JP6003399B2 - Polymer compound and organic photoelectric conversion device using the same - Google Patents

Description

  The present invention relates to a polymer compound, and an organic photoelectric conversion element and an organic thin film transistor using the same.

  An organic semiconductor material is used for organic photoelectric conversion elements, such as an organic solar cell and an optical sensor, for example. In particular, when a high molecular compound is used among organic semiconductor materials, a thin film can be produced by an inexpensive coating method, and the manufacturing cost of the element can be reduced.

  In order to improve various characteristics of the organic photoelectric conversion element, various polymer compounds have been studied for organic semiconductor materials constituting the element. For example, a polymer compound obtained by polymerizing 9,9-dioctylfluorene-2,7-diboronate and 5,5 ″ ″-dibromo-3 ″, 4 ″ -dihexyl-α-pentathiophene is proposed. (Patent Document 1).

Special table 2007-529596 gazette

  However, the polymer compound has a problem that long-wavelength light is not sufficiently absorbed.

  Then, an object of this invention is to provide the high molecular compound with the large light absorbency of long wavelength light.

〔式（Ａ）及び式（Ｂ）中、Ｒは、同一又は相異なり、水素原子、フッ素原子、アルキル基、アルコキシ基、アリール基、ヘテロアリール基、式（２ａ）で表される基、又は（２ｂ）で表される基を表す。これらの基に含まれる水素原子はフッ素原子で置換されていてもよい。Ａｒ^１、Ａｒ^２は、置換基を有してもよい炭素数６〜６０の３価の芳香族炭化水素基又は置換基を有してもよい炭素数４〜６０の３価の複素環基を示す。Ａｒ^３は、置換基を有してもよい炭素数６〜６０の２価の芳香族炭化水素基又は置換基を有してもよい炭素数４〜６０の２価の複素環基を示す。〕

（２ａ）
（式（２ａ）中、ｍ１は、０〜６の整数を表し、ｍ２は、０〜６の整数を表す。Ｒ’は、アルキル基、アリール基又はヘテロアリール基を表す。）〕

（２ｂ）
（式（２ｂ）中、ｍ３は、０〜６の整数を表し、ｍ４は、０〜６の整数を表す。Ｒ’’は、アルキル基、アリール基又はヘテロアリール基を表す。）〕 That is, the present invention first provides a polymer compound containing a repeating unit represented by the formula (A) and a repeating unit represented by the formula (B).

[In the formulas (A) and (B), R is the same or different and is a hydrogen atom, a fluorine atom, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, a group represented by the formula (2a), or The group represented by (2b) is represented. The hydrogen atom contained in these groups may be substituted with a fluorine atom. Ar ¹ and Ar ² are a trivalent aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent or a trivalent heterocyclic group having 4 to 60 carbon atoms which may have a substituent. Indicates. Ar ³ represents an optionally substituted divalent aromatic hydrocarbon group having 6 to 60 carbon atoms or an optionally substituted divalent heterocyclic group having 4 to 60 carbon atoms. ]

(2a)
(In the formula (2a), m1 represents an integer of 0 to 6, m2 represents an integer of 0 to 6. R ′ represents an alkyl group, an aryl group, or a heteroaryl group.)]

(2b)
(In Formula (2b), m3 represents an integer of 0 to 6, m4 represents an integer of 0 to 6. R ″ represents an alkyl group, an aryl group, or a heteroaryl group.)]

（１）
〔式（１）中、Ｒは、同一又は相異なり、水素原子、フッ素原子、アルキル基、アルコキシ基、アリール基、ヘテロアリール基、式（２ａ）で表される基、又は（２ｂ）で表される基を表す。これらの基に含まれる水素原子はフッ素原子で置換されていてもよい。

（２ａ）
（式（２ａ）中、ｍ１は、０〜６の整数を表し、ｍ２は、０〜６の整数を表す。Ｒ’は、アルキル基、アリール基又はヘテロアリール基を表す。）〕

（２ｂ）
（式（２ｂ）中、ｍ３は、０〜６の整数を表し、ｍ４は、０〜６の整数を表す。Ｒ’’は、アルキル基、アリール基又はヘテロアリール基を表す。）〕 Secondly, the present invention provides a polymer compound containing a repeating unit represented by the formula (1).

(1)
[In Formula (1), R is the same or different and is represented by a hydrogen atom, a fluorine atom, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, a group represented by Formula (2a), or (2b). Represents a group. The hydrogen atom contained in these groups may be substituted with a fluorine atom.

(2a)
(In the formula (2a), m1 represents an integer of 0 to 6, m2 represents an integer of 0 to 6. R ′ represents an alkyl group, an aryl group, or a heteroaryl group.)]

(2b)
(In Formula (2b), m3 represents an integer of 0 to 6, m4 represents an integer of 0 to 6. R ″ represents an alkyl group, an aryl group, or a heteroaryl group.)]

  Thirdly, the present invention provides an organic photoelectric conversion element having a pair of electrodes and a functional layer provided between the electrodes, wherein the functional layer includes an electron accepting compound and the polymer compound.

  Fourthly, the present invention provides an organic thin film transistor comprising a source electrode, a drain electrode, an organic semiconductor layer, and a gate electrode, wherein the organic semiconductor layer includes the polymer compound.

  The polymer compound of the present invention is extremely useful because it has a large absorbance for light having a long wavelength.

2 is a graph showing an absorption spectrum of polymer compound A. FIG. 2 is a diagram showing an absorption spectrum of a polymer compound B. FIG. 2 is a graph showing an absorption spectrum of a polymer compound C. FIG. 2 is a diagram showing an absorption spectrum of a polymer compound D. FIG. 2 is a graph showing an absorption spectrum of a polymer compound E. FIG. 3 is a diagram showing an absorption spectrum of a polymer compound F. FIG. 2 is a diagram showing an absorption spectrum of a polymer compound G. FIG. 2 is a graph showing an absorption spectrum of a polymer compound J. FIG. 2 is a graph showing an absorption spectrum of a polymer compound K. FIG. 2 is a diagram showing an absorption spectrum of a polymer compound L. FIG.

  Hereinafter, the present invention will be described in detail.

〔式（Ａ）及び式（Ｂ）中、Ｒは、同一又は相異なり、水素原子、フッ素原子、アルキル基、アルコキシ基、アリール基、ヘテロアリール基、式（２ａ）で表される基、又は（２ｂ）で表される基を表す。これらの基に含まれる水素原子はフッ素原子で置換されていてもよい。Ａｒ^１、Ａｒ^２は、置換基を有してもよい炭素数６〜６０の３価の芳香族炭化水素基又は置換基を有してもよい炭素数４〜６０の３価の複素環基を示す。Ａｒ^３は、置換基を有してもよい炭素数６〜６０の２価の芳香族炭化水素基又は置換基を有してもよい炭素数４〜６０の２価の複素環基を示す。〕

（２ａ）
（式（２ａ）中、ｍ１は、０〜６の整数を表し、ｍ２は、０〜６の整数を表す。Ｒ’は、アルキル基、アリール基又はヘテロアリール基を表す。）〕

（２ｂ）
（式（２ｂ）中、ｍ３は、０〜６の整数を表し、ｍ４は、０〜６の整数を表す。Ｒ’’は、アルキル基、アリール基又はヘテロアリール基を表す。）〕 <Polymer compound>
The polymer compound of the present invention includes a repeating unit represented by the formula (A) and a repeating unit represented by the formula (B).

[In the formulas (A) and (B), R is the same or different and is a hydrogen atom, a fluorine atom, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, a group represented by the formula (2a), or The group represented by (2b) is represented. The hydrogen atom contained in these groups may be substituted with a fluorine atom. Ar ¹ and Ar ² are a trivalent aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent or a trivalent heterocyclic group having 4 to 60 carbon atoms which may have a substituent. Indicates. Ar ³ represents an optionally substituted divalent aromatic hydrocarbon group having 6 to 60 carbon atoms or an optionally substituted divalent heterocyclic group having 4 to 60 carbon atoms. ]

(2a)
(In the formula (2a), m1 represents an integer of 0 to 6, m2 represents an integer of 0 to 6. R ′ represents an alkyl group, an aryl group, or a heteroaryl group.)]

(2b)
(In Formula (2b), m3 represents an integer of 0 to 6, m4 represents an integer of 0 to 6. R ″ represents an alkyl group, an aryl group, or a heteroaryl group.)]

  Examples of the alkyl group represented by R include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n- Examples include a pentyl group, n-hexyl group, n-octyl group, iso-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, and n-octadecyl group. A hydrogen atom in the alkyl group may be substituted with a fluorine atom. Examples of the alkyl group in which a hydrogen atom is substituted with a fluorine atom include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.

  Examples of the alkoxy group represented by R include methoxy group, ethoxy group, propoxy group, iso-propoxy group, butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy Group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group. A hydrogen atom in the alkoxy group may be substituted with a fluorine atom. Examples of the alkoxy group in which a hydrogen atom is substituted with a fluorine atom include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, and a perfluorooctyloxy group.

  The aryl group represented by R is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon which may have a substituent. The aryl group includes a group containing a benzene ring, a group containing a condensed ring having aromaticity, a group having a structure in which two or more benzene rings or a condensed ring having aromaticity are directly bonded, and two or more benzenes Examples include a group in which a ring or an aromatic condensed ring is bonded via a group such as vinylene. The aryl group preferably has 6 to 60 carbon atoms, more preferably 6 to 30 carbon atoms. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Examples of the substituent that the aromatic hydrocarbon may have include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group, and an alkoxy group. Specific examples of the alkyl group and alkoxy group are the same as the specific examples of the alkyl group and alkoxy group represented by R.

  The heteroaryl group represented by R is an atomic group obtained by removing one hydrogen atom from an aromatic heterocyclic compound which may have a substituent. Examples of the heteroaryl group include a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a quinolyl group, and an isoquinolyl group. Examples of the substituent that the aromatic heterocyclic compound may have include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group, and an alkoxy group. Specific examples of the alkyl group and alkoxy group are the same as the specific examples of the alkyl group and alkoxy group represented by R.

  In the group represented by the formula (2a), m1 represents an integer of 0 to 6, and m2 represents an integer of 0 to 6. R 'represents an alkyl group, an aryl group or a heteroaryl group. The definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R ′ are the same as the definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R. A hydrogen atom in the group represented by the formula (2a) may be substituted with a fluorine atom.

In the group represented by the formula (2b), m3 represents an integer of 0 to 6, and m4 represents an integer of 0 to 6. R ″ represents an alkyl group, an aryl group, or a heteroaryl group. The definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R ″ are the same as the definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R. The hydrogen atom in the group represented by the formula (2b) may be substituted with a fluorine atom.

  When R is an alkyl group or an alkoxy group, from the viewpoint of solubility of the polymer compound in a solvent, the alkyl group or alkoxy group preferably has 1 to 20 carbon atoms, and preferably 2 to 18 carbon atoms. Is more preferable, and it is further more preferable that it is 3-12.

In formulas (A) and (B), Ar ¹ and Ar ² may have a substituent, a trivalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or a substituent. A trivalent heterocyclic group having 4 to 60 carbon atoms is shown, and Ar ³ may have a divalent aromatic hydrocarbon group or substituent having 6 to 60 carbon atoms which may have a substituent. A divalent heterocyclic group having 4 to 60 carbon atoms is shown.

In Ar ¹ and Ar ² , an optionally substituted trivalent aromatic hydrocarbon group having 6 to 60 carbon atoms is an aromatic carbon atom having 6 to 60 carbon atoms that may have a substituent. The trivalent group remove | excluding three hydrogen atoms on the aromatic ring in a hydrogen compound is shown. In Ar ^3, the divalent aromatic hydrocarbon group which may having 6 to 60 carbon atoms which may have a substituent, an aromatic hydrocarbon compound of carbon atoms which may 6 to 60 have a substituent The bivalent group remove | excluding two hydrogen atoms on the aromatic ring in is shown. The aromatic hydrocarbon compound may be a single ring or a condensed ring. Among these, since excellent solubility is obtained and production is easy, a condensed ring or a single ring in which five or less rings are condensed is preferable, and a condensed ring or a single ring in which two rings are condensed is preferable. A ring is more preferable, and a single ring is more preferable.

  Examples of the aromatic hydrocarbon compound include benzene, naphthalene, anthracene, fluorene, pyrene, and perylene. Of these, benzene or naphthalene is preferable, and benzene is more preferable.

  The aromatic hydrocarbon group may further have a substituent, and in this case, the whole including the substituent is an aromatic hydrocarbon group. However, in this case, the carbon number of the above-described preferred aromatic hydrocarbon group does not include the carbon number of the substituent. Examples of the substituent include those shown for R above.

  The trivalent heterocyclic group having 4 to 60 carbon atoms which may have a substituent refers to three hydrogens on the heterocyclic ring in the heterocyclic compound having 4 to 60 carbon atoms which may have a substituent. A trivalent group excluding atoms is shown. In addition, the divalent heterocyclic group having 4 to 60 carbon atoms which may have a substituent refers to two of the heterocyclic rings in the heterocyclic compound having 4 to 60 carbon atoms which may have a substituent. A divalent group excluding a hydrogen atom is shown. The heterocyclic compound may be a single ring or a condensed ring. Among these, since excellent solubility is obtained and production is easy, a condensed ring or a single ring in which five or less rings are condensed is preferable, and a condensed ring or a single ring in which two rings are condensed is preferable. Is more preferable, and a single ring is more preferable.

  Examples of the heterocyclic compound include pyridine, thiophene, thienothiophene, dithienothiophene, benzothiophene, benzodithiophene, dibenzothiophene, pyrrole, quinoline, and indole. Of these, thiophene, thienothiophene or pyridine is preferable, and thiophene is more preferable.

  The heterocyclic group may further have a substituent. In this case, the carbon number of the preferable heterocyclic group described above does not include the carbon number of the substituent. Examples of the substituent include a halogen atom, a saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms, an aryl group having 6 to 60 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkanoyl group having 1 to 12 carbon atoms, Examples thereof include an aryloxy group having 6 to 60 carbon atoms, a heterocyclic group having 3 to 60 carbon atoms, an amino group, a nitro group, and a cyano group. Examples of these substituents include the same groups as those described above for R.

Ar ¹ and Ar ² are preferably trivalent groups excluding three hydrogen atoms on the aromatic ring in benzene or thiophene. Ar ³ is preferably a divalent group excluding three hydrogen atoms on the aromatic ring in benzene or thiophene.

Examples of the repeating unit represented by the formula (A) include the following repeating units.

Examples of the repeating unit represented by the formula (B) include the following repeating units.

