JP7129279B2 - Condensed ring polymer compound having dibenzoanthracenothiophene skeleton as repeating unit and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a condensed ring polymer compound, a method for producing the same, and an organic transistor element thereof.

π-Conjugated organic compounds are well known as organic semiconductors used in organic thin-film solar cells, organic transistors, and organic EL. It is expected as a coating material that can be applied to ted electronics.

Pentacene derivatives shown in Non-Patent Document 1, [1]benzothieno[3,2-b]benzothiophene (BTBT) derivatives shown in Patent Documents 1 and 2, and Non-Patent Document 2, etc. It is known as an organic semiconductor that exhibits high mobility. On the other hand, problems such as instability in air and low solubility in organic solvents have been pointed out for these fused-ring polymer compounds, which are polymer compounds with an increased number of fused rings.

WO2006/077888 WO2014/038708

Chemical Reviews, Vol. 107, pp. 1117-1160, 2007. Journal of the American Chemical Society, Vol. 129, pp. 15732-15733, 2007.

The present invention provides a novel fused ring polymer compound having both heat resistance and solvent solubility, a method for producing the fused ring polymer compound, a film-forming composition containing the fused ring polymer compound, and the film-forming composition. and an organic transistor element having the organic thin film as an active layer.

In order to solve the above problems, the present inventors conducted extensive studies and found that a polymer compound obtained by ring-condensing BTBT and a terphenylene skeleton, that is, a ring-condensed polymer compound consisting of a dibenzoanthracenothiophene skeleton has high atmospheric stability. properties, solvent solubility, heat resistance, and film-forming properties. The condensed ring polymer compound comprising a dibenzoanthracenothiophene skeleton of the present invention is novel, and its various physical properties such as carrier mobility, solvent solubility and heat resistance as well as its production method have not been reported at all. In addition, they also found that an organic thin film can be easily formed using a film-forming composition containing the condensed ring polymer compound, and that an organic transistor element prepared using the organic thin film exhibits p-type characteristics. , which led to the completion of the present invention described below.

That is, the present invention has the general formula (1)

（式中、Ｒ^１は炭素数１から１３のアルコキシ基で置換されていてもよい炭素数６～３０のアルキル基、炭素数１～１３のアルコキシ基で置換されていてもよい炭素数６～３０のアルコキシ基又は水素原子を表す。複数のＲ^１は同一又は相異なっていてもよい。Ｒ^２は炭素数６～２０のアルキル基、炭素数１～８のアルキル基で置換されていてもよいチエニル基又は水素原子を表す。ｎは２以上の整数を表す。ｍは０又は１を表す。ｎ個のｍは同一又は相異なっていてもよい。）で示される縮環高分子化合物に関する。

(In the formula, R ¹ is an alkyl group having 6 to 30 carbon atoms optionally substituted by an alkoxy group having 1 to 13 carbon atoms, an alkyl group having 6 to 30 carbon atoms optionally substituted by an alkoxy group having 1 to 13 carbon atoms, represents an alkoxy group or a hydrogen atom of 30. A plurality of R ¹ may be the same or different, and R ² may be substituted with an alkyl group having 6 to 20 carbon atoms or an alkyl group having 1 to 8 carbon atoms. represents a thienyl group or a hydrogen atom, n represents an integer of 2 or more, m represents 0 or 1, and n m may be the same or different. .

Further, the present invention is represented by general formula (2)

（式中、Ｒ^１は炭素数１から１３のアルコキシ基で置換されていてもよい炭素数６～３０のアルキル基、炭素数１から１３のアルコキシ基で置換されていてもよい炭素数６～３０のアルコキシ基又は水素原子を表す。複数のＲ^１は同一又は相異なっていてもよい。Ｒ^２は炭素数６～２０のアルキル基、炭素数１～８のアルキル基で置換されていてもよいチエニル基又は水素原子を表す。ｎは２以上の整数を表す。ｍは０又は１を表す。ｎ個のｍは同一又は相異なっていてもよい。）で示される高分子前駆体に酸化剤を作用させることを特徴とする、一般式（１）

(wherein R ¹ is an alkyl group having 6 to 30 carbon atoms optionally substituted by an alkoxy group having 1 to 13 carbon atoms, an alkyl group having 6 to 30 carbon atoms optionally substituted by an alkoxy group having 1 to 13 carbon atoms, represents an alkoxy group or a hydrogen atom of 30. A plurality of R ¹ may be the same or different, and R ² may be substituted with an alkyl group having 6 to 20 carbon atoms or an alkyl group having 1 to 8 carbon atoms. represents a thienyl group or a hydrogen atom, n represents an integer of 2 or more, m represents 0 or 1, and n m may be the same or different. General formula (1), characterized by acting an agent

（式中、Ｒ^１、Ｒ^２、ｍ及びｎは前記と同じ意味を表す。）で示される縮環高分子化合物の製造方法に関する。

(wherein R ¹ , R ² , m and n have the same meanings as above).

The present invention also provides a film-forming composition containing a condensed ring polymer compound having a repeating unit represented by the general formula (1), an organic thin film that can be prepared using the film-forming composition, and the organic It relates to transistor elements made from thin films.

The condensed ring polymer compound of the present invention is an organic semiconductor having both high solvent solubility and heat resistance, and can efficiently drive an organic transistor element having this as an active layer.

The present invention will be described in detail below.

The alkyl group having 6 to 30 carbon atoms which may be substituted with an alkoxy group having 1 to 13 carbon atoms and represented by R ¹ may be linear, branched or cyclic, and may be a methyl group. , ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl nonadecyl group, eicosyl group, heneicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triancosyl group and other linear alkyl groups, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, 2-decyltetradecyl group, 2-dodecyltetradecyl group, 2-dodecylhexadecyl group, 2-tetradecylhexadecyl a branched alkyl group such as a cyclopentyl group, a cycloalkyl group such as a cyclohexyl group, a methoxymethyl group (3-1), a (2-methoxyethoxy) methyl group (3-2), (2-(2-methoxyethoxy ) ethoxy) methyl group (3-3), (2-(2-(2-methoxyethoxy) ethoxy) ethoxy) methyl group (3-4), (2-(2-(2-(2-methoxyethoxy) ethoxy) ethoxy) ethoxy) methyl group (3-5), (2-(2-(2-(2-(2-methoxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) methyl group (3-6), (2 -(2-(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)ethoxy)ethoxy)methyl group (3-7), 3-(2-methoxyethoxy)-2-(( 2-methoxyethoxy)methyl)propyl group (3-8), 3-(2-(2-methoxyethoxy)ethoxy)-2-((2-(2-methoxyethoxy)ethoxy)methyl)propyl group (3- 9), 3-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-2-((2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methyl)propyl group (3-10) , 3-(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)-2-((2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)methyl ) propyl group (3-11), 3-(2-(2-( 2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)ethoxy)-2-((2-(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)ethoxy)methyl ) propyl group (3-12), 3-(2-(2-(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)ethoxy)ethoxy)-2-((2-( 2-(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)ethoxy)ethoxy)methyl)propyl group (3-13), 3-(2-methoxyethoxy)-2-(2 -Methoxyethoxy) propyl group (3-14), 3-(2-(2-methoxyethoxy) ethoxy) -2-(2-(2-methoxyethoxy) ethoxy) propyl group (3-15), 3-( 2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)propyl group (3-16), 3-(2-(2- (2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)-2-(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)propyl group (3-17), 3-( 2-(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)ethoxy)-2-(2-(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy) ethoxy)ethoxy)propyl group (3-18), 3-(2-(2-(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)ethoxy)ethoxy)-2-(2 -(2-(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)ethoxy)ethoxy)ethoxy) alkoxy group-substituted alkyl groups such as propyl group (3-19), etc. can be exemplified. .

炭素数１～１３のアルコキシ基で置換されていてもよい炭素数６～３０のアルキル基としては、溶解性がよい点で、２－ドデシルヘキサデシル基、及び式（３－１０）～式（３－１３）、式（３－１６）～式（３－１９）で示される基が好ましい。

As the alkyl group having 6 to 30 carbon atoms which may be substituted with an alkoxy group having 1 to 13 carbon atoms, 2-dodecylhexadecyl group and formula (3-10) to formula ( 3-13) and groups represented by formulas (3-16) to (3-19) are preferred.

The alkoxy group having 6 to 30 carbon atoms which may be substituted with an alkoxy group having 1 to 13 carbon atoms and represented by R ¹ may be linear, branched or cyclic. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, eicosyloxy group, heneicosyloxy group, docosyloxy group, tricosyloxy group, tetracosyloxy group, pen linear alkoxy groups such as tacosyloxy, hexacosyloxy, heptacosyloxy, octacosyloxy, nonacosyloxy, triancosyloxy, isopropoxy, isobutoxy, sec-butoxy, tert-butoxy group, 2-ethylhexyloxy group, 3,7-dimethyloctyloxy group, 2-decyltetradecyloxy group, 2-dodecyltetradecyloxy group, 2-dodecylhexadecyloxy group, 2-tetradecylhexadecyl Branched alkoxy groups such as oxy groups, cyclopentyloxy groups, cycloalkoxy groups such as cyclohexyloxy groups, 2-methoxyethoxy groups (4-1), 2-(2-methoxyethoxy) ethoxy groups (4-2), 2- (2-(2-methoxyethoxy)ethoxy)ethoxy group (4-3), 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy group (4-4), 2-(2- (2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)ethoxy group (4-5), 2-(2-(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy) ethoxy) ethoxy) ethoxy group (4-6), 2-(2-(2-(2-(2-(2-(2-methoxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethoxy group (4- 7), 3-(2-methoxyethoxy)-2-((2-methoxyethoxy)methyl)propoxy group (4-8), 3-(2-(2-methoxyethoxy)ethoxy)-2-((2 -(2-methoxyethoxy)ethoxy)methyl)propoxy group (4-9), 3-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-2-((2-(2-( 2-methoxyethoxy)ethoxy)ethoxy)methyl)propoxy group (4-10), 3-(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)-2-((2-( 2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)methyl)propoxy group (4-11), 3-(2-(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy) )ethoxy)ethoxy)-2-((2-(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)ethoxy)methyl)propoxy group (4-12), 3-((2 -(2-(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)ethoxy)ethoxy)-2-((2-(2-(2-(2-(2-(2 -methoxyethoxy)ethoxy)ethoxy)ethoxy)ethoxy)ethoxy)methyl)propoxy group (4-13), 3-(2-methoxyethoxy)-2-(2-methoxyethoxy)propoxy group (4-14), 3 -(2-(2-methoxyethoxy)ethoxy)-2-(2-(2-methoxyethoxy)ethoxy)propoxy group (4-15), 3-(2-(2-(2-methoxyethoxy)ethoxy) ethoxy)-2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)propoxy group (4-16), 3-(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy) ethoxy)-2-(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)propoxy group (4-17), 3-(2-(2-(2-(2-(2 -methoxyethoxy)ethoxy)ethoxy)ethoxy)ethoxy)-2-(2-(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)ethoxy)propoxy group (4-18), 3 -(2-(2-(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)ethoxy)ethoxy)-2-(2-(2-(2-(2-(2- Examples include alkoxy group-substituted alkoxy groups such as (2-methoxyethoxy)ethoxy)ethoxy)ethoxy)ethoxy)ethoxy)propoxy group (4-19).

炭素数１～１３のアルコキシ基で置換されていてもよい炭素数６～３０のアルコキシ基としては、溶解性がよい点で、２－デシルテトラデシルオキシ基、２－ドデシルテトラデシルオキシ基、２－ドデシルヘキサデシルオキシ基、２－テトラデシルヘキサデシルオキシ基、及び式（４－１）～式（４－１９）で示される基が好ましく、２－ドデシルテトラデシルオキシ基がさらに好ましい。

As the alkoxy group having 6 to 30 carbon atoms which may be substituted with an alkoxy group having 1 to 13 carbon atoms, 2-decyltetradecyloxy group, 2-dodecyltetradecyloxy group, 2 A -dodecylhexadecyloxy group, a 2-tetradecylhexadecyloxy group, and groups represented by formulas (4-1) to (4-19) are preferred, and a 2-dodecyltetradecyloxy group is more preferred.

R ¹ is preferably an alkyl group or an alkoxy group, from the viewpoint of easiness in synthesizing a monomer that serves as a raw material for the fused ring polymer compound of the present invention, and is preferably a heneicosyl group, a 2-dodecylhexadecyl group, an eicosyloxy group, or A 2-dodecylhexadecyloxy group is more preferred.

The alkyl group having 6 to 20 carbon atoms represented by R ² may be linear, branched or cyclic. Among the alkyl groups, straight-chain alkyl groups and branched alkyl groups are preferred, and branched alkyl groups are more preferred. Specific examples of alkyl groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, Straight-chain alkyl groups such as pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl groups, 2-ethylhexyl, 3,7-dimethyloctyl, 2-decyltetradecyl, and 2-dodecyltetradecyl groups , 2-dodecylhexadecyl group, 2-tetradecylhexadecyl group and other branched alkyl groups, cyclopentyl group, cyclohexyl group and other cyclic alkyl groups.

R ² is a thienyl group optionally substituted with an alkyl group having 1 to 8 carbon atoms, and the alkyl group may be linear, branched or cyclic. Specific examples of the thienyl group optionally substituted with an alkyl group having 1 to 8 carbon atoms include 5-methyl-2-thienyl group, 5-ethyl-2-thienyl group, 5-propyl-2-thienyl group, 5-butyl-2-thienyl group, 5-pentyl-2-thienyl group, 5-hexyl-2-thienyl group, 5-heptyl-2-thienyl group, 5-octyl-2-thienyl group and other linear alkyl groups thienyl group substituted with, 5-isopropyl-2-thienyl group, 5-isobutyl-2-thienyl group, 5-(sec-butyl)-2-thienyl group, 5-(tert-butyl)-2-thienyl group , 5-(2-ethylhexyl)-2-thienyl group substituted with branched alkyl group such as thienyl group, 5-cyclopentyl-2-thienyl group, 5-cyclohexyl-2-thienyl group substituted with cycloalkyl group A thienyl group is mentioned. A thienyl group substituted with a branched alkyl group having 4 to 8 carbon atoms is preferable, and a 5-(2-ethylhexyl)-2-thienyl group is more preferable because of good solubility.

Although n is not particularly limited as long as it is an integer of 1 or more, it is preferably 1 to 1000, more preferably 10 to 100, from the viewpoint of ease of synthesis.

m is preferably 0 or 1, and when n is 2 or more, m may be the same or different.

Next, the production method of the present invention will be explained.

The condensed ring polymer compound (1) of the present invention can be produced by reacting the polymer precursor (2) with an oxidizing agent.

