Compound, method for producing the same, and use thereof

Abstract

To provide a novel aromatic condensed ring compound exhibiting superior solubility in an organic solvent.SOLUTION: A compound according to one embodiment of the present invention is represented by formula (I) or formula (II) below.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to compounds, as well as methods for their preparation and uses. [Background technology]

[0002] Aromatic fused rings are widely used as molecular skeletons of functional molecules, and are used as the skeletons of hole transport materials, hole introduction materials, hole extraction materials, electron transport materials, electron introduction materials, electron extraction materials, host materials, and the like used in organic semiconductor materials and organic-inorganic semiconductors, such as organic electroluminescence (OLED), organic thin-film solar cells (OPV), organic field-effect transistors (OFET), perovskite solar cells, and multilayer thin-film organic semiconductors such as perovskite quantum dots (e.g., Non-Patent Document 1). Compounds having aromatic fused rings are called "aromatic fused ring compounds."

[0003] In order to produce a multilayer thin film using an organic semiconductor of an aromatic fused ring compound having hole or electron transport properties, it is essential to improve the solubility of the aromatic fused ring compound in organic solvents. However, aromatic fused ring compounds generally have very poor solubility in organic solvents.

[0004] To address this issue, conventional methods have been adopted to ensure solubility by introducing long-chain alkyl groups into aromatic fused ring compounds, converting them into liquid crystal type molecules, or oligomerizing them (Non-Patent Document 2).

[0005] Furthermore, studies have been conducted to apply the aromatic fused ring compound to coating methods by improving its solubility (Non-Patent Document 3).

[0006] Furthermore, methods for producing aromatic fused ring compounds, particularly aromatic heterocyclic compounds, are limited, and ring construction has traditionally been carried out using noble metal catalysts, particularly palladium catalysts (Non-Patent Document 4). [Prior art documents] [Non-patent literature]

[0007] [Non-Patent Document 1] Journal of the American Chemical Society, 131, 13596-13597(2009). [Non-patent document 2] Macromol. Rapid Commun., 30, 1179-1202 (2009) [Non-patent document 3] Solution-Processed Organic Light-emitting Devices, 2024 Published by Elsevier [Non-patent document 4] Science, 359, 435-439 (2018) Summary of the Invention [Problem to be solved by the invention]

[0008] However, conventional techniques for ensuring solubility by introducing solubility-enhancing moieties into aromatic fused ring compounds have the major drawback that the solubility-enhancing effect of these moieties is limited, and that the proportion of aromatic fused rings in a molecule required for hole and electron transfer is relatively reduced. In addition, there is also the problem of increased intramolecular vibration, which reduces the semiconductor's function.

[0009] For this reason, there is a limit to the application of conventional aromatic fused ring compounds to coating methods in which they are dissolved in organic solvents, and this has hindered their practical use.

[0010] Therefore, the evaporation method is currently used for OLED smartphones and OLED TVs.

[0011] Furthermore, conventional techniques for improving the solubility of aromatic fused ring compounds themselves require the use of multi-stage synthesis, which makes purification at each synthesis stage difficult. Furthermore, even after purification, trace amounts of impurities remain, making these techniques impractical and limiting them to academic research.

[0012] Furthermore, while conventional production methods that use precious metal catalysts to construct rings are being developed, there is an urgent need to develop production methods that use non-precious metal catalysts from the perspective of realizing a sustainable society and green transformation. However, it remains difficult to produce a variety of aromatic fused ring compounds with desirable physical properties using non-precious metal catalysts.

[0013] An object of the present invention is to provide a novel aromatic fused ring compound that has high solubility in organic solvents, and a production method suitable for a sustainable society for producing the novel aromatic fused ring compound using a non-noble metal catalyst. [Means for solving the problem]

[0014] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have constructed novel aromatic fused ring compounds having highly soluble spiro skeletons and established a method for producing the novel aromatic fused ring compounds using non-precious metal catalysts without using precious metals, aiming at a sustainable society. Furthermore, they have demonstrated that highly soluble p-type or n-type organic semiconductor compounds having these aromatic fused ring skeletons can be derived in situ continuously, thereby arriving at the present invention.

[0015] That is, the gist of the present invention is as follows. [1] A compound represented by the following formula (I) or (II): [ka] (In the formula (I), Ar a and Ar b each independently represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocycle which may have a substituent; Ar 1 and Ar 2 each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent, Ar 1 and Ar 2 and are bonded to each other directly or via a linker, and may have any substituents; Z 1 represents a hydrogen atom or an optional substituent; In the formula (II), Ar c , Ar d and Ar e each independently represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocycle which may have a substituent; Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent, Ar 1 and Ar 2 , and Ar 3 and Ar 4 are bonded to each other directly or via a linker, and may each have an optional substituent, Z 1 and Z 2 each independently represents a hydrogen atom or an arbitrary substituent.

[0016] [2] The compound represented by formula (I) is 1 and Ar 2 and have a solubility in chlorobenzene solvent that is at least twice as high as that of a compound in which they are not bonded to each other directly or via a linker; The compound represented by formula (II) is 1 and Ar 2 , and Ar 3 and Ar 4 The compound according to [1], wherein the solubility in chlorobenzene solvent is at least twice as high as that of a compound in which the compounds are not bonded to each other directly or via a linker.

[0017] [3] A method for producing the compound according to [1] or [2], comprising a production step of cyclizing an anion intermediate generated from a compound represented by the following formula (IV) or the following formula (V) and a nucleophilic reagent in the presence of a divalent zinc compound and a diamine derivative represented by formula (III): [ka] (In the formula (III), R 1 , R 2 , R 3 , and R 4 each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon ring which may have a substituent, or an aromatic heterocycle which may have a substituent, and n represents an integer of 1 to 4. [ka] (Ar in the formula (IV) and the formula (V) a , Ar b , Ar c , Ar d , Ar e , Ar 1 , Ar 2 , Ar 3 , and Ar 4 respectively represent Ar in the formula (I) or (II). a , Ar b , Ar c , Ar d , Ar e , Ar 1 , Ar 2 , Ar 3 , and Ar 4 is equivalent to

[0018] [4] A method for producing the compound according to [3], further comprising the step of adding a transition metal catalyst to a zinc-modified intermediate of a compound represented by the following formula (VI) or the following formula (VII), and carrying out a tandem coupling reaction in the system: [ka] (Ar in the formula (VI) and the formula (VII) a , Ar b , Ar c , Ar d , Ar e , Ar 1 , Ar 2 , Ar 3 , and Ar 4 respectively represent Ar in the formula (I) or (II). a, Ar b , Ar c , Ar d , Ar e , Ar 1 , Ar 2 , Ar 3 , and Ar 4 is equivalent to

[0019] [5] A method for producing the compound according to [3], further comprising the step of adding a halogenated compound, a boronated compound or a trialkylstannylated compound to a zincated intermediate of a compound represented by the following formula (VI) or the following formula (VII), to produce a compound represented by the following formula (VIII) or the following formula (IX): [ka] (Ar in the formula (VI) and the formula (VII) a , Ar b , Ar c , Ar d , Ar e , Ar 1 , Ar 2 , Ar 3 , and Ar 4 respectively represent Ar in the formula (I) or (II). a , Ar b , Ar c , Ar d , Ar e , Ar 1 , Ar 2 , Ar 3 , and Ar 4 is equivalent to [ka] (Ar in the formula (VIII) and the formula (IX) a , Ar b , Ar c , Ar d , Ar e , Ar 1 , Ar 2 , Ar 3 , and Ar 4 respectively represent Ar in the formula (I) or (II). a , Arb , Ar c , Ar d , Ar e , Ar 1 , Ar 2 , Ar 3 , and Ar 4 is synonymous with Z 3 and Z 4 each independently represents a halogen atom, a boron atom having a substituent, or a tin atom having a substituent.

[0020] [6] A composition containing the compound according to [1] or [2]. [7] An organic semiconductor compound having a skeleton represented by the following formula (I) or (II): [ka] (In the formula (I), Ar a and Ar b each independently represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocycle which may have a substituent; Ar 1 and Ar 2 each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent, Ar 1 and Ar 2 and are bonded to each other directly or via a linker, and may have any substituents; Z 1 represents a hydrogen atom or an optional substituent; In the formula (II), Ar c , Ar d and Ar e each independently represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocycle which may have a substituent. Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent; Ar 1 and Ar2 , and Ar 3 and Ar 4 are bonded to each other directly or via a linker, and may each have an optional substituent, Z 1 and Z 2 each independently represents a hydrogen atom or an arbitrary substituent. [8] An organic semiconductor device comprising an organic semiconductor device film containing the organic semiconductor compound according to [7]. [9] A film-forming ink for an organic semiconductor device, comprising the organic semiconductor compound according to [7] and an organic solvent. [Effects of the Invention]

[0021] According to one aspect of the present invention, it is possible to provide a novel aromatic fused ring compound that has high solubility in organic solvents, and a production method suitable for a sustainable society for producing this aromatic fused ring compound using a non-noble metal catalyst. DETAILED DESCRIPTION OF THE INVENTION

[0022] Hereinafter, embodiments of the present invention will be described, but the embodiments of the present invention are not limited to the following embodiments. Unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more and B or less."

[0023] [1. Compound] One aspect of the present invention is a compound represented by the following formula (I) or the following formula (II): [ka] (In the formula (I), Ar a and Ar b each independently represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocycle which may have a substituent; Ar 1 and Ar 2 each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent, Ar1 and Ar 2 and are bonded to each other directly or via a linker, and may have any substituents; Z 1 represents a hydrogen atom or an optional substituent; In the formula (II), Ar c , Ar d and Ar e each independently represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocycle which may have a substituent; Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent, Ar 1 and Ar 2 , and Ar 3 and Ar 4 are bonded to each other directly or via a linker, and may each have an optional substituent, Z 1 and Z 2 each independently represents a hydrogen atom or an arbitrary substituent.

[0024] The compound according to one aspect of the present invention is a compound represented by the formula (I) or the formula (II), and therefore, in the formula (I), Ar 1 and Ar 2 Or, in the formula (II), Ar 1 and Ar 2 and Ar 3 and Ar 4 are aromatic fused ring compounds having a spiro skeleton bonded to each other directly or via a linker.

[0025] The compound according to one aspect of the present invention is a compound represented by the formula (I) or (II), and therefore has the following effects.

[0026] First, the compound according to one embodiment of the present invention has high solubility in organic solvents. The mechanism by which the compound according to one embodiment of the present invention has high solubility in organic solvents is thought to be as follows.

[0027] That is, an example of a partial structure in a compound according to one aspect of the present invention is shown below. In the following description, this partial structure is referred to as "partial structure (A)". In partial structure (A), the C1 carbon atom is sp 3 This carbon atom forms an approximately 90° angle between the upper and lower aromatic rings bonded to it, which is thought to fix the structure while avoiding steric hindrance, thereby imparting high solubility. [ka]

[0028] The high solubility of a compound according to one embodiment of the present invention in an organic solvent can be confirmed by measuring its solubility in chlorobenzene, which may be measured as described in the Examples below, at a solvent temperature of 25°C.

