formulas (a-1) to (a-7) are as follows.

[0015] <R 11 ~R 74 > (Alkyl group) R 11 ~R 74 The optionally substituted alkyl group having 1 to 18 carbon atoms represented by the formula (I) is preferably, for example, a linear or branched alkyl group having 1 to 18 carbon atoms. Examples of the alkyl group 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.

[0016] (alkenyl group) R 11 ~R 74 The alkenyl group having 1 to 18 carbon atoms represented by the formula (I) is preferably an alkenyl group having 2 to 18 carbon atoms. Examples of the alkenyl group include ethenyl, propenyl, butenyl, 2-methylpropenyl, n-pentenyl, 2-methylbutenyl, n-hexenyl, 2-methylpentenyl, n-heptenyl, n-octenyl, 2-ethylhexenyl, n-nonenyl, 2-ethylheptenyl, n-decenyl, n-dodecenyl, cyclopentenyl-1-, cyclohexenyl-1-, and cycloheptenyl-1- groups.

[0017] (cycloalkyl group) R 11 ~R 74 The cycloalkyl group having 1 to 18 carbon atoms represented by the formula (I) is preferably a cycloalkyl group having 3 to 18 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0018] (bicycloalkyl group) R 11 ~R74 The bicycloalkyl group having 1 to 18 carbon atoms represented by the formula (I) is preferably a bicycloalkyl group having 6 to 18 carbon atoms. Examples of the bicycloalkyl group include an exo-2-norbornyl group, an endo-2-norbornyl group, a 3-pinanyl group, a bicyclo[1,2,2]heptan-2-yl group, and a bicyclo[2,2,2]octan-3-yl group.

[0019] (tricycloalkyl group) R 11 ~R 74 The tricycloalkyl group having 1 to 20 carbon atoms represented by the formula (I) is preferably a tricycloalkyl group having 9 to 20 carbon atoms. Examples of the tricycloalkyl include a 1-adamantyl group and a 2-adamantyl group.

[0020] (aromatic hydrocarbon group) R 11 ~R 74 The optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, represented by the formula (I), is preferably a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 18 carbon atoms.

[0021] Examples of the aromatic hydrocarbon group include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a chrysenyl group, a triphenylenyl group, a benzochrysenyl group, a dibenzochrysenyl group, a fluorenyl group, a benzofluorenyl group, a naphthylphenyl group, a phenylnaphthyl group, a naphthylnaphthyl group, a phenanthrylphenyl group, a phenylphenanthryl group, a triphenylenylphenyl group, and a phenyltriphenylenyl group.

[0022] (heteroaromatic group) R 11 ~R 74The optionally substituted heteroaromatic group having 3 to 30 carbon atoms and represented by the formula (I) is preferably a monocyclic, linked or fused ring heteroaromatic group having 3 to 30 carbon atoms and containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom on the aromatic ring.

[0023] Examples of the heteroaromatic group include a dibenzofuranyl group, a dibenzothionyl group, a carbazolyl group, 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 pyrimidyl group, a pyrazyl group, an indolyl group, a benzothienyl group, a benzofuranyl group, a benzimidazolyl group, 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 dibenzothienyl group, a dibenzofuranyl group, a phenoxazinyl group, a phenothiazinyl group, a phenazine group, and a thianthrenyl group.

[0024] (-NR 75 R 76 , -OR 77 ) R 11 ~R 74 -NR, which is represented by 75 R 76 and-OR 77 In R 75 ~R 77 are preferably each independently an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or an optionally substituted heteroaromatic group having 3 to 30 carbon atoms. Examples of the alkyl group, aromatic hydrocarbon group, and heteroaromatic group include those described above for R 11 ~R 74 Examples of the alkyl group, aromatic hydrocarbon group, and heteroaromatic group are the same as those in the above.

[0025] <R a ~Rl > (Alkyl group) R a ~R l The optionally substituted alkyl group having 1 to 18 carbon atoms represented by the formula (I) is preferably, for example, a linear or branched alkyl group having 1 to 18 carbon atoms. Examples of the alkyl group 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.

[0026] (alkenyl group) R a ~R l The alkenyl group having 1 to 18 carbon atoms represented by the formula (I) is preferably an alkenyl group having 2 to 18 carbon atoms. Examples of the alkenyl group include ethenyl, propenyl, butenyl, 2-methylpropenyl, n-pentenyl, 2-methylbutenyl, n-hexenyl, 2-methylpentenyl, n-heptenyl, n-octenyl, 2-ethylhexenyl, n-nonenyl, 2-ethylheptenyl, n-decenyl, n-dodecenyl, cyclopentenyl-1-, cyclohexenyl-1-, and cycloheptenyl-1- groups.

[0027] (cycloalkyl group) R a ~R l The cycloalkyl group having 1 to 18 carbon atoms represented by the formula (I) is preferably a cycloalkyl group having 3 to 18 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0028] (bicycloalkyl group) R a ~R lThe bicycloalkyl group having 1 to 18 carbon atoms represented by the formula (I) is preferably a bicycloalkyl group having 6 to 18 carbon atoms. Examples of the bicycloalkyl group include an exo-2-norbornyl group, an endo-2-norbornyl group, a 3-pinanyl group, a bicyclo[1,2,2]heptan-2-yl group, and a bicyclo[2,2,2]octan-3-yl group.

[0029] (tricycloalkyl group) R a ~R l The tricycloalkyl group having 1 to 20 carbon atoms represented by the formula (I) is preferably a tricycloalkyl group having 9 to 20 carbon atoms. Examples of the tricycloalkyl include a 1-adamantyl group and a 2-adamantyl group.

[0030] (aromatic hydrocarbon group) R a ~R l The optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, represented by the formula (I), is preferably a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 18 carbon atoms.

[0031] Examples of the aromatic hydrocarbon group include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a chrysenyl group, a triphenylenyl group, a benzochrysenyl group, a dibenzochrysenyl group, a fluorenyl group, a benzofluorenyl group, a naphthylphenyl group, a phenylnaphthyl group, a naphthylnaphthyl group, a phenanthrylphenyl group, a phenylphenanthryl group, a triphenylenylphenyl group, and a phenyltriphenylenyl group.

[0032] (heteroaromatic group) R a ~R lThe optionally substituted heteroaromatic group having 3 to 30 carbon atoms and represented by the formula (I) is preferably a monocyclic, linked or fused ring heteroaromatic group having 3 to 30 carbon atoms and containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom on the aromatic ring.

