Compound and organic semiconductor material

Abstract

To provide a novel organic compound that can serve as an organic semiconductor material.SOLUTION: Provided is a compound represented by the following general formula (1) (where R101, R102, R103, R104, R105, R106, R107, R108, R109, R110, R111, R112, R113, R114, R115, R116, R117, and R118 each independently represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylethynyl group, an arylethynyl group, a trialkylsilyl ethynyl group, or a trialkylsilyl group; and n11 and n12 each independently represent 0 or 1).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to compounds and organic semiconductor materials. [Background technology]

[0002] It is expected that the use of organic compounds as semiconductor materials or light-emitting materials will lead to the realization of electronic devices that are lightweight, have excellent design, and are highly energy efficient. The discovery of organic semiconductor molecules such as pentacene and rubrene that exhibit high carrier mobility (sometimes simply referred to as "mobility" in this specification) has led to the search for organic compounds that exhibit even higher mobility. As a result, it has been reported that various polycyclic π-conjugated compounds can be used as semiconductor materials.

[0003] For example, it has been disclosed that a compound containing at least one biphenylene ring as a partial structure can form an organic semiconductor film that exhibits high carrier mobility, a high ON / OFF ratio, and high durability (see Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2007-208032 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, organic compounds have a wide variety of structures, and even now, organic compounds that can be used as organic semiconductor materials have not been sufficiently explored.

[0006] An object of the present invention is to provide a novel organic compound that can be used as an organic semiconductor material. [Means for solving the problem]

[0007] In order to solve the above problems, the present invention employs the following configuration. [1] The following general formula (1)

[0008] [ka] (In the formula, R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 , R 110 , R 111 , R 112 , R 113 , R 114 , R 115 , R 116 , R 117 and R 118 each independently represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylethynyl group, an arylethynyl group, a trialkylsilylethynyl group, or a trialkylsilyl group; 11 and n 12 are each independently 0 or 1. A compound represented by the formula: [2] R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 , R 110 , R 111 , R 112 , R 113 , R 114 , R 115 , R 116 , R 117 and R 118are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms. [3] The compound represented by the general formula (1) is represented by the following general formula (11):

[0009] [ka] (In the formula, R 1011 , R 1041 , R 1051 , R 1081 , R 1111 and R 1121 each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms; 11 and n 12 is the same as above.) The compound according to [1], which is a compound represented by the formula: [4] The following general formula (2)

[0010] [ka] (In the formula, R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 , R 209 , R 210 , R 211 , R 212 , R 213 , R 214 , R 215 , R 216 , R 217 , R 218 , R 219 , R 220 , R221 , R 222 , R 223 and R 224 each independently represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylethynyl group, an arylethynyl group, a trialkylsilylethynyl group, or a trialkylsilyl group; 21 , n 22 and n 23 are each independently 0 or 1. A compound represented by the formula: [5] R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 , R 209 , R 210 , R 211 , R 212 , R 213 , R 214 , R 215 , R 216 , R 217 , R 218 , R 219 , R 220 , R 221 , R 222 , R 223 and R 224 are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms. [6] The compound represented by the general formula (2) is represented by the following general formula (21):

[0011] [ka] (In the formula, R 2031 , R 2041 , R 2091 , R 2101 , R 2151 and R 2161each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms; 21 , n 22 and n 23 is the same as above.) The compound according to [4], which is a compound represented by the formula: [7] The following general formula (3)

[0012] [ka] (In the formula, R 301 , R 302 , R 303 , R 304 , R 305 , R 306 , R 307 , R 308 , R 309 , R 310 , R 311 , R 312 , R 313 , R 314 , R 315 , R 316 , R 317 , R 318 , R 319 and R 320 each independently represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylethynyl group, an arylethynyl group, a trialkylsilylethynyl group, or a trialkylsilyl group; 31 and n 32 are each independently 0 or 1. A compound represented by the formula: [8] R 301 , R 302 , R 303 , R 304 , R 305 , R 306 , R 307 , R 308 , R 309 , R 310 , R 311 , R 312, R 313 , R 314 , R 315 , R 316 , R 317 , R 318 , R 319 and R 320 are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms. [9] The compound represented by the general formula (3) is represented by the following general formula (31):

[0013] [ka] (In the formula, R 3011 , R 3021 , R 3051 , R 3061 , R 3091 , R 3101 , R 3131 and R 3141 each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms; 31 and n 32 is the same as above.) The compound according to [7], which is a compound represented by the formula:

[10] An organic semiconductor material comprising the compound according to any one of [1] to [9]. Effect of the Invention

[0014] According to the present invention, there is provided a novel organic compound that can be used as an organic semiconductor material. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] In this specification, the following abbreviations for functional groups or compounds may be used. Me: Methyl group (-CH 3 ) Et: Ethyl group (-CH 2 CH 3 ) n-Bu: n-butyl group (-(CH 2 ) 3 CH 3 ) Ac: Acetyl group (-C(=O)-CH 3 ) Ph: Phenyl group (-C 6 H 5 )

[0016] In this specification, the concentration unit "M" means "mol / L".

[0017] In this specification, when a compound is represented by a general formula or other formula (non-generalized formula, sometimes simply referred to as "formula" in this specification), a symbol may be added to the general formula or other formula. In such cases, the compound may be given a name with the symbol added. For example, a compound represented by the general formula (1) described below may be referred to as "compound (1)" in this specification.

[0018] <<Compound (1)>> The compound according to one embodiment of the present invention is represented by the following general formula (1):

[0019] [ka] (In the formula, R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 , R 110 , R 111 , R 112 , R 113 , R 114 , R115 , R 116 , R 117 and R 118 each independently represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylethynyl group, an arylethynyl group, a trialkylsilylethynyl group, or a trialkylsilyl group; 11 and n 12 are each independently 0 or 1. (In this specification, this compound may be referred to as "compound (1)").

[0020] Compound (1) is a compound having a biphenylene ring structure, i.e., R 102 , R 103 , R 104 , R 105 , R 106 and R 107 and a biphenylene ring skeleton having R 109 , R 110 , R 111 , R 112 , R 113 and R 114 The biphenylene ring structure having the formula (I) is linked to the compound (1), and the linking portion forms a pentalene ring structure, which has antiaromaticity. Compound (1) having such a structure is a novel compound, and can be used as an organic semiconductor material by itself, and is suitable for forming a novel organic semiconductor material.

[0021] In the general formula (1), R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 , R 110 , R 111 , R 112 , R 113 , R 114 , R 115 , R 116 , R 117 and R 118 (In the present specification, these groups are collectively referred to as "R101 ~R 118 ") are each independently a hydrogen atom (-H), an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylethynyl group, an arylethynyl group, a trialkylsilylethynyl group, or a trialkylsilyl group. R 101 ~R 118 may all be the same, may all be different, or may only be partially the same. 101 ~R 118 When two or more of the above are different from each other, their combination can be arbitrarily selected depending on the purpose, and is not particularly limited.

[0022] In this specification, unless otherwise specified, the term "group" includes not only an atomic group formed by bonding multiple atoms, but also a single atom.

[0023] R 101 ~R 118 The alkyl group in may be linear, branched or cyclic, and may have both a chain structure (linear or branched) and a cyclic structure. When the alkyl group has a cyclic structure, including the case where the alkyl group is cyclic, the cyclic structure may be either monocyclic or polycyclic.

[0024] R 101 ~R 118 The alkyl group in the formula (I) preferably has 1 to 18 carbon atoms.

[0025] R 101 ~R 118Among the alkyl groups in the above, examples of the chain (straight-chain or branched-chain) alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a 1-methylbutyl group, an n-hexyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, an n-heptyl group, a 2-methylhexyl group, a Examples of chain alkyl groups having 1 to 18 carbon atoms include a chain alkyl group having 1 to 18 carbon atoms, such as a 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group.

[0026] R 101 ~R 118 Among the alkyl groups in the above formula, examples of the cyclic (monocyclic or polycyclic) alkyl group include cyclic alkyl groups having 3 to 18 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a norbornyl group, an isobornyl group, a 1-adamantyl group, a 2-adamantyl group, and a tricyclodecyl group.

[0027] R 101 ~R 118 The alkyl group in the formula may have any one of 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, and 1 to 2 carbon atoms, for example.

[0028] R 101 ~R 118 The aryl group in the formula (I) may be either monocyclic or polycyclic. R 101 ~R 118Examples of the aryl group in the above formula include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 4-methylphenyl group (p-tolyl group), a 3-methylphenyl group (m-tolyl group), a 2-methylphenyl group (o-tolyl group), a 2,3-dimethylphenyl group (2,3-xylyl group), a 2,4-dimethylphenyl group (2,4-xylyl group), a 2,5-dimethylphenyl group (2,5-xylyl group), a 2,6-dimethylphenyl group (2,6-xylyl group), a 3,4-dimethylphenyl group (3,4-xylyl group), a 3,5-dimethylphenyl group (3,5-xylyl group), and a 2,4,6-trimethylphenyl group (mesityl group). R 101 ~R 118 In the above-mentioned aryl group, one or more hydrogen atoms of the aryl group may be further substituted with these aryl groups, or R 101 ~R 118 Also included are groups substituted with the above alkyl groups.

[0029] R 101 ~R 118 The aryl group in the above formula (I) preferably has 6 to 18 carbon atoms, and may have, for example, any one of 6 to 15, 6 to 10, and 6 to 8 carbon atoms.

[0030] In this specification, the "number of carbon atoms in an aryl group" means the number of carbon atoms including that of the substituent in the case of an aryl group having the above-mentioned substituent.

[0031] R 101 ~R 118 The alkoxy group in R 101 ~R 118 In the above-mentioned alkyl group, a carbon atom having a free valence is bonded to an oxygen atom (-O-).

[0032] R 101 ~R 118The alkoxy group in may be linear, branched or cyclic, and may have both a chain structure (linear or branched) and a cyclic structure. When the alkoxy group has a cyclic structure, including the case where the alkoxy group is cyclic, the cyclic structure may be either monocyclic or polycyclic.

[0033] R 101 ~R 118 The alkoxy group in the formula (I) preferably has 1 to 10 carbon atoms.

[0034] R 101 ~R 118 Among the alkoxy groups in the above, examples of the chain (straight-chain or branched-chain) alkyl group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentyloxy group, an isopentyloxy group, a neopentyloxy group, a tert-pentyloxy group, a 1-methylbutyloxy group, an n-hexyloxy group, a 2-methylpentyloxy group, a 3-methylpentyloxy group, a 2,2-dimethylbutyloxy group, a 2,3- Examples of such alkyl groups include chain alkoxy groups having 1 to 10 carbon atoms, such as a dimethylbutyloxy group, an n-heptyloxy group, a 2-methylhexyloxy group, a 3-methylhexyloxy group, a 2,2-dimethylpentyloxy group, a 2,3-dimethylpentyloxy group, a 2,4-dimethylpentyloxy group, a 3,3-dimethylpentyloxy group, a 3-ethylpentyloxy group, a 2,2,3-trimethylbutyloxy group, an n-octyloxy group, an isooctyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, and a decyloxy group.

[0035] R 101 ~R 118Among the alkoxy groups in the above, examples of the cyclic (monocyclic or polycyclic) alkoxy group include cyclic alkoxy groups having 3 to 10 carbon atoms, such as a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, a cyclononyloxy group, a cyclodecyloxy group, a norbornyloxy group, an isobornyloxy group, a 1-adamantyloxy group, a 2-adamantyloxy group, and a tricyclodecyloxy group.

[0036] R 101 ~R 118 The alkoxy group in the formula may have any one of 1 to 8 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, and 1 to 2 carbon atoms, for example.

[0037] R 101 ~R 118 The aryloxy group in R 101 ~R 118 In the above formula, a carbon atom having a free valence in the aryl group is bonded to an oxygen atom (-O-).

[0038] R 101 ~R 118 The aryloxy group in the above formula may be either monocyclic or polycyclic. R 101 ~R 118Examples of the aryloxy group in the above formula include a phenyloxy group (phenoxy group), a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenyloxy group (p-tolyloxy group), a 3-methylphenyloxy group (m-tolyloxy group), a 2-methylphenyloxy group (o-tolyloxy group), a 2,3-dimethylphenyloxy group (2,3-xylyloxy group), a 2,4-dimethylphenyloxy group (2,4-xylyloxy group), a 2,5-dimethylphenyloxy group (2,5-xylyloxy group), a 2,6-dimethylphenyloxy group (2,6-xylyloxy group), a 3,4-dimethylphenyloxy group (3,4-xylyloxy group), a 3,5-dimethylphenyloxy group (3,5-xylyloxy group), and a 2,4,6-trimethylphenyloxy group (mesityloxy group). R 101 ~R 118 In the aryloxy group in the above, one or more hydrogen atoms of the aryl group are further 101 ~R 118 The aryl group in 101 ~R 118 Also included are groups substituted with the above alkyl groups.

[0039] R 101 ~R 118 The aryloxy group in the above formula (I) preferably has 6 to 15 carbon atoms, and may have, for example, 6 to 10 or 6 to 8 carbon atoms.

[0040] R 101 ~R 118 In the alkylethynyl group, the hydrogen atom (-H) in the ethynyl group (-C≡CH) is 101 ~R 118 Examples of the monovalent group include a monovalent group having a structure substituted with the alkyl group as described above. The alkylethynyl group is, in other words, an alk-1-yn-1-yl group.

[0041] R 101 ~R 118The alkylethynyl group in the formula (I) may have only a chain structure (which may be a straight-chain structure or a branched-chain structure), or may have both a chain structure and a cyclic structure, and the cyclic structure may be either a monocyclic structure or a polycyclic structure.

[0042] R 101 ~R 118 The alkylethynyl group in the formula (I) preferably has 3 to 12 carbon atoms.

[0043] R 101 ~R 118 Among the alkylethynyl groups in the above, examples of groups having only a chain structure include a methylethynyl group (prop-1-yn-1-yl group, -C≡C-CH 3 ), ethylethynyl group, n-propylethynyl group, isopropylethynyl group, n-butylethynyl group, isobutylethynyl group, sec-butylethynyl group, tert-butylethynyl group, n-pentylethynyl group, isopentylethynyl group, neopentylethynyl group, tert-pentylethynyl group, 1-methylbutylethynyl group, n-hexylethynyl group, 2-methylpentylethynyl group, 3-methylpentylethynyl group, 2,2-dimethylbutylethynyl group, 2,3-dimethylbutylethynyl group, n-heptylethynyl group, 2-methylhexylethynyl group, 3-methylhexylethynyl group, 2,2-dimethylpentylethynyl group, 2,3-dimethylpentylethynyl group, 2,4-dimethylpentylethynyl group, 3,3-dimethylpentylethynyl group, 3-ethylpentylethynyl group, 2,2,3-trimethylbutylethynyl group, n-octylethynyl group, isooctylethynyl group, 2-ethylhexylethynyl group, nonylethynyl group, decylethynyl group (dodec-1-yn-1-yl group, -C≡CC 10 H 21 ) and the like.

[0044] R 101 ~R 118 Among the alkylethynyl groups in the above, examples of the group having a cyclic structure include a cyclopropylethynyl group (-C≡C-CHCH2 CH 2 ), a cyclobutylethynyl group, a cyclopentylethynyl group, a cyclohexylethynyl group, a cycloheptylethynyl group, a cyclooctylethynyl group, a cyclononylethynyl group, a cyclodecylethynyl group, a norbornylethynyl group, an isobornylethynyl group, a 1-adamantylethynyl group, a 2-adamantylethynyl group, and a tricyclodecylethynyl group.

[0045] R 101 ~R 118 The alkylethynyl group in the formula (I) may have any one of 3 to 10, 3 to 8, 3 to 6, and 3 to 4 carbon atoms.

[0046] R 101 ~R 118 In the above-mentioned arylethynyl group, a hydrogen atom (-H) in the ethynyl group (-C≡CH) is 101 ~R 118 Examples of the monovalent group include a monovalent group having a structure substituted with an aryl group as described above.

