JP7555538B2 - METHOD FOR PRODUCING AROMATIC POLYCYCLIC FUNCTIONAL COMPOUND, NOVEL AROMATIC POLYCYCLIC FUNCTIONAL COMPOUND, ORGANIC SEMICONDUCTOR INK, AND ORGANIC SEMICONDUCTOR DEVICE - Google Patents

Description

The present invention relates to a method for producing an aromatic polycyclic fused ring compound, a novel aromatic polycyclic fused ring compound, an organic semiconductor ink, and an organic semiconductor device.

The roles required of image sensors are becoming more diverse, with increasing opportunities for their use in areas such as machine processing for motion recognition, spatial measurement, spatial mapping, and shape recognition. Recognition using sensors involves processing not only visible light, but also reflected infrared light that humans cannot sense, but photoelectric conversion efficiency in the near-infrared range has been insufficient (see, for example, non-patent documents 1 and 2).

To improve photoelectric conversion efficiency (external quantum efficiency) in the near-infrared region, studies have been conducted so far on the principle of CMOS photoelectric conversion, in which the photoelectric conversion layer absorbs light to generate excitons and separate charges, thereby creating a photoelectric conversion layer with high absorbance and improved internal quantum efficiency, or on increasing the thickness of the photoelectric conversion layer to improve absorbance.

Non-Patent Document 3 describes a non-fullerene compound with a narrowed band gap and a method for synthesizing the same. This non-fullerene compound has a skeleton with an electron-donating site in the center of the molecule and electron-withdrawing sites on both sides. In order to improve the photoelectric conversion efficiency (external quantum efficiency) in the near-infrared region, the photoelectric conversion layer absorbs light to generate excitons and separate charges based on the principle of CMOS photoelectric conversion, so it is necessary to make the photoelectric conversion layer have high absorbance with improved internal quantum efficiency, or to increase the thickness of the photoelectric conversion layer to improve absorbance, but it is difficult to synthesize a site that serves as a sufficient electron-donating group, and the types of preferred electron-donating sites are limited (see Non-Patent Document 3).

DOI:10.1021/acs. chemmater. 9b00966, Chem. Mater. (2019) ACS Appl. Mater. Interfaces 2018, 10, 11063-11069. Adv. Energy Mater. , 2018, 8, 1801212.

Molecular design of n-type semiconductors for use in semiconductor devices with higher photoelectric conversion efficiency has been underway, but the synthesis of the electron-donating moiety skeleton has been difficult. Furthermore, these electron-donating moieties use coupling reactions that use precious metals, which poses the problem of precious metals remaining in the compound. In order to improve the external quantum efficiency of organic semiconductor devices such as near-infrared sensors, it is necessary to extend the wavelength of the absorption region, and it has been essential to establish a method for synthesizing aromatic polycyclic fused ring compounds with high electron-donating properties. The objective of the present invention is to provide a new method for producing aromatic polycyclic fused ring compounds with high electron-donating properties.

As a result of intensive research to solve the above problems, the present inventors established a synthesis method for aromatic polycyclic fused rings, which are electron-donating moieties, with a wide range of applications without using precious metals, and produced novel compounds using the synthesis method. Furthermore, they found that an organic semiconductor device having a high external quantum efficiency (EQE) can be obtained by producing an n-type compound incorporating the electron-donating moiety and constructing an organic semiconductor device having an active layer containing a p-type conjugated polymer and the n-type compound, and arrived at the present invention. That is, the gist of the present invention is as follows.

（式（Ｉ）及び式（ＩＩ）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、及びＲ^８は、それぞれ独立に置換基を有していてもよいアルキル基及び置換基を有していてもよい芳香族環基から選択され、Ａｒ^１、及びＡｒ^２はそれぞれ独立に５員環または６員環を有する、置換基を有していてもよい芳香族炭化水素及び芳香族複素環から選択される。式（Ｉ）中、Ｚ^１、Ｚ^２、Ｚ^３、及びＺ^４は、それぞれ独立に置換基を有していてもよいシリル基またはメチル基から選択され、ｎは０以上の整数を示す。）
（２）前記反応工程において、マグネシウム環化体を形成する際に、ハロゲン化リチウムを共存させる、（１）に記載の製造方法。
（３）前記反応工程において、酸化反応が、空気、酸素、ハロゲン化合物、及び有機過酸化物からなる群より選ばれる少なくとも一つを酸化剤として用いる、（１）又は（２）に記載の製造方法。
（４）前記式（ＩＩ）中、Ａｒ^１およびＡｒ^２がチオフェン環である、（１）乃至（３）のいずれかに記載の製造方法。
（５）下記式（ＩＩ）’で表される芳香族多環縮合環化合物。

（式（ＩＩ）’中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、及びＲ^８は、それぞれ独立に置換基を有していてもよいアルキル基及び置換基を有していてもよい芳香族環基から選択され、Ａｒ^１及びＡｒ^２はチオフェン環であり、ｎは０以上の整数を示す。）
（６）（５）に記載の化合物を中間体として用いて反応させ、製造される、下記一般式（ＩＩＩ）で表されるｎ型半導体化合物の製造方法。

（式（ＩＩＩ）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、及びＲ^８は、上式（ＩＩ）’と同義であり、Ｒ^９、Ｒ^１０は、それぞれ独立に置換基を有していてもよいアルキル基及び置換基を有していてもよい芳香族環基から選択され、Ｘ^１、Ｘ^２は、それぞれ独立にハロゲン原子を示し、ｐ、ｑは、それぞれ独立に０から４までの整数を示す。ｒ、ｓは、それぞれ独立に０または１を示し、ｎは０以上の整数を示す。）
（７）ｐ型共役高分子、および、下記一般式（ＩＩＩ）で表されるｎ型化合物を含有する活性層、を備える有機半導体デバイス。