[0033] Examples of the heteroaromatic group include a dibenzofuranyl group, a dibenzothionyl group, a carbazolyl group, 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 pyrimidyl group, a pyrazyl group, an indolyl group, a benzothienyl group, a benzofuranyl group, a benzimidazolyl group, 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 dibenzothienyl group, a dibenzofuranyl group, a phenoxazinyl group, a phenothiazinyl group, a phenazine group, and a thianthrenyl group.

[0034] (-NR 78 R 79 , -OR 80 ) R a ~R l -NR, which is represented by 78 R 79 and-OR 80 In R 78 ~R 80 are each independently an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or an optionally substituted heteroaromatic group having 3 to 30 carbon atoms. The alkyl group, aromatic hydrocarbon group, and heteroaromatic group can be any of the groups described above for R 11 ~R 74 Examples of the alkyl group, aromatic hydrocarbon group, and heteroaromatic group are the same as those in the above.

[0035] In the above formulas (a-1) to (a-7), R 11~R 18 , R 19 ~R 28 , R 29 ~R 40 , R 41 ~R 52 , R 53 ~R 56 , R 57 ~R 64 , and R 65 ~R 74 Among these, it is preferred that two adjacent groups do not bond to each other to form a ring.

[0036] <R a ~R l > (Alkyl group, alkenyl group, cycloalkyl group, bicycloalkyl group, tricycloalkyl group, aromatic hydrocarbon group, heteroaromatic group) R a ~R l Examples of the optionally substituted alkyl group having 1 to 18 carbon atoms, alkenyl group having 1 to 18 carbon atoms, cycloalkyl group having 1 to 18 carbon atoms, bicycloalkyl group having 1 to 18 carbon atoms, tricycloalkyl group having 1 to 20 carbon atoms, aromatic hydrocarbon group having 6 to 30 carbon atoms, and heteroaromatic group having 3 to 30 carbon atoms, which are represented by the formula (I), include the above-mentioned R 11 ~R 74 Examples of the alkyl group include the same as the optionally substituted alkyl group having 1 to 18 carbon atoms, the alkenyl group having 1 to 18 carbon atoms, the cycloalkyl group having 1 to 18 carbon atoms, the bicycloalkyl group having 1 to 18 carbon atoms, the tricycloalkyl group having 1 to 20 carbon atoms, the optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, and the optionally substituted heteroaromatic group having 3 to 30 carbon atoms.

[0037] (-NR 78 R 79 , -OR 80 ) R a ~R l -NR, which is represented by 78 R 79 and-OR 80 In R 78~R 80 are preferably each independently an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or an optionally substituted heteroaromatic group having 3 to 30 carbon atoms. Examples of the alkyl group, aromatic hydrocarbon group, and heteroaromatic group include those described above for R 11 ~R 74 Examples of the alkyl group, aromatic hydrocarbon group, and heteroaromatic group are the same as those in the above.

[0038] In the above formulas (a-1) to (a-7), R 11 ~R 18 , R 19 ~R 28 , R 29 ~R 40 , R 41 ~R 52 , R 53 ~R 56 , R 57 ~R 64 , and R 65 ~R 74 each independently represents a hydrogen atom, 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 n-octyl group, an n-decyl group, an n-dodecyl group, an n-octadecyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, -NR 78 R 79 , and -OR 80 is at least one group selected from the group consisting of R 78 ~R 80 are each independently at least one group selected from the group consisting of a hydrogen atom, a benzyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, and an optionally substituted dibenzothienyl group.

[0039] In the above formulas (a-1) to (a-7), R a ~R d and R e ~R l are preferably all hydrogen atoms.

[0040] <Mechanochemical reaction> Hereinafter, the process of hydrogenating the fused ring compound containing a benzene ring by a mechanochemical reaction will be described.

[0041] The pulverizer may be any device that pulverizes the fused ring compound containing a benzene ring, and increases the activity of the compound, the rhodium metal complex, and the diboron by imparting mechanical energy to them, thereby causing a mechanochemical reaction.

[0042] Examples of the grinding machine include a ball mill, a bead mill, a rod mill, a jet mill, and a rocking mill. Among these, a ball mill is preferred because of its excellent efficiency in the mechanochemical reaction.

[0043] The rhodium metal complex is used as a catalyst. Examples of the rhodium metal complex include Rh(PPh3)3Cl, [Rh(COD)Cl]2, [Rh(C2H4)Cl]2, [Rh(COD)OH]2, and Rh(COD)2BF4. Among these, [Rh(COD)OH]2, [Rh(COD)Cl]2, and Rh(COD)2BF4 are preferred. These can be used alone or in combination of two or more.

[0044] The amount of the rhodium metal complex used is not particularly limited, and is, for example, preferably 0.001 equivalents or more and 1.0 equivalents or less, more preferably 0.01 equivalents or more and 1.0 equivalents or less, and even more preferably 0.04 equivalents or more and 1.0 equivalents or less, relative to 1 equivalent of the fused ring compound.

[0045] The diboron is used as a hydrogen equivalent. Examples of the diboron include B2(OH)4, B2(pin)2 (bis(pinacolato)diboron), B2(cat)2 (bis(catecholato)diboron), and B2(neop)2 (bis(neopentylglycolato)diboron). Of these, B2(OH)4 and B2(pin)2 are preferred. These can be used alone or in combination of two or more.

[0046] The amount of diboron used is not particularly limited, and is, for example, preferably 1 equivalent or more and 30 equivalents or less, more preferably 2 equivalents or more and 25 equivalents or less, and even more preferably 3 equivalents or more and 20 equivalents or less, relative to 1 equivalent of the fused ring compound.

[0047] In the mechanochemical reaction, it is preferable to use a solvent-based additive together with the fused ring compound, the rhodium metal complex, and diboron. By using the solvent-based additive, the mechanochemical reaction in this embodiment can be accelerated and the yield of the product can be improved.

[0048] Examples of the solvent-based additives include methanol, ethanol, propanol, butanol, pentanol, and ethylene glycol. Of these, methanol, ethanol, propanol, and butanol are preferred. These may be used alone or in combination of two or more.

[0049] The amount of the solvent-based additive used is not particularly limited and can be set appropriately.

[0050] The reaction temperature and reaction time of the mechanochemical reaction are not particularly limited, and may be generally carried out under mild conditions for a short reaction time.

