Compounds, their manufacturing methods and their uses

Abstract

To provide a novel aromatic condensed ring compound having a spiro ring skeleton. 【Solution means】A compound represented by the following formula (I). JPEG2026061884000029.jpg36141 (In the above formula (I), Ar 1 and Ar 2 each independently represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocyclic ring which may have a substituent, and R 1 , R 2 , R 3 and R 4 each independently represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent, and R 1 and R 2 , and / or, R 3 and R 4 are bonded to each other directly or via a linker, and each independently has an arbitrary substituent.)

Description

[Technical Field]

[0001] This invention relates to compounds, as well as methods for producing the same and their uses. [Background technology]

[0002] Aromatic condensed rings are widely used as molecular frameworks for functional molecules. For example, they are used as the framework for hole transport materials, hole introduction materials, hole extraction materials, electron transport materials, electron introduction materials, electron extraction materials, and host materials in multilayer thin-film organic semiconductors such as organic electroluminescent (OLEDs), organic thin-film solar cells (OPVs), organic field-effect transistors (OFETs), perovskite solar cells, and perovskite quantum dots. Compounds containing aromatic condensed rings are called "aromatic condensed ring compounds."

[0003] To manufacture multilayer thin films using organic semiconductors of hole- or electron-transporting aromatic condensed ring compounds, it is essential to improve the solubility of aromatic condensed ring compounds in organic solvents. However, aromatic condensed ring compounds generally have very low solubility in organic solvents.

[0004] In response to this, conventional methods have been employed to ensure solubility by introducing long-chain alkyl groups into aromatic condensed ring compounds, forming liquid crystal molecules, or oligomerizing them. However, these methods have the major drawbacks of having limited solubility-enhancing effects and low synthesis yields. The long-chain alkyl groups introduced to improve solubility eliminate polarity, making high purity difficult, and the presence of trace impurities can degrade the semiconductor's functionality.

[0005] Therefore, there are limitations to applying conventional aromatic condensed ring compounds to coating methods that dissolve them in organic solvents, which hinders their practical application by coating methods.

[0006] Therefore, vapor deposition is currently used for OLED smartphones and OLED televisions.

[0007] Studies have also been conducted to explore applying aromatic condensed ring compounds to coating methods by improving their solubility (Non-Patent Document 1). However, conventional techniques require multi-step synthesis, making purification at each synthesis step difficult. Furthermore, the number of structures with desirable short-chain substituents that achieve high solubility is limited, and practical application remains problematic (Patent Document 1).

[0008] Furthermore, while the production methods for aromatic condensed ring compounds, particularly aromatic heterocyclic compounds, have become possible with non-precious metal iron catalysts from the perspective of palladium removal, there are still limitations, such as the synthesis yield being substrate-dependent, and new methods are needed. From the perspective of realizing a sustainable society and green transformation, the development of production methods using non-precious metal catalysts is urgently needed, but the production of aromatic condensed ring compounds with desirable physical properties and high solubility using non-precious metal catalysts remains limited. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] Japanese Patent Publication No. 2022-026650 [Non-patent literature]

[0010] [Non-Patent Document 1] Solution-Processed Organic Light-emitting Devices, 2024 Published by Elsevier [Overview of the project] [Problems that the invention aims to solve]

[0011] The object of the present invention is to provide a novel aromatic condensed ring compound having a spiro ring skeleton, and a method for producing the novel aromatic condensed ring compound using a non-precious metal catalyst, which is suitable for a sustainable society. [Means for solving the problem]

[0012] As a result of intensive studies to solve the above problems, the present inventors constructed a new aromatic condensed ring having a spiro ring skeleton, and established a method for producing the novel aromatic condensed ring compound by a synthesis method using a non-noble metal catalyst that does not use a noble metal. Furthermore, the inventors elucidated that it is possible to derive these aromatic condensed rings into p-type or n-type organic semiconductor compounds, and thus arrived at the present invention.

[0013] That is, the gist of the present invention is as follows: [1] A compound represented by the following formula (I). [Chemical formula] (In the above formula (I), Ar 1 and Ar 2 each independently represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocyclic ring which may have a substituent, R 1 , R 2 , R 3 and R 4 each independently represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent, R 1 and R 2 , and / or, R 3 and R 4 are bonded to each other directly or via a linker, and each independently has an arbitrary substituent.) [2] The compound represented by the formula (I) has a solubility in a chlorobenzene solvent that is 2 times or more that of a compound in which R 1 and R 2 , and, R 3 and R 4 are not bonded to each other directly or via a linker. The compound according to [2]. [3] In the formula (I), the condensed ring formed by Ar 1 and Ar 2 and the 5-5 condensed ring shown therebetween is a 4-condensed ring. The compound according to [1] or [2]. A method for producing the compound represented by formula (I) as described in any one of [4] [1] to [3], (A) A step of cyclizing an acetylene derivative represented by the following formula (II) in the presence of a nucleophile, a diamine derivative represented by the following formula (III), and a divalent zinc compound to form a compound represented by the following formula (IV), (B) After step (A), a step is taken in which a divalent or monovalent copper compound is added to the compound represented by formula (IV) below in a one-pot reaction, and a coupling reaction is carried out continuously in situ to form the compound represented by formula (I), A method for producing the compound, including the compound. [ka] (Ar in formulas (II) and (IV) above) 1 Ar 2 , R 1 , R 2 , R 3 and R 4 These are, respectively, Ar in formula (I) above. 1 Ar 2 , R 1 , R 2 , R 3 and R 4 It is synonymous with [the above]. R in equation (III) above a , R b , R c , and R d Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic hydrocarbon ring, or an optionally substituted aromatic heterocycle, where n is an integer from 1 to 4. [5] The method for producing the compound according to [4], wherein the nucleophile is a lithium salt reagent or a potassium salt reagent. [6] A method for producing a compound according to [4] or [5], wherein in step (B), an iodine compound or a bromine compound is further present in the reaction system. [7] [1] A hole-transport or electron-transport organic semiconductor compound represented by the following formula (V), having the skeleton represented by formula (I). [ka] (Ar in formula (V) above) 1 Ar 2 , R 1 , R 2 , R 3 and R 4 These are, respectively, Ar in formula (I) above. 1 Ar 2 , R 1 , R 2 , R 3 and R 4 It is synonymous with, Z 1 and Z 2 Each of these independently represents an arbitrary hole transport group or electron transport group. A composition containing a hole transport or electron transport organic semiconductor compound as described in [8] [7]. [9] [7] An organic semiconductor compound having the skeleton represented by formula (V). An organic semiconductor device comprising an organic semiconductor device film containing the organic semiconductor compound described in

[10] [9]. An ink for forming films for organic semiconductor devices, comprising the organic semiconductor compound described in

[11] [9] and an organic solvent. [Effects of the Invention]

[0014] According to one aspect of the present invention, a novel aromatic condensed ring compound having a spiro ring skeleton and a non-precious metal catalyst can be used to provide a sustainable manufacturing method suitable for a sustainable society for producing the novel aromatic condensed ring compound. [Brief explanation of the drawing]

[0015] [Figure 1] This figure shows the three-dimensional structure of compound 8 synthesized in the example. [Modes for carrying out the invention]

[0016] The embodiments for carrying out the present invention will be described below, but the embodiments of the present invention are not limited to the following embodiments. Unless otherwise specified herein, "A to B" representing a numerical range means "greater than or equal to A and less than or equal to B".

[0017] In this specification, the terms "aromatic hydrocarbon ring" and "aromatic heterocycle" are not limited to monocyclic aromatic hydrocarbon rings and aromatic heterocycles, but also include aromatic hydrocarbon rings and aromatic heterocycles that are fused rings of two or more rings.