[0029] Furthermore, a highly soluble aromatic fused ring skeleton can be provided without employing methods such as the introduction of a long-chain alkyl group, liquid crystal molecularization, or oligomerization. Methods such as the introduction of a long-chain alkyl group, liquid crystal molecularization, and oligomerization have generally been used conventionally to improve the organic solvent solubility of aromatic fused ring skeletons. However, these methods have a significant drawback in that the solubility-enhancing effect of introducing a solubility-enhancing moiety is limited and the proportion of aromatic fused rings in a molecule required for hole and electron transfer is relatively reduced. In addition, there is also the problem of increased intramolecular vibration, resulting in reduced semiconductor function. The compound according to one embodiment of the present invention can provide a highly soluble aromatic fused ring skeleton without employing such methods, and therefore does not reduce the effect of hole or electron transfer by introducing a functional group that is effective in improving solubility in organic solvents but is not involved in hole or electron transfer.

[0030] The aromatic fused ring of the spiro skeleton of the compound according to one aspect of the present invention is Ar 1 and Ar 2 or Ar in the formula (II) 1 and Ar 2 , and Ar 3 and Ar 4 are bonded to each other directly or via a linker to form a fused ring, which results in a rigid molecular structure, and an effective skeleton can be constructed from the viewpoints of improving the mobility of electrons and holes and suppressing side absorption in the absorption spectrum.

[0031] Furthermore, by further introducing a p-type skeleton or an n-type skeleton into the compound according to one aspect of the present invention, the compound can be applied as a p-type or n-type small molecule semiconductor compound for organic semiconductor devices. Due to its excellent solubility in organic solvents (e.g., chlorobenzene), the compound can be made into an ink using an organic solvent, and can be applied to thin film formation by a coating method.

[0032] <Ar a , Ar b , Ar c , Ar d and Ar e > Ar in the formula (I) a and Ar b and Ar in the formula (II). c , Ar d and Ar e each independently represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocycle which may have a substituent.

[0033] (aromatic hydrocarbon ring) An aromatic hydrocarbon ring is also called an aryl ring. The "aryl ring" is not particularly limited, and examples thereof include an aryl ring having 6 to 30 carbon atoms, preferably an aryl ring having 6 to 16 carbon atoms, more preferably an aryl ring having 6 to 12 carbon atoms, and particularly preferably an aryl ring having 6 to 10 carbon atoms.

[0034] Specific examples of such "aryl rings" include a monocyclic benzene ring; a bicyclic bicyclic ring; a naphthalene ring and an indene ring; a tricyclic terphenyl ring (e.g., m-terphenyl, o-terphenyl, p-terphenyl); a fused tricyclic ring such as an acenaphthylene ring, a fluorene ring, a phenalene ring, a phenanthrene ring, and an anthracene ring; a tetracyclic ring such as a benzofluorene ring; a fused tetracyclic ring such as a triphenylene ring, a pyrene ring, a naphthacene ring, and a chrysene ring; and a fused pentacyclic ring such as a perylene ring and a pentacene ring.

[0035] Furthermore, the fluorene ring, benzofluorene ring, and indene ring each include a structure in which a fluorene ring, a benzofluorene ring, a cyclopentane ring, etc. are spiro-bonded. Note that the fluorene ring, benzofluorene ring, and indene ring also include rings in which two of the two hydrogen atoms of the methylene in the ring structure are replaced with alkyl such as methyl, resulting in a dimethylfluorene ring, dimethylbenzofluorene ring, dimethylindene ring, etc.

[0036] (aromatic heterocycle) Aromatic heterocycles are also called heteroaryl rings. The "heteroaryl ring" is not particularly limited, and examples thereof include heteroaryl rings having 2 to 30 carbon atoms, preferably heteroaryl rings having 2 to 25 carbon atoms, more preferably heteroaryl rings having 2 to 20 carbon atoms, still more preferably heteroaryl rings having 2 to 15 carbon atoms, and particularly preferably heteroaryl rings having 2 to 10 carbon atoms. In addition, examples of the "heteroaryl ring" include heterocycles containing, as ring-constituting atoms other than carbon, 1 to 5 heteroatoms selected from the group consisting of oxygen, sulfur, nitrogen, selenium, phosphorus, and tellurium.

[0037] Specific examples of such a "heteroaryl ring" include a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxadiazole ring (such as a furazan ring), a thiadiazole ring, a triazole ring, a tetrazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, an indole ring, an isoindole ring, a 1H-indazole ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, a 1H-benzotriazole ring, a quinoline ring, an isoquinoline ring, and a cinnoline ring. , a quinazoline ring, a quinoxaline ring, a phthalazine ring, a naphthyridine ring, a purine ring, a pteridine ring, a carbazole ring, an acridine ring, a phenoxathiin ring, a phenoxazine ring, a phenothiazine ring, a phenazine ring, a phenazasiline ring, an indolizine ring, a furan ring, a benzofuran ring, a dibenzothiophene ring, a thianthrene ring, an indolocarbazole ring, a benzoindolocarbazole ring, a dibenzoindolocarbazole ring, a naphthobenzofuran ring, a dioxin ring, a dihydroacridine ring, a xanthene ring, a thioxanthene ring, a dibenzodioxin ring, and a benzoselenophene ring.

[0038] In addition, dihydroacridine rings, xanthene rings, and thioxanthene rings are also preferably those in which two of the two hydrogen atoms of the methylene in the structure are replaced by alkyl groups such as methyl, thereby forming dimethyldihydroacridine rings, dimethylxanthene rings, dimethylthioxanthene rings, etc. Also included as "heteroaryl rings" are bicyclic rings such as bipyridine rings, phenylpyridine rings, and pyridylphenyl rings; and tricyclic rings such as terpyridyl rings, bispyridylphenyl rings, and pyridylbiphenyl rings. Furthermore, "heteroaryl rings" also include pyran rings.

[0039] (Preferred Examples of Aromatic Hydrocarbon Rings and Aromatic Heterocycles) Ar in the formula (I) a and Ar b or Ar of the formula (II) c , Ar d and Ar eIn the formula (I), the aromatic hydrocarbon ring or aromatic heterocycle is preferably a monocyclic or bicondensed aromatic hydrocarbon ring or a monocyclic or bicondensed aromatic heterocycle having 12 or less carbon atoms, and more preferably an aromatic hydrocarbon ring or aromatic heterocycle having 6 or less carbon atoms, such as a benzene ring, a thiophene ring, a pyrrole ring, a furan ring, or a pyridine ring.

[0040] In addition, Ar in formula (II) d and Ar e may be the same or different, but are preferably the same in terms of maintaining the symmetry of the molecule.

[0041] (Ar a and Ar c (Preferred example of Ar in the formula (I) a and Ar of the formula (II) cFrom the viewpoint of solubility in organic solvents, the aromatic hydrocarbon ring and aromatic heterocycle preferably have a small number of 6-membered or 5-membered rings, specifically, those having 1 to 10 6-membered or 5-membered rings are preferred, and aromatic fused rings having 3 to 5 6-membered or 5-membered rings are more preferred. Specific examples of such aromatic hydrocarbon rings and aromatic heterocycles are listed in the "organic compounds" section. "Guide to Nomenclature," Kagaku Dojin, (1990), pp. 10-14, 14, 32-34, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, an indacene ring, an acenaphthylene ring, a fluorene ring, a phenalene ring, a fluoracene ring, a chrysene ring, a naphthacene ring, a perylene ring, a pentaphene ring, a pentacene ring, a tetraphenylene ring, a hexaphene ring, a hexacene ring, a rubicene ring, a coronene ring, a trinaphthalene ring, an acephenanthrylene ring, an aceanthrylene ring, a triphenylene ring, a pleiadene ring, a picene ring, a thiophene ring, a furan ring, a picene ring, a pyr ... Examples include a benzoyl ring, an imidazole ring, a pyrazole ring, an isothiazole ring, an isoxazole ring, a thianthrene ring, a pyran ring, a pyridine ring, an isobenzofuran ring, a chromene ring, a xanthene ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolizine ring, a phenoxathine ring, a phthalazine ring, an isoindole ring, a naphthyridine ring, a quinoxaline ring, a quinazoline ring, a cinnoline ring, an indole ring, an indazole ring, a pteridine ring, a carbazole ring, a quinolizine ring, a carboline ring, an isoquinoline ring, a quinoline ring, a phenanthridine ring, an acridine ring, a phenothiazine ring, a perimidine ring, a phenanthroline ring, a phenoxazine ring, and a phenazine ring.

[0042] <Ar 1 , Ar 2 , Ar 3 , and Ar 4 > In the formula (I), Ar 1 and Ar 2 each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent, and Ar 1 and Ar 2and are bonded to each other directly or via a linker, and may have any substituent.

[0043] In addition, in the formula (II), Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent, and Ar 1 and Ar 2 , and Ar 3 and Ar 4 are bonded to each other directly or via a linker, and may each have an optional substituent.

[0044] In this specification, Ar 1 and Ar 2 and are bonded to each other directly or via a linker to form a fused ring called "Ar 1 -Ar 2 Also, Ar 3 and Ar 4 and are bonded to each other directly or via a linker to form a fused ring called "Ar 3 -Ar 4 "Ar" 1 -Ar 2 Ring" and "Ar 3 -Ar 4 The “ring” is a “spiro ring.” The compound according to one embodiment of the present invention has a skeleton containing a spiro ring.

[0045] In this specification, Ar 1 and Ar 2 Toga or Ar 3 and Ar 4 When they are bonded to each other directly or via a linker, examples of the linker include -C-, -O-, -S-, -N-, etc. (more specifically, see the structural formulas shown below as examples of aromatic fused rings). From the viewpoint of suppressing molecular vibration, it is preferable that the linker be connected via one or less atoms.

[0046] Ar 1 -Ar2 Ring or Ar 3 -Ar 4 The aromatic hydrocarbon ring or aromatic heterocyclic ring which may have a substituent contained in the ring includes Ar a or Ar c The aromatic hydrocarbon ring or aromatic heterocyclic ring may be any of the aromatic hydrocarbon rings or aromatic heterocyclic rings exemplified above. 1 -Ar 2 Ring or Ar 3 -Ar 4 The aromatic fused ring of the ring is an aromatic hydrocarbon ring having a total of 20 or less carbon atoms and 3 or less fused rings, which may have a substituent, or an aromatic heterocyclic ring having a total of 20 or less carbon atoms and 3 or less fused rings, which may have a substituent. Specific examples of the aromatic fused ring include the following:

[0047] In the following structural formulas, the dashed lines represent the carbon-carbon bonds of the five-membered ring in the formula (I) or (II). [ka]

[0048] The above aromatic fused ring may have a substituent not shown in the above structural formula, which will be described later.