（式（ＩＩＩ）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、及びＲ^１０は、それぞれ独立に置換基を有していてもよいアルキル基及び置換基を有していてもよい芳香族環基から選択され、Ｘ^１、Ｘ^２は、それぞれ独立にハロゲン原子を示し、ｐ、ｑは、それぞれ独立に０から４までの整数を示す。ｒ、ｓは、それぞれ独立に０または１を示し、ｎは０以上の整数を示す。）
（８）前記活性層は、［６０］フラーレン、［７０］フラーレン、［６０］ＰＣＢＭ、［７０］ＰＣＢＭ、ｂｉｓ［６０］ＰＣＢＭ、ｂｉｓ［７０］ＰＣＢＭ、［６０］ＳＩＭＥＦ、［７０］ＳＩＭＥＦ、［６０］ＩＣＢＡ、［７０］ＩＣＢＡ、［６０］ＩＣＭＡ、および［７０］ＩＣＭＡからなる群より選択される少なくとも１種類のフラーレン化合物を含有する、（７）に記載の有機半導体デバイス。
（９）前記活性層は、多環芳香族化合物又は１，８－ジヨードオクタンを含有する、（７）又は（８）に記載の有機半導体デバイス。
（１０）前記有機半導体デバイスが光電変換素子である（７）～（９）のいずれかに記載の有機半導体デバイス。
（１１）波長９４０ｎｍの光を照射した際の外部量子効率（ＥＱＥ）が５０％以上である、（７）乃至（１０）のいずれかに記載の有機半導体デバイス。
（１２）ｐ型共役高分子と、式（ＩＩＩ）で表されるｎ型化合物と、［６０］フラーレン、［７０］フラーレン、［６０］ＰＣＢＭ、［７０］ＰＣＢＭ、ｂｉｓ［６０］ＰＣＢＭ、ｂｉｓ［７０］ＰＣＢＭ、［６０］ＳＩＭＥＦ、［７０］ＳＩＭＥＦ、［６０］ＩＣＢＡ、［７０］ＩＣＢＡ、［６０］ＩＣＭＡ、および［７０］ＩＣＭＡからなる群より選択される少なくとも１種類のフラーレン化合物と、溶剤と、を含み、前記ｎ型化合物に対する前記フラーレン化合物の重量比が２．０以下である、有機半導体インク。
（１３）多環芳香族化合物及び／又は１，８－ジヨードオクタンを含有する、（１２）に記載の有機半導体インク。
（１４）（７）～（１１）のいずれかに記載の有機半導体デバイスを用いたフォトディテクタ。
（１５）波長７００～１２００ｎｍの光を検知するために用いる、（１４）に記載のフォトディテクタ。 (1) A method for producing an aromatic polycyclic fused ring compound represented by the following formula (II), comprising a reaction step of causing an oxidation reaction between a compound represented by the following formula (I), a divalent iron compound, a trivalent phosphorus compound, and magnesium.

(In formula (I) and formula (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently selected from an alkyl group which may have a substituent and an aromatic ring group which may have a substituent, Ar ¹ and Ar ² are each independently selected from an aromatic hydrocarbon and an aromatic heterocycle having a 5- or 6-membered ring which may have a substituent. In formula (I), Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently selected from a silyl group or a methyl group which may have a substituent, and n represents an integer of 0 or more.)
(2) The method according to (1), wherein in the reaction step, lithium halide is allowed to coexist when the magnesium cyclized product is formed.
(3) The method according to (1) or (2), wherein in the reaction step, the oxidation reaction uses at least one selected from the group consisting of air, oxygen, a halogen compound, and an organic peroxide as an oxidizing agent.
(4) The method according to any one of (1) to (3), wherein, in the formula (II), Ar ¹ and Ar ² are thiophene rings.
(5) An aromatic polycyclic fused ring compound represented by the following formula (II)′:

(In formula (II)', ^R1 , ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , and ^R8 are each independently selected from an alkyl group which may have a substituent and an aromatic ring group which may have a substituent, ^Ar1 and ^Ar2 are thiophene rings, and n is an integer of 0 or more.)
(6) A method for producing an n-type semiconductor compound represented by the following general formula (III), which is produced by reacting the compound according to (5) as an intermediate:

(In formula (III), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are defined as in formula (II)′ above, R ⁹ and R ¹⁰ are each independently selected from an alkyl group which may have a substituent and an aromatic ring group which may have a substituent, X ¹ and X ² each independently represent a halogen atom, p and q each independently represent an integer from 0 to 4, r and s each independently represent 0 or 1, and n represents an integer of 0 or greater.)
(7) An organic semiconductor device comprising an active layer containing a p-type conjugated polymer and an n-type compound represented by the following general formula (III):

(In formula (III), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently selected from an alkyl group which may have a substituent and an aromatic ring group which may have a substituent; X ¹ and X ² each independently represent a halogen atom; p and q each independently represent an integer from 0 to 4; r and s each independently represent 0 or 1; and n represents an integer of 0 or greater.)
(8) The organic semiconductor device according to (7), wherein the active layer contains at least one fullerene compound selected from the group consisting of [60]fullerene, [70]fullerene, [60]PCBM, [70]PCBM, bis[60]PCBM, bis[70]PCBM, [60]SIMEF, [70]SIMEF, [60]ICBA, [70]ICBA, [60]ICMA, and [70]ICMA.
(9) The organic semiconductor device according to (7) or (8), wherein the active layer contains a polycyclic aromatic compound or 1,8-diiodooctane.
(10) The organic semiconductor device according to any one of (7) to (9), which is a photoelectric conversion element.
(11) The organic semiconductor device according to any one of (7) to (10), which has an external quantum efficiency (EQE) of 50% or more when irradiated with light having a wavelength of 940 nm.
(12) An organic semiconductor ink comprising: a p-type conjugated polymer; an n-type compound represented by formula (III); at least one fullerene compound selected from the group consisting of [60]fullerene, [70]fullerene, [60]PCBM, [70]PCBM, bis[60]PCBM, bis[70]PCBM, [60]SIMEF, [70]SIMEF, [60]ICBA, [70]ICBA, [60]ICMA, and [70]ICMA; and a solvent, wherein the weight ratio of the fullerene compound to the n-type compound is 2.0 or less.
(13) The organic semiconductor ink according to (12), which contains a polycyclic aromatic compound and/or 1,8-diiodooctane.
(14) A photodetector using the organic semiconductor device according to any one of (7) to (11).
(15) The photodetector according to (14), which is used to detect light having a wavelength of 700 to 1200 nm.

According to the present invention, a new method for producing an aromatic polycyclic fused ring compound having high electron donating properties is provided. The aromatic polycyclic fused ring compound produced by the method includes a novel aromatic polycyclic fused ring compound. Furthermore, the compound obtained by the method can be used as an n-type low molecular weight compound for an organic semiconductor device having an aromatic polycyclic fused ring containing a highly electron donating moiety. Furthermore, by using the compound, an organic semiconductor device having a high external quantum efficiency (EQE) can be provided.

The following describes the form for implementing the present invention, but the embodiment of the present invention is not limited to the form below.

One aspect of the present invention is a method for producing an aromatic polycyclic fused ring compound represented by formula (II) below, comprising a reaction step of causing a compound represented by formula (I) below, a divalent iron compound, a trivalent phosphorus compound, and magnesium to coexist, forming a magnesium cyclized product in a system, and carrying out an oxidation reaction.

In formula (I) and formula (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently selected from an alkyl group which may have a substituent, and an aromatic ring group which may have a substituent.
Examples of the alkyl group include linear, branched or cyclic alkyl groups such as methyl, ethyl, n-propyl, n-butyl, 2-methylpropyl, 2-methylbutyl, 3-methylbutyl, cyclohexylmethyl, neopentyl, 2-ethylbutyl, isopropyl, 2-butyl, cyclohexyl, 3-pentyl, tert-butyl, 1,1-dimethylpropyl, 2-ethylhexyl, 2-butyloctyl, etc. Among these, preferred are alkyl groups having 20 or less carbon atoms.

The aromatic group may be an aryl group such as a phenyl group, a naphthyl group, an anthranyl group, a fluorenyl group, a phenanthrenyl group, or an azulenyl group, or a heteroaryl group such as a thienyl group, an imidazolyl group, a pyrazolyl group, or a thiazolyl group. Of these, a monocyclic or two-condensed ring aryl group or a monocyclic heteroaryl group having 12 or less carbon atoms is preferred. A monocyclic aryl group having 6 or less carbon atoms or a thienyl group is even more preferred.