  From the viewpoint of photoelectric conversion efficiency, the polymer compound of the present invention preferably includes a repeating unit in which the repeating unit represented by the formula (A) and the repeating unit represented by the formula (B) are directly bonded.

  The total amount of the repeating unit represented by the formula (A) and the repeating unit represented by the formula (B) contained in the polymer compound of the present invention is that of the organic photoelectric conversion element having a functional layer containing the polymer compound. From the viewpoint of increasing the photoelectric conversion efficiency, it is preferably 20 to 100 mol%, more preferably 30 to 100 mol%, based on the total amount of repeating units contained in the polymer compound.

  The ratio of the number of repeating units represented by formula (A) contained in the polymer compound of the present invention to the number of repeating units represented by formula (B) is, for example, 1: 9 to 9: 1. Yes, 3: 7-7: 3 is preferred.

（１）
〔式（１）中、Ｒは、前述と同じ意味を表す。〕 Another embodiment of the polymer compound of the present invention is a polymer compound containing a repeating unit represented by the formula (1).

(1)
[In the formula (1), R represents the same meaning as described above. ]

Examples of the repeating unit represented by the formula (1) include the following repeating units.

  The amount of the repeating unit represented by the formula (1) contained in the polymer compound of the present invention is selected from the viewpoint of increasing the photoelectric conversion efficiency of an organic photoelectric conversion device having a functional layer containing the polymer compound. The amount is preferably 20 to 100 mol%, more preferably 30 to 100 mol%, based on the total amount of repeating units contained in the compound.

The weight average molecular weight in terms of polystyrene of the polymer compound of the present invention is preferably 10 ³ to 10 ⁸ , more preferably 10 ³ to 10 ⁷ , and still more preferably 10 ³ to 10 ⁶ .

  The polymer compound of the present invention is preferably a conjugated polymer compound. Here, the conjugated polymer compound means a compound in which atoms constituting the main chain of the polymer compound are substantially conjugated.

  The polymer compound of the present invention may have a repeating unit other than the repeating unit represented by the formula (A), the repeating unit represented by the formula (B), and the repeating unit represented by the formula (1). Good. Examples of the repeating unit include an arylene group and a heteroarylene group. Examples of the arylene group include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a pyrenediyl group, and a fluorenediyl group. Examples of the heteroarylene group include a flangyl group, a pyrrole diyl group, a pyridinediyl group, and the like.

<Method for producing polymer compound>
The polymer compound of the present invention may be produced by any method. For example, after synthesizing a monomer having a functional group suitable for the polymerization reaction to be used, the monomer is dissolved in an organic solvent, if necessary, , And can be synthesized by polymerization using a known aryl coupling reaction using a catalyst, a ligand and the like. The synthesis of the monomer can be performed, for example, with reference to the methods disclosed in JP-A Nos. 2006-182920 and 2006-335933.

  Examples of the polymerization by the aryl coupling reaction include polymerization by Stille coupling reaction, polymerization by Suzuki coupling reaction, polymerization by Yamamoto coupling reaction, and polymerization by Kumada-Tamao coupling reaction.

  Polymerization by Stille coupling reaction is necessary using palladium complexes such as palladium [tetrakis (triphenylphosphine)], [tris (dibenzylideneacetone)] dipalladium, palladium acetate, bis (triphenylphosphine) palladium dichloride as catalysts. Depending on the ligand, ligands such as triphenylphosphine, tri (2-methylphenyl) phosphine, tri (2-methoxyphenyl) phosphine, diphenylphosphinopropane, tri (cyclohexyl) phosphine, tri (tert-butyl) phosphine A monomer having an organotin residue and a monomer having a halogen atom such as a bromine atom, an iodine atom or a chlorine atom, or a sulfonate group such as a trifluoromethanesulfonate group or a p-toluenesulfonate group. This is a polymerization in which the monomer is reacted. The details of the polymerization by the Stille coupling reaction are described in, for example, Angewante Chemie International Edition, 2005, Vol. 44, p. 4442-4489.

  Polymerization by Suzuki coupling reaction uses a palladium complex or nickel complex as a catalyst in the presence of an inorganic base or an organic base, and a ligand is added as necessary to have a boronic acid residue or a boric acid ester residue. This is a polymerization in which a monomer is reacted with a monomer having a halogen atom such as a bromine atom, an iodine atom or a chlorine atom, or a monomer having a sulfonate group such as a trifluoromethanesulfonate group or a p-toluenesulfonate group.

  Examples of the inorganic base include sodium carbonate, potassium carbonate, cesium carbonate, tripotassium phosphate, and potassium fluoride. Examples of the organic base include tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, and tetraethylammonium hydroxide. Examples of the palladium complex include palladium [tetrakis (triphenylphosphine)], [tris (dibenzylideneacetone)] dipalladium, palladium acetate, and bis (triphenylphosphine) palladium dichloride. Examples of the nickel complex include bis (cyclooctadiene) nickel. Examples of the ligand include triphenylphosphine, tri (2-methylphenyl) phosphine, tri (2-methoxyphenyl) phosphine, diphenylphosphinopropane, tri (cyclohexyl) phosphine, and tri (tert-butyl) phosphine. It is done.

  Details of the polymerization by the Suzuki coupling reaction are described in, for example, Journal of Polymer Science: Part A: Polymer Chemistry (Part A: Polymer Chemistry), 2001, Vol. 39, p. 1533-1556.

  Polymerization by Yamamoto coupling reaction uses a catalyst and a reducing agent to react monomers having halogen atoms, monomers having sulfonate groups such as trifluoromethanesulfonate groups, or monomers having halogen atoms and monomers having sulfonate groups. Polymerization.

  Catalysts include nickel zero-valent complexes such as bis (cyclooctadiene) nickel and ligands such as bipyridyl, [bis (diphenylphosphino) ethane] nickel dichloride, [bis (diphenylphosphino) propane] nickel. A catalyst comprising a nickel complex other than a nickel zero-valent complex such as dichloride and a ligand such as triphenylphosphine, diphenylphosphinopropane, tri (cyclohexyl) phosphine, tri (tert-butyl) phosphine, if necessary. . Examples of the reducing agent include zinc and magnesium. Polymerization by the Yamamoto coupling reaction may be performed using a dehydrated solvent in the reaction, may be performed in an inert atmosphere, or may be performed by adding a dehydrating agent to the reaction system.

  Details of the polymerization by Yamamoto coupling are described in, for example, Macromolecules, 1992, Vol. 25, p. 1214-1223.

  Polymerization by Kumada-Tamao coupling reaction uses a nickel catalyst such as [bis (diphenylphosphino) ethane] nickel dichloride, [bis (diphenylphosphino) propane] nickel dichloride, and a compound having a magnesium halide group and a halogen atom. Polymerization to react with the compound having For the reaction, a dehydrated solvent may be used for the reaction, the reaction may be performed in an inert atmosphere, or a dehydrating agent may be added to the reaction system.

  In the polymerization by the aryl coupling reaction, a solvent is usually used. The solvent may be selected in consideration of the polymerization reaction used, the solubility of the monomer and polymer, and the like. Specifically, tetrahydrofuran, toluene, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, an organic solvent such as a mixed solvent obtained by mixing two or more of these solvents, an organic solvent A solvent having two phases of a phase and an aqueous phase. The solvent used in the Stille coupling reaction is preferably an organic solvent such as tetrahydrofuran, toluene, N, N-dimethylformamide, a mixed solvent obtained by mixing two or more of these solvents, or a solvent having two phases of an organic solvent phase and an aqueous phase. The solvent used for the Stille coupling reaction is preferably deoxygenated before the reaction in order to suppress side reactions. Solvents used in the Suzuki coupling reaction are organic solvents such as tetrahydrofuran, toluene, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, and mixed solvents in which two or more of these solvents are mixed. A solvent and a solvent having two phases of an organic solvent phase and an aqueous phase are preferred. The solvent used for the Suzuki coupling reaction is preferably deoxygenated before the reaction in order to suppress side reactions. The solvent used for the Yamamoto coupling reaction is an organic solvent such as tetrahydrofuran, toluene, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, or a mixed solvent in which two or more of these solvents are mixed. A solvent is preferred. The solvent used for the Yamamoto coupling reaction is preferably deoxygenated before the reaction in order to suppress side reactions.

  Among the polymerizations by the aryl coupling reaction, from the viewpoint of reactivity, a method of polymerizing by a Stille coupling reaction, a method of polymerizing by a Suzuki coupling reaction, a method of polymerizing by a Yamamoto coupling reaction are preferable, and a Stille coupling reaction More preferred are a method of polymerizing, a method of polymerizing by a Suzuki coupling reaction, and a method of polymerizing by a Yamamoto coupling reaction using a nickel zero-valent complex.

  The lower limit of the reaction temperature of the aryl coupling reaction is preferably −100 ° C., more preferably −20 ° C., and particularly preferably 0 ° C. from the viewpoint of reactivity. The upper limit of the reaction temperature is preferably 200 ° C., more preferably 150 ° C., and particularly preferably 120 ° C. from the viewpoint of the stability of the monomer and the polymer compound.

  In the polymerization by the aryl coupling reaction, a known method can be used as a method for removing the polymer compound of the present invention from the reaction solution after completion of the reaction. For example, the polymer compound of the present invention can be obtained by adding a reaction solution to a lower alcohol such as methanol, filtering the deposited precipitate, and drying the filtrate. When the purity of the obtained polymer compound is low, it can be purified by recrystallization, continuous extraction with a Soxhlet extractor, column chromatography, or the like.

  When the polymer compound of the present invention is used for the production of an organic photoelectric conversion element, if a polymerization active group remains at the terminal of the polymer compound, characteristics such as durability of the organic photoelectric conversion element may be deteriorated. It is preferable to protect the terminal of the polymer compound with a stable group.

Examples of the stable group for protecting the terminal include an alkyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkoxy group, an aryl group, an arylamino group, and a monovalent heterocyclic group. Examples of the arylamino group include a phenylamino group and a diphenylamino group.
Examples of the monovalent heterocyclic group include thienyl group, pyrrolyl group, furyl group, pyridyl group, quinolyl group, and isoquinolyl group. Further, the polymerization active group remaining at the terminal of the polymer compound may be replaced with a hydrogen atom instead of a stable group. From the viewpoint of enhancing hole transportability, it is preferable that the stable group for protecting the terminal is a group imparting electron donating properties such as an arylamino group. When the polymer compound is a conjugated polymer compound, the end of a group having a conjugated bond in which the conjugated structure of the main chain of the polymer compound and the conjugated structure of a stable group protecting the end are continuous is also protected. It can preferably be used as a stable group. Examples of the group include an aryl group and a monovalent heterocyclic group having aromaticity.

（３）
（式（３）中、Ｒは、前述と同じ意味を表す。複数あるＲは、同一でも相異なっていてもよい。Ｚは、臭素原子、ヨウ素原子又は塩素原子を表す。２個あるＺは、同一でも相異なっていてもよい。）

（４）
（式（４）中、Ｒは前述と同じ意味を表す。２個あるＲは、同一でも相異なっていてもよい。Ｚ^２は有機スズ残基を表す。） When the polymer compound of the present invention is produced using Stille coupling, for example, the polymer compound is produced by polymerizing the compound represented by the formula (3) and the compound represented by the formula (4). be able to.

(3)
(In formula (3), R represents the same meaning as described above. Plural Rs may be the same or different. Z represents a bromine atom, an iodine atom or a chlorine atom. May be the same or different.)

(4)
(In formula (4), R represents the same meaning as described above. Two Rs may be the same or different. Z ² represents an organotin residue.)

  In the formula (3), Z is preferably a bromine atom or a chlorine atom, and more preferably a bromine atom, from the viewpoint of increasing the reactivity during polymerization. The compound represented by the formula (3) can be synthesized using, for example, the method described in Organic Electronics 2010, 11, 1740-1745. In general, 2,4-dibromo-3,4-dicarboxylic acid obtained by bromine under glacial acetic acid with 3,4-thiophenedicarboxylic acid in a solvent such as halogenated hydrocarbons such as chloroform and dichloromethane An acid chloride compound obtained by reacting a chlorinating agent such as thionyl chloride or oxalyl dichloride is reacted with R in the presence of a Lewis acid, for example, aluminum (III) chloride, in a halogenated hydrocarbon such as chloroform or dichloromethane. It can be synthesized by reacting a defined substituted benzene (Friedel-Crafts reaction).

As a compound represented by Formula (3), the following compounds are mentioned, for example.

In the formula (4), ease From the point of view of the synthesis of the compound represented by formula (4), ^{Z 2} is -SnMe _3, preferably a -SnEt ₃ or -SnBu _3. Here, Me represents a methyl group, Et represents an ethyl group, and Bu represents a butyl group.

（式（５）中、Ｒは前述と同じ意味を表す。） The compound represented by the formula (4) is prepared by, for example, reacting the compound represented by the formula (5) with an organolithium compound to produce an intermediate, and then reacting the intermediate with a trialkyltin halide. Can be manufactured.

(In formula (5), R represents the same meaning as described above.)

  Examples of the organic lithium compound include n-butyllithium, sec-butyllithium, tert-butyllithium, and lithium diisopropylamide. Of the organic lithium compounds, n-butyllithium is preferable. Examples of the trialkyltin halide include trimethyltin chloride, triethyl chloride, and tributyl chloride.

  The reaction for producing an intermediate from a compound represented by formula (5) and an organolithium compound and the reaction for producing a compound represented by formula (4) from the intermediate and trialkyltin halide are usually carried out in a solvent. Done. As the solvent, sufficiently dehydrated tetrahydrofuran, fully dehydrated 1,4-dioxane, and fully dehydrated diethyl ether are preferably used.

  The temperature at which the organolithium compound and the compound represented by formula (5) are reacted is usually -100 to 50 ° C, preferably -80 to 0 ° C. The time for reacting the organolithium compound with the compound represented by the formula (5) is usually 1 minute to 10 hours, preferably 30 minutes to 5 hours. The amount of the organolithium compound to be reacted is usually 2 to 5 molar equivalents (hereinafter, the molar equivalent is simply referred to as equivalent), preferably 2 to 3 with respect to the compound represented by the formula (5). Is equivalent.

  The temperature at the time of reacting the intermediate and the trialkyltin halide is usually −100 to 100 ° C., preferably −80 ° C. to 50 ° C. The reaction time of the intermediate and the trialkyltin halide is usually 1 minute to 30 hours, preferably 1 to 10 hours. The amount of the trialkyl tin halide to be reacted is usually 2 to 6 equivalents, preferably 2 to 3 equivalents, relative to the compound represented by the formula (5).

  After the reaction, normal post-treatment can be performed to obtain the compound represented by the formula (4). For example, after the reaction is stopped by adding water, the product is extracted with an organic solvent and the solvent is distilled off. The product can be isolated and purified by a method such as fractionation by chromatography or recrystallization.