[0051] The reaction temperature is preferably 30° C. or higher, more preferably 50° C. or higher, and even more preferably 90° C. or higher. The reaction temperature is preferably 200° C. or lower, and more preferably 150° C. or lower. The preferred combination of the upper and lower limits of the reaction temperature can be appropriately set from the above preferred ranges.

[0052] The reaction time is preferably from 20 minutes to 300 minutes, more preferably from 30 minutes to 200 minutes.

[0053] The conditions for pulverization by the pulverizer are not particularly limited and may be appropriately set depending on the type of pulverizer used. For example, when a ball mill is used as the pulverizer, the rotation speed of the reaction vessel is usually set as high as possible, but is not particularly limited, and the rotation speed of the reaction vessel is preferably 1000 rpm or more and 3500 rpm or less.

[0054] The mechanochemical reaction causes a hydrogenation reaction of the benzene ring contained in the fused ring compound to proceed, resulting in the production of a hydrogenated fused ring compound. Note that, in this specification, hydrogenation of the benzene ring includes both partial hydrogenation and complete hydrogenation.

[0055] <Hydrogenated condensed ring compounds> When a compound represented by any one of the above formulas (a-1) to (a-7) is used as a reaction raw material for the above mechanochemical reaction, a compound represented by any one of the following formulas (A-1) to (A-7) is preferably obtained. [ka]

[0056] In the above formulas (A-1) to (A-7), Rings I to V represent a structure represented by the following formula (B) or (C): R 11 ~R 18 , R 19 ~R 28 , R 29 ~R 40 , R 41 ~R 52 , R 53 ~R 56 , R 57 ~R 64 , and R 65 ~R 74 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR 75 R 76 , or -OR 77 represents R 75 ~R 77 each independently represents an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or an optionally substituted heteroaromatic group having 3 to 30 carbon atoms; R 11 ~R 18 , R 19 ~R 28 , R 29 ~R 40 , R 41 ~R 52 , R 53 ~R56 , R 57 ~R 64 , and R 65 ~R 74 Two adjacent groups may be bonded to each other to form a ring; [ka] In formulas (B) and (C), * represents a bond; R a ~R d and R e ~R l are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR 78 R 79 , or -OR 80 represents; R 78 ~R 80 each independently represents an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or an optionally substituted heteroaromatic group having 3 to 30 carbon atoms; R a ~R d Among these, two adjacent groups may be bonded to each other to form a ring.

[0057] In the above formulas (A-1) to (A-7), R 11 ~R 74 , R a ~R l Specific examples of the various substituents represented by the formulas (a-1) to (a-7) include R 11 ~R 74 , R a ~R l Specific examples of the various substituents represented by the following formula are exemplified.

[0058] <Hydrogenated condensed ring compounds> Among the hydrogenated fused ring compounds obtainable by the above-mentioned mechanochemical reaction, preferred hydrogenated fused ring compounds will be described below.

[0059] The hydrogenated fused ring compound is represented by any one of the following formulas (D) to (F). [ka]

[0060] In the above formulas (D) to (F), Rings I to V represent a structure represented by the following formula (G) or (H): R A1 ~R A4 , R A5 ~R A28 , and R A29 ~R A38 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR A39 R A40 , or -OR A41 represents R A1 ~R A4 , R A5 ~R A28 , and R A29 ~R A38 Two adjacent groups may be bonded to each other to form a ring; [ka] In formulas (G) and (H), * represents a bond; R Aa ~R Ad and R Ae ~R Alare each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR A42 R A43 , or -OR A44 represents; R Aa ~R Ad Among these, two adjacent groups may be bonded to each other to form a ring.

[0061] Preferred embodiments of the definitions in the above formulas (D) to (F) are as follows.

[0062] <R A1 ~R A38 > (Alkyl group) R A1 ~R A38 The optionally substituted alkyl group having 1 to 18 carbon atoms represented by the formula (I) is preferably, for example, a linear or branched alkyl group having 1 to 18 carbon atoms. Examples of the alkyl group 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.

[0063] (alkenyl group) R A1 ~R A38The alkenyl group having 1 to 18 carbon atoms represented by the formula (I) is preferably an alkenyl group having 2 to 18 carbon atoms. Examples of the alkenyl group include ethenyl, propenyl, butenyl, 2-methylpropenyl, n-pentenyl, 2-methylbutenyl, n-hexenyl, 2-methylpentenyl, n-heptenyl, n-octenyl, 2-ethylhexenyl, n-nonenyl, 2-ethylheptenyl, n-decenyl, n-dodecenyl, cyclopentenyl-1-, cyclohexenyl-1-, and cycloheptenyl-1- groups.

[0064] (cycloalkyl group) R A1 ~R A38 The cycloalkyl group having 1 to 18 carbon atoms represented by the formula (I) is preferably a cycloalkyl group having 3 to 18 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0065] (bicycloalkyl group) R A1 ~R A38 The bicycloalkyl group having 1 to 18 carbon atoms represented by the formula (I) is preferably a bicycloalkyl group having 6 to 18 carbon atoms. Examples of the bicycloalkyl group include an exo-2-norbornyl group, an endo-2-norbornyl group, a 3-pinanyl group, a bicyclo[1,2,2]heptan-2-yl group, and a bicyclo[2,2,2]octan-3-yl group.

[0066] (tricycloalkyl group) R A1 ~R A38 The tricycloalkyl group having 1 to 20 carbon atoms represented by the formula (I) is preferably a tricycloalkyl group having 9 to 20 carbon atoms. Examples of the tricycloalkyl include a 1-adamantyl group and a 2-adamantyl group.

[0067] (aromatic hydrocarbon group) R A1 ~RA38 The optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, represented by the formula (I), is preferably a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 18 carbon atoms.

[0068] Examples of the aromatic hydrocarbon group include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a chrysenyl group, a triphenylenyl group, a benzochrysenyl group, a dibenzochrysenyl group, a fluorenyl group, a benzofluorenyl group, a naphthylphenyl group, a phenylnaphthyl group, a naphthylnaphthyl group, a phenanthrylphenyl group, a phenylphenanthryl group, a triphenylenylphenyl group, and a phenyltriphenylenyl group.

[0069] (heteroaromatic group) R A1 ~R A38 The optionally substituted heteroaromatic group having 3 to 30 carbon atoms and represented by the formula (I) is preferably a monocyclic, linked or fused ring heteroaromatic group having 3 to 30 carbon atoms and containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom on the aromatic ring.