Examples of the substituent of the optionally substituted group 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 sulfonamide 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.

Specifically, alkyl groups having about 1 to 15 carbon atoms, such as methyl and ethyl groups;
Alkenyl groups having about 2 to 10 carbon atoms, such as an ethynyl group or a propylenyl group;
Alkynyl groups having about 2 to 10 carbon atoms, such as an acetylenyl group;
Aryl groups having about 6 to 20 carbon atoms, such as a phenyl group or a naphthyl group;
Heteroaryl groups having about 3 to 20 carbon atoms, such as a thienyl group, a furyl group, or a pyridyl group;
Alkoxy groups having about 1 to 15 carbon atoms, such as a methoxy group, an ethoxy group, or a propoxy group;
Aryloxy groups having about 6 to 20 carbon atoms, such as a phenoxy group or a naphthoxy group;
Heteroaryloxy groups having about 3 to 20 carbon atoms, such as a pyridyloxy group, a thienyloxy group, etc.;
Alkylthio groups having about 1 to 15 carbon atoms, such as a methylthio group or an ethylthio group;
Arylthio groups having about 6 to 20 carbon atoms, such as a phenylthio group and a naphthylthio group;
Heteroarylthio groups having about 3 to 20 carbon atoms, such as a pyridylthio group, a thienylthio group, etc.;
an amino group which may have a substituent having about 1 to 20 carbon atoms, such as a dimethylamino group or a diphenylamino group;
Acyl groups having about 2 to 20 carbon atoms, such as an acetyl group or a pivaloyl group;
Acylamino groups having about 2 to 20 carbon atoms, such as an acetylamino group or a propionylamino group; ureido groups having about 2 to 20 carbon atoms, such as a 3-methylureido group;
Sulfonamide groups having about 1 to 20 carbon atoms, such as a methanesulfonamide group or a benzenesulfonamide group;
Carbamoyl groups having about 1 to 20 carbon atoms, such as a dimethylcarbamoyl group and an ethylcarbamoyl group;
Sulfamoyl groups having about 1 to 20 carbon atoms, such as an ethylsulfamoyl group;
Sulfamoylamino groups having about 1 to 20 carbon atoms, such as a dimethylsulfamoylamino group; alkoxycarbonyl groups having about 2 to 6 carbon atoms, such as a methoxycarbonyl group and an ethoxycarbonyl group;
Aromatic hydrocarbon oxycarbonyl groups having about 7 to 20 carbon atoms, such as a phenoxycarbonyl group and a naphthoxycarbonyl group;
Aromatic heterocyclic hydrocarbon oxycarbonyl groups having about 6 to 20 carbon atoms, such as a pyridyloxycarbonyl group;
Alkylsulfonyl groups having about 1 to 6 carbon atoms, such as a methanesulfonyl group, an ethanesulfonyl group, or a trifluoromethanesulfonyl group;
Arylsulfonyl groups having about 6 to 20 carbon atoms, such as a benzenesulfonyl group or a monofluorobenzenesulfonyl group;
Heteroaryloxysulfonyl groups having about 3 to 20 carbon atoms, such as thienylsulfonyl groups; imido groups having about 4 to 20 carbon atoms, such as phthalimide groups;
Alternatively, a silyl group which is substituted with three substituents selected from the group consisting of an alkyl group and an aryl group can be mentioned.

Particularly preferred as R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are an alkyl group having a total of 15 or less carbon atoms which may have a substituent, a monocyclic aryl group having a total of 20 or less carbon atoms which may have a substituent, or a monocyclic heteroaryl group having a total of 15 or less carbon atoms which may have a substituent.

Ar ¹ and Ar ² are each independently selected from an aromatic hydrocarbon and an aromatic heterocycle having a 5- or 6-membered ring, which may have a substituent. Ar ¹ and Ar ² are preferably each independently an aryl group which may be substituted, or a heteroaryl group which may be substituted.

Specific examples include the aryl and heteroaryl groups listed above as specific examples of R ¹ to R ^8. Examples of the substituents of the groups that may have a substituent include the same as those listed above for R ¹ to R ⁸ .
More preferably, Ar ¹ and Ar ² are monocyclic aryl groups having a total of 15 or less carbon atoms which may have a substituent, or monocyclic heteroaryl groups having a total of 15 or less carbon atoms which may have a substituent. Particularly preferred is a thiophene ring which may have a substituent. Among the above-mentioned substituents, more preferred are alkyl groups having about 1 to 15 carbon atoms, alkoxy groups having about 1 to 15 carbon atoms, and halogen atoms.

In formula (1), Z ¹ , Z ² , Z ³ and Z ⁴ are each independently selected from a silyl group or a methyl group which may have a substituent.
Examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a t-butyldiphenylsilyl group, a n-butyldimethylsilyl group, a dimethylethylsilyl group, a dimethylphenylsilyl group, a dimethylisopropylsilyl group, a triisopropylsilyl group, and a tert-butyldimethyl group. Particularly preferred are a methoxy group or a trimethylsilyl group, which have little steric hindrance.

n represents an integer of 0 or more, preferably an integer from 0 to 5.

(Divalent iron compounds)
The "divalent iron compound" that is allowed to coexist with the compound of formula (I) in the reaction step of this embodiment means that the iron in the compound is divalent.
Examples of the divalent iron compound include compounds such as FeCl ₂ , FeBr ₂ , FeI ₂ , Fe(OAc) ₂ , and Fe(acac) ₂ . The amount of the divalent iron compound to be coexisted in the reaction step is not particularly limited, but the amount of the divalent iron compound relative to the compound of general formula (I) is within the range of 1 mol % to 30 mol %, and more preferably within the range of 1 mol % to 20 mol %.

(Trivalent phosphorus compounds)
The "trivalent phosphorus compound" that is allowed to coexist with the compound of formula (I) in the reaction step of this embodiment means that phosphorus in the compound is trivalent.
The trivalent phosphorus compound is selected from the trivalent phosphorus ligands described in, for example, Sigma-Aldrich's "Buchwald Portfolio 2019 Palladacycles and Ligands" and "Pd Catalysts and Ligands Application Guide for Cross-Coupling Reactions". Among these, triphenylphosphine and tri(orthotolyl)phosphine are preferred because they can be used simply and inexpensively, and tri-tert-butylphosphine is preferred because it can increase reactivity. Buchwald phosphorus ligands are preferred because the yield of the compound of general formula (II) in the reaction of this embodiment can be improved by selecting the optimal ligand depending on the substrate. It is preferable to use a trivalent phosphorus compound in a molar ratio of 1:1 to 1:3 relative to the divalent iron compound, and particularly preferably in a ratio of 1:1.5 to 1:2.5.

(magnesium)
The magnesium to be coexisted with the compound of formula (I) in the reaction step of this embodiment is not particularly limited, and may be magnesium metal or a magnesium-containing compound. Examples of the magnesium-containing compound include Rieke magnesium and turbo magnesium manufactured by Aldrich. The amount of magnesium to be coexisted is preferably 3 to 10 moles per mole of the compound of general formula (I), and is particularly preferably 3 to 5 moles in order not to reduce the stirring efficiency in the system.