[0049] In addition, Ar in formula (II) 1 -Ar 2 Ring and Ar 3 -Ar 4 The rings may be the same or different. 1 -Ar 2 Ar in the ring 1 and Ar 2 The binding mode with Ar (direct bond or bond via a linker) 3 -Ar 4 Ar in the ring 3 and Ar 4 The bonding mode (direct bond or bond via a linker) with Ar in formula (II) may be the same or different. 1-Ar 2 Ring and Ar 3 -Ar 4 Preferably, the rings are identical.

[0050] <Ar a , Ar b , Ar c , Ar d , Ar e , Ar 1 -Ar 2 Ring or Ar 3 -Ar 4 Substituents that the ring may have> Ar a or Ar c Aromatic hydrocarbon ring or aromatic heterocyclic ring; Ar b , Ar d or Ar e an aromatic hydrocarbon ring or aromatic heterocycle; or Ar 1 -Ar 2 Ring or Ar 3 -Ar 4 The substituent that the ring may have is not particularly limited, and examples thereof include a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group, a heteroarylthio group, an amino group, an acyl group, an aminoacyl group, a ureido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a sulfamoylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a heteroarylsulfonyl group, an imido group, and a silyl group.

[0051] Specific examples of such substituents include: Alkyl groups with approximately 1 to 15 carbon atoms, such as methyl and ethyl groups; Alkenyl groups having approximately 2 to 10 carbon atoms, such as ethynyl and propylenyl groups; Alkynyl groups with 2 to 10 carbon atoms, such as acetylenyl groups; Aryl groups with approximately 6 to 20 carbon atoms, such as phenyl and naphthyl groups; Heteroaryl groups having approximately 3 to 20 carbon atoms, such as thienyl, furyl, and pyridyl groups; Alkoxy groups having approximately 1 to 15 carbon atoms, such as methoxy, ethoxy, and propoxy groups; Aryloxy groups with approximately 6 to 20 carbon atoms, such as phenoxy and naphthoxy groups; heteroaryloxy groups having about 3 to 20 carbon atoms, such as pyridyloxy groups and thienyloxy groups; Alkylthio groups having approximately 1 to 15 carbon atoms, such as methylthio and ethylthio groups; Arylthio groups having approximately 6 to 20 carbon atoms, such as phenylthio and naphthylthio groups; Heteroarylthio groups having about 3 to 20 carbon atoms, such as a pyridylthio group and a thienylthio group; an amino group having about 1 to 20 carbon atoms, such as a dimethylamino group or a diphenylamino group, which may have a substituent; Acyl groups with approximately 2 to 20 carbon atoms, such as acetyl and pivaloyl groups; Acylamino groups with approximately 2 to 20 carbon atoms, such as acetylamino and propionylamino groups; Ureido groups with approximately 2 to 20 carbon atoms, such as 3-methylureido groups; Sulfonamide groups having approximately 1 to 20 carbon atoms, such as methanesulfonamide groups and benzenesulfonamide groups; Carbamoyl groups having approximately 1 to 20 carbon atoms, such as dimethylcarbamoyl and ethylcarbamoyl groups; Sulfamoyl groups with approximately 1 to 20 carbon atoms, such as ethylsulfamoyl groups; Sulfamoylamino groups with approximately 1 to 20 carbon atoms, such as dimethylsulfamoylamino groups; Alkoxycarbonyl groups having approximately 2 to 6 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl groups; Aryloxycarbonyl groups having approximately 7 to 20 carbon atoms, such as phenoxycarbonyl and naphthoxycarbonyl groups; Heteroaryloxycarbonyl groups having approximately 6 to 20 carbon atoms, such as pyridyloxycarbonyl groups; Alkylsulfonyl groups having about 1 to 6 carbon atoms, such as methanesulfonyl, ethanesulfonyl, and trifluoromethanesulfonyl groups; Arylsulfonyl groups having approximately 6 to 20 carbon atoms, such as benzenesulfonyl and monofluorobenzenesulfonyl groups; Heteroaryloxysulfonyl groups having approximately 3 to 20 carbon atoms, such as thienylsulfonyl groups; Imide groups with carbon atoms of 4 to 20, such as phthalimide; a silyl group substituted with three substituents selected from the group consisting of alkyl groups and aryl groups; Examples include:

[0052] Among these, Ar 1 -Ar 2 Ring and Ar 3 -Ar 4 Since the ring has high solubility, in consideration of the influence on hole or electron transfer, the substituent is preferably a shortest substituent such as a methyl group or a methoxy group.

[0053] <Z 1 and Z 2 > Z in the formula (I) 1 and Z in the formula (II) 1 and Z 2 each independently represents a hydrogen atom or an arbitrary substituent.

[0054] Z 1 and Z 2 are each independently a hydrogen atom or an arbitrary substituent selected therefrom. Preferred examples of such substituents include halogen atoms, boron derivatives, trialkyltin groups, formyl groups, cyano groups, electron transport functional groups, and hole transport functional groups.

[0055] in particular, Halogen atoms such as iodine, bromine, and chlorine atoms; Boron derivatives containing boron atoms, such as boric acid and boric acid esters; Trialkyltin groups containing tin atoms, such as trimethyltin and tributyltin groups; Formyl groups such as formaldehyde and acetaldehyde; cyano group; The electron transport or hole transport functional group or moiety is preferably one listed in the Lumtec 2024 General Catalog. For example, electron transporting functional groups such as carbazole, carbodiimide, and perylenedicarboxylic diimide; hole-transporting functional groups such as diphenylamine, thiophene, and fused-ring thiophene derivatives; Examples include:

[0056] <Specific examples of compounds> Specific examples of the compounds represented by formula (I) or (II) are listed below, but the compounds according to one embodiment of the present invention are not limited to the following exemplary compounds. [ka] [ka] [ka] [ka] [ka]

[0057] The above compound is Ar of the formula (I) or (II). a , Ar b , Ar c , Ar d , Ar e , Ar 1 -Ar 2 Ring or Ar 3 -Ar 4 The portion corresponding to the ring may have the above-mentioned substituents not shown in the structural formula.

[0058] <Solubility of Compounds> The compound according to one aspect of the present invention has improved solubility in organic solvents, and preferably has the following characteristics: 1 -Ar 2 The compound according to one embodiment of the present invention having a ring structure is Ar 1 -Ar 2 They have the advantage of being more soluble in organic solvents than compounds that do not form a ring.

[0059] In addition, in the formula (II), Ar 1 -Ar 2 Ring and Ar 3 -Ar 4 The compound according to one embodiment of the present invention having a ring structure is Ar 1 -Ar 2 Ring and Ar 3 -Ar 4 They have the advantage of being more soluble in organic solvents than compounds that do not form a ring.

[0060] The type of organic solvent in which the compound according to one embodiment of the present invention can be dissolved is not particularly limited, and may be any conventionally known organic solvent used as an ink solvent, such as chlorobenzene, toluene, or xylene.

[0061] The compound to be used as a comparison in measuring the solubility of the compound according to one embodiment of the present invention in an organic solvent may be any compound as long as it does not have a spiro ring. However, the following comparative compounds used as comparisons in the examples described later are preferred. [ka]

[0062] In the formula (I), Ar 1 -Ar 2 The compound according to one embodiment of the present invention having a ring structure is Ar 1 -Ar 2The solubility in chlorobenzene is preferably at least twice as high as that of a compound that does not form a ring, more preferably at least 2.5 times, and even more preferably at least 3 times as high.

[0063] In addition, in the formula (II), Ar 1 -Ar 2 Ring and Ar 3 -Ar 4 The compound according to one embodiment of the present invention having a ring structure is Ar 1 -Ar 2 Ring and Ar 3 -Ar 4 The solubility in chlorobenzene is preferably at least twice as high as that of a compound that does not form a ring, more preferably at least 2.5 times, and even more preferably at least 3 times as high.

[0064] Here, "solubility" means the maximum amount of a compound that can be dissolved in 1 mL of chlorobenzene at 25° C. The solubility is measured by the method described in the Examples below.

[0065] [2. Method for producing a compound according to one embodiment of the present invention] A method for producing a compound according to one embodiment of the present invention includes a production step of cyclizing an anion intermediate generated from a compound represented by the following formula (IV) or (V) and a nucleophilic reagent in the presence of a divalent zinc compound and a diamine derivative represented by formula (III): [ka] (In the formula (III), R 1 , R 2 , R 3 , and R 4 each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon ring which may have a substituent, or an aromatic heterocycle which may have a substituent, and n represents an integer of 1 to 4. [ka] (Ar in the formula (IV) and the formula (V)a , Ar b , Ar c , Ar d , Ar e , Ar 1 , Ar 2 , Ar 3 , and Ar 4 respectively represent Ar in the formula (I) or (II). a , Ar b , Ar c , Ar d , Ar e , Ar 1 , Ar 2 , Ar 3 , and Ar 4 is equivalent to In the following description, for convenience, this step will be referred to as "step (A)".

[0066] The method for producing a compound according to one aspect of the present invention may further include, following the step (A), a step of adding a transition metal catalyst to a Zn-substituted intermediate of a compound represented by the following formula (VI) or the following formula (VII) and carrying out a tandem coupling reaction in situ: [ka] (Ar in the formula (VI) and the formula (VII) a , Ar b , Ar c , Ar d , Ar e , Ar 1 , Ar 2 , Ar 3 , and Ar 4 respectively represent Ar in the formula (I) or (II). a , Ar b , Ar c , Ar d , Ar e , Ar 1 , Ar 2 , Ar 3 , and Ar 4 is equivalent to In the following description, for convenience, this step will be referred to as "step (B-1)" or "in situ tandem coupling reaction step."

[0067] Furthermore, the method for producing a compound according to one aspect of the present invention may further include, following step (A), a step of adding a halogenated compound, a boronated compound, or a trialkylstannylated compound to a zincated intermediate of a compound represented by formula (VI) or formula (VII) below to produce a compound represented by formula (VIII) or formula (IX) below: [ka] (Ar in the formula (VI) and the formula (VII) a , Ar b , Ar c , Ar d , Ar e , Ar 1 , Ar 2 , Ar 3 , and Ar 4 respectively represent Ar in the formula (I) or (II). a , Ar b , Ar c , Ar d , Ar e , Ar 1 , Ar 2 , Ar 3 , and Ar 4 is equivalent to [ka] (Ar in the formula (VIII) and the formula (IX) a , Ar b , Ar c , Ar d , Ar e , Ar 1 , Ar 2 , Ar 3 , and Ar 4 respectively represent Ar in the formula (I) or (II). a , Ar b , Ar c , Ar d , Ar e , Ar 1 , Ar 2 , Ar 3 , and Ar 4 is synonymous with Z3 and Z 4 each independently represents a halogen atom, a boron atom having a substituent, or a tin atom having a substituent. In the following description, for convenience, this step will be referred to as "step (B-2)" or "cross-coupling reaction step."

