New regulations for compounds

Abstract

To provide a compound useful as an ingredient of a new conjugated polymer with all of high carrier mobility, high thermostability and high solubility useful as an active layer of a semiconductor element and an organic thin film transistor element.SOLUTION: The compound is represented by general formula (int-1).SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a novel compound useful as a raw material for conjugated polymers containing an oligoheteroacene containing chalcogenochalcogenofen as a structural unit. [Background technology]

[0002] Conjugated organic compounds are well known as organic semiconductors used in organic thin-film solar cells, organic thin-film transistors, organic LEDs, and the like. Conjugated organic compounds have characteristics not found in inorganic compounds, such as energy saving, low cost, solubility in organic solvents, light weight, and flexibility, and can also be used as coating materials applied to printed electronics (Patent Document 1).

[0003] Conjugated organic compounds such as oligoacenes, including pentacene, disclosed in Non-Patent Document 1, and oligoacenes having thiophene and thienothiophene skeletons, disclosed in Non-Patent Document 2 (hereinafter referred to as oligoheteroacenes), are being studied for their application to organic thin-film transistors. Among these, oligoheteroacenes having a thienothiophene skeleton tend to exhibit high carrier mobility. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2017-59668 [Non-patent literature]

[0005] [Non-Patent Document 1] Polymer Journal, Vol. 49, pp. 23-30, 2017. [Non-Patent Document 2] Chemical Reviews, Vol. 115, pp. 3036-3140, 2015. [Non-Patent Document 3] Tetrahedron Letters, Vol. 55, pp. 5663-5666, 2014. [Overview of the project] [Problems that the invention aims to solve]

[0006] However, oligoheterocenes have been criticized for problems such as low solubility, poor film-forming ability, and low atmospheric stability (Non-Patent Literature 3). Therefore, there is a need for the development of new conjugated organic compounds and monomers and monomer intermediates that are useful as raw materials for these compounds.

[0007] To solve the above problems, the present invention aims to provide compounds that can be suitably used as intermediates for organic semiconductors, fluorescent probes, fillers, pharmaceuticals and agrochemicals, intermediates for low molecular weight organic semiconductors, and especially monomer intermediates for polymer organic semiconductors. [Means for solving the problem]

[0008] To solve the above problems, the inventors conducted diligent research and found that the compound represented by the general formula (int-1) is useful as an intermediate compound for monomers used in the production of conjugated polymers that can be applied to transistor elements, thus completing the present invention.

[0009] In other words, the present invention consists of the following gist. [Abstract 1] A compound represented by the following general formula (int-1). [ka] (In the formula, R 1 and R 2 Each of these independently represents an alkyl group having 1 to 50 carbon atoms. 1 and R 2 They may also form a ring together with the carbon atoms to which they are bonded. 3 J represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. 1 and J 2each independently represents a chalcogen atom. M 1 represents one group selected from the group consisting of a hydrogen atom, a halogen atom, and a silicon-containing group. Y 1 represents one group selected from the group consisting of a hydrogen atom, a halogen atom, and an aryl group having 6 to 50 carbon atoms which may be substituted with a halogen atom. Y 2 represents one group selected from the group consisting of an alkyl group having 3 to 50 carbon atoms which may be substituted with a hydroxyl group, a hydrogen atom, and a halogen atom.) Regarding Summary 1, R 1 and R 2 are each independently an alkyl group having 1 to 34 carbon atoms, and R 1 and R 2 [[ID= sixteen]]may together form a ring with the carbon atom to which they are attached, and R 3 is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 34 carbon atoms, and J 1 and J 2 are each independently an oxygen atom, a sulfur atom, or a selenium atom, and M 1 is a hydrogen atom, a bromine atom, an iodine atom, or a silicon-containing group, and Y 1 is an aryl group having 6 to 50 carbon atoms which may be substituted with a halogen atom or a halogen atom, and Y 2 may be an alkyl group having 3 to 50 carbon atoms which may be substituted with a hydroxyl group or a halogen atom.) Regarding Summary 1, R 3 is a hydrogen atom, and J 1 and J 2 are sulfur atoms, and M 1 is a hydrogen atom, a bromine atom, or a silicon-containing group, and Y 1 is an aryl group having 5 to 10 carbon atoms which may be substituted with a halogen atom or a halogen atom, and Y 2 may be an alkyl group having 3 to 33 carbon atoms which may be substituted with a hydroxyl group or a halogen atom.)