(lithium halide)
In the reaction step of this embodiment, it is preferable to further coexist with lithium halide. By further coexisting with lithium halide, it is preferable to activate the magnesium reagent. Examples of lithium halide include lithium chloride, lithium bromide, and lithium iodide, and it is preferable to coexist these lithium halides in an equimolar amount with magnesium. Specifically, the molar ratio of magnesium:lithium halide is preferably 1:0.5 to 1:1.5, and more preferably 1:0.8 to 1:1.2.

(solvent)
The reaction of this embodiment is usually carried out in a solvent. Examples of the solvent that can be used at that time include aromatic solvents such as toluene and chlorobenzene;
Ether solvents such as ether, 1,4-dioxane, and THF;
Aliphatic solvents such as hexane and heptane;
The solvent can be selected from halogen-based solvents such as methylene chloride, chloroform, and 1,2-dichloroethane. Of these, toluene and tetrahydrofuran are preferably used. These solvents may be used alone or in combination of two or more. For example, when a solvent having low solubility for the substrate is used, the reaction results are improved by combining it with a halogen-based solvent or an ether-based solvent, and when a solvent having a low dissolved oxygen concentration is used, the reaction results are improved by combining it with a non-polar solvent, more preferably a hydrocarbon-based solvent.

(Oxidizing Agent)
In the reaction step of this embodiment, it is preferable to carry out the oxidation reaction using an oxidizing agent. Examples of the oxidizing agent include air, oxygen, and halogen compounds; for example, iodine, bromine, tetrabutylammonium tribromide, bromine-1,4-dioxane complex, 1,2-dibromo-1,1,2,2-tetrachloroethane, 1,2-dichloroethane pyridinium bromide perbromide, 1,8-diazabicyclo[5.4.0]-7-undecene hydrogen tribromide, NBS, 5,5-dibromo Meldrum's acid, trimethylsilyl bromide, 1-chloro-2-iodoethane, NIS, and tetramethylammonium dichloroiodide. peroxide, pyridine iodine monochloride, TMSI, organic peroxides; for example, diacyl peroxide, alkyl peroxy ester, peroxydicarbonate, peroxycarbonate, peroxyketal, dialkyl peroxide, alkyl hydroperoxide, mCPBA, t-butyl hydroperoxide, bis(trimethylsilyl) peroxide, di-t-butyl peroxide, 2-hydroperoxy-4,5-diphenyl-1,3,5-triazine, and methyl ethyl ketone peroxide.
In order to suppress side reactions, an oxidizing agent having a weak nucleophilicity is preferred.

(Reaction temperature)
The reaction temperature in the reaction step of this embodiment 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, and can be arbitrarily set within the range up to the reflux temperature of the solvent used depending on the reaction proceeding speed. When the oxidation is slow (i.e., when the yield is poor), it is preferable to irradiate the reaction solution with ultrasound or microwaves or to autoclave the reaction solution.

The reaction time is usually 30 minutes 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. The progress of the reaction can be confirmed using high performance liquid chromatography (HPLC). After the reaction is completed, the target compound of general formula (II) can be obtained using a known isolation and purification method. In addition, it is preferable to further extract with a dilute hydrochloric acid aqueous solution to remove the iron compound.

By the above method, an aromatic polycyclic fused ring compound represented by the general formula (II) can be produced. Specific examples of such a compound represented by the above general formula (II) are shown below.

式（ＩＩ）’中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、及びＲ^８は、それぞれ独立に置換基を有していてもよいアルキル基及び置換基を有していてもよい芳香族環基から選択され、Ａｒ^１、及びＡｒ^２はチオフェン環であり、ｎは０以上の整数を示す。 Another aspect of the present invention is a novel aromatic polycyclic fused ring compound represented by the following formula (II)'.

In formula (II)', ^R1 , ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , and ^R8 are each independently selected from an alkyl group which may have a substituent and an aromatic ring group which may have a substituent, ^Ar1 and ^Ar2 are thiophene rings, and n is an integer of 0 or more.

Another aspect of the present invention is a method for producing an n-type semiconductor compound, comprising the steps of preparing an aromatic polycyclic fused intercyclic compound represented by the above formula (II)', and producing a compound represented by the following general formula (III) using the above compound as an intermediate.

In formula (III), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are the same as those in formula (II), R ⁹ and R ¹⁰ are each independently selected from an alkyl group which may have a substituent and an aromatic ring group which may have a substituent, X ¹ and X ² each independently represent a halogen atom, and p and q each independently represent an integer from 0 to 4. r and s each independently represent 0 or 1, and n represents an integer of 0 or more.

The alkyl group represented by ^R9 and ^R10 is preferably a linear or branched alkyl group having 6 to 20 carbon atoms, more preferably 7 or more carbon atoms, even more preferably 8 or more carbon atoms, and still more preferably 15 or less carbon atoms, even more preferably 12 or less carbon atoms.

Examples of the linear or branched hydrocarbon group having from 6 to 20 carbon atoms include linear alkyl groups such as n-octyl, n-decyl, lauryl, myristyl, and palmityl groups; branched primary alkyl groups such as 2-ethylhexyl and 2-butyloctyl groups; and branched secondary alkyl groups such as 2-octyl, 2-nonyl, and 2-decyl groups.
Of these, R ⁹ and R ¹⁰ are preferably primary branched chain hydrocarbon groups.

^X1 and ^X2 are preferably fluorine atoms from the viewpoint of improving solubility, and are preferably chlorine atoms from the viewpoint of molecular arrangement when an active layer is formed.

It is preferable that r and s are 1 or one is 0. It is preferable that p and q are 1 or 2. It is preferable that n is 0 or 1 from the viewpoint of solubility.

The n-type compound represented by general formula (III) can be synthesized, for example, by the method described in Non-Patent Document 3 (Adv. Energy Mater., Vol. 8, 1801212 (2018)).

(n-type organic semiconductor compound)
The compound of the above formula (III) can be contained in the active layer of an organic semiconductor device as an n-type organic semiconductor compound. The n-type compound represented by general formula (III) has an absorption maximum in a solution in the range of 850 nm or more and 1200 nm or less, and has a band gap suitable for use as a photoelectric conversion element for an infrared photodetector.
The active layer of the organic semiconductor device may contain, in addition to the n-type organic semiconductor compound, an n-type fullerene compound and a p-type conjugated polymer. Such an active layer of the organic semiconductor device is another embodiment of the present invention.

(n-type fullerenes)
The active layer of the organic semiconductor device according to this embodiment may contain n-type fullerenes as an n-type organic semiconductor. The n-type fullerenes may be used alone or in combination of two or more. In this embodiment, by adding n-type fullerenes to the active layer containing a p-type conjugated polymer and an n-type compound, it is possible to improve the electron mobility and absorb the n-type compound in the near infrared region.