[0070] Examples of the heteroaromatic group include a dibenzofuranyl group, a dibenzothionyl group, a carbazolyl group, 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 pyrimidyl group, a pyrazyl group, an indolyl group, a benzothienyl group, a benzofuranyl group, a benzimidazolyl group, 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 dibenzothienyl group, a dibenzofuranyl group, a phenoxazinyl group, a phenothiazinyl group, a phenazine group, and a thianthrenyl group.

[0071] (-NR A39 R A40 , -OR A41 ) R A1 ~R A38 -NR, which is represented by A39 R A40 and-OR A41 In R A39 ~R A41 are each independently an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or an optionally substituted heteroaromatic group having 3 to 30 carbon atoms. The alkyl group, aromatic hydrocarbon group, and heteroaromatic group can be any of the above-mentioned R A1 ~R A38 Examples of the alkyl group, aromatic hydrocarbon group, and heteroaromatic group are the same as those in the above.

[0072] <R Aa ~R Al > (Alkyl group, alkenyl group, cycloalkyl group, bicycloalkyl group, tricycloalkyl group, aromatic hydrocarbon group, heteroaromatic group) R Aa ~R Al Examples of the optionally substituted alkyl group having 1 to 18 carbon atoms, alkenyl group having 1 to 18 carbon atoms, cycloalkyl group having 1 to 18 carbon atoms, bicycloalkyl group having 1 to 18 carbon atoms, tricycloalkyl group having 1 to 20 carbon atoms, aromatic hydrocarbon group having 6 to 30 carbon atoms, and heteroaromatic group having 3 to 30 carbon atoms, which are represented by the formula (I), include the above-mentioned R A1 ~R A38 Examples of the alkyl group include the same as the optionally substituted alkyl group having 1 to 18 carbon atoms, the alkenyl group having 1 to 18 carbon atoms, the cycloalkyl group having 1 to 18 carbon atoms, the bicycloalkyl group having 1 to 18 carbon atoms, the tricycloalkyl group having 1 to 20 carbon atoms, the optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, and the optionally substituted heteroaromatic group having 3 to 30 carbon atoms.

[0073] (-NR A42 R A43 , -OR A44 ) R Aa ~R Al -NR, which is represented by A42 R A43 and-OR A44 In R A42 ~R A44 are each independently an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or an optionally substituted heteroaromatic group having 3 to 30 carbon atoms. The alkyl group, aromatic hydrocarbon group, and heteroaromatic group can be any of the groups described above for R A1 ~R A38 Examples of the alkyl group, aromatic hydrocarbon group, and heteroaromatic group are the same as those in the above.

[0074] In the above formulas (D) to (F), R A1 ~R A4 , R A5 ~R A28 , and R A29 ~R A38 Among these, it is preferred that two adjacent groups do not bond to each other to form a ring.

[0075] In the above formulas (D) to (F), R A1 ~R A4 , R A5 ~R A28 , and R A29 ~R A38each independently represents a hydrogen atom, 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, an n-pentyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, an n-octadecyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, -NR A39 R A40 , and -OR A41 is at least one group selected from the group consisting of R A39 ~R A41 are each independently at least one group selected from the group consisting of a hydrogen atom, a benzyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, an optionally substituted trimethylsilyl group, an optionally substituted phenyldimethylsilyl group, an optionally substituted diphenylmethylsilyl group, an optionally substituted acetyl group, and an optionally substituted benzoyl group.

[0076] In the above formulas (D) to (F), R Aa ~R Ad and R Ae ~R Al are preferably all hydrogen atoms.

[0077] <Physical properties of hydrogenated fused ring compounds> Preferred physical properties of the hydrogenated fused ring compound represented by any one of the above formulas (D) to (F) will be described below.

[0078] (HOMO value) The HOMO value of the hydrogenated fused ring compound represented by any one of the above formulae (D) to (F) is not particularly limited, but from the viewpoint of suitability as a material for a photoelectric conversion device, it is preferably 5.0 to 6.5 eV. Note that this HOMO value is a value obtained by measuring a vapor-deposited film using an atmospheric photoelectron yield spectrometer.

[0079] (band gap) The band gap of the hydrogenated fused ring compound represented by any one of the above formulas (D) to (F) is not particularly limited, but from the viewpoint of suitability as a material for photoelectric conversion devices, it is preferably 2.5 to 4.0 eV. Note that this band gap is a value obtained from the wavelength edge of the absorption spectrum of the vapor-deposited film.

[0080] (LUMO value) The LUMO value of the hydrogenated fused ring compound represented by any one of the formulas (D) to (F) is not particularly limited, but from the viewpoint of suitability as a material for a photoelectric conversion element, it is preferably 2.0 to 3.5 eV. This LUMO value is a value obtained from the HOMO value and the band gap.

[0081] <Specific examples of fused ring compounds> Specific examples of compounds obtained by the above-mentioned mechanochemical reaction are described below. Among the following compounds (P-1) to (P-124), compounds (P-55) to (P-124) are preferred specific examples of hydrogenated fused ring compounds represented by any of the above formulas (D) to (F). [ka]

[0082] [ka]

[0083] [ka]

[0084] [ka]

[0085] [ka]

[0086] [ka]

[0087] [ka]

[0088] <Uses of hydrogenated fused ring compounds> The hydrogenated fused ring compound represented by any one of the above formulas (D) to (F) can be used as a material for a photoelectric conversion device. That is, the material for a photoelectric conversion device of this embodiment contains a hydrogenated fused ring compound represented by any one of the above formulas (D) to (F). The material for a photoelectric conversion device is suitably applied to, for example, organic thin films and photoelectric conversion devices. Examples of photoelectric conversion devices include photoelectric conversion devices for imaging devices.

[0089] The organic thin film contains a hydrogenated fused ring compound represented by any one of the above formulas (D) to (F).

[0090] The photoelectric conversion element contains a hydrogenated fused ring compound represented by any one of the above formulas (D) to (F).

[0091] The photoelectric conversion element for an imaging device contains a hydrogenated fused ring compound represented by any one of the above formulas (D) to (F).

[0092] Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments. [Example]

[0093] The present invention will be described in more detail below based on examples, but the present invention should not be construed as being limited to these examples.