[0068] [Process (A)] In the method for producing a compound according to one embodiment of the present invention, step (A) is a reaction step in which a compound represented by formula (IV) or (V) (hereinafter, these may be referred to as "raw material compound") is converted into an anion species with a nucleophilic reagent, and then cyclized by reacting a divalent zinc compound with a diamine derivative represented by formula (III) (hereinafter, may be referred to as "diamine (III)").

[0069] As an example, the following reaction is carried out. In the following reaction scheme, "-H + " represents the reaction of eliminating hydrogen cations, and "Zn 2+ " represents zinc ions derived from divalent zinc compounds, and "heat" represents a heating reaction. [ka]

[0070] In the method for producing a compound according to one embodiment of the present invention, the compound according to one embodiment of the present invention can be produced via the step (A). The method for producing a compound according to one embodiment of the present invention can provide a novel method for producing an aromatic fused ring compound using a non-noble metal catalyst, which is suitable for a sustainable society.

[0071] <Compounds represented by formula (IV) and formula (V)> The compounds represented by the formula (IV) and the formula (V) can be produced by converting the hydroxyl group of the corresponding compound represented by the formula (IV') and the formula (V') to hydrogen by a known method. Specifically, the hydroxyl group of the compound represented by the formula (IV') or the formula (V') can be converted to hydrogen by stirring in acetonitrile in the presence of 3 to 6 equivalents of sodium iodide and 1.5 to 3 equivalents of dichlorodimethylsilane for 2 to 12 hours at room temperature to reflux temperature, particularly preferably at reflux temperature, relative to one hydroxyl group (herein also referred to as a reaction site) in the compound represented by the formula (IV') or the formula (V'). [ka] (Ar in the formula (IV') and the formula (V') a , Ar b , Ar c , Ar d , Ar e , Ar 1 , Ar 2 , Ar 3 , and Ar 4 respectively represent Ar in the formula (I) or (II). a , Ar b , Ar c , Ar d , Ar e , Ar 1 , Ar 2 , Ar 3 , and Ar 4 is equivalent to

[0072] <Nucleophilic reagent> The nucleophilic reagent used in step (A) may be a conventionally known nucleophilic reagent, such as a lithium reagent, a sodium reagent, a potassium reagent, etc. Among these, a lithium reagent is preferably used as the nucleophilic reagent from the viewpoint of not causing side reactions.

[0073] The lithium reagent that can be used in step (A) is generally n-butyllithium, which is the most widely used, but other reagents that can be used include sec-butyllithium, tert-butyllithium, iso-propyllithium, etc. Furthermore, these may coexist with N,N,N',N'-tetramethylethylenediamine (TMEDA), hexamethylphosphoramide (HMPA), dimethylpropyleneurea (DMPU), etc.

[0074] Furthermore, lithium amide reagents obtained by lithiating bulky secondary amines, such as lithium diisopropylamide (LDA), lithium 2,2,6,6-tetramethylpiperidide (LiTMP), and lithium hexamethyldisilazide (LHMDS), can also be used. Schlosser-Lochmann bases such as the nBuLi-KOtBu combination, NaH, and tert-BuONa can also be used. It is preferable to use 1.0 to 1.2 equivalents of these lithium reagents per reaction site (hydrogen atom converted from a hydroxyl group).

[0075] <Divalent zinc compounds> Divalent zinc compounds that can be used in step (A) are generally those described in Stephan Enthaler, ed., Zinc Catalysis: Applications in Organic Synthesis, Wiley-VCH, 2015. From the viewpoint of versatility, examples include ZnCl2, Zn(OAc)2, Zn(acac)2, ZnBr2, and ZnI2. Furthermore, a reagent pre-ligated with a diamine, such as dichloro(N,N,N',N'-tetramethylethylenediamine)zinc (hereinafter sometimes referred to as "ZnCl2-TMEDA"), may also be used. The divalent zinc compound is preferably used in an amount of 1.0 to 1.5 equivalents per reaction site (hydrogen atom converted from a hydroxyl group), and particularly preferably 1.05 to 1.2 equivalents.

[0076] <Diamine derivatives> The diamine derivative that can be used in step (A) is a diamine compound (diamine (III)) represented by the above formula (III). Examples of commonly used diamine derivatives include tetramethylethylenediamine (TMEDA), 1,5,7-triazabicyclo[4.4.0]deca-1,3,5-triene (TBD), 1,4-diazabicyclo[2.2.2]octane (DABCO), 4-dimethylaminopyridine (DMAP), and N,N-diisopropylethylamine (DIPEA).

[0077] In the formula (III), R 1 , R 2 , R 3 , and R 4 each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon ring which may have a substituent, or an aromatic heterocycle which may have a substituent, and n is an integer of 1 to 4.

[0078] (aliphatic hydrocarbon group) Examples of the aliphatic hydrocarbon group include an alkyl group and a cycloalkyl group.

[0079] The "alkyl" may be either straight-chain or branched-chain, and is, for example, a straight-chain alkyl having 1 to 24 carbon atoms or a branched-chain alkyl having 3 to 24 carbon atoms, and is preferably an alkyl having 1 to 18 carbon atoms (branched-chain alkyl having 3 to 18 carbon atoms), an alkyl having 1 to 12 carbon atoms (branched-chain alkyl having 3 to 12 carbon atoms), an alkyl having 1 to 6 carbon atoms (branched-chain alkyl having 3 to 6 carbon atoms), an alkyl having 1 to 5 carbon atoms (branched-chain alkyl having 3 to 5 carbon atoms), or an alkyl having 1 to 4 carbon atoms (branched-chain alkyl having 3 to 4 carbon atoms).

[0080] Specific examples of "alkyl" include methyl, ethyl, n-propyl, isopropyl, 1-ethyl-1-methylpropyl, 1,1-diethylpropyl, 1,1,2-trimethylpropyl, 1,1,2,2-tetramethylpropyl, 1-ethyl-1,2,2-trimethylpropyl, n-butyl, isobutyl, s-butyl, t-butyl, 2-ethylbutyl, 1,1-dimethylbutyl, 3,3-dimethylbutyl, 1,1-diethylbutyl, 1-ethyl-1-methylbutyl, 1-propyl-1-methylbutyl, 1,1,3-trimethylbutyl, 1-ethyl-1,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, t-pentyl (t-amyl), 1-methylpentyl, 2-propylpentyl, 1,1-dimethylpentyl, 1-ethyl-1-methylpentyl, 1-propyl- 1-Methylpentyl, 1-butyl-1-methylpentyl, 1,1,4-trimethylpentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 1,1-dimethylhexyl, 1-ethyl-1-methylhexyl, 1,1,5-trimethylhexyl, 3,5,5-trimethylhexyl, n-butyl, 1-methylheptyl, 1-hexylheptyl, 1,1-dimethylheptyl, 2,2- Examples of the alkyl group include dimethylheptyl, 2,6-dimethyl-4-heptyl, n-octyl, t-octyl (1,1,3,3-tetramethylbutyl), 1,1-dimethyloctyl, n-nonyl, n-decyl, 1-methyldecyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, and n-eicosyl.

[0081] The "cycloalkyl" is, for example, a cycloalkyl having 3 to 24 carbon atoms, and preferably includes a cycloalkyl having 3 to 20 carbon atoms, a cycloalkyl having 3 to 16 carbon atoms, a cycloalkyl having 3 to 14 carbon atoms, a cycloalkyl having 3 to 12 carbon atoms, a cycloalkyl having 5 to 10 carbon atoms, a cycloalkyl having 5 to 8 carbon atoms, a cycloalkyl having 5 to 6 carbon atoms, or a cycloalkyl having 5 carbon atoms.

[0082] Specific examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, or alkyl (particularly methyl) substituted derivatives thereof having 1 to 5 carbon atoms or 1 to 4 carbon atoms, bicyclo[1.1.0]butyl, bicyclo[1.1.1]pentyl, bicyclo[2.1.0]pentyl, bicyclo[2.1.1]hexyl, bicyclo[3.1.0]hexyl, bicyclo[2.2.1]heptyl (norbornyl), bicyclo[2.2.2]octyl, adamantyl, diamantyl, decahydronaphthalenyl, and decahydroazulenyl.

[0083] In the formula (III), the aliphatic hydrocarbon group is preferably a methyl group, an ethyl group, a propyl group, a pentyl group, a butyl group, an isopropyl group, a 2-butyl group, a 1,3-dimethylbutyl group, a 2-methylpropyl group, a 3,3-dimethylbutyl group, or a 2,2-dimethylpropyl group, which is particularly suitable for coordinating with divalent zinc.

[0084] (Aromatic hydrocarbon rings and aromatic heterocycles) The aromatic hydrocarbon ring and aromatic heterocycle in the formula (III) are each independently selected from the group consisting of Ar in the formula (I) and Ar in the formula (II). a , Ar b , Ar c , Ar d and Ar e The same can be mentioned.

[0085] (Substituents that may be possessed by an aliphatic hydrocarbon group, an aromatic hydrocarbon ring, or an aromatic heterocycle) The substituent that the aliphatic hydrocarbon group, aromatic hydrocarbon ring or aromatic heterocycle in the formula (III) may have is the Z in the formula (I) or (II). 1 , Z 2 The same can be mentioned.

[0086] (n in formula (III)) In the formula (III), n is 1 to 4, but from the viewpoint of reactivity, it is preferable that n can form a 5- or 6-membered ring when coordinated with divalent zinc, and n is particularly preferably 1 or 2.

[0087] <Solvent> Step (A) is usually carried out in a solvent. Examples of the solvent used at that time include: aromatic solvents such as toluene and xylene; ether solvents such as ether, 1,4-dioxane, tetrahydrofuran (THF), 4-methylhydropyran, 2-methyltetrahydrofuran, and cyclopentyl methyl ether; Aliphatic solvents such as hexane, heptane, and octane; You can choose from, etc.

[0088] Among these, it is preferable to use tetrahydrofuran (THF) from the viewpoint of increasing the solubility of the reaction compound (starting compound) in the reaction system as much as possible, and it is preferable to use tetrahydrofuran equivalents such as 4-methylhydropyran, 2-methyltetrahydrofuran, and cyclopentyl methyl ether from the viewpoint of increasing the boiling point.

[0089] These solvents may be used alone or in combination. For example, to improve the production of lithium intermediates such as raw material compounds, a combination of an ether-based solvent and an aliphatic solvent such as hexane improves the reaction results. Furthermore, to perform a continuous coupling reaction from the Zn intermediate, a combination of an ether-based solvent and an aromatic solvent improves the reaction results.

[0090] The amount of solvent used in the reaction system in step (A) is usually preferably in the range of 1 to 50 mL per 1 mmol of the starting compound. This upper limit is preferred from the viewpoint of production efficiency, while the lower limit is preferred from the viewpoint of stirring efficiency in the reaction system. In particular, the amount of reaction solvent used is preferably about 5 to 30 mL per 1 mmol of the starting compound.