The n-type fullerenes are not particularly limited, and fullerenes known as n-type semiconductors can be used. Known fullerenes include unmodified fullerenes such as fullerene-C60, fullerene-C70, fullerene-C76, fullerene-C78, fullerene-C84, fullerene-C240, fullerene-C540, mixed fullerene, and fullerene nanotubes; and fullerene derivatives in which a portion of these is substituted with a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, a cycloalkyl group, a silyl group, an ether group, an amino group, a silyl group, or the like.

Specific fullerene derivatives include [60]PCBM, [70]PCBM, bis[60]PCBM, bis[70]PCBM, [60]SIMEF, [70]SIMEF, [60]ICBA, [70]ICBA, [60]ICMA, [70]ICMA, MP-C60, [60]PCBiB, [60]PCBH, and the like.
Of these, the unmodified fullerene is preferably [60]fullerene or [70]fullerene.

The fullerene derivative is preferably [60]PCBM, [70]PCBM, bis[60]PCBM, bis[70]PCBM, [60]SIMEF, [70]SIMEF, [60]ICBA, [70]ICBA, [60]ICMA, or [70]ICMA, and more preferably [60]PCBM, [70]PCBM, or [70]SIMEF.

The weight ratio of n-type fullerenes to the n-type compound in the active layer is not particularly limited,
The weight ratio is usually 0.2 or more, preferably 0.3 or more, more preferably 0.5 or more, and usually 2.0 or less, preferably 1.5 or less, more preferably 1.0 or less. By setting the weight ratio within the above range, the solubility of the active layer in the mixed solution can be ensured.

(p-type conjugated polymer)
The active layer of the organic semiconductor device according to this embodiment contains a p-type conjugated polymer as a p-type organic semiconductor. For example, the p-type conjugated polymer may be a hole transporting polymer, and is preferably a hole transporting polymer having a structural unit that has a tendency to donate electrons. In addition, it is preferable that the p-type conjugated polymer is one that can be mixed with an n-type organic semiconductor and coated to form a film.

In the hole transporting polymer, specific examples of a partial structure having excellent hole transporting properties include a benzodithiophene structure, a thiophene structure, a carbazole structure, a dibenzofuran structure, a triarylamine structure, a naphthalene structure, a phenanthrene structure, and a pyrene structure.
A specific example of the p-type conjugated polymer is a p-type conjugated polymer represented by general formula (IV): In formula (IV), n is a positive number.

In the active layer, the weight ratio of the n-type compound to the p-type conjugated polymer is usually 0.5 or more, preferably 0.6 or more, more preferably 0.65 or more, and usually 1.5 or less, preferably 1.3 or less, more preferably 1.0 or less.
In the active layer, the weight ratio of n-type fullerenes to p-type conjugated polymer is usually 0.4 or more, preferably 0.5 or more, more preferably 0.6 or more, and usually 2.0 or less, preferably 1.5 or less, more preferably 1.0 or less.
The method for forming the active layer is not particularly limited, and the active layer can be formed by a known method, but is typically a coating method.

When forming an active layer by a coating method, an organic semiconductor ink is prepared by dissolving the organic semiconductors, p-type conjugated polymers, n-type compounds, and n-type fullerenes, as well as other necessary substances as additives, in an organic solvent, and the organic semiconductor ink is applied to a substrate by a spin coating method or the like, and then dried to form the active layer. The spin coating conditions may be appropriately determined according to a standard method, taking into consideration the viscosity of the organic semiconductor ink, etc. 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 the organic semiconductor ink at 70°C to 130°C for 5 to 20 minutes under atmospheric pressure. These organic semiconductor inks are also another aspect of the present invention.

The contents of the p-type conjugated polymer, the n-type compound, and the n-type fullerenes in the organic semiconductor ink are not particularly limited as long as an active layer can be formed by coating.
The content of the p-type conjugated polymer in the organic semiconductor ink is usually 0.5% by mass or more, and may be 0.7% by mass or more, and is usually 1.5% by mass or less, and may be 1.3% by mass or less.
The content of n-type fullerenes in the organic semiconductor ink is usually 0.3% by mass or more, and may be 0.4% by mass or more, and is usually 1.5% by mass or less, and may be 1.0% by mass or less.

Furthermore, the content of the n-type compound in the organic semiconductor ink 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.
In this embodiment, the weight ratio of n-type fullerenes to n-type compounds in the organic semiconductor ink is usually 0.3 or more, preferably 0.5 or more, more preferably 0.6 or more, and usually 2.0 or less, preferably 1.5 or less, more preferably 1.0 or less. By setting the weight ratio within the above range, there is an effect of improving the EQE due to the high electron mobility of the n-type fullerene.

The organic solvent used in the organic semiconductor ink is not particularly limited, and organic solvents generally used in coating liquids for forming active layers of organic semiconductor devices can be used. Specific examples include organic solvents such as 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. This is because organic semiconductors generally have high solubility in these organic solvents. Furthermore, the use of these organic solvents is expected to improve photoelectric conversion efficiency.

Of the above organic solvents, the organic solvent depends on the type of organic semiconductor, but is preferably xylene, chlorobenzene, or chloroform. In addition, when adjusting the solubility, 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.

In addition to the p-type conjugated polymer, the n-type compound, and the n-type fullerene, the organic semiconductor ink preferably contains an additive for the purpose of stabilizing the bulk heterostructure.
The additives include compounds that can promote stacking of the aromatic moiety of a p-type organic semiconductor and the aromatic moiety of an n-type organic semiconductor, and can also promote the formation of a bulk heterostructure between a p-type organic semiconductor and an n-type organic semiconductor, such as polycyclic aromatic compounds and 1,8-diiodooctane.

Examples of polycyclic aromatic compounds include naphthalene, anthracene, pyrene, etc. Among these, the additive is preferably a bicyclic condensed ring such as 1-chloronaphthalene.
The content of additives in the organic semiconductor ink 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.

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

(Example Compound)
Specific examples of the compound of formula (III) are given below.

(device)
When the organic semiconductor device is a photoelectric conversion element, the structure of the photoelectric conversion element can be, for example, reference to the description in JP 2007-324587 A and is not particularly limited. For example, the photoelectric conversion element may have a structure in which a transparent electrode, an electron transport layer, an active layer (photoelectric conversion layer), a hole transport layer, and a metal electrode are laminated in this order on a transparent substrate, or may have a structure in which a transparent electrode, a hole transport layer, an active layer (photoelectric conversion layer), an electron transport layer, and a metal electrode are laminated in this order on a transparent substrate.

The transparent electrode is an electrode made of a material having an average transmittance of 80% or more in visible light of 450 nm or more. There is no particular limitation on the material for forming the transparent electrode as long as it can form a transparent electrode, and examples of the material include tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), tungsten-doped indium oxide (IWO), zinc aluminum oxide (AZO), indium oxide (In ₂ O ₃ ), zinc oxide (ZnO), titanium oxide (TiO ₂ ), etc.