[0094] <Synthesis Examples of Various Hydrogenated Fused Ring Compounds>

[0095] [Synthesis Example 1] [ka]

[0096] A 7 mm diameter stainless steel ball was placed in a 1.5 mL stainless steel container. Compound (p-6) (26.2 mg, 0.20 mmol, 1.0 eq), [Rh(COD)OH] (4.4 mg, 0.0096 mmol, 0.047 eq), and B(OH) (142.1 mg, 1.6 mmol, 7.8 eq) were weighed and placed in the container. EtOH (0.20 mL) was measured using a microsyringe and similarly placed in the stainless steel container. An O-shaped Teflon packing (Teflon is a registered trademark; the same applies below) was placed between the containers, and the container was sealed with a stainless steel lid. The container was then attached to a mixer mill reactor (Retsch MM400). A 7 mm diameter stainless steel ball was placed in a stainless steel vessel of the same weight, and the lid was closed with a Teflon gasket. The vessel was then fixed as a counterpart to a mixer mill reactor. The two vessels were shaken and stirred at a frequency of 30 Hz (equivalent to 1800 rpm) at a reaction temperature of 100 °C for 60 minutes. After the reaction, the mixture was extracted with chloroform, passed through silica gel, and the solvent was removed under reduced pressure using a rotary evaporator. The crude product was purified by silica gel column chromatography (eluent: hexane) and then by gel permeation chromatography (eluent: chloroform) to obtain compound (P-6) (18.3 mg, 0.13 mmol, 65% yield) as a white solid. 1 HNMR(600MHz,C6D6):δ1.64-1.44(m,10H),1.40-1.20(m,8H)

[0097] [Synthesis Example 2] [ka]

[0098] A 7 mm diameter stainless steel ball was placed in a 1.5 mL stainless steel container. Compound (p-14) (17.9 mg, 0.10 mmol, 1.0 eq), [Rh(COD)OH] (9.1 mg, 0.020 mmol, 0.20 eq), and B(OH) (89.7 mg, 1.0 mmol, 10.0 eq) were weighed and placed in the container. n-BuOH (0.10 mL) was weighed using a microsyringe and similarly placed in the container. An O-shaped Teflon packing was placed between the container and the container, and the container was then sealed with a stainless steel lid and attached to a mixer mill reactor (Retsch MM400). A 7 mm diameter stainless steel ball was placed in a stainless steel vessel of the same weight, and the lid was closed with a Teflon gasket. The vessel was then fixed as a counterpart to a mixer mill reactor. The two vessels were shaken and stirred at a frequency of 30 Hz (equivalent to 1800 rpm) at a reaction temperature of 100 °C for 99 minutes. After the reaction, the mixture was extracted with chloroform, passed through silica gel, and the solvent was removed under reduced pressure using a rotary evaporator. The crude product was purified by silica gel column chromatography (eluent: hexane) and then by gel permeation chromatography (eluent: chloroform) to obtain compound (P-14) (12.8 mg, 0.069 mmol, 69% yield) as a white solid. 1 HNMR(600MHz,CDCl3):δ6.79(s,2H),2.70(m,8H),1.78-1.75(m,8H)

[0099] [Synthesis Example 3] [ka]

[0100] A 7 mm diameter stainless steel ball was placed in a 1.5 mL stainless steel container. Compound (p-30) (22.9 mg, 0.10 mmol, 1.0 eq), [Rh(COD)OH] (9.2 mg, 0.020 mmol, 0.20 eq), and B(OH) (71.2 mg, 0.79 mmol, 7.9 eq) were weighed and placed in the container. n-BuOH (0.10 mL) was weighed using a microsyringe and similarly placed in the container. An O-shaped Teflon packing was placed between the container and the container, and the container was then sealed with a stainless steel lid and attached to a mixer mill reactor (Retsch MM400). A 7 mm diameter stainless steel ball was placed in a stainless steel vessel of the same weight, and the lid was closed with a Teflon gasket. The vessel was then fixed as a counterpart to a mixer mill reactor. The two vessels were shaken and stirred at a frequency of 30 Hz (equivalent to 1800 rpm) at a reaction temperature of 100 °C for 99 minutes. After the reaction, the mixture was extracted with chloroform, passed through silica gel, and the solvent was removed under reduced pressure using a rotary evaporator. The crude product was purified by silica gel column chromatography (eluent: hexane) and then by gel permeation chromatography (eluent: chloroform) to obtain compound (P-30) (19.6 mg, 0.082 mmol, 82% yield) as a white solid. 1 HNMR(600MHz,CDCl3):δ2.58(brs,12H),1.78(brs,12H)

[0101] [Synthesis Example 4] [ka]

[0102] A 7 mm diameter stainless steel ball was placed in a 1.5 mL stainless steel container. Compound (p-36) (21.1 mg, 0.084 mmol, 1.0 eq), [Rh(COD)OH] (8.1 mg, 0.018 mmol, 0.21 eq), and B(OH) (127.4 mg, 1.4 mmol, 17.0 eq) were weighed and placed in the container. n-BuOH (0.20 mL) was weighed using a microsyringe and similarly placed in the container. An O-shaped Teflon packing was placed between the container and the container, and the container was then sealed with a stainless steel lid and attached to a mixer mill reactor (Retsch MM400). A 7 mm diameter stainless steel ball was placed in a stainless steel vessel of the same weight, and the lid was closed with a Teflon gasket. The vessel was then fixed as a counterpart to a mixer mill reactor. The two vessels were shaken and stirred at a frequency of 30 Hz (equivalent to 1800 rpm) at a reaction temperature of 70 °C for 60 minutes. After the reaction, the mixture was extracted with chloroform, passed through silica gel, and the solvent was removed under reduced pressure using a rotary evaporator. The crude product was purified by silica gel column chromatography (eluent: hexane) and then by gel permeation chromatography (eluent: chloroform) to obtain compound (P-36) (17.8 mg, 0.067 mmol, 80% yield) as a white solid. 1 HNMR(600MHz, CDCl3): δ2.76(dd,J=17.2,6.3Hz,3H),2.67-2.42(m,7H),2.05-1.9 5(m,4H),1.92-1.85(m,4H),1.82-1.68(m,4H),1.34(ddd,J=25.0,12.3,3.2Hz,4H)

[0103] [Synthesis Example 5] [ka]