（式（６）中、Ｒは前述と同じ意味を表す） The compound represented by the formula (5) can be produced, for example, by reacting the compound represented by the formula (6) in the presence of an acid.

(In formula (6), R represents the same meaning as described above.)

  The acid used in the reaction for producing the compound represented by formula (5) from the compound represented by formula (6) may be Lewis acid or Bronsted acid, Hydrochloric acid, bromic acid, hydrofluoric acid, sulfuric acid, nitric acid, formic acid, acetic acid, propionic acid, oxalic acid, benzoic acid, boron fluoride, aluminum chloride, tin chloride (IV), iron chloride (II), titanium tetrachloride, Examples include benzenesulfonic acid, p-toluenesulfonic acid and mixtures of these compounds.

  The reaction for producing the compound represented by formula (5) from the compound represented by formula (6) is preferably carried out in the presence of a solvent. The reaction temperature is preferably from −80 ° C. to the boiling point of the solvent.

  Solvents used in the reaction include saturated hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene and xylene, carbon tetrachloride, chloroform, dichloromethane, chlorobutane, bromobutane, chloro Halogenated saturated hydrocarbons such as pentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene, methanol, ethanol, propanol, isopropanol, butanol, Alcohols such as tert-butyl alcohol, carboxylic acids such as formic acid, acetic acid and propionic acid, dimethyl ether, diethyl ether, methyl-te t- butyl ether, tetrahydrofuran, tetrahydropyran, and the like ethers such as dioxane. These solvents may be used alone or in combination.

  After the reaction, normal post-treatment can be performed to obtain the compound represented by the formula (5). For example, after the reaction is stopped by adding water, the product is extracted with an organic solvent and the solvent is distilled off. The product can be isolated and purified by a method such as fractionation by chromatography or recrystallization.

The compound represented by the formula (6) can be produced, for example, by reacting the compound represented by the formula (7) with a Grignard reagent or an organolithium (Li) compound.

  Grignard reagents used in the above reaction include methyl magnesium chloride, methyl magnesium bromide, ethyl magnesium chloride, ethyl magnesium bromide, propyl magnesium chloride, propyl magnesium bromide, butyl magnesium chloride, butyl magnesium bromide, hexyl magnesium bromide, octyl magnesium bromide, Examples include decylmagnesium bromide, allylmagnesium chloride, allylmagnesium bromide, benzylmagnesium chloride, phenylmagnesium bromide, naphthylmagnesium bromide, and tolylmagnesium bromide.

  Examples of the organic Li compound include methyl lithium, ethyl lithium, propyl lithium, butyl lithium, phenyl lithium, naphthyl lithium, benzyl lithium, and tolyl lithium.

  The reaction for producing the compound represented by the formula (6) from the compound represented by the formula (7) and a Grignard reagent or an organolithium (Li) compound is carried out in an inert gas atmosphere such as nitrogen or argon. It is preferable to do. Moreover, it is preferable to implement this reaction in presence of a solvent. The reaction temperature is preferably from −80 ° C. to the boiling point of the solvent.

  Solvents used in the reaction include saturated hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene and xylene, dimethyl ether, diethyl ether, methyl-tert-butyl ether, tetrahydrofuran, And ethers such as tetrahydropyran and dioxane. These solvents may be used alone or in combination.

  After the reaction, normal post-treatment can be performed to obtain the compound represented by the formula (6). For example, after the reaction is stopped by adding water, the product is extracted with an organic solvent and the solvent is distilled off. The product can be isolated and purified by a method such as fractionation by chromatography or recrystallization.

The compound represented by the formula (7) can be produced, for example, by reacting the compound represented by the formula (8) with a peroxide.

  Examples of the peroxide include sodium perborate, m-chloroperbenzoic acid, hydrogen peroxide, and benzoyl peroxide. Preferred are sodium perborate and m-chloroperbenzoic acid, and particularly preferred is sodium perborate.

  The reaction for producing the compound represented by the formula (7) from the compound represented by the formula (8) and the peroxide is carried out in the presence of a carboxylic acid solvent such as acetic acid, trifluoroacetic acid, propionic acid and butyric acid. It is preferable.

  In order to increase the solubility of the compound represented by formula (8), a mixed solvent in which one or more solvents selected from the group consisting of carbon tetrachloride, chloroform, dichloromethane, benzene, and toluene are mixed with a carboxylic acid solvent. It is preferable to carry out the reaction. The reaction temperature is preferably 0 ° C. or higher and 50 ° C. or lower.

  After the reaction, normal post-treatment can be performed to obtain the compound represented by the formula (7). For example, after the reaction is stopped by adding water, the product is extracted with an organic solvent and the solvent is distilled off. The product can be isolated and purified by methods such as chromatographic fractionation and recrystallization.

（式中、Ｂｕはｎ−ブチル基を表す。） As a compound represented by Formula (4), the following compound is mentioned, for example.

(In the formula, Bu represents an n-butyl group.)

In the polymer compound of the present invention, the structural unit represented by the formula (C-1) to the formula (C-12) may be included as a third structural unit.

  In formula (C-1) to formula (C-12), X represents a sulfur atom, an oxygen atom or a selenium atom. When there are a plurality of Xs, the plurality of Xs may be the same or different.

  In the formulas (C-1) to (C-12), R represents the same one as described above. When there are a plurality of Rs, the plurality of Rs may be the same or different.

<Organic photoelectric conversion element>
Since the polymer compound of the present invention has a high absorbance of light having a long wavelength such as 600 nm light and efficiently absorbs sunlight, an organic photoelectric conversion element manufactured using the polymer compound of the present invention has a short-circuit current. Density increases. Moreover, the high molecular compound of this invention can obtain a big open end voltage.

The organic photoelectric conversion device of the present invention has a pair of electrodes and a functional layer between the electrodes, and the functional layer contains the electron-accepting compound and the polymer compound of the present invention. As an electron-accepting compound, fullerene or a fullerene derivative is preferable. As a specific example of the organic photoelectric conversion element,
1. An organic photoelectric conversion element having a pair of electrodes and a functional layer between the electrodes, the functional layer containing an electron-accepting compound and the polymer compound of the present invention;
2. An organic photoelectric conversion element comprising a pair of electrodes and a functional layer between the electrodes, the functional layer containing an electron-accepting compound and the polymer compound of the present invention, wherein the electron-accepting compound is a fullerene An organic photoelectric conversion element which is a derivative;
Is mentioned. In general, at least one of the pair of electrodes is transparent or translucent. Hereinafter, this case will be described as an example.

  1 above. In the organic photoelectric conversion element, the amount of the electron-accepting compound in the functional layer containing the electron-accepting compound and the polymer compound is 10 to 1000 parts by weight with respect to 100 parts by weight of the polymer compound. Is preferable, and it is more preferable that it is 20-500 weight part. In addition, 2. In the organic photoelectric conversion element, the amount of the fullerene derivative in the functional layer containing the fullerene derivative and the polymer compound is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of the polymer compound, More preferably, it is -500 weight part. From the viewpoint of increasing the photoelectric conversion efficiency, the amount of the fullerene derivative in the functional layer is preferably 20 to 400 parts by weight, and preferably 40 to 250 parts by weight with respect to 100 parts by weight of the polymer compound. More preferably, it is 80 to 120 parts by weight. From the viewpoint of increasing the short-circuit current density, the amount of the fullerene derivative in the functional layer is preferably 20 to 250 parts by weight, and preferably 40 to 120 parts by weight with respect to 100 parts by weight of the polymer compound. More preferred.

  In order for the organic photoelectric conversion element to have high photoelectric conversion efficiency, the electron-accepting compound and the polymer compound of the present invention have an absorption region that can efficiently absorb the spectrum of desired incident light. It is important that the heterojunction interface includes many heterojunction interfaces in order to efficiently separate excitons, and that the heterojunction interface has a charge transporting property for quickly transporting charges generated by the heterojunction interface to the electrode.

  From such a viewpoint, as the organic photoelectric conversion element, the above 1. , 2. From the standpoint of including a large number of heterojunction interfaces, the organic photoelectric conversion element is preferable. The organic photoelectric conversion element is more preferable. Further, in the organic photoelectric conversion element of the present invention, an additional layer may be provided between at least one electrode and the functional layer in the element. Examples of the additional layer include a charge transport layer that transports holes or electrons, and a buffer layer.

  The organic photoelectric conversion element of the present invention is usually formed on a substrate. The substrate may be any substrate that does not chemically change when an electrode is formed and an organic layer is formed. Examples of the material for the substrate include glass, plastic, polymer film, and silicon. In the case of an opaque substrate, the opposite electrode (that is, the electrode far from the substrate) is preferably transparent or translucent.

  As a material for the pair of electrodes, a metal, a conductive polymer, or the like can be used. The material of one of the pair of electrodes is preferably a material having a low work function. For example, metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and those metals An alloy of two or more of these metals, or one or more of those metals and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin An alloy with metal, graphite, a graphite intercalation compound, or the like is used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.

  Examples of the material of the transparent or translucent electrode include a conductive metal oxide film and a translucent metal thin film. Specifically, a film formed using a conductive material made of indium oxide, zinc oxide, tin oxide, and indium tin oxide (ITO), indium zinc oxide, etc., which is a composite thereof, NESA Gold, platinum, silver, and copper are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the method for producing the electrode include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an electrode material.

  As a material used for the charge transport layer as the additional layer, that is, the hole transport layer or the electron transport layer, an electron donating compound and an electron accepting compound described later can be used, respectively.

  As a material used for the buffer layer as an additional layer, halides or oxides of alkali metals or alkaline earth metals such as lithium fluoride can be used. In addition, fine particles of an inorganic semiconductor such as titanium oxide can be used.

<Organic thin film>
As the functional layer in the organic photoelectric conversion element of the present invention, for example, an organic thin film containing the polymer compound of the present invention and an electron-accepting compound can be used.

  The organic thin film has a thickness of usually 1 nm to 100 μm, preferably 2 nm to 1000 nm, more preferably 5 nm to 500 nm, and further preferably 20 nm to 200 nm.

  The organic thin film may contain the polymer compound alone or in combination of two or more. Moreover, in order to improve the hole transport property of the organic thin film, a low molecular compound and / or a high molecular compound other than the high molecular compound can be mixed and used as the electron donating compound in the organic thin film.

  Examples of the electron-donating compound that the organic thin film may contain in addition to the polymer compound of the present invention include, for example, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophene and its derivatives, polyvinylcarbazole and its Derivatives, polysilanes and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof Is mentioned.

Examples of the electron-accepting compound include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinones and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, and fluorenone derivatives. , diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, 8-hydroxyquinoline and metal complexes of derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and its derivatives, polyfluorene and its derivatives, fullerene and derivatives thereof such as C _60, carbon nanotube And phenanthroline derivatives such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, and fullerene and derivatives thereof are particularly preferable.

  The electron-donating compound and the electron-accepting compound are relatively determined from the energy levels of these compounds.

Fullerenes and derivatives thereof include C ₆₀ , C ₇₀ , C ₈₄ and derivatives thereof.
A fullerene derivative represents a compound in which at least a part of fullerene is modified.

（Ｉ） （ＩＩ） （ＩＩＩ） （ＩＶ）
（式（Ｉ）〜（ＩＶ）中、Ｒ^ａは、アルキル基、アリール基、ヘテロアリール基又はエステル構造を有する基である。複数個あるＲ^ａは、同一であっても相異なってもよい。Ｒ^ｂはアルキル基又はアリール基を表す。複数個あるＲ^ｂは、同一であっても相異なってもよい。） Examples of the fullerene derivative include a compound represented by the formula (I), a compound represented by the formula (II), a compound represented by the formula (III), and a compound represented by the formula (IV).

(I) (II) (III) (IV)
(In formulas (I) to (IV), R ^a is an alkyl group, aryl group, heteroaryl group or group having an ester structure. A plurality of R ^a may be the same or different. R ^b represents an alkyl group or an aryl group, and a plurality of R ^b may be the same or different.)

The definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R ^a and R ^b are the same as the definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R.

（Ｖ）
（式（Ｖ）中、ｕ１は、１〜６の整数を表す、ｕ２は、０〜６の整数を表す、Ｒ^ｃは、アルキル基、アリール基又はヘテロアリール基を表す。） Examples of the group having an ester structure represented by ^Ra include a group represented by the formula (V).

(V)
(In formula (V), u1 represents an integer of 1 to 6, u2 represents an integer of 0 to 6, and R ^c represents an alkyl group, an aryl group, or a heteroaryl group.)

The definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R ^c are the same as the definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R.

Specific examples of the C ₆₀ derivative include the following.

Specific examples of the C ₇₀ derivative include the following.

<Method for producing organic thin film>
The organic thin film may be produced by any method. For example, the organic thin film may be produced by a film formation method from a solution containing the polymer compound of the present invention, or an organic thin film may be formed by a vacuum deposition method. Good. Examples of the method for producing an organic thin film by film formation from a solution include a method of producing an organic thin film by applying the solution on one electrode and then evaporating the solvent.

  The solvent used for film formation from a solution is not particularly limited as long as it dissolves the polymer compound of the present invention. Examples of the solvent include unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane. Halogenated saturated hydrocarbon solvents such as dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, and halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene Examples of the solvent include ether solvents such as tetrahydrofuran and tetrahydropyran. The polymer compound of the present invention can usually be dissolved in the solvent in an amount of 0.1% by weight or more.

  For film formation from solution, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic method Coating methods such as a printing method, an offset printing method, an ink jet printing method, a dispenser printing method, a nozzle coating method, a capillary coating method can be used, and a spin coating method, a flexographic printing method, an ink jet printing method, and a dispenser printing method are preferable.

<Application of device>
By irradiating light such as sunlight from a transparent or translucent electrode, the organic photoelectric conversion element generates a photovoltaic force between the electrodes and can be operated as an organic thin film solar cell. It can also be used as an organic thin film solar cell module by integrating a plurality of organic thin film solar cells.

  In addition, by applying light from a transparent or translucent electrode in a state where a voltage is applied between the electrodes, a photocurrent flows and it can be operated as an organic photosensor. It can also be used as an organic image sensor by integrating a plurality of organic photosensors.

<Organic transistor>
The organic thin film transistor of the present invention includes a source electrode, a drain electrode, an organic semiconductor layer, and a gate electrode. The organic semiconductor layer is represented by the repeating unit represented by the formula (A) and the formula (B). A polymer compound containing a repeating unit or a polymer compound containing a repeating unit represented by formula (1).