[0047] R 101 ~R 118 The cyclic structure in the arylethynyl group in the above formula may be either a monocyclic structure or a polycyclic structure. R 101 ~R 118 The arylethynyl group in the formula (I) is, for example, a phenylethynyl group (-C≡CC 6 H 5), 1-naphthylethynyl group, 2-naphthylethynyl group, 4-methylphenylethynyl group (p-tolylethynyl group), 3-methylphenylethynyl group (m-tolylethynyl group), 2-methylphenylethynyl group (o-tolylethynyl group), 2,3-dimethylphenylethynyl group (2,3-xylylethynyl group), 2,4-dimethylphenylethynyl group (2,4-xylylethynyl group), 2,5-dimethylphenylethynyl group (2,5-xylylethynyl group), 2,6-dimethylphenylethynyl group (2,6-xylylethynyl group), 3,4-dimethylphenylethynyl group (3,4-xylylethynyl group), 3,5-dimethylphenylethynyl group (3,5-xylylethynyl group), 2,4,6-trimethylphenylethynyl group (mesitylethynyl group), and the like. R 101 ~R 118 In the above-mentioned arylethynyl group, one or more hydrogen atoms of the above-mentioned arylethynyl group are further 101 ~R 118 The aryl group in 101 ~R 118 Also included are groups substituted with the above alkyl groups.

[0048] R 101 ~R 118 The arylethynyl group in the above formula (I) preferably has 8 to 17 carbon atoms, and may have, for example, 8 to 12 or 8 to 10 carbon atoms.

[0049] R 101 ~R 118 In the trialkylsilyl group, the three alkyl groups bonded to the silicon atom are the same as those in the above R 101 ~R 118 The alkyl groups mentioned above are the same as those mentioned above.

[0050] R 101 ~R 118In the trialkylsilyl group, the three alkyl groups bonded to the silicon atom may be the same or different, or only some (i.e., only two) may be the same. When the two or three alkyl groups bonded to the silicon atom are different from one another, the combination of these alkyl groups can be arbitrarily selected depending on the purpose and is not particularly limited.

[0051] R 101 ~R 118 The trialkylsilyl group in the formula (i.e., the total number of carbon atoms in the three alkyl groups) preferably has 3 to 12 carbon atoms, and may be, for example, 3 to 9 or 3 to 6. Preferred examples of the trialkylsilyl group include tripropylsilyl groups such as trimethylsilyl group (TMS), triethylsilyl group (TES), and triisopropylsilyl group (TIPS), tributylsilyl group, and tert-butyldimethylsilyl group (TBDMS).

[0052] R 101 ~R 118 In the trialkylsilylethynyl group, a hydrogen atom (-H) in the ethynyl group (-C≡CH) is 101 ~R 118 Examples of the monovalent group include a monovalent group having a structure substituted with a trialkylsilyl group as described above.

[0053] R 101 ~R 118 The trialkylsilylethynyl group in the formula (I) preferably has 5 to 14 carbon atoms, and may have, for example, 5 to 11 or 5 to 8 carbon atoms. Preferred examples of the trialkylsilylethynyl group include tripropylsilylethynyl groups such as a trimethylsilylethynyl group (-C≡C-TMS), a triethylsilylethynyl group (-C≡C-TES), a triisopropylsilylethynyl group (-C≡C-TIPS), a tributylsilylethynyl group, and a tert-butyldimethylsilylethynyl group (-C≡C-TBDMS).

[0054] In the general formula (1), n 11 and n 12 are each independently 0 or 1. That is, (n 11 , n 12 ) combinations include (0,0), (0,1), (1,0), and (1,1). Among these, compound (1) is particularly preferred in terms of ease of production. 11 and n 12 are preferably all 0 or 1.

[0055] n 11 and n 12 When both are 0, the compound is represented by the following general formula (1A) (in this specification, this compound may be referred to as "compound (1A)").

[0056] [ka] (In the formula, R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 , R 110 , R 111 , R 112 , R 113 and R 114 are the same as above and may be the same or different.)

[0057] n 11 and n 12 When both are 1, the compound is represented by the following general formula (1B) (in this specification, this compound may be referred to as "compound (1B)").

[0058] [ka] (In the formula, R 101 , R 102, R 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 , R 110 , R 111 , R 112 , R 113 , R 114 , R 115 , R 116 , R 117 and R 118 are the same as above and may be the same or different.)

[0059] The compound (1A) has a skeleton in which benzene ring skeletons are bonded to each other to form a four-membered ring, that is, two biphenylene ring skeletons. Compound (1B) has a skeleton in which a benzene ring skeleton and a naphthalene ring skeleton are bonded to each other while forming a four-membered ring, and this skeleton contains one biphenylene ring skeleton. Compound (1B) has two such biphenylene ring skeletons.

[0060] In the general formula (1), R 101 ~R 118 are preferably each independently a hydrogen atom, an alkyl group, an aryl group, an alkylethynyl group, an arylethynyl group, a trialkylsilylethynyl group, or a trialkylsilyl group, and more preferably each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms.

[0061] In the general formula (1), R 101 and R 108are preferably each independently a hydrogen atom, an alkyl group, an aryl group, an alkylethynyl group, an arylethynyl group, a trialkylsilylethynyl group, or a trialkylsilyl group, more preferably each independently an alkyl group, an aryl group, an alkylethynyl group, an arylethynyl group, a trialkylsilylethynyl group, or a trialkylsilyl group, and further preferably each independently an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms.

[0062] In the general formula (1), R 102 , R 103 , R 106 , R 107 , R 109 , R 110 , R 113 , R 114 , R 115 , R 116 , R 117 and R 118 Preferably, one or more selected from the group consisting of is a hydrogen atom, and R 102 , R 103 , R 106 , R 107 , R 109 , R 110 , R 113 , R 114 , R 115 , R 116 , R 117 and R 118 More preferably, all of are hydrogen atoms.

[0063] In the general formula (1), R 104 , R 105 , R 111 and R 112are preferably each independently a hydrogen atom, an alkyl group, an aryl group, an alkylethynyl group, an arylethynyl group, a trialkylsilylethynyl group, or a trialkylsilyl group, more preferably each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms, and further preferably a hydrogen atom.

[0064] The compound (1) is preferably a compound represented by the following general formula (11).

[0065] [ka] (In the formula, R 1011 , R 1041 , R 1051 , R 1081 , R 1111 and R 1121 each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms; 11 and n 12 is the same as above.)

[0066] In the general formula (11), R 1011 , R 1041 , R 1051 , R 1081 , R 1111 and R 1121 (In the present specification, these groups are collectively referred to as "R 1011 ~R 1121 ") are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms. R 1011 ~R 1121 may all be the same, may all be different, or may only be partially the same. 1011 ~R 1121 When two or more of the above are different from each other, the combination thereof is not particularly limited.

[0067] R 1011 ~R 1121 The alkyl group having 1 to 18 carbon atoms in R 101 ~R 118 Among the alkyl groups in the above, the alkyl group having 1 to 18 carbon atoms is the same as the alkyl group having 1 to 18 carbon atoms. R 1011 ~R 1121 The alkyl group in may be linear, branched or cyclic, and may have both a chain structure (linear or branched) and a cyclic structure. When the alkyl group has a cyclic structure, including the case where the alkyl group is cyclic, the cyclic structure may be either monocyclic or polycyclic. R 1011 ~R 1121 The alkyl group in the formula may have any one of 1 to 8 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, and 1 to 2 carbon atoms, for example.

[0068] R 1011 ~R 1121 The aryl group having 6 to 18 carbon atoms in R 101 ~R 118 Among the aryl groups in the above formula, the aryl group is the same as the aryl group having 6 to 18 carbon atoms. R 1011 ~R 1121 The aryl group in the formula (I) may be either monocyclic or polycyclic. R 1011 ~R 1121 The aryl group in the formula (I) may have, for example, 6 to 10 carbon atoms or 6 to 8 carbon atoms.

[0069] R 1011 ~R 1121 The alkylethynyl group having 3 to 12 carbon atoms in R 101 ~R118 Among the alkylethynyl groups in the above formula, the alkylethynyl group is the same as the alkylethynyl group having 3 to 12 carbon atoms. R 1011 ~R 1121 The alkylethynyl group in the formula (I) may have only a chain structure (which may be a straight-chain structure or a branched-chain structure), or may have both a chain structure and a cyclic structure, and the cyclic structure may be either a monocyclic structure or a polycyclic structure. R 1011 ~R 1121 The alkylethynyl group in the formula (I) may have any one of 3 to 10, 3 to 8, 3 to 6, and 3 to 4 carbon atoms.

[0070] R 1011 ~R 1121 The arylethynyl group having 8 to 17 carbon atoms in R 101 ~R 118 Among the arylethynyl groups in the above formula, the arylethynyl group is the same as the arylethynyl group having 8 to 17 carbon atoms. R 1011 ~R 1121 The cyclic structure in the arylethynyl group in the above formula may be either a monocyclic structure or a polycyclic structure. R 1011 ~R 1121 The arylethynyl group in the formula (I) may have, for example, 8 to 12 or 8 to 10 carbon atoms.

[0071] R 1011 ~R 1121 The trialkylsilylethynyl group having 5 to 14 carbon atoms in R 101 ~R 118 Among the trialkylsilylethynyl groups in the above formula, the trialkylsilylethynyl group has 5 to 14 carbon atoms. R 1011 ~R 1121 The trialkylsilylethynyl group in the formula (I) may have, for example, 5 to 11 or 5 to 8 carbon atoms.

[0072] R 1011 ~R 1121The trialkylsilyl group having 3 to 12 carbon atoms in R 101 ~R 118 Among the trialkylsilyl groups in the above formula, the trialkylsilyl group is the same as the trialkylsilyl group having 3 to 12 carbon atoms. R 1011 ~R 1121 The number of carbon atoms in the trialkylsilyl group (that is, the total number of carbon atoms in the three alkyl groups) in the formula (I) may be, for example, any one of 3 to 9 and 3 to 6.

[0073] In the general formula (11), R 1011 and R 1081 are preferably each independently an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms.

[0074] In the general formula (11), R 1041 , R 1051 , R 1111 and R 1121 are each independently preferably a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms, and more preferably a hydrogen atom.

[0075] In the general formula (11), n 11 and n 12 Each of n in the general formula (1) is 11 and n 12 is the same as:

[0076] Preferable examples of compound (1) are shown below, however, compound (1) is not limited thereto.

[0077] [ka]

[0078] [ka]

[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082] When the electronic state of compound (1) is predicted by performing quantum chemical calculations using a known method described later in the Examples, the energy level of the HOMO (Highest Occupied Molecular Orbital) is preferably −5.3 to −4.7 eV, the energy level of the LUMO (Lowest Unoccupied Molecular Orbital) is preferably −3.3 to −2.3 eV, and the HOMO-LUMO energy gap (EGap) is preferably 1.8 to 3.5 eV. Compound (1) has an appropriate HOMO energy level and a molecular structure in which the π-electron conjugated system is easily in contact with each other over a wide range, and thus satisfies the conditions for exhibiting high carrier mobility. Such compound (1) is suitable, for example, as an organic semiconductor material.

[0083] <<Method for producing compound (1)>> Compound (1) is, for example, a compound represented by the following general formula (01a):

[0084] [ka] (In the formula, R 101, R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , R 115 , R 116 and n 11 is the same as above; X 1a is a leaving group.) (hereinafter, may be referred to as "compound (01a)") represented by the following formula: The following general formula (01b)

[0085] [ka] (In the formula, R 108 , R 109 , R 110 , R 111 , R 112 , R 113 , R 114 , R 117 , R 118 and n 12 is the same as above; X 1b is a leaving group.) (Herein, this may be referred to as "compound (01b)") is reacted with the following general formula (1):

[0086] [ka] (In the formula, R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 , R 110 , R 111 , R 112 , R 113 , R 114 , R 115 , R 116 , R 117 , R 118 , n 11 and n 12is the same as above.) The compound (compound (1)) represented by the following formula (sometimes referred to as "reaction step (1)" in this specification) can be produced by a production method having a step of obtaining a compound represented by the following formula (compound (1)): The reaction between compound (01a) and compound (01b) is a reaction for linking these compounds through a condensed ring. However, the method for producing compound (1) is not limited to this.

[0087] In the general formula (01a), X 1a and X in the general formula (01b) 1b are each independently a leaving group, and X 1a and X 1b may be the same or different, and are preferably the same. Examples of the leaving group include halogen atoms such as a chlorine atom (-Cl), a bromine atom (-Br), and an iodine atom (-I).

[0088] Compound (01a) and compound (01b) may be the same or different. When compound (01a) and compound (01b) are identical to each other, a compound that is symmetrical in the molecular length direction (in other words, the linking direction of the hydrocarbon rings) to compound (1) is obtained. On the other hand, when compound (01a) and compound (01b) are different from each other, a compound that is asymmetric in the molecular length direction is obtained as compound (1).

[0089] The reaction between compound (01a) and compound (01b) can be carried out in the presence of a palladium catalyst. The palladium catalyst is, for example, palladium(II) acetate (Pd(OAc) 2 ) etc.

[0090] The reaction of compound (01a) with compound (01b) is preferably carried out in the presence of a palladium catalyst and tetraalkylammonium acetate. The tetraalkylammonium acetate is, for example, tetrabutylammonium acetate (n-Bu 4 NOAc) and the like.

[0091] In the reaction step (1), the amount (mol) of the palladium catalyst used is preferably 0.02 to 0.3 times, and more preferably 0.03 to 0.2 times, the total amount (mol) of compound (01a) and compound (01b) used.

[0092] In the reaction step (1), the amount (mol) of the tetraalkylammonium acetate used is preferably 0.9 to 2 times, and more preferably 0.9 to 1.3 times, the total amount (mol) of the compound (01a) and the compound (01b) used.

[0093] The reaction between compound (01a) and compound (01b) is preferably carried out in the presence of a solvent. The solvent is preferably one capable of dissolving compound (01a) and compound (01b), and is preferably an organic solvent. Preferred examples of the organic solvent include amides such as N,N-dimethylformamide (DMF).

[0094] In this specification, unless otherwise specified, the term "solvent" is a concept that encompasses both a component that is liquid at room temperature and that dissolves a solute, and a component that is liquid at room temperature and that functions as a dispersion medium for dispersing a dispersoid.

[0095] In the reaction step (1), the amount of the solvent used is not particularly limited. For example, the amount of the solvent used may be any of 15 to 100 mL, 15 to 70 mL, and 15 to 40 mL per 1 g of the total amount of the compound (01a), the compound (01b), the palladium catalyst, and the tetraalkylammonium acetate used.

[0096] The reaction between compound (01a) and compound (01b) is preferably carried out in an environment with reduced concentrations of moisture and oxygen gas. For example, the reaction between compound (01a) and compound (01b) is preferably carried out under an inert gas atmosphere. Examples of the inert gas include helium gas, argon gas, and nitrogen gas.

[0097] The reaction temperature during the reaction of compound (01a) with compound (01b) can be appropriately adjusted depending on the types of components used, such as the type of solvent, etc. In general, the reaction temperature is preferably 100 to 150°C, more preferably 120 to 140°C. The reaction time of the compound (01a) and the compound (01b) can be appropriately adjusted depending on, for example, the reaction temperature. Usually, the reaction time is preferably 1 to 24 hours, more preferably 2 to 12 hours. In particular, when the reaction temperature is within the above-mentioned range, such a reaction time is particularly suitable.

[0098] In the above-mentioned production method, after the completion of the reaction step (1), the reaction solution may be subjected to post-treatment by a known method, and the compound (1) may be extracted by a known method. That is, after-treatment operations such as filtration, washing, extraction, pH adjustment, dehydration, and concentration may be performed alone or in combination of two or more, and the compound (1) may be extracted by concentration, crystallization, reprecipitation, distillation, sublimation, column chromatography, etc., as appropriate and necessary. In addition, the extracted compound (1) may be purified by performing operations such as crystallization, reprecipitation, distillation, sublimation, column chromatography, extraction, stirring and washing of crystals with a solvent, alone or in combination of two or more, once or more, as necessary. Alternatively, after the completion of the reaction step (1), the reaction solution may be subjected to post-treatment as necessary, and then the compound (1) may be used for the intended purpose without being extracted. For example, the compound (1) may be subjected to the next intended reaction without being extracted.

[0099] The structure of compound (1) can be confirmed by known techniques such as nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), and infrared spectroscopy (IR).

[0100] Both the compound (01a) and the compound (01b) are biphenylene derivatives and can be produced by applying a known synthesis method, and the production method thereof is not particularly limited.