[0104] A 10 mm diameter stainless steel ball was placed in a 5.0 mL stainless steel container. Compound (p-46) (128.3 mg, 0.51 mmol, 1.0 eq), [Rh(COD)OH] (48.4 mg, 0.11 mmol, 0.21 eq), and B(OH) (359.1 mg, 4.0 mmol, 7.8 eq) were weighed and placed in the container. n-BuOH (0.35 mL) was weighed using a microsyringe and similarly placed in the container. An O-shaped Teflon packing was placed between the container and the container, and the container was sealed with a stainless steel lid and attached to a mixer mill reactor (Retsch MM400). A 10 mm diameter stainless steel ball was placed in a stainless steel vessel of the same weight, and the lid was closed with a Teflon gasket. The vessel was then fixed as a counterpart to a mixer mill reactor. The two vessels were shaken and stirred at a frequency of 30 Hz (equivalent to 1800 rpm) at a reaction temperature of 100 °C for 99 minutes. After the reaction, the mixture was extracted with chloroform, passed through silica gel, and the solvent was removed under reduced pressure using a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane) and then by gel permeation chromatography (eluent: chloroform) to obtain compound (P-46) (11.8 mg, 0.045 mmol, 9% yield) as a white solid. 1 HNMR(600MHz,C6D6):δ6.88(s,2H),3.06(t,J=6.2Hz,2H),2.66-2.57(m,5H),2.04-2.00(m,2H),1.85-1. 79(m,2H),1.75-1.71(m,2H),1.51-1.48(m,1H),1.29-1.24(m,2H),1.14-1.03(m,4H),0.90-0.85(m,2H)

[0105] [Synthesis Example 6] [ka]

[0106] A 7 mm diameter stainless steel ball was placed in a 1.5 mL stainless steel container. Compound (p-52) (20.8 mg, 0.091 mmol, 1.0 eq), [Rh(COD)OH] (9.2 mg, 0.020 mmol, 0.22 eq), and B(OH) (71.2 mg, 0.79 mmol, 8.7 eq) were weighed and placed in the container. n-BuOH (0.10 mL) was weighed using a microsyringe and similarly placed in the container. An O-shaped Teflon packing was placed between the container and the container, and the container was sealed with a stainless steel lid and attached to a mixer mill reactor (Retsch MM400). A 7 mm diameter stainless steel ball was placed in a stainless steel vessel of the same weight, and the lid was closed with a Teflon gasket. The vessel was then fixed as a counterpart to a mixer mill reactor. The two vessels were shaken and stirred at a frequency of 30 Hz (equivalent to 1800 rpm) at a reaction temperature of 100 °C for 99 minutes. After the reaction, the mixture was extracted with chloroform, passed through silica gel, and the solvent was removed under reduced pressure using a rotary evaporator. The crude product was purified by silica gel column chromatography (eluent: hexane) and then by gel permeation chromatography (eluent: chloroform) to obtain compound (P-52) (13.9 mg, 0.059 mmol, 63% yield) as a white solid. 1 HNMR(600MHz,C6D6):δ7.43(s,4H),2.79(m,8H),1.64-1.62(m,8H)

[0107] [Synthesis Example 7] [ka]

[0108] A 7 mm diameter stainless steel ball was placed in a 1.5 mL stainless steel container. Compound (p-56) (53.1 mg, 0.10 mmol, 1.0 eq), [Rh(COD)OH] (9.1 mg, 0.020 mmol, 0.20 eq), and B(OH) (71.9 mg, 0.80 mmol, 8.0 eq) were weighed and placed in the container. n-BuOH (0.20 mL) was weighed using a microsyringe and similarly placed in the container. An O-shaped Teflon packing was placed between the container and the container, and the container was then sealed with a stainless steel lid and attached to a mixer mill reactor (Retsch MM400). A 7 mm diameter stainless steel ball was placed in a stainless steel vessel of the same weight, and the lid was closed with a Teflon gasket. The vessel was then fixed as a counterpart to a mixer mill reactor. The two vessels were shaken and stirred at a frequency of 30 Hz (equivalent to 1800 rpm) at a reaction temperature of 100 °C for 99 minutes. After the reaction, the mixture was extracted with chloroform, passed through silica gel, and the solvent was removed under reduced pressure using a rotary evaporator. The crude product was purified by silica gel column chromatography (eluent: hexane) and then by gel permeation chromatography (eluent: chloroform) to obtain compound (P-56) (27.8 mg, 0.051 mmol, 51% yield) as a pale yellow solid. 1 HNMR(600MHz,CDCl3):δ6.97-6.91(m,12H),6.64(d,J=7.6Hz,8H),2.25(m,8H),1.51(m,8H)

[0109] [Synthesis Example 8] [ka]

[0110] A 7 mm diameter stainless steel ball was placed in a 1.5 mL stainless steel container. Compound (p-62) (65.8 mg, 0.20 mmol, 1.0 eq), [Rh(COD)OH] (9.2 mg, 0.020 mmol, 0.10 eq), and B(OH) (151.0 mg, 1.7 mmol, 8.4 eq) were weighed and placed in the container. n-BuOH (0.10 mL) was weighed using a microsyringe and similarly placed in the stainless steel container. An O-shaped Teflon packing was placed between the container and the container, and the container was sealed with a stainless steel lid and attached to a mixer mill reactor (Retsch MM400). A 7 mm diameter stainless steel ball was placed in a stainless steel vessel of the same weight, and the lid was closed with a Teflon gasket. The vessels were then fixed as a mixer mill reactor counterpart. The two vessels were shaken and stirred at a frequency of 30 Hz (equivalent to 1800 rpm) at a reaction temperature of 90 °C for 60 minutes. After the reaction, the mixture was extracted with chloroform, passed through silica gel, and the solvent was removed under reduced pressure using a rotary evaporator. The resulting crude product was purified by gel permeation chromatography (eluent: chloroform) to give compound (P-57) (2.3 mg, 0.0069 mmol, 3.5% yield), compound (P-58) (11.3 mg, 0.034 mmol, 17% yield), compound (P-61) (8.0 mg, 0.023 mmol, 12% yield), and compound (P-62) (6.7 mg, 0.019 mmol, 9.7% yield) as white solids. <Compound (P-57)> 1 HNMR(600MHz,CDCl3):δ8.71(d,J=8.2Hz,1H),8.67-8.65(m,3H),8.43(d,J=8.2Hz,1H),8.15(d,J=8.2Hz, 1H),7.65-7.54(m,6H),3.46(t,J=5.8Hz,2H),3.34(t,J=6.9Hz,2H),2.17-2.12(m,2H),1.75-1.71(m,2H) <Compound (P-58)> 1HNMR (600MHz, CDCl3): δ8.51(d,J=7.6Hz,2H),8.37(d,J=8.2Hz,2H),7.54(t,J=7.2Hz,2H),7.48( t,J=7.2Hz,2H),3.41(t,J=5.8Hz,4H),2.86(t,J=6.9Hz,4H),2.02-1.98(m,4H),1.67-1.63(m,4H) <Compound (P-61)> 1 HNMR (600MHz, CDCl3): δ8.44(d,J=8.2Hz,1H),8.00(d,J=8.2Hz,1H),7.49(t,J=7.6Hz,1H),7.40(t,J=8.2Hz,1H),3.41(t,J=5.8Hz,2H),3. 16(t,J=6.5Hz,2H),3.11-3.09(m,4H),2.82(t,J=7.2Hz,2H),2.79(t,J=6.9Hz,2H)2.04-1.98(m,4H),1.97-1.92(m,2H),1.69-1.58(m,6H) <Compound (P-62)> 1 HNMR (600MHz, CDCl3): δ3.06(t,J=5.5Hz,8H),2.71(t,J=6.9Hz,8H),1.92-1.88(m,8H),1.61-1.57(m,8H)