[0018] [1. Compound (I)] One embodiment of the present invention is a compound represented by the following formula (I). [ka]

[0019] In formula (I), Ar 1 and Ar 2 Each of these independently represents an optionally substituted aromatic hydrocarbon ring or an optionally substituted aromatic heterocycle.

[0020] R 1 , R 2 , R 3 and R 4 Each independently represents an aromatic hydrocarbon ring group that may have substituents or an aromatic heterocyclic group that may have substituents, and R 1 and R 2 , and / or, R 3 and R 4 Each of these elements is bonded to one another, either directly or via a linker, to form a fused ring containing an aromatic hydrocarbon ring which may have substituents and / or an aromatic heterocycle which may have substituents.

[0021] In this specification, the compound represented by formula (I) may be referred to as "compound (I)".

[0022] According to the present invention, it is possible to provide a compound (I) having a rigid spiro ring skeleton and a highly soluble aromatic fused ring skeleton without employing methods such as introducing long-chain alkyl groups, liquid crystal molecularization, or oligomerization to improve the organic solvent solubility of the parent skeleton of a typical aromatic fused ring. Therefore, compound (I) according to one aspect of the present invention does not reduce the effect of hole or electron transfer by introducing functional groups that are effective in improving solubility in organic solvents but do not involve the transfer of holes or electrons.

[0023] The aromatic fused ring of the spiro ring skeleton of compound (I) is R in formula (I). 1 and R 2 , and / or, R 3 and R 4 Because these elements are bonded to each other directly or via linkers to form fused rings containing optionally substituted aromatic hydrocarbon rings and / or optionally substituted aromatic heterocycles, the molecular structure is rigid, molecular vibrations are suppressed, and high solubility is achieved. This allows for the construction of an effective base skeleton in terms of improving electron or hole mobility and suppressing sub-absorption in the absorption spectrum.

[0024] Furthermore, by derivatizing compound (I) to form the compound of formula (V) described later, it can be applied as a p-type or n-type low-molecular-weight semiconductor compound for organic semiconductor devices. Due to its excellent solubility in organic solvents, it can be made into an ink using organic solvents and applied to thin film formation by coating methods.

[0025] The mechanism by which compound (I) exhibits high solubility in organic solvents is thought to be as follows.

[0026] Specifically, an example of a substructure in compound (I) according to one aspect of the present invention is shown below. In the substructure shown below, at least one of the carbon atoms, C1 or C2, of the spiro ring becomes an unstrained sp3 carbon atom, and the angle of the upper and lower aromatic rings bonded to it is fixed at approximately 90°. This avoids steric hindrance, resulting in structural fixation, which is thought to impart high solubility. [ka]

[0027] Let's explain with a more specific example. Figure 1 shows the three-dimensional structure of compound 8 synthesized in the example. As shown in Figure 1, the angle of the aromatic rings bonded to C1 and C2 of the spiro ring is fixed at approximately 90° with respect to the 6-5-5-6 membered ring in the center of the figure, and it can be seen that the 6-5-5-6 membered ring is upright. It can also be seen that the thiophene and acceptor sites adjacent to the spiro ring do not come into contact with the spiro ring.

[0028] The characteristic three-dimensional structure of the spiro ring in compound (I) and its derivatives of the present invention contributes to their high solubility in organic solvents. Even when the side chain adjacent to the spiro ring is larger than that of the example compound 8, the characteristic three-dimensional structure of the spiro ring prevents the side chain from contacting the spiro ring. Therefore, compounds with large side chains adjacent to such spiro rings also exhibit high solubility in organic solvents.

[0029] The structure of compound (I) according to one aspect of the present invention will be described in detail below. <Ar 1 and Ar 2 > In the above formula (I), Ar 1 Ar 2 Each of these independently represents an optionally substituted aromatic hydrocarbon ring or an optionally substituted aromatic heterocycle.

[0030] In the above formula (I), Ar 1 Ar 2 Examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, anthracene rings, fluorene rings, phenanthrene rings, and azulene rings, all of which have 6 to 12 carbon atoms.

[0031] Furthermore, Ar in formula (I) 1 Ar 2Examples of aromatic heterocycles include pyrrole rings, furan rings, pyridine rings, thiophene rings, imidazole rings, pyrazole rings, thiazole rings, dibenzofuran rings, and dibenzothiophene rings, which have 2 to 10 carbon atoms and contain one or more heteroatoms selected from the group consisting of sulfur atoms, oxygen atoms, and nitrogen atoms.

[0032] Of these, monocyclic or difused aromatic hydrocarbon rings with 12 or fewer carbon atoms, or monocyclic or difused aromatic heterocycles are preferred, and more preferably are aromatic heterocycles with 6 or fewer carbon atoms, such as benzene rings, thiophene rings, pyrrole rings, furan rings, and pyridine rings.

[0033] In the above formula (I), Ar 1 Ar 2 The aromatic hydrocarbon ring and the substituents that the aromatic hydrocarbon ring may have will be described later. Note that the Ar in formula (I) 1 and Ar 2 They may be identical or very different.

[0034] <R 1 , R 2 , R 3 and R 4 > R in equation (I) above 1 , R 2 , R 3 and R 4 Each of these independently represents an optionally substituted aromatic hydrocarbon ring group or an optionally substituted aromatic heterocyclic group. 1 , R 2 , R 3 and R 4 The aromatic hydrocarbon rings and aromatic heterocycles are Ar 1 and Ar 2 As explained earlier regarding aromatic hydrocarbon rings and aromatic heterocycles, we will not repeat the explanation here.

[0035] R in equation (I) above 1 , R 2 , R 3 and R4 The aromatic hydrocarbon ring and the substituents that the aromatic hydrocarbon ring may have will be described later. In the formula (I), R 1 , R 2 , R 3 and R 4 may be the same or different from each other.

[0036] In the formula (I), R 1 and R 2 , and / or, R 3 and R 4 [[ID=The 21]]are each directly or via a linker to bond to each other to form a condensed ring containing an aromatic hydrocarbon ring which may have a substituent and / or an aromatic heterocyclic ring which may have a substituent.

[0037] In this specification, the condensed ring formed by bonding R 1 and R 2 to each other is referred to as the "R 1 -R 2 ring", and the condensed ring formed by bonding R 3 and R 4 to each other is referred to as the "R 3 -R 4 ring".

[0038] <At In the formula (I), either one of the R 1 -R 2 ring and the R 3 -R 4 ring may be formed, and both the R 1 -R 2 ring and the R 3 -R 4 ring may be formed. In the formula (I), when both the R 1 -R 2 ring and the R 3 -R 4 ring are formed, the R 1 -R 2 ring and the R 3 -R 4 ring may be the same or different from each other. R 1 -R 2 ring and R 3 -R 4If it is different from the ring, R 1 -R 2 The ring is an aromatic hydrocarbon ring which may have substituents, R 3 -R 4 The ring may be an aromatic heterocycle having substituents, or vice versa.

[0039] R 1 -R 2 Ring and R 3 -R 4 The optionally substituted aromatic hydrocarbon ring or optionally substituted aromatic heterocycle included in the ring is Ar 1 and Ar 2 Examples of aromatic hydrocarbon rings and aromatic heterocycles include the aforementioned aromatic hydrocarbon rings and aromatic heterocycles, but preferably, R 1 -R 2 Ring and R 3 -R 4 The fused rings of the ring are aromatic hydrocarbon rings with a total of 20 or fewer carbon atoms, which may have substituents and consist of three or fewer fused rings, or aromatic heterocycles with a total of 20 or fewer carbon atoms, which may have substituents and consist of three or fewer fused rings. Specifically, the following aromatic fused rings are examples.

[0040] <Specific examples of aromatic fused rings> In the following structural formula, the dashed line indicates the carbon-carbon bond of the five-membered ring in formula (I). [ka]

[0041] The aromatic condensed ring described above may have substituents not shown in the structural formula above. Such substituents will be described later.