  Since the polymer compound of the present invention has high charge mobility, the organic thin film transistor having the organic semiconductor layer containing the polymer compound of the present invention has high field effect mobility.

  Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.

  The polystyrene equivalent weight average molecular weight of the polymer compound was determined by size exclusion chromatography (SEC).

  Column: TOSOH TSKgel SuperHM-H (2) + TSKgel SuperH2000 (4.6 mm I.d. x 15 cm); Detector: RI (SHIMADZU RID-10A); Mobile phase: Tetrahydrofuran (THF)

フラスコ内の気体をアルゴンで置換した２００ｍＬ四つ口フラスコに、WO2011/052709A1に記載の方法で合成した化合物１を２．００ｇ（９．６０ｍｍｏｌ）と脱水ＴＨＦ（テトラヒドロフラン）を６０ｍＬ入れて均一な溶液とした。フラスコを−２０℃に保ちながら、反応液に２．８８Ｍの３−メチルブチルマグネシウムブロマイドのジエチルエーテル溶液を１０．０ｍＬ（２８．８ｍｍｏｌ）加えた。その後、３０分かけて温度を−５℃まで上げ、そのままの温度で反応液を３０分攪拌した。その後、１０分かけて温度を０℃に上げ、そのままの温度で反応液を１．５時間攪拌した。その後、反応液に水を加えて反応を停止し、さらに酢酸エチルを加え、反応生成物を含む有機層を抽出した。酢酸エチル溶液である有機層を硫酸ナトリウムで乾燥し、有機層をろ過後、ろ液の溶媒を留去し、化合物２を３．１７ｇ（８．９９ｍｍｏｌ）得た。 Reference example 1
(Synthesis of Compound 2)

A homogeneous solution containing 2.00 g (9.60 mmol) of Compound 1 synthesized by the method described in WO2011 / 052709A1 and 60 mL of dehydrated THF (tetrahydrofuran) in a 200 mL four-necked flask in which the gas in the flask is replaced with argon. It was. While maintaining the flask at −20 ° C., 10.0 mL (28.8 mmol) of 2.88 M 3-methylbutylmagnesium bromide in diethyl ether was added to the reaction solution. Thereafter, the temperature was raised to −5 ° C. over 30 minutes, and the reaction solution was stirred at the same temperature for 30 minutes. Thereafter, the temperature was raised to 0 ° C. over 10 minutes, and the reaction solution was stirred at the same temperature for 1.5 hours. Thereafter, water was added to the reaction solution to stop the reaction, and ethyl acetate was further added to extract an organic layer containing the reaction product. The organic layer, which is an ethyl acetate solution, was dried over sodium sulfate, and the organic layer was filtered, and then the solvent of the filtrate was distilled off to obtain 3.17 g (8.99 mmol) of Compound 2.

フラスコ内の気体をアルゴンで置換した３００ｍＬフラスコに、化合物２を３．１７ｇ（８．９９ｍｍｏｌ）、トルエンを９０ｍＬ入れて均一な溶液とした。該溶液にｐ−トルエンスルホン酸ナトリウム１水和物を３１０ｍｇ（１．６３ｍｍｏｌ）入れて１２０℃で３時間攪拌を行った。反応液を室温（２５℃）まで冷却後、水５０ｍＬを加え、さらにトルエンを加えて反応生成物を含む有機層を抽出した。トルエン溶液である有機層を硫酸ナトリウムで乾燥し、有機層をろ過後、溶媒を留去した。得られた粗生成物を、展開溶媒がヘキサンであるシリカゲルカラムで生成し、化合物３を３．２１ｇ（９．５９ｍｍｏｌ）得た。 Reference example 2
(Synthesis of Compound 3)

A 300 mL flask in which the gas in the flask was replaced with argon was charged with 3.17 g (8.99 mmol) of Compound 2 and 90 mL of toluene to obtain a uniform solution. To the solution, 310 mg (1.63 mmol) of sodium p-toluenesulfonate monohydrate was added and stirred at 120 ° C. for 3 hours. After cooling the reaction solution to room temperature (25 ° C.), 50 mL of water was added, and toluene was further added to extract the organic layer containing the reaction product. The organic layer which is a toluene solution was dried with sodium sulfate, the organic layer was filtered, and then the solvent was distilled off. The obtained crude product was produced on a silica gel column whose developing solvent was hexane, and 3.21 g (9.59 mmol) of Compound 3 was obtained.

¹ H NMR (CDCl ₃ ): δ 0.83 (d, 6H), 0.85 (d, 6H), 1.18 (m, 2H), 1.27 (m, 2H), 1.44 (m, 2H), 1.87 (m, 4H) , 6.68 (d, 1H), 6.69 (d, 1H), 6.97 (d, 1H), 7.03 (d, 1H).

フラスコ内の気体をアルゴンで置換した３００ｍＬフラスコに、化合物３を１．５２ｇ(４．５４ ｍｍｏｌ)、脱水ＴＨＦを８０ｍＬ入れて均一な溶液とした。該溶液を−７８℃に保ち、該溶液に１．６Ｍのｎ−ブチルリチウムのヘキサン溶液７．０６ｍＬ（１１．３ｍｍｏｌ）を１０分かけて滴下した。滴下後、反応液を−７８℃で３０分攪拌し、次いで、室温（２５℃）で２．５時間攪拌した。その後、フラスコを−７８℃に冷却し、反応液にトリブチルスズクロリドを３．９７ｇ（１２．２ｍｍｏｌ）加えた。添加後、反応液を−７８℃で３０分攪拌し、次いで、室温（２５℃）で３時間攪拌した。その後、反応液に水１００ｍｌを加えて反応を停止し、酢酸エチルを加えて反応生成物を含む有機層を抽出した。酢酸エチル溶液である有機層を硫酸ナトリウムで乾燥し、有機層をろ過後、ろ液をエバポレーターで濃縮し、溶媒を留去した。得られたオイル状の物質を展開溶媒がヘキサンであるシリカゲルカラムで精製した。シリカゲルカラムのシリカゲルには、あらかじめ５ｗｔ％のトリエチルアミンを含むヘキサンに５分間浸し、その後、ヘキサンで濯いだシリカゲルを用いた。精製後、化合物４を３．７７ｇ（４．１３ｍｍｏｌ）得た。 Reference example 3
(Synthesis of Compound 4)

A 300 mL flask in which the gas in the flask was replaced with argon was charged with 1.52 g (4.54 mmol) of Compound 3 and 80 mL of dehydrated THF to obtain a uniform solution. The solution was kept at −78 ° C., and 7.06 mL (11.3 mmol) of 1.6M n-butyllithium in hexane was added dropwise to the solution over 10 minutes. After the dropping, the reaction solution was stirred at −78 ° C. for 30 minutes, and then stirred at room temperature (25 ° C.) for 2.5 hours. Thereafter, the flask was cooled to −78 ° C., and 3.97 g (12.2 mmol) of tributyltin chloride was added to the reaction solution. After the addition, the reaction solution was stirred at −78 ° C. for 30 minutes, and then stirred at room temperature (25 ° C.) for 3 hours. Thereafter, 100 ml of water was added to the reaction solution to stop the reaction, and ethyl acetate was added to extract an organic layer containing the reaction product. The organic layer, which is an ethyl acetate solution, was dried over sodium sulfate, the organic layer was filtered, the filtrate was concentrated with an evaporator, and the solvent was distilled off. The obtained oily substance was purified by a silica gel column whose developing solvent was hexane. As the silica gel of the silica gel column, silica gel previously immersed in hexane containing 5 wt% triethylamine for 5 minutes and then rinsed with hexane was used. After purification, 3.77 g (4.13 mmol) of compound 4 was obtained.

¹ H NMR (CDCl ₃ ): δ 0.82 (d, 6H), 0.84 (d, 6H), 0.89 (t, 18H), 0.98-1.62 (m, 42H), 1.88 (m, 4H), 6.68 (s, 1H), 6.71 (s, 1H).

窒素気流雰囲気下ジムロートを取付けた500ml３口フラスコに化合物５（10.2g、59.2mmol）、氷酢酸100mllを室温下にて仕込、溶解攪拌した。同温度で臭素18mlを滴下した後、７０℃にて１６時間加熱攪拌した。冷却後反応液を800mlの氷冷水に注ぎ、攪拌しながら亜硫酸ナトリウムを臭素色が消えるまで加えた。１５分間攪拌した後得られた結晶をろ取し、結晶を水50mlずつ用いて２回洗浄した。結晶を水で再結晶し、60℃、10mmHgにて恒量になるまで減圧乾燥することで化合物６を8.0g（24.2mmol、収率40.9%）得た。
¹Ｈ−ＮＭＲ（２７０ＭＨｚ／ＤＭＳＯ-d6）：
δ１３．７（brs、２Ｈ） Reference example 4
(Synthesis of Compound 6)

Compound 5 (10.2 g, 59.2 mmol) and 100 ml of glacial acetic acid were charged at room temperature in a 500 ml three-necked flask equipped with a Dimroth in a nitrogen stream atmosphere and dissolved and stirred. After 18 ml of bromine was added dropwise at the same temperature, the mixture was heated and stirred at 70 ° C. for 16 hours. After cooling, the reaction solution was poured into 800 ml of ice-cold water, and sodium sulfite was added with stirring until the bromine color disappeared. The crystals obtained after stirring for 15 minutes were collected by filtration, and the crystals were washed twice with 50 ml of water. The crystals were recrystallized from water and dried under reduced pressure at 60 ° C. and 10 mmHg to a constant weight to obtain 8.0 g (24.2 mmol, yield 40.9%) of Compound 6.
¹ H-NMR (270 MHz / DMSO-d6):
δ 13.7 (brs, 2H)

窒素気流雰囲気下ジムロートを取付けた200ml３口フラスコに化合物６（3.0g、9.1mmol）、トルエン150ml、Ｎ、N-ジメチルホルムアミド1滴を室温下にて仕込み、オギザリルクロリド（3.18ml、36mmol）を滴下した。発泡に気をつけながら１時間加熱還流した。還流後室温まで下げ、反応液をエバポレータにて濃縮することで化合物７の粗体を3.33g得た（収率99.7%）。本粗体はそのまま化合物１１の合成に使用した。 Reference Example 5
(Synthesis of Compound 7)

Into a 200 ml three-necked flask equipped with a Dimroth in a nitrogen atmosphere, compound 6 (3.0 g, 9.1 mmol), 150 ml of toluene, and 1 drop of N, N-dimethylformamide are charged at room temperature, and oxalyl chloride (3.18 ml, 36 mmol) is added. It was dripped. The mixture was heated to reflux for 1 hour while paying attention to foaming. After refluxing, the temperature was lowered to room temperature, and the reaction solution was concentrated with an evaporator to obtain 3.33 g of a crude product of Compound 7 (yield 99.7%). This crude product was directly used for the synthesis of Compound 11.

窒素気流雰囲気下ジムロートを取付けた500ml３口フラスコにヘキシルマグネシウムブロミド／ＴＨＦ1.0M溶液（142.9ml、143mmol）、無水ジエチルエーテル100mlを仕込み、ここにo-ジクロロベンゼン８（10.0g、68.0mmol）を20mlの無水ジエチルエーテルに溶解した液を室温下滴下した、滴下の最中にNiCl₂(dppp)（0.18g、0.33mmol）を断続的に加えていった後、１．５時間加熱還流下攪拌した。室温まで冷却後さらに８時間攪拌し、反応液を氷冷6M硫酸水200ml中にあけ、分液漏斗を用いてよく攪拌した後静置、分液した。有機層を飽和炭酸水素ナトリウム水溶液で中和後、無水硫酸マグネシウムで乾燥後エバポレータで濃縮、さらに5mmHg、180℃にて3時間減圧濃縮することで化合物９の粗体を得た。
これをシリカゲルカラムクロマトグラフィー（展開液n−ヘキサン）にて精製することで化合物９を14.4g（純度81.3%、47.5mmol）得た。
^１Ｈ−ＮＭＲ（２７０ＭＨｚ／ＣＤＣｌ₃）：
δ７．１７−７．０７（ｍ、４Ｈ）、２．５９(ｔ、４Ｈ）、１．６６−１．４９（ｍ、４Ｈ）、１．４９−１．２１（ｍ、１２Ｈ）、０．９２−０．８７（ｍ、６Ｈ） Reference Example 6
(Synthesis of Compound 9)

A 500 ml three-necked flask fitted with a Dimroth in a nitrogen stream atmosphere was charged with hexyl magnesium bromide / THF 1.0M solution (142.9 ml, 143 mmol) and 100 ml of anhydrous diethyl ether, and 20 ml of o-dichlorobenzene 8 (10.0 g, 68.0 mmol). A solution dissolved in anhydrous diethyl ether was added dropwise at room temperature. NiCl ₂ (dppp) (0.18 g, 0.33 mmol) was added intermittently during the dropwise addition, and the mixture was stirred for 1.5 hours with heating under reflux. . After cooling to room temperature, the mixture was further stirred for 8 hours. The reaction solution was poured into 200 ml of ice-cold 6M aqueous sulfuric acid, stirred well using a separatory funnel, allowed to stand, and then separated. The organic layer was neutralized with a saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, concentrated with an evaporator, and further concentrated under reduced pressure at 5 mmHg and 180 ° C. for 3 hours to obtain a crude product of Compound 9.
This was purified by silica gel column chromatography (developing solution n-hexane) to obtain 14.4 g (purity 81.3%, 47.5 mmol) of compound 9.
¹ H-NMR (270 MHz / CDCl ₃ ):
δ 7.17-7.07 (m, 4H), 2.59 (t, 4H), 1.66-1.49 (m, 4H), 1.49-1.21 (m, 12H), 0. 92-0.87 (m, 6H)

窒素気流雰囲気下ジムロートを取付けた500ml３口フラスコにマグネシウム（1.81g 、74.5mmol）、無水ＴＨＦ200mlを仕込み、注意深く３、７−ジメチルオクチルブロミド（15.0g、67.8mmol）を注加、加熱攪拌することでグリニア試薬を調製した。室温まで冷却後該グリニア試薬に無水ジエチルエーテル200mlを加え、o-ジクロロベンゼン８（4.75g、32.3mmol）を20mlの無水ジエチルエーテルに溶解した液を室温下滴下した、滴下の最中にNiCl₂(dppp)（0.09g、0.17mmol）を断続的に加えていった後、１．５時間加熱還流下攪拌した。室温まで冷却後さらに８時間攪拌し、反応液を氷冷6M硫酸水200ml中にあけ、分液漏斗を用いてよく攪拌した後静置、分液した。有機層を飽和炭酸水素ナトリウム水溶液で中和後、無水硫酸マグネシウムで乾燥後エバポレータで濃縮、さらに5mmHg、180℃にて3時間減圧濃縮することで化合物１０の粗体を得た。これをシリカゲルカラムクロマトグラフィー（展開液n−ヘキサン）にて精製することで化合物１０を7.41g（純度80.7%、16.7mmol）得た。
^１Ｈ−ＮＭＲ（２７０ＭＨｚ／ＣＤＣｌ₃）：
δ７．１５−７．０９（ｍ、４Ｈ）、２．６７−２．５３(ｍ、４Ｈ）、１．６１−１．１１（ｍ、２０Ｈ）、０．９６（ｄ、６Ｈ）、０．８７（ｄ、１２Ｈ） Reference Example 7
(Synthesis of Compound 10)