[0111] [Synthesis example-9] Compound (p-117) is disclosed in Japanese Patent Application Publication No. 2018-184393 and its synthesis method is disclosed.

[0112]

change

[0113] A 7 mm diameter stainless steel ball was placed in a 1.5 mL stainless steel container. Compound (p-117) (43.1 mg, 0.10 mmol, 1.0 eq), [Rh(COD)OH]2 (120.1 mg, 0.044 mmol, 0.44 eq), and B2(OH)4 (90.8 mg, 1.01 mmol, 10.0 eq) were weighed and placed in the container. n-BuOH (0.25 mL) was weighed using a microsyringe and similarly placed in the stainless steel container. An O-shaped Teflon packing was placed between the container and the container, and the container was sealed with a stainless steel lid and attached to a mixer mill reactor (Retsch MM400). A 7 mm diameter stainless steel ball was placed in a stainless steel vessel of the same weight, and the lid was closed with a Teflon gasket. The vessel was then fixed as a counterpart to a mixer mill reactor. The two vessels were shaken and stirred at a frequency of 30 Hz (equivalent to 1800 rpm) at a reaction temperature of 100 °C for 99 minutes. After the reaction, the mixture was extracted with chloroform, passed through silica gel, and the solvent was removed under reduced pressure using a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane) and then by gel permeation chromatography (eluent: chloroform) to obtain compound (P-117) (4.9 mg, 0.011 mmol, 11% yield) as a yellow solid. 1 HNMR(600MHz, CDCl3): δ8.45(d,J=4.4Hz,2H),7.48-7.42(m,2H),3.65(t,J=5.5Hz ,4H),3.15-3.01(m,12H),2.19-2.11(m,4H),2.10-2.01(m,4H),1.72-1.61(m,4H)

[0114] [Synthesis Example 10] Compound (p-121) was synthesized according to the method disclosed in J. Am. Chem. Soc. 2023, 145, 14, 8163-8175.

[0115] [ka]

[0116] A 7 mm diameter stainless steel ball was placed in a 1.5 mL stainless steel container. Compound (p-121) (34.3 mg, 0.10 mmol, 1.0 eq), [Rh(COD)OH] (19.3 mg, 0.042 mmol, 0.40 eq), and B(OH) (133.0 mg, 1.48 mmol, 14.1 eq) were weighed and placed in the container. n-BuOH (0.20 mL) was weighed using a microsyringe and similarly placed in the container. An O-shaped Teflon packing was placed between the container and the container, and the container was sealed with a stainless steel lid and attached to a mixer mill reactor (Retsch MM400). A 7 mm diameter stainless steel ball was placed in a stainless steel vessel of the same weight, and the lid was closed with a Teflon gasket. The vessel was then fixed as a counterpart to a mixer mill reactor. The two vessels were shaken and stirred at a frequency of 30 Hz (equivalent to 1800 rpm) at a reaction temperature of 100 °C for 99 minutes. After the reaction, the mixture was extracted with chloroform, passed through silica gel, and the solvent was removed under reduced pressure using a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane) and then by gel permeation chromatography (eluent: chloroform) to obtain compound (P-121) (21.4 mg, 0.063 mmol, 63% yield) as a white solid. 1 HNMR(600MHz,C6D6):δ7.70(s,1H),7.25(d,J=6.9Hz,1H),7.21(d,J=6.9Hz, 1H),3.20(dd,J=16.2,5.8Hz,1H),3.16-3.02(m,6H),2.97(t,J=5.8Hz,2H), 2.95-2.89(m,1H),2.85-2.77(m,1H),2.72-2.65(m,1H),2.62-2.56(m,1H), 2.00-1.70(m,8H),1.36(qd,J=12.3,3.6Hz,1H),1.28(qd,J=12.3,3.6Hz,1H)

[0117] [Comparative Synthesis Example 1] [ka]

[0118] Compound (p-117) (43.1 mg, 0.10 mmol, 1.0 eq), [Rh(COD)OH]2 (20.0 mg, 0.044 mmol, 0.43 eq), and B2(OH)4 (90.8 mg, 1.01 mmol, 10.0 eq) were weighed into a pressure vessel equipped with a magnetic stirrer, and the pressure vessel was then degassed for 15 minutes. Subsequently, n-BuOH (5 mL) was weighed and added to the reaction mixture. The pressure vessel was sealed, and the reaction was carried out at 80°C for 99 minutes. After the reaction, the mixture was extracted with chloroform and passed through silica gel. Subsequently, the mixture was subjected to liquid separation and extraction with chloroform and aqueous sodium bicarbonate solution. The organic phase was dried with anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure using a rotary evaporator. The crude product obtained was 1 1 HNMR analysis did not confirm the production of compound (P-117).

Claims

1. A method for producing a hydrogenated fused ring compound, comprising the steps of mixing a fused ring compound containing a benzene ring with a rhodium metal complex and diboron using a grinder, and hydrogenating the benzene ring by a mechanochemical reaction.