（式中、Ｒ^１、Ｒ^２、ｍ及びｎは前記と同じ意味を表す。）

(In the formula, R ¹ , R ² , m and n have the same meanings as above.)

The oxidizing agent that can be used in the production method of the present invention is not particularly limited, but examples include pyridinium fluorochromate, pyridinium chlorochromate, pyridinium dichromate, bis(tetrabutylammonium) dichromate, Quinolinium dichromate, sodium hypochlorite pentahydrate, 3-chloroperbenzoic acid, magnesium monoperoxyphthalate hexahydrate, tert-butyl hydroperoxide, bis(trimethylsilyl) peroxide, cumene hydroperoxide, di- tert-butyl peroxide, hydrogen peroxide, methyl ethyl ketone peroxide, 1-acetoxy-5-bromo-1,2-benziodoxol-3(1H)-one, [bis(trifluoroacetoxy)iodo]benzene, [bis( trifluoroacetoxy)iodo]pentafluorobenzene, 1-(tert-butylperoxy)-1,2-benziodoxol-3-(3H)-one, bis(pyridine)iodonium tetrafluoroborate, 1,1, 1-triacetoxy-1,1-dihydro-1,2-benzoiodoxol-3-(1H)-one, iodosobenzene, 2-iodosobenzoic acid, iodobenzene diacetate, iodomesitylene diacetate, 2-iodoxybenzoic acid, trisodium paraperiodate, [hydroxy(tosyloxy)iodo]benzene, poly[4-(diacetoxyiodo)styrene], [bis(trifluoroacetoxy)iodo]benzene, bis(tetrabutylammonium) ) peroxydisulfate, pyridine-sulfur trioxide complex, sulfur trioxide-triethylamine complex, 4-acetamido-2,2,6,6-tetramethyl-1-oxopiperidinium tetrafluoroborate, benzenesulfonechloramide sodium hydrate, p-toluenesulfone chloride sodium trihydrate, ceric ammonium nitrate, 1,1-diphenyl-2-picrylhydrazyl free radical, 2-hydroxy-2-azaadamantane, 4-methylmorpholine N -oxide, potassium permanganate, phosphomolybdic acid, ferric chloride, molybdenum pentachloride, tetrapropylammonium perruthenate, chloranil, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, trimethylamine N -oxide, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and the like. It is preferable to use ferric chloride in that the reaction yield is good.

Although the amount of the oxidizing agent to be used is not particularly limited, it is preferably in the range of 1 to 100 equivalents with respect to the molar ratio of the repeating units of the polymer precursor (2) in terms of good reaction yield. More preferably it is in the range of 1 to 10 equivalents.

The production method of the present invention can be carried out in a solvent. Solvents that can be used include ethers such as diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane and dimethoxyethane, benzene, toluene, xylene and mesitylene. , tetralin and other aromatic hydrocarbon solvents, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 4-fluoroethylene carbonate and other carbonate ester solvents, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate , methyl butyrate, ester solvents such as γ-lactone, amide solvents such as dimethylsulfoxide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N,N,N',N'-tetramethylurea ( TMU), urea solvents such as N,N'-dimethylpropyleneurea (DMPU), sulfonamide solvents such as dimethylsulfoxide (DMSO), methanol, ethanol, 2-propanol, butanol, octanol, benzyl alcohol, ethylene glycol, propylene glycol. , diethylene glycol, triethylene glycol, alcohol solvents such as 2,2,2-trifluoroethanol, halogen solvents such as chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, orthodichlorobenzene, nitromethane, water, etc. can be exemplified, and these may be mixed in any ratio and used. Among these, a halogen solvent and a mixed solvent of a halogen solvent and nitromethane are preferable in terms of a good reaction yield, and a mixed solvent of methylene chloride and nitromethane or a mixed solvent of ortho-dichlorobenzene and nitromethane is more preferable.

The amount of the solvent used is not particularly limited, but it is preferably in the range of 0.1 to 100 mL/mg, more preferably in the range of 0.1 to 10 mL/mg, based on the weight of the polymer precursor (2) used. It is more preferable to be in

The production method of the present invention is preferably carried out in an inert gas atmosphere such as argon gas or nitrogen gas.

Although the reaction temperature for carrying out the production method of the present invention is not limited, it is preferably carried out in the range of -78°C to 100°C, more preferably in the range of 0°C to 30°C.

Although the reaction time varies depending on the type of polymer precursor (2), solvent, and reaction temperature, it is preferably 0.1 to 100 hours, more preferably 1 to 78 hours.

A condensed ring polymer compound (1) can be obtained by carrying out a normal treatment after completion of the production method of the present invention. If necessary, it may be purified by precipitation, filtration, column chromatography, preparative HPLC and the like.

The polymer precursor (2) used in the production method of the present invention can be produced by a cross-coupling reaction using a transition metal catalyst, which is well known to those skilled in the art, and is described in Journal of the American Chemical Society, Vol. 7725 pages, 2016, Macromolecules, 44 volumes, 1788 pages, 2011, etc. It can manufacture according to the method disclosed.

For example, cross-coupling of aromatic compound derivative (6-1) shown below with 1,4-dibromo-2,5-diphenylenebenzene-1,2,4,5-tetrayl derivative (6-2) It can be produced by reaction.

（式中、Ｒ^１、Ｒ^２、ｍ及びｎは前記と同じ意味を表す。Ｒ^３は炭素数１～４のアルキル基、フェニル基又は塩素原子を表し、複数のＲ^３は同一又は相異なっていてもよい。）
芳香族化合物誘導体（６－１）に含まれるＲ^３としては、メチル基、エチル基、プロピル基、ブチル基、フェニル基又は塩素原子であり、Ｒ^３ _３Ｓｎ基としては、次の（７ａ）～（７ｆ）で示される基が例示できる。収率がよい点で（７ａ）、（７ｄ）が好ましく、（７ｄ）がより好ましい。

(In the formula, R ¹ , R ² , m and n have the same meanings as above; R ³ represents an alkyl group having 1 to 4 carbon atoms, a phenyl group or a chlorine atom; a plurality of R ³ are the same or different; may be present.)
R ³ contained in the aromatic compound derivative (6-1) is a methyl group, ethyl group, propyl group, butyl group, phenyl group or chlorine atom, and the R ³ ₃ Sn group is the following (7a) Groups represented by (7f) can be exemplified. (7a) and (7d) are preferable, and (7d) is more preferable in that the yield is good.

用いる触媒としては、特に限定するものではないが、具体的には、塩化パラジウム、酢酸パラジウム、トリフルオロ酢酸パラジウム、硝酸パラジウムなどの塩、π－アリルパラジウムクロリドダイマ－、パラジウムアセチルアセトナト、トリス（ジベンジリデンアセトン）ジパラジウムなどの錯化合物、ジクロロビス（トリフェニルホスフィン）パラジウム、テトラキス（トリフェニルホスフィン）パラジウム、ジクロロ（１，１’－ビス（ジフェニルホスフィノ）フェロセン）パラジウム、ビス（トリ－ｔｅｒｔ－ブチルホスフィン）パラジウム、ビス（トリシクロヘキシルホスフィン）パラジウム、ビス（トリシクロヘキシルホスフィン）塩化パラジウムなどの第三級ホスフィンを配位子として有するパラジウム錯体を例示することができ、これらはパラジウム塩、または錯化合物に第三級ホスフィンを添加し、反応系中で調製することもできる。この際用いることのできる第三級ホスフィンとしては、トリフェニルホスフィン、トリメチルホスフィン、トリブチルホスフィン、トリ（ｔｅｒｔ－ブチル）ホスフィン、トリシクロへキシルホスフィン、ｔｅｒｔ－ブチルジフェニルホスフィン、９，９－ジメチル－４，５－ビス（ジフェニルホスフィノ）キサンテン、２－（ジフェニルホスフィノ）－２’－（Ｎ，Ｎ－ジメチルアミノ）ビフェニル、２－（ジ－ｔｅｒｔ－ブチルホスフィノ）ビフェニル、２－（ジシクロへキシルホスフィノ）ビフェニル、ビス（ジフェニルホスフィノ）メタン、１，２－ビス（ジフェニルホスフィノ）エタン、１，３－ビス（ジフェニルホスフィノ）プロパン、１，４－ビス（ジフェニルホスフィノ）ブタン、１，１’－ビス（ジフェニルホスフィノ）フェロセン、トリ（２－フリル）ホスフィン、トリ（ｏ－トリル）ホスフィン、トリス（２，５－キシリル）ホスフィン、（±）－２，２’－ビス（ジフェニルホスフィノ）－１，１’－ビナフチル、２－ジシクロへキシルホスフィノ－２’，４’、６’－トリイソプロピルビフェニルなどが例示できる。中でも、反応収率が良い点で第三級ホスフィンを配位子として有するパラジウム錯体が好ましく、トリフェニルホスフィンを配位子として有するパラジウム錯体がさらに好ましい。第三級ホスフィンとパラジウム塩、または錯化合物とのモル比は１：１０～１０：１の範囲にあることが好ましく、収率がよい点で１：３～４：１の範囲にあることがさらに好ましい。

The catalyst to be used is not particularly limited, but specifically, salts such as palladium chloride, palladium acetate, palladium trifluoroacetate, palladium nitrate, π-allyl palladium chloride dimer, palladium acetylacetonate, tris ( complex compounds such as dibenzylideneacetone)dipalladium, dichlorobis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)palladium, dichloro(1,1'-bis(diphenylphosphino)ferrocene)palladium, bis(tri-tert- Palladium complexes having tertiary phosphines as ligands such as butylphosphine)palladium, bis(tricyclohexylphosphine)palladium, and bis(tricyclohexylphosphine)chloride palladium can be exemplified, and these are palladium salts or complex compounds. can also be prepared in situ by adding a tertiary phosphine to Tertiary phosphines that can be used in this case include triphenylphosphine, trimethylphosphine, tributylphosphine, tri(tert-butyl)phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine, 9,9-dimethyl-4, 5-bis(diphenylphosphino)xanthene, 2-(diphenylphosphino)-2'-(N,N-dimethylamino)biphenyl, 2-(di-tert-butylphosphino)biphenyl, 2-(dicyclohexylphosphino) ) biphenyl, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1 '-bis(diphenylphosphino)ferrocene, tri(2-furyl)phosphine, tri(o-tolyl)phosphine, tris(2,5-xylyl)phosphine, (±)-2,2'-bis(diphenylphosphino )-1,1′-binaphthyl, 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl and the like. Among them, a palladium complex having a tertiary phosphine as a ligand is preferable, and a palladium complex having a triphenylphosphine as a ligand is more preferable in terms of good reaction yield. The molar ratio of the tertiary phosphine and the palladium salt or the complex compound is preferably in the range of 1:10 to 10:1, preferably in the range of 1:3 to 4:1 in terms of good yield. More preferred.

The amount of the catalyst to be used is not limited, but the molar equivalent of the catalyst is preferably 0.005 to 50 mol percent relative to the aromatic compound derivative (6-1), and 0.05 to 0.05 More preferably in the range of 10 mole percent.

The preparation of (2) can be carried out in a solvent. Solvents that can be used include diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, ether solvents such as dimethoxyethane, benzene, toluene, xylene, Aromatic hydrocarbon solvents such as mesitylene and tetralin Carbonic acid ester solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, and 4-fluoroethylene carbonate Ethyl acetate, butyl acetate, methyl propionate, propionic acid Ester solvents such as ethyl, methyl butyrate, γ-lactone, amide solvents such as dimethylsulfoxide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N,N,N',N'-tetramethylurea (TMU), urea solvents such as N,N'-dimethylpropyleneurea (DMPU), sulfonamide solvents such as dimethylsulfoxide (DMSO), methanol, ethanol, 2-propanol, butanol, octanol, benzyl alcohol, ethylene glycol, propylene. Alcohol solvents such as glycol, diethylene glycol, triethylene glycol, 2,2,2-trifluoroethanol, halogen solvents such as chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, orthodichlorobenzene, nitromethane, water etc. can be exemplified, and these may be used by mixing them in an arbitrary ratio. Among these, an aromatic hydrocarbon solvent, a mixed solvent of an aromatic hydrocarbon solvent and water, and a mixed solvent of an ether solvent and water are preferable because of good reaction yield, and toluene is more preferable.

This step can be carried out at a temperature suitably selected from 0° C. to 200° C., and is preferably carried out at a temperature suitably selected from 100° C. to 140° C. from the viewpoint of good reaction yield.

This step is preferably performed in an inert gas atmosphere such as argon gas or nitrogen gas.

Although the reaction temperature for carrying out this step is not limited, it is preferably 20°C to 150°C, more preferably 100°C to 130°C.

The reaction time depends on the type of compound represented by the aromatic compound derivative (6-1) and the 1,4-dibromo-2,5-diphenylenebenzene-1,2,4,5-tetrayl derivative (6-2), Depending on the solvent and reaction temperature, 1 to 100 hours are preferred, and 24 to 78 hours are more preferred.

Polymer precursor (2) can be obtained by normal treatment after completion of the manufacturing process. If necessary, purification may be performed by precipitation, filtration, column chromatography, preparative HPLC, Soxhlet extraction, beads, and the like.

The aromatic compound derivative (6-1) may be a commercially available product, or may be produced by combining known methods. For example, Journal of Materials Chemistry A, Vol. , Journal of Materials Chemistry C, Vol. 4, pp. 2170-2177, 2016.
The 1,4-dibromo-2,5-diphenylenebenzene-1,2,4,5-tetrayl derivative (6-2) can be produced by combining known methods. , 16, 1826, 2010, Macromolecules, 45, 2609, 2012, Macromolecules, 46, 2141, 2013, Chemistry of Materials, 29, 4109, 2017. It can be manufactured according to the method

Next, a film-forming composition containing the condensed ring polymer compound (1) having a repeating unit represented by the general formula (1) of the present invention (hereinafter referred to as "the film-forming composition of the present invention"). ) will be described.

The film-forming composition of the present invention can be prepared by dissolving or dispersing the condensed ring polymer compound (1) of the present invention in a solvent.

The solvent is not particularly limited as long as it can dissolve or disperse the fused ring polymer compound (1) of the present invention in the solvent. Ether solvents such as 2-methyltetrahydrofuran, 1,4-dioxane, and dimethoxyethane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, and tetralin; ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate; , 4-fluoroethylene carbonate and other carbonate solvents, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, γ-lactone and other ester solvents, dimethyl sulfoxide (DMF), dimethylacetamide (DMAc), N - amide solvents such as methylpyrrolidone (NMP), N,N,N',N'-tetramethylurea (TMU), urea solvents such as N,N'-dimethylpropyleneurea (DMPU), dimethylsulfoxide (DMSO), etc. sulfonamide solvents, alcohol solvents such as methanol, ethanol, 2-propanol, butanol, octanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 2,2,2-trifluoroethanol, chloroform, methylene chloride , carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, orthodichlorobenzene, and other halogen solvents, nitromethane, water, and the like, and these may be mixed in any ratio and used. Among these, aromatic hydrocarbons and halogen solvents are preferable, and toluene, xylene, mesitylene, cyclohexylbenzene, tetralin, 3,4-dimethylanisole, chlorobenzene, and orthodichlorobenzene are more preferable because they have a high boiling point and volatilize gently. .