[0042] <Ar 1 Ar 2 , R 1 , R 2 , R 3 and R 4 Aromatic hydrocarbon ring groups and aromatic heterocyclic groups, and R 1 -R 2Ring and R 3 -R 4 Substituents that the ring may have > In the above formula (I), Ar 1 Ar 2 , R 1 , R 2 , R 3 and R 4 Aromatic hydrocarbon ring groups and aromatic heterocyclic groups, and R 1 -R 2 Ring and R 3 -R 4 There are no particular restrictions on the substituents that the ring may have, and examples include halogen atoms, hydroxyl groups, nitro groups, cyano groups, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthio groups, arylthio groups, heteroarylthio groups, amino groups, acyl groups, aminoacyl groups, ureido groups, sulfonamide groups, carbamoyl groups, sulfamoyl groups, sulfamoylamino groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heteroaryloxycarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, heteroarylsulfonyl groups, imide groups, and silyl groups.

[0043] in particular, Alkyl groups with approximately 1 to 15 carbon atoms, such as methyl and ethyl groups; Alkenyl groups with approximately 2 to 10 carbon atoms, such as ethynyl and propyrenyl groups; Alkynyl groups, such as acetylenyl groups, with approximately 2 to 10 carbon atoms; Aryl groups with approximately 6 to 20 carbon atoms, such as phenyl and naphthyl groups; Heteroaryl groups with approximately 3 to 20 carbon atoms, such as thienyl, furyl, and pyridyl groups; Alkoxy groups with 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 with approximately 3 to 20 carbon atoms, such as pyridyloxy groups and thienyloxy groups; Alkylthio groups with approximately 1 to 15 carbon atoms, such as methylthio groups and ethylthio groups; Arylthio groups with approximately 6 to 20 carbon atoms, such as phenylthio groups and naphthylthio groups; Heteroarylthio groups with approximately 3 to 20 carbon atoms, such as pyridylthio groups and thienylthio groups; Amino groups that may have substituents with approximately 1 to 20 carbon atoms, such as dimethylamino groups and diphenylamino groups; Acyl groups with approximately 2 to 20 carbon atoms, such as acetyl groups and pivaloyl groups; Acylamino groups with approximately 2 to 20 carbon atoms, such as acetylamino groups and propionylamino groups; Ureid groups with approximately 2 to 20 carbon atoms, such as the 3-methylureid group; Sulfonamide groups with approximately 1 to 20 carbon atoms, such as methanesulfonamide groups and benzenesulfonamide groups; Carbamoyl groups with approximately 1 to 20 carbon atoms, such as dimethylcarbamoyl groups and ethylcarbamoyl groups; Sulfamoyl groups with approximately 1 to 20 carbon atoms, such as ethyl sulfamoyl groups; Sulfamoylamino groups with approximately 1 to 20 carbon atoms, such as dimethylsulfamoylamino groups; Alkoxycarbonyl groups with approximately 2 to 6 carbon atoms, such as methoxycarbonyl groups and ethoxycarbonyl groups; Aryloxycarbonyl groups with approximately 7 to 20 carbon atoms, such as phenoxycarbonyl groups and naphthoxycarbonyl groups; Heteroaryloxycarbonyl groups with approximately 6 to 20 carbon atoms, such as pyridyloxycarbonyl groups; Alkyl sulfonyl groups with approximately 1 to 6 carbon atoms, such as methanesulfonyl groups, ethanesulfonyl groups, and trifluoromethanesulfonyl groups; Aryl sulfonyl groups with approximately 6 to 20 carbon atoms, such as benzenesulfonyl groups and monofluorobenzenesulfonyl groups; Heteroaryloxysulfonyl groups with approximately 3 to 20 carbon atoms, such as thienylsulfonyl groups; Imide groups with approximately 4 to 20 carbon atoms, such as phthalimides; A silyl group triply substituted with substituents selected from the group consisting of alkyl and aryl groups; These are some examples.

[0044] Of these, in particular, R 1 -R 2 Ring and R 3 -R 4 The ring is more preferably composed of a hydrogen atom, an alkyl group having approximately 1 to 3 carbon atoms, or an alkoxy group having approximately 1 to 3 carbon atoms, as this allows for further adjustment of solubility.

[0045] <Specific examples of compound (I)> Specific examples of compounds represented by formula (I) are given below, but the compounds of the present invention are not limited in any way to the following exemplary compounds. [ka] JPEG2026061884000009.jpg255136

[0046] Compound (I) according to one aspect of the present invention comprises Ar in formula (I). 1 and Ar 2 Preferably, the condensed ring formed from the 5-5 condensed ring shown between these is a 4-condensed ring. In this specification, the "5-5 condensed ring" is, in formula (I), Ar 1 and Ar 2 It means a fused ring formed by the fusion of two 5-membered rings shown between them. Also, the "4-fused ring" means a fused ring with 4 fused rings. In formula (I), Ar 1 and Ar 2 And the fused ring formed from the 5-5 fused ring shown between these is not limited to a 4-fused ring, Ar 1 and Ar 2 Depending on the type of aromatic hydrocarbon ring or aromatic heterocycle selected, the fused ring can have 4 to 6 rings.

[0047] <Solubility of compound (I)> Compound (I) according to one aspect of the present invention has improved solubility in organic solvents, and preferably has the following characteristics. That is, compound (I) according to one aspect of the present invention has R in formula (I). 1 -R 2 Ring, and / or, R 3 -R 4 Compound (I) according to one embodiment of the present invention, which forms a ring, 1 -R 2 Ring and R 3 -R 4 It has the characteristic of having better solubility in organic solvents than compounds that do not form a ring.

[0048] The type of organic solvent in which compound (I) according to one aspect of the present invention can be dissolved is not particularly limited and may be conventionally known organic solvents used as solvents for inks. Examples of such organic solvents include chlorobenzene, toluene, and xylene.

[0049] Preferably, compound (I) according to one aspect of the present invention is R 1 -R 2 Ring and R 3 -R 4 Compared to a comparative compound that does not form a ring, the solubility in chlorobenzene solvent is preferably twice as high, more preferably 2.5 times higher, and even more preferably 3 times higher.

[0050] In this specification, "solubility" refers to the maximum amount of a compound that can be dissolved in 1 mL of chlorobenzene under conditions of 25°C. The high solubility of the compounds of the present invention in organic solvents can be measured by their solubility in chlorobenzene. This measurement may be carried out as described in the examples, and the solubility will be measured at 25°C.

[0051] In measuring the solubility of compound (I) in an organic solvent according to one aspect of the present invention, the compound used for comparison (comparative compound) is R in formula (1) above. 1 -R 2 Ring and R 3 -R 4Any compound that does not form a ring is acceptable, but it is preferable that it be comparative compound 1 or comparative compound 2, which were used as comparison subjects in the examples described later.

[0052] [2. Method for producing compound (I)] A method for producing compound (I) according to one aspect of the present invention is: (A) A step of cyclizing an acetylene derivative represented by the following formula (II) in the presence of a nucleophile, a diamine derivative represented by the following formula (III), and a divalent zinc compound to form a compound represented by the following formula (IV), (B) After step (A), a step is taken in which a divalent or monovalent copper compound is added to the compound represented by formula (IV) below in a one-pot reaction, and a coupling reaction is carried out continuously in situ to form the compound represented by formula (I), Includes: [ka] (Ar in formulas (II) and (IV) above) 1 Ar 2 , R 1 , R 2 , R 3 and R 4 These are, respectively, Ar in formula (I) above. 1 Ar 2 , R 1 , R 2 , R 3 and R 4 It is synonymous with [the above]. R in equation (III) above a , R b , R c , and R d Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic hydrocarbon ring, or an optionally substituted aromatic heterocycle, where n is an integer from 1 to 4.