[0091] <Reaction conditions> The reaction temperature in step (A) is usually -5°C or higher, preferably 0°C or higher, more preferably 10°C or higher, and particularly preferably in the range of about 25°C to the boiling point of the solvent. The reaction temperature in step (A) can be set arbitrarily within the range up to the reflux temperature of the solvent used, depending on the rate of reaction. When the yield of the product is poor, it is preferable to irradiate the reaction solution with ultrasound or microwaves and autoclave the reaction solution in combination.

[0092] The reaction time in step (A) is usually 4 hours or more and 24 hours or less, but may be set arbitrarily since it depends on the type of solvent used and other reaction conditions.

[0093] The degree of progress of the reaction in step (A) can be confirmed using high performance liquid chromatography (HPLC).

[0094] After completion of the reaction in step (A), the target compound according to one aspect of the present invention, represented by formula (I) or (II), can be obtained using known isolation and purification methods.

[0095] [Process (B-1)] In the method for producing a compound according to one aspect of the present invention, step (B-1) is a step of adding a transition metal catalyst to a Zn-substituted intermediate of the compound represented by formula (VI) or formula (VII) obtained in step (A) and carrying out a tandem coupling reaction in situ.

[0096] As an example, the following reaction is carried out. [ka]

[0097] In the method for producing a compound according to one embodiment of the present invention, in the step (B-1), a transition metal catalyst is added to the compound obtained in the step (A) to form a Zn-substituted intermediate of the compound represented by formula (VI) or (VII) (hereinafter also referred to as a "Zn compound"). Thereafter, by adding ArX, ArOTf, RN, or the like, a coupling reaction can be carried out in a tandem reaction.

[0098] Here, ArX is an aromatic hydrocarbon ring halogen compound or an aromatic heterocyclic ring halogen compound.

[0099] ArOTf is an aromatic hydrocarbon ring triflate compound or an aromatic heterocyclic ring triflate compound.

[0100] R2N is a diaromatic hydrocarbon ring amine compound or a diaromatic heterocyclic amine compound.

[0101] In the step (B-1), the coupling reaction is carried out in a tandem reaction without removing the Zn compound. However, in the method for producing a compound according to one embodiment of the present invention, the solvent may be removed from the reaction system containing the Zn compound and replaced with an aromatic ring solvent suitable for the coupling reaction, and then the coupling reaction may be carried out.

[0102] <Transition metal catalyst> The transition metal catalyst used in step (B-1) can be a conventionally known transition metal catalyst, such as a noble metal catalyst. Among these, from the viewpoint of versatility of the reaction and yield, it is preferable to use palladium as the transition metal catalyst. The transition metal catalyst may be used in an equal amount to the substrate, but in the case of a palladium reaction, it is preferable to use 20 mol % or less, and particularly preferably 10 mol % to 1 mol %.

[0103] <Z 1 and Z 2 > The Zn moiety of the formula (VI) and the formula (VII) formed in the system is1 , Z 2 To obtain a compound having a functional group as a specific example of the above, 1 to 20 equivalents, preferably 2 to 5 equivalents of an electrophilic reagent is added to one reaction site, and the mixture is stirred at room temperature to the boiling point of the solvent, whereby the above-mentioned Z 1 , Z 2 The functional groups given in the specific examples can be introduced.

[0104] On the other hand, when cross-coupling is carried out successively on the compounds of formula (VI) and formula (VII), the Negishi cross-coupling can be carried out by the method described in, for example, Handbook of Organopalladium Chemistry for Organic Synthesis (ed. Negishi, Ei-Ichi, Wiley, 2002). Here, from the viewpoint of increasing the reaction rate of the cross-coupling, it is preferable to remove the tetrahydrofuran-based solvent used in the system containing the compounds of formula (VI) and formula (VII) under reduced pressure and then replace it with an aromatic solvent.

[0105] <Electrophilic Reagents> The electrophilic reagent used in step (B-1) can be any known electrophilic reagent, such as iodine, bromine, diiodoethane, dibromoethane, tetrabutylammonium tribromide, iodine chloride, dimethylformamide, dimethylacetamide, trimethyltin chloride, tributyltin chloride, trimethylborate, or triethylborate. It is preferable to further react the compound introduced by this with an electron transport moiety or a hole transport moiety. I, Br, B(OH)2, or SnR3 derivatives can be isolated and subsequently transformed into functional molecules.

[0106] <Reaction conditions> The reaction temperature in step (B-1) is from room temperature to the boiling point of the solvent.

[0107] The reaction time in the step (B-1) is from 1 hour to 24 hours.

[0108] The degree of progress of the reaction in step (B-1) can be confirmed using high performance liquid chromatography (HPLC).

[0109] After completion of the reaction in step (B-1), the target compound according to one embodiment of the present invention represented by formula (I) or (II) can be obtained using known isolation and purification methods.

[0110] [Process (B-2)] In the method for producing a compound according to one aspect of the present invention, step (B-2) is a step of adding a halogenated compound, a boronated compound, or a trialkylstannylated compound to the Zn-substituted intermediate of the compound represented by formula (VI) or formula (VII) obtained in step (A), halogenating, boronating, or stannylating the compound, removing the compound from the reaction system, and then performing various coupling reactions.

[0111] As an example, the following reaction is carried out. [ka]

[0112] <Z 3 and Z 4 > Z 3 , Z 4 represents a halogen atom, a boron atom having a substituent, a tin atom having a substituent, or a silicon atom having a substituent. To obtain the compounds represented by formula (VIII) and formula (IX), the halogenated compound, the boronated compound, and the trialkylstannyl compound may be a reagent described in, for example, "Comprehensive Organic Transformations, 4 Volume Set: A Guide to Functional Group Preparations" by Richard C. Larock, published by Wiley, 2018.

[0113] Examples of halogenated compounds include iodine, bromine, diiodoethane, and dibromoethane. Examples of boronated compounds include trimethyl borate and triethyl borate. Examples of trialkyl stannylated compounds include tributyltin chloride and trimethyltin chloride. The halogenated compounds, boronated compounds, and trialkyl stannylated compounds are preferably used in an amount of 1 to 1.2 equivalents, and particularly preferably 1.05 to 1.1 equivalents, relative to the anion generating sites of the substrate.

[0114] <Isolation of halogenated, boronated, or stannylated compounds from reaction systems> The halogenated, boronated or stannate compound can be removed from the reaction system by the same method as that used for the post-treatment of ordinary organic compounds.

[0115] <Z 3 and Z 4 Cross-coupling reaction from Z of the compounds represented by the formula (VIII) and the formula (IX) 3 and Z 4On the other hand, the CC bonding reaction or C-hetero bonding reaction can be carried out by a conventionally known cross-coupling reaction. For example, CC bond formation and C-N bond formation can be performed by methods such as Suzuki-Miyaura cross-coupling reaction, Stille cross-coupling reaction, Heck cross-coupling reaction, Buchwald-Hartwig coupling reaction, etc., using methods such as those described in Metal Catalyzed Cross-Coupling Reactions and More, edited by Armin de Meijere et al., published by Wiley-VCH (2013); Cross Coupling and Heck-Type Reactions (Science of Synthesis), edited by Gary A. Molander; Cross Coupling and Heck-Type Reactions 1: CC Cross Coupling Using Organometallic Partners Cross Coupling and Heck-Type Reactions 2: Carbon-Heteroatom Cross Coupling and CC Cross Couplings of Acidic CH Nucleophiles Cross Coupling and Heck-Type Reactions 3: Metal-Catalyzed Heck-Type Reactions and CH Couplings via CH Activation, published by Thieme (2013).

[0116] <Solvent> The solvent used in the reaction of step (B-2) is, for example, toluene or xylene.

[0117] <Reaction conditions> The reaction temperature in step (B-2) is usually from room temperature to the boiling point of the solvent.

[0118] The reaction time in step (B-2) is usually from 1 hour to 24 hours.

[0119] The degree of progress of the reaction in step (B-2) can be confirmed using high performance liquid chromatography (HPLC).

[0120] After completion of the reaction in step (B-2), the target compound according to one embodiment of the present invention represented by formula (I) or (II) can be obtained using known isolation and purification methods.

[0121] [3. Composition] The composition according to one aspect of the present invention contains the compound according to one aspect of the present invention described above. The compound according to one aspect of the present invention in the composition according to one aspect of the present invention has already been described, and therefore will not be described again here.

[0122] The content of the compound according to an embodiment of the present invention in the composition according to an embodiment of the present invention is not particularly limited, and is typically 0.5% by mass or more, and may be 0.7% by mass or more, and is typically 1.5% by mass or less, and may be 1.3% by mass or less.

[0123] The composition according to one embodiment of the present invention may contain components other than those described above, as necessary, to the extent that the effects of the present invention are not impaired. The composition according to one embodiment of the present invention may contain, for example, an organic solvent, specifically, a halogen-based solvent such as chloroform or dichloroethane; an aromatic hydrocarbon solvent such as toluene, xylene, chlorobenzene, or dichlorobenzene; or an ether-based solvent such as THF or dibutyl ether. The content of other components, i.e., additives that promote alignment, is typically 1.5% by mass or more, preferably 2.0% by mass or more, and typically 4.0% by mass or less, preferably 3.5% by mass or less, of the composition according to one embodiment of the present invention.

[0124] The form of the composition according to one embodiment of the present invention is not particularly limited, and may be, for example, a solid or a liquid containing an organic solvent.

[0125] The composition according to one embodiment of the present invention can be produced, for example, by appropriately blending and mixing the compound according to one embodiment of the present invention and other components.

[0126] <Uses of the composition> The composition according to one embodiment of the present invention contains the compound according to one embodiment of the present invention, and thus can take advantage of the characteristics of the compound to be used as a skeleton of an organic semiconductor electronic material (a hole transport material, hole introduction material, hole extraction material, electron transport material, electron introduction material, or electron extraction material for OLED, OPV, PSC, OFET, PeQD, etc.). Thus, the composition according to one embodiment of the present invention can be used as a composition for an organic semiconductor electronic material, etc.

[0127] Furthermore, when the composition according to one aspect of the present invention is in a liquid state containing an organic solvent, it can be used as, for example, an ink composition for forming a film for an organic semiconductor device. The ink for forming a film for an organic semiconductor device will be described later.

[0128] [4. Organic Semiconductor Compounds] An organic semiconductor compound according to one aspect of the present invention is an organic semiconductor compound having a skeleton represented by the formula (I) or (II).

[0129] In this specification, "having a skeleton represented by formula (I) or formula (II)" means having a structure represented by formula (I) or formula (II) as a minimum unit. The organic semiconductor compound according to one aspect of the present invention may be, for example, a small molecule having a structure represented by formula (I) or formula (II) as a minimum unit, or an oligomer, polymer, or the like in which such small molecules are linked together.