Advantages of the Invention

[0010] The conjugated polymer produced using the compound of the present invention as a raw material is an organic semiconductor that possesses both high solubility and heat resistance, and can efficiently drive organic thin-film transistor elements using it as the active layer. [Modes for carrying out the invention]

[0011] Embodiments of the present invention will be described in detail below. However, the present invention is not limited thereto, and various modifications are possible within the scope described. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included within the technical scope of the present invention. In this specification, unless otherwise specified, "A to B" representing a numerical range means "A or greater, B or less".

[0012] [Compound] A compound according to one embodiment of the present invention (which may also be referred to as "the compound of this embodiment" in this specification) is a compound represented by the general formula (int-1).

[0013] [ka]

[0014] (In the formula, R 1 and R 2 Each of these independently represents an alkyl group having 1 to 50 carbon atoms. 1 and R 2 They may also form a ring together with the carbon atoms to which they are bonded. 3 J represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. 1 and J 2 Each of these independently represents a chalcogen atom. 1 Y represents one group selected from the group consisting of hydrogen atoms, halogen atoms, and silicon-containing groups. 1 Y represents one group selected from the group consisting of a hydrogen atom, a halogen atom, and an aryl group having 6 to 50 carbon atoms that may be substituted with a halogen atom. 2(This represents one group selected from the group consisting of alkyl groups having 3 to 50 carbon atoms, hydrogen atoms, and halogen atoms, which may be substituted with a hydroxyl group.)

[0015] (general formula (int-1)) R 1 , R 2 or R 3 The alkyl group having 1 to 50 carbon atoms represented by can be linear, branched, or cyclic, and may include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, hentricoroctyl, dodoriacontyl, tritricoroctyl, tetratricoroctyl, pentatricoroctyl, hexatricoroctyl, tetracontyl, hentetracontyl Examples include linear alkyl groups such as 3-L, 3-Tetracontyl, 3-Tetracontyl, 3-Tetracontyl, 3-Tetracontyl, 3-Tetracontyl, 3-Isopropyl, 3-Isobutyl, 3-Sec-butyl, 3-Tetracontyl, 3-Isopropyl, 3-Isobutyl, 3-Sec-butyl, 3-Tetracontyl, 3-Isopropyl, 3-Isobutyl, 3-Isobutyl, 3-Tetracontyl, 3-Isopropyl

[0016] R 1 and R 2As the alkyl group represented by , a C1 to C34 alkyl group is preferred in that it increases the solubility of the compound in this embodiment, and includes 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 group, nonadecyl group, icosyl group, henicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, hentriacontyl group, dodoriacontyl group, tritriacontyl group, tetratriacontyl group, and pentatria More preferably, contyl group, hexatriacontyl group, tetracontyl group, hentetracontyl group, dotetracontyl group, tritetracontyl group, tetratetracontyl group, pentacontyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, 2-hexyloctyl group, 2-hexyldecyl group, 2-octyldodecyl group, 2-decyltetradecyl group, 2-dodecyltetradecyl group, 2-dodecylhexadecyl group, 2-tetradecylhexadecyl group, 3-decylpentadecyl group, 3-dodecylheptadecyl group, 3-tetradecylnonacosyl group, 4-decylhexadecyl group, 4-dodecyloctadecyl group, or 4-tetradecylicosyl group are preferred, and hexyl or decyl groups are even more preferred.

[0017] R 1 and R 2These may form a ring together with the carbon atoms to which they are bonded. Examples of such rings include cyclopropane-1,1-diyl group, cyclobutane-1,1-diyl group, cyclopentane-1,1-diyl group, cyclohexane-1,1-diyl group, cycloheptane-1,1-diyl group, cyclooctane-1,1-diyl group, indene-1,1-diyl group, or fluorene-9,9-diyl group. In terms of increasing the solubility of the compound in this embodiment, the ring is preferably cyclopentane-1,1-diyl group, cyclohexane-1,1-diyl group, indene-1,1-diyl group, or fluorene-9,9-diyl group, and more preferably cyclohexane-1,1-diyl group or fluorene-9,9-diyl group.

[0018] R 3As the alkyl group represented by , alkyl groups having 1 to 50 carbon atoms are preferred in terms of increasing the solubility of the compound in this embodiment, and alkyl groups having 1 to 34 carbon atoms are more preferred, including 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 group, nonadecyl group, icosyl group, henicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, octacosyl group, nonacosyl group, triacontyl group, hentrichocontyl group, dodoriacontyl group, tritrichocontyl group, tetratrichocontyl group, pentacosyl group, hexacosyl group, tetracontyl group, hentetracontyl 3-ethylhexyl group, 3,7-dimethyloctyl group, 2-hexyloctyl group, 2-hexyldecyl group, 2-octyldodecyl group, 2-decyltetradecyl group, 2-dodecyltetradecyl group, 2-dodecylhexadecyl group, 2-tetradecylhexadecyl group, 3-decylpentadecyl group, 3-dodecylhexadecyl group Tadecyl group, 3-tetradecylnonacosyl group, 4-decylhexadecyl group, 4-dodecyloctadecyl group, or 4-tetradecylicosyl group are more preferred, and 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 group, nonadecyl group, or icosyl group are particularly preferred.