By charging magnesium (1.81 g, 74.5 mmol) and anhydrous THF 200 ml into a 500 ml three-necked flask equipped with a Dimroth in a nitrogen stream atmosphere, carefully adding 3,7-dimethyloctyl bromide (15.0 g, 67.8 mmol), and stirring with heating. A Grineer reagent was prepared. After cooling to room temperature, 200 ml of anhydrous diethyl ether was added to the Grineer reagent, and a solution of o-dichlorobenzene 8 (4.75 g, 32.3 mmol) dissolved in 20 ml of anhydrous diethyl ether was added dropwise at room temperature. During the addition, NiCl ₂ (dppp) (0.09 g, 0.17 mmol) was intermittently added, and then the mixture was stirred with heating under reflux for 1.5 hours. After cooling to room temperature, the mixture was further stirred for 8 hours. The reaction solution was poured into 200 ml of ice-cold 6M aqueous sulfuric acid, stirred well using a separatory funnel, allowed to stand, and then separated. The organic layer was neutralized with a saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, concentrated with an evaporator, and further concentrated under reduced pressure at 5 mmHg and 180 ° C. for 3 hours to obtain a crude compound 10. This was purified by silica gel column chromatography (developing solution n-hexane) to obtain 7.41 g (purity 80.7%, 16.7 mmol) of Compound 10.
¹ H-NMR (270 MHz / CDCl ₃ ):
δ 7.15-7.09 (m, 4H), 2.67-1.53 (m, 4H), 1.61-1.11 (m, 20H), 0.96 (d, 6H), 0. 87 (d, 12H)

窒素気流雰囲気下ジムロートを取付けた200ml３口フラスコに参考例５で得た化合物７の粗体（3.33g、9.1mmol）、無水ジクロロメタン100mlを加え攪拌、溶解する。0℃まで冷却後塩化アルミニウム（III）（4.80g、36.3mmol）をゆっくりと加え0℃で攪拌する。そこへ化合物９を3.83g（12.6mmol）を無水ジクロロメタン20mlに溶解した液を滴下しさらに3時間攪拌した。攪拌後氷水30ml中にあけ、クロロホルム50mlずつ用い２回抽出、有機層を水洗した後無水硫酸ナトリウムで乾燥後エバポレータで濃縮、得られた残渣をシリカゲルカラムクロマトグラフィー（展開液：ヘキサン／酢酸エチル＝１０／１（ｖ／ｖ））で精製後エタノールで２回再結晶を行い１１を1.6g（3.0mmol、収率33%）得た。
¹Ｈ−ＮＭＲ（２７０ＭＨｚ／ＣＤＣｌ₃）：
δ８．０５（ｓ、２Ｈ）、２．７４(ｔ、４Ｈ）、１．６９−１．５５（ｍ、４Ｈ）、１．５８−１．２５（ｍ、１２Ｈ）、０．９２−０．８８（ｍ、６Ｈ） Reference Example 8
(Synthesis of Compound 11)

In a 200 ml three-necked flask equipped with a Dimroth in a nitrogen stream atmosphere, add the crude compound 7 (3.33 g, 9.1 mmol) obtained in Reference Example 5 and 100 ml of anhydrous dichloromethane, and dissolve by stirring. After cooling to 0 ° C, aluminum (III) chloride (4.80 g, 36.3 mmol) is slowly added and stirred at 0 ° C. Thereto was added dropwise a solution prepared by dissolving 3.83 g (12.6 mmol) of compound 9 in 20 ml of anhydrous dichloromethane, and the mixture was further stirred for 3 hours. After stirring, the mixture was poured into 30 ml of ice water, extracted twice with 50 ml of chloroform, the organic layer was washed with water, dried over anhydrous sodium sulfate and concentrated with an evaporator. The resulting residue was subjected to silica gel column chromatography (developing solution: hexane / ethyl acetate = 10/1 (v / v)) and then recrystallized twice with ethanol to obtain 11 g of 11 (3.0 mmol, yield 33%).
¹ H-NMR (270 MHz / CDCl ₃ ):
δ 8.05 (s, 2H), 2.74 (t, 4H), 1.69-1.55 (m, 4H), 1.58-1.25 (m, 12H), 0.92-0. 88 (m, 6H)

窒素気流雰囲気下ジムロートを取付けた200ml３口フラスコに化合物６（3.8g、11.5mmol）を用い前記の参考例４の処方に従い得られた化合物７の粗体（4.10g、11.2mmol）、無水ジクロロメタン100mlを加え攪拌、溶解した。0℃まで冷却後塩化アルミニウム（III）（6.0g、45.0mmol）をゆっくりと加え0℃で攪拌した。そこへ化合物１０を 7.0g（15.8 mmol）を無水ジクロロメタン20mlに溶解した液を滴下しさらに3時間攪拌した。攪拌後氷水30ml中にあけ、クロロホルム50mlずつ用い２回抽出、有機層を水洗した後無水硫酸ナトリウムで乾燥後エバポレータで濃縮、得られた残渣をシリカゲルカラムクロマトグラフィー（展開液：ヘキサン／酢酸エチル＝１０／１（ｖ／ｖ））で精製後エタノールで２回再結晶を行い化合物１２を2.3g（3.5mmol、収率31.3%）得た。
¹Ｈ−ＮＭＲ（２７０ＭＨｚ／ＣＤＣｌ₃）：
δ８．０５（ｓ、２Ｈ）、２．８３−２．６４(ｍ、４Ｈ）、１．６８−０．９４（ｍ、２０Ｈ）、０．９８（ｄ、６Ｈ）、０．８７（ｄ、１２Ｈ） Reference Example 9
(Synthesis of Compound 12)

Compound 7 (4.10 g, 11.2 mmol) obtained in accordance with the prescription in Reference Example 4 above using Compound 6 (3.8 g, 11.5 mmol) in a 200 ml three-necked flask fitted with a Dimroth in a nitrogen atmosphere, 100 ml of anhydrous dichloromethane Was added and stirred and dissolved. After cooling to 0 ° C., aluminum (III) chloride (6.0 g, 45.0 mmol) was slowly added and stirred at 0 ° C. Thereto was added dropwise a solution prepared by dissolving 7.0 g (15.8 mmol) of Compound 10 in 20 ml of anhydrous dichloromethane, and the mixture was further stirred for 3 hours. After stirring, the mixture was poured into 30 ml of ice water, extracted twice with 50 ml of chloroform, the organic layer was washed with water, dried over anhydrous sodium sulfate and concentrated with an evaporator. The resulting residue was subjected to silica gel column chromatography (developing solution: hexane / ethyl acetate = 10/1 (v / v)) and then recrystallized twice with ethanol to obtain 2.3 g (3.5 mmol, 31.3% yield) of Compound 12.
¹ H-NMR (270 MHz / CDCl ₃ ):
δ 8.05 (s, 2H), 2.83-2.64 (m, 4H), 1.68-0.94 (m, 20H), 0.98 (d, 6H), 0.87 (d, 12H)

Reference Example 11
(Synthesis of Compound 2)

  In a 200 mL flask, 1.83 g (5.0 mmol) of Compound 7 and 50 mL of dehydrated dichloromethane were placed and cooled to 0 ° C. Thereto was slowly added 2.67 g (20 mmol) of aluminum chloride, and the mixture was stirred at 0 ° C. for 30 minutes. Thereto, 20 mL of a dichloromethane solution of 0.89 g (5.3 mmol) of hexylbenzene was slowly added dropwise with a dropping funnel and stirred at that temperature for 1 hour. The mixture was warmed to room temperature and further stirred for 2 hours. Then, water was added, the aqueous layer was neutralized with an aqueous sodium hydrogen carbonate solution, the organic layer was extracted with chloroform, and the organic layer was washed 3 times with 50 mL of water. The obtained organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography (developing solvent hexane: chloroform: ethyl acetate = 200: 80: 5, Rf = 0.41), and 1.03 g (2.25 mmol, 45%) of Compound 17 was obtained.

¹ H NMR (CDCl ₃ ): δ 0.88 (t, 3H), 1.32-1.73 (m, 8H), 2.78 (t, 2H), 7.60 (d, 1H), 8.10 (s, 1H), 8.21 (d, 1H).

窒素で置換した200ｍＬフラスコ内に、化合物７を1.83 g (5.0 mmol)、脱水ジクロロメタンを50 mL入れ、0℃に冷却した。そこに塩化アルミニウム 2.67 g (20 mmol)をゆっくり加え、0℃で30分間攪拌した。そこに、1,2-ジフルオロベンゼン 0.56 g (5.3 mmol)のジクロロメタン溶液20 mLを滴下ロートでゆっくりと滴下し、1時間その温度で攪拌した。室温まで昇温させ1時間攪拌した後に、加熱還流下で10時間攪拌を続けた。その後、水を加え、炭酸水素ナトリウム水溶液で水層を中和し、有機層をクロロホルムで抽出し、有機層を水50 mLで3回洗浄した。得られた有機層を無水硫酸マグネシウムで乾燥した後に、ろ過し、減圧下で溶媒を留去した。得られた粗生物をシリカゲルカラムクロマトグラフィーで精製し（展開溶媒 クロロホルム）、クロロホルム/ヘキサン混合溶媒で再結晶を行うことにより目的物１８を0.86 g（2.1 mmol, 45%）得た。 Reference Example 12
(Synthesis of Compound 3)

In a 200 mL flask substituted with nitrogen, 1.83 g (5.0 mmol) of Compound 7 and 50 mL of dehydrated dichloromethane were placed and cooled to 0 ° C. Thereto was slowly added 2.67 g (20 mmol) of aluminum chloride, and the mixture was stirred at 0 ° C. for 30 minutes. Thereto, 20 mL of a dichloromethane solution of 0.56 g (5.3 mmol) of 1,2-difluorobenzene was slowly dropped with a dropping funnel and stirred at that temperature for 1 hour. After raising the temperature to room temperature and stirring for 1 hour, stirring was continued for 10 hours under heating to reflux. Then, water was added, the aqueous layer was neutralized with an aqueous sodium hydrogen carbonate solution, the organic layer was extracted with chloroform, and the organic layer was washed 3 times with 50 mL of water. The obtained organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography (developing solvent: chloroform) and recrystallized with a chloroform / hexane mixed solvent to obtain 0.86 g (2.1 mmol, 45%) of the target product 18.

¹ H NMR (CDCl ₃ ): δ 8.09 (t, 2H).

フラスコ内の気体をアルゴンで置換した１００ｍＬフラスコに、化合物４を２７３ｍｇ（０．３００ｍｍｏｌ）、参考例８で合成した化合物１１を１６２ｍｇ（０．３００ｍｍｏｌ）、トリス(２−トリル)ホスフィンを８．２ｍｇ（０．０２７ｍｍｏｌ）、脱水トルエン２３ｍｌを入れて均一溶液とした。得られたトルエン溶液を、アルゴンで３０分バブリングした。その後、トルエン溶液に、トリス（ジベンジリデンアセトン）ジパラジウムを４．１ｍｇ（０．００４５ｍｍｏｌ）加え、１０５℃で３時間攪拌した後にさらに１２０℃で３時間攪拌した。その後、反応液にフェニルブロミドを３７０ｍｇ加え、さらに２時間攪拌した。その後、フラスコを室温までに冷却し、反応液をメタノール２００ｍＬと濃塩酸２０ｍＬの混合溶液に注いだ。析出したポリマーをろ過して回収し、得られたポリマーを、円筒ろ紙に入れ、ソックスレー抽出器を用いて、メタノール、アセトン及びヘキサンでそれぞれ３時間洗浄した。円筒ろ紙内に残ったポリマーを、トルエン１５ｍＬに溶解させ、ジエチルジチオカルバミン酸ナトリウム０．２５ｇと水３．０ｍＬを加え、９０℃で３時間攪拌を行った。水層を除去後、有機層を水５０ｍｌで２回洗浄し、次いで、３ｗｔ%の酢酸水溶液５０ｍＬで２回洗浄し、次いで、水５０ｍＬで２回洗浄し、得られた溶液をメタノールに注いでポリマーを析出させた。ポリマーをろ過後、乾燥し、得られたポリマーをトルエン１１ｍＬに再度溶解し、アルミナ／シリカゲルカラムを通した。得られた溶液をメタノールに注いでポリマーを析出させ、ポリマーをろ過後、乾燥し、精製された重合体１８９ｍｇを得た。以下、この重合体を高分子化合物Ａと呼称する。ＧＰＣで測定した高分子化合物Ａの分子量（ポリスチレン換算）はＭｗ＝６０１００、Ｍｎ＝２０３００であった。 Example 1
(Synthesis of polymer compound A)

In a 100 mL flask in which the gas in the flask was replaced with argon, 273 mg (0.300 mmol) of compound 4, 162 mg (0.300 mmol) of compound 11 synthesized in Reference Example 8, and 8.2 mg of tris (2-tolyl) phosphine (0.027 mmol) and 23 ml of dehydrated toluene were added to obtain a uniform solution. The resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 4.1 mg (0.0045 mmol) of tris (dibenzylideneacetone) dipalladium was added to the toluene solution, stirred at 105 ° C. for 3 hours, and further stirred at 120 ° C. for 3 hours. Thereafter, 370 mg of phenyl bromide was added to the reaction solution, and the mixture was further stirred for 2 hours. Thereafter, the flask was cooled to room temperature, and the reaction solution was poured into a mixed solution of 200 mL of methanol and 20 mL of concentrated hydrochloric acid. The precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol, acetone and hexane for 3 hours using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 15 mL of toluene, 0.25 g of sodium diethyldithiocarbamate and 3.0 mL of water were added, and the mixture was stirred at 90 ° C. for 3 hours. After removing the aqueous layer, the organic layer was washed twice with 50 ml of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution, then twice with 50 mL of water, and the resulting solution was poured into methanol. A polymer was precipitated. The polymer was filtered and dried, and the resulting polymer was dissolved again in 11 mL of toluene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 189 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound A. The molecular weight (polystyrene conversion) of the high molecular compound A measured by GPC was Mw = 60100 and Mn = 20300.