2. The method according to claim 1, wherein the fused ring compound containing a benzene ring is a compound represented by any one of the following formulas (a-1) to (a-7): 【Chemistry 1】 In the above formulas (a-1) to (a-7), Rings I to V represent a structure represented by the following formula (B) or (C): R １１ ~R １８ , R １９ ~R ２８ , R ２９ ~R ４０ , R ４１ ~R ５２ , R ５３ ~R ５６ , R ５７ ~R ６４ , and R ６５ ~R ７４ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR ７５ R ７６ , or -OR ７７ represents R ７５ ~R ７７ each independently represents an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or an optionally substituted heteroaromatic group having 3 to 30 carbon atoms; R １１ ~R １８ , R １９ ~R ２８ , R ２９ ~R ４０ , R ４１ ~R ５２ , R ５３ ~R ５６ , R ５７ ~R ６４ , and R ６５ ~R ７４ Two adjacent groups may be bonded to each other to form a ring; 【Chemistry 2】 In formulas (B) and (C), * represents a bond; R ａ ~R ｄ and R ｅ ~R ｌ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR ７８ R ７９ , or -OR ８０ represents; R ７８ ~R ８０ each independently represents an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or an optionally substituted heteroaromatic group having 3 to 30 carbon atoms; R ａ ~R ｄ Among these, two adjacent groups may be bonded to each other to form a ring.

3. In the above formulas (a-1) to (a-7), R １１ ~R １８ , R １９ ~R ２８ , R ２９ ~R ４０ , R ４１ ~R ５２ , R ５３ ~R ５６ , R ５７ ~R ６４ , and R ６５ ~R ７４ The method according to claim 2, wherein two adjacent groups of the formula (I) are not bonded to each other to form a ring.

4. In the above formulas (a-1) to (a-7), R １１ ~R １８ , R １９ ~R ２８ , R ２９ ~R ４０ , R ４１ ~R ５２ , R ５３ ~R ５６ , R ５７ ~R ６４ , and R ６５ ~R ７４ each independently represents a hydrogen atom, 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 n-octyl group, an n-decyl group, an n-dodecyl group, an n-octadecyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, -NR ７８ R ７９ , and -OR ８０ is at least one group selected from the group consisting of R ７８ ~R ８０ are each independently at least one group selected from the group consisting of a hydrogen atom, a benzyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, and an optionally substituted dibenzothienyl group.

5. In the above formulas (a-1) to (a-7), R ａ ~R ｄ and R ｅ ~R ｌ The method according to claim 4, wherein all of are hydrogen atoms.

6. The method according to claim 1, wherein the pulverizer is at least one selected from the group consisting of a ball mill, a bead mill, a rod mill, a jet mill, and a rocking mill.

7. The rhodium metal complex is Rh(PPh ３ ) ３ Cl, [Rh(COD)Cl] ２ [Rh(C ２ H ４ ) Cl] ２ , [Rh(COD)OH] ２ , and Rh(COD) ２ BF ４ The method according to claim 1, wherein the compound is at least one selected from the group consisting of:

8. The diboron is B ２ (OH) ４ , B ２ (pin) ２ , B ２ (cat) ２ , and B ２ (neop) ２ The method according to claim 1, wherein the compound is at least one selected from the group consisting of:

9. The method according to claim 1 , wherein the mechanochemical reaction is carried out in the presence of a solvent additive.

10. 10. The method of claim 9, wherein the solvent-based additive is selected from the group consisting of methanol, ethanol, propanol, butanol, pentanol, and ethylene glycol.

11. The method according to claim 1, wherein the reaction temperature in the mechanochemical reaction is 50°C or higher.

12. The method according to claim 11, wherein the reaction temperature in the mechanochemical reaction is 90°C or higher.

13. A hydrogenated fused ring compound represented by any one of the following formulas (D) to (F): 【Transformation 3】 In the above formulas (D) to (F), Rings I to V represent a structure represented by the following formula (G) or (H): R Ａ１ ~R Ａ４ , R Ａ５ ~R Ａ２８ , and R Ａ２９ ~R Ａ３８ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR Ａ３９ R Ａ４０ , or -OR Ａ４１ represents R Ａ３９ ~R Ａ４１ each independently represents an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or an optionally substituted heteroaromatic group having 3 to 30 carbon atoms; R Ａ１ ~R Ａ４ , R Ａ５ ~R Ａ２８ , and R Ａ２９ ~R Ａ３８ Two adjacent groups may be bonded to each other to form a ring; 【Chemistry 4】 In formulas (G) and (H), * represents a bond; R Ａａ ~R Ａｄ and R Ａｅ ~R Ａｌ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR Ａ４２ R Ａ４３ , or -OR Ａ４４ represents; R Ａ４２ ~R Ａ４４ each independently represents an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or an optionally substituted heteroaromatic group having 3 to 30 carbon atoms; R Ａａ ~R Ａｄ Among these, two adjacent groups may be bonded to each other to form a ring.

14. In the above formulas (D) to (F), R Ａ１ ~R Ａ４ , R Ａ５ ~R Ａ２８ , and R Ａ２９ ~R Ａ３８ The hydrogenated fused ring compound according to claim 13 , wherein two adjacent groups of the formula (I) are not bonded to each other to form a ring.

15. In the above formulas (D) to (F), R Ａ１ ~R Ａ４ , R Ａ５ ~R Ａ２８ , and R Ａ２９ ~R Ａ３８ each independently represents a hydrogen atom, 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, an n-pentyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, an n-octadecyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, -NR Ａ３９ R Ａ４０ , and -OR Ａ４１ is at least one group selected from the group consisting of R Ａ３９ ~R Ａ４１ are each independently at least one group selected from the group consisting of a hydrogen atom, a benzyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, an optionally substituted trimethylsilyl group, an optionally substituted phenyldimethylsilyl group, an optionally substituted diphenylmethylsilyl group, an optionally substituted acetyl group, and an optionally substituted benzoyl group.

16. In the above formulas (D) to (F), R Ａａ ~R Ａｄ and R Ａｅ ~R Ａｌ The hydrogenated fused ring compound according to claim 15, wherein all of are hydrogen atoms.

17. An organic thin film comprising a material for a photoelectric conversion device, the material comprising the hydrogenated fused ring compound according to any one of claims 13 to 16.

18. A photoelectric conversion element comprising a material for a photoelectric conversion element, the material comprising the hydrogenated fused ring compound according to any one of claims 13 to 16.

19. A photoelectric conversion element for an imaging device, comprising a material for a photoelectric conversion element containing the hydrogenated fused ring compound according to any one of claims 13 to 16.

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