[0130] The organic semiconductor compound according to one aspect of the present invention is a compound having a skeleton represented by the formula (I) or the formula (II). 1 and Ar 2 Or, in the formula (II), Ar 1 and Ar 2 and Ar 3 and Ar4 are aromatic fused ring compounds having a spiro skeleton bonded to each other directly or via a linker.

[0131] The compound according to one aspect of the present invention is a compound having a skeleton represented by formula (I) or formula (II), and therefore exhibits the same effects as the compound according to one aspect of the present invention described above. The skeleton represented by formula (I) or formula (II) has already been explained in the section [1. Compound], and therefore will not be explained again here.

[0132] The organic semiconductor compound according to one aspect of the present invention may be a p-type semiconductor or an n-type semiconductor.

[0133] (p-type organic semiconductor compound) By introducing a hole transporting moiety such as a benzodithiophene structure, a thiophene structure, a dibenzofuran structure, a diarylamine structure, or a naphthalene structure into the compound represented by formula (I) or formula (II), the compound can be made to function as a p-type organic semiconductor.

[0134] That is, a p-type organic semiconductor compound can be provided by the following method.

[0135] Construction of long conjugated systems: Molecules with long conjugated systems, such as polycyclic aromatic compounds and extended conjugation, can achieve efficient hole transport. The longer the conjugated system is, the more free the π electrons can move, thereby increasing the hole mobility; Introduction of electron-rich functional groups: For example, electron-rich functional groups such as amino groups and alkoxy groups increase the electron density of the molecule and facilitate hole injection and transport; Construction of planar molecular structure: When molecules have a planar structure, the π-π interactions between molecules become stronger, which promotes efficient hole transport. As a result, better intermolecular stacking is promoted, thereby increasing hole mobility. Furthermore, the high solubility of these frameworks is ensured by the rigid spiro ring, which allows for smaller molecular angles and the introduction of π-π stacking effects.

[0136] (n-type organic semiconductor compound) It is also possible to introduce into the compound represented by formula (I) or (II) a polycyclic aromatic ring containing a conjugated system such as fullerene, naphthalenediimide, perylenediimide, or carbazole structure, which serves as an electron transport moiety. Furthermore, by introducing the ITIC moiety of a non-fullerene acceptor (NFA), it is possible to produce a non-fullerene acceptor (NFA) with high solubility.

[0137] That is, the electron transport properties can be improved by introducing an electron-deficient functional group (e.g., a cyano group or a fluoro group). As a structural moiety that contributes to electron transport, a functional group with a high ability to attract electrons is preferred, and a rigid structure that promotes highly planar intermolecular π-π interactions is preferred. These functional groups can be introduced into the compound represented by formula (I) or (II), which can also impart high solubility.

[0138] An organic semiconductor having a skeleton represented by the formula (I) or (II) has excellent solubility in organic solvents, and therefore can be formed into a thin film by a coating method. In addition, the rigid conjugated skeleton constituting the compound allows a certain intermolecular orientation, and therefore the formed thin film exhibits excellent semiconductor properties.

[0139] [5. Film-forming ink for organic semiconductor devices] The ink for forming a film for an organic semiconductor device according to one embodiment of the present invention contains the organic semiconductor compound according to one embodiment of the present invention and an organic solvent. The organic semiconductor compound according to one embodiment of the present invention has already been explained in the section [4. Organic semiconductor compound] above, and therefore will not be explained again here.

[0140] When forming an active layer by a coating method, an ink for forming a film for an organic semiconductor device according to one embodiment of the present invention can be prepared by dissolving an organic semiconductor compound, such as a p-type organic semiconductor compound or an n-type organic semiconductor compound, in an organic solvent, along with other necessary substances as additives. The ink for forming a film for an organic semiconductor device according to one embodiment of the present invention (hereinafter referred to as "organic semiconductor ink") is applied to a substrate by a method such as spin coating, and dried to form a thin film. This thin film can be called an organic semiconductor device film, and the organic semiconductor device film is also included in the scope of the present invention.

[0141] In this case, the conditions for spin coating may be appropriately determined in accordance with a standard method, taking into consideration the viscosity of the organic semiconductor ink, etc.

[0142] The drying conditions are not particularly limited as long as they allow the organic solvent in the organic semiconductor ink to be removed. For example, the organic semiconductor ink can be dried by heat annealing at atmospheric pressure at 70 to 130°C for 5 to 20 minutes.

[0143] These organic semiconductor inks are also another aspect of the present invention.

[0144] The content of the organic semiconductor compound according to an embodiment of the present invention in the organic semiconductor ink according to an embodiment of the present invention is not particularly limited as long as an active layer can be formed by coating.

[0145] The content of the p-type organic semiconductor compound in the organic semiconductor ink according to one embodiment of the present invention is typically 0.5% by mass or more, and may be 0.7% by mass or more, and is typically 1.5% by mass or less, and may be 1.3% by mass or less.

[0146] Furthermore, the content of the n-type organic semiconductor compound in the organic semiconductor ink according to one embodiment of the present invention is typically 0.7% by mass or more, and may be 1.0% by mass or more, and is typically 2.0% by mass or less, and may be 1.8% by mass or less.

[0147] The organic solvent used in the organic semiconductor ink according to one embodiment of the present invention is not particularly limited, and any organic solvent generally used in a coating liquid for forming an active layer of an organic semiconductor device can be used. Specific examples include halogen-based solvents such as chloroform and dichloroethane; aromatic hydrocarbon-based solvents such as toluene, xylene, chlorobenzene, and dichlorobenzene; and ether-based solvents such as THF, CPME, MTHP, 2-Me-THF, and dibutyl ether.

[0148] The organic semiconductor compound according to one embodiment of the present invention has high solubility in these organic solvents, and the use of these organic solvents is expected to improve photoelectric conversion efficiency.

[0149] Of the organic solvents, xylene, chlorobenzene, or chloroform is preferred, although this depends on the type of organic semiconductor compound according to one embodiment of the present invention. Furthermore, when adjusting the solubility of the organic semiconductor compound according to one embodiment of the present invention, the organic solvent may be a mixed organic solvent of two or more kinds. The content ratio is not particularly limited, and may be in the range of 1:9 to 9:1. The difference in boiling point between these organic solvents is preferably 50°C or less, more preferably 40°C or less, and even more preferably 30°C or less.

[0150] The organic semiconductor ink according to one embodiment of the present invention preferably contains, in addition to a p-type organic semiconductor compound or an n-type organic semiconductor compound, an additive that promotes alignment. Examples of such additives include compounds that promote stacking of the aromatic moiety of the p-type organic semiconductor compound and the aromatic moiety of the n-type organic semiconductor compound, and that have the effect of shortening the intermolecular distance between the p-type organic semiconductor compound and the n-type organic semiconductor compound, such as polycyclic aromatic compounds and 1,8-diiodooctane.

[0151] Examples of polycyclic aromatic compounds include naphthalene, anthracene, pyrene, etc. Among these, the additive is preferably a bicyclic fused ring such as 1-chloronaphthalene.

[0152] The content of additives in the organic semiconductor ink according to one embodiment of the present invention is usually 1.5% by mass or more, preferably 2.0% by mass or more, and usually 4.0% by mass or less, preferably 3.5% by mass or less.

[0153] Furthermore, the organic semiconductor ink according to one embodiment of the present invention may contain other components to the extent that the effects of the present invention are not impaired. The content of other components is typically 2.0% by mass or less relative to the organic solvent.

[0154] [6. Organic Semiconductor Devices] The organic semiconductor device according to one embodiment of the present invention includes an organic semiconductor device film containing the organic semiconductor compound according to one embodiment of the present invention. The organic semiconductor compound according to one embodiment of the present invention has already been described in the section [4. Organic semiconductor compound] above, and therefore will not be described again here.

[0155] The organic semiconductor ink according to one embodiment of the present invention can be used by a coating method to manufacture an organic semiconductor device having an organic semiconductor device film containing the organic semiconductor compound according to one embodiment of the present invention. The method for forming an organic semiconductor device film using the organic semiconductor ink according to one embodiment of the present invention has already been explained in the section [5. Ink for forming a film for an organic semiconductor device] above, so the explanation will not be repeated here.

[0156] The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in the embodiments are also included in the technical scope of the present invention. [Example]

[0157] The following examples will explain the present invention in more detail, but the present invention is not limited to these examples as long as they do not depart from the gist of the present invention. The numbers below the compounds in the reaction formulas are the compound numbers.

[0158] The produced compounds were identified using TOP-MS spectra (model number: Shimadzu LCMS-IT-TOF).

[0159] [Production of Compounds] (Production of raw material compounds 1) [ka] A hexane solution of BuLi (1.58 mol / L, 11.34 mL, 17.9 mmol) was added dropwise to a solution of 1-bromo-2-(phenylethynyl)benzene (4.61 g, 17.9 mmol) in THF (35 mL) at 0°C. After stirring for 1 hour, 9-fluorenone (3.39 g, 18.8 mmol) was added and stirred at room temperature for 1 hour. The reaction mixture was treated with saturated aqueous ammonium chloride, and the mixture was extracted three times with methylene chloride. The combined organic layers were washed with saturated brine, and the organic layer was dried over sodium sulfate. The solvent was evaporated under reduced pressure to give the crude product. This was recrystallized from dichloromethane / methanol to give the product as a white solid (5.70 g, 89%).

[0160] (Production of raw material compounds 2) [ka] 9-(2-(phenylethynyl)phenyl)-9H-fluoren-9-ol (1.79 g, 5.0 mmol) obtained in Preparation 1 of the starting compound and sodium iodide (1.65 g, 2.2 equivalents) were added to acetonitrile (25 mL). Dichlorodimethylsilane (0.657 mL, 5.5 mmol) was added to this mixed solution, and the mixture was stirred at 50°C for 4 hours. After cooling to room temperature, diethyl ether was added to the reaction solution, and the organic layer was washed twice with cold aqueous sodium bicarbonate solution and dried over sodium sulfate. The solvent was evaporated under reduced pressure to obtain a crude product. This was purified using silica gel chromatography (developing solvent: hexane / dichloromethane) to obtain the product as a colorless solid (1.36 g, 80%).

[0161] Example 1 [ka] A hexane solution of BuLi (1.56 mol / L, 0.352 mL, 0.55 mmol) was added dropwise to a THF (2.5 mL) solution of the starting compound 9-(2-(phenylethynyl)phenyl)-9H-fluorene (171 mg, 0.50 mmol) at 0°C. After stirring for 10 minutes, ZnCl-TMEDA (139 mg, 0.55 mmol) was added and stirred at room temperature for 10 minutes, followed by heating and stirring at 80°C for 8 hours. The reaction solution was cooled to room temperature, post-treated with 1 M aqueous hydrochloric acid, and extracted three times with methylene chloride. The combined organic layers were dried over sodium sulfate, and the solvent was evaporated under reduced pressure. The crude product was passed through a short-path column of silica gel (developing solvent: dichloromethane) to obtain Example Compound 1 as a white solid (169 mg, 98%). HRMS (ESI+): m / z scaled for C 27 H 19 [M+H] 343.1487; found: 343.1489.