[0019] R 3 As the group represented by , a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 34 carbon atoms is preferred, a hydrogen atom or a fluorine atom is more preferred, and a hydrogen atom is even more preferred, in that it increases the carrier mobility of the conjugated polymer made from the compound of this embodiment.

[0020] J 1 and J 2As the chalcogen atom represented by , oxygen atoms, sulfur atoms, and selenium atoms are preferred in terms of increasing the solubility of the compound in this embodiment, oxygen atoms and sulfur atoms are more preferred, and sulfur atoms are even more preferred.

[0021] M 1 As the halogen atom represented, chlorine, bromine, or iodine atoms are preferred, bromine or iodine atoms are more preferred, and bromine atoms are even more preferred, in that they increase the solubility of the compound in this embodiment.

[0022] M 1 Examples of silicon-containing groups represented by the formulas (procSi-1) to (procSi-8) are preferred, groups represented by (procSi-1) to (procSi-5) are more preferred, and the group represented by (procSi-3) is even more preferred, in terms of increasing the solubility of the compound in this embodiment.

[0023] [ka]

[0024] [ka]

[0025] M 1 In terms of increasing the solubility of the compound in this embodiment, hydrogen atoms, bromine atoms, iodine atoms, or silicon-containing groups are preferred, and hydrogen atoms, bromine atoms, or silicon-containing groups are more preferred.

[0026] Y 1 represents one group selected from the group consisting of a hydrogen atom, a halogen atom, and an aryl group having 6 to 50 carbon atoms that may be substituted with a halogen atom, and is preferably an aryl group having 5 to 10 carbon atoms that may be substituted with a halogen atom, or a halogen atom.

[0027] Y 1 As the halogen atom represented, chlorine, bromine, or iodine atoms are preferred, bromine or iodine atoms are more preferred, and iodine atoms are even more preferred, in that they increase the solubility of the compound in this embodiment.

[0028] Y 1 Examples of aryl groups with 6 to 50 carbon atoms represented by the following general formula (Yarom) include aromatic groups.

[0029] [ka] (In the formula, R 4 represents a hydrogen atom or a fluorine atom. 3 and J 4 Each of these independently represents a chalcogen atom. 2 (This represents one group selected from the group consisting of a hydrogen atom or a halogen atom and a silicon-containing group.)

[0030] J 3 and J 4 As the chalcogen atom represented by , oxygen atoms, sulfur atoms, and selenium atoms are preferred in terms of increasing the solubility of the compound in this embodiment, oxygen atoms and sulfur atoms are more preferred, and sulfur atoms are even more preferred.

[0031] More specific structures of aryl groups with 6 to 50 carbon atoms represented by the general formula (Yarom) can be found in the following general formulas (Yarom-1) to (Yarom-54).

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[0050] Y 1 The substituents represented are preferably a bromine atom, an iodine atom, a halogen atom, and an aryl group having 6 to 50 carbon atoms that may be substituted with a halogen atom; more preferably a bromine atom, an iodine atom, and formulas (Yarom-1) to (Yarom-24); even more preferably a bromine atom, an iodine atom, and formulas (Yarom-1) to (Yarom-6) or (Yarom-19) to (Yarom-24); even more preferably a bromine atom, an iodine atom, and formulas (Yarom-1) to (Yarom-6); and especially preferably an iodine atom, formula (Yarom-1) or formula (Yarom-2).

[0051] Y 2 represents one group selected from the group consisting of C3-C50 alkyl groups, hydrogen atoms, and halogen atoms, which may be substituted with a hydroxyl group, and is preferably a C3-C33 alkyl group or halogen atom, which may be substituted with a hydroxyl group.