[0053] According to a method for producing compound (I) according to one aspect of the present invention, the above-mentioned compound (I) can be produced. Furthermore, according to a method for producing compound (I) according to one aspect of the present invention, compound (I) can be produced by a non-metallic catalyst one-pot reaction, which is more versatile and highly reactive than conventional aromatic condensation ring synthesis using iron catalysts. Since the method for producing compound (I) according to one aspect of the present invention is a method for producing compound (I) using a new non-precious metal catalyst that improves the synthesis yield, the present invention can provide a novel production method suitable for a sustainable society.

[0054] Each step in the method for producing compound (I) according to one aspect of the present invention will be described in detail below. [Process (A)] In a method for producing compound (I) according to one aspect of the present invention, step (A) is a reaction step in which an acetylene derivative represented by formula (II) (hereinafter sometimes referred to as the "raw material compound") is converted into an anionic species with a nucleophile, and then cyclized by reacting it with a divalent zinc compound and a diamine derivative represented by formula (III) (hereinafter sometimes referred to as "diamine (III)").

[0055] As an example, the reaction A to B shown below is carried out. In the following reaction equation 1, "-H + " represents the reaction in which a hydrogen cation is removed, and "Zn 2+ " represents zinc ions derived from divalent zinc compounds, and "heat" represents a heating reaction. [ka]

[0056] <Compound represented by formula (II)> The compound represented by formula (II) can be produced by converting the hydroxyl group of the compound represented by the corresponding formula (II') to hydrogen by a known method. Specifically, the hydroxyl group in the compound represented by formula (II') can be converted to hydrogen by stirring in acetonitrile for 2 to 12 hours at room temperature to the reflux temperature, particularly preferably at the reflux temperature, in the presence of 3 to 6 equivalents of sodium iodide and 1.5 to 3 equivalents of dichlorodimethylsilane for each hydroxyl group (also called a reaction site) in the compound represented by formula (II'). [ka] (Ar in formula (II') above) 1 Ar 2 , R 1 , R 2 , R 3 and R 4 These are, respectively, Ar in formula (II) above. 1 Ar 2 , R 1 , R 2 , R 3 and R 4 (This is synonymous with...)

[0057] <Nucleophile> In step (A), conventionally known nucleophiles can be used as the nucleophile, such as lithium salt reagents, sodium salt reagents, and potassium salt reagents. Among these, from the viewpoint of avoiding side reactions, lithium salt reagents or potassium salt reagents can be preferably used as the nucleophile, and lithium salt reagents can be particularly preferably used.

[0058] In step (A), the most commonly used lithium salt reagent is generally n-butyllithium, but other options such as sec-butyllithium, tert-butyllithium, and iso-propyllithium can also be used. Furthermore, these may coexist with N,N,N',N'-tetramethylethylenediamine (TMEDA), hexamethylphosphoramide (HMPA), dimethylpropylene urea (DMPU), etc.

[0059] Furthermore, lithium amide reagents obtained by lithiating bulky secondary amines such as LDA (Lithium diisopropylamide), LiTMP (Lithium 2,2,6,6-tetramethylpiperidide), and LHMDS (Lithium hexamethyldisilazide) can also be used. Schlosser-Lochmann bases of nBuLi-KOtBu combinations, NaH, and tert-BuONa can also be used. It is preferable to use 1.0 to 1.2 equivalents of each of these lithium salt reagents and sodium salt reagents for each reaction site (corresponding hydrogen atom).

[0060] Furthermore, examples of potassium salt reagents that can be used in step (A) include KOtBu and KH. It is preferable to use 1.0 to 1.2 equivalents of these potassium salt reagents for each reaction site (corresponding hydrogen atom).

[0061] <Divalent zinc compounds> "Divalent zinc compound" means that the zinc in the compound is divalent. 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 standpoint of versatility, examples include ZnCl2, ZnBr2, and ZnI2 as halides; Zn(OAc)2 as an acetate; and Zn(acac)2 as a fatty acid salt. In this specification, "OAc" means acetonate and "acac" means acetylacetonate.

[0062] Furthermore, reagents with pre-contained diamine ligands, such as dichloro(N,N,N',N'-tetramethylethylenediamine)zinc (hereinafter sometimes referred to as "ZnCl2-TMEDA"), may be used from the outset. It is preferable to use 1.0 to 1.5 equivalents of the divalent zinc compound per reaction site (hydrogen atom converted from a hydroxyl group), and particularly preferable to 1.05 to 1.2 equivalents.

[0063] <Diamine derivatives> In step (A), diamine derivatives that can be used include diamine compounds represented by formula (III) (diamine(III)). Common examples include TMEDA (tetramethylethylenediamine), TBD (1,5,7-triazabicyclo[4.4.0]deca-1,3,5-triene), DABCO (1,4-diazabicyclo[2.2.2]octane), DMAP (4-dimethylaminopyridine), and DIPEA (N,N-diisopropylethylamine).

[0064] In the above equation (III), R a , R b , R c , and R d Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic hydrocarbon ring, or an optionally substituted aromatic heterocycle, where n is an integer from 1 to 4.

[0065] (Aliphatic hydrocarbon group) In formula (III) above, examples of aliphatic hydrocarbon groups include alkyl groups and cycloalkyl groups.

[0066] "Alkyl" can be either a linear or branched alkyl group, for example, a linear alkyl group having 1 to 24 carbon atoms or a branched alkyl group having 3 to 24 carbon atoms. Preferably, it is an alkyl group having 1 to 18 carbon atoms (branched alkyl group having 3 to 18 carbon atoms), an alkyl group having 1 to 12 carbon atoms (branched alkyl group having 3 to 12 carbon atoms), an alkyl group having 1 to 6 carbon atoms (branched alkyl group having 3 to 6 carbon atoms), an alkyl group having 1 to 5 carbon atoms (branched alkyl group having 3 to 5 carbon atoms), or an alkyl group having 1 to 4 carbon atoms (branched alkyl group having 3 to 4 carbon atoms).

[0067] 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-hebutyl, 1-methylheptyl, 1-hexylheptyl, 1,1-dimethylheptyl, 2,2- Examples 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, or n-eicosyl.

[0068] "Cycloalkyl" refers to, for example, cycloalkyls having 3 to 24 carbon atoms, preferably cycloalkyls having 3 to 20 carbon atoms, 3 to 16 carbon atoms, 3 to 14 carbon atoms, 3 to 12 carbon atoms, 5 to 10 carbon atoms, 5 to 8 carbon atoms, 5 to 6 carbon atoms, or 5 carbon atoms.

[0069] Specific examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, or alkyl (especially methyl) substituted derivatives of these with 1-5 or 1-4 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, or decahydroazlenyl.

[0070] In formula (III) above, the aliphatic hydrocarbon group is preferably a methyl group, ethyl group, propyl group, pentyl group, butyl group, isopropyl group, 2-butyl group, 1,3-dimethylbutyl group, 2-methylpropyl group, 3,3-dimethylbutyl group, or 2,2-dimethylpropyl group, which coordinate with divalent zinc.

[0071] (Aromatic hydrocarbon rings and aromatic heterocycles) The aromatic hydrocarbon ring and aromatic heterocycle in formula (III) are the same as the Ar in formula (I). 1 Ar 2 , R 1 , R 2 , R 3 and R 4 Similar examples include the above.

[0072] (n in equation (III)) In formula (III) above, n is 1 to 4, but from the viewpoint of reactivity, it is preferable that a 5-membered ring or a 6-membered ring can be formed when coordinated with divalent zinc, and n is particularly preferred to be 1 to 2.