[0101] In this specification, when a structure in which one or more hydrogen atoms in a certain specific compound are replaced with a group other than a hydrogen atom is assumed, the compound having such a replaced structure is referred to as a "derivative" of the above-mentioned specific compound.

[0102] <<Compound (2)>> The compound according to one embodiment of the present invention is represented by the following general formula (2):

[0103] [ka] (In the formula, R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 , R 209 , R 210 , R 211 , R 212 , R 213 , R 214 , R 215 , R 216 , R 217 , R 218 , R 219 , R 220 , R 221 , R 222 , R 223 and R 224 each independently represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylethynyl group, an arylethynyl group, a trialkylsilylethynyl group, or a trialkylsilyl group; 21 , n 22 and n 23 are each independently 0 or 1. (In this specification, this compound may be referred to as “compound (2)”).

[0104] Compound (2) has a structure in which biphenylene ring skeletons are connected to each other via a skeleton having antiaromaticity. More specifically, compound (2) has a structure in which R 201 , R 202 , R 203 , R 204 , R 205 and R 206 and a biphenylene ring skeleton having R 207 , R 208 , R 209 , R 210 , R 211 and R 212 and a biphenylene ring skeleton having R 213 , R 214 , R 215 , R 216 , R 217 and R 218 and a biphenylene ring skeleton having the formula: Compound (2) having such a structure is a novel compound and, for example, can be used as an organic semiconductor material by itself and is suitable for constituting a novel organic semiconductor material.

[0105] In the general formula (2), R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 , R 209 , R 210 , R 211 , R 212 , R 213 , R 214 , R 215 , R 216 , R 217 , R 218 , R 219 , R 220 , R 221 , R 222 , R 223 and R 224 (In the present specification, these groups are collectively referred to as "R201 ~R 224 ") are each independently a hydrogen atom (-H), an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylethynyl group, an arylethynyl group, a trialkylsilylethynyl group, or a trialkylsilyl group. R 201 ~R 224 may all be the same, may all be different, or may only be partially the same. 201 ~R 224 When two or more of the above are different from each other, their combination can be arbitrarily selected depending on the purpose, and is not particularly limited.

[0106] R 201 ~R 224 The alkyl group in R 101 ~R 118 The alkyl group in the formula (I) is the same as the alkyl group in the formula (I). R 201 ~R 224 The alkyl group in may be linear, branched or cyclic, and may have both a chain structure (linear or branched) and a cyclic structure. When the alkyl group has a cyclic structure, including the case where the alkyl group is cyclic, the cyclic structure may be either monocyclic or polycyclic. R 201 ~R 224 The alkyl group in the formula (I) preferably has 1 to 18 carbon atoms, and may be, for example, 1 to 10, 1 to 8, 1 to 6, 1 to 4, or 1 to 2 carbon atoms.

[0107] R 201 ~R 224 The aryl group in R 101 ~R 118 The aryl groups are the same as those in the above-mentioned formula (I). R 201 ~R 224 The aryl group in the formula (I) may be either monocyclic or polycyclic. R 201 ~R 224The aryl group in the above formula (I) preferably has 6 to 18 carbon atoms, and may have, for example, any one of 6 to 15, 6 to 10, and 6 to 8 carbon atoms.

[0108] R 201 ~R 224 The alkoxy group in R 101 ~R 118 The alkoxy group is the same as the alkoxy group in the above. R 201 ~R 224 The alkoxy group in may be linear, branched or cyclic, and may have both a chain structure (linear or branched) and a cyclic structure. When the alkoxy group has a cyclic structure, including the case where the alkoxy group is cyclic, the cyclic structure may be either monocyclic or polycyclic. R 201 ~R 224 The alkoxy group in the above formula preferably has 1 to 10 carbon atoms, and may be, for example, any one of 1 to 8, 1 to 6, 1 to 4, and 1 to 2 carbon atoms.

[0109] R 201 ~R 224 The aryloxy group in R 101 ~R 118 The above-mentioned aryloxy groups are the same as those in the above-mentioned formula (I). R 201 ~R 224 The aryloxy group in the above formula may be either monocyclic or polycyclic. R 201 ~R 224 The aryloxy group in the above formula (I) preferably has 6 to 15 carbon atoms, and may have, for example, 6 to 10 or 6 to 8 carbon atoms.

[0110] R 201 ~R 224 The alkylethynyl group in R 101 ~R 118 The alkylethynyl group is the same as the alkylethynyl group in the above formula (I). R 201 ~R 224The alkylethynyl group in the formula (I) may have only a chain structure (which may be a straight-chain structure or a branched-chain structure), or may have both a chain structure and a cyclic structure, and the cyclic structure may be either a monocyclic structure or a polycyclic structure. R 201 ~R 224 The alkylethynyl group in the formula (I) preferably has 3 to 12 carbon atoms, and may have, for example, 3 to 10, 3 to 8, 3 to 6, or 3 to 4 carbon atoms.

[0111] R 201 ~R 224 The arylethynyl group in R 101 ~R 118 The above-mentioned arylethynyl group is the same as that in the above-mentioned arylethynyl group. R 201 ~R 224 The cyclic structure in the arylethynyl group in the above formula may be either a monocyclic structure or a polycyclic structure. R 201 ~R 224 The arylethynyl group in the above formula (I) preferably has 8 to 17 carbon atoms, and may have, for example, 8 to 12 or 8 to 10 carbon atoms.

[0112] R 201 ~R 224 The trialkylsilylethynyl group in R 101 ~R 118 The above-mentioned trialkylsilylethynyl group is the same as the above-mentioned trialkylsilylethynyl group. R 201 ~R 224 The trialkylsilylethynyl group in the formula (I) preferably has 5 to 14 carbon atoms, and may have, for example, 5 to 11 or 5 to 8 carbon atoms.

[0113] R 201 ~R 224 The trialkylsilyl group in R 101 ~R 118 The above-mentioned trialkylsilyl group is the same as the trialkylsilyl group in the above-mentioned formula (I). R 201 ~R 224The trialkylsilyl group in the formula (i.e., the total number of carbon atoms in the three alkyl groups) preferably has 3 to 12 carbon atoms, and may be, for example, 3 to 9 or 3 to 6.

[0114] In the general formula (2), n 21 , n 22 and n 23 are each independently 0 or 1. That is, (n 21 , n 22 , n 23 ) combinations include (0,0,0), (0,0,1), (0,1,0), (1,0,0), (0,1,1), (1,0,1), (1,1,0), and (1,1,1). Among these, compound (1) is particularly preferred in terms of ease of production. 21 , n 22 and n 23 are preferably all 0 or 1.

[0115] n 21 , n 22 and n 23 When both are 0, the compound is represented by the following general formula (2A) (in this specification, this compound may be referred to as "compound (2A)").

[0116] [ka] (In the formula, R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 , R 209 , R 210 , R 211 , R 212 , R 213 , R 214 , R 215 , R 216 , R 217 and R 218are the same as above and may be the same or different.)

[0117] n 21 , n 22 and n 23 When both are 1, the compound is represented by the following general formula (2B) (in this specification, this compound may be referred to as "compound (2B)").

[0118] [ka] (In the formula, R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 , R 209 , R 210 , R 211 , R 212 , R 213 , R 214 , R 215 , R 216 , R 217 , R 218 , R 219 , R 220 , R 221 , R 222 , R 223 and R 224 are the same as above and may be the same or different.)

[0119] The compound (2A) has a skeleton in which benzene ring skeletons are bonded to each other to form a four-membered ring, that is, three biphenylene ring skeletons. Compound (2B) has a skeleton in which a benzene ring skeleton and a naphthalene ring skeleton are bonded to each other while forming a four-membered ring, and this skeleton contains one biphenylene ring skeleton. Compound (2B) has three such biphenylene ring skeletons.

[0120] In the general formula (2), R 201 ~R 224are preferably each independently a hydrogen atom, an alkyl group, an aryl group, an alkylethynyl group, an arylethynyl group, a trialkylsilylethynyl group, or a trialkylsilyl group, and more preferably each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms.

[0121] In the general formula (2), R 203 , R 204 , R 209 , R 210 , R 215 and R 216 are preferably each independently a hydrogen atom, an alkyl group, an aryl group, an alkylethynyl group, an arylethynyl group, a trialkylsilylethynyl group, or a trialkylsilyl group, more preferably each independently an alkyl group, an aryl group, an alkylethynyl group, an arylethynyl group, a trialkylsilylethynyl group, or a trialkylsilyl group, and further preferably each independently an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms.

[0122] In the general formula (2), R 201 , R 202 , R 205 , R 206 , R 207 , R 208 , R 211 , R 212 , R 213 , R 214 , R 217 , R 218 , R 219 , R 220 , R 221 , R 222 , R 223 and R 224Preferably, one or more selected from the group consisting of is a hydrogen atom, and R 201 , R 202 , R 205 , R 206 , R 207 , R 208 , R 211 , R 212 , R 213 , R 214 , R 217 , R 218 , R 219 , R 220 , R 221 , R 222 , R 223 and R 224 More preferably, all of are hydrogen atoms.

[0123] The compound (2) is preferably a compound represented by the following general formula (21).

[0124] [ka] (In the formula, R 2031 , R 2041 , R 2091 , R 2101 , R 2151 and R 2161 each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms; 21 , n 22 and n 23 is the same as above.)

[0125] In the general formula (21), R 2031 , R 2041 , R 2091 , R 2101 , R 2151 and R 2161 (In the present specification, these groups are collectively referred to as "R 2031 ~R 2161") are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms. R 2031 ~R 2161 may all be the same, may all be different, or may only be partially the same. 2031 ~R 2161 When two or more of the above are different from each other, the combination thereof is not particularly limited.

[0126] R 2031 ~R 2161 The alkyl group having 1 to 18 carbon atoms in R 201 ~R 224 Among the alkyl groups in the above, the alkyl group having 1 to 18 carbon atoms is the same as the alkyl group having 1 to 18 carbon atoms. R 2031 ~R 2161 The alkyl group in may be linear, branched or cyclic, and may have both a chain structure (linear or branched) and a cyclic structure. When the alkyl group has a cyclic structure, including the case where the alkyl group is cyclic, the cyclic structure may be either monocyclic or polycyclic. R 2031 ~R 2161 The alkyl group in the formula may have any one of 1 to 8 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, and 1 to 2 carbon atoms, for example.

[0127] R 2031 ~R 2161 The aryl group having 6 to 18 carbon atoms in R 201 ~R 224 Among the aryl groups in the above formula, the aryl group is the same as the aryl group having 6 to 18 carbon atoms. R 2031 ~R 2161 The aryl group in the formula (I) may be either monocyclic or polycyclic. R 2031 ~R 2161The aryl group in the formula (I) may have, for example, 6 to 10 carbon atoms or 6 to 8 carbon atoms.

[0128] R 2031 ~R 2161 The alkylethynyl group having 3 to 12 carbon atoms in R 201 ~R 224 Among the alkylethynyl groups in the above formula, the alkylethynyl group is the same as the alkylethynyl group having 3 to 12 carbon atoms. R 2031 ~R 2161 The alkylethynyl group in the formula (I) may have only a chain structure (which may be a straight-chain structure or a branched-chain structure), or may have both a chain structure and a cyclic structure, and the cyclic structure may be either a monocyclic structure or a polycyclic structure. R 2031 ~R 2161 The alkylethynyl group in the formula (I) may have any one of 3 to 10, 3 to 8, 3 to 6, and 3 to 4 carbon atoms.

[0129] R 2031 ~R 2161 The arylethynyl group having 8 to 17 carbon atoms in R 201 ~R 224 Among the arylethynyl groups in the above formula, the arylethynyl group is the same as the arylethynyl group having 8 to 17 carbon atoms. R 2031 ~R 2161 The cyclic structure in the arylethynyl group in the above formula may be either a monocyclic structure or a polycyclic structure. R 2031 ~R 2161 The arylethynyl group in the formula (I) may have, for example, 8 to 12 or 8 to 10 carbon atoms.

[0130] R 2031 ~R 2161 The trialkylsilylethynyl group having 5 to 14 carbon atoms in R 201 ~R 224 Among the trialkylsilylethynyl groups in the above formula, the trialkylsilylethynyl group has 5 to 14 carbon atoms. R2031 ~R 2161 The trialkylsilylethynyl group in the formula (I) may have, for example, 5 to 11 or 5 to 8 carbon atoms.

[0131] R 2031 ~R 2161 The trialkylsilyl group having 3 to 12 carbon atoms in R 201 ~R 224 Among the trialkylsilyl groups in the above formula, the trialkylsilyl group is the same as the trialkylsilyl group having 3 to 12 carbon atoms. R 2031 ~R 2161 The number of carbon atoms in the trialkylsilyl group (that is, the total number of carbon atoms in the three alkyl groups) in the formula (I) may be, for example, any one of 3 to 9 and 3 to 6.

[0132] In the general formula (21), R 2031 , R 2041 , R 2091 , R 2101 , R 2151 and R 2161 are preferably each independently an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms.

[0133] In the general formula (21), n 21 , n 22 and n 23 Each of n in the general formula (2) is 21 , n 22 and n 23 is the same as:

[0134] Preferable examples of compound (2) are shown below, however, compound (2) is not limited thereto.

[0135] [ka]

[0136] [ka]

[0137] [ka]

[0138] [ka]

[0139] [ka]

[0140] [ka]

[0141] [ka]

[0142] When the electronic state of compound (2) is predicted by performing quantum chemical calculations using a known method described later in the Examples, the energy level of the HOMO (Highest Occupied Molecular Orbital) is preferably −5.3 to −4.7 eV, the energy level of the LUMO (Lowest Unoccupied Molecular Orbital) is preferably −3.0 to −2.0 eV, and the HOMO-LUMO energy gap (EGap) is preferably 1.6 to 3.0 eV. Compound (2) has an appropriate HOMO energy level and a molecular structure in which the π-electron conjugated system is easily in contact with each other over a wide range, and thus satisfies the conditions for exhibiting high carrier mobility. Such compound (2) is suitable, for example, as an organic semiconductor material.

[0143] <<Method for producing compound (2)>> Compound (2) is, for example, a compound represented by the following general formula (02a):

[0144] [ka] (In the formula, R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 219 , R 220 and n 21 is the same as above; X 2a is a leaving group.) (hereinafter, may be referred to as “compound (02a)”) represented by the following formula: The following general formula (02b)

[0145] [ka] (In the formula, R 207 , R 208 , R 209 , R 210 , R 211 , R 212 , R 221 , R 222 and n 22 is the same as above; X 2b is a leaving group.) (hereinafter, may be referred to as “compound (02b)”) represented by the following formula: The following general formula (02c)

[0146] [ka] (In the formula, R 213 , R 214 , R 215 , R 216 , R 217 , R 218 , R 223 , R 224 and n 23 is the same as above; X 2cis a leaving group.) (Herein, this may be referred to as "compound (02c)") is reacted with the following general formula (2):

[0147] [ka] (In the formula, R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 , R 209 , R 210 , R 211 , R 212 , R 213 , R 214 , R 215 , R 216 , R 217 , R 218 , R 219 , R 220 , R 221 , R 222 , R 223 , R 224 , n 21 , n 22 and n 23 is the same as above.) The compound (compound (2)) represented by the following formula (sometimes referred to as "reaction step (2)" in this specification) can be produced by a production method having a step of obtaining a compound represented by the following formula (compound (2)): The reaction of compound (02a), compound (02b) and compound (02c) is a reaction for linking these compounds through a condensed ring. However, the method for producing compound (2) is not limited to this.

[0148] In the general formula (02a), X 2a and X in the general formula (02b) 2b and X in the general formula (02c) 2c are each independently a leaving group, and X 2a And, X 2b And, X 2cmay be the same or different from each other. That is, X 2a And, X 2b And, X 2c may be all the same, may be all different, or may be only some (any two kinds) the same. 2a And, X 2b And, X 2c are preferably all the same. Examples of the leaving group include halogen atoms such as a chlorine atom (-Cl), a bromine atom (-Br), and an iodine atom (-I).

[0149] Compound (02a), compound (02b), and compound (02c) may be the same or different from each other. That is, compound (02a), compound (02b), and compound (02c) may be all the same, all different, or only some (any two kinds) of them may be the same.

[0150] The reaction of compound (02a), compound (02b), and compound (02c) can be carried out using triphenylphosphine (PPh 3 ) and copper(I) iodide (CuI).