[0052] Y 2C3-C50 alkyl groups that may be substituted with hydroxyl groups represented by include 1-methyl-1-hydroxymethyl group, 1-ethyl-1-hydroxyethyl group, 1-ethyl-1-hydroxyethyl group, 1-propyl-1-hydroxypropyl group, 1-butyl-1-hydroxybutyl group, 1-pentyl-1-hydroxypentyl group, 1-hexyl-1-hydroxyhexyl group, 1-heptyl-1-hydroxyheptyl group, 1-octyl-1-hydroxyoctyl group, 1-nonyl-1-hydroxynonyl group, 1-decyl-1-hydroxydecyl group, 1-undecyl- Examples include 1-hydroxyundecyl group, 1-dodecyl-1-hydroxydodecyl group, 1-tridecyl-1-hydroxytridecyl group, 1-tetradecyl-1-hydroxytetradecyl group, 1-pentadecyl-1-hydroxypentadecyl group, 1-hexadecyl-1-hydroxyhexadecyl group, 1-heptadecyl-1-hydroxyheptadecyl group, 1-octadecyl-1-hydroxyoctadecyl group, 1-nonadecyl-1-hydroxynonadecyl group, 1-icosyl-1-hydroxyicosyl group, and 1-phenyl-1-hydroxymethylphenyl group.

[0053] Y 2The substituents represented are preferably C3-C50 alkyl groups which may be substituted with halogen atoms or hydroxyl groups, such as bromine atoms, iodine atoms, 1-methyl-1-hydroxymethyl group, 1-ethyl-1-hydroxyethyl group, 1-ethyl-1-hydroxyethyl group, 1-propyl-1-hydroxypropyl group, 1-butyl-1-hydroxybutyl group, 1-pentyl-1-hydroxypentyl group, 1-hexyl-1-hydroxyhexyl group, 1-heptyl-1-hydroxyheptyl group, 1-octyl-1-hydroxyoctyl group, 1-nonyl-1-hydroxynonyl group, 1-decyl-1-hydroxydecyl group, 1-undecyl-1-hydroxyundecyl group, 1-dodecyl-1-hydroxydodecyl group, 1-tridecyl-1-hydroxytridecyl group, 1-tetradecyl-1-hydroxytetradecyl group, and 1-pentadecyl-1-hydroxy Sipentadecyl group, 1-hexadecyl-1-hydroxyhexadecyl group, 1-heptadecyl-1-hydroxyheptadecyl group, 1-octadecyl-1-hydroxyoctadecyl group, 1-nonadecyl-1-hydroxynonadecyl group, 1-icosyl-1-hydroxyicosyl group, and 1-phenyl-1-hydroxymethylphenyl group are more preferred, and iodine atom, 1-methyl-1-hydroxymethyl group, 1-ethyl-1-hydroxyethyl group, 1-ethyl-1-hydroxyethyl group, 1-propyl-1-hydroxypropyl group, 1-butyl-1-hydroxybutyl group, 1-pentyl-1-hydroxypentyl group, 1-hexyl-1-hydroxyhexyl group, 1-heptyl-1-hydroxyheptyl group, 1-octyl-1-hydroxyoctyl group, 1-nonyl-1-hydroxynonyl group, and 1-decyl-1-hydroxydecyl group are even more preferred.

[0054] Examples of compounds of the present invention include those with the following general formulas (int-1-1) to (int-1-260).

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[0155] In terms of increasing the solubility of the compounds in this embodiment, formulas (int-1-1) to (int-1-195) are preferred, formulas (int-1-1) to (int-1-208) are more preferred, formulas (int-1-1) to (int-1-184) are even more preferred, and formulas (int-1-119), (int-1-121), (int-1-124), (int-1-128), or (int-1-129) are particularly preferred.

[0156] [Method for producing compounds] Next, the method for producing the compound of this embodiment (hereinafter referred to as "the production method of this embodiment") will be described. The compound of this embodiment can be produced by the following production methods (A) to (F).

[0157] <Manufacturing method (A)> [ka] (In the formula, R 1 , R 2 , R 3 , J 1 and J 2 M expresses the same meaning as above. 1-Si Y represents a silicon-containing group. int-1-hal and Y int-2-hal (This represents a halogen atom.)

[0158] Manufacturing method (A) is a method for producing the compound represented by the general formula (Si-int-1-hal-hal), which is the compound of this embodiment, by reacting a halogenating agent with a compound represented by the general formula (int-2).

[0159] Examples of halogenating agents include chlorine, bromine, iodine, N-chlorosuccinimide, N-bromosuccinimide, and N-iodinosuccinimide.

[0160] <Manufacturing method (B)> [ka] (In the formula, R 1 , R 2 , R 3 , J 1 , J 2 M 1-Si , Y int-1-hal and Y int-2-hal This has the same meaning as above. int-2-alk (This represents an alkyl group having 3 to 50 carbon atoms, which may be substituted with a hydroxyl group.)

[0161] Manufacturing method (B) is a method for producing the compound represented by the general formula (Si-int-1-hal-alk), which is the compound of this embodiment, by reacting a ketone compound with a compound represented by the general formula (Si-int-1-hal-hal).