The amount of the solvent used is not particularly limited, and the concentration of the condensed ring polymer compound (1) of the present invention is 0.001 to 95% by weight, and the concentration is appropriately selected from 0.01 to 30% by weight. It is more preferable to add a solvent such as

As the method of dissolution or dispersion, methods well known to those skilled in the art, such as stirring, shaking, and ball milling, can be used. At this time, heating may be performed.

A binder may be added to the film-forming composition of the present invention to improve film-forming properties. Examples of such binders include polystyrene, poly-α-methylstyrene, polyvinylnaphthalene, poly(ethylene-co-norbornene), polymethylmethacrylate, polytriarylamine, poly(9,9-dioctylfluorene-co- dimethyltriphenylamine) can be exemplified. Although the concentration of the binder is not particularly limited, it is preferably 0.1 to 10.0% by weight from the viewpoint of good coatability.

Next, a method for forming an organic thin film (hereinafter referred to as "the organic thin film of the present invention") using the film-forming composition of the present invention will be described.

The method for forming the organic thin film of the present invention using the film-forming composition of the present invention is not particularly limited. Printing methods such as inkjet, slit coating, blade coating, flexographic printing, screen printing, gravure printing, and offset printing can be exemplified. Among them, spin coating, drop casting, and inkjet are preferred in terms of efficient film formation.

Although the thickness of the organic thin film of the present invention is not particularly limited, it is preferably 1 nm to 1000 nm, more preferably 10 nm to 500 nm, in terms of high carrier mobility.

The organic thin film of the present invention can be obtained by drying the solvent after forming the film. Annealing may be performed at a temperature appropriately selected from the range of 40 to 400° C., if necessary.

Further, a method for producing an organic transistor element (hereinafter referred to as "the organic transistor element of the present invention") containing the condensed ring polymer compound of the present invention in the active layer will be described.

The organic transistor element of the present invention is obtained by forming the organic thin film of the present invention as an insulating layer and an active layer on a substrate, and attaching a source electrode, a drain electrode and a gate electrode thereto.

FIG. 1 shows the structure of an element included in the organic transistor element of the present invention. Here, (A) is a bottom gate-top contact type, (B) is a bottom gate-bottom contact type, (C) is a top gate-top contact type, and (D) is a top gate-bottom contact type. 1 is an active layer, 2 is a substrate, 3 is a gate electrode, 4 is a gate insulating layer, 5 is a source electrode, and 6 is a drain electrode.

Substrates include, for example, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polymethyl acrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefin, polyimide, polycarbonate, polyvinylphenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), poly(diisopropyl maleate), polyethersulfone, polyphenylene sulfide, cellulose triacetate plastic substrates, glass, quartz, aluminum oxide, silicon, hydrated silicon, silicon oxide, tantalum dioxide, tantalum pentoxide, indium tin Inorganic substrates such as oxides, metal substrates such as gold, copper, chromium, titanium, and aluminum can be used. Among these, glass, silicon, and highly doped silicon are preferred, and glass is more preferred, in terms of good transistor performance.

As the gate electrode, for example, inorganic electrodes such as aluminum, gold, silver, copper, highly doped silicon, tin oxide, indium oxide, indium tin oxide, chromium, titanium, tantalum, chromium, graphene, carbon nanotubes, or doped and organic electrodes such as conductive polymer (PEDOT-PSS). Among these, an inorganic electrode is preferred because of its good conductivity, and gold is more preferred.

Examples of insulating layers include inorganic materials such as silicon oxide, silicon nitride, aluminum oxide, aluminum nitride, titanium oxide, tantalum dioxide, tantalum pentoxide, indium tin oxide, tin oxide, vanadium oxide, barium titanate, and bismuth titanate. Insulating layer, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polymethyl acrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefin, polyimide, polycarbonate, polyvinylphenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate) , poly(diisopropyl maleate), polyethersulfone, polyphenylene sulfide, cellulose triacetate, polycyclopentane, polycyclohexane-ethylene copolymer, polyfluorinated cyclopentane, polyfluorinated cyclohexane, polyfluorinated cyclohexane-ethylene copolymer , parylene N, parylene C, parylene D, parylene HT, and parylene C-UVF. Among these, an organic insulating layer is preferred because of its good insulating properties, and parylene C is more preferred. In addition, these insulating layer surfaces are, for example, octadecyltrichlorosilane, decyltrichlorosilane, decyltrimethoxysilane, octyltrichlorosilane, octadecyltrimethoxysilane, β-phenethyltrichlorosilane, β-phenethyltrimethoxysilane, phenyltrichlorosilane, It may be modified with silanes such as phenyltrimethoxysilane, phosphonic acids such as octadecylphosphonic acid, decylphosphonic acid and octylphosphonic acid, and amines such as hexamethyldisilazane. Among these, octadecyltrichlorosilane, octyltrichlorosilane, β-phenethyltrichlorosilane, and octadecylphosphonic acid are preferred in terms of improving the carrier mobility and current on/off ratio of the organic transistor device of the present invention and lowering the threshold voltage. , octylphosphonic acid and hexamethyldisilazane are preferred.

As the source electrode and the drain electrode, electrodes similar to those exemplified for the gate electrode can be exemplified. Among these, an inorganic electrode is preferred because of its good conductivity, and gold is more preferred. Moreover, in order to increase the efficiency of carrier injection, these electrodes can be surface-treated using a surface-treating material. Examples of such surface treatment materials include benzenethiol and pentafluorobenzenethiol.

The condensed ring polymer compound of the present invention can be used for electronic materials such as organic EL display materials, organic semiconductor laser materials, organic thin film solar cell materials, and photonic crystal materials. Moreover, the organic transistor element of the present invention can be used for electronic paper, organic EL displays, liquid crystal displays, IC tags (RFID tags), pressure sensors, and the like.

It is a figure which shows the structure by the cross-sectional shape of an organic transistor element.

(A): Bottom gate-top contact organic thin film transistor (B): Bottom gate-bottom contact organic thin film transistor (C): Top gate-top contact organic thin film transistor (D): Top gate-bottom contact organic thin film transistor 1: Condensed ring polymer compound layer 2: substrate 3: gate electrode 4: gate insulating layer 5: source electrode 6: drain electrode

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

The compounds obtained in Examples were structurally analyzed by ¹ H-NMR measurement. The molecular weight and molecular weight distribution of the polymer compound are measured by GPC, and the maximum absorption wavelength (Absλ _max ), optical bandgap (E _g ), maximum fluorescence wavelength (Emλ _max ), and Stokes shift (Δλ _max ) are measured by ultraviolet-visible absorption ( UV-Vis) Estimated by spectral measurement and fluorescence spectral measurement. The highest occupied molecular orbital (HOMO) of the polymer compound was estimated by CV measurement, and the lowest unoccupied molecular orbital (LUMO) was determined from _Eg and HOMO. 3%, 5%, 10% weight loss temperatures ( _Td3 , _Td5 , _Td10 ) were measured by thermogravimetric analysis (TGA). Commercially available reagents were used.
<NMR measurement conditions>
Measuring device: Bruker ASCEND ^™ ADVANCE III HD (400MHz)
Measurement solvent: deuterated chloroform (CDCl ₃ ), deuterated methylene chloride (CD ₂ Cl ₂ ), deuterated ortho-dichlorobenzene (o-DCB-d ₄ )
Internal standard substance: tetramethylsilane (TMS), methylene chloride, orthodichlorobenzene <GPC measurement conditions>
Measuring device: Tosoh Corporation high-speed GPC device HLC-8320GPC EcoSEC
Column: TSKgel SuperMultiporeHZ-H, TSKgel SuperHZ2000
Measurement solvent: THF
Calibration curve: polystyrene standard <TGA measurement conditions>
Measurement device: SII Nanotechnology Co., Ltd. Differential thermal thermogravimetric simultaneous measurement device TG/DTA6200
Measurement conditions: Nitrogen atmosphere, 10°C/min
<UV-Vis spectrum measurement conditions>
Measuring device: Hitachi-Science & Technology U-1800 UV/Vis Spectrometer
Measurement solvent: methylene chloride, ortho-dichlorobenzene <Fluorescence spectrum measurement conditions>
Measuring device: Hitachi High-Technologies spectrofluorophotometer F-2500
Measurement solvent: methylene chloride, ortho-dichlorobenzene <CV measurement conditions>
Measuring device: Hokuto Denko Co., Ltd. Automatic Polarization System HSV-110
Working electrode: glassy carbon Reference electrode: Ag/AgCl
Counter electrode: Platinum Measuring solvent: Methylene chloride
Supporting electrolyte: Tetrabutylammonium hexafluorophosphate Sweep rate: 100 mV/s
[Reference example 1]

４－ブロモフェノール（１０．２ｇ，５８．７ｍｍｏｌ）と２－デシル－１－テトラデカノール（２４．６ｇ，６９．４ｍｍｏｌ）、トリフェニルホスフィン（１９．９ｇ，７６．０ｍｍｏｌ）、ならびにＴＨＦ（５６０ｍＬ）の混合物に、０℃で１．９Ｍ－アゾジカルボン酸ジイソプロピルのトルエン溶液（３６．５ｍＬ，６９．０ｍｍｏｌ）を加えて室温で４４．５時間撹拌した。反応終了後、減圧下で溶媒を留去した。得られた残渣に少量のクロロホルムを加えて溶解し、ヘキサンに滴下した。生じた白色固体をろ別したのちに、得られた溶液を減圧下で濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィー（ヘキサン）で精製し、無色透明液体の１－ブロモ－４－（２－デシルテトラデシルオキシ）ベンゼンを得た（２６．７ｇ，８９％）。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．３４（ｄ，Ｊ＝９．０Ｈｚ，２Ｈ），６．７７（ｄ，Ｊ＝９．０Ｈｚ，２Ｈ），３．７８（ｄ，Ｊ＝５．７Ｈｚ，２Ｈ），１．８１－１．６９（ｍ，１Ｈ），１．４９－１．０６（ｍ，４０Ｈ），０．９３－０．８２（ｍ，６Ｈ）．
［参考例２］

4-bromophenol (10.2 g, 58.7 mmol) and 2-decyl-1-tetradecanol (24.6 g, 69.4 mmol), triphenylphosphine (19.9 g, 76.0 mmol), and THF (560 mL) ) at 0° C., a toluene solution of 1.9 M-diisopropyl azodicarboxylate (36.5 mL, 69.0 mmol) was added, and the mixture was stirred at room temperature for 44.5 hours. After completion of the reaction, the solvent was distilled off under reduced pressure. A small amount of chloroform was added to the resulting residue to dissolve it, and the solution was added dropwise to hexane. After filtering off the resulting white solid, the resulting solution was concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to give 1-bromo-4-(2-decyltetradecyloxy)benzene as a colorless transparent liquid (26.7 g, 89%).
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.34 (d, J=9.0 Hz, 2H), 6.77 (d, J=9.0 Hz, 2H), 3.78 (d, J=5. 7Hz, 2H), 1.81-1.69 (m, 1H), 1.49-1.06 (m, 40H), 0.93-0.82 (m, 6H).
[Reference example 2]

１－ブロモ－４－（２－デシルテトラデシルオキシ）ベンゼン（２５．６ｇ、５０．２ｍｍｏｌ）とＤＭＳＯ（３００ｍＬ）の混合物を３０分間アルゴンバブリングした。この混合物にアルゴン気流下でＰｄＣｌ_２（ｄｐｐｆ）・ＣＨ_２Ｃｌ_２（１．２４ｇ、１．５２ｍｍｏｌ）と酢酸カリウム（１４．９ｇ、１５２ｍｍｏｌ）、ならびにＢ_２Ｐｉｎ_２（１５．６ｇ，６１．２ｍｍｏｌ）を加えて８０℃で２６時間撹拌した。反応終了後に室温まで冷却し、エーテルとヘキサンの混合液（１／３）で抽出した。集めた有機層を水と飽和食塩水で洗浄したのちに飽和硫酸マグネシウムで乾燥し、ろ過後に減圧下で溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（クロロホルム／ヘキサン＝１／６→１／３→１／１）で精製して、黄色液体の４－（２－デシルテトラデシルオキシ）フェニルボロン酸ピナコールエステルを得た（２１．１ｇ，７５％）。
^１Ｈ ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．７３（ｄ，Ｊ＝８．７Ｈｚ，２Ｈ），６．８５（ｄ，Ｊ＝８．７Ｈｚ，２Ｈ），３．８４（ｄ，Ｊ＝５．７Ｈｚ，２Ｈ），１．８４－１．７１（ｍ，１Ｈ），１．４９－１．１８（ｍ，５２Ｈ），０．９０－０．８６（ｍ，６Ｈ）．
［参考例３］

A mixture of 1-bromo-4-(2-decyltetradecyloxy)benzene (25.6 g, 50.2 mmol) and DMSO (300 mL) was bubbled with argon for 30 minutes. To this mixture under argon was added _PdCl2 (dppf) _{.CH2Cl2 (} 1.24 g, 1.52 mmol) and potassium acetate (14.9 g, 152 mmol), and B2 _{Pin2 (} 15.6 g, 61.2 mmol). ) was added and stirred at 80° C. for 26 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted with a mixed solution (1/3) of ether and hexane. The collected organic layer was washed with water and saturated brine, dried over saturated magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (chloroform/hexane=1/6→1/3→1/1) to give 4-(2-decyltetradecyloxy)phenylboronic acid pinacol ester as a yellow liquid. Obtained (21.1 g, 75%).
¹ H NMR (CDCl ₃ , 400 MHz) δ 7.73 (d, J = 8.7 Hz, 2H), 6.85 (d, J = 8.7 Hz, 2H), 3.84 (d, J = 5.7 Hz , 2H), 1.84-1.71 (m, 1H), 1.49-1.18 (m, 52H), 0.90-0.86 (m, 6H).
[Reference example 3]