The metal electrode is an electrode that forms a pair with the transparent electrode. The material constituting the metal electrode is not particularly limited, and examples thereof include metals such as gold, platinum, silver, aluminum, nickel, titanium, magnesium, calcium, barium, sodium, chromium, copper, and cobalt, or alloys thereof.
It is preferable that the metal electrode is a transparent electrode, that is, the pair of electrodes are transparent electrodes. In this case, the metal electrode is formed from the material forming the transparent electrode, and the pair of electrodes may be formed from the same material or different materials.
The thickness of the metal electrode is not particularly limited, and if transparency is desired, it is usually about 10 nm, whereas if transparency is not required, the thickness may be 40 nm or more, more preferably 100 nm or more, taking durability and the like into consideration.

There are no particular limitations on the constituent members and manufacturing methods of the electron transport layer and hole transport layer, and well-known techniques can be used. For example, members and manufacturing methods described in publicly known documents such as WO 2013/171517, WO 2013/180230, or JP 2012-191194 can be used.

When the organic semiconductor device is a photoelectric conversion element, the photoelectric conversion element is provided in an optical sensor or an image sensor as a photodetector and used. In this case, the optical sensor and the image sensor may have a known configuration.
In the organic semiconductor device according to this embodiment, by forming an active layer in combination with a p-type organic semiconductor appropriate for an n-type organic semiconductor, it is possible to make the external quantum efficiency (EQE) in the range of 700 to 1200 nm 50% or more at least for a part of the wavelengths, more preferably 50% or more for an EQE of 940 nm, and even more preferably 50% or more for all wavelengths in the range of 700 to 1200 nm.

By using an organic semiconductor device (photoelectric conversion element) with such an active layer, a photodetector can be obtained that can be used to detect light with wavelengths of 700 to 1200 nm.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples as long as the gist of the present invention is not exceeded. Note that the numbers given below the compounds in the reaction formulas are the compound numbers.
The compounds were identified by APCI (atmospheric pressure chemical ionization) using a mass spectrometer (LCMS-IT-TOF, manufactured by Shimadzu Corporation).

化合物１（１．０５ｇ，４．０ｍｍｏｌ）、化合物２（２２８．１ｍｇ，２．０ｍｍｏｌ）、Ｐｄ（ＰＰｈ_３）_２Ｃｌ_２（７０．２ｍｇ，０．１ｍｍｏｌ）、ｄｐｐｂ（８５．３ｍｇ，０．２ｍｍｏｌ）をシュレンク管に入れ、窒素置換した。これに、ＤＢＵ（６０９ｍｇ，４．０ｍｍｏｌ）とＤＭＳＯ（１０ｍＬ）を加え、８０℃で４時間加熱した。室温まで冷却後、飽和塩化アンモニウム水（１５ｍＬ）を加え、エーテル（５０ｍＬ×２回）で抽出した。有機層を飽和食塩水（５０ｍＬ）で洗い、有機層を硫酸ナトリウムで乾燥後、濾過した。有機層を減圧濃縮し、得られた粗生成物をシリカゲルカラムクロマトグラフィー（展開溶媒；１０％酢酸エチル／ヘキサン）で精製し、化合物３を６９％の収率で得た。
ＭＳ （ＡＰＣＩ＋）２９４．１ <Experimental Example 1>

Compound 1 (1.05 g, 4.0 mmol), compound 2 (228.1 mg, 2.0 mmol), Pd(PPh ₃ ) ₂ Cl ₂ (70.2 mg, 0.1 mmol), and dppb (85.3 mg, 0.2 mmol) were placed in a Schlenk flask and substituted with nitrogen. DBU (609 mg, 4.0 mmol) and DMSO (10 mL) were added to the flask and heated at 80° C. for 4 hours. After cooling to room temperature, saturated ammonium chloride water (15 mL) was added and extracted with ether (50 mL x 2 times). The organic layer was washed with saturated saline (50 mL), dried over sodium sulfate, and then filtered. The organic layer was concentrated under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (developing solvent: 10% ethyl acetate/hexane), and compound 3 was obtained in a yield of 69%.
MS (APCI+)294.1

フェニルマグネシウムブロマイドのＴＨＦ溶液（１１．０ｍＬ，９．０ｍｍｏｌ）をシュレンク管に入れ、０℃まで冷やした。これに、ＴＨＦ（２ｍＬ）に溶かした化合物３（５８８．６ｍｇ，２．０ｍｍｏｌ）を５分かけて滴下した後、室温まで昇温し、１２時間撹拌した。反応溶液を氷水に注ぎ、酢酸エチル（１５ｍＬｘ２）で抽出した。有機層を硫酸ナトリウムで乾燥後濾過した。有機層を減圧濃縮し、得られた粗生成物を酢酸エチル／ヘキサンに溶かして再結晶させ、化合物４を８３％の収率で得た。
ＭＳ （ＡＰＣＩ＋）５４５．２ <Experimental Example 2>

A THF solution of phenylmagnesium bromide (11.0 mL, 9.0 mmol) was placed in a Schlenk flask and cooled to 0°C. Compound 3 (588.6 mg, 2.0 mmol) dissolved in THF (2 mL) was added dropwise over 5 minutes, and then the mixture was warmed to room temperature and stirred for 12 hours. The reaction solution was poured into ice water and extracted with ethyl acetate (15 mL x 2). The organic layer was dried over sodium sulfate and filtered. The organic layer was concentrated under reduced pressure, and the resulting crude product was dissolved in ethyl acetate/hexane and recrystallized to obtain compound 4 in an 83% yield.
MS (APCI+)545.2

化合物４（５４５．６ｍｇ，１．０ｍｍｏｌ）のメタノール（１０ｍＬ）のサスペンシ
ョン溶液にＣＡＮ（２１９．３ｍｇ，０．４ｍｍｏｌ）を加えた後、５０℃まで昇温し、１２時間撹拌した。室温まで冷却後、反応溶液を濾過し、沈殿をメタノールで懸洗し、化合物５を９０％収率で得た。
ＭＳ （ＡＰＣＩ＋）５７０．３ <Experimental Example 3>

CAN (219.3 mg, 0.4 mmol) was added to a suspension solution of compound 4 (545.6 mg, 1.0 mmol) in methanol (10 mL), and the mixture was heated to 50° C. and stirred for 12 hours. After cooling to room temperature, the reaction solution was filtered, and the precipitate was washed by suspending in methanol to obtain compound 5 in a 90% yield.
MS (APCI+)570.3

シュレンク管にＬｉＣｌ（２５．４ｍｇ，０．６０ｍｍｏｌ）を加え、加熱乾燥した後、これにＦｅＣｌ_２（５．２ｍｇ，０．０４ｍｍｏｌ）、ＰＰｈ_３（２１．０ｍｇ，０．０８ｍｍｏｌ）、Ｍｇ粉末（１４．６ｍｇ，０．６０ｍｍｏｌ）、化合物５（１１４．１ｍｇ，０．２０ｍｍｏｌ）を窒素気流下で加えた。この混合物にＴＨＦ（０．４ｍＬ）を加え、室温で７時間撹拌した後、１，２－ジクロロプロパン（３９μＬ，０．４０ｍｍｏｌ）をゆっくり加え、さらに室温で１２時間撹拌した。反応溶液をクロロホルム（３０ｍＬ）で希釈し、有機層を１Ｍ塩酸（１５ｍＬ）で洗い、有機層を硫酸ナトリウムで乾燥後濾過した。有機層を減圧濃縮し、得られた粗生成物をクロロホルムーメタノールに溶かして再結晶させ、実施例１の化合物を９２％の収率で得た。
ＭＳ （ＡＰＣＩ＋）５０８．７ Example 1