[0073] <Solvent> Step (A) is usually carried out in a solvent. The solvent used is, for example, Aromatic solvents such as toluene and xylene; ether-based solvents such as ether, 1,4-dioxane, tetrahydrofuran (THF), 4-methylhydropyran, 2-methyltetrahydrofuran, and cyclopentyl methyl ether; and aliphatic solvents such as hexane, heptane, and octane can be selected.

[0074] Of these, tetrahydrofuran (THF) is preferred from the viewpoint of maximizing the solubility of the reaction compound (starting compound) in the reaction system, and tetrahydrofuran equivalents such as 4-methylhydropyran, 2-methyltetrahydrofuran, and cyclopentyl methyl ether are preferred from the viewpoint of further raising the boiling point.

[0075] These solvents may be used individually or in combination of two or more. For example, to improve the formation of lithium intermediates such as starting compounds, combining ether-based and hexanealiphatic solvents improves the reaction performance. Furthermore, to carry out a continuous coupling reaction from the Zn intermediate, combining an ether-based solvent and an aromatic solvent improves the reaction performance.

[0076] The amount of solvent used in the reaction system of step (A) is usually preferably in the range of 1 to 50 mL per 1 mmol of the starting compound. The upper limit is preferred from the viewpoint of production efficiency, and 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.

[0077] <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 arbitrarily set within the range up to the reflux temperature of the solvent used, depending on the rate of reaction. If 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.

[0078] The reaction time in step (A) is usually between 4 and 24 hours, but it can be set arbitrarily as it depends on the type of solvent used and other reaction conditions.

[0079] The progress of the reaction in step (A) can be confirmed using high-performance liquid chromatography (HPLC).

[0080] After the reaction in step (A) is complete, the target compound represented by formula (IV) may be obtained using known isolation and purification methods. However, from the viewpoint of efficiency and high yield, as it can be carried out in a one-pot reaction without removing the active species, it is preferable to proceed with step (B) in a one-pot reaction without the isolation and purification of the compound represented by formula (IV).

[0081] [Process (B)] In a method for producing compound (I) according to one aspect of the present invention, step (B) is the compound represented by formula (IV) obtained in step (A), which is Zn 2+ This process involves adding a divalent or monovalent copper compound catalyst to the cyclization intermediate and carrying out a continuous coupling reaction in situ.

[0082] As an example, the process involves carrying out the reactions shown in B to C in the above reaction formula 1. In a method for producing a compound according to one aspect of the present invention, in step (B), the Zn obtained in step (A) 2+ By adding a divalent or monovalent copper compound catalyst to the cyclization intermediate (hereinafter also referred to as the "Zn compound"), compound (IV), the second five-membered ring of formula (I) can be constructed, resulting in a condensed polycyclic compound.

[0083] <Divalent or monovalent copper compound catalysts> "Divalent or monovalent copper compound catalyst" means that the copper in the compound is either divalent or monovalent. Specifically, examples of divalent or monovalent copper compound catalysts used in step (B) include those described in Copper-Mediated Cross-Coupling Reactions, Gwilherm Evano, Nicolas Blanchard (Eds.), 2013, Wiley, such as copper halides, organocopper complexes, and carbene copper complexes.

[0084] Preferably, due to the simplicity of the reagent, copper halides, copper oxides, etc., specifically monovalent inorganic copper compounds: CuCl, CuBr, CuI, CuOAc, CuSCN, CuCN, Cu(CH3CN)4BF4, Cu(CH3CN)4PF6, etc., divalent inorganic copper compounds: CuCl2, CuF2, CuBr2, CuI2, CuOTf2, CuOAc2, Cu(acac)2, Cu(NO3)2, Cu(ClO4)2, Cu[(CF3SO2)2N)]2, Cu(OH)2, etc., and Cu(I) complexes (containing one or more reversibly removable anions) CuL 3 X, CuL 2 X, CuL 1 2X, CuL 1 Examples include 2X. Here, L 1 =PR3 (R = alkyl group or aromatic group), monodentate ligands such as pyridine and carbene; L 2 =Bidentate ligands [bis(diphenylphosphino)ferrocene (dppf), bis(diphenylphosphino)butane (dppb), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos), 2,2-bipyridine (bpy), 1,10-phenanthroline (phen), etc.; L 2 = Tridentate ligands such as terpyridine; X = Counter anions such as Cl, Br, I, OAc, OTf, BF4, etc.

[0085] Among these, the use of inorganic copper reagents such as CuI, CuBr, and CuCl is preferred in terms of general-purpose reagents. Divalent or monovalent copper compound catalysts may be used in equal amounts to the substrate, but it is preferable to use 20 mol% or less, and particularly preferable to 10 mol% to 1 mol% equivalent.

[0086] <Iodine compounds or bromine compounds> In step (B) above, it is preferable to further include an iodine compound or a bromine compound in the reaction system. This has the effect of stabilizing the anions generated in the system.

[0087] Examples of iodine compounds that can be used in step (B) include diiodoethane, diiodopropane, and iodine molecules. Among these, diiodoethane and dibromopropane are preferred from the viewpoint of having a homogeneous reaction solvent. The iodine compound is preferably used in an amount of 1.0 to 5.0 equivalents relative to the starting material (compound represented by formula (IV)), and particularly preferably in an amount of 1.5 to 3.0 equivalents.

[0088] Examples of bromine compounds that can be used in step (B) include dibromoethane, dibromopropane, and bromine molecules. Among these, dibromoethane and dibromopropane are preferred from the viewpoint of ease of measuring the equivalent amount. The equivalent amount of the bromine compound is the same as that of the iodine compound described above.

[0089] <Reaction conditions> The reaction temperature in process (B) is the same as the heating temperature in process (A). The reaction time in process (B) is between 1 and 24 hours.

[0090] The progress of the reaction in step (B) can be confirmed using high-performance liquid chromatography (HPLC).

[0091] After the reaction in step (B) is complete, the target compound (I) according to one embodiment of the present invention, represented by formula (I), can be obtained using known isolation and purification methods.

[0092] [3. Hole transport or electron transport organic semiconductor compounds (V)] One embodiment of the present invention is a hole-transporting or electron-transporting organic semiconductor compound represented by the following formula (V), having a framework represented by formula (I). [ka] (Ar in formula (V) above) 1 Ar 2 , R 1 , R 2 , R 3 and R 4 These are, respectively, Ar in formula (I) above. 1 Ar 2 , R 1 , R 2 , R 3 and R 4 It is synonymous with, Z 1 and Z 2 Each of these independently represents an arbitrary hole transport group or electron transport group.

[0093] In this specification, the compound represented by formula (V) may be referred to as "compound (V)".

[0094] Compound (V) is obtained by derivatization of compound (I) as described above, and compound (V) has a skeleton represented by formula (I). Therefore, compound (V) has high solubility in organic solvents, similar to compound (I).

[0095] <Z 1 and Z 2 > In the above equation (V), Z 1 and Z 2 Each of these independently represents an arbitrary hole transport group or electron transport group.

[0096] In the above equation (V), Z1 and Z 2 Examples of hole transport groups include the relevant compounds listed in the LUMINESCENCE TECHNOLOGY CORP. Catalog 2024.

[0097] In the above equation (V), Z 1 and Z 2 Examples of electron transport groups include the relevant compounds listed in the LUMINESCENCE TECHNOLOGY CORP. Catalog 2024.

[0098] Compound (V) according to one aspect of the present invention may be a hole-transporting organic semiconductor compound or an electron-transporting organic semiconductor compound.

[0099] (Hole-transporting organic semiconductor compounds) By introducing a benzodithiophene structure, thiophene structure, dibenzofuran structure, diarylamine structure, naphthalene structure, etc., which serve as hole transport sites, into the compound represented by formula (I), a compound (V) that functions as a hole-transporting organic semiconductor can be obtained. A "hole-transporting organic semiconductor" is also called a "p-type organic semiconductor."