４－（２－デシルテトラデシルオキシ）フェニルボロン酸ピナコールエステル（２０．１ｇ、３６．２ｍｍｏｌ）と１，４－ジブロモ－２，５－ジヨードベンゼン（８．０１ｇ、１６．４ｍｍｏｌ）、ジメトキシエタン（４００ｍＬ）、ならびに２Ｍ炭酸カリウム水溶液（１７０ｍＬ、３４０ｍｍｏｌ）の混合物を３０分間アルゴンバブリングした。この混合液に、アルゴン気流下でＰｄ（ＰＰｈ_３）_４（２．４２ｇ、２０．９ｍｍｏｌ）を加えて二日間還流した。得られた混合物を室温まで冷やしたのちに飽和塩化アンモニウム水溶液を加えてエーテルで抽出した。集めた有機層を飽和塩化アンモニウム、水、ならびに飽和食塩水で洗浄したのちに無水硫酸マグネシウムで乾燥してろ過し、減圧下で溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（ヘキサン）と分取ＨＰＬＣ（クロロホルム）で精製したのちに、さらにシリカゲルカラムクロマトグラフィー（ヘキサン／クロロホルム＝３／１）で精製することで無色透明液体の２’，５’－ジブロモ－４，４’’－ビス（２－デシルテトラデシルオキシ）－ｐ－ターフェニルを得た（７．９４ｇ，４４％）。
^１ＨＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．６１（ｓ，２Ｈ），７．３６（ｄ，Ｊ＝８．８Ｈｚ，４Ｈ），６．９６（ｄ，Ｊ＝８．８Ｈｚ，４Ｈ），３．８８（ｄ，Ｊ＝５．６Ｈｚ，４Ｈ），１．８６－１．７４（ｍ，２Ｈ），１．５２－１．１６（ｍ，８０Ｈ），０．９３－０．８１（ｍ，１２Ｈ）．
［参考例４］

4-(2-decyltetradecyloxy)phenylboronic acid pinacol ester (20.1 g, 36.2 mmol) and 1,4-dibromo-2,5-diiodobenzene (8.01 g, 16.4 mmol), dimethoxyethane (400 mL), and 2M aqueous potassium carbonate (170 mL, 340 mmol) were argon bubbled for 30 minutes. Pd(PPh ₃ ) ₄ (2.42 g, 20.9 mmol) was added to this mixture under an argon stream, and the mixture was refluxed for two days. After the resulting mixture was cooled to room temperature, a saturated aqueous ammonium chloride solution was added and the mixture was extracted with ether. The collected organic layer was washed with saturated ammonium chloride, water and saturated brine, dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) and preparative HPLC (chloroform), and then further purified by silica gel column chromatography (hexane/chloroform=3/1) to give 2′ as a colorless transparent liquid. ,5′-dibromo-4,4″-bis(2-decyltetradecyloxy)-p-terphenyl was obtained (7.94 g, 44%).
¹ H NMR (CDCl ₃ , 400 MHz) δ 7.61 (s, 2H), 7.36 (d, J = 8.8 Hz, 4H), 6.96 (d, J = 8.8 Hz, 4H), 3.88 (d, J = 5.6Hz, 4H), 1.86-1.74 (m, 2H), 1.52-1.16 (m, 80H), 0.93-0.81 (m, 12H) .
[Reference Example 4]

２’，５’―ジブロモ―４，４’’―ビス（２―デシルテトラデシルオキシ）ｐ―ターフェニル（１１０ｍｇ，０．１０ｍｍｏｌ）と２，５―ビス（トリメチルスズ）―チエノ［３，２―ｂ］チオフェン（４７．１ｍｇ，０．１０ｍｍｏｌ）、ならびにトルエン（３ｍＬ）の混合物を凍結脱気した。この混合液に、アルゴン気流下でＰｄ（ＰＰｈ_３）_４（５．９ｍｇ，０．００５１ｍｍｏｌ）を加えて１２０℃で６４時間撹拌して室温まで冷やした。この混合液をセライトを用いてろ過し、溶媒を減圧下で留去した。得られた残渣をクロロホルムに溶解させたのちに再度セライトを用いてろ過し、減圧下で溶媒を留去した。得られた固体を少量のクロロホルムに溶解し、ジエチルエーテルとエタノール（＝９／１０）に加え、生じた沈殿をろ別した。この操作を合計３回繰り返し、得られた固体を９０℃で減圧乾燥することで、淡黄色固体の（１１―１）を得た（１１０ｍｇ，ｑｕａｎｔ．）。
ＧＰＣ（ＴＨＦ）Ｍ_ｎ＝２１７４０ｇ／ｍｏｌ．Ｍ_ｗ＝４１７４０ｇ／ｍｏｌ，ＰＤＩ＝１．９２．
^１ＨＮＭＲ（ＣＤ_２Ｃｌ_２，４００ＭＨｚ）δ７．２８（ｄ，Ｊ＝８．３Ｈｚ，４Ｈ），６．９４（ｓ，２Ｈ），６．９０（ｄ，Ｊ＝８．５Ｈｚ，４Ｈ），４．０４―３．７０（ｂｒ，４Ｈ），１．８８―１．７６（ｂｒ，２Ｈ），１．５３―１．１８（ｂｒ，８２Ｈ），０．９４―０．８６（ｂｒ，１２Ｈ）．
Ｔ_ｄ３＝３５８℃、Ｔ_ｄ５＝３８０℃、Ｔ_ｄ１０＝４０７℃．
Ａｂｓλ_ｍａｘ＝４１１ｎｍ、Ｅｍλ_ｍａｘ＝４８９ｎｍ、Δλ_ｍａｘ＝７８ｎｍ、Ｅ_ｇ＝２．６７ｅＶ．
ＨＯＭＯ＝-４．８８ｅＶ、ＬＵＭＯ＝-２．２１ｅＶ．
［参考例５］

2′,5′-dibromo-4,4″-bis(2-decyltetradecyloxy)p-terphenyl (110 mg, 0.10 mmol) and 2,5 -bis(trimethyltin)-thieno[3,2 A mixture of -b]thiophene (47.1 mg, 0.10 mmol), and toluene (3 mL) was freeze degassed. Pd(PPh ₃ ) ₄ (5.9 mg, 0.0051 mmol) was added to this mixture under an argon stream, stirred at 120° C. for 64 hours, and cooled to room temperature. This mixture was filtered using celite, and the solvent was distilled off under reduced pressure. After dissolving the resulting residue in chloroform, it was filtered again using celite, and the solvent was distilled off under reduced pressure. The resulting solid was dissolved in a small amount of chloroform, added to diethyl ether and ethanol (=9/10), and the resulting precipitate was separated by filtration. This operation was repeated 3 times in total, and the resulting solid was dried under reduced pressure at 90° C. to obtain pale yellow solid (11-1) (110 mg, quant.).
GPC(THF) _Mn = 21740 g/mol. Mw = ₄₁₇₄₀ g/mol, PDI = 1.92.
¹ H NMR (CD ₂ Cl ₂ , 400 MHz) δ 7.28 (d, J=8.3 Hz, 4 H), 6.94 (s, 2 H), 6.90 (d, J=8.5 Hz, 4 H), 4 .04-3.70 (br, 4H), 1.88-1.76 (br, 2H), 1.53-1.18 (br, 82H), 0.94-0.86 (br, 12H) .
_Td3 = 358°C, _Td5 = 380°C, _Td10 = 407°C.
Absλ _max =411 nm, Emλ _max =489 nm, Δλ _max =78 nm, E _g =2.67 eV.
HOMO=-4.88 eV, LUMO=-2.21 eV.
[Reference Example 5]

２’，５’―ジブロモ―４，４’’―ビス（２―デシルテトラデシルオキシ）ｐ―ターフェニル（２４２ｍｇ，０．２２０ｍｍｏｌ）と２，６－ビス（トリメチルスズ）－４，８－ビス［５－（２－エチルヘキシル）－２－チエニル］ベンゾ［１，２－ｂ：４，５－ｂ’］ジチオフェン（２００ｍｇ，０．２２０ｍｍｏｌ）、ならびにトルエン（６．６ｍＬ）の混合物を凍結脱気した。この混合液にアルゴン気流下でＰｄ（ＰＰｈ_３）_４（１４．２ｍｇ，０．０１２２ｍｍｏｌ）を加えて１２０℃で三日間撹拌し、室温まで冷やした。この混合物をセライトを用いてろ過し、減圧下で溶媒を留去した。得られた固体をクロロホルムに溶解させたのちに再度セライトを用いてろ過し、減圧下で溶媒を留去した。得られた固体を少量のトルエンに溶解し、メタノールと濃塩酸の混合液に沈殿する操作を三回行ったのちに、さらにジエチルエーテルとエタノール（＝９／１０）に沈殿する操作を三回行った。得られた固体を減圧下で乾燥することで、オレンジ色固体の（１２―１）を得た（２７１ｍｇ，８１％）。ＧＰＣ（ＴＨＦ）Ｍ_ｎ＝１１５００ｇ／ｍｏｌ，Ｍ_ｗ＝２３５３０ｇ／ｍｏｌ，ＰＤＩ＝２．０５．
^１ＨＮＭＲ（ＣＤ_２Ｃｌ_２，４００ＭＨｚ）δ８．０４―５．４９（ｂｒ，１６Ｈ），４．２０―３．６２（ｂｒ，４Ｈ），３．１７―２．５７（ｂｒ，４Ｈ），２．０２―１．１３（ｂｒ，１００Ｈ），１．１０―０．５７（ｂｒ，２４Ｈ）．
Ｔ_ｄ３＝３１６℃、Ｔ_ｄ５＝３３９℃、Ｔ_ｄ１０＝４１９℃．
Ａｂｓλ_ｍａｘ＝４８６ｎｍ、Ｅｍλ_ｍａｘ＝４９５ｎｍ、Δλ_ｍａｘ＝９ｎｍ、Ｅ_ｇ＝２．４８ｅＶ．
［参考例６］

2′,5′-dibromo-4,4″-bis(2-decyltetradecyloxy)p-terphenyl (242 mg, 0.220 mmol) and 2,6-bis(trimethyltin)-4,8-bis A mixture of [5-(2-ethylhexyl)-2-thienyl] benzo[1,2-b:4,5-b′]dithiophene (200 mg, 0.220 mmol) and toluene (6.6 mL) was freeze-degassed. did. Pd(PPh ₃ ) ₄ (14.2 mg, 0.0122 mmol) was added to this mixed solution under an argon stream, stirred at 120° C. for three days, and cooled to room temperature. The mixture was filtered using celite, and the solvent was distilled off under reduced pressure. After dissolving the obtained solid in chloroform, it was filtered again using celite, and the solvent was distilled off under reduced pressure. The obtained solid was dissolved in a small amount of toluene and precipitated in a mixture of methanol and concentrated hydrochloric acid three times, and further precipitated in diethyl ether and ethanol (=9/10) three times. rice field. The obtained solid was dried under reduced pressure to obtain (12-1) as an orange solid (271 mg, 81%). GPC(THF) _Mn = 11500 g/mol, Mw = ₂₃₅₃₀ g/mol, PDI = 2.05.
¹ H NMR (CD ₂ Cl ₂ , 400 MHz) δ 8.04-5.49 (br, 16H), 4.20-3.62 (br, 4H), 3.17-2.57 (br, 4H), 2 .02-1.13 (br, 100H), 1.10-0.57 (br, 24H).
_Td3 = 316°C, _Td5 = 339°C, _Td10 = 419°C.
Absλ _max =486 nm, Emλ _max =495 nm, Δλ _max =9 nm, E _g =2.48 eV.
[Reference Example 6]

炭酸カリウム（３９．３ｇ，２８４ｍｍｏｌ）、ＤＭＦ（９００ｍＬ）、４－ブロモフェノール（４０．１ｇ，２３２ｍｍｏｌ）と１－ブロモエイコサン（１００ｇ，２７７ｍｍｏｌ）を加えて２３．５時間還流した。飽和塩化アンモニウム水溶液を加えて反応を停止し、エーテルとヘキサンの混合溶媒で抽出した。集めた有機層を飽和塩化アンモニウム水溶液、水、飽和食塩水で洗浄し、無水硫酸マズネシウムで乾燥した。ろ過後に得られた溶液の溶媒を減圧下で留去した。得られた固体を再結晶（酢酸エチル／ヘキサン）で精製し、白色固体の１－ブロモ－４－エイコシルオキシベンゼンを得た（６６．４ｇ，５３％）。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．３５（ｄ，Ｊ＝９．０Ｈｚ，２Ｈ），６．７７（ｄ，Ｊ＝９．０Ｈｚ，２Ｈ），３．９１（ｔ，Ｊ＝６．６Ｈｚ，２Ｈ），１．８０－１．７２（ｍ，２Ｈ），１．４９－１．１９（ｍ，３４Ｈ），０．８８（ｔ，Ｊ＝６．７Ｈｚ，３Ｈ）．
［参考例７］

Potassium carbonate (39.3 g, 284 mmol), DMF (900 mL), 4-bromophenol (40.1 g, 232 mmol) and 1-bromoeicosane (100 g, 277 mmol) were added and refluxed for 23.5 hours. A saturated ammonium chloride aqueous solution was added to terminate the reaction, and the mixture was extracted with a mixed solvent of ether and hexane. The collected organic layer was washed with saturated aqueous ammonium chloride solution, water and saturated brine, and dried over anhydrous maznesium sulfate. The solvent of the solution obtained after filtration was distilled off under reduced pressure. The obtained solid was purified by recrystallization (ethyl acetate/hexane) to obtain 1-bromo-4-eicosyloxybenzene as a white solid (66.4 g, 53%).
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.35 (d, J=9.0 Hz, 2H), 6.77 (d, J=9.0 Hz, 2H), 3.91 (t, J=6. 6Hz, 2H), 1.80-1.72 (m, 2H), 1.49-1.19 (m, 34H), 0.88 (t, J = 6.7Hz, 3H).
[Reference Example 7]

１－ブロモ－４－エイコシルオキシベンゼン（１３．６ｇ、３０．０ｍｍｏｌ）とＤＭＳＯ（１８２ｍＬ）の混合物を３０分間アルゴンバブリングした。この混合物にアルゴン気流下でＰｄＣｌ_２（ｄｐｐｆ）・ＣＨ_２Ｃｌ_２（７４５ｍｇ、９１２μｍｏｌ）と酢酸カリウム（８．８４ｇ、９０．１ｍｍｏｌ）、ならびにＢ_２Ｐｉｎ_２（１１．４ｇ，４４．９ｍｍｏｌ）を加えて８０℃で６０時間撹拌した。反応終了後に室温まで冷却し、エーテルとヘキサンの混合液（１／３）で抽出した。集めた有機層を水と飽和食塩水で洗浄したのちに飽和硫酸マグネシウムで乾燥し、ろ過後に減圧下で溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（酢酸エチル／ヘキサン＝１／１５）で精製して、黄色液体の４－エイコシルオキシフェニルボロン酸ピナコールエステルを得た（１４．４ｇ，９５％）。
^１Ｈ ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．７３（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），６．８８（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），３．９７（ｔ，Ｊ＝６．６Ｈｚ，２Ｈ），１．８１－１．７４（ｍ，２Ｈ），１．４９－１．２５（ｍ，４６Ｈ），０．９０－０．８６（ｍ，３Ｈ）．
［参考例８］