[0151] The reaction of compound (02a), compound (02b) and compound (02c) is preferably carried out in the presence of triphenylphosphine, copper(I) iodide and a base. The base is, for example, potassium carbonate (K 2 CO 3 ) etc.

[0152] In the reaction step (2), the amount (mol) of triphenylphosphine used is preferably 0.1 to 1 times the total amount (mol) of compound (02a), compound (02b), and compound (02c) used.

[0153] In the reaction step (2), the amount (mol) of copper(I) iodide used is preferably 1 to 5 times the total amount (mol) of compound (02a), compound (02b), and compound (02c) used.

[0154] In the reaction step (2), the amount (mol) of the base used is preferably 1 to 6 times the total amount (mol) of the compounds (02a), (02b) and (02c).

[0155] The reaction of compound (02a), compound (02b) and compound (02c) is preferably carried out in the presence of a solvent. The solvent is preferably one capable of dissolving compound (02a), compound (02b), and compound (02c), and is preferably an organic solvent. Preferred examples of the organic solvent include amides such as N,N-dimethylformamide (DMF).

[0156] In the reaction step (2), the amount of the solvent used may be 5 to 20 mL per 1 g of the total amount of the compounds (02a), (02b), and (02c) used.

[0157] The reaction between compound (02a), compound (02b) and compound (02c) is preferably carried out in an environment with reduced concentrations of moisture and oxygen gas. For example, the reaction between compound (02a), compound (02b), and compound (02c) is preferably carried out under an inert gas atmosphere. The inert gas may be the same as the inert gas used in the reaction step (1).

[0158] The reaction temperature during the reaction of compound (02a), compound (02b), and compound (02c) can be appropriately adjusted depending on the types of components used, such as the type of solvent, etc. In general, the reaction temperature is preferably 110 to 170°C, more preferably 130 to 160°C. The reaction time of the compound (02a), the compound (02b), and the compound (02c) can be appropriately adjusted depending on, for example, the reaction temperature. In general, the reaction time is preferably 4 to 24 hours, and more preferably 8 to 18 hours. In particular, when the reaction temperature is within the above-mentioned range, such a reaction time is particularly suitable.

[0159] In the above-mentioned production method, after completion of the reaction step (2), if necessary, the reaction solution may be post-treated in the same manner as in the reaction step (1), and compound (2) may be extracted in the same manner as in the reaction step (1). Furthermore, the extracted compound (2) may be further purified as necessary in the same manner as in the reaction step (1). Alternatively, after completion of the reaction step (2), if necessary, the reaction solution may be post-treated, and then the compound (2) may be used for the intended purpose without being extracted, in the same manner as in the reaction step (1).

[0160] Among the compounds (2), the compound (2A) is represented by the following general formula (02d):

[0161] [ka] (In the formula, R 201 , R 206 , R 207 , R 212 , R 213 and R 218 is the same as above; Z 2d is a trialkylsilyl group, and six Z 2d may be the same or different.) A compound represented by the formula (hereinafter, sometimes referred to as "compound (02d)") is used, 2d Alternatively, the compound can be produced by substituting a hydrogen atom with an ethynyl group and then carrying out a known reaction to form a biphenylene ring skeleton.

[0162] Z in compound (02d) 2d The trialkylsilyl group in R 201 ~R 224The trialkylsilyl groups are the same as those in the above formula (1). Six Z's in compound (02d) 2d are preferably all the same.

[0163] After the reaction, compound (2A) can be isolated by carrying out the same operation as in the case of carrying out reaction step (2), or compound (2A) can be used for the intended purpose without being isolated.

[0164] The structure of compound (2) can be confirmed by known techniques such as nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), and infrared spectroscopy (IR).

[0165] The compound (02a), the compound (02b), and the compound (02c) are all biphenylene derivatives and can be produced by applying known synthesis methods, and the production methods thereof are not particularly limited.

[0166] <<Compound (3)>> The compound according to one embodiment of the present invention is represented by the following general formula (3):

[0167] [ka] (In the formula, R 301 , R 302 , R 303 , R 304 , R 305 , R 306 , R 307 , R 308 , R 309 , R 310 , R 311 , R 312 , R 313 , R 314 , R 315 , R 316 , R 317 , R 318 , R 319 and R 320each independently represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylethynyl group, an arylethynyl group, a trialkylsilylethynyl group, or a trialkylsilyl group; 31 and n 32 are each independently 0 or 1. (In this specification, this compound may be referred to as “compound (3)”).

[0168] Compound (3) has a structure in which biphenylene ring skeletons are connected to each other via a skeleton having aromaticity. More specifically, compound (3) has a structure in which R 303 , R 304 , R 305 , R 306 , R 307 and R 308 and a biphenylene ring skeleton having R 311 , R 312 , R 313 , R 314 , R 315 and R 316 and a biphenylene ring skeleton having the following structure: wherein the linking portion forms a 12-membered ring skeleton, and the central 6-membered ring has aromaticity. Compound (3) having such a structure is a novel compound and, for example, can be used as an organic semiconductor material by itself and is suitable for constituting a novel organic semiconductor material.

[0169] In the general formula (3), R 301 , R 302 , R 303 , R 304 , R 305 , R 306 , R 307 , R 308 , R 309 , R 310 , R 311 , R 312 , R 313 , R 314 , R 315 , R 316 , R 317 , R 318 , R 319 and R320 (In the present specification, these groups are collectively referred to as "R 301 ~R 320 ") are each independently a hydrogen atom (-H), an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylethynyl group, an arylethynyl group, a trialkylsilylethynyl group, or a trialkylsilyl group. R 301 ~R 320 may all be the same, may all be different, or may only be partially the same. 301 ~R 320 When two or more of the above are different from each other, their combination can be arbitrarily selected depending on the purpose, and is not particularly limited.

[0170] R 301 ~R 320 The alkyl group in R 101 ~R 118 The alkyl group in the formula (I) is the same as the alkyl group in the formula (I). R 301 ~R 320 The alkyl group in may be linear, branched or cyclic, and may have both a chain structure (linear or branched) and a cyclic structure. When the alkyl group has a cyclic structure, including the case where the alkyl group is cyclic, the cyclic structure may be either monocyclic or polycyclic. R 301 ~R 320 The alkyl group in the formula (I) preferably has 1 to 18 carbon atoms, and may be, for example, 1 to 10, 1 to 8, 1 to 6, 1 to 4, or 1 to 2 carbon atoms.

[0171] R 301 ~R 320 The aryl group in R 101 ~R 118 The aryl groups are the same as those in the above-mentioned formula (I). R 301 ~R 320 The aryl group in the formula (I) may be either monocyclic or polycyclic. R 301 ~R 320The aryl group in the above formula (I) preferably has 6 to 18 carbon atoms, and may have, for example, any one of 6 to 15, 6 to 10, and 6 to 8 carbon atoms.

[0172] R 301 ~R 320 The alkoxy group in R 101 ~R 118 The alkoxy group is the same as the alkoxy group in the above. R 301 ~R 320 The alkoxy group in may be linear, branched or cyclic, and may have both a chain structure (linear or branched) and a cyclic structure. When the alkoxy group has a cyclic structure, including the case where the alkoxy group is cyclic, the cyclic structure may be either monocyclic or polycyclic. R 301 ~R 320 The alkoxy group in the above formula preferably has 1 to 10 carbon atoms, and may be, for example, any one of 1 to 8, 1 to 6, 1 to 4, and 1 to 2 carbon atoms.

[0173] R 301 ~R 320 The aryloxy group in R 101 ~R 118 The above-mentioned aryloxy groups are the same as those in the above-mentioned formula (I). R 301 ~R 320 The aryloxy group in the above formula may be either monocyclic or polycyclic. R 301 ~R 320 The aryloxy group in the above formula (I) preferably has 6 to 15 carbon atoms, and may have, for example, 6 to 10 or 6 to 8 carbon atoms.

[0174] R 301 ~R 320 The alkylethynyl group in R 101 ~R 118 The alkylethynyl group is the same as the alkylethynyl group in the above formula (I). R 301 ~R 320The alkylethynyl group in the formula (I) may have only a chain structure (which may be a straight-chain structure or a branched-chain structure), or may have both a chain structure and a cyclic structure, and the cyclic structure may be either a monocyclic structure or a polycyclic structure. R 301 ~R 320 The alkylethynyl group in the formula (I) preferably has 3 to 12 carbon atoms, and may have, for example, 3 to 10, 3 to 8, 3 to 6, or 3 to 4 carbon atoms.

[0175] R 301 ~R 320 The arylethynyl group in R 101 ~R 118 The above-mentioned arylethynyl group is the same as that in the above-mentioned arylethynyl group. R 301 ~R 320 The cyclic structure in the arylethynyl group in the above formula may be either a monocyclic structure or a polycyclic structure. R 301 ~R 320 The arylethynyl group in the above formula (I) preferably has 8 to 17 carbon atoms, and may have, for example, 8 to 12 or 8 to 10 carbon atoms.

[0176] R 301 ~R 320 The trialkylsilylethynyl group in R 101 ~R 118 The above-mentioned trialkylsilylethynyl group is the same as the above-mentioned trialkylsilylethynyl group. R 301 ~R 320 The trialkylsilylethynyl group in the formula (I) preferably has 5 to 14 carbon atoms, and may have, for example, 5 to 11 or 5 to 8 carbon atoms.

[0177] R 301 ~R 320 The trialkylsilyl group in R 101 ~R 118 The above-mentioned trialkylsilyl group is the same as the trialkylsilyl group in the above-mentioned formula (I). R 301 ~R 320The trialkylsilyl group in the formula (i.e., the total number of carbon atoms in the three alkyl groups) preferably has 3 to 12 carbon atoms, and may be, for example, 3 to 9 or 3 to 6.

[0178] In the general formula (3), n 31 and n 32 are each independently 0 or 1. That is, (n 31 , n 32 ) combinations include (0,0), (0,1), (1,0), and (1,1). Among these, compound (3) is particularly preferred in terms of ease of production. 31 and n 32 are preferably all 0 or 1.

[0179] n 31 and n 32 When both are 0, the compound is represented by the following general formula (3A) (in this specification, this compound may be referred to as "compound (3A)").

[0180] [ka] (In the formula, R 301 , R 302 , R 303 , R 304 , R 305 , R 306 , R 307 , R 308 , R 309 , R 310 , R 311 , R 312 , R 313 , R 314 , R 315 and R 316 are the same as above and may be the same or different.)

[0181] n 31 and n 32When both are 1, the compound is represented by the following general formula (3B) (in this specification, this compound may be referred to as "compound (3B)").

[0182] [ka] (In the formula, R 301 , R 302 , R 303 , R 304 , R 305 , R 306 , R 307 , R 308 , R 309 , R 310 , R 311 , R 312 , R 313 , R 314 , R 315 , R 316 , R 317 , R 318 , R 319 and R 320 are the same as above and may be the same or different.)

[0183] The compound (3A) has a skeleton in which benzene ring skeletons are bonded to each other to form a four-membered ring, that is, two biphenylene ring skeletons. Compound (3B) has a skeleton in which a benzene ring skeleton and a naphthalene ring skeleton are bonded to each other while forming a four-membered ring, and this skeleton contains one biphenylene ring skeleton. Compound (3B) has two such biphenylene ring skeletons.

[0184] In the general formula (3), R 301 ~R 320are preferably each independently a hydrogen atom, an alkyl group, an aryl group, an alkylethynyl group, an arylethynyl group, a trialkylsilylethynyl group, or a trialkylsilyl group, and more preferably each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms.

[0185] In the general formula (3), R 301 , R 302 , R 309 and R 310 are preferably each independently a hydrogen atom, an alkyl group, an aryl group, an alkylethynyl group, an arylethynyl group, a trialkylsilylethynyl group, or a trialkylsilyl group, more preferably each independently an alkyl group, an aryl group, an alkylethynyl group, an arylethynyl group, a trialkylsilylethynyl group, or a trialkylsilyl group, and further preferably each independently an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms.

[0186] In the general formula (3), R 303 , R 304 , R 305 , R 306 , R 307 , R 308 , R 311 , R 312 , R 313 , R 314 , R 315 , R 316 , R 317 , R 318 , R 319 and R 320 Preferably, one or more selected from the group consisting of is a hydrogen atom, and R 303 , R 304 , R 305 , R306 , R 307 , R 308 , R 311 , R 312 , R 313 , R 314 , R 315 , R 316 , R 317 , R 318 , R 319 and R 320 More preferably, all of are hydrogen atoms.

[0187] The compound (3) is preferably a compound represented by the following general formula (31).

[0188] [ka] (In the formula, R 3011 , R 3021 , R 3051 , R 3061 , R 3091 , R 3101 , R 3131 and R 3141 each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms; 31 and n 32 is the same as above.)

[0189] In the general formula (31), R 3011 , R 3021 , R 3051 , R 3061 , R 3091 , R 3101 , R 3131 and R 3141 (In the present specification, these groups are collectively referred to as "R 3011 ~R 3141") are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms. R 3011 ~R 3141 may all be the same, may all be different, or may only be partially the same. 3011 ~R 3141 When two or more of the above are different from each other, the combination thereof is not particularly limited.

[0190] R 3011 ~R 3141 The alkyl group having 1 to 18 carbon atoms in R 301 ~R 320 Among the alkyl groups in the above, the alkyl group having 1 to 18 carbon atoms is the same as the alkyl group having 1 to 18 carbon atoms. R 3011 ~R 3141 The alkyl group in may be linear, branched or cyclic, and may have both a chain structure (linear or branched) and a cyclic structure. When the alkyl group has a cyclic structure, including the case where the alkyl group is cyclic, the cyclic structure may be either monocyclic or polycyclic. R 3011 ~R 3141 The alkyl group in the formula may have any one of 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, and 1 to 2 carbon atoms, for example.

[0191] R 3011 ~R 3141 The aryl group having 6 to 18 carbon atoms in R 301 ~R 320 Among the aryl groups in the above formula, the aryl group is the same as the aryl group having 6 to 18 carbon atoms. R 3011 ~R 3141 The aryl group in the formula (I) may be either monocyclic or polycyclic. R 3011 ~R 3141The aryl group in the formula (I) may have, for example, 6 to 10 carbon atoms or 6 to 8 carbon atoms.

[0192] R 3011 ~R 3141 The alkylethynyl group having 3 to 12 carbon atoms in R 301 ~R 320 Among the alkylethynyl groups in the above formula, the alkylethynyl group is the same as the alkylethynyl group having 3 to 12 carbon atoms. R 3011 ~R 3141 The alkylethynyl group in the formula (I) may have only a chain structure (which may be a straight-chain structure or a branched-chain structure), or may have both a chain structure and a cyclic structure, and the cyclic structure may be either a monocyclic structure or a polycyclic structure. R 3011 ~R 3141 The alkylethynyl group in the formula (I) may have any one of 3 to 10, 3 to 8, 3 to 6, and 3 to 4 carbon atoms.

[0193] R 3011 ~R 3141 The arylethynyl group having 8 to 17 carbon atoms in R 301 ~R 320 Among the arylethynyl groups in the above formula, the arylethynyl group is the same as the arylethynyl group having 8 to 17 carbon atoms. R 3011 ~R 3141 The cyclic structure in the arylethynyl group in the above formula may be either a monocyclic structure or a polycyclic structure. R 3011 ~R 3141 The arylethynyl group in the formula (I) may have, for example, 8 to 12 or 8 to 10 carbon atoms.

[0194] R 3011 ~R 3141 The trialkylsilylethynyl group having 5 to 14 carbon atoms in R 301 ~R 320 Among the trialkylsilylethynyl groups in the above formula, the trialkylsilylethynyl group has 5 to 14 carbon atoms. R3011 ~R 3141 The trialkylsilylethynyl group in the formula (I) may have, for example, 5 to 11 or 5 to 8 carbon atoms.

[0195] R 3011 ~R 3141 The trialkylsilyl group having 3 to 12 carbon atoms in R 301 ~R 320 Among the trialkylsilyl groups in the above formula, the trialkylsilyl group is the same as the trialkylsilyl group having 3 to 12 carbon atoms. R 3011 ~R 3141 The number of carbon atoms in the trialkylsilyl group (that is, the total number of carbon atoms in the three alkyl groups) in the formula (I) may be, for example, any one of 3 to 9 and 3 to 6.