[0100] In other words, hole-transporting organic semiconductor compounds can be provided by the following methods: Construction of long conjugated systems: Molecules with long conjugated systems, such as polycyclic aromatic compounds and conjugated extensions, enable efficient hole transport. The longer the conjugated system remains unbroken, the more freely π electrons can move, thus increasing 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 a molecule, facilitating hole injection and transport; Construction of planar molecular structures: When molecules have a planar structure, the π-π interactions between molecules become stronger, which promotes efficient hole transport. As a result, hole mobility can be increased by promoting better intermolecular stacking. Furthermore, the high solubility of these skeletons is ensured by rigid spiro rings, allowing for the introduction of π-π stacking effects with smaller molecular skeleton angles.

[0101] (Electron transport organic semiconductor compounds) It is also possible to introduce polycyclic aromatic rings, including conjugated systems such as fullerenes, naphthalenediimides, perylenediimides, and carbazole structures, which serve as electron transport sites, into the compound represented by formula (I). Furthermore, by introducing the ITIC moiety of a non-fullerene acceptor (sometimes abbreviated as NFA), it is possible to produce NFA with high solubility.

[0102] In other words, electron transport properties can be improved by introducing electron-deficient functional groups (e.g., cyano groups, fluoro groups). Functional groups with a high ability to attract electrons are preferred as structural sites contributing to electron transport, and rigid structures that promote highly planar intermolecular π-π interactions are preferred. These functional groups can be induced in the compound represented by formula (I), and high solubility can also be imparted. This allows for the creation of compound (V) that functions as an electron-transporting organic semiconductor. "Electron-transporting organic semiconductors" are also called "n-type organic semiconductors."

[0103] The organic semiconductor having the framework represented by formula (I) exhibits excellent solubility in organic solvents, allowing for the formation of thin films by coating methods. Furthermore, the rigid conjugated framework constituting the compound enables a certain orientation between molecules, resulting in excellent semiconductor properties in the formed thin film.

[0104] For example, the following is a method for producing compound (V) by derivatizing compound (I). Compound (I) typically has two reaction sites. These sites can be reacted with butyllithium at an amount of 1.05 to 1.2 equivalents per reaction site, after which halogenation can be carried out by adding iodinating or brominating halogenating agents at an amount of 1.2 equivalents or more per reaction site. After halogenation, the compound (V) can be converted using, for example, the coupling method described in "Metal-Catalyzed Cross-Coupling Reactions and More" edited by Armin de Meijere, Stefan Brase, and Martin Oestreich, published by Wiley-VCH.

[0105] [4. Composition] A composition according to one aspect of the present invention contains a hole-transport or electron-transport organic semiconductor compound represented by formula (V) according to the above-described aspect of the present invention (hereinafter referred to as "compound (V)"). The hole-transport or electron-transport organic semiconductor compound represented by formula (V) according to one aspect of the present invention in the composition according to one aspect of the present invention has already been described, so it will not be described again here.

[0106] The content of compound (V) in the composition according to one aspect of the present invention is not particularly limited. The content of compound (V) in the composition according to one aspect of the present invention is usually 0.5% by mass or more, may be 0.7% by mass or more, and is usually 1.5% by mass or less, may be 1.3% by mass or less.

[0107] A composition according to one aspect of the present invention may, if necessary, contain components other than those described above, to the extent that they do not impair the effects of the present invention. A composition according to one aspect of the present invention may contain, for example, organic solvents, specifically halogenated solvents such as chloroform and dichloroethane, aromatic hydrocarbon solvents such as toluene, xylene, chlorobenzene, and dichlorobenzene, and ether solvents such as THF and dibutyl ether. The content of other components; additives that promote orientation 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, relative to the composition according to one aspect of the present invention.

[0108] The form of the composition according to one aspect of the present invention is not particularly limited. For example, it may be in solid form or in liquid form containing an organic solvent.

[0109] A composition according to one aspect of the present invention can be produced, for example, by appropriately blending and mixing compound (V) with other components.

[0110] <Uses of the composition> A composition according to one aspect of the present invention contains compound (V), and therefore, by taking advantage of the properties of this compound, it can be used as a base structure for organic semiconductor electronic materials (such as OLEDs, OPVs, PSCs, OFETs, and PeQDs, which are hole transport materials, hole introduction materials, hole extraction materials, electron transport materials, electron introduction materials, and electron extraction materials). Accordingly, a composition according to one aspect of the present invention can be used as a composition for organic semiconductor electronic materials, etc.

[0111] Furthermore, if the composition according to one aspect of the present invention is in liquid form containing an organic solvent, it can be, for example, an ink composition for forming films for organic semiconductor devices. The ink for forming films for organic semiconductor devices will be described later.

[0112] [5. Organic semiconductor compounds] An organic semiconductor compound according to one aspect of the present invention has a skeleton represented by formula (V). Because the organic semiconductor compound according to one aspect of the present invention has a skeleton represented by formula (V), it has excellent solubility in organic solvents. The skeleton represented by formula (V) has already been explained in the previous section, so it will not be explained again here.

[0113] The organic semiconductor compound according to one aspect of the present invention may be a hole transport material (also called a p-type semiconductor) or an electron donating material (also called an n-type semiconductor).

[0114] The organic semiconductor compound having the skeleton represented by formula (V) exhibits excellent solubility in organic solvents, allowing for the formation of thin films by coating. Furthermore, the rigid conjugated skeleton constituting the compound enables a certain orientation between molecules, resulting in excellent semiconductor properties in the formed thin film.

[0115] [6. Inks for forming films in organic semiconductor devices]

[0116] An ink for forming films for organic semiconductor devices according to one aspect of the present invention contains the organic semiconductor compound according to one aspect of the present invention described above and an organic solvent. The organic semiconductor compound according to one aspect of the present invention has already been described in section [5. Organic Semiconductor Compound] above, so it will not be described again here.

[0117] When forming an active layer by coating, an ink for forming an organic semiconductor device according to one aspect of the present invention can be prepared by dissolving a p-type or n-type organic semiconductor compound, which is an organic semiconductor compound, in an organic solvent, along with other necessary substances as additives. The ink for forming an organic semiconductor device according to one aspect of the present invention (hereinafter referred to as "organic semiconductor ink") is applied to a substrate by a spin coating method or the like, and dried to form a thin film. This thin film can be called an organic semiconductor device film, and this organic semiconductor device film is also included in the scope of the present invention.

[0118] In this case, the spin-coating conditions should be determined appropriately according to standard methods, taking into account factors such as the viscosity of the organic semiconductor ink.

[0119] The drying conditions are not particularly limited as long as the organic solvent in the organic semiconductor ink can be removed. For example, the organic semiconductor ink can be dried by heating and annealing it at atmospheric pressure at 70-130°C for 5-20 minutes.

[0120] These organic semiconductor inks also represent another embodiment of the present invention.

[0121] The content of the organic semiconductor compound according to one aspect of the present invention in the organic semiconductor ink according to one aspect of the present invention is not particularly limited as long as an active layer can be formed by coating.

[0122] The content of the p-type organic semiconductor compound in the organic semiconductor ink according to one aspect of the present invention is usually 0.5% by mass or more, may be 0.7% by mass or more, and is usually 1.5% by mass or less, may be 1.3% by mass or less.

[0123] Furthermore, the content of the n-type organic semiconductor compound in the organic semiconductor ink according to one embodiment of the present invention is usually 0.7% by mass or more, may be 1.0% by mass or more, and is usually 2.0% by mass or less, may be 1.8% by mass or less.

[0124] The organic solvent used in the organic semiconductor ink according to one aspect of the present invention is not particularly limited, and organic solvents generally used in coating solutions for forming the active layer of organic semiconductor devices can be used. Specifically, examples include halogenated solvents such as chloroform and dichloroethane; aromatic hydrocarbon solvents such as toluene, xylene, chlorobenzene, and dichlorobenzene; and ether solvents such as THF, CPME, MTHP, 2-Me-THF, and dibutyl ether.