A mixture of 1-bromo-4-eicosyloxybenzene (13.6 g, 30.0 mmol) and DMSO (182 mL) was bubbled with argon for 30 minutes. PdCl ₂ (dppf).CH ₂ Cl ₂ (745 mg, 912 μmol) and potassium acetate (8.84 g, 90.1 mmol), and B ₂ Pin ₂ (11.4 g, 44.9 mmol) were added to this mixture under an argon stream. In addition, the mixture was stirred at 80° C. for 60 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted with a mixed solution (1/3) of ether and hexane. The collected organic layer was washed with water and saturated brine, dried over saturated magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (ethyl acetate/hexane=1/15) to give 4-eicosyloxyphenylboronic acid pinacol ester as a yellow liquid (14.4 g, 95%).
¹ H NMR (CDCl ₃ , 400 MHz) δ 7.73 (d, J = 8.6 Hz, 2H), 6.88 (d, J = 8.6 Hz, 2H), 3.97 (t, J = 6.6 Hz , 2H), 1.81-1.74 (m, 2H), 1.49-1.25 (m, 46H), 0.90-0.86 (m, 3H).
[Reference Example 8]

４－エイコシルオキシフェニルボロン酸ピナコールエステル（１１．１ｇ、２２．２ｍｍｏｌ）と１，４－ジブロモ－２，５－ジヨードベンゼン（４．８９ｇ、１０．０ｍｍｏｌ）、ジメトキシエタン（２５０ｍＬ）、ならびに２Ｍ炭酸カリウム水溶液（１００ｍＬ、２００ｍｍｏｌ）の混合物を３０分間アルゴンバブリングした。この混合液に、アルゴン気流下でＰｄ（ＰＰｈ_３）_４（１．１６ｇ、１．００ｍｍｏｌ）を加えて三日間還流した。得られた混合物を室温まで冷やしたのちに飽和塩化アンモニウム水溶液を加えてエーテルで抽出した。集めた有機層を飽和塩化アンモニウム、水、ならびに飽和食塩水で洗浄したのちに無水硫酸マグネシウムで乾燥した。ろ過後に減圧下で溶媒を留去した。得られた固体を再結晶（クロロホルム）で精製することで白色固体の２’，５’－ジブロモ－４，４’’－ビスエイコシルオキシ－ｐ－ターフェニルを得た（５．４１ｇ，５５％）。
^１ＨＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ９．６１（ｓ，２Ｈ），７．３６（ｄ，Ｊ＝８．８Ｈｚ，４Ｈ），６．９６（ｄ，Ｊ＝８．８Ｈｚ，４Ｈ），４．０１（ｔ，Ｊ＝６．５Ｈｚ，４Ｈ），１．８５－１．７８（ｍ，４Ｈ），１．５１－１．２６（ｍ，６８Ｈ），０．９０－０．８６（ｍ，６Ｈ）．
［参考例９］

4-eicosyloxyphenylboronic acid pinacol ester (11.1 g, 22.2 mmol) and 1,4-dibromo-2,5-diiodobenzene (4.89 g, 10.0 mmol), dimethoxyethane (250 mL), and A mixture of 2M aqueous potassium carbonate (100 mL, 200 mmol) was bubbled with argon for 30 minutes. Pd(PPh ₃ ) ₄ (1.16 g, 1.00 mmol) was added to this mixed solution under an argon stream, and the mixture was refluxed for three days. After the resulting mixture was cooled to room temperature, a saturated aqueous ammonium chloride solution was added and the mixture was extracted with ether. The collected organic layer was washed with saturated ammonium chloride, water and saturated brine, and then dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure. The obtained solid was purified by recrystallization (chloroform) to obtain 2′,5′-dibromo-4,4″-biseicosyloxy-p-terphenyl as a white solid (5.41 g, 55 %).
¹ H NMR (CDCl ₃ , 400 MHz) δ 9.61 (s, 2H), 7.36 (d, J = 8.8 Hz, 4H), 6.96 (d, J = 8.8 Hz, 4H), 4.01 (t, J = 6.5 Hz, 4H), 1.85-1.78 (m, 4H), 1.51-1.26 (m, 68H), 0.90-0.86 (m, 6H) .
[Reference Example 9]

２’，５’―ジブロモ―４，４’’―ビスエイコシルオキシ―ｐ―ターフェニル（２５０ｍｇ，２５５μｍｏｌ）と２，５―ビス（トリメチルスズ）―チエノ［３，２―ｂ］チオフェン（１１８ｍｇ，２５３μｍｏｌ）、ならびにトルエン（９ｍＬ）の混合物を凍結脱気した。この混合液に、アルゴン気流下でＰｄ（ＰＰｈ_３）_４（１５．２ｍｇ，１３．１μｍｏｌ）を加えて１２０℃で７０時間撹拌した。室温まで冷やした後にセライトを用いてろ過し、減圧下で溶媒を留去した。得られた残渣を再度クロロホルムに溶解させたのちにセライトを用いてろ過し、減圧下で溶媒を留去した。得られた固体を少量のクロロホルムに溶解し、ジエチルエーテルとエタノール（＝９／１０）に沈殿する操作を３回繰り返した。得られた固体を９０℃で減圧乾燥することで、淡黄色固体の（１６―１）を得た（２１０ｍｇ，８６％）。
^１ＨＮＭＲ（ｏ－ＤＣＢ－ｄ_４，４００ＭＨｚ）δ７．６０―７．５３（ｂｒ，２Ｈ），７．３６―７．２７（ｂｒ，４Ｈ），７．０６（７．０２（ｂｒ，２Ｈ），６．９３―６．８２（ｂｒ，４Ｈ），４．２５―３．５３（ｂｒ，４Ｈ），２．０９―０．７１（ｂｒ，７８Ｈ）．
Ａｂｓλ_ｍａｘ＝４１６ｎｍ、Ｅｍλ_ｍａｘ＝４９８ｎｍ、Δλ_ｍａｘ＝８２ｎｍ．
［参考例１０］

2′,5′-dibromo-4,4″-biseicosyloxy-p-terphenyl (250 mg, 255 μmol) and 2,5 -bis(trimethyltin)-thieno[3,2-b]thiophene (118 mg , 253 μmol), and toluene (9 mL) were freeze-degassed. Pd(PPh ₃ ) ₄ (15.2 mg, 13.1 μmol) was added to this mixed solution under an argon stream, and the mixture was stirred at 120° C. for 70 hours. After cooling to room temperature, the mixture was filtered using celite, and the solvent was distilled off under reduced pressure. The resulting residue was dissolved again in chloroform, filtered through celite, and the solvent was distilled off under reduced pressure. The operation of dissolving the obtained solid in a small amount of chloroform and precipitating it in diethyl ether and ethanol (=9/10) was repeated three times. The obtained solid was dried under reduced pressure at 90° C. to obtain pale yellow solid (16-1) (210 mg, 86%).
¹ H NMR (o-DCB-d ₄ , 400 MHz) δ 7.60-7.53 (br, 2H), 7.36-7.27 (br, 4H), 7.06 (7.02 (br, 2H) , 6.93-6.82 (br, 4H), 4.25-3.53 (br, 4H), 2.09-0.71 (br, 78H).
Absλ _max =416 nm, Emλ _max =498 nm, Δλ _max =82 nm.
[Reference Example 10]

１－エイコサノール（１５．３ｇ，５１．２ｍｍｏｌ）とセライト（２０ｇ）、ならびにジクロロメタン（２００ｍＬ）の混合物にクロロクロム酸ピリジニウム（１６．６ｇ，７６．９ｍｍｏｌ）を加えて室温で２時間撹拌した。得られた混合物をシリカゲルカラムクロマトグラフィー（クロロホルム）で精製し、白色固体の１－エイコサナールを得た（１４．２ｇ，９４％）。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ９．７６（ｔ，Ｊ＝２．０Ｈｚ，１Ｈ），２．４２（ｄｔ，Ｊ＝７．４Ｈｚ，２．０Ｈｚ，２Ｈ），１．６３（ｑｕｉｎｔ，Ｊ＝７．３Ｈｚ，２Ｈ），１．３４－１．２５（ｍ，３２Ｈ），０．８８（ｔ，Ｊ＝６．８Ｈｚ，３Ｈ）．
［参考例１１］

Pyridinium chlorochromate (16.6 g, 76.9 mmol) was added to a mixture of 1-eicosanol (15.3 g, 51.2 mmol), celite (20 g), and dichloromethane (200 mL), and the mixture was stirred at room temperature for 2 hours. The resulting mixture was purified by silica gel column chromatography (chloroform) to obtain 1-eicosanal as a white solid (14.2 g, 94%).
¹ H-NMR (CDCl ₃ , 400 MHz) δ 9.76 (t, J = 2.0 Hz, 1 H), 2.42 (dt, J = 7.4 Hz, 2.0 Hz, 2 H), 1.63 (quint, J=7.3 Hz, 2H), 1.34-1.25 (m, 32H), 0.88 (t, J=6.8 Hz, 3H).
[Reference Example 11]

四臭化炭素（３３．２ｇ，１００ｍｍｏｌ）とジクロロメタン（２００ｍＬ）の混合物を０℃に冷却し、トリフェニルホスフィン（５２．５ｇ，２００ｍｍｏｌ）を加えた。その後、１－エイコサナール（１４．８ｇ，５０．０ｍｍｏｌ）とジクロロメタン（１００ｍＬ）の混合物を加えて室温で２．５時間撹拌した。生じた白色固体をろ別したのちに、得られた溶液を減圧下で濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィー（ヘキサン）で精製し、白色固体の１，１－ジブロモヘンエイコサン－１－エンを得た（１７．７ｇ，７８％）。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ６．３８（ｔ，Ｊ＝７．０Ｈｚ，１Ｈ），２．０９（ｑ，Ｊ＝７．３Ｈｚ，２Ｈ），１．４５－１．３８（ｍ，２Ｈ），１．３２－１．２６（ｍ，３２Ｈ），０．８８（ｔ，Ｊ＝６．８Ｈｚ，３Ｈ）．
［参考例１２］

A mixture of carbon tetrabromide (33.2 g, 100 mmol) and dichloromethane (200 mL) was cooled to 0° C. and triphenylphosphine (52.5 g, 200 mmol) was added. After that, a mixture of 1-eicosanal (14.8 g, 50.0 mmol) and dichloromethane (100 mL) was added and stirred at room temperature for 2.5 hours. After filtering off the resulting white solid, the resulting solution was concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to give 1,1-dibromoheneicosan-1-ene as a white solid (17.7 g, 78%).
¹ H-NMR (CDCl ₃ , 400 MHz) δ 6.38 (t, J=7.0 Hz, 1 H), 2.09 (q, J=7.3 Hz, 2 H), 1.45-1.38 (m, 2H), 1.32-1.26 (m, 32H), 0.88 (t, J=6.8Hz, 3H).
[Reference Example 12]

１，１－ジブロモヘンエイコサン－１－エン（１１．４ｇ，２５．１ｍｍｏｌ）とＴＨＦ（１００ｍＬ）の混合物に、０℃でｎ－ブチルリチウム（３５ｍＬ，５５．０ｍｍｏｌ）を加えた。室温で３時間撹拌した後に水を加えてヘキサンで抽出した。集めた有機層を水と飽和食塩水で洗浄したのちに無水硫酸マグネシウムで乾燥した。ろ過後に減圧下で溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（ヘキサン）で精製し、白色固体の１－ヘンエイコシンを得た（７．２２ｇ，ｑｕａｎｔ）。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ２．１８（ｄｔ，Ｊ＝７．０Ｈｚ，２．８Ｈｚ，２Ｈ），１．９３（ｔ，Ｊ＝２．６Ｈｚ，１Ｈ），１．５６－１．４９（ｍ，２Ｈ），１．４０－１．３７（ｍ，２Ｈ），１．３２－１．２５（ｍ，３０Ｈ），０．８８（ｔ，Ｊ＝６．８Ｈｚ，３Ｈ）．
［参考例１３］

To a mixture of 1,1-dibromoheneicosan-1-ene (11.4 g, 25.1 mmol) and THF (100 mL) at 0° C. was added n-butyllithium (35 mL, 55.0 mmol). After stirring at room temperature for 3 hours, water was added and the mixture was extracted with hexane. The collected organic layer was washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane) to obtain 1-heneicosine as a white solid (7.22 g, quant).
¹ H-NMR (CDCl ₃ , 400 MHz) δ 2.18 (dt, J = 7.0 Hz, 2.8 Hz, 2H), 1.93 (t, J = 2.6 Hz, 1H), 1.56-1. 49 (m, 2H), 1.40-1.37 (m, 2H), 1.32-1.25 (m, 30H), 0.88 (t, J=6.8Hz, 3H).
[Reference Example 13]

１－ブロモ－４－ヨードベンゼン（０．９９０ｇ，３．５０ｍｍｏｌ）とトルエン（８ｍＬ）ならびにジイソプロピルアミン（８ｍＬ）の混合物を３０分間アルゴンバブリングした。この混合溶液に、アルゴン気流下で１－ヘンエイコシン（１．０２ｇ，３．５０ｍｍｏｌ）とヨウ化銅（Ｉ）（１３ｍｇ，７０μｍｏｌ）ならびにＰｄ（ＰＰｈ_３）_２Ｃｌ_２（２５ｍｇ，３５μｍｏｌ）を加えて２３．５時間還流した。得られた混合物を室温まで冷やしたのちに飽和塩化アンモニウム水溶液を加えてジエチルエーテルで抽出した。集めた有機層を水と飽和食塩水で洗浄したのちに無水硫酸マグネシウムで乾燥した。ろ過後に減圧下で溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（ヘキサン）で精製し、白色固体の１－ブロモ－４－（１－ヘンエイコシニル）ベンゼンを得た（１．１９ｇ，７６％）。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．４０（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），７．２４（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），２．３８（ｔ，Ｊ＝７．２Ｈｚ，２Ｈ），１．５９（ｐｅｎｔｅｔ，Ｊ＝７．４Ｈｚ，２Ｈ），１．４７－１．３９（ｍ，２Ｈ），１．３５－１．２５（ｍ，３０Ｈ），０．８８（ｔ，Ｊ＝６．８Ｈｚ，３Ｈ）．
［参考例１４］