LiCl (25.4 mg, 0.60 mmol) was added to a Schlenk flask, and the mixture was dried by heating. FeCl ₂ (5.2 mg, 0.04 mmol), PPh ₃ (21.0 mg, 0.08 mmol), Mg powder (14.6 mg, 0.60 mmol), and compound 5 (114.1 mg, 0.20 mmol) were then added to the mixture under a nitrogen stream. THF (0.4 mL) was added to the mixture, and the mixture was stirred at room temperature for 7 hours. Then, 1,2-dichloropropane (39 μL, 0.40 mmol) was slowly added, and the mixture was further stirred at room temperature for 12 hours. The reaction solution was diluted with chloroform (30 mL), and the organic layer was washed with 1 M hydrochloric acid (15 mL). The organic layer was dried over sodium sulfate and then filtered. The organic layer was concentrated under reduced pressure, and the resulting crude product was dissolved in chloroform-methanol and recrystallized to obtain the compound of Example 1 in a yield of 92%.
MS (APCI+)508.7

ｎＢｕＬｉ（１．６Ｍ，６６ｍＬ）とジイソプロピルアミン（１０．６ｇ）のＴＨＦ（４０ｍＬ）から調製された、ＬＤＡ（１０５ｍｍｏｌ）に、化合物６（６．４ｇ，５０ｍｍｏｌ）のＴＨＦ（５０ｍＬ）溶液を－７８℃で１０分かけて滴下した。混合溶液をさらに－７８℃で撹拌し、ヨウ素（１３．９ｇ，５５ｍｍｏｌ）のエーテル溶液（４０ｍＬ）を１０分かけて滴下した。反応溶液を室温まで昇温し、さらに１時間撹拌した後、エーテル（１００ｍＬ）を加え、氷水（３００ｍＬ）に注いだ。水層を１Ｍ塩酸で弱酸性にし、酢酸エチル（３００ｍＬ）で抽出した。これらの有機層を合わせ、硫酸ナトリウムで乾燥後、濾過した。有機層を減圧濃縮し、得られた粗生成物をエタノール－水から再結晶させ，化合物７を８４％の収率で得た。
ＭＳ （ＡＰＣＩ＋）２５３．９ <Experimental Example 4>

A solution of compound 6 (6.4 g, 50 mmol) in THF (50 mL) was added dropwise to LDA (105 mmol) prepared from nBuLi (1.6 M, 66 mL) and diisopropylamine (10.6 g) in THF (40 mL) at -78 ° C. over 10 minutes. The mixed solution was further stirred at -78 ° C., and an ether solution (40 mL) of iodine (13.9 g, 55 mmol) was added dropwise over 10 minutes. The reaction solution was warmed to room temperature and further stirred for 1 hour, after which ether (100 mL) was added and poured into ice water (300 mL). The aqueous layer was made weakly acidic with 1 M hydrochloric acid and extracted with ethyl acetate (300 mL). These organic layers were combined, dried over sodium sulfate, and then filtered. The organic layer was concentrated under reduced pressure, and the resulting crude product was recrystallized from ethanol-water to obtain compound 7 in 84% yield.
MS (APCI+)253.9

化合物７（１０．６ｇ，４１．７ｍｍｏｌ）のメタノール（８０ｍＬ）溶液に、濃硫酸１ｍＬを加え、８０℃で１４時間撹拌した。室温まで冷却後、氷水（１００ｍＬ）に注ぎ、炭酸水素ナトリウムを加え中和した。エーテル（１００ｍＬ×２回）で抽出し、有機層を硫酸ナトリウムで乾燥後、濾過した。有機層を減圧濃縮し、化合物８を定量的（収率１００％）に得た。
ＭＳ （ＡＰＣＩ＋）２６７．９ <Experimental Example 5>

To a solution of compound 7 (10.6 g, 41.7 mmol) in methanol (80 mL), 1 mL of concentrated sulfuric acid was added and stirred at 80° C. for 14 hours. After cooling to room temperature, the mixture was poured into ice water (100 mL) and neutralized by adding sodium bicarbonate. The mixture was extracted with ether (100 mL x 2), and the organic layer was dried over sodium sulfate and filtered. The organic layer was concentrated under reduced pressure to obtain compound 8 quantitatively (yield 100%).
MS (APCI+)267.9

化合物８（１．０７ｇ，４．０ｍｍｏｌ）、化合物２（２５０．９ｍｇ，２．２ｍｍｏｌ）、Ｐｄ（ＰＰｈ_３）_２Ｃｌ_２（１４０．４ｍｇ，０．２ｍｍｏｌ）、ｄｐｐｂ（１７０．６ｍｇ，０．４ｍｍｏｌ）をシュレンク管に入れ、窒素置換した。これにＤＭＳＯ（４０ｍＬ）を加え、ＤＢＵ（１．２２ｍｇ，８．０ｍｍｏｌ）を５分で滴下した。この反応溶液を８０℃で６時間加熱した。室温まで冷却後、飽和塩化アンモニウム水（６０ｍＬ）を加え、酢酸エチル（６０ｍＬ×２回）で抽出した。有機層を飽和食塩水（５０ｍＬ）で洗い、有機層を硫酸ナトリウムで乾燥後、濾過した。有機層を減圧濃縮し、得られた粗生成物をシリカゲルカラムクロマトグラフィー（展開溶媒；１０％酢酸エチル／ヘキサン）で精製し、化合物９を４８％の収率で得た。
ＭＳ （ＡＰＣＩ＋）３０６．０ <Experimental Example 6>

Compound 8 (1.07 g, 4.0 mmol), compound 2 (250.9 mg, 2.2 mmol), Pd(PPh ₃ ) ₂ Cl ₂ (140.4 mg, 0.2 mmol), and dppb (170.6 mg, 0.4 mmol) were placed in a Schlenk flask and substituted with nitrogen. DMSO (40 mL) was added thereto, and DBU (1.22 mg, 8.0 mmol) was added dropwise over 5 minutes. This reaction solution was heated at 80° C. for 6 hours. After cooling to room temperature, saturated ammonium chloride water (60 mL) was added, and extraction was performed with ethyl acetate (60 mL x 2 times). The organic layer was washed with saturated saline (50 mL), dried over sodium sulfate, and then filtered. The organic layer was concentrated under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (developing solvent: 10% ethyl acetate/hexane), and compound 9 was obtained in a yield of 48%.
MS (APCI+)306.0

フェニルマグネシウムブロマイドのＴＨＦ溶液（１０．０ｍＬ，１０ｍｍｏｌ）をシュレンク管に入れ、０℃まで冷やした。これに、ＴＨＦ（５ｍＬ）に溶かした化合物９（６１２．７ｍｇ，２．０ｍｍｏｌ）を５分かけて滴下した後、室温まで昇温し１２時間撹拌した。反応溶液を氷水に注ぎ、酢酸エチル（１５ｍＬ×２回）で抽出した。有機層を硫酸ナトリウムで乾燥後、濾過した。有機層を減圧濃縮し、得られた粗生成物を酢酸エチル／ヘキサンに溶かして再結晶させ、化合物１０を４９％の収率で得た。
ＭＳ （ＡＰＣＩ＋）５５４．１ <Experimental Example 7>