[0125] The organic semiconductor compound according to one aspect of the present invention exhibits high solubility in these organic solvents. Furthermore, by using these organic solvents, an improvement in photoelectric conversion efficiency can be expected.

[0126] Depending on the type of organic semiconductor compound according to one aspect of the present invention, the organic solvent is preferably xylene, chlorobenzene, or chloroform. Furthermore, when adjusting the solubility of the organic semiconductor compound according to one aspect of the present invention, the organic solvent may be a mixture of two or more organic solvents. The content ratio is not particularly limited and may be in the range of 1:9 to 9:1. The difference in boiling points of these organic solvents is preferably 50°C or less, more preferably 40°C or less, and even more preferably 30°C or less.

[0127] An organic semiconductor ink according to one aspect of the present invention preferably contains an additive that promotes orientation in addition to a p-type organic semiconductor compound or an n-type organic semiconductor compound. Examples of such additives include compounds that promote stacking of the aromatic moieties of the p-type organic semiconductor compound and the n-type organic semiconductor compound, and that shorten 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-diiodoctane.

[0128] Examples of polycyclic aromatic compounds include naphthalene, anthracene, and pyrene. Of these, the additive is preferably a bicyclic fused ring such as 1-chloronaphthalene.

[0129] The additive content in the organic semiconductor ink according to one aspect of the present invention 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.

[0130] Furthermore, an organic semiconductor ink according to one aspect of the present invention may contain other components as long as they do not impair the effects of the present invention. The content of the other components is usually 2.0% by mass or less relative to the organic solvent.

[0131] [7. Organic Semiconductor Devices] An organic semiconductor device according to one aspect of the present invention comprises an organic semiconductor device film containing the organic semiconductor compound according to one aspect of the present invention described above. The organic semiconductor compound according to one aspect of the present invention has already been described in section [5. Organic Semiconductor Compounds] above, so it will not be described again here.

[0132] Using an organic semiconductor ink according to one aspect of the present invention, an organic semiconductor device comprising an organic semiconductor device film containing an organic semiconductor compound according to one aspect of the present invention can be manufactured by a coating method. The method for forming an organic semiconductor device film using an organic semiconductor ink according to one aspect of the present invention has already been described in section [6. Ink for Forming Films for Organic Semiconductor Devices], so it will not be repeated here.

[0133] The present invention is not limited to the embodiments described above, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in each embodiment are also included within the technical scope of the present invention. [Examples]

[0134] The embodiments of the present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto unless it exceeds the essence of the invention. The numbers below the compounds in the reaction equations are the compound numbers.

[0135] The synthesized compounds were identified using TOP-MS spectroscopy (Shimadzu LCMS-IT-TOF).

[0136] [Manufacturing of compounds] (Experimental Example 1) 9,9'-(ethylene-1,2-diylbis(2,1-phenylene))bis(9H-fluoren-9-ol) [ka] To a solution of 1,2-bis(2-bromophenyl)ethine (4.61 g, 17.9 mmol) in ether (35 mL), a solution of BuLi (1.51 mol / L, 13.9 mL, 21.0 mmol) in hexane was added dropwise at 0°C. After stirring for 1 hour, a 1 M solution of 9-fluorenone (3.78 g, 21 mmol) in THF was added dropwise. The reaction mixture was gradually heated to room temperature and stirred for 3 hours. The reaction was work-treated with saturated aqueous ammonium chloride solution, and the aqueous layer was extracted three times with dichloromethane. The combined organic layers were washed with saturated brine and dried over sodium sulfate. The solvent was removed under reduced pressure to obtain the crude product. This was recrystallized from dichloromethane / MeOH to obtain product 1 as a white solid in 84% yield.

[0137] (Experimental Example 2) 1,2-bis(2-(9H-fluoren-9-yl)phenyl)ethylene [ka] A mixture of 9,9'-(ethylene-1,2-diylbis(2,1-phenylene))bis(9H-fluoren-9-ol) (Product 1) (2.69 g, 5.0 mmol) in acetonitrile (25 mL) and sodium iodide (4.5 g, 6.0 equiv) was mixed with dichlorodimethylsilane (1.79 ml, 3.0 equiv) and stirred at 50°C for 4 hours. The reaction mixture was quenched with aqueous sodium bisulfite solution, and the aqueous layer was extracted three times with dichloromethane. The combined organic layers were dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The resulting crude product was recrystallized with dichloromethane / methanol to obtain Product 2 as a colorless solid in 80% yield.

[0138] (Experimental Example 3) Dispiro[fluorene-9,5'-indeno[2,1-a]indene-10',9''-fluorene] (SFCPV) [ka] A hexane solution of n-BuLi (1.51 mol / L, 0.146 mL, 0.22 mmol) was added dropwise at 0°C to a THF (1.0 mL) solution of 1,2-bis(2-(9H-fluoren-9-yl)phenyl)ethine (product 2) (101 mg, 0.20 mmol). After stirring for 10 minutes, zinc(II) iodide TMEDA complex (96 mg, 0.22 mmol) was added and the mixture was stirred at room temperature for 10 minutes. After cooling to room temperature, CuI (3.8 mg, 10 mol%) and 1,2-diiodoethane (85 mg, 0.30 mmol) were added and the mixture was stirred at 80°C for 8 hours. The reaction mixture was quenched with an aqueous sodium bisulfite solution, and the aqueous layer was extracted three times with dichloromethane. The combined organic layers were dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The crude product obtained was passed through a short-pass silica gel (dichloromethane) column to obtain compound 1 as a white solid in 87% yield. HRMS (ESI+): m / z caled for C 40 H 25 [M+H] 505.1956; found: 505.1954.

[0139] (Experimental Example 4) 2',7'-Dibromodispiro[Fluorene-9,5'-Indeno[2,1-a]Indene-10',9''-Fluorene] (SFCPV-Br2) [ka] SFCPV (compound 1) (1.51 g, 3 mmol) and a solution of iron(III) chloride (48 mg, 10 mol%) in acetonitrile (30 ml) were stirred at room temperature, and a chloroform solution of bromine (0.5 M, 12.6 ml, 6.3 mmol) was added dropwise. After stirring for 3 hours, the reaction was quenched with water, and the aqueous layer was extracted three times with dichloromethane. The combined organic layers were dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The resulting crude product was recrystallized with dichloromethane / methanol to obtain compound 2 in 95% yield as a colorless solid. HRMS (ESI+): m / z caled for C 40 H 23 Br2[M+H] 661.0167; found: 661.0164.