フラスコ内の気体をアルゴンで置換した１００ｍＬフラスコに、WO2011/052709A1に記載の方法で合成した化合物１３を３１６ｍｇ（０．３００ｍｍｏｌ）、化合物１１を１６２．１ｍｇ（０．３００ｍｍｏｌ）、トリス(２−トリル)ホスフィンを８．２ｍｇ（０．０２７ｍｍｏｌ）、脱水トルエン２５ｍｌを入れて均一溶液とした。得られたトルエン溶液を、アルゴンで３０分バブリングした。その後、トルエン溶液に、トリス（ジベンジリデンアセトン）ジパラジウムを４．１ｍｇ（０．００４５ｍｍｏｌ）加え、１０５℃で２時間攪拌した後にさらに１２０℃で４時間攪拌した。その後、反応液にフェニルブロミドを３７０ｍｇ加え、さらに２時間攪拌した。その後、フラスコを室温まで冷却し、反応液をメタノール２００ｍＬと濃塩酸２０ｍＬの混合溶液に注いだ。析出したポリマーをろ過して回収し、得られたポリマーを、円筒ろ紙に入れ、ソックスレー抽出器を用いて、メタノールおよびアセトンでそれぞれ３時間洗浄した。円筒ろ紙内に残ったポリマーを、トルエン１２ｍＬに溶解させ、ジエチルジチオカルバミン酸ナトリウム０．２６ｇと水３．０ｍＬを加え、９０℃で３時間攪拌を行った。水層を除去後、有機層を水５０ｍｌで２回洗浄し、次いで、３ｗｔ%の酢酸水溶液５０ｍＬで２回洗浄し、次いで、水５０ｍＬで２回洗浄し、得られた溶液をメタノールに注いでポリマーを析出させた。ポリマーをろ過後、乾燥し、得られたポリマーをトルエン１３ｍＬに再度溶解し、アルミナ／シリカゲルカラムを通した。得られた溶液をメタノールに注いでポリマーを析出させ、ポリマーをろ過後、乾燥し、精製された重合体２２１ｍｇを得た。以下、この重合体を高分子化合物Ｂと呼称する。ＧＰＣで測定した高分子化合物Ｂの分子量（ポリスチレン換算）はＭｗ＝４９２００、Ｍｎ＝１８６００であった。 Example 2
(Synthesis of polymer compound B)

In a 100 mL flask in which the gas in the flask was replaced with argon, 316 mg (0.300 mmol) of compound 13 synthesized by the method described in WO2011 / 052709A1, 162.1 mg (0.300 mmol) of compound 11, tris (2-tolyl) ) 8.2 mg (0.027 mmol) of phosphine and 25 ml of dehydrated toluene were added to obtain a uniform solution. The resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 4.1 mg (0.0045 mmol) of tris (dibenzylideneacetone) dipalladium was added to the toluene solution, stirred at 105 ° C. for 2 hours, and further stirred at 120 ° C. for 4 hours. Thereafter, 370 mg of phenyl bromide was added to the reaction solution, and the mixture was further stirred for 2 hours. Thereafter, the flask was cooled to room temperature, and the reaction solution was poured into a mixed solution of 200 mL of methanol and 20 mL of concentrated hydrochloric acid. The precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol and acetone for 3 hours using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 12 mL of toluene, 0.26 g of sodium diethyldithiocarbamate and 3.0 mL of water were added, and the mixture was stirred at 90 ° C. for 3 hours. After removing the aqueous layer, the organic layer was washed twice with 50 ml of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution, then twice with 50 mL of water, and the resulting solution was poured into methanol. A polymer was precipitated. The polymer was filtered and dried, and the resulting polymer was dissolved again in 13 mL of toluene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 221 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound B. The molecular weight (polystyrene conversion) of the high molecular compound B measured by GPC was Mw = 49200 and Mn = 18600.

フラスコ内の気体をアルゴンで置換した１００ｍＬフラスコに、化合物１３を１５８ｍｇ（０．１５０ｍｍｏｌ）、WO2011/052709A1に記載の方法で合成した化合物を出発原料に、化合物１４を１７８ｍｇ（０．１５０ｍｍｏｌ）、化合物１１を１６２ｍｇ（０．３００ｍｍｏｌ）、トリス(２−トリル)ホスフィンを８．２ｍｇ（０．０２７ｍｍｏｌ）、脱水トルエン２６ｍｌを入れて均一溶液とした。得られたトルエン溶液を、アルゴンで３０分バブリングした。その後、トルエン溶液にトリス（ジベンジリデンアセトン）ジパラジウムを４．１ｍｇ（０．００４５ｍｍｏｌ）加え、１０５℃で２時間攪拌した後にさらに１２０℃で４時間攪拌した。その後、反応液にフェニルブロミドを３７０ｍｇ加え、さらに２時間攪拌した。その後、フラスコを室温まで冷却し、反応液をメタノール２００ｍＬと濃塩酸２０ｍＬの混合溶液に注いだ。析出したポリマーをろ過して回収し、得られたポリマーを、円筒ろ紙に入れ、ソックスレー抽出器を用いて、メタノールおよびアセトンでそれぞれ３時間洗浄した。円筒ろ紙内に残ったポリマーを、トルエン１５ｍＬに溶解させ、ジエチルジチオカルバミン酸ナトリウム０．２６ｇと水３．０ｍＬを加え、９０℃で３時間攪拌を行った。水層を除去後、有機層を水５０ｍｌで２回洗浄し、次いで、３ｗｔ%の酢酸水溶液５０ｍＬで２回洗浄し、次いで、水５０ｍＬで２回洗浄し、得られた溶液をメタノールに注いでポリマーを析出させた。ポリマーをろ過後、乾燥し、得られたポリマーをトルエン１３ｍＬに再度溶解し、アルミナ／シリカゲルカラムを通した。得られた溶液をメタノールに注いでポリマーを析出させ、ポリマーをろ過後、乾燥し、精製された重合体２３３ｍｇを得た。以下、この重合体を高分子化合物Ｃと呼称する。ＧＰＣで測定した高分子化合物Ｃの分子量（ポリスチレン換算）はＭｗ＝４０５００、Ｍｎ＝１７６００であった。高分子化合物Ｃは、単量体の仕込み比から、上記式においてｎ＝５０、ｍ＝５０のモル比率を有する高分子化合物と推定される。 Example 3
(Synthesis of polymer compound C)

In a 100 mL flask in which the gas in the flask was replaced with argon, 158 mg (0.150 mmol) of compound 13 and 178 mg (0.150 mmol) of compound 14 as a starting material were synthesized from the compound synthesized by the method described in WO2011 / 052709A1. No. 11 (162 mg, 0.300 mmol), tris (2-tolyl) phosphine (8.2 mg, 0.027 mmol), and dehydrated toluene (26 ml) were added to obtain a homogeneous solution. The resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 4.1 mg (0.0045 mmol) of tris (dibenzylideneacetone) dipalladium was added to the toluene solution, stirred at 105 ° C. for 2 hours, and further stirred at 120 ° C. for 4 hours. Thereafter, 370 mg of phenyl bromide was added to the reaction solution, and the mixture was further stirred for 2 hours. Thereafter, the flask was cooled to room temperature, and the reaction solution was poured into a mixed solution of 200 mL of methanol and 20 mL of concentrated hydrochloric acid. The precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol and acetone for 3 hours using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 15 mL of toluene, 0.26 g of sodium diethyldithiocarbamate and 3.0 mL of water were added, and the mixture was stirred at 90 ° C. for 3 hours. After removing the aqueous layer, the organic layer was washed twice with 50 ml of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution, then twice with 50 mL of water, and the resulting solution was poured into methanol. A polymer was precipitated. The polymer was filtered and dried, and the resulting polymer was dissolved again in 13 mL of toluene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 233 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound C. The molecular weight (polystyrene conversion) of the high molecular compound C measured by GPC was Mw = 40500 and Mn = 17600. From the monomer charge ratio, polymer compound C is estimated to be a polymer compound having a molar ratio of n = 50 and m = 50 in the above formula.

フラスコ内の気体をアルゴンで置換した１００ｍＬフラスコに、化合物１から化合物４を合成する方法と同様の方法を用いて合成した化合物１５を２９９ｍｇ（０．３００ｍｍｏｌ）、化合物１１を１６２ｍｇ（０．３００ｍｍｏｌ）、トリス(２−トリル)ホスフィンを８．２ｍｇ（０．０２７ｍｍｏｌ）、脱水トルエン２４ｍｌを入れて均一溶液とした。得られたトルエン溶液を、アルゴンで３０分バブリングした。その後、トルエン溶液に、トリス（ジベンジリデンアセトン）ジパラジウムを４．１ｍｇ（０．００４５ｍｍｏｌ）加え、１０５℃で２．５時間攪拌した後にさらに１２０℃で２時間攪拌した。その後、反応液にフェニルブロミドを１３０ｍｇ加え、さらに１．５時間攪拌した。その後、フラスコを室温までに冷却し、反応液をメタノール２００ｍＬと濃塩酸２０ｍＬの混合溶液に注いだ。析出したポリマーをろ過して回収し、得られたポリマーを、円筒ろ紙に入れ、ソックスレー抽出器を用いて、メタノール、アセトンでそれぞれ３時間洗浄した。円筒ろ紙内に残ったポリマーを、トルエン１２ｍＬに溶解させ、ジエチルジチオカルバミン酸ナトリウム０．２５ｇと水３．０ｍＬを加え、９０℃で３時間攪拌を行った。水層を除去後、有機層を水５０ｍｌで２回洗浄し、次いで、３ｗｔ%の酢酸水溶液５０ｍＬで２回洗浄し、次いで、水５０ｍＬで２回洗浄し、得られた溶液をメタノールに注いでポリマーを析出させた。ポリマーをろ過後、乾燥し、得られたポリマーをトルエン１１ｍＬに再度溶解し、アルミナ／シリカゲルカラムを通した。得られた溶液をメタノールに注いでポリマーを析出させ、ポリマーをろ過後、乾燥し、精製された重合体１７６ｍｇを得た。以下、この重合体を高分子化合物Dと呼称する。ＧＰＣで測定した高分子化合物Dの分子量（ポリスチレン換算）はＭｗ＝４５１００、Ｍｎ＝１７６００であった。 Example 4
(Synthesis of polymer compound D)

In a 100 mL flask in which the gas in the flask was replaced with argon, 299 mg (0.300 mmol) of compound 15 synthesized using the same method as the method of synthesizing compound 4 from compound 1 and 162 mg (0.300 mmol) of compound 11 were synthesized. Then, 8.2 mg (0.027 mmol) of tris (2-tolyl) phosphine and 24 ml of dehydrated toluene were added to obtain a uniform solution. The resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 4.1 mg (0.0045 mmol) of tris (dibenzylideneacetone) dipalladium was added to the toluene solution, stirred at 105 ° C. for 2.5 hours, and further stirred at 120 ° C. for 2 hours. Thereafter, 130 mg of phenyl bromide was added to the reaction solution, and the mixture was further stirred for 1.5 hours. Thereafter, the flask was cooled to room temperature, and the reaction solution was poured into a mixed solution of 200 mL of methanol and 20 mL of concentrated hydrochloric acid. The precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol and acetone for 3 hours using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 12 mL of toluene, 0.25 g of sodium diethyldithiocarbamate and 3.0 mL of water were added, and the mixture was stirred at 90 ° C. for 3 hours. After removing the aqueous layer, the organic layer was washed twice with 50 ml of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution, then twice with 50 mL of water, and the resulting solution was poured into methanol. A polymer was precipitated. The polymer was filtered and dried, and the resulting polymer was dissolved again in 11 mL of toluene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 176 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound D. The molecular weight (polystyrene conversion) of the high molecular compound D measured by GPC was Mw = 45100 and Mn = 17600.

フラスコ内の気体をアルゴンで置換した１００ｍＬフラスコに、化合物４を２７３ｍｇ（０．３００ｍｍｏｌ）、化合物１２を１９６ｍｇ（０．３００ｍｍｏｌ）、トリス(２−トリル)ホスフィンを８．２ｍｇ（０．０２７ｍｍｏｌ）、脱水トルエン２４ｍｌを入れて均一溶液とした。得られたトルエン溶液を、アルゴンで３０分バブリングした。その後、トルエン溶液に、トリス（ジベンジリデンアセトン）ジパラジウムを４．１ｍｇ（０．００４５ｍｍｏｌ）加え、１０５℃で４時間攪拌した後にさらに１２０℃で１時間攪拌した。その後、反応液にフェニルブロミドを１３０ｍｇ加え、さらに１．５時間攪拌した。その後、フラスコを室温までに冷却し、反応液をメタノール２００ｍＬと濃塩酸２０ｍＬの混合溶液に注いだ。析出したポリマーをろ過して回収し、得られたポリマーを、円筒ろ紙に入れ、ソックスレー抽出器を用いて、メタノール、アセトンでそれぞれ３時間洗浄した。円筒ろ紙内に残ったポリマーを、トルエン１２ｍＬに溶解させ、ジエチルジチオカルバミン酸ナトリウム０．２５ｇと水３．０ｍＬを加え、９０℃で２時間攪拌を行った。
水層を除去後、有機層を水５０ｍｌで２回洗浄し、次いで、３ｗｔ%の酢酸水溶液５０ｍＬで２回洗浄し、次いで、水５０ｍＬで２回洗浄し、得られた溶液をメタノールに注いでポリマーを析出させた。ポリマーをろ過後、乾燥し、得られたポリマーをトルエン１２ｍＬに再度溶解し、アルミナ／シリカゲルカラムを通した。得られた溶液をメタノールに注いでポリマーを析出させ、ポリマーをろ過後、乾燥し、精製された重合体１７８ｍｇを得た。以下、この重合体を高分子化合物Ｅと呼称する。ＧＰＣで測定した高分子化合物Ｅの分子量（ポリスチレン換算）はＭｗ＝５２６００、Ｍｎ＝２１１００であった。 Example 5
(Synthesis of polymer compound E)

In a 100 mL flask in which the gas in the flask was replaced with argon, 273 mg (0.300 mmol) of compound 4, 196 mg (0.300 mmol) of compound 12, 8.2 mg (0.027 mmol) of tris (2-tolyl) phosphine, 24 ml of dehydrated toluene was added to make a uniform solution. The resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 4.1 mg (0.0045 mmol) of tris (dibenzylideneacetone) dipalladium was added to the toluene solution, stirred at 105 ° C. for 4 hours, and further stirred at 120 ° C. for 1 hour. Thereafter, 130 mg of phenyl bromide was added to the reaction solution, and the mixture was further stirred for 1.5 hours. Thereafter, the flask was cooled to room temperature, and the reaction solution was poured into a mixed solution of 200 mL of methanol and 20 mL of concentrated hydrochloric acid. The precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol and acetone for 3 hours using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 12 mL of toluene, 0.25 g of sodium diethyldithiocarbamate and 3.0 mL of water were added, and the mixture was stirred at 90 ° C. for 2 hours.
After removing the aqueous layer, the organic layer was washed twice with 50 ml of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution, then twice with 50 mL of water, and the resulting solution was poured into methanol. A polymer was precipitated. The polymer was filtered and dried, and the resulting polymer was dissolved again in 12 mL of toluene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 178 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound E. The molecular weight (polystyrene conversion) of the high molecular compound E measured by GPC was Mw = 52600 and Mn = 21100.