[0162] Example 2 [ka] Example compound 2 was obtained in a yield of 93% in the same manner as in Starting Compound Production 1, Starting Compound Production 2, and Example 1, except that 10,10-dimethylanthracen-9(10H)-one was used instead of 9-fluorenone in Starting Compound Production 1. HRMS (ESI+): m / z scaled for C 30 H 25 [M+H] 385.1956; found: 385.1953.

[0163] Example 3 [ka] Example compound 3 was obtained in a yield of 96% in the same manner as in Starting Compound Production 1, Starting Compound Production 2, and Example 1, except that 2,7-diphenyl-9H-fluoren-9-one was used instead of 9-fluorenone in Starting Compound Production 1. HRMS (ESI+): m / z scaled for C 39 H 27 [M+H] 495.2113; found: 495.2117.

[0164] Example 4 [ka] Example compound 4 was obtained in a yield of 95% in the same manner as in Starting Compound Production 1, Starting Compound Production 2, and Example 1, except that 9H-thioxanthen-9-one was used instead of 9-fluorenone in Starting Compound Production 1. HRMS (ESI+): m / z scaled for C 27 H 19 S [M+H] 375.1207; found: 375.1204.

[0165] Example 5 [ka] Example compound 5 was obtained in a yield of 86% in the same manner as in Starting Compound Production 1, Starting Compound Production 2, and Example 1, except that ((2,5-dibromo-1,4-phenylene)bis(ethyne-2,1-diyl))dibenzene was used instead of 1-bromo-2-(phenylethynyl)benzene in Starting Compound Production 1. HRMS (ESI+): m / z scaled for C 48 H 31 [M+H] 607.2426; found: 607.2423.

[0166] Example 6 [ka] Example compound 6 was obtained in a yield of 97% in the same manner as in Production of Starting Compound 1, Production of Starting Compound 2, and Example 1, except that 9H-xanthen-9-one was used instead of 9-fluorenone in Production of Starting Compound 1. HRMS (ESI+): m / z scaled for C 27 H 19 O [M+H] 359.1436; found: 359.1434.

[0167] Example 7 [ka] Similar procedures were carried out as in Preparation 1 and Preparation 2 of Starting Compound 1. To a solution of 9-(2-(phenylethynyl)phenyl)-9H-fluorene (171 mg, 0.50 mmol) in THF (2.5 mL), a hexane solution of BuLi (1.56 mol / L, 0.352 mL, 0.55 mmol) was added dropwise at 0 °C. After stirring for 10 minutes, ZnCl-TMEDA (139 mg, 0.55 mmol) was added and stirred at room temperature for 10 minutes. The reaction mixture was then heated to 80 °C and stirred for 8 hours. After cooling to 0 °C, 1,2-diiodoethane (211 mg, 0.75 mmol) was added and stirred for 1 hour. The reaction mixture was then quenched with 1 M aqueous hydrochloric acid and extracted three times with methylene chloride (20 mL). The combined organic layers were dried over sodium sulfate, and the solvent was removed under reduced pressure. The crude product was subjected to a silica gel (dichloromethane) short-path column to obtain Example Compound 7 as a white solid (209 mg, 90%). HRMS (ESI+): m / z scaled for C 27 H 18 I [M+H] 469.0453; found: 469.0457.

[0168] Example 8 [ka] Starting compound production 1 and starting compound production 2 were carried out in the same manner as in Example 7, except that tributyltin chloride was used instead of 1,2-diiodoethane in Example 7, and Example compound 8 was obtained in a yield of 65%. HRMS (ESI+): m / z scaled for C 39 H 45 Sn [M+H] 633.2543; found: 633.2540.

[0169] Example 9 [ka] Example compound 9 was obtained in a yield of 86% in the same manner as in Starting Compound Production 1, Starting Compound Production 2, and Example 7, except that 1,4-bis((2-bromophenyl)ethynyl)benzene was used instead of 1-bromo-2-(phenylethynyl)benzene in Starting Compound Production 1. HRMS (ESI+): m / z scaled for C 49 H 29 I2[M+H] 859.0359; found: 859.0355.

[0170] Example 10 [ka] After the same procedures as in Example 1 up to Production 1 of the Starting Compound and Production 2 of the Starting Compound and post-treatment, 2-bromonaphthalene (1.1 mol equivalent) and tetrakistriphenylphosphine palladium(0) (5 mol%) were added and the mixture was heated and stirred for 8 hours, and then post-treatment similar to that in Example 1 was carried out to obtain Example Compound 10 in a yield of 88%. HRMS (ESI+): m / z scaled for C 37 H 25 [M+H] 469.1956; found: 469.1958.

[0171] Example 11 [ka] Starting compound production 1, starting compound production 2, and post-treatment were carried out in the same manner as in Example 1, and then phenyl bromide (1.1 mol equivalent) and tetrakistriphenylphosphine palladium(0) (5 mol%) were added and the mixture was heated and stirred for 8 hours, and then post-treatment was carried out in the same manner as in Example 1, to obtain Example Compound 11 in a yield of 71%. HRMS (ESI+): m / z scaled for C 27 H 19 [M+H] 419.1800; found: 419.1798.

[0172] Example 12 [ka] Starting compound production 1, starting compound production 2, and post-treatment were carried out in the same manner as in Example 1, and then 4-bromo-N,N-diphenylaniline (1.1 mol equivalent) and tetrakistriphenylphosphine palladium(0) (5 mol%) were added and the mixture was heated and stirred for 8 hours, and then post-treatment was carried out in the same manner as in Example 1, to obtain Example Compound 12 in a yield of 88%. HRMS (ESI+): m / z scaled for C 45 H 31 N [M+H] 585.2457; found: 585.2458.

[0173] Example 13 [ka] The procedures of Starting Compound Production 1, Starting Compound Production 2, and work-up were the same as in Example 1, except that 10,10-dimethylanthracen-9(10H)-one was used instead of 9-fluorenone in Starting Compound Production 1. Then, 4-bromo-N,N-diphenylaniline (1.1 mol equivalent) and tetrakistriphenylphosphine palladium(0) (5 mol%) were added, and the mixture was heated and stirred for 8 hours. After that, work-up was carried out in the same manner as in Example 1, to obtain Example Compound 13 in a yield of 80%. HRMS (ESI+): m / z scaled for C 48 H 36 N [M+H] 626.3848; found: 626.3845.

[0174] Example 14 [ka] The procedures of Starting Compound Production 1, Starting Compound Production 2, and post-treatment were the same as in Example 1, except that 9H-thioxanthen-9-one was used instead of 9-fluorenone in Starting Compound Production 1. Then, 4,4′-dibromo-1,1′-biphenyl (0.6 mol equivalent) and tetrakistriphenylphosphine palladium(0) (5 mol%) were added, and the mixture was heated and stirred for 8 hours. After that, post-treatment was carried out in the same manner as in Example 1, to obtain Example Compound 14 in a yield of 83%. HRMS (ESI+): m / z scaled for C 66 H 43 S2[M+H] 899.2806; found: 899.2802.

[0175] Example 15 [ka] The procedures of Starting Compound Production 1, Starting Compound Production 2, and post-treatment were the same as in Example 1, except that 10,10-dimethylanthracen-9(10H)-one was used instead of 9-fluorenone in Starting Compound Production 1. Then, p-dibromobenzene (0.6 mol equivalent) and tetrakistriphenylphosphine palladium(0) (5 mol%) were added, and the mixture was heated and stirred for 8 hours. After that, post-treatment was carried out in the same manner as in Example 1, to obtain Example Compound 15 in a yield of 78%. HRMS (ESI+): m / z scaled for C 66 H 51 [M+H] 843.3991; found: 843.3993.

[0176] Example 16 [ka] The procedures of Starting Compound Production 1, Starting Compound Production 2, and post-treatment were the same as in Example 1, except that 9H-thioxanthen-9-one was used instead of 9-fluorenone in Starting Compound Production 1. Then, 5,5′-dibromo-2,2′-thiphene (0.6 mol equivalent) and tetrakistriphenylphosphine palladium(0) (5 mol%) were added, and the mixture was heated and stirred for 8 hours. After that, post-treatment was carried out in the same manner as in Example 1, to obtain Example Compound 16 in a yield of 83%. HRMS (ESI+): m / z scaled for C 62 H 39 S4[M+H] 911.1935; found: 911.1932.

[0177] Example 17 [ka] After the same procedures as in Production 1 of Starting Compound, Production 2 of Starting Compound, and Example 1, tris(4-bromophenyl)amine (0.35 mol equivalent) and tetrakistriphenylphosphinepalladium(0) (5 mol%) were further added, and the mixture was heated and stirred for 8 hours, and then post-treatment similar to that in Example 1 was carried out to obtain Example Compound 17 in a yield of 80%. HRMS (ESI+): m / z scaled for C 99 H 64 N [M+H] 1266.5039; found: 1266.5036.

[0178] Example 18 [ka] Example compound 18 was obtained in a yield of 84% in the same manner as in Starting Compound Production 1, Starting Compound Production 2, and Example 1, except that ((2,5-dibromo-1,4-phenylene)bis(ethyne-2,1-diyl))dibenzene was used instead of 1-bromo-2-(phenylethynyl)benzene in Starting Compound Production 1. HRMS (ESI+): m / z scaled for C 48 H 31 [M+H] 607.2426; found: 607.2429.

[0179] Example 19 [ka] Example compound 19 was obtained in a yield of 86% in the same manner as in Starting Compound Production 1, Starting Compound Production 2, and Example 7, except that ((2,5-dibromo-1,4-phenylene)bis(ethyne-2,1-diyl))dibenzene was used instead of 1-bromo-2-(phenylethynyl)benzene in Starting Compound Production 1. HRMS (ESI+): m / z scaled for C 48 H 29 I2[M+H] 859.0359; found: 859.0356.

[0180] Example 20 [ka] Example compound 20 was obtained in a yield of 90% in the same manner as in Starting Compound Production 1, Starting Compound Production 2, and Example 11, except that ((2,5-dibromo-1,4-phenylene)bis(ethyne-2,1-diyl))dibenzene was used instead of 1-bromo-2-(phenylethynyl)benzene in Starting Compound Production 1. HRMS (ESI+): m / z scaled for C 60 H 39[M+H] 759.9720; found: 759.9722.

[0181] Example 21 [ka] Starting compound production 1 and starting compound production 2 were carried out, except that ((2,5-dibromo-1,4-phenylene)bis(ethyne-2,1-diyl))dibenzene was used instead of 1-bromo-2-(phenylethynyl)benzene in starting compound production 1, and in the same manner as in Example 11, except that imidazole was used instead of phenyl bromide in Example 11, Example compound 21 was obtained in a yield of 82%. HRMS (ESI+): m / z scaled for C 54 H 35 N4[M+H] 739.2862; found: 739.2860.