[0196] In the general formula (31), R 3011 , R 3021 , R 3091 and R 3101 are preferably each independently an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms.

[0197] In the general formula (31), R 3051 , R 3061 , R 3131 and R 3141 are each independently preferably a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms, and more preferably a hydrogen atom.

[0198] In the general formula (31), n 31 and n 32 Each of n in the general formula (3) is 31 and n 32 is the same as:

[0199] Preferable examples of compound (3) are shown below, however, compound (3) is not limited thereto.

[0200] [ka]

[0201] [ka]

[0202] [ka]

[0203] [ka]

[0204] [ka]

[0205] [ka]

[0206] When the electronic state of compound (3) is predicted by performing quantum chemical calculations using a known method described later in the Examples, the energy level of the HOMO (Highest Occupied Molecular Orbital) is preferably −5.5 to −4.9 eV, the energy level of the LUMO (Lowest Unoccupied Molecular Orbital) is preferably −2.5 to −1.7 eV, and the HOMO-LUMO energy gap (EGap) is preferably 2.5 to 3.5 eV. Compound (3) has an appropriate HOMO energy level and a molecular structure in which the π-electron conjugated system can easily contact with each other over a wide range, and thus satisfies the conditions for exhibiting high carrier mobility. Such compound (3) is suitable, for example, as an organic semiconductor material.

[0207] <<Method for producing compound (3)>> Compound (3) is, for example, a compound represented by the following general formula (03a):

[0208] [ka] (In the formula, R 303 , R 304 , R 305 , R 306 , R 307 , R 308 , R 311 , R 312 , R 313 , R 314 , R 315 , R 316 , R 317 , R 318 , R 319 , R 320 , n 31 and n 32 is the same as above.) In the compound represented by the formula (hereinafter, sometimes referred to as “compound (03a)”), 303 The carbonyl group (-C(=O)-) on the side is represented by the general formula -C(-R 301 )(-R 302 )-, and R 311 The carbonyl group (-C(=O)-) on the side is represented by the general formula -C(-R 309 )(-R 310 )-, to obtain a group represented by the following general formula (3):

[0209] [ka] (In the formula, R 301 , R 302 , R 303 , R 304 , R 305 , R306 , R 307 , R 308 , R 309 , R 310 , R 311 , R 312 , R 313 , R 314 , R 315 , R 316 , R 317 , R 318 , R 319 and R 320 , n 31 and n 32 is the same as above.) The compound (compound (3)) can be produced by a production method including a step of obtaining a compound represented by the following formula (sometimes referred to as "reaction step (3)" in this specification). However, the method for producing compound (3) is not limited to this.

[0210] The reaction step (3) can be carried out by a known method. For example, R 301 , R 302 , R 309 and R 310 When is an alkylethynyl group, an arylethynyl group, or a trialkylsilylethynyl group, compound (03a) and a compound represented by the general formula Li-C≡CZ are reacted in the presence of tin(II) chloride. 3 (In the formula, Z 3 is an alkyl group, an aryl group, or a trialkylsilyl group.) (sometimes referred to as "compound (3Z)" in this specification) is reacted with to obtain compound (3).

[0211] Z in compound (3Z) 3 is an alkyl group, an aryl group, or a trialkylsilyl group, and each of the alkyl group, the aryl group, and the trialkylsilyl group is represented by R 301 , R 302 , R 309 or R 310 The alkyl group in the alkylethynyl group, the aryl group in the arylethynyl group, and the trialkylsilyl group in the trialkylsilylethynyl group in the above-mentioned formula (I) are the same as those in the above-mentioned formula (I).

[0212] The reaction of compound (03a) with compound (3Z) is preferably carried out in the coexistence of butyllithium. Examples of the butyllithium include n-BuLi, sec-BuLi, and tert-BuLi.

[0213] In the reaction step (3), the amount (mol) of the compound (3Z) used is preferably 2 to 6 times the amount (mol) of the compound (03a) used.

[0214] In the reaction step (3), the amount (mol) of butyllithium used is preferably 2 to 6 times the amount (mol) of (compound (03a)) used.

[0215] The reaction of compound (03a) with compound (3Z) is preferably carried out in the presence of a solvent. The solvent is preferably one capable of dissolving compound (03a) and compound (3Z), and is preferably an organic solvent. Preferred organic solvents include, for example, ethers such as tetrahydrofuran (THF); 6 H 14 ) and other hydrocarbons; and amides such as N,N-dimethylformamide (DMF).

[0216] In the reaction step (3), the amount of the solvent used may be 100 to 200 mL per 1 g of the compound (03a) used.

[0217] The reaction between compound (03a) and compound (3Z) is preferably carried out in an environment with reduced concentrations of moisture and oxygen gas. For example, the reaction between compound (03a) and compound (3Z) is preferably carried out under an inert gas atmosphere. The inert gas may be the same as the inert gas used in the reaction step (1).

[0218] The reaction temperature during the reaction of compound (03a) with compound (3Z) is preferably -80 to 0°C. The reaction time of the compound (03a) and the compound (3Z) can be appropriately adjusted depending on, for example, the reaction temperature. Usually, the reaction time is preferably 1 to 6 hours. In particular, when the reaction temperature is within the above-mentioned range, such a reaction time is particularly suitable.

[0219] In the above-mentioned production method, after completion of the reaction step (3), if necessary, the reaction solution may be post-treated in the same manner as in the reaction step (1), and compound (3) may be extracted in the same manner as in the reaction step (1). Furthermore, the extracted compound (3) may be further purified as necessary in the same manner as in the reaction step (1). Alternatively, after completion of the reaction step (3), if necessary, the reaction solution may be post-treated, and then the compound (3) may be used for the intended purpose without being extracted, in the same manner as in the reaction step (1).

[0220] The structure of compound (3) can be confirmed by known techniques such as nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), and infrared spectroscopy (IR).

[0221] The compound (03a) can be produced by applying a known synthesis method, and the production method thereof is not particularly limited.

[0222] <<Organic semiconductor materials>> An organic semiconductor material according to one embodiment of the present invention contains the compound according to one embodiment of the present invention described above. The organic semiconductor material of this embodiment contains the compound, and therefore has sufficient properties to constitute an organic semiconductor.

[0223] The organic semiconductor material of the present embodiment may contain only one type of the compound, or two or more types. When two or more types are contained, the combination and ratio thereof can be arbitrarily selected depending on the purpose. That is, the organic semiconductor material of the present embodiment contains one or more types selected from the group consisting of compound (1), compound (2), and compound (3). When compound (1) is contained, the organic semiconductor material contains one or more types of compound (1). When compound (2) is contained, the organic semiconductor material contains one or more types of compound (2). When compound (3) is contained, the organic semiconductor material contains one or more types of compound (3).

[0224] The organic semiconductor material may or may not contain other components in addition to the compound (one or more selected from the group consisting of compound (1), compound (2), and compound (3)). That is, the organic semiconductor material may be a material consisting of the compound, or may be a material consisting of the compound and the other components.

[0225] The other components contained in the organic semiconductor material can be arbitrarily selected depending on the purpose, and are not particularly limited. For example, the other component may be either an organic compound or an inorganic compound. Among the other components, examples of the organic compound include known compounds that exhibit properties as an organic semiconductor, such as acenes such as anthracene, tetracene, and pentacene; acene derivatives; phthalocyanine; phthalocyanine derivatives; polythiophene; polythiophene derivatives; polyphenylene; polyphenylene derivatives; polyphenylene vinylene; polyphenylene vinylene derivatives; polypyrrole; polypyrrole derivatives; triarylamine; triarylamine derivatives; fullerene; and fullerene derivatives.

[0226] The other components contained in the organic semiconductor material may be one type only, or two or more types. When there are two or more types, the combination and ratio thereof can be arbitrarily selected depending on the purpose.

[0227] In the organic semiconductor material, the ratio of the content of the compound to the total mass of the organic semiconductor material ([content of the compound in the organic semiconductor material (parts by mass)] / [total mass of the organic semiconductor material (parts by mass)]×100) can be selected arbitrarily depending on the purpose, and may be, for example, any of 10% by mass or more, 30% by mass or more, 50% by mass or more, 70% by mass or more, 80% by mass or more, and 90% by mass or more. On the other hand, the proportion is 100% by mass or less. The higher the ratio, the greater the effect obtained by using the compound, and the lower the ratio, the greater the effect obtained by using the other component.

[0228] The organic semiconductor material can be produced, for example, by forming a film by a known method such as vapor deposition using the compound for producing the organic semiconductor material or a raw material composition containing the compound and the other components. EXAMPLES

[0229] The present invention will be described in more detail below with reference to specific examples, although the present invention is not limited to the following examples.

[0230] <<Production of compound (1)>> <Production of 6,13-dihexylpentaleno[1,2-b:4,5-b']dibiphenylene> [Example 1] ◎Production of 1,2-bis[(trimethylsilyl)ethynyl]benzene The atmosphere in a two-necked eggplant flask (200 mL) equipped with a reflux condenser and a three-way cock was replaced with argon gas, and o-dibromobenzene (3.98 g, 16.9 mmol), bis(triphenylphosphine)palladium(II) dichloride (PdCl 2 (PPh 3 ) 2 , 589 mg, 839 μmol) and copper(I) iodide (CuI, 224 mg, 1.18 mmol). 3N, 86 mL) was added and stirred at room temperature. (Trimethylsilyl)acetylene (TMSA, 8.31 g, 84.6 mmol) was added and the mixture was heated and stirred in an 85°C oil bath for 14 hours. The reaction solution was allowed to cool, and the solid was filtered off and washed with ether. The filtrate was distilled under reduced pressure to obtain a crude product, which was purified by silica gel column chromatography (mobile phase: hexane) to obtain 1,2-Bis[(trimethylsilyl)ethynyl]benzene as an orange oil (yield 91%, yield 4.16 g (15.4 mmol)).

[0231] The product obtained is 1,2-bis[(trimethylsilyl)ethynyl]benzene. 1 The analysis was confirmed by 1 H NMR. The analytical data obtained at this time are shown below. The spectrum data was consistent with the previously reported values. 1 H NMR (500 MHz, CDCl 3 , 25℃) δ 7.45 (dd, J = 5.5 Hz, J = 3.5 Hz, 2H), 7.23 (dd, J =5.5 Hz, J = 3.5 Hz, 2H), 0.27 (s, 18H).

[0232] ◎Production of 2,3-bis(trimethylsilyl)biphenylene In a 500 mL eggplant flask, add 1,2-bis[(trimethylsilyl)ethynyl]benzene (3.65 g, 13.5 mmol) and potassium carbonate (K 2 CO 3 , 11.9 g, 86.1 mmol) was added. Then, methanol (MeOH, 150 mL) and diethyl ether (Et 2 O, 150 mL) was added and stirred at room temperature for 1 hour. Stirring was stopped, and water and diethyl ether were added to separate the phases. The organic matter was extracted three times from the aqueous layer. The combined organic layer was washed with water and saturated saline, dried over magnesium sulfate, and filtered. The solvent was distilled off under reduced pressure, and the resulting 1,2-diethynylbenzene was used as it was in the next reaction.

[0233] A two-necked eggplant flask (200 mL) equipped with a reflux condenser was flame dried, and the atmosphere inside the flask was replaced with argon gas. Bis(trimethylsilyl)acetylene (BTMSA, 50 mL) was added to the flask. Next, 1,2-diethynylbenzene and (C 5 H 5 )Co(CO) 2 A mixed solution of 243 mg (1.35 mmol) and BTMSA (10 mL) was added dropwise at a rate of 2 mL / h. During the addition, the reaction mixture was heated to reflux at 155°C while being irradiated with a halogen lamp. After the addition of all the mixture, the light irradiation and heating were continued for 4 hours. The excess BTMSA was distilled off under reduced pressure to obtain a crude product. This was purified by silica gel column chromatography (mobile phase: hexane) to obtain 2,3-Bis(trimethylsilyl)biphenylene as an orange oil (yield 82%, yield 3.29 g (11.1 mmol)).

[0234] The product obtained is 2,3-bis(trimethylsilyl)biphenylene. 1 The analysis was confirmed by 1 H NMR. The analytical data obtained at this time are shown below. The spectrum data was consistent with the previously reported values. 1 H NMR (500 MHz, CDCl 3 , 25℃) δ 6.96 (s, 2H), 6.72 (dd, J = 4.5 Hz, J = 2.5 Hz, 4H), 6.66 (dd, J = 4.5 Hz, J = 3.0 Hz, 4H).

[0235] ◎Production of 2,3-diiodobiphenylene A two-necked recovery flask (100 mL) was flame dried and the atmosphere inside the flask was replaced with argon gas. 2,3-Bis(trimethylsilyl)biphenylene (1.03 g, 3.47 mmol) and dichloromethane (CH 2 Cl 2 , 40 mL) was added. The reaction vessel was placed in an ice bath and the mixture was stirred. A 1 M solution of iodine monochloride (ICl) in dichloromethane (9.3 mmol as iodine monochloride) was added dropwise, and the mixture was slowly allowed to warm to room temperature and stirred for 13 hours. Analysis of the reaction solution by thin layer chromatography (TLC) confirmed that the reaction was not complete, so the reaction vessel was cooled again in an ice bath and a 1 M solution of iodine monochloride in dichloromethane (2 mmol as iodine monochloride) was added dropwise. After stirring for 10 hours, a portion of the reaction mixture was withdrawn and 1 The reaction was confirmed to be complete by H NMR spectroscopy. The reaction was stopped by adding aqueous sodium thiosulfate to the mixture. Dichloromethane and water were added to separate the phases, and the organic matter was extracted twice from the aqueous layer. The combined organic layers were washed with water and saturated saline, dehydrated with magnesium sulfate, and filtered. The solvent was distilled off under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (mobile phase: hexane), and the fraction containing the target product was collected and concentrated. Ethanol (EtOH) was added to this to make a suspension, which was then irradiated with ultrasound and filtered under suction to obtain the target product. The residue was also purified by recycling preparative HPLC (mobile phase: chloroform). Together with the separated target product, 2,3-diiodobiphenylene was obtained as a yellow solid (yield 78%, yield 1.09 g (2.7 mmol)).

[0236] The product obtained is 2,3-diiodobiphenylene. 1 The analysis was confirmed by 1 H NMR. The analytical data obtained at this time are shown below. The spectrum data was consistent with the previously reported values. 1 H NMR (500 MHz, CDCl 3, 25℃) δ 7.16 (s, 2H), 6.81 (dd, J = 5.0 Hz, J = 2.8 Hz, 4H), 6.70 (dd, J = 5.0 Hz, J = 3.0 Hz, 4H).

[0237] ◎Production of 2-iodo-3-(oct-1-yn-1-yl)biphenylene A Schlenk tube (100 mL) was flame dried, and the atmosphere in the Schlenk tube was replaced with argon gas. 2,3-diiodobiphenylene (1.03 g, 2.55 mmol), bis(triphenylphosphine)palladium(II) dichloride (88.0 mg, 125 μmol), copper(I) iodide (21.9 mg, 115 μmol), and triethylamine (15 mL) were added thereto. 1-octyne (366 mg, 3.32 mmol) was added dropwise while stirring the reaction mixture at room temperature. Then, the reaction mixture was heated and stirred at 90°C for 19 hours. After cooling the reaction mixture, the solid was filtered off. The filtered solid was washed with diethyl ether. The solvent was distilled off from the filtrate under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (mobile phase: hexane) and recycling preparative HPLC (mobile phase: chloroform). As a result, 2-iodo-3-(oct-1-yn-1-yl)biphenylene was obtained as a bright yellow oil (yield 16%, yield 155 mg (401 mmol)).

[0238] The product obtained is 2-iodo-3-(oct-1-yn-1-yl)biphenylene. 1 H NMR, 13 The analysis was confirmed by C NMR and field desorption mass spectrometry (FD-MS). The analytical data obtained are shown below. 1 H NMR (400 MHz, CDCl 3, 25℃) δ 7.07 (s, 1H), 6.83-6.75 (m, 2H), 6.72-6.61 (m, 3H), 2.44 (t, J = 8.8 Hz, 2H), 1.62 (quint, J = 8.5 Hz, 2H), 1.56-1.43 (m, 2H), 1.40-1.24 (m, 2H), 0.91 (t, J = 8.5 Hz, 3H). 13 C NMR (126 MHz, CDCl 3 , 25℃) δ 150.6, 150.4, 150.0, 149.9, 129.6, 129.1, 128.8, 127.0, 120.6, 118.4, 118.3, 100.1, 95.6, 84.0, 31.4, 28.6, 28.5, 22.6, 19.7, 14.1. FD-MS m / z calcd. for C 20 H 19 I 1 (M + ): 386.0531, found 386.0527.