フラスコ内の気体をアルゴンで置換した１００ｍＬフラスコに、化合物１から化合物４を合成する方法と同様の方法を用いて合成した化合物１６を３０２ｍｇ（０．３００ｍｍｏｌ）、化合物１２を１９６ｍｇ（０．３００ｍｍｏｌ）、トリス(２−トリル)ホスフィンを８．２ｍｇ（０．０２７ｍｍｏｌ）、脱水トルエン２６ｍｌを入れて均一溶液とした。得られたトルエン溶液を、アルゴンで３０分バブリングした。その後、トルエン溶液に、トリス（ジベンジリデンアセトン）ジパラジウムを４．１ｍｇ（０．００４５ｍｍｏｌ）加え、１０５℃で３時間攪拌した後にさらに１２０℃で１．５時間攪拌した。その後、反応液にフェニルブロミドを１３０ｍｇ加え、さらに１．５時間攪拌した。その後、フラスコを室温までに冷却し、反応液をメタノール２００ｍＬと濃塩酸２０ｍＬの混合溶液に注いだ。析出したポリマーをろ過して回収し、得られたポリマーを、円筒ろ紙に入れ、ソックスレー抽出器を用いて、メタノール、アセトンでそれぞれ３時間洗浄した。円筒ろ紙内に残ったポリマーを、トルエン１４ｍＬに溶解させ、ジエチルジチオカルバミン酸ナトリウム０．２５ｇと水３．０ｍＬを加え、９０℃で１．５時間攪拌を行った。水層を除去後、有機層を水５０ｍｌで２回洗浄し、次いで、３ｗｔ%の酢酸水溶液５０ｍＬで２回洗浄し、次いで、水５０ｍＬで２回洗浄し、得られた溶液をメタノールに注いでポリマーを析出させた。ポリマーをろ過後、乾燥し、得られたポリマーをトルエン１４ｍＬに再度溶解し、アルミナ／シリカゲルカラムを通した。得られた溶液をメタノールに注いでポリマーを析出させ、ポリマーをろ過後、乾燥し、精製された重合体２４４ｍｇを得た。以下、この重合体を高分子化合物Ｆと呼称する。ＧＰＣで測定した高分子化合物Ｆの分子量（ポリスチレン換算）はＭｗ＝１８２５００、Ｍｎ＝３２５００であった。 Example 6
(Synthesis of polymer compound F)

302 mg (0.300 mmol) of Compound 16 synthesized using the same method as the method of synthesizing Compound 4 from Compound 1 and 196 mg (0.300 mmol) of Compound 12 in a 100 mL flask in which the gas in the flask was replaced with argon Then, 8.2 mg (0.027 mmol) of tris (2-tolyl) phosphine and 26 ml of dehydrated toluene were added to obtain a uniform solution. The resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 4.1 mg (0.0045 mmol) of tris (dibenzylideneacetone) dipalladium was added to the toluene solution, stirred at 105 ° C. for 3 hours, and further stirred at 120 ° C. for 1.5 hours. Thereafter, 130 mg of phenyl bromide was added to the reaction solution, and the mixture was further stirred for 1.5 hours. Thereafter, the flask was cooled to room temperature, and the reaction solution was poured into a mixed solution of 200 mL of methanol and 20 mL of concentrated hydrochloric acid. The precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol and acetone for 3 hours using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 14 mL of toluene, 0.25 g of sodium diethyldithiocarbamate and 3.0 mL of water were added, and the mixture was stirred at 90 ° C. for 1.5 hours. After removing the aqueous layer, the organic layer was washed twice with 50 ml of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution, then twice with 50 mL of water, and the resulting solution was poured into methanol. A polymer was precipitated. The polymer was filtered and dried, and the resulting polymer was dissolved again in 14 mL of toluene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 244 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound F. The molecular weight (polystyrene conversion) of the high molecular compound F measured by GPC was Mw = 182500 and Mn = 32500.

フラスコ内の気体をアルゴンで置換した１００ｍＬフラスコに、化合物１から化合物４を合成する方法と同様の方法を用いて合成した化合物１６を１３４ｍｇ（０．１３３ｍｍｏｌ）、化合物１１を７１．６ｍｇ（０．１３３ｍｍｏｌ）、トリス(２−トリル)ホスフィンを３．６ｍｇ（０．０１２ｍｍｏｌ）、脱水トルエン１１ｍｌを入れて均一溶液とした。得られたトルエン溶液を、アルゴンで３０分バブリングした。その後、トルエン溶液に、トリス（ジベンジリデンアセトン）ジパラジウムを１．８ｍｇ（０．００２０ｍｍｏｌ）加え、１０５℃で３時間攪拌した後にさらに１２０℃で１．５時間攪拌した。その後、反応液にフェニルブロミドを１３０ｍｇ加え、さらに１．５時間攪拌した。その後、フラスコを室温までに冷却し、反応液をメタノール２００ｍＬと濃塩酸２０ｍＬの混合溶液に注いだ。析出したポリマーをろ過して回収し、得られたポリマーを、円筒ろ紙に入れ、ソックスレー抽出器を用いて、メタノール、アセトンおよびヘキサンでそれぞれ３時間洗浄した。円筒ろ紙内に残ったポリマーを、トルエン６ｍＬに溶解させ、ジエチルジチオカルバミン酸ナトリウム０．１１ｇと水１．０ｍＬを加え、９０℃で２．５時間攪拌を行った。水層を除去後、有機層を水５０ｍｌで２回洗浄し、次いで、３ｗｔ%の酢酸水溶液５０ｍＬで２回洗浄し、次いで、水５０ｍＬで２回洗浄し、得られた溶液をメタノールに注いでポリマーを析出させた。ポリマーをろ過後、乾燥し、得られたポリマーをトルエン５ｍＬに再度溶解し、アルミナ／シリカゲルカラムを通した。得られた溶液をメタノールに注いでポリマーを析出させ、ポリマーをろ過後、乾燥し、精製された重合体２４４ｍｇを得た。以下、この重合体を高分子化合物Ｇと呼称する。ＧＰＣで測定した高分子化合物Ｇの分子量（ポリスチレン換算）はＭｗ＝３１１７００、Ｍｎ＝３５１００であった。 Example 7
(Synthesis of polymer compound G)

In a 100 mL flask in which the gas in the flask was replaced with argon, 134 mg (0.133 mmol) of Compound 16 synthesized using the same method as the method of synthesizing Compound 4 from Compound 1 and 71.6 mg (0. 133 mmol), 3.6 mg (0.012 mmol) of tris (2-tolyl) phosphine, and 11 ml of dehydrated toluene were added to obtain a uniform solution. The resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 1.8 mg (0.0020 mmol) of tris (dibenzylideneacetone) dipalladium was added to the toluene solution, stirred at 105 ° C. for 3 hours, and further stirred at 120 ° C. for 1.5 hours. Thereafter, 130 mg of phenyl bromide was added to the reaction solution, and the mixture was further stirred for 1.5 hours. Thereafter, the flask was cooled to room temperature, and the reaction solution was poured into a mixed solution of 200 mL of methanol and 20 mL of concentrated hydrochloric acid. The precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol, acetone and hexane for 3 hours using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 6 mL of toluene, 0.11 g of sodium diethyldithiocarbamate and 1.0 mL of water were added, and the mixture was stirred at 90 ° C. for 2.5 hours. After removing the aqueous layer, the organic layer was washed twice with 50 ml of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution, then twice with 50 mL of water, and the resulting solution was poured into methanol. A polymer was precipitated. The polymer was filtered and dried, and the resulting polymer was dissolved again in 5 mL of toluene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 244 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound G. The molecular weight (polystyrene conversion) of the high molecular compound G measured by GPC was Mw = 311700 and Mn = 35100.

窒素雰囲気下、還流管を取り付けた１００ｍＬ三つ口フラスコに化合物４を１８２．５ｍｇ（０．２００ｍｍｏｌ）、化合物１７を９１．２ｍｇ（０．２００ｍｍｏｌ）、トリス(２−トリル)ホスフィンを５．８ｍｇ(９．０ｍｏｌ％)、脱水トルエンを１６ｍＬ入れ、均一溶液とした。３０分のアルゴンバブリング後、トリス（ジベンジリデンアセトン）ジパラジウムを２．８ｍｇ(１．５ｍｏｌ％)を加え、得られた溶液を１０５℃のオイルバスに浸して2時間加熱下で攪拌した。温度を１２０ ℃に上昇させ1時間攪拌した後に、再度トリス（ジベンジリデンアセトン）ジパラジウムを2.0mgとトリス(２−トリル)ホスフィンを４．０ｍｇ加え、２時間攪拌した。そこに末端封止材として、フェニルブロミドを３０ｍｇ加え、１．５時間加熱還流下で攪拌した。その後、フラスコを冷却し、反応液を１０ｗｔ％塩化水素メタノール溶液２００ｍＬに注いだ。析出したポリマーをろ過して回収し、得られたポリマーを、円筒ろ紙に入れ、ソックスレー抽出器を用いて、メタノール、アセトン、ヘキサンでそれぞれ３時間洗浄した。円筒ろ紙内に残ったポリマーを、オルトジクロロベンゼン９ｍＬに溶解させ、ジエチルジチオカルバミン酸ナトリウム０．１７ｇと水３．０ｍＬを加え、９０ ℃で2時間攪拌を行った。水層を除去後、有機層を水５０ｍＬで２回洗浄し、次いで、３ｗｔ％の酢酸水溶液５０ｍＬで２回洗浄し、次いで、水５０ｍＬで２回洗浄し、得られた溶液をメタノールに注いでポリマーを析出させた。ポリマーをろ過後、乾燥し、得られたポリマーをオルトジクロロベンゼン １０ｍＬに再度溶解させ、アルミナ／シリカゲルカラムに通した。得られた溶液をメタノールに注いでポリマーを析出させ、ポリマーをろ過後、乾燥し、精製された重合体を７３ mg得た。以下、この重合体を高分子化合物Ｋと呼称する。ＧＰＣで測定した高分子化合物Ｋの分子量（ポリスチレン換算）はＭｗ＝１６３００、Ｍｎ＝９６００であった。 Example 11
(Synthesis of polymer compound K)

Under a nitrogen atmosphere, 182.5 mg (0.200 mmol) of compound 4, 91.2 mg (0.200 mmol) of compound 17, and 5.8 mg of tris (2-tolyl) phosphine were placed in a 100 mL three-necked flask equipped with a reflux tube. (9.0 mol%) and 16 mL of dehydrated toluene were added to obtain a uniform solution. After 30 minutes of argon bubbling, 2.8 mg (1.5 mol%) of tris (dibenzylideneacetone) dipalladium was added, and the resulting solution was immersed in an oil bath at 105 ° C. and stirred for 2 hours while heating. After raising the temperature to 120 ° C. and stirring for 1 hour, 2.0 mg of tris (dibenzylideneacetone) dipalladium and 4.0 mg of tris (2-tolyl) phosphine were added again and stirred for 2 hours. Thereto, 30 mg of phenyl bromide was added as a terminal sealing material, and the mixture was stirred for 1.5 hours while heating under reflux. Thereafter, the flask was cooled, and the reaction solution was poured into 200 mL of a 10 wt% hydrogen chloride methanol solution. The precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol, acetone and hexane for 3 hours using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 9 mL of orthodichlorobenzene, 0.17 g of sodium diethyldithiocarbamate and 3.0 mL of water were added, and the mixture was stirred at 90 ° C. for 2 hours. After removing the aqueous layer, the organic layer was washed twice with 50 mL of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution, then twice with 50 mL of water, and the resulting solution was poured into methanol. A polymer was precipitated. The polymer was filtered and dried, and the obtained polymer was redissolved in 10 mL of orthodichlorobenzene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and then dried to obtain 73 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound K. The molecular weight (polystyrene conversion) of the high molecular compound K measured by GPC was Mw = 16300 and Mn = 9600.