A THF solution of phenylmagnesium bromide (10.0 mL, 10 mmol) was placed in a Schlenk flask and cooled to 0°C. Compound 9 (612.7 mg, 2.0 mmol) dissolved in THF (5 mL) was added dropwise over 5 minutes, and then the mixture was warmed to room temperature and stirred for 12 hours. The reaction solution was poured into ice water and extracted with ethyl acetate (15 mL x 2). The organic layer was dried over sodium sulfate and filtered. The organic layer was concentrated under reduced pressure, and the resulting crude product was dissolved in ethyl acetate/hexane and recrystallized to obtain compound 10 in a yield of 49%.
MS (APCI+)554.1

化合物１０（４４３．８ｍｇ，０．８ｍｍｏｌ）のメタノール（２ｍＬ）サスペンション溶液に、ＣＡＮ（１７５．４ｍｇ，０．３２ｍｍｏｌ）を加えた後、４０℃まで昇温し１２時間撹拌した。室温まで冷却後、反応溶液を濾過し、沈殿をメタノールで懸洗し、化合物１１を７５％収率で得た。
ＭＳ （ＡＰＣＩ＋）５８２．２ <Experimental Example 8>

CAN (175.4 mg, 0.32 mmol) was added to a suspension solution of compound 10 (443.8 mg, 0.8 mmol) in methanol (2 mL), and the mixture was heated to 40° C. and stirred for 12 hours. After cooling to room temperature, the reaction solution was filtered, and the precipitate was washed by suspending in methanol to obtain compound 11 in 75% yield.
MS (APCI+)582.2

シュレンク管に、ＬｉＣｌ（２５．４ｍｇ，０．６０ｍｍｏｌ）を加え、加熱乾燥した後、これにＦｅＣｌ_２（２．６ｍｇ，０．０２ｍｍｏｌ）、ＰＰｈ_３（１０．５ｍｇ，０．０４ｍｍｏｌ）、Ｍｇ粉末（１４．６ｍｇ，０．６０ｍｍｏｌ）、化合物１１（１１６．６ｍｇ，０．２０ｍｍｏｌ）を窒素気流下で加えた。この混合物に、ＴＨＦ（０．４ｍＬ）を加え、室温で７時間撹拌した後、１，２－ジクロロプロパン（３９μＬ，０．４０ｍｍｏｌ）をゆっくり加え、さらに室温で１２時間撹拌した。反応溶液をクロロホルム（２０ｍＬ）で希釈し、有機層を１Ｍ塩酸（１５ｍＬ）で洗い、有機層を硫酸ナトリウムで乾燥後濾過した。有機層を減圧濃縮し、得られた粗生成物をクロロホルムーメタノールに溶かして再結晶させ、実施例２の化合物を９３％の収率で得た。
ＭＳ （ＡＰＣＩ＋）５２０．１ Example 2

LiCl (25.4 mg, 0.60 mmol) was added to a Schlenk flask, and the mixture was dried by heating. FeCl ₂ (2.6 mg, 0.02 mmol), PPh ₃ (10.5 mg, 0.04 mmol), Mg powder (14.6 mg, 0.60 mmol), and compound 11 (116.6 mg, 0.20 mmol) were then added to the mixture under a nitrogen stream. THF (0.4 mL) was added to the mixture, and the mixture was stirred at room temperature for 7 hours. Then, 1,2-dichloropropane (39 μL, 0.40 mmol) was slowly added, and the mixture was further stirred at room temperature for 12 hours. The reaction solution was diluted with chloroform (20 mL), and the organic layer was washed with 1 M hydrochloric acid (15 mL). The organic layer was dried over sodium sulfate and then filtered. The organic layer was concentrated under reduced pressure, and the obtained crude product was dissolved in chloroform-methanol and recrystallized to obtain the compound of Example 2 in a yield of 93%.
MS (APCI+)520.1

<Examples 3 to 9>
In Examples 1 and 2, the compounds in which the substituent Ar of the compounds in Examples 1 and 2 shown in the structure column in Table 1 was changed to the substituent shown in the substituent column in Table 1, and the compounds in which the aromatic rings of the compounds in Examples 1 and 2 were increased were synthesized.

Claims (10)

An aromatic polycyclic fused ring compound represented by the following formula (II)'.

(In formula (II)', ^R1 , ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , and ^R8 are each independently selected from an alkyl group which may have a substituent and an aromatic ring group which may have a substituent, ^Ar1 and ^Ar2 are thiophene rings, and n is an integer of 0 or more.) An organic semiconductor device comprising an active layer containing a p-type conjugated polymer and an n-type compound represented by the following general formula (III):

(In formula (III), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently selected from an alkyl group which may have a substituent and an aromatic ring group which may have a substituent; X ¹ and X ² each independently represent a halogen atom; p and q each independently represent an integer from 0 to 4; r and s each independently represent 0 or 1; and n represents an integer of 0 or greater.) 3. The organic semiconductor device of claim 2, wherein the active layer contains at least one fullerene compound selected from the group consisting of [60]fullerene, [70]fullerene, [60]PCBM, [70]PCBM, bis[60]PCBM, bis[70]PCBM, [60]SIMEF, [ 70]SIMEF, [60]ICBA, [70]ICBA, [60]ICMA, and [70]ICMA. 4. The organic semiconductor device according to claim 2 , wherein the active layer contains a polycyclic aromatic compound or 1,8-diiodooctane. The organic semiconductor device according to any one of claims 2 to 4 , which is a photoelectric conversion element. 6. The organic semiconductor device according to claim 2 , which has an external quantum efficiency (EQE) of 50% or more when irradiated with light having a wavelength of 940 nm. 1. An organic semiconductor ink comprising: a p-type conjugated polymer; an n-type compound represented by the following general formula (III); at least one fullerene compound selected from the group consisting of [60]fullerene, [70]fullerene, [60]PCBM, [70]PCBM, bis[60]PCBM, bis[70]PCBM, [60]SIMEF, [70]SIMEF, [60]ICBA, [70]ICBA, [60]ICMA, and [70]ICMA; and a solvent, wherein the weight ratio of the fullerene compound to the n-type compound is 2.0 or less.

(In formula (III), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently selected from an alkyl group which may have a substituent and an aromatic ring group which may have a substituent; X ¹ and X ² each independently represent a halogen atom; p and q each independently represent an integer from 0 to 4; r and s each independently represent 0 or 1; and n represents an integer of 0 or greater.) 8. The organic semiconductor ink according to claim 7 , which contains a polycyclic aromatic compound and/or 1,8-diiodooctane. A photodetector using the organic semiconductor device according to any one of claims 2 to 6 . 10. The photodetector according to claim 9 , which is used to detect light having a wavelength of 700 to 1200 nm.