A mixture of 1-bromo-4-iodobenzene (0.990 g, 3.50 mmol), toluene (8 mL) and diisopropylamine (8 mL) was bubbled with argon for 30 minutes. To this mixed solution, 1-heneicosine (1.02 g, 3.50 mmol), copper (I) iodide (13 mg, 70 μmol) and Pd(PPh ₃ ) ₂ Cl ₂ (25 mg, 35 μmol) were added under an argon stream. Refluxed for 23.5 hours. After the resulting mixture was cooled to room temperature, a saturated ammonium chloride aqueous solution was added and the mixture was extracted with diethyl ether. The collected organic layer was washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to give 1-bromo-4-(1-heneicosinyl)benzene as a white solid (1.19 g, 76%).
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.40 (d, J=8.4 Hz, 2H), 7.24 (d, J=8.4 Hz, 2H), 2.38 (t, J=7. 2Hz, 2H), 1.59 (pentet, J = 7.4Hz, 2H), 1.47-1.39 (m, 2H), 1.35-1.25 (m, 30H), 0.88 ( t, J=6.8 Hz, 3H).
[Reference Example 14]

１－ブロモ－４－（１－ヘンエイコシニル）ベンゼン（０．８９５ｇ，２．００ｍｍｏｌ）とテトラヒドロフラン（１０ｍＬ）の混合物に５％パラジウム炭素（９０ｍｇ）を加え、水素雰囲気下室温で４時間撹拌した。ろ過後に得られた溶液の溶媒を減圧下で留去した。得られた残渣を再結晶（エタノール）で精製し、白色固体の１－ブロモ－４－ヘンエイコシルベンゼンを得た（０．５８７ｇ，６５％）。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．３８（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），７．０４（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），２．５５（ｔ，Ｊ＝７．８Ｈｚ，２Ｈ），１．６１－１．５５（ｍ，２Ｈ），１．２９－１．２５（ｍ，３６Ｈ），０．８８（ｔ，Ｊ＝６．８Ｈｚ，３Ｈ）．
［参考例１５］

5% palladium on carbon (90 mg) was added to a mixture of 1-bromo-4-(1-heneicosinyl)benzene (0.895 g, 2.00 mmol) and tetrahydrofuran (10 mL), and the mixture was stirred at room temperature for 4 hours under hydrogen atmosphere. The solvent of the solution obtained after filtration was distilled off under reduced pressure. The obtained residue was purified by recrystallization (ethanol) to obtain 1-bromo-4-heneicosylbenzene as a white solid (0.587 g, 65%).
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.38 (d, J=8.4 Hz, 2H), 7.04 (d, J=8.4 Hz, 2H), 2.55 (t, J=7. 8Hz, 2H), 1.61-1.55 (m, 2H), 1.29-1.25 (m, 36H), 0.88 (t, J = 6.8Hz, 3H).
[Reference Example 15]

１－ブロモ－４－ヘンエイコシルベンゼン（０．５８７ｇ，１．３０ｍｍｏｌ）と１，４－ジオキサン（７．８ｍＬ）の混合物を３０分間アルゴンバブリングした。この混合溶液に、アルゴン気流下でＰｄ（ｄｐｐｆ）Ｃｌ_２・ＣＨ_２Ｃｌ_２（３２ｍｇ，３９μｍｏｌ）と酢酸カリウム（０．３８３ｇ，３．９０ｍｍｏｌ）、ならびにＢ_２Ｐｉｎ_２（０．３９６ｇ，１．５６ｍｍｏｌ）を加えて８０℃で５４時間還流した。反応終了後に室温まで冷却し、エーテルとヘキサンの混合液（１／３）で抽出した。集めた有機層を水と飽和食塩水で洗浄したのちに無水硫酸マグネシウムで乾燥した。ろ過後に減圧下で溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（クロロホルム／ヘキサン＝１／５）で精製して、白色固体の４－ヘニコシルフェニルボロン酸ピナコールエステルを得た（０．４００ｇ，６２％）。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．７３（ｄ，Ｊ＝８．０Ｈｚ，２Ｈ），７．１９（ｄ，Ｊ＝８．０Ｈｚ，２Ｈ），２．６１（ｔ，Ｊ＝７．６Ｈｚ，２Ｈ），１．６４－１．５６（ｍ，２Ｈ），１．３３－１．２５（ｍ，４８Ｈ），０．８８（ｔ，Ｊ＝６．８Ｈｚ，３Ｈ）．
［参考例１６］

A mixture of 1-bromo-4-heneicosylbenzene (0.587 g, 1.30 mmol) and 1,4-dioxane (7.8 mL) was bubbled with argon for 30 minutes. Pd(dppf)Cl ₂ .CH ₂ Cl ₂ (32 mg, 39 μmol), potassium acetate (0.383 g, 3.90 mmol), and B ₂ Pin ₂ (0.396 g, 1.0 mmol) were added to this mixed solution under an argon stream. 56 mmol) was added and refluxed at 80° C. for 54 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted with a mixed solution (1/3) of ether and hexane. The collected organic layer was washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (chloroform/hexane=1/5) to give 4-henicosylphenylboronic acid pinacol ester as a white solid (0.400 g, 62%).
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.73 (d, J=8.0 Hz, 2H), 7.19 (d, J=8.0 Hz, 2H), 2.61 (t, J=7. 6Hz, 2H), 1.64-1.56 (m, 2H), 1.33-1.25 (m, 48H), 0.88 (t, J = 6.8Hz, 3H).
[Reference Example 16]

４－ヘンエイコシルフェニルボロン酸ピナコールエステル（０．３６５ｇ，０．７３２ｍｍｏｌ）と１，４－ジブロモ－２，５－ジヨードベンゼン（０．１６２ｇ，０．３３３ｍｍｏｌ）、ジメトキシエタン（８．２ｍＬ）、ならびに２Ｍ炭酸カリウム水溶液（３．３ｍＬ，６．６ｍｍｏｌ）の混合物を３０分間アルゴンバブリングした。この混合液に、アルゴン気流下でＰｄ（ＰＰｈ_３）_２Ｃｌ_２（２３ｍｇ，３３μｍｏｌ）を加えて３８時間還流した。得られた混合物を室温まで冷やしたのちに飽和塩化アンモニウム水溶液を加えてエーテルで抽出した。集めた有機層を水と飽和食塩水で洗浄したのちに無水硫酸マグネシウムで乾燥してろ過し、減圧下で溶媒を留去した。得られた残渣を再結晶（クロロホルム）で精製し、白色固体の２’，５’ －ジブロモ－４，４’’ －ジヘンエイコシル－ｐ－ターフェニルを得た（０．１２２ｇ，３８％）。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．６３（ｓ，２Ｈ），７．３５（ｄ，Ｊ＝８．４Ｈｚ，４Ｈ），７．２３（ｄ，Ｊ＝８．０Ｈｚ，４Ｈ），２．６６（ｔ，Ｊ＝８．０Ｈｚ，４Ｈ），１．６７（ｐｅｎｔｅｔ，Ｊ＝７．４Ｈｚ，４Ｈ），１．３９－１．２６（ｍ，７２Ｈ），０．８８（ｔ，Ｊ＝７．４Ｈｚ，６Ｈ）．
［参考例１７］

4-heneicosylphenylboronic acid pinacol ester (0.365 g, 0.732 mmol) and 1,4-dibromo-2,5-diiodobenzene (0.162 g, 0.333 mmol), dimethoxyethane (8.2 mL) , and 2M potassium carbonate aqueous solution (3.3 mL, 6.6 mmol) was bubbled with argon for 30 minutes. Pd(PPh ₃ ) ₂ Cl ₂ (23 mg, 33 μmol) was added to this mixed solution under an argon stream, and the mixture was refluxed for 38 hours. After the resulting mixture was cooled to room temperature, a saturated aqueous ammonium chloride solution was added and the mixture was extracted with ether. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The obtained residue was purified by recrystallization (chloroform) to obtain 2′,5′-dibromo-4,4″-diheneicosyl-p-terphenyl as a white solid (0.122 g, 38%).
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.63 (s, 2H), 7.35 (d, J = 8.4 Hz, 4H), 7.23 (d, J = 8.0 Hz, 4H), 2 .66 (t, J = 8.0 Hz, 4H), 1.67 (pentet, J = 7.4 Hz, 4H), 1.39-1.26 (m, 72H), 0.88 (t, J = 7.4Hz, 6H).
[Reference Example 17]

２’，５’―ジブロモ―４，４’’―ビス（ヘンエイコシル）ｐ―ターフェニル（９６．２ｍｇ，１０１μｍｏｌ）と２，５―ビス（トリメチルスズ）―チエノ［３，２―ｂ］チオフェン（４７．４ｍｇ，１０２μｍｏｌ）、ならびにトルエン（３ｍＬ）の混合物を凍結脱気した。この混合液に、アルゴン気流下でＰｄ（ＰＰｈ_３）_４（６．０６ｍｇ，５．２４μｍｏｌ）を加えて１２０℃で８８時間撹拌して室温まで冷やした。この混合液をセライトを用いてろ過し、溶媒を減圧下で留去した。得られた残渣をクロロホルムに溶解させたのちに再度セライトを用いてろ過し、減圧下で溶媒を留去した。得られた固体を少量のクロロホルムに溶解し、ジエチルエーテルとエタノール（＝９／１０）に加え、生じた沈殿をろ別した。この操作を合計３回繰り返し、得られた固体を９０℃で減圧乾燥することで、淡黄色固体の（２４―１）を得た（７８．４ｍｇ，８３％）。
^１ＨＮＭＲ（ｏ－ＤＣＢ－ｄ_４，４００ＭＨｚ）δ７．６１―７．５１（ｂｒ，２Ｈ），７．３９―７．３７（ｂｒ，４Ｈ），７．１９―７．１０（ｂｒ，４Ｈ），６．８７（－６．７８（ｂｒ，２Ｈ），２．７４―２．５１（ｂｒ，４Ｈ），１．７３―１．５１（ｂｒ，４Ｈ），１．４６―１．０２（ｂｒ，７２Ｈ），０．９２―０．７７（ｂｒ，６Ｈ）．
Ａｂｓλ_ｍａｘ＝４１３ｎｍ、Ｅｍλ_ｍａｘ＝４９７ｎｍ、Δλ_ｍａｘ＝８４ｎｍ．
［参考例１８］

2′,5′-dibromo-4,4″-bis(heneicosyl)p-terphenyl (96.2 mg, 101 μmol) and 2,5 -bis(trimethyltin)-thieno[3,2-b]thiophene ( 47.4 mg, 102 μmol), and toluene (3 mL) were freeze degassed. Pd(PPh ₃ ) ₄ (6.06 mg, 5.24 μmol) was added to this mixed solution under an argon stream, stirred at 120° C. for 88 hours, and cooled to room temperature. This mixture was filtered using celite, and the solvent was distilled off under reduced pressure. After dissolving the resulting residue in chloroform, it was filtered again using celite, and the solvent was distilled off under reduced pressure. The resulting solid was dissolved in a small amount of chloroform, added to diethyl ether and ethanol (=9/10), and the resulting precipitate was separated by filtration. This operation was repeated three times in total, and the obtained solid was dried under reduced pressure at 90°C to obtain (24-1) as a pale yellow solid (78.4 mg, 83%).
¹ H NMR (o-DCB-d ₄ , 400 MHz) δ 7.61-7.51 (br, 2H), 7.39-7.37 (br, 4H), 7.19-7.10 (br, 4H) , 6.87 (-6.78 (br, 2H), 2.74-2.51 (br, 4H), 1.73-1.51 (br, 4H), 1.46-1.02 (br , 72H), 0.92-0.77 (br, 6H).
Absλ _max =413 nm, Emλ _max =497 nm, Δλ _max =84 nm.
[Reference Example 18]

トリフェニルホスフィン（２４．４ｇ，６８．９ｍｍｏｌ）と塩化メチレン（１００ｍＬ）の混合液に０℃で臭素（６．８ｍL，１３３ｍｍｏｌ）を加え、そこに２－デシル－１－テトラデカノール（３０ｇ，８４．６ｍｍｏｌ）と塩化メチレン（２０ｍL）の混合液を０℃で加えて室温で１８時間撹拌した。減圧下で溶媒を留去した後に得られた残渣に少量のクロロホルムを加えて溶解し、ヘキサンに滴下した。生じた白色固体をろ別したのちに、得られた溶液の溶媒を減圧下で留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（ヘキサン）で精製し、無色透明液体の１－ブロモ－２－デシルテトラデカンを得た（３３．３ｇ，９４％）。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ３．４５（ｄ，Ｊ＝４．８Ｈｚ，２Ｈ），１．６２－１．５６（ｍ，１Ｈ），１．４６－１．２６（ｍ，４０Ｈ），０．９３－０．８２（ｍ，６Ｈ）．
［参考例１９］

Bromine (6.8 mL, 133 mmol) was added to a mixture of triphenylphosphine (24.4 g, 68.9 mmol) and methylene chloride (100 mL) at 0°C, and 2-decyl-1-tetradecanol (30 g, 84.6 mmol) and methylene chloride (20 mL) was added at 0° C. and stirred at room temperature for 18 hours. A small amount of chloroform was added to dissolve the residue obtained after the solvent was distilled off under reduced pressure, and the solution was added dropwise to hexane. After filtering off the resulting white solid, the solvent of the resulting solution was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to give 1-bromo-2-decyltetradecane as a colorless transparent liquid (33.3 g, 94%).
¹ H-NMR (CDCl ₃ , 400 MHz) δ 3.45 (d, J = 4.8 Hz, 2H), 1.62-1.56 (m, 1H), 1.46-1.26 (m, 40H) , 0.93-0.82 (m, 6H).
[Reference Example 19]

マグネシウム（４．４８ｇ，１８４ｍｍｏｌ）と塩化リチウム（７．８０ｇ，１８４ｍｍｏｌ）を加熱減圧乾燥させた後に、室温でテトラヒドロフラン（３０ｍL）と１，２－ジブロモエタン（０．１５ｍL，１．７４ｍｍｏｌ）を加えた。ヒートガンを用いてこの溶液を１５秒間加熱還流した後に、１－ブロモ－２－デシルテトラデカン（２０．２ｇ，４８．３ｍｍｏｌ）とテトラヒドロフラン（２０ｍL）の混合液を室温で加えて、室温で２時間攪拌した。この溶液を０．５Ｍ－塩化亜鉛のテトラヒドロフラン溶液（４０ｍL、２０ｍｍｏｌ）に０度で加え、室温で１時間攪拌した（アルキル亜鉛溶液）。１－ブロモ－４－ヨードベンゼン（８．８２ｇ，３１．２ｍｍｏｌ）とＰｄＣｌ_２（ｄｐｐｆ）・ＣＨ_２Ｃｌ_２（２２５ｍｇ，２７６μｍｏｌ）、ならびにテトラヒドロフラン（３０ｍL）の混合液を３０分間アルゴンバブリングし後に、調整したアルキル亜鉛溶液を滴下し、５５度で１９．５時間攪拌した。得られた混合物を室温まで冷やし、１Ｍ－塩酸を加えてエーテルで抽出した。集めた有機層を飽和炭酸水素ナトリウム水溶液、水、ならびに飽和食塩水で洗浄したのちに無水硫酸マグネシウムで乾燥してろ過し、減圧下で溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（ヘキサン）で精製して、無色透明液体の１－ブロモ－４－（２－デシルテトラデシル）ベンゼンを得た（２６．７ｇ，８９％）。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．３７（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），７．００（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），２．４７（ｄ，Ｊ＝７．０Ｈｚ，２Ｈ），１．６０－１．５４（ｍ，１Ｈ），１．４５－１．１８（ｍ，４０Ｈ），０．９０－０．８６（ｍ，６Ｈ）．
［参考例２０］