窒素雰囲気下、還流管を取り付けた１００ｍＬ三つ口フラスコに化合物１３を２１０．６ｍｇ（０．２００ｍｍｏｌ）、化合物１８を８１．６ｍｇ（０．２００ｍｍｏｌ）、トリス(２−トリル)ホスフィンを５．６ｍｇ(９．０ｍｏｌ％)、脱水トルエンを１６ｍＬ (２．０ｗｔ％)入れ、均一溶液とした。３０分のアルゴンバブリング後、トリス（ジベンジリデンアセトン）ジパラジウムを５．６ｍｇ(１．５ｍｏｌ％)を加え、得られた溶液を１０５℃のオイルバスに浸して２時間加熱下で攪拌した。温度を１２０ ℃に上昇させ1時間攪拌した後に、再度トリス（ジベンジリデンアセトン）ジパラジウムを2.0mgとトリス(２−トリル)ホスフィンを４．０ｍｇ加え、２時間攪拌した。そこに末端封止材として、フェニルブロミドを３０ｍｇ加え、１．５時間加熱還流下で攪拌した。反応液を室温まで冷却後、１０ｗｔ％塩化水素メタノール溶液２００ｍＬに注ぎ、析出したポリマーをろ過して回収した。析出したポリマーをろ過して回収し、得られたポリマーを、円筒ろ紙に入れ、ソックスレー抽出器を用いて、メタノール、アセトン、ヘキサンでそれぞれ３時間洗浄した。円筒ろ紙内に残ったポリマーを、オルトジクロロベンゼン８．０ｍＬに溶解させ、ジエチルジチオカルバミン酸ナトリウム０．１７ｇと水３．０ｍＬを加え、９０ ℃で２時間攪拌を行った。水層を除去後、有機層を水５０ｍＬで２回洗浄し、次いで、３．０ｗｔ％の酢酸水溶液５０ｍＬで２回洗浄し、次いで、水５０ｍＬで２回洗浄し、得られた溶液をメタノールに注いでポリマーを析出させた。ポリマーをろ過後、乾燥し、得られたポリマーをオルトジクロロベンゼン ７．０ｍＬに再度溶解させ、アルミナ／シリカゲルカラムに通した。得られた溶液をメタノールに注いでポリマーを析出させ、ポリマーをろ過後、乾燥し、精製された重合体を８３ mgを得た。以下、この重合体を高分子化合物Ｌと呼称する。ＧＰＣで測定した高分子化合物Ｌの分子量（ポリスチレン換算）はＭｗ＝７５００、Ｍｎ＝２９５０であった。 Example 12
(Synthesis of polymer compound L)

Under a nitrogen atmosphere, 210.6 mg (0.200 mmol) of compound 13, 81.6 mg (0.200 mmol) of compound 18, and 5.6 mg of tris (2-tolyl) phosphine were placed in a 100 mL three-necked flask equipped with a reflux tube. (9.0 mol%) and 16 mL (2.0 wt%) dehydrated toluene were added to obtain a uniform solution. After argon bubbling for 30 minutes, 5.6 mg (1.5 mol%) of tris (dibenzylideneacetone) dipalladium was added, and the resulting solution was immersed in an oil bath at 105 ° C. and stirred for 2 hours while heating. After raising the temperature to 120 ° C. and stirring for 1 hour, 2.0 mg of tris (dibenzylideneacetone) dipalladium and 4.0 mg of tris (2-tolyl) phosphine were added again and stirred for 2 hours. Thereto, 30 mg of phenyl bromide was added as a terminal sealing material, and the mixture was stirred for 1.5 hours while heating under reflux. The reaction solution was cooled to room temperature, poured into 200 mL of a 10 wt% hydrogen chloride methanol solution, and the precipitated polymer was collected by filtration. The precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol, acetone and hexane for 3 hours using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 8.0 mL of orthodichlorobenzene, 0.17 g of sodium diethyldithiocarbamate and 3.0 mL of water were added, and the mixture was stirred at 90 ° C. for 2 hours. After removing the aqueous layer, the organic layer was washed twice with 50 mL of water, then twice with 50 mL of a 3.0 wt% aqueous acetic acid solution, then twice with 50 mL of water, and the resulting solution was taken up in methanol. The polymer was precipitated by pouring. The polymer was filtered and dried, and the obtained polymer was redissolved in 7.0 mL of orthodichlorobenzene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 83 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer compound L. The molecular weight (polystyrene conversion) of the high molecular compound L measured by GPC was Mw = 7500 and Mn = 2950.

フラスコ内の気体をアルゴンで置換した２Ｌ四つ口フラスコに、化合物（Ｈ）を７．９２８ｇ（１６．７２ｍｍｏｌ）、化合物（Ｉ）を１３．００ｇ（１７．６０ｍｍｏｌ）、トリオクチルメチルアンモニウムクロリド（商品名Ａｌｉｑｕａｔ３３６（登録商標）、アルドリッチ社製、CH₃N[(CH₂)₇CH₃]₃Cl、density 0.884g/ml、25℃）を４．９７９ｇ、及びトルエンを４０５ｍｌ入れ、撹拌しながら反応系内を３０分間アルゴンバブリングした。フラスコ内にジクロロビス（トリフェニルホスフィン）パラジウム（ＩＩ）を０．０２ｇ加え、１０５℃に昇温し、撹拌しながら２ｍｏｌ／Ｌの炭酸ナトリウム水溶液４２．２ｍｌを滴下した。滴下終了後５時間反応させ、その後、フェニルボロン酸２．６ｇとトルエン１．８ｍｌとを加え、１０５℃で１６時間撹拌した。その後、反応液にトルエン７００ｍｌ及び７．５ｗｔ％のジエチルジチオカルバミン酸ナトリウム三水和物水溶液２００ｍｌを加え、８５℃で３時間撹拌した。反応液の水層を除去後、有機層を６０℃のイオン交換水３００ｍｌで２回、６０℃の３ｗｔ％酢酸３００ｍｌで１回、さらに６０℃のイオン交換水３００ｍｌで３回洗浄した。有機層をセライト、アルミナ及びシリカを充填したカラムに通し、ろ液を回収した。その後、熱トルエン８００ｍｌでカラムを洗浄し、洗浄後のトルエン溶液をろ液に加えた。得られた溶液を７００ｍｌまで濃縮した後、濃縮した溶液を２Ｌのメタノールに加え、重合体を再沈殿させた。重合体をろ過して回収し、５００ｍｌのメタノール、５００ｍｌのアセトン、５００ｍｌのメタノールで重合体を洗浄した。重合体を５０℃で一晩真空乾燥することにより、ペンタチエニル−フルオレンコポリマー（高分子化合物Ｊ）１２．２１ｇを得た。高分子化合物Ｊのポリスチレン換算の重量平均分子量は１．１×１０⁵であった。 Reference Example 10
(Synthesis of polymer compound J)

Into a 2 L four-necked flask in which the gas in the flask was replaced with argon, 7.928 g (16.72 mmol) of compound (H), 13.00 g (17.60 mmol) of compound (I), trioctylmethylammonium chloride ( 4.979 g of trade name Aliquat 336 (registered trademark), manufactured by Aldrich, CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ Cl, density 0.884 g / ml, 25 ° C.) and 405 ml of toluene are added and stirred. The reaction system was bubbled with argon for 30 minutes. 0.02 g of dichlorobis (triphenylphosphine) palladium (II) was added to the flask, the temperature was raised to 105 ° C., and 42.2 ml of a 2 mol / L sodium carbonate aqueous solution was added dropwise with stirring. After completion of the dropwise addition, the reaction was allowed to proceed for 5 hours, and then 2.6 g of phenylboronic acid and 1.8 ml of toluene were added, followed by stirring at 105 ° C. for 16 hours. Thereafter, 700 ml of toluene and 200 ml of a 7.5 wt% sodium diethyldithiocarbamate trihydrate aqueous solution were added to the reaction solution, followed by stirring at 85 ° C. for 3 hours. After removing the aqueous layer of the reaction solution, the organic layer was washed twice with 300 ml of ion exchange water at 60 ° C., once with 300 ml of 3 wt% acetic acid at 60 ° C., and further three times with 300 ml of ion exchange water at 60 ° C. The organic layer was passed through a column packed with celite, alumina and silica, and the filtrate was recovered. Thereafter, the column was washed with 800 ml of hot toluene, and the washed toluene solution was added to the filtrate. After the obtained solution was concentrated to 700 ml, the concentrated solution was added to 2 L of methanol to reprecipitate the polymer. The polymer was recovered by filtration, and the polymer was washed with 500 ml of methanol, 500 ml of acetone, and 500 ml of methanol. The polymer was vacuum-dried at 50 ° C. overnight to obtain 12.21 g of a pentathienyl-fluorene copolymer (polymer compound J). The weight average molecular weight in terms of polystyrene of the polymer compound J was 1.1 × 10 ⁵ .

Measurement example 1
(Measurement of absorbance of organic thin film)
The polymer compound A was dissolved in o-dichlorobenzene at a concentration of 0.75% by weight to prepare a coating solution. The obtained coating solution was applied onto a glass substrate by spin coating. The coating operation was performed at 23 ° C. Then, it baked for 5 minutes on the conditions of 120 degreeC in air | atmosphere, and obtained the organic thin film about 100 nm in thickness. The absorption spectrum of the organic thin film was measured with a spectrophotometer (trade name: V-670, manufactured by JASCO Corporation). The measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm, 700 nm, 800 nm, and 900 nm.

Measurement example 2
(Measurement of absorbance of organic thin film)
An organic thin film was formed in the same manner as in Measurement Example 1 except that the polymer compound B was used in place of the polymer compound A, and the absorption spectrum thereof was measured. The measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm, 700 nm, 800 nm, and 900 nm.

Measurement example 3
(Measurement of absorbance of organic thin film)
An organic thin film was formed in the same manner as in Measurement Example 1 except that the polymer compound C was used instead of the polymer compound A, and the absorption spectrum thereof was measured. The measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm, 700 nm, 800 nm, and 900 nm.

Measurement example 4
(Measurement of absorbance of organic thin film)
The absorption spectrum of the organic thin film was measured in the same manner as in Measurement Example 1 except that the polymer compound D was used instead of the polymer compound A. The measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm, 700 nm, 800 nm, and 900 nm.

Measurement example 5
(Measurement of absorbance of organic thin film)
The absorption spectrum of the organic thin film was measured in the same manner as in Measurement Example 1 except that the polymer compound E was used instead of the polymer compound A. The measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm, 700 nm, 800 nm, and 900 nm.

Measurement example 6
(Measurement of absorbance of organic thin film)
The absorption spectrum of the organic thin film was measured in the same manner as in Measurement Example 1 except that the polymer compound F was used instead of the polymer compound A. The measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm, 700 nm, 800 nm, and 900 nm.

Measurement example 7
(Measurement of absorbance of organic thin film)
The absorption spectrum of the organic thin film was measured in the same manner as in Measurement Example 1 except that the polymer compound G was used instead of the polymer compound A. The measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm, 700 nm, 800 nm, and 900 nm.

Measurement example 8
(Measurement of absorbance of organic thin film)
The absorption spectrum of the organic thin film was measured in the same manner as in Measurement Example 1 except that the polymer compound K was used instead of the polymer compound A. The measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm, 700 nm, 800 nm, and 900 nm.

Measurement example 9
(Measurement of absorbance of organic thin film)
The absorption spectrum of the organic thin film was measured in the same manner as in Measurement Example 1 except that the polymer compound L was used instead of the polymer compound A. The measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm, 700 nm, 800 nm, and 900 nm.

Comparative Example 1
(Measurement of absorbance of organic thin film)
Polymer compound J was dissolved in o-dichlorobenzene at a concentration of 0.5% by weight to prepare a coating solution. The obtained coating solution was applied onto a glass substrate by spin coating. The coating operation was performed at 23 ° C. Then, it baked for 5 minutes on the conditions of 120 degreeC in air | atmosphere, and obtained the organic thin film about 100 nm in thickness. The absorption spectrum of the organic thin film was measured with a spectrophotometer (trade name: V-670, manufactured by JASCO Corporation). The measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm, 700 nm, 800 nm, and 900 nm.

Example 8
(Production and evaluation of organic thin-film solar cells)
A fullerene derivative C70PCBM (Phenyl C71-butyric acid methyl ester, manufactured by American Daissource Co., Ltd., trade name: ADS71BFA (lot number 10K037E), which is an electron-accepting compound, and a polymer compound A, which is an electron-donating compound, are 2: The mixture was dissolved in o-dichlorobenzene so that the concentration of the mixture was 2.25% by weight, and the resulting solution was filtered through a Teflon filter having a pore size of 0.5 μm. A coating solution 1 was prepared.

A glass substrate provided with an ITO film with a thickness of 150 nm by a sputtering method was subjected to surface treatment by ozone UV treatment. Next, a PEDOT: PSS solution (CleviosP VP AI4083 manufactured by HC Starck Co., Ltd.) is applied onto the ITO film by spin coating, and heated at 120 ° C. for 10 minutes in the atmosphere to thereby form a hole injection layer having a thickness of 50 nm. It was created. Next, the coating solution 1 was applied onto the ITO film by spin coating to obtain a functional layer of an organic thin film solar cell. The film thickness of the functional layer was 100 nm. Then, the organic thin film solar cell was produced by vapor-depositing calcium with a film thickness of 4 nm with a vacuum evaporation machine, and vapor-depositing aluminum with a film thickness of 100 nm. The degree of vacuum at the time of vapor deposition was 1 to 9 × 10 ⁻³ Pa in all cases. The shape of the organic thin film solar cell thus obtained was a square of 2 mm × 2 mm. The obtained organic thin film solar cell is irradiated with a certain amount of light using a solar simulator (trade name: OTENTO-SUNII: AM1.5G filter, irradiance: 100 mW / cm ² ), and the generated current and voltage are measured. did. The photoelectric conversion efficiency is 5.7%, Jsc (short circuit current density) is 13.4 mA / cm ² , Voc (open end voltage) is 0.79 V, and FF (fill factor) is 0.54. there were.

Example 9
(Production and evaluation of organic thin-film solar cells)
An organic thin film solar cell was prepared and evaluated in the same manner as in Example 8 except that the polymer compound G was used instead of the polymer compound A. The photoelectric conversion efficiency is 6.25%, Jsc (short circuit current density) is 13.2 mA / cm ² , Voc (open circuit voltage) is 0.88 V, and FF (fill factor) is 0.54. there were.

Example 10
(Production and evaluation of organic thin-film solar cells)
An organic thin film solar cell was prepared and evaluated in the same manner as in Example 8 except that tetralin was used instead of o-dichlorobenzene. The photoelectric conversion efficiency is 6.33%, Jsc (short circuit current density) is 15.2 mA / cm ² , Voc (open circuit voltage) is 0.76 V, and FF (fill factor) is 0.55. there were.

Example 13
(Production and evaluation of organic thin-film solar cells)
An organic thin film solar cell was prepared and evaluated in the same manner as in Example 8 except that the polymer compound K was used instead of the polymer compound A. The photoelectric conversion efficiency is 6.14%, Jsc (short circuit current density) is 16.2 mA / cm ² , Voc (open circuit voltage) is 0.76 V, and FF (fill factor) is 0.50. there were.

Claims (5)

The high molecular compound containing the repeating unit represented by Formula (1).

(1)
[In Formula (1), R is the same or different and is represented by a hydrogen atom, a fluorine atom, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, a group represented by Formula (2a), or (2b). Represents a group. The hydrogen atom contained in these groups may be substituted with a fluorine atom.

(2a)
(In the formula (2a), m1 represents an integer of 0 to 6, m2 represents an integer of 0 to 6. R ′ represents an alkyl group, an aryl group, or a heteroaryl group.)]

(2b)
(In Formula (2b), m3 represents an integer of 0 to 6, m4 represents an integer of 0 to 6. R ″ represents an alkyl group, an aryl group, or a heteroaryl group.)] An organic photoelectric conversion element comprising a pair of electrodes and a functional layer provided between the electrodes, wherein the functional layer includes an electron-accepting compound and the polymer compound according to claim 1 . The organic photoelectric conversion element according to claim 2 , wherein the amount of the electron-accepting compound contained in the functional layer is 10 to 1000 parts by weight with respect to 100 parts by weight of the polymer compound. The organic photoelectric conversion element according to claim 3, wherein the electron-accepting compound is a fullerene derivative. An organic thin film transistor comprising a source electrode, a drain electrode, an organic semiconductor layer, and a gate electrode, wherein the organic semiconductor layer includes the polymer compound according to claim 1 .

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