[0162] Examples of ketone compounds include acetone, 2-propanone, 3-pentanone, 4-heptanone, 5-nonanone, 6-undecanone, 7-tridecanone, 8-pentadecanone, 9-heptadecanone, 10-nonadecanone, 11-heneicosanone, 12-heneicosanone, 13-tricosanone, 14-pentacosanone, 15-heptacosanone, 16-nonacosanone, 17-hentriaconanone, 18-tritriaconanone, 19-pentatriaconanone, and 20-tetraconanone.

[0163] <Manufacturing method (C)> [ka] (In the formula, R 1 , R 2 , R 3 , J 1 , J 2 M 1-Si , Y int-1-hal and Y int-2-alk This has the same meaning as above. int-1-arom (This represents an aryl group with 6 to 50 carbon atoms, which may be substituted with halogen atoms.)

[0164] Method (C) is a method for producing the compound represented by the general formula (Si-int-1-arom-alk), which is the compound of this embodiment, by reacting a compound represented by the general formula (Si-int-1-hal-alk) with an arylboronic acid or an arylboronic acid ester in the presence of a palladium catalyst.

[0165] Examples of arylboronic acids include thieno[3,2-b]thiophene-2-boronic acid, 5-bromo-thieno[3,2-b]thiophene-2-boronic acid, 5-chloro-thieno[3,2-b]thiophene-2-boronic acid, and 5-iodo-thieno[3,2-b]thiophene-2-boronic acid.

[0166] Examples of arylboronic acid esters include thieno[3,2-b]thiophene-2-boronic acid pinacol ester, 5-bromo-thieno[3,2-b]thiophene-2-boronic acid pinacol ester, 5-chloro-thieno[3,2-b]thiophene-2-boronic acid pinacol ester, and 5-iodo-thieno[3,2-b]thiophene-2-boronic acid pinacol ester.

[0167] The palladium catalyst is not particularly limited, and palladium metals such as palladium black and palladium sponge can be exemplified. Further, supported palladium metals such as palladium / alumina, palladium / carbon, palladium / silica, palladium / Y-type zeolite, etc. can also be exemplified as the palladium catalyst. Also, metal salts such as palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium trifluoroacetate, palladium nitrate, etc., π-allylpalladium chloride dimer, palladium acetylacetonate, dichlorobis(acetonitrile)palladium, dichlorobis(benzonitrile)palladium, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, dichlorodiamminepalladium, dichlorobis(triphenylphosphine)palladium, dichlorobis(tricyclohexylphosphine)palladium, tetrakis(triphenylphosphine)palladium, dichloro[1,2-bis(diphenylphosphino)ethane]palladium, dichloro[1,3-bis(diphenylphosphino)propane]palladium, dichloro[1,4-bis(diphenylphosphino)butane]palladium and dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium, bis(tri-tert-butylphosphine)palladium, bis(tricyclohexylphosphine)palladium, [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(II) dichloride (Pd-PEPPSI-IPent), [1,3-bis(2,6-di-3-pentylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(II) dichloride (Pd-PEPPSI-IPr), [1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene](3-chloropyridyl)palladium(II) dichloride (Pd-PEPPSI-SIPr) and other palladium catalysts can be exemplified.

[0168] <Production Method (D)>

Chemical

[0169] Production method (D) is a method for producing a compound represented by the general formula (H-int-1-arom-alk), which is a compound of this embodiment, by allowing a fluorine compound to act on a compound represented by the general formula (Si-int-1-arom-alk).

[0170] Examples of the fluorine compound include lithium fluoride, sodium fluoride, potassium fluoride, cesium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, tetrabutylammonium difluorotriphenylsilicate, hydrogen fluoride-pyridine, etc.

[0171] <Production method (E)>

Chemical formula

[0172] Production method (E) is a method for producing a compound represented by the general formula (hal-int-1-arom-alk), which is a compound of this embodiment, by allowing a halogenating agent to act on a compound represented by the general formula (Si-int-1-arom-alk).

[0173] Examples of the halogenating agent include chlorine, bromine, iodine, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, etc.

[0174] <Manufacturing method (F)> [ka] (In the formula, R 1 , R 2 , R 3 , J 1 , J 2 M 1-H M 1-hal , Y int-1-arom and Y int-2-alk (This has the same meaning as above.)

[0175] Manufacturing method (F) is a method for producing the compound represented by the general formula (hal-int-1-arom-alk), which is the compound of this embodiment, by reacting a halogenating agent with a compound represented by the general formula (H-int-1-arom-alk).

[0176] Examples of halogenating