[0239] ◎Production of 6,13-dihexylpentaleno[1,2-b:4,5-b']dibiphenylene (Compound (1)-101) A Schlenk tube (100 mL) was flame dried and the atmosphere in the Schlenk tube was replaced with argon gas. 2-iodo-3-(oct-1-yn-1-yl)biphenylene (226 mg, 585 μmol), palladium(II) acetate (Pd(OAc) 2 , 6.6mg, 29μmol), tetrabutylammonium acetate (n-Bu 4NOAc (184 mg, 610 μmol) and N,N-dimethylformamide (DMF, 12 mL) were added. The mixture was deoxygenated by bubbling argon gas for 10 minutes while stirring at room temperature, and then heated and stirred at 130°C for 4 hours. Ethyl acetate and water were added to separate the phases, and the organic matter was extracted from the aqueous layer three times with ethyl acetate. The combined organic layer was washed with water and saturated saline, dried over magnesium sulfate, and then filtered. The solvent in the filtrate was distilled off under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (mobile phase: hexane / dichloromethane = 5 / 1 (volume ratio)) and recycling preparative HPLC (mobile phase: chloroform) to obtain the target product, 6,13-dihexylpentaleno[1,2-b:4,5-b']dibiphenylene (compound (1)-101)) as a brown solid (yield 12%, yield 18.9 mg (36.4 mmol)).

[0240] The product obtained is 6,13-dihexylpentaleno[1,2-b:4,5-b']dibiphenylene. 1 H NMR, 13 The analysis was confirmed by C NMR, infrared spectroscopy (IR) and field desorption mass spectrometry (FD-MS). The analytical data obtained are shown below. 1 H NMR (500 MHz, CDCl 3 , 25℃) δ 6.72-6.66 (m, 4H), 6.55-6.49 (m, 4H), 6.43 (s, 4H), 6.31 (s, 4H). 13 C NMR (126 MHz, CDCl 3 , 25℃) δ 150.5, 149.93, 149.90, 149.8, 49.5, 144.1, 142.0, 136.4, 127.8, 127.7, 116.1, 115.9, 112.3, 112.2, 31.8, 29.6, 28.8, 26.7, 22.6, 14.1. IR (KBr) 3063, 2951, 2927, 2855, 1616, 1560, 1466, 1443, 1413, 1376, 1279, 1251, 1212, 1194, 1156, 1119, 973, 914, 873, 739cm -1 . FD-MS m / z calcd. for C 40 H 38 (M + ): 518.2974, found 518.2952.

[0241] [ka]

[0242] <<Evaluation of compound (1)>> <Prediction of electronic states by quantum chemical calculations> The electronic state of compound (1)-101 was predicted by density functional theory (B3LYP-D3BJ / 6-311G(d,p)). Stable calculations confirmed that compound (1)-101 is in a closed-shell singlet state. The energies of the frontier orbitals (HOMO and LUMO) were calculated by TD-DFT (B3LYP-D3BJ / 6-311+G(d,p)). As a result, the HOMO energy level was -4.87 eV, the LUMO energy level was -2.64 eV, and the HOMO-LUMO energy gap (EGap) was 2.23 eV. The above HOMO energy level is close to the work function (~-5.1 eV) of gold and platinum electrodes used in field effect transistors (FETs), confirming that compound (1)-101 can be used as a p-type semiconductor.

[0243] <Production of 6,13-dihexylpentaleno[1,2-b:4,5-b']dibiphenylene> [Example 2] ◎Production of 2-iodo-3-(phenylethynyl)biphenylene 2,3-Diiodobiphenylene was prepared in the same manner as in Example 1. A Schlenk tube (100 mL) was flame dried, and the atmosphere in the Schlenk tube was replaced with argon gas. 2,3-diiodobiphenylene (853 mg, 2.11 mmol), bis(triphenylphosphine)palladium(II) dichloride (147 mg, 209 μmol), copper(I) iodide (44.0 mg, 231 μmol), diisopropylamine (8.0 mL) and 1,4-dioxane (16 mL) were added thereto. Ethynylbenzene (321 mg, 3.15 mmol) was added dropwise, and the reaction mixture was heated and stirred at 90° C. for 34 hours. The reaction mixture was cooled, and the solid was filtered off. The filtered solid was washed with diethyl ether. The solvent was distilled off from the filtrate under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (mobile phase: hexane). As a result, 2-iodo-3-(phenylethynyl)biphenylene was obtained as a yellow solid (yield 31%, yield 246 mg (650 mmol)).

[0244] The product obtained is 2-iodo-3-(phenylethynyl)biphenylene. 1 H NMR, 13 The analysis was confirmed by C NMR and field desorption mass spectrometry (FD-MS). The analytical data obtained are shown below. 1 H NMR (500 MHz, CDCl 3 , 25℃) δ 7.60-7.53 (m, 2H), 7.39-7.33 (m, 3H), 7.14 (s, 1H), 6.86-6.77 (m, 3H), 6.75-6.67 (m, 2H). 13 C NMR (126 MHz, CDCl 3 , 25℃) δ 151.5, 150.6, 149.9, 149.8, 131.6, 129.3, 129.0, 128.8, 128.6, 128.4, 127.2, 123.0, 120.3, 118.6, 118.5, 100.9, 93.7, 92.9. FD-MS m / z calcd. for C 20 H 11 I 1 (M + ): 377.9905, found 377.9920.

[0245] ◎Production of 6,13-diphenylpentaleno[1,2-b:4,5-b']dibiphenylene (Compound (1)-201) A Schlenk tube (100 mL) was flame dried and the atmosphere in the Schlenk tube was replaced with argon gas. 2-iodo-3-(phenylethynyl)biphenylene (287 mg, 759 μmol), palladium(II) acetate (Pd(OAc) 2 , 18.2 mg, 81.1 μmol), tetrabutylammonium acetate (n-Bu 4 NOAc (228 mg, 756 μmol) and N,N-dimethylformamide (DMF, 15 mL) were added. The mixture was deoxygenated by bubbling argon gas for 10 minutes while stirring at room temperature, and then heated and stirred at 130°C for 8 hours. The reaction solution was cooled to stop the reaction. Chloroform and water were added to separate the phases, and the organic matter was extracted from the aqueous layer with chloroform three times. The combined organic layer was washed with water and saturated saline, dried over magnesium sulfate, and then filtered. The solvent in the filtrate was distilled off under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (mobile phase: hexane / dichloromethane = 3 / 1 (volume ratio)) and recycling preparative HPLC (mobile phase: chloroform) to obtain the target product, 6,13-diphenylpentaleno[1,2-b:4,5-b']dibiphenylene (Compound (1)-201), as a brown solid (yield less than 1%, yield 1.3 mg (2.6 μmol)).

[0246] The product obtained is 6,13-diphenylpentaleno[1,2-b:4,5-b']dibiphenylene. 1 The analysis was confirmed by H NMR and field desorption-high resolution mass spectrometry (FD-HRMS). The analytical data obtained are shown below. 1 H NMR (500 MHz, CDCl 3 , 25℃) δ 7.59-7.48 (m, 4H), 7.47-7.40 (m, 1H), 6.71-6.64 (m, 2H), 6.50-6.44 (m, 1H), 6.42 (d, J = 1.2 Hz, 1H), 6.36 (d, J = 0.8 Hz, 1H). FD-HRMS m / z calcd. for C 40 H 22 (M + ): 502.1722, found 502.1717.

[0247] [ka]

[0248] <<Evaluation of compound (1)>> <Prediction of electronic states by quantum chemical calculations> The electronic state of compound (1)-201 was predicted by the same method as in Example 1. A stable calculation was performed, and it was confirmed that compound (1)-201 takes a closed shell singlet state. The HOMO energy level was -4.92 eV, the LUMO energy level was -2.97 eV, and the HOMO-LUMO energy gap (EGap) was 1.95 eV. From these results, it was confirmed that compound (1)-201 can be used as a p-type semiconductor.

[0249] <<Production of compound (2)>> <Production of hexahexyltris(biphenyleno)dehydro

[12] annulene> [Example 3] ◎Production of 1,2-dihexylbenzene Magnesium shavings (Mg, 5.12 g, 210 mmol) were added to a three-necked eggplant flask (500 mL) equipped with a reflux condenser and a dropping funnel, and the flask was flame-dried in this state, and the atmosphere in the flask was replaced with argon gas.2 O, 210.5 mL) and iodine (I 2 1-bromohexane (29.5 mL, 211 mmol) was added to the dropping funnel and added dropwise to the system. After the dropwise addition was completed, the reaction mixture was heated to reflux at 50°C for 1 hour. The reaction system was then cooled to room temperature. The reaction mixture was cooled on ice and [1,2-bis(diphenylphosphino)ethane]nickel(II) dichloride (NiCl 2 (dppe, 104 mg + 128 mg, 439 μmol) was added to the reaction vessel. 1,2-Dichlorobenzene (10.8 mL, 96.2 mmol) and ultra-dehydrated diethyl ether (Et 2 After the dropwise addition, the reaction mixture was heated to reflux at 50°C. 35 minutes after the start of the heating and reflux, the inside of the system solidified due to the precipitation of salts and the stirrer could no longer rotate, so further ultra-dehydrated diethyl ether (Et 2 45 minutes after the addition of ultra-dehydrated diethyl ether was completed, the disappearance of the raw materials was confirmed by thin layer chromatography (TLC) analysis of the reaction solution, so heating was stopped and the mixture was cooled to room temperature.

[0250] The reaction mixture was transferred into 1M hydrochloric acid while being crushed. Diethyl ether was added to the mixture to separate the organic layer from the aqueous layer. The product was extracted from the aqueous layer three times using diethyl ether. The combined organic layer was then washed with 1M hydrochloric acid, water, an aqueous solution of sodium bicarbonate (NaHCO3), and saturated saline. The organic layer was dehydrated with magnesium sulfate and filtered. The solvent in the filtrate was removed under reduced pressure using an evaporator, and the resulting crude product (28.7 g) was subjected to silica gel short-path column chromatography (mobile phase: hexane) and fractionated by reduced pressure distillation to obtain 1,2-dihexylbenzene as a colorless, transparent liquid (yield 59%, yield 14.0 g (56.8 mmol)).

[0251] The product obtained is 1,2-dihexylbenzene. 1 The analysis was confirmed by 1 H NMR. The analytical data obtained at this time are shown below. The spectrum data was consistent with the previously reported values. 1 H NMR (500 MHz, CDCl 3 , 25℃) δ 7.14-7.09 (m, 4H), 2.61-2.57 (t, 4H,J = 8.0 Hz), 1.60-1.26 (m, 16H), 0.91-0.88 (t, 6H, J = 7.0 Hz).

[0252] ◎Manufacture of 1,2-dihexyl-4,5-diiodobenzene In a two-necked flask (100 mL), 1,2-dihexylbenzene (6.97 g, 28.3 mmol) and iodine (I 2 , 8.68 g, 34.2 mmol) and orthoperiodic acid (H 5 IO 6 3.87 g, 17.0 mmol) was added. Water (8.5 mL), acetic acid (AcOH, 160 mL) and sulfuric acid (H 2 SO 4 , 32 mL) were mixed and added to the reaction vessel, followed by heating to reflux at 80°C. 20 hours after the start of heating to reflux, analysis of the reaction solution by thin layer chromatography (TLC, mobile phase: hexane) confirmed that the raw materials had disappeared. The reaction mixture was cooled to room temperature, and then neutralized using an aqueous solution of sodium hydroxide (NaOH). Water and dichloromethane were added to the neutralized reaction mixture, and the organic layer and aqueous layer were separated. The product was extracted from the aqueous layer three times using dichloromethane, and the combined organic layer was extracted with sodium thiosulfate (Na 2 S 2 O 3The organic layer was then washed with saturated saline, dried over magnesium sulfate, and filtered. The solvent in the filtrate was removed under reduced pressure using an evaporator, and the resulting crude product (14.1 g) was subjected to silica gel short-path column chromatography (mobile phase: hexane) to remove the origin component in TLC, yielding 1,2-dihexyl-4,5-diiodobenzene as a colorless, transparent liquid (yield 76%, yield 10.7 g (21.5 mmol)).

[0253] The product obtained is 1,2-dihexyl-4,5-diiodobenzene. 1 The analysis was confirmed by 1 H NMR. The analytical data obtained at this time are shown below. The spectrum data was consistent with the previously reported values. 1 H NMR (500 MHz, CDCl 3 , 25℃) δ 7.60 (s, 2H), 2.48-2.45 (t,4H,J = 8.0 Hz), 1.53-1.30 (m, 16H), 0.91-0.88 (t, 6H, J = 6.5 Hz).

[0254] ◎Manufacture of 1,2-dihexyl-4,5-bis[(trimethylsilyl)ethynyl]benzene A Schlenk tube (10 mL) was flame dried and the atmosphere inside the Schlenk tube was replaced with argon gas. Copper (I) iodide (CuI, 9.2 mg, 48 μmol), bis(triphenylphosphine)palladium (II) dichloride (PdCl 2 (PPh 3 ) 2, 15.5mg, 22.1μmol) and 1,2-dihexyl-4,5-diiodobenzene (117mg, 234μmol) were added. Next, diisopropylamine (Diisopropylamine, 2.8mL) degassed by bubbling with argon gas was added. (Trimethylsilyl)acetylene (TMSA, 90.0μL, 637μmol) was added dropwise to the reaction mixture and stirred at room temperature. 23 hours after the start of stirring, analysis of the reaction solution by thin layer chromatography (TLC, mobile phase: hexane) confirmed that the raw materials had disappeared. The reaction mixture was filtered and washed with diethyl ether. The solvent was distilled off under reduced pressure using an evaporator, and the obtained crude product (216mg) was subjected to silica gel column chromatography (mobile phase: hexane) and further purified by gel permeation chromatography (GPC). As a result, 1,2-dihexyl-4,5-bis[(trimethylsilyl)ethynyl]benzene was obtained as a yellow oil (yield 53%, yield 54.1 mg (0.12 mmol)).

[0255] The product obtained is 1,2-dihexyl-4,5-bis[(trimethylsilyl)ethynyl]benzene. 1 The analysis was confirmed by 1 H NMR. The analytical data obtained at this time are shown below. The spectrum data was consistent with the previously reported values. 1 H NMR (500 MHz, CDCl 3 , 25℃) δ 7.23 (s, 2H), 2.54-2.51 (t, 4H, J = 8.0 Hz), 1.52-1.30 (m, 16H), 0.90-0.87 (t, 6H, J = 6.5 Hz), 0.26 (s, 18H).

[0256] ◎Production of 1,2-diethynyl-4,5-dihexylbenzene Potassium carbonate (69.5 mg, 503 μmol) and 1,2-dihexyl-4,5-bis[(trimethylsilyl)ethynyl]benzene (54.1 mg, 12.3 μmol) were added to a Schlenk tube (10 mL). Tetrahydrofuran (THF, 1.5 mL) and methanol (1.6 mL) were then added. The reaction mixture was stirred at room temperature for 30 minutes, and the disappearance of the raw materials was confirmed by analysis of the reaction solution by thin layer chromatography (TLC, mobile phase: hexane). The reaction mixture was diluted with ammonium chloride (NH 4 After washing twice with an aqueous solution of 1,2-diethyl-4,5-dihexylbenzene (Cl), the product was extracted from the aqueous layer three times using diethyl ether and washed with water and saturated saline. The organic layer was dehydrated with magnesium sulfate and filtered. The solvent in the filtrate was distilled off under reduced pressure using an evaporator to obtain 1,2-diethynyl-4,5-dihexylbenzene (34.8 mg) containing a small amount of impurities. The fact that 1,2-diethynyl-4,5-dihexylbenzene was obtained was 1 Confirmed by 1 H NMR.