Magnesium (4.48 g, 184 mmol) and lithium chloride (7.80 g, 184 mmol) were heated and dried under reduced pressure, and then tetrahydrofuran (30 mL) and 1,2-dibromoethane (0.15 mL, 1.74 mmol) were added at room temperature. rice field. After heating and refluxing this solution for 15 seconds using a heat gun, a mixture of 1-bromo-2-decyltetradecane (20.2 g, 48.3 mmol) and tetrahydrofuran (20 mL) was added at room temperature and stirred at room temperature for 2 hours. did. This solution was added to a 0.5M zinc chloride tetrahydrofuran solution (40 mL, 20 mmol) at 0° C. and stirred at room temperature for 1 hour (alkyl zinc solution). A mixture of 1-bromo-4-iodobenzene (8.82 g, 31.2 mmol), PdCl ₂ (dppf).CH ₂ Cl ₂ (225 mg, 276 μmol), and tetrahydrofuran (30 mL) was bubbled with argon for 30 minutes, The adjusted alkylzinc solution was added dropwise and stirred at 55 degrees for 19.5 hours. The resulting mixture was cooled to room temperature, 1M-hydrochloric acid was added, and the mixture was extracted with ether. The collected organic layer was washed with a saturated aqueous solution of sodium hydrogencarbonate, water and saturated brine, dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to give 1-bromo-4-(2-decyltetradecyl)benzene as a colorless transparent liquid (26.7 g, 89%).
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.37 (d, J=8.3 Hz, 2H), 7.00 (d, J=8.3 Hz, 2H), 2.47 (d, J=7. 0Hz, 2H), 1.60-1.54 (m, 1H), 1.45-1.18 (m, 40H), 0.90-0.86 (m, 6H).
[Reference Example 20]

１－ブロモ－４－（２－デシルテトラデシル）ベンゼン（２．３５ｇ、４．７５ｍｍｏｌ）と酢酸カリウム（１．５５ｇ、１５．８ｍｍｏｌ）、ならびにＢ_２Ｐｉｎ_２（１．６８ｇ，６．６０ｍｍｏｌ）とＤＭＳＯ（３０ｍＬ）の混合物を３０分間アルゴンバブリングした。この混合物にアルゴン気流下でＰｄＣｌ_２（ｄｐｐｆ）・ＣＨ_２Ｃｌ_２（１２６ｍｇ、０．１５４ｍｍｏｌ）を加えて８０℃で７０．５時間撹拌した。室温まで冷却した後に水にあけ、エーテルとヘキサンの混合液（１／３）で抽出した。集めた有機層を水と飽和食塩水で洗浄した後に飽和硫酸マグネシウムで乾燥し、ろ過後に減圧下で溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（クロロホルム／ヘキサン＝１／２）で精製して、淡黄色液体の４－（２－デシルテトラデシル）フェニルボロン酸ピナコールエステルを得た（１．５７０ｇ，６１％）。
^１Ｈ ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．７１（ｄ，Ｊ＝８．０Ｈｚ，２Ｈ），７．１５（ｄ，８．０Ｈｚ，２Ｈ），２．５３（ｄ，７．０Ｈｚ，２Ｈ），１．６７－１．５６（ｍ，１Ｈ），１．３７－１．１４（ｍ，５２Ｈ），０．８８（ｔ，Ｊ＝６．７Ｈｚ，６Ｈ）．
［参考例２１］

1-bromo-4-(2-decyltetradecyl)benzene (2.35 g, 4.75 mmol) and potassium acetate (1.55 g, 15.8 mmol) and B ₂ Pin ₂ (1.68 g, 6.60 mmol) and DMSO (30 mL) was bubbled with argon for 30 minutes. PdCl ₂ (dppf).CH ₂ Cl ₂ (126 mg, 0.154 mmol) was added to the mixture under an argon stream, and the mixture was stirred at 80° C. for 70.5 hours. After cooling to room temperature, it was poured into water and extracted with a mixed solution (1/3) of ether and hexane. The collected organic layer was washed with water and saturated brine, dried over saturated magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (chloroform/hexane=1/2) to give pale yellow liquid 4-(2-decyltetradecyl)phenylboronic acid pinacol ester (1.570 g, 61 %).
¹ H NMR (CDCl ₃ , 400 MHz) δ 7.71 (d, J = 8.0 Hz, 2H), 7.15 (d, 8.0 Hz, 2H), 2.53 (d, 7.0 Hz, 2H), 1.67-1.56 (m, 1H), 1.37-1.14 (m, 52H), 0.88 (t, J=6.7Hz, 6H).
[Reference Example 21]

４－（２－デシルテトラデシル）フェニルボロン酸ピナコールエステル（１．４２ｇ、２．６２ｍｍｏｌ）と１，４－ジブロモ－２，５－ジヨードベンゼン（５３３ｍｇ、１．０９ｍｍｏｌ）、ジメトキシエタン（２２ｍＬ）、ならびに２Ｍ炭酸カリウム水溶液（１０ｍＬ、２０ｍｍｏｌ）の混合物を３０分間アルゴンバブリングした。この混合液に、アルゴン気流下でＰｄ（ＰＰｈ_３）_４（３０．２ｍｇ、０．０２６１ｍｍｏｌ）を加えて４０時間還流した。得られた混合物を室温まで冷やしたのちに飽和塩化アンモニウム水溶液を加えてエーテルで抽出した。集めた有機層を水、ならびに飽和食塩水で洗浄したのちに無水硫酸マグネシウムで乾燥してろ過し、減圧下で溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（ヘキサン）と分取ＨＰＬＣ（クロロホルム）で精製することで無色透明液体の２’，５’－ジブロモ－４，４’’－ビス（２－デシルテトラデシル）－ｐ－ターフェニルを得た（３７９ｍｇ，３３％）。
^１ＨＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．６４（ｓ，２Ｈ），７．３５（ｄ，Ｊ＝８．２Ｈｚ，４Ｈ），７．２２（ｄ，Ｊ＝８．２Ｈｚ，４Ｈ），２．５８（ｄ，Ｊ＝６．９Ｈｚ，４Ｈ），１．７１－１．６２（ｍ，２Ｈ），１．３８－１．１７（ｍ，８０Ｈ），０．９０－０．８５（ｍ，１２Ｈ）．
［参考例２２］

4-(2-decyltetradecyl)phenylboronic acid pinacol ester (1.42 g, 2.62 mmol) and 1,4-dibromo-2,5-diiodobenzene (533 mg, 1.09 mmol), dimethoxyethane (22 mL) , and 2M aqueous potassium carbonate (10 mL, 20 mmol) was bubbled with argon for 30 minutes. Pd(PPh ₃ ) ₄ (30.2 mg, 0.0261 mmol) was added to this mixed solution under an argon stream, and the mixture was refluxed for 40 hours. After the resulting mixture was cooled to room temperature, a saturated aqueous ammonium chloride solution was added and the mixture was extracted with ether. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) and preparative HPLC (chloroform) to give 2',5'-dibromo-4,4''-bis(2-decyltetradecyl) as a colorless transparent liquid. -p-terphenyl was obtained (379 mg, 33%).
¹ H NMR (CDCl ₃ , 400 MHz) δ 7.64 (s, 2H), 7.35 (d, J = 8.2 Hz, 4H), 7.22 (d, J = 8.2 Hz, 4H), 2.58 (d, J = 6.9Hz, 4H), 1.71-1.62 (m, 2H), 1.38-1.17 (m, 80H), 0.90-0.85 (m, 12H) .
[Reference Example 22]

２’，５’―ジブロモ―４，４’’―ビス（２―デシルテトラデシル）ｐ―ターフェニル（１４７ｍｇ，１３９μｍｏｌ）と２，５―ビス（トリメチルスズ）―チエノ［３，２―ｂ］チオフェン（６４．８ｍｇ，１３９μｍｏｌ）、ならびにトルエン（５ｍＬ）の混合物を凍結脱気した。この混合液に、アルゴン気流下でＰｄ（ＰＰｈ_３）_４（８．５６ｍｇ，７．４１μｍｏｌ）を加えて１２０℃で三日間撹拌して室温まで冷やした。この混合液をセライトを用いてろ過し、減圧下で溶媒を留去した。得られた残渣をクロロホルムに溶解させたのちに再度セライトを用いてろ過し、減圧下で溶媒を留去した。得られた固体を少量のクロロホルムに溶解し、ジエチルエーテルとエタノール（＝９／１０）に加え、生じた沈殿をろ別した。この操作を合計３回繰り返し、得られた固体を９０℃で減圧乾燥することで、淡黄色固体の（２９―１）を得た（１２３ｍｇ，８６％）。
ＧＰＣ（ＴＨＦ）Ｍ_ｎ＝２６３００ｇ／ｍｏｌ，Ｍ_ｗ＝５２７００ｇ／ｍｏｌ，ＰＤＩ＝２．００．
^１ＨＮＭＲ（ＣＤ_２Ｃｌ_２，４００ＭＨｚ）δ７．５４（ｓ，２Ｈ），７．２２（ｄ，Ｊ＝７．７Ｈｚ，４Ｈ），７．０９（ｄ，Ｊ＝８．０Ｈｚ，４Ｈ），１．６６―１．５８（ｍ，２Ｈ），１．４４―１．０４（ｍ，８０Ｈ），０．８７―０．８４（ｍ，１２Ｈ）．
Ａｂｓλ_ｍａｘ＝４１０ｎｍ、Ｅｍλ_ｍａｘ＝４９３ｎｍ、Δλ_ｍａｘ＝８３ｎｍ．
［実施例１］

2′,5′-dibromo-4,4″-bis(2-decyltetradecyl)p-terphenyl (147 mg, 139 μmol) and 2,5 -bis(trimethyltin)-thieno[3,2-b] A mixture of thiophene (64.8 mg, 139 μmol) and toluene (5 mL) was freeze degassed. Pd(PPh ₃ ) ₄ (8.56 mg, 7.41 μmol) was added to this mixed solution under an argon stream, stirred at 120° C. for 3 days, and cooled to room temperature. This mixed solution was filtered using celite, and the solvent was distilled off under reduced pressure. After dissolving the resulting residue in chloroform, it was filtered again using celite, and the solvent was distilled off under reduced pressure. The resulting solid was dissolved in a small amount of chloroform, added to diethyl ether and ethanol (=9/10), and the resulting precipitate was separated by filtration. This operation was repeated three times in total, and the obtained solid was dried under reduced pressure at 90°C to obtain (29-1) as a pale yellow solid (123 mg, 86%).
GPC(THF) _Mn = 26300 g/mol, Mw = ₅₂₇₀₀ g/mol, PDI = 2.00.
¹ H NMR (CD ₂ Cl ₂ , 400 MHz) δ 7.54 (s, 2H), 7.22 (d, J = 7.7 Hz, 4H), 7.09 (d, J = 8.0 Hz, 4H) , 1.66-1.58 (m, 2H), 1.44-1.04 (m , 80H), 0.87-0.84 (m, 12H).
Absλ _max =410 nm, Emλ _max =493 nm, Δλ _max =83 nm.
[Example 1]

（１１－１）（１００．３ｍｇ）を１０分間アルゴンバブリングした塩化メチレン（１０ｍＬ）に溶解し、この溶液をアルゴンバブリングしながら、ニトロメタン（５ｍＬ）に溶かした塩化第二鉄（１３８ｍｇ，０．８５０ｍｍｏｌ）の溶液をゆっくりと滴下した。アルゴンバブリングを１時間続けたのちにアルゴンガスを停止し、アルゴン雰囲気下でさらに２４時間撹拌した。得られた混合物をメタノールと濃塩酸の混合液（３００ｍＬ／３０ｍＬ）に滴下してろ過した。得られた固体を少量のクロロホルムに溶解し、メタノールに沈殿させることで析出した固体をろ過した。得られた固体をメタノールと水で洗浄したのちに９０℃で減圧乾燥することで黄色固体の（３０－１）を得た（９６．４ｍｇ，９６％）。ＧＰＣ（ＴＨＦ）Ｍ_ｎ＝３１９３０ｇ／ｍｏｌ．Ｍ_ｗ＝１４１３１０ｇ／ｍｏｌ，ＰＤＩ＝４．４３．
^１ＨＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ９．３２－６．５２（ｂｒ，８Ｈ），４．８１－３．２６（ｂｒ，４Ｈ），２．１８－０．９９（ｂｒ，８２Ｈ），０．９２－０．６６（ｂｒ，１２Ｈ）．
Ｔ_ｄ３＝３１４℃、Ｔ_ｄ５＝３３７℃、Ｔ_ｄ１０＝３６１℃．
Ａｂｓλ_ｍａｘ＝４８８ｎｍ、Ｅｍλ_ｍａｘ＝５０６ｎｍ、Δλ_ｍａｘ＝１８ｎｍ、Ｅ_ｇ＝２．４０ｅＶ．
ＨＯＭＯ＝-５．２４ｅＶ、ＬＵＭＯ＝-２．８８ｅＶ．
［実施例２］

(11-1) (100.3 mg) was dissolved in methylene chloride (10 mL) bubbled with argon for 10 minutes, and ferric chloride (138 mg, 0.850 mmol) dissolved in nitromethane (5 mL) was dissolved while bubbling this solution with argon. ) was slowly added dropwise. After argon bubbling was continued for 1 hour, the argon gas was stopped, and the mixture was stirred for another 24 hours under an argon atmosphere. The resulting mixture was added dropwise to a mixture of methanol and concentrated hydrochloric acid (300 mL/30 mL) and filtered. The obtained solid was dissolved in a small amount of chloroform, precipitated in methanol, and the precipitated solid was filtered. The resulting solid was washed with methanol and water and then dried under reduced pressure at 90° C. to obtain yellow solid (30-1) (96.4 mg, 96%). GPC(THF) _Mn = 31930 g/mol. Mw = ₁₄₁₃₁₀ g/mol, PDI = 4.43.
¹ H NMR (CDCl ₃ , 400 MHz) δ 9.32-6.52 (br, 8H), 4.81-3.26 (br, 4H), 2.18-0.99 (br, 82H), 0.92 -0.66 (br, 12H).
_Td3 = 314°C, _Td5 = 337°C, _Td10 = 361°C.
Absλ _max =488 nm, Emλ _max =506 nm, Δλ _max =18 nm, E _g =2.40 eV.
HOMO=-5.24 eV, LUMO=-2.88 eV.
[Example 2]