[0182] Example 22 [ka] Example compound 22 was obtained in a yield of 78% in the same manner as in Starting Compound Production 1, Starting Compound Production 2, and Example 1, except that 9H-xanthen-9-one was used instead of 9-fluorenone and ((2,5-dibromo-1,4-phenylene)bis(ethyne-2,1-diyl))dibenzene was used instead of 1-bromo-2-(phenylethynyl)benzene in Starting Compound Production 1. HRMS (ESI+): m / z scaled for C 48 H 31 O2[M+H] 639.2324; found: 639.2321.

[0183] Example 23 [ka] Example compound 23 was obtained in a yield of 81% in the same manner as in Starting Compound Production 1, Starting Compound Production 2, and Example 1, except that 9H-thioxanthen-9-one was used instead of 9-fluorenone and ((2,5-dibromo-1,4-phenylene)bis(ethyne-2,1-diyl))dibenzene was used instead of 1-bromo-2-(phenylethynyl)benzene in Starting Compound Production 1. HRMS (ESI+): m / z scaled for C 48 H 31 S2[M+H] 671.1867; found: 671.1869.

[0184] Example 24 [ka] Starting compound production 1 and starting compound production 2 were carried out, except that ((2,5-dibromo-1,4-phenylene)bis(ethyne-2,1-diyl))dibenzene was used instead of 1-bromo-2-(phenylethynyl)benzene in starting compound production 1, and example compound 24 was obtained in a yield of 78% in the same manner as in Example 11, except that p-isobutylphenyl bromide was used instead of phenyl bromide in Example 11. HRMS (ESI+): m / z scaled for C 66 H 51 [M+H] 843.3991; found: 843.3994.

[0185] Example 25 [ka] Starting compound preparations 1 and 2 were carried out, except that 1-bromo-2-(phenylethynyl)benzene was replaced with ((2,5-dibromo-1,4-phenylene)bis(ethyne-2,1-diyl))dibenzene in starting compound preparation 1, and the procedure was the same as in Example 11, except that 2-naphthyl bromide was used instead of phenyl bromide in Example 11. Example compound 25 was obtained in a yield of 92%. HRMS (ESI+): m / z scaled for C 27 H 19 [M+H] 343.1487; found: 343.1489.

[0186] Example 26 [ka] Starting compound production 1 and starting compound production 2 were carried out in the same manner as in Example 1, except that ((2,5-dibromo-1,4-phenylene)bis(ethyne-2,1-diyl))dibenzene was used instead of 1-bromo-2-(phenylethynyl)benzene in starting compound production 1, and that 4-bromo-1,1′-biphenyl was used instead of phenyl bromide in Example 11. Example compound 26 was obtained in a yield of 88%. HRMS (ESI+): m / z scaled for C 72 H 47 [M+H] 911.3678; found: 911.3675.

[0187] Example 27 [ka] Starting compound production 1 and starting compound production 2 were carried out, except that ((2,5-dibromo-1,4-phenylene)bis(ethyne-2,1-diyl))dibenzene was used instead of 1-bromo-2-(phenylethynyl)benzene in starting compound production 1, and example compound 27 was obtained in a yield of 93% in the same manner as in Example 11, except that 9-(4-bromophenyl)-9H-carbazole was used instead of phenyl bromide in Example 11. HRMS (ESI+): m / z scaled for C 84 H 53 N2[M+H] 1089.4209; found: 1089.4207.

[0188] Example 28 [ka] Example compound 28 was obtained in a yield of 83% in the same manner as in Example 11, except that 9H-xanthen-9-one was used instead of 9-fluorenone in Production of Starting Compound 1 and Production of Starting Compound 2, and that bis(4-bromophenyl)diphenylsilane was used instead of phenyl bromide in Example 11. HRMS (ESI+): m / z scaled for C 78 H 53 O2Si [M+H] 1049.3815; found: 1049.3811.

[0189] Example 29 [ka] To a mixture of Example Compound 19, phenylboronic acid (3.3 equivalents), tripotassium phosphate hydrate (6 equivalents), Pd(dba) (2 mol%), and SPhos (8 mol%), anhydrous toluene (2.5 mL) was added and stirred at 110 °C for 12 hours under an argon atmosphere. After cooling to room temperature, the reaction mixture was extracted three times with dichloromethane, and the organic layer was dried over sodium sulfate. The solvent was evaporated under reduced pressure, and the crude product was recrystallized from dichloromethane / methanol to give Example Compound 29 as a white solid (yield 96%). HRMS (ESI+): m / z scaled for C 60 H 39 [M+H] 759.9720; found: 759.9722.

[0190] (Comparative Example) The following compounds were synthesized as comparative compounds by the method described in Non-Patent Document 1 [Journal of the American Chemical Society (2009), 131, 13596-13597.]. [ka]

[0191] [Evaluation of solubility] The solubility of Example Compound 18 and the comparative compounds prepared in the examples in organic solvents was evaluated.

[0192] The specified amount of each compound shown in Table 1 was added to 1 mL of chlorobenzene, and the mixture was stirred at 1200 rpm on a hot plate at 60°C for 5 minutes, then allowed to stand at 25°C for 24 hours, after which the presence or absence of compound precipitation was checked visually. [Table 1] As shown in Table 1, the solubility of Example Compound 18 was estimated to be 14 mg, while the solubility of the comparative compound was estimated to be less than 5 mg. This result indicates that Example Compound 18 has superior solubility in chlorobenzene to the comparative compound, with a solubility at least twice as high. [Industrial Applicability]

[0193] The compound according to one embodiment of the present invention can be used as a skeleton of an organic semiconductor electronic material (a hole transport material, a hole introduction material, a hole extraction material, an electron transport material, an electron introduction material, an electron extraction material, such as an OLED, an OPV, a PSC, an OFET, or a PeQD).

Claims

1. A compound represented by the following formula (I) or the following formula (II): 【Chemical 1】 (In the formula (I), Ar ａ and Ar ｂ each independently represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocycle which may have a substituent, Ar １ and Ar ２ each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent, Ar １ and Ar ２ and are bonded to each other directly or via a linker, and may have any substituents; Z １ represents a hydrogen atom or an arbitrary substituent; In the formula (II), Ar ｃ , Ar ｄ and Ar ｅ each independently represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocycle which may have a substituent, Ar １ , Ar ２ , Ar ３ and Ar ４ each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent, Ar １ and Ar ２ , and Ar ３ and Ar ４ are bonded to each other directly or via a linker, and may each have an optional substituent, Z １ and Z ２ each independently represents a hydrogen atom or an arbitrary substituent.

2. The compound represented by formula (I) is １ and Ar ２ and have a solubility in chlorobenzene solvent that is at least twice as high as that of a compound in which they are not bonded to each other directly or via a linker; The compound represented by formula (II) is １ and Ar ２ , and Ar ３ and Ar ４ are at least twice as soluble in chlorobenzene as compounds that are not bonded to each other directly or via a linker; The compound of claim 1.

3. 3. A method for producing the compound according to claim 1 or 2, comprising a production step of cyclizing an anion intermediate generated from a compound represented by the following formula (IV) or the following formula (V) and a nucleophilic reagent in the presence of a divalent zinc compound and a diamine derivative represented by formula (III): 【Chemistry 2】 (In the formula (III), R １ , R ２ , R ３ , and R ４ each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon ring which may have a substituent, or an aromatic heterocycle which may have a substituent, and n represents an integer of 1 to 4. 【Chemistry 3】 (Ar in the formula (IV) and the formula (V) ａ , Ar ｂ , Ar ｃ , Ar ｄ , Ar ｅ , Ar １ , Ar ２ , Ar ３ , and Ar ４ respectively represent Ar in the formula (I) or (II). ａ , Ar ｂ , Ar ｃ , Ar ｄ , Ar ｅ , Ar １ , Ar ２ , Ar ３ , and Ar ４ is synonymous with

4. The method further comprises a step of adding a transition metal catalyst to a Zn-modified intermediate of a compound represented by the following formula (VI) or the following formula (VII), and carrying out a tandem coupling reaction in situ: A method for producing the compound of claim 3. 【Chemistry 4】 (Ar in the formula (VI) and the formula (VII) ａ , Ar ｂ , Ar ｃ , Ar ｄ , Ar ｅ , Ar １ , Ar ２ , Ar ３ , and Ar ４ respectively represent Ar in the formula (I) or (II). ａ , Ar ｂ , Ar ｃ , Ar ｄ , Ar ｅ , Ar １ , Ar ２ , Ar ３ , and Ar ４ is synonymous with

5. The method further comprises a step of adding a halogenated compound, a boronated compound or a trialkylstannylated compound to a Zn-containing intermediate of a compound represented by the following formula (VI) or the following formula (VII), to produce a compound represented by the following formula (VIII) or the following formula (IX): A method for producing the compound of claim 3. 【Chemistry 5】 (Ar in the formula (VI) and the formula (VII) ａ , Ar ｂ , Ar ｃ , Ar ｄ , Ar ｅ , Ar １ , Ar ２ , Ar ３ , and Ar ４ respectively represent Ar in the formula (I) or (II). ａ , Ar ｂ , Ar ｃ , Ar ｄ , Ar ｅ , Ar １ , Ar ２ , Ar ３ , and Ar ４ is synonymous with 【Chemistry 6】 (Ar in the formula (VIII) and the formula (IX) ａ , Ar ｂ , Ar ｃ , Ar d , Ar ｅ , Ar １ , Ar ２ , Ar ３ , and Ar ４ respectively represent Ar in the formula (I) or (II). ａ , Ar ｂ , Ar ｃ , Ar ｄ , Ar ｅ , Ar １ , Ar ２ , Ar ３ , and Ar ４ is synonymous with Z ３ and Z ４ each independently represents a halogen atom, a boron atom having a substituent, or a tin atom having a substituent.

6. A composition comprising the compound of claim 1.

7. An organic semiconductor compound having a skeleton represented by the following formula (I) or (II): 【Chemistry 7】 (In the formula (I), Ar ａ and Ar ｂ each independently represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocycle which may have a substituent, Ar １ and Ar ２ each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent, Ar １ and Ar ２ and are bonded to each other directly or via a linker, and may have any substituents; Z １ represents a hydrogen atom or an arbitrary substituent; In the formula (II), Ar ｃ , Ar ｄ and Ar ｅ each independently represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocycle which may have a substituent. Ar １ , Ar ２ , Ar ３ and Ar ４ each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent; Ar １ and Ar ２ , and Ar ３ and Ar ４ are bonded to each other directly or via a linker, and may each have an optional substituent, Z １ and Z ２ each independently represents a hydrogen atom or an arbitrary substituent.

8. An organic semiconductor device comprising an organic semiconductor device film containing the organic semiconductor compound according to claim 7.

9. A film-forming ink for an organic semiconductor device, comprising the organic semiconductor compound according to claim 7 and an organic solvent.

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