[0257] ◎Production of 6,7-dihexyl-2,3-bis(trimethylsilyl)biphenylene A two-necked eggplant flask (50 mL) was flame dried, and the atmosphere in the flask was replaced with argon gas. Bis(trimethylsilyl)acetylene (BTMSA, 6.50 mL, 28.6 mmol) was added thereto, and the mixture was heated and stirred at 50°C. Separately, 1,2-diethynyl-4,5-dihexylbenzene (34.8 mg), (C 5 H 5 )Co(CO) 2A mixed solution of 1.0 mL of 1.2-TETRA-2-(2.40 mL, 10.6 mmol) and BTMSA (8.0 μL, 60 μmol) was weighed out in a gas-tight syringe (5.0 mL). At this time, the gas-tight syringe was shielded from light with aluminum foil. The reaction mixture obtained above after heating and stirring at 50° C. was further heated and stirred at 155° C. while irradiating light from a halogen lamp, and the mixed solution in the gas-tight syringe was dropped over 1 hour to the reaction mixture being heated and stirred in this manner. After the dropwise addition was completed, the reaction mixture was further stirred at 155° C. for 2 hours. Next, the disappearance of the raw materials was confirmed by analysis of the reaction mixture by thin layer chromatography (TLC, mobile phase: hexane), the light irradiation and heating were stopped, and the reaction mixture was cooled to room temperature. The reaction mixture was distilled under reduced pressure to remove excess BTMSA, and a crude product (75.0 mg) was obtained. This crude product was purified by silica gel column chromatography (mobile phase: hexane) and further gel permeation chromatography (GPC). As a result, 6,7-dihexyl-2,3-bis(trimethylsilyl)biphenylene was obtained as a yellow oil (yield 61%, yield 33.4 mg (71.8 μmol)).

[0258] The product obtained is 6,7-dihexyl-2,3-bis(trimethylsilyl)biphenylene. 1 The analysis was confirmed by 1 H NMR. The analytical data obtained at this time are shown below. The spectrum data was consistent with the previously reported values. 1 H NMR (500 MHz, CDCl 3 , 25℃) δ 6.89 (s, 2H), 6.49 (s, 2H), 2.41-2.38 (t, 4H, J = 8.0 Hz), 1.51-1.31 (m, 16H), 0.91-0.88 (t, 6H, J = 7 Hz), 0.32 (s, 18H).

[0259] ◎Production of 2,3-dihexyl-6,7-diiodobiphenylene The Schlenk tube was flame-dried, and the atmosphere inside the Schlenk tube was replaced with argon gas. 6,7-Dihexyl-2,3-bis(trimethylsilyl)biphenylene (179 mg, 384 μmol) and dichloromethane (10.5 mL) were added thereto. The reaction vessel was placed in an ice bath containing salt, and the reaction mixture was stirred. A separately prepared 1 M dichloromethane solution of iodine monochloride (ICl) (850 μL, 850 μmol as iodine monochloride) was added dropwise to the reaction mixture. After the addition was completed, the reaction mixture was stirred at room temperature for 23 hours. Analysis of the reaction mixture by thin layer chromatography (TLC, mobile phase: hexane) confirmed the disappearance of the raw materials, and sodium thiosulfate (Na 2 S 2 O 3 The reaction was stopped by adding an aqueous solution of 6,7-diiodobiphenylene. Water and dichloromethane were added to the reaction mixture, and the organic layer and the aqueous layer were separated. The product was extracted from the aqueous layer three times using dichloromethane. The combined organic layers were then washed with water and saturated saline, dried over magnesium sulfate, and filtered. The solvent in the filtrate was distilled off under reduced pressure using an evaporator, and the obtained crude product was purified by silica gel column chromatography (mobile phase: hexane) to obtain 2,3-dihexyl-6,7-diiodobiphenylene as a yellow oil (yield 96%, yield 212 mg (370 μmol)).

[0260] The product obtained is 2,3-dihexyl-6,7-diiodobiphenylene. 1 H NMR, 13 The analysis was confirmed by C NMR and field desorption-high resolution mass spectrometry (FD-HRMS). The analytical data obtained are shown below. 1 H NMR (500 MHz, CDCl 3 , 25℃) δ 7.07 (s, 2H), 6.52 (s, 2H), 2.43-2.39 (t, 4H, J = 8.5 Hz), 1.50-1.29 (m, 16H), 0.91-0.88 (t, 6H, J = 7.0 Hz). 13 C NMR (125.8 MHz, CDCl 3 , 25℃) δ 152.0, 146.9, 141.3, 126.9, 120.5, 105.6, 33.2, 31.7, 31.1, 29.3, 22.6, 14.1. FD-HRMS m / z calcd. for C 24 H 30 I 2 : 572.0437, found 572.0453 (M + ).

[0261] ◎Production of 2,3-dihexyl-6-iodo-7-(trimethylsilyl)ethynylbiphenylene A Schlenk tube (100 mL) was flame dried and the atmosphere inside the Schlenk tube was replaced with argon gas. Copper (I) iodide (CuI, 6.2 mg, 33 μmol), bis(triphenylphosphine)palladium (II) dichloride (PdCl 2 (PPh 3 ) 2 , 22.5mg, 32.1μmol) and 2,3-dihexyl-6,7-diiodobiphenylene (177mg, 309μmol) were added. Next, diisopropylamine (5.0mL) and tetrahydrofuran (3.1mL) that had been degassed by bubbling with argon gas were added. (Trimethylsilyl)acetylene (TMSA, 952.5μL, 372μmol) was added dropwise to the reaction mixture, and the reaction mixture was stirred at 40°C. 23 hours after the start of stirring, heating and stirring were stopped, and the reaction mixture was filtered and washed with diethyl ether. The solvent was distilled off under reduced pressure using an evaporator, and the obtained crude product (201mg) was purified by silica gel column chromatography (mobile phase: hexane). As a result, 2,3-dihexyl-6-iodo-7-(trimethylsilyl)ethynylbiphenylene was obtained as a yellow oil (yield 24%, yield 39.7 mg (0.07 mmol)).

[0262] The product obtained is 2,3-dihexyl-6-iodo-7-(trimethylsilyl)ethynylbiphenylene. 1 H NMR, 13 The results were confirmed by C NMR, infrared spectroscopy (IR) and field desorption-high resolution mass spectrometry (FD-HRMS). The analytical data obtained are shown below. 1 H NMR (500 MHz, CDCl 3 , 25℃) δ 7.01 (s, 1H), 6.63(s, 1H), 6.53(s, 1H), 6.50 (s, 1H), 2.44-2.38 (m, 4H), 1.52-1.25 (m, 16H), 0.91-0.85 (m, 6H, J = 6.5 Hz), 0.26 (s, 9H). 13 C NMR (125.8 MHz, CDCl 3 , 25℃) δ 152.4, 151.0, 147.4, 147.3, 141.9, 141.4, 128.3, 126.7, 120.9, 120.6, 120.1, 108.2, 101.1, 99.3, 33.6, 32.1, 31.6, 31.5, 29.8, 29.7, 23.0, 14.5. IR (NaCl) 2956, 2926, 2856, 2150, 1249, 863, 843, 760. FD-HRMS m / z calcd. for C 29 H 39 I 1 S 1 : 542.1866, found 542.1876 (M + ).

[0263] ◎Production of 2,3-dihexyl-7-iodo-6-ethynylbiphenylene Potassium carbonate (86.2 mg, 624 μmol) and 2,3-dihexyl-6-iodo-7-(trimethylsilyl)ethynylbiphenylene (159 mg, 293 μmol) were added to a recovery flask (50 mL), followed by diethyl ether (7.0 mL) and methanol (7.0 mL). The mixture was then stirred at room temperature for 1 hour, and the disappearance of the raw materials was confirmed by analysis of the reaction mixture by thin layer chromatography (TLC, mobile phase: hexane). The reaction mixture was washed once with an aqueous ammonium chloride solution, and the product was extracted three times from the aqueous layer using diethyl ether. The combined organic layers were then washed with water and saturated saline, dried over magnesium sulfate, and filtered. The solvent of the filtrate was distilled off under reduced pressure using an evaporator to obtain 2,3-dihexyl-7-iodo-6-ethynylbiphenylene containing a small amount of impurities. The fact that 2,3-dihexyl-7-iodo-6-ethynylbiphenylene was obtained 1 Confirmed by 1 H NMR.

[0264] ◎Production of hexahexyltris(biphenyleno)dehydro

[12] annulene (compound (2)-101) The Schlenk tube was flame-dried, and the atmosphere inside the Schlenk tube was replaced with argon gas. The 2,3-dihexyl-7-iodo-6-ethynylbiphenylene containing a small amount of impurity obtained above was transferred to the Schlenk tube using chloroform. The pressure inside the system was reduced, and the chloroform was distilled off. Copper (I) iodide (17.1 mg, 89.6 μmol), triphenylphosphine (PPh 3, 24.5mg, 93.4μmol) and potassium carbonate (121mg, 875μmol)) were added. Next, DMF (2.0mL) degassed by bubbling with argon gas was added. The reaction mixture was heated and stirred at 150℃, and after 12 hours, the disappearance of the raw materials was confirmed by analysis of the reaction mixture by thin layer chromatography (TLC, mobile phase: hexane). Water and ethyl acetate were added to the reaction mixture, and the organic layer and the aqueous layer were separated. The product was extracted from the aqueous layer three times using diethyl ether. The combined organic layer was then washed with an aqueous ammonium chloride solution, water, and saturated saline, dried over magnesium sulfate, and filtered. The solvent of the filtrate was distilled off under reduced pressure using an evaporator, and the obtained crude product was purified by silica gel column chromatography (mobile phase: hexane / dichloromethane = 10 / 1 (volume ratio)) and further by gel permeation chromatography (GPC). As a result, the target product, hexahexyltris(biphenyleno)dehydro

[12] annulene (compound (2)-101), was obtained as a brown solid (yield 3%, yield 3.0 mg (2.9 μmol)).

[0265] The product obtained is hexahexyltris(biphenyleno)dehydro

[12] annulene. 1 H NMR, 13 The analysis was confirmed by C NMR and field desorption-high resolution mass spectrometry (FD-HRMS). The analytical data obtained are shown below. 1 H NMR (500 MHz, CDCl 3 , 25℃) δ 6.52 (s, 6H), 6.31 (s, 6H), 2.44-2.41 (t, 12H, J = 8.0 Hz), 1.51-1.26 (m, 48H), 0.90-0.88 (t, 6H, J = 7.0 Hz). 13 C NMR (125.8 MHz, CDCl 3, 25℃) δ 150.9, 146.7, 141.2, 127.0, 119.8, 118.9, 95.1, 33.2, 31.8, 31.2, 29.3, 22.6, 14.1. FD-HRMS m / z calcd. for C 78 H 90 : 1026.7046, found 1026.7028 (M + ).

[0266] [ka]

[0267] <<Evaluation of compound (2)>> <Prediction of electronic states by quantum chemical calculations> The electronic state of compound (2)-101 was predicted by the same method as in Example 1. A stable calculation was performed, and it was confirmed that compound (2)-101 takes a closed shell singlet state. The HOMO energy level was -4.79 eV, the LUMO energy level was -2.63 eV, and the HOMO-LUMO energy gap (EGap) was 2.16 eV. From these results, it was confirmed that compound (2)-101 can be used as a p-type semiconductor.

[0268] <Production of hexahex(trimethylsilyl)tris(biphenyleno)dehydro

[12] annulene> [Example 4] ◎Production of hexaethynyldehydrobenzo

[12] annulene Hexakis[(triisopropylsilyl)ethynyl]dehydrobenzo

[12] annulene (153 mg, 110 μmol), a 1 M solution of tetrabutylammonium fluoride (TBAF) in tetrahydrofuran (1.7 mL, 1.7 mmol as TBAF), and tetrahydrofuran (8.0 mL) were added to a recovery flask. The mixture was stirred at room temperature for 30 minutes, and the disappearance of the raw material was confirmed by analyzing the reaction mixture by thin layer chromatography (TLC, mobile phase: hexane). An aqueous solution of ammonium chloride and chloroform were added to the reaction mixture to separate the phases, and the product was extracted from the aqueous layer three times using chloroform. The combined organic layers were then washed with water and saturated saline, dried over magnesium sulfate, and filtered. The solvent in the filtrate was removed under reduced pressure using an evaporator, and the resulting crude product was purified by reprecipitation (solvent: chloroform / methanol) to obtain hexaethynyldehydrobenzo

[12] annulene (32.3 mg) containing a small amount of impurities.

[0269] ◎Production of hexahex(trimethylsilyl)tris(biphenyleno)dehydro

[12] annulene The two-necked eggplant flask was flame-dried, and the atmosphere in the flask was replaced with argon gas. Bis(trimethylsilyl)acetylene (BTMSA, 8.00 mL, 35.3 mmol) was added thereto, and the mixture was heated and stirred at 130°C. Separately, the hexaethynyldehydrobenzo

[12] annulene (32.3 mg), (C 5 H 5 )Co(CO) 2A mixed solution of 1.0μL (3.0μL, 23μmol), BTMSA (6.00mL, 26.5mmol) and cyclopentyl methyl ether (CPME, 6.0mL) was weighed into a gas-tight syringe. At this time, the gas-tight syringe was shielded from light with aluminum foil. The reaction mixture obtained above after heating and stirring at 130°C was further heated and stirred at 140°C while irradiating light from a halogen lamp, and the mixed solution in the gas-tight syringe was dropped into the reaction mixture being heated and stirred in this manner over a period of 4 hours. After the end of the dropwise addition, the reaction mixture was further stirred at 140°C for 2.5 hours. Next, the disappearance of the raw materials was confirmed by analysis of the reaction mixture by thin layer chromatography (TLC, mobile phase: hexane), the light irradiation and heating were stopped, and the reaction mixture was cooled to room temperature. CPME was distilled off from the reaction mixture under reduced pressure using an evaporator, and the excess BTMSA was removed by further distillation under reduced pressure to obtain a crude product. This crude product was subjected to silica gel column chromatography (mobile phase: hexane / dichloromethane = 3 / 1 (volume ratio)) and further purified by crystallization (solvent: dichloromethane / methanol) to obtain the target product, hexahex(trimethylsilyl)tris(biphenyleno)dehydro

[12] annulene (compound (2)-501, 2 mg).

[0270] The product obtained is hexahex(trimethylsilyl)tris(biphenyleno)dehydro

[12] annulene. 1 H NMR, 13 The analysis was confirmed by C NMR and field desorption-high resolution mass spectrometry (FD-HRMS). The analytical data obtained are shown below. 1 H NMR (500 MHz, CDCl 3 , 25℃) δ 7.02 (s, 6H), 6.42 (s, 6H), 0.33 (s, 54H). 13 C NMR (125.8 MHz, CDCl 3, 25℃) δ 151.9, 148.6, 127.3, 123.5, 120.0, 95.1, 2.1. FD-HRMS m / z calcd. for C 60 H 66 S 6 : 954.3780 found 954.3788 (M + ).

[0271] [ka]

[0272] <<Evaluation of compound (2)>> <Prediction of electronic states by quantum chemical calculations> The electronic state of compound (2)-501 was predicted by the same method as in Example 1. The HOMO energy level of compound (2)-501 was −4.97 eV, the LUMO energy level was −2.79 eV, and the HOMO-LUMO energy gap (EGap) was 2.18 eV. From these results, it was confirmed that compound (2)-501 can be used as a p-type semiconductor.

[0273] <<Production of compound (3)>> <Production of Compound (3)-601> [Example 5] ◎Production of 2,2'-dibromobiphenyl A three-necked eggplant flask (300 mL) equipped with a three-way cock was flame-dried, and the atmosphere in the three-necked eggplant flask was replaced with argon gas. o-Dibromobenzene (8.26 g, 35.0 mmol) and tetrahydrofuran (90 mL) were added to the flask, and the flask was cooled to -78°C. A hexane solution (11.1 mL, 17.5 mmol as n-BuLi) with a concentration of 1.58 M was added dropwise to the flask over 10 minutes, and after the addition was completed, the mixture was stirred for another 20 minutes. The reaction mixture was then gradually warmed to room temperature, and after 1.5 hours, hydrochloric acid with a concentration of 2 M was added. Ethyl acetate and water were then added to the reaction mixture to separate the phases, and the product was extracted from the aqueous layer three times using ethyl acetate. The combined organic layers were then washed with water and saturated saline, dried over magnesium sulfate, and filtered. The solvent in the filtrate was distilled off under reduced pressure using an evaporator, and the resulting crude product was purified by silica gel column chromatography (mobile phase: hexane) to obtain 2,2'-dibromobiphenyl as a white solid (yield 71%, yield 3.86 g (12.4 mmol)).