（１６－１）（１９．７ｍｇ）を１０分間アルゴンバブリングした塩化メチレン（４ｍＬ）に溶解し、この溶液をアルゴンバブリングしながら、ニトロメタン（０．２ｍＬ）に溶かした塩化第二鉄（３０ｍｇ，０．１９ｍｍｏｌ）の溶液をゆっくりと滴下した。アルゴンバブリングを３０分間続けたのちにアルゴンガスを停止し、アルゴン雰囲気下でさらに三日間撹拌した。得られた混合物をメタノールと濃塩酸の混合液（３００ｍＬ／３０ｍＬ）に滴下してろ過した。得られた固体を少量のクロロホルムに溶解し、メタノールに沈殿させることで析出した固体をろ過した。得られた固体をメタノールと水で洗浄したのちにソックスレー抽出（メタノール→アセトン→ヘキサン→クロロホルム→モノクロロベンゼン→o－ジクロロベンゼン）を行い、o－ジクロロベンゼンに可溶部をメタノールに沈殿させ、析出した固体をろ過した。得られた固体をメタノールで洗浄したのちに９０℃で減圧乾燥することで赤褐色固体の（３１－１）を得た（９６．４ｍｇ，９６％）。
Ａｂｓλ_ｍａｘ＝４９０ｎｍ、Ｅｍλ_ｍａｘ＝５４７ｎｍ、Δλ_ｍａｘ＝５７ｎｍ．
［実施例３］

(16-1) (19.7 mg) was dissolved in methylene chloride (4 mL) bubbled with argon for 10 minutes, and while bubbling this solution with argon, ferric chloride dissolved in nitromethane (0.2 mL) (30 mg, 0 .19 mmol) was slowly added dropwise. After continuing the argon bubbling for 30 minutes, the argon gas was stopped, and the mixture was stirred under an argon atmosphere for three days. The resulting mixture was added dropwise to a mixture of methanol and concentrated hydrochloric acid (300 mL/30 mL) and filtered. The obtained solid was dissolved in a small amount of chloroform, precipitated in methanol, and the precipitated solid was filtered. The obtained solid was washed with methanol and water, and then subjected to Soxhlet extraction (methanol → acetone → hexane → chloroform → monochlorobenzene → o-dichlorobenzene). The resulting solid was filtered. The obtained solid was washed with methanol and then dried under reduced pressure at 90° C. to obtain reddish brown solid (31-1) (96.4 mg, 96%).
Absλ _max =490 nm, Emλ _max =547 nm, Δλ _max =57 nm.
[Example 3]

（２４－１）（１１．８ｍｇ）を１０分間アルゴンバブリングしたo－ジクロロベンゼン（１ｍＬ）に溶解し、この溶液をアルゴンバブリングしながら、ニトロメタン（０．５ｍＬ）に溶かした塩化第二鉄（２１ｍｇ，０．１３ｍｍｏｌ）の溶液をゆっくりと滴下した。アルゴンバブリングを３０分間続けたのちにアルゴンガスを停止し、アルゴン雰囲気下でさらに三日間撹拌した。得られた混合物をメタノールと濃塩酸の混合液（３００ｍＬ／３０ｍＬ）に滴下してろ過した。得られた固体を少量のクロロホルムに溶解し、メタノールに沈殿させることで析出した固体をろ過した。得られた固体をメタノールと水で洗浄したのちにソックスレー抽出（メタノール→アセトン→ヘキサン→クロロホルム→モノクロロベンゼン）を行い、モノクロロベンゼンに可溶部をメタノールに沈殿させて析出した固体をろ過した。得られた固体をメタノールで洗浄したのちに９０℃で減圧乾燥することで赤褐色固体の（３２－１）を得た（５．５２ｍｇ，４７％）。
Ａｂｓλ_ｍａｘ＝４６２ｎｍ、Ｅｍλ_ｍａｘ＝５００ｎｍ、Δλ_ｍａｘ＝３８ｎｍ．
［実施例４］

(24-1) (11.8 mg) was dissolved in o-dichlorobenzene (1 mL) bubbled with argon for 10 minutes, and ferric chloride (21 mg) dissolved in nitromethane (0.5 mL) was dissolved while bubbling this solution with argon. , 0.13 mmol) was slowly added dropwise. After continuing the argon bubbling for 30 minutes, the argon gas was stopped, and the mixture was stirred under an argon atmosphere for three days. The resulting mixture was added dropwise to a mixture of methanol and concentrated hydrochloric acid (300 mL/30 mL) and filtered. The obtained solid was dissolved in a small amount of chloroform, precipitated in methanol, and the precipitated solid was filtered. The obtained solid was washed with methanol and water, and then subjected to Soxhlet extraction (methanol -> acetone -> hexane -> chloroform -> monochlorobenzene). The resulting solid was washed with methanol and dried under reduced pressure at 90° C. to obtain reddish brown solid (32-1) (5.52 mg, 47%).
Absλ _max =462 nm, Emλ _max =500 nm, Δλ _max =38 nm.
[Example 4]

（２９－１）（１０．２ｍｇ）を１０分間アルゴンバブリングした塩化メチレン（２ｍＬ）に溶解し、この溶液をアルゴンバブリングしながら、ニトロメタン（０．１ｍＬ）に溶かした塩化第二鉄（１４ｍｇ，０．０８７μｍｏｌ）の溶液をゆっくりと滴下した。アルゴンバブリングを３０分間続けたのちにアルゴンガスを停止し、アルゴン雰囲気下でさらに三日間撹拌した。得られた混合物をメタノールと濃塩酸の混合液（３００ｍＬ／３０ｍＬ）に滴下してろ過した。得られた固体を少量のクロロホルムに溶解し、メタノールに沈殿させることで析出した固体をろ過した。得られた固体をメタノールと水で洗浄したのちにソックスレー抽出（メタノール→アセトン→ヘキサン→クロロホルム）を行い、クロロホルムに可溶部をメタノールに沈殿させて析出した固体をろ過した。得られた固体をメタノールで洗浄したのちに９０℃で減圧乾燥することで赤褐色固体の（３３－１）を得た（５．４２ｍｇ，５４％）。ＧＰＣ（ＴＨＦ）Ｍ_ｎ＝４０６００ｇ／ｍｏｌ．Ｍ_ｗ＝９９７００ｇ／ｍｏｌ，ＰＤＩ＝２．４６．
^１ＨＮＭＲ（ＣＤ_２Ｃｌ_２，４００ＭＨｚ）δ８．９９－６．１６（ｂｒ，８Ｈ），４．０２－２．４５（ｂｒ，４Ｈ），２．２８－０．９３（ｂｒ，８２），０．９３－０．５０（ｂｒ，１２Ｈ）．
Ａｂｓλ_ｍａｘ＝４７０ｎｍ、Ｅｍλ_ｍａｘ＝４８８ｎｍ、Δλ_ｍａｘ＝１８ｎｍ．
［実施例５］
実施例１で作成した（１３－１）（１ｍｇ）を、トルエン（１ｍＬ）、キシレン（１ｍＬ）、テトラリン（１ｍＬ）、ジクロロベンゼン（１ｍＬ）にそれぞれ溶解することで三種類の製膜用組成物を調製した。
［実施例４］
実施例３で調製した製膜用組成物をガラス基板上に滴下した後に、スピンコーターで有機薄膜を作成し、該薄膜を減圧下２００℃で一晩乾燥させることで黄色の有機薄膜を得た。加熱減圧乾燥後に有機薄膜のひび割れなどがないことを確認した。
［実施例５］
実施例１で合成した（１３－１）の０．１ｗｔ％トルエン溶液を調整し、メンブランフィルター（０．２２μｍ）でろ過することで有機薄膜製膜用組成物を得た。

(29-1) (10.2 mg) was dissolved in methylene chloride (2 mL) with argon bubbling for 10 minutes, and while bubbling this solution with argon, ferric chloride (14 mg, 0 .087 μmol) solution was slowly added dropwise. After continuing the argon bubbling for 30 minutes, the argon gas was stopped, and the mixture was stirred under an argon atmosphere for three days. The resulting mixture was added dropwise to a mixture of methanol and concentrated hydrochloric acid (300 mL/30 mL) and filtered. The obtained solid was dissolved in a small amount of chloroform, precipitated in methanol, and the precipitated solid was filtered. The obtained solid was washed with methanol and water, and then subjected to Soxhlet extraction (methanol→acetone→hexane→chloroform). The chloroform-soluble portion was precipitated in methanol, and the precipitated solid was filtered. The resulting solid was washed with methanol and dried under reduced pressure at 90° C. to obtain reddish brown solid (33-1) (5.42 mg, 54%). GPC(THF) _Mn = 40600 g/mol. Mw = ₉₉₇₀₀ g/mol, PDI = 2.46.
¹ H NMR (CD ₂ Cl ₂ , 400 MHz) δ 8.99-6.16 (br, 8H), 4.02-2.45 (br, 4H), 2.28-0.93 (br, 82), 0 .93-0.50 (br, 12H).
Absλ _max =470 nm, Emλ _max =488 nm, Δλ _max =18 nm.
[Example 5]
(13-1) (1 mg) prepared in Example 1 was dissolved in toluene (1 mL), xylene (1 mL), tetralin (1 mL), and dichlorobenzene (1 mL) to prepare three types of film-forming compositions. was prepared.
[Example 4]
After dropping the film-forming composition prepared in Example 3 onto a glass substrate, an organic thin film was formed using a spin coater, and the thin film was dried overnight at 200°C under reduced pressure to obtain a yellow organic thin film. . It was confirmed that there were no cracks in the organic thin film after drying under reduced pressure by heating.
[Example 5]
A 0.1 wt % toluene solution of (13-1) synthesized in Example 1 was prepared and filtered through a membrane filter (0.22 μm) to obtain a composition for forming an organic thin film.

Next, an aluminum electrode was formed on a glass substrate in the air by a vapor deposition method. After forming a film of parylene C as a gate insulating film on the aluminum electrode by the CVD method, the solution described above was drop-cast. This was air-dried to form an organic thin film (13-1).

A shadow mask having a channel length of 100 μm and a channel width of 500 μm was placed on the organic thin film, and gold was vapor-deposited under vacuum to attach source and drain electrodes to prepare a bottom-gate/top-contact type organic thin-film transistor element (gate electrode is aluminum, the gate insulating layer is Parylene C, the source electrode is gold, and the drain electrode is gold).

Under the atmosphere, the organic transistor element was connected to a semiconductor parameter analyzer (4200-SCS manufactured by Keithley), and the drain voltage (Vd = -50 V) and the gate voltage (Vg) were scanned from +10 to -120 V in increments of 1 V, The transfer characteristics were evaluated. The organic transistor device exhibited p-type characteristics, and its hole carrier mobility was 1.4×10 ⁻⁵ cm ² /Vs. The hole carrier mobility after annealing at 100° C. for 15 minutes is 1.0×10 ⁻⁵ cm ² /Vs, and the hole carrier mobility after annealing at 140° C. for 15 minutes is 1.0×10 −5 cm 2 /Vs. It was 5×10 ⁻⁵ cm ² /Vs. From this, it was confirmed that the semiconductor/electrical characteristics did not deteriorate even after the heat treatment.

In the same manner as for (32-1) and (33-1) synthesized in Examples 3 and 4, a composition for forming an organic thin film, an organic thin film, and an organic transistor element were prepared. Their hole carrier mobilities were 2.0×10 ⁻⁵ cm ² /Vs and 3.0×10 ⁻⁵ cm ² /Vs. After annealing at 100° C. for 15 minutes, the carrier mobilities of holes were 3.0×10 ⁻⁵ cm ² /Vs and 2.0×10 ⁻⁵ cm ² /Vs, respectively.

The condensed ring polymer compound provided by the present invention is expected to be applied as a semiconductor device material represented by an organic transistor element because it provides high carrier mobility and is excellent in solubility in solvents and heat resistance.

Claims (8)

General formula (1)

(In the formula, R ¹ is an alkyl group having 6 to 30 carbon atoms optionally substituted by an alkoxy group having 1 to 13 carbon atoms, an alkyl group having 6 to 30 carbon atoms optionally substituted by an alkoxy group having 1 to 13 carbon atoms, represents an alkoxy group or a hydrogen atom of 30. A plurality of R ¹ may be the same or different, and R ² may be substituted with an alkyl group having 6 to 20 carbon atoms or an alkyl group having 1 to 8 carbon atoms. a thienyl group or a hydrogen atom, n represents an integer of 2 or more, m represents 0 or 1, and n m may be the same or different. R ¹ is an alkoxy group having 6 to 30 carbon atoms optionally substituted by an alkoxy group having 1 to 13 carbon atoms, and R ² is 5-alkyl optionally substituted by an alkyl group having 1 to 8 carbon atoms. The condensed ring polymer compound according to claim 1, which is a -2-thienyl group. general formula (2)

(wherein R ¹ is an alkyl group having 6 to 30 carbon atoms optionally substituted by an alkoxy group having 1 to 13 carbon atoms, an alkyl group having 6 to 30 carbon atoms optionally substituted by an alkoxy group having 1 to 13 carbon atoms, represents an alkoxy group or a hydrogen atom of 30. A plurality of R ¹ may be the same or different, and R ² may be substituted with an alkyl group having 6 to 20 carbon atoms or an alkyl group having 1 to 8 carbon atoms. represents a thienyl group or a hydrogen atom, n represents an integer of 2 or more, m represents 0 or 1, and n m may be the same or different. General formula (1), characterized by acting an agent

(wherein R ¹ , R ² , m and n have the same meanings as defined above). R ¹ is an alkoxy group having 6 to 30 carbon atoms optionally substituted by an alkoxy group having 1 to 13 carbon atoms, and R ² is 5-alkyl optionally substituted by an alkyl group having 1 to 8 carbon atoms. -2-thienyl group, the production method according to claim 3. 5. The production method according to claim 3 or 4, wherein the oxidizing agent is ferric chloride. A film-forming composition comprising the condensed ring polymer compound according to claim 1 or 2. An organic thin film produced using the film-forming composition according to claim 6 . A transistor device comprising the organic thin film according to claim 7 .

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