[0140] (Experimental Example 5) 2',7'-Diiododispiro[fluorene-9,5'-Indeno[2,1-a]indene-10',9''-Fluorine(SFCPV-I2) [ka] To a solution of SFCPV-Br2 (compound 2) (662 mg, 1.0 mmol) in ether (10 mL), a solution of n-BuLi (1.51 mol / L, 1.46 mL, 2.2 mmol) in hexane was added dropwise at 0°C. After stirring for 1 hour, 1,2-diiodoethane (705 mg, 2.5 mmol) was added, and the mixture was stirred at room temperature for a further 2 hours. The reaction was work-treated with aqueous NaOH solution, and the aqueous layer was extracted three times with dichloromethane. The combined organic layers were dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The resulting crude product was purified by recrystallization with dichloromethane / methanol to obtain compound 3 as a colorless solid in 92% yield. HRMS (ESI+): m / z caled for C 40 H 23I2[M+H] 756.9889; found: 756.9890。

[0141] (Experimental Example 6) 2’,7’-Di(9H-carbazol-9-yl)dispiro[fluorene-9,5’-inden[2,1-a]inden-10’,9’’-fluorene] (SFCPV-Cz2)

Chemical formula

[0142] (Experimental Example 7) 2’,7’-Bis(4-(9H-carbazol-9-yl)phenyl)dispiro[fluorene-9,5’-inden[2,1-a]inden-10’,9’’-fluorene] (SFCPV-PhCz2)

Chemical formula

[0143] (Experimental Example 8) 2',7'-bis(trimethylstanyl)dispiro[fluorene-9,5'-indeno[2,1-a]indene-10',9''-fluorene(SFCPV-(SnMe3)2) [ka] To a solution of SFCPV-Br2 (compound 2) (662 mg, 1.0 mmol) in ether (10 mL), a solution of n-BuLi (1.51 mol / L, 1.46 mL, 2.2 mmol) in hexane was added dropwise at 0°C. After stirring for 1 hour, trimethyltin chloride (498 mg, 2.5 mmol) was added, and the mixture was stirred at room temperature for a further 2 hours. The reaction solution was quenched with water, and the aqueous layer was extracted three times with dichloromethane. The combined organic layers were dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The resulting crude product was recrystallized with dichloromethane / methanol to obtain compound 6 in 80% yield as a colorless solid. HRMS (ESI+): m / z caled for C 46 H 41 Sn2[M+H] 833.1252; found: 833.1254.

[0144] (Experimental Example 9) 5,5'-(dispiro[fluorene-9,5'-indeno[2,1-a]indene-10',9''-fluorene]-2',7'-diyl)bis(4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde) [ka] Under a nitrogen atmosphere, compound 6 (0.83 g, 1.0 mmol), 5-bromo-4-(2-ethylhexyl 5-bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (0.67 g, 2.1 mmol), tetrakistriphenylphosphine palladium (0) 3 mol%, and 10 mL of toluene were added and heated at 80°C for 5 hours. The reaction solution was cooled to room temperature and the solvent was removed from the reaction solution under reduced pressure. The residue was removed by distillation. The crude product obtained was purified by column chromatography (hexane:ethyl acetate = 90:10 (v / v)) to obtain 5,5'-(dispiro[fluorene-9,5'-indeno[2,1-a]indene-10',9''-fluorene]-2',7'-diyl)bis(4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde) (compound 7) in 84% yield in oil form. HRMS (ESI+): m / z caled for C 66 H 61 O4S2[M+H] 981.4011; found: 981.4014.

[0145] (Experimental Example 10) 2,2'-((2Z,2'Z)-((Dispiro[fluorene-9,5'-indeno[2,1-a]indene-10',9''-fluorene]-2',7'-diylbis(4-((2-ethylhexyl)oxy)thiophene-5,2-diyl))bis(metanylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalonitrile [ka] Under a nitrogen atmosphere, compound 7 (0.76 g, 0.77 mmol) obtained in Experimental Example 9 and 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-1-ylidene)malononitrile (0.39 g, 1.70 mmol) were completely dissolved in 10 mL of chloroform in a 50 mL four-necked flask. 0.8 mL of pyridine was added to the resulting solution, and the mixture was heated at 60°C for 5 hours. After the reaction mixture was cooled to room temperature, 20 mL of methanol was added to the reaction mixture. The precipitated compound was filtered off to obtain 2,2'-((2Z,2'Z)-((dispiro[fluorene-9,5'-indeno[2,1-a]indene-10',9''-fluorene]-2',7'-diylbis(4-((2-ethylhexyl)oxy)thiophene-5,2-diyl))bis(metanylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile (compound 8) in solid form in 82% yield. HRMS (ESI+): m / z caled for C 90 H 65 F4N4O4S2[M+H] 1405.4383; found: 1405.4386.

[0146] (Comparative Examples 1 and 2) The following compounds were synthesized as comparative compounds 1 and 2 using the method described in Journal of the American Chemical Society (2009), 131(38), 13596-13597. [ka]

[0147] [Evaluation of solubility] The solubility of compound 1, prepared in Example 1, and comparative compounds 1 and 2 in organic solvents was evaluated.

[0148] Each compound was added to 1 mL of chlorobenzene in the amounts shown in Table 1. The mixture was stirred on a 60°C hot plate at 1200 rpm for 5 minutes, and then allowed to stand for 24 hours at 25°C. The presence or absence of compound precipitation was then checked visually.

[0149]

Table 1

[0150] As shown in Table 1, it can be seen that Compound 1 of Example 1 is excellent in solubility in chlorobenzene compared to Comparative Compounds 1 and 2, and the solubility is more than twice as high.

Industrial Applicability

[0151] The compound according to one aspect of the present invention can be used as a skeleton of organic semiconductor electronic materials (such as hole transport materials, hole injection materials, hole extraction materials, electron transport materials, electron injection materials, electron extraction materials for OLED, OPV, PSC, OFET, PeQD, etc.).

Claims

1. A compound represented by the following formula (I). 【Chemistry 1】 (In the above formula (I), Ar １ and Ar ２ Each of these independently represents an aromatic hydrocarbon ring or an aromatic heterocycle that may have substituents, R １ , R ２ , R ３ and R ４ Each of these independently represents an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group. R １ and R ２ , and / or, R ３ and R ４ are bonded to each other directly or via a linker and each independently has any substituent.)

2. The compound represented by formula (I) is R １ and R ２ , and R ３ and R ４ For compounds that are not directly or via linkers bonded to each other, the solubility in chlorobenzene solvent is more than twice as high. The compound according to claim 1.

3. In the above formula (I), Ar １ and Ar ２ The compound according to claim 1 or 2, wherein the condensed ring formed from the 5-5 condensed ring shown between these is a 4-condensed ring.

4. A method for producing the compound represented by formula (I) as described in claim 1, (A) A step of cyclizing an acetylene derivative represented by the following formula (II) in the presence of a nucleophile, a diamine derivative represented by the following formula (III), and a divalent zinc compound to form a compound represented by the following formula (IV), (B) After step (A), a step is taken in which a divalent or monovalent copper compound is added to the compound represented by formula (IV) below in a one-pot reaction, and a coupling reaction is carried out continuously in situ to form the compound represented by formula (I), A method for producing the compound, including the compound. 【Chemistry 2】 (Ar in formulas (II) and (IV) above) １ Ar ２ , R １ , R ２ , R ３ and R ４ These are, respectively, Ar in formula (I) above. １ Ar ２ , R １ , R ２ , R ３ and R ４ It is synonymous with [the above]. R in formula (III) above ａ , R ｂ , R ｃ , and R ｄ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic hydrocarbon ring, or an optionally substituted aromatic heterocycle, and n represents an integer from 1 to 4.

5. The method for producing the compound according to claim 4, wherein the nucleophile is a lithium salt reagent or a potassium salt reagent.

6. A method for producing a compound according to claim 4 or 5, wherein in step (B), an iodine compound or a bromine compound is further present in the reaction system.

7. An organic semiconductor compound having the skeleton represented by formula (I) as described in claim 1, and represented by the following formula (V), which is for hole transport or electron transport. 【Transformation 3】 (Ar in formula (V) above) １ Ar ２ , R １ , R ２ , R ３ and R ４ These are, respectively, Ar in formula (I) above. １ Ar ２ , R １ , R ２ , R ３ and R ４ It is synonymous with, Z １ and Z ２ Each of these independently represents an arbitrary hole transport group or electron transport group.

8. A composition comprising the hole transport or electron transport organic semiconductor compound described in claim 7.

9. An organic semiconductor compound having a skeleton represented by formula (V) as described in claim 7.

10. An organic semiconductor device comprising an organic semiconductor device film containing the organic semiconductor compound described in claim 9.

11. An ink for forming films for organic semiconductor devices, comprising the organic semiconductor compound described in claim 9 and an organic solvent.

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