[0274] The product obtained is 2,2'-dibromobiphenyl. 1 The analysis was confirmed by 1 H NMR. The analytical data obtained at this time are shown below. 1 H NMR (500 MHz, CDCl 3 , 25℃) δ 7.23-7.27 (m, 4H), 7.36-7.39 (m, 2H), 7.66-7.67 (m, 2H).

[0275] ◎Production of biphenylene A two-necked eggplant flask (50 mL) equipped with a three-way cock was flame-dried, and the atmosphere in the two-necked eggplant flask was replaced with argon gas. 2,2'-dibromobiphenyl (250 mg, 802 μmol) and tetrahydrofuran (16.9 mL) were added and cooled to -78°C. A hexane solution (1.18 mL, 1.79 mmol as n-BuLi) with a concentration of 1.58 M was added to the flask. The reaction mixture was gradually warmed to room temperature while stirring, and after 16.5 hours, an aqueous ammonium chloride solution was added to stop the reaction. Next, ethyl acetate and water were added to the reaction mixture to separate the phases, and organic matter was extracted twice from the aqueous layer using ethyl acetate. The combined organic layer was then washed with water and saturated saline, dried over magnesium sulfate, and filtered. The solvent in the filtrate was removed under reduced pressure using an evaporator, and the resulting crude product was purified by silica gel column chromatography (mobile phase: hexane) and recycling preparative HPLC (mobile phase: chloroform) to obtain biphenylene as a white solid (yield 54%, yield 65.4 mg (430 mmol)).

[0276] The fact that the product obtained is biphenylene is 1 The analysis was confirmed by 1 H NMR. The analytical data obtained at this time are shown below. 1 H NMR (500 MHz, CDCl 3 , 25℃) δ6.63-6.61 (m, 4H), 6.73-6.72 (m, 4H).

[0277] ◎Production of 2-bromobiphenylene Biphenylene (310 mg, 2.04 mmol) and N-bromosuccinimide (418 mg, 2.25 mmol) were dissolved in N,N-dimethylformamide (5.0 mL) and stirred at room temperature for 10 minutes, after which water and dichloromethane were added. The product was extracted with dichloromethane. The organic layer was washed with saturated saline, dried over magnesium sulfate, and the magnesium sulfate was filtered off. The solvent in the filtrate was removed under reduced pressure using an evaporator, and the resulting crude product was purified by silica gel column chromatography (mobile phase: hexane) to obtain 2-bromobiphenylene (yield 480 mg) containing impurities.

[0278] The product obtained is 2-bromobiphenylene. 1 The analysis was confirmed by 1 H NMR. The analytical data obtained at this time are shown below. 1 H NMR (500 MHz, CDCl 3 , 25℃) δ 6.90 (dd, J = 7.2, 2.0 Hz, 1H), 6.81-6.74 (m, 3H), 6.69-6.62 (m, 2H), 6.49 (d, J = 7.2 Hz, 1H).

[0279] ◎Production of diethyl 2,5-bis(2-biphenylenyl)-1,4-benzenedicarboxylate A two-necked eggplant flask (50 mL) equipped with a condenser was flame dried, and the atmosphere inside the flask was replaced with argon gas. 2-Bromobiphenylene (907 mg) containing a small amount of impurities and tetrahydrofuran (5.0 mL) were added thereto, and the mixture was cooled to -78°C. A hexane solution (2.5 mL, 4.0 mmol as n-BuLi) with a concentration of 1.58 M was added thereto over a period of 5 minutes. As the reaction mixture solidified within the system, tetrahydrofuran (5.0 mL) was further added to the reaction mixture, and the mixture was stirred for 1 hour. 1.0 M zinc chloride (ZnCl 2 ) in tetrahydrofuran (4.3 mL, ZnCl 2The mixture was stirred in an ice bath for 1 hour. The system was then removed from the ice bath, and tetrakis(triphenylphosphine)palladium(0) (150 mg, 130 μmol), diethyl 2,5-dibromoterephthalate (496 mg, 1.30 mmol), and tetrahydrofuran (5.0 mL) were added. The reaction mixture was stirred at 75° C. for 24 hours, and then an aqueous ammonium chloride solution was added to stop the reaction. Ethyl acetate and water were added to the reaction mixture to separate the phases, and organic matter was extracted from the aqueous layer three times using ethyl acetate. The combined organic layer was then washed with water and saturated saline, dried over magnesium sulfate, and filtered. The solvent in the filtrate was distilled off under reduced pressure using an evaporator, and the resulting crude product was purified by silica gel column chromatography (mobile phase: hexane / dichloromethane = 1 / 1 (volume ratio)) and recycling preparative HPLC (mobile phase: chloroform) to obtain 1,4-Diethyl-2,5-bis(2-biphenylenyl)-1,4-benzenedicarboxylate as a yellow solid (yield 51%, yield 349 mg (668 mmol)).

[0280] The product obtained is diethyl 2,5-bis(2-biphenylenyl)-1,4-benzenedicarboxylate. 1 H NMR, 13 The analysis was confirmed by C NMR and field desorption-high resolution mass spectrometry (FD-HRMS). The analytical data obtained are shown below. 1 H NMR (500 MHz, CDCl 3 , 25℃) δ 7.73 (s, 2H), 6.80-6.62 (m, 14H), 4.25-4.19 (q, J = 7.5 Hz, 4H), 1.22-1.17 (t, J = 7.5 Hz, 6H). 13 C NMR (126 MHz, CDCl 3, 25℃) δ 168.0, 151.2, 150.8, 150.6, 141.1, 140.2, 133.3, 131.2, 128.6, 128.5, 128.2, 117.9, 117.7, 117.6, 117.0, 61.5, 13.9. FD-HRMS m / z calcd. for C 36 H 26 O 4 (M + ): 522.18311, found 522.18322.

[0281] ◎Production of 2,5-bis(2-biphenylenyl)-1,4-benzenedicarboxylic acid In a two-necked eggplant flask (50 mL) equipped with a condenser and a reflux condenser, 2,5-bis(2-biphenylenyl)-1,4-benzenedicarboxylate diethyl (312 mg, 597 mmol), sodium hydroxide (NaOH, 403 mg, 10.1 mmol), ethanol (EtOH, 9.0 mL) and water (6.0 mL) were added, and the reaction mixture was stirred at 110° C. for 24 hours. After cooling to room temperature, hydrochloric acid with a concentration of 10% by mass was added to the reaction mixture, which was then subjected to suction filtration and washed with water. The solid obtained was dried overnight in a dryer. As a result, 2,5-bis(2-biphenylenyl)-1,4-benzenedicarboxylic acid (yield 379 mg) containing a small amount of impurities was obtained as a yellow solid.

[0282] ◎Production of benzo[3',4']cyclobuta[1',2':5,6]indeno[1,2-b]benzo[3,4]cyclobuta[1,2-h]fluorene-7,15-dione A two-necked eggplant flask (50 mL) equipped with a three-way cock was flame dried, and the atmosphere inside the flask was replaced with argon gas. The 2,5-bis(2-biphenylenyl)-1,4-benzenedicarboxylic acid (379 mg) obtained above and dichloromethane (20 mL) were added thereto, and the mixture was stirred at room temperature. Three drops of dehydrated N,N-dimethylformamide were added with a pipette. The mixture was then mixed with thionyl chloride (SOCl 2 After the completion of the dropwise addition, the mixture was stirred at room temperature for another 22.5 hours. The solvent in the system was then removed under reduced pressure and the atmosphere was replaced with argon gas. Aluminum chloride (AlCl 3 , 320mg, 2.40mmol) and dichloromethane (20mL) were added, and the mixture was stirred at room temperature for 4 hours, after which dilute hydrochloric acid with a concentration of 3% by mass was added to stop the reaction. The reaction mixture was suction filtered, and the solid was washed with acetone, dichloromethane, and water. The obtained solid was collected, ethanol and water were added, and the mixture was irradiated with ultrasonic waves. Then, suction filtration was performed, and the obtained solid was dried in a dryer. As a result, Benzo[3',4']cyclobuta[1',2':5,6]indeno[1,2-b]benzo[3,4]cyclobuta[1,2-h]fluorene-7,15-dione (Benzo[3',4']cyclobuta[1',2':5,6]indeno[1,2-b]benzo[3,4]cyclobuta[1,2-h]fluorene-7,15-dione) containing impurities was obtained as a brown-green solid (yield 280mg). This solid had low solubility in the solvent.

[0283] Preparation of Compound (3)-601 A two-necked recovery flask (100 mL) equipped with a three-way cock was flame dried, and the atmosphere in the two-necked recovery flask was replaced with argon gas. Tetrahydrofuran (40 mL) and lithium (triisopropylsilyl) acetylide (TIPSA, 667 μL, 3.00 mmol) were added thereto, and the flask was cooled to -78°C. A hexane solution (1.82 mL, 2.88 mmol as n-BuLi) with a concentration of 1.58 M was added dropwise to the mixture, and 30 minutes after the end of the addition, the impurity-containing benzo[3',4']cyclobuta[1',2':5,6]indeno[1,2-b]benzo[3,4]cyclobuta[1,2-h]fluorene-7,15-dione (280 mg) obtained above was added. After stirring at room temperature for 2 hours, an aqueous solution of ammonium chloride was added to the reaction mixture to stop the reaction. Then, dichloromethane and water were added to the reaction mixture to separate the phases, and organic matter was extracted from the aqueous layer three times using dichloromethane. The combined organic layer was then washed with water and saturated saline, dried over magnesium sulfate, and filtered. The solvent of the filtrate was distilled off under reduced pressure using an evaporator, and the obtained crude product was transferred to a two-necked eggplant flask (100 mL). Then, dry toluene (40 mL) and tin(II) chloride (SnCl 2 , 458 mg, 2.42 mmol) was added, followed by stirring at 40°C. After 2 hours, the disappearance of the raw materials was confirmed by analysis of the reaction mixture by thin layer chromatography (mobile phase: hexane / dichloromethane = 1 / 1 (volume ratio)). The reaction mixture was filtered, and the solvent in the filtrate was distilled off under reduced pressure to obtain a crude product. Dichloromethane was used as a good solvent, and acetonitrile (CH 3 The crude product was reprecipitated using hexane / dichloromethane (CN) as a poor solvent, filtered, and the resulting solid was purified by silica gel column chromatography (mobile phase: hexane / dichloromethane = 1 / 3 (volume ratio)) and recycling preparative HPLC (mobile phase: chloroform) to obtain compound (3)-601 as a yellow-green solid (yield 3%, yield 17.4 mg (15.48 μmol)).

[0284] The compound obtained is compound (3)-601. 1 H NMR, 13The analysis was confirmed by C NMR and field desorption-high resolution mass spectrometry (FD-HRMS). The analytical data obtained are shown below. 1 H NMR (500 MHz, CDCl 3 , 25℃) δ 7.74 (s, 2H),7.02-7.01 (m, 4H), 6.91-6.79 (m, 4H) 6.74-6.70 (m, 4H), 1.04 (s, 84H). 13 C NMR (126 MHz, CDCl 3 , 25℃) δ 151.9, 151.5, 150.6, 150.0, 147.0, 146.6, 139.3, 139.0, 128.7, 128.5, 117.5, 117.4, 115.3, 114.5, 110.0, 105.7, 81.7, 44.1, 18.6, 11.2. FD-HRMS m / z calcd. for C 76 H 98 S 4 (M + ): 1122.6746, found 1122.6789.

[0285] [ka]

[0286] <<Evaluation of compound (3)>> <Prediction of electronic states by quantum chemical calculations> The electronic state of a compound (compound (3)-602) having a structure in which four triisopropylsilyl groups in compound (3)-601 are replaced with trimethylsilyl groups was predicted by the same method as in Example 1. A stable calculation was performed, and it was confirmed that compound (3)-602 takes a closed shell singlet state. The HOMO energy level was -5.26 eV, the LUMO energy level was -2.08 eV, and the HOMO-LUMO energy gap (EGap) was -3.18 eV. From these results, it was confirmed that compound (3)-602 and its analogous compound, compound (3)-601, can be used as p-type semiconductors. [Industrial Applicability]

[0287] The present invention can be used as an organic functional material, including an organic semiconductor material.

Claims

1. The following general formula (1) 【Chemistry 1】 (In the formula, R １０１ , R １０２ , R １０３ , R １０４ , R １０５ , R １０６ , R １０７ , R １０８ , R １０９ , R １１０ , R １１１ , R １１２ , R １１３ , R １１４ , R １１５ , R １１６ , R １１７ and R １１８ are each independently a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylethynyl group, an arylethynyl group, a trialkylsilylethynyl group, or a trialkylsilyl group; １１ and n １２ are each independently 0 or 1. A compound represented by the formula:

2. The R １０１ , R １０２ , R １０３ , R １０４ , R １０５ , R １０６ , R １０７ , R １０８ , R １０９ , R １１０ , R １１１ , R １１２ , R １１３ , R １１４ , R １１５ , R １１６ , R １１７ and R １１８ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms.

3. The compound represented by the general formula (1) is represented by the following general formula (11): 【Chemistry 2】 (In the formula, R １０１１ , R １０４１ , R １０５１ , R １０８１ , R １１１１ and R １１２１ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms; １１ and n １２ is the same as above.) The compound according to claim 1, which is a compound represented by the formula:

4. The following general formula (2) 【Chemistry 3】 (In the formula, R ２０１ , R ２０２ , R ２０３ , R ２０４ , R ２０５ , R ２０６ , R ２０７ , R ２０８ , R ２０９ , R ２１０ , R ２１１ , R ２１２ , R ２１３ , R ２１４ , R ２１５ , R ２１６ , R ２１７ , R ２１８ , R ２１９ , R ２２０ , R ２２１ , R ２２２ , R ２２３ and R ２２４ are each independently a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylethynyl group, an arylethynyl group, a trialkylsilylethynyl group, or a trialkylsilyl group; ２１ , n ２２ and n ２３ are each independently 0 or 1. A compound represented by the formula:

5. The R ２０１ , R ２０２ , R ２０３ , R ２０４ , R ２０５ , R ２０６ , R ２０７ , R ２０８ , R ２０９ , R ２１０ , R ２１１ , R ２１２ , R ２１３ , R ２１４ , R ２１５ , R ２１６ , R ２１７ , R ２１８ , R ２１９ , R ２２０ , R ２２１ , R ２２２ , R ２２３ and R ２２４ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms.

6. The compound represented by the general formula (2) is represented by the following general formula (21): 【Chemistry 4】 (In the formula, R ２０３１ , R ２０４１ , R ２０９１ , R ２１０１ , R ２１５１ and R ２１６１ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms; ２１ , n ２２ and n ２３ is the same as above.) The compound according to claim 4, which is a compound represented by the formula:

7. The following general formula (3) 【Chemistry 5】 (In the formula, R ３０１ , R ３０２ , R ３０３ , R ３０４ , R ３０５ , R ３０６ , R ３０７ , R ３０８ , R ３０９ , R ３１０ , R ３１１ , R ３１２ , R ３１３ , R ３１４ , R ３１５ , R ３１６ , R ３１７ , R ３１８ , R ３１９ and R ３２０ are each independently a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylethynyl group, an arylethynyl group, a trialkylsilylethynyl group, or a trialkylsilyl group; ３１ and n ３２ are each independently 0 or 1. A compound represented by the formula:

8. The R ３０１ , R ３０２ , R ３０３ , R ３０４ , R ３０５ , R ３０６ , R ３０７ , R ３０８ , R ３０９ , R ３１０ , R ３１１ , R ３１２ , R ３１３ , R ３１４ , R ３１５ , R ３１６ , R ３１７ , R ３１８ , R ３１９ and R ３２０ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms.

9. The compound represented by the general formula (3) is represented by the following general formula (31): 【Chemistry 6】 (In the formula, R ３０１１ , R ３０２１ , R ３０５１ , R ３０６１ , R ３０９１ , R ３１０１ , R ３１３１ and R ３１４１ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylethynyl group having 3 to 12 carbon atoms, an arylethynyl group having 8 to 17 carbon atoms, a trialkylsilylethynyl group having 5 to 14 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms; ３１ and n ３２ is the same as above.) The compound according to claim 7, which is a compound represented by the formula:

10. An organic semiconductor material comprising the compound according to any one of claims 1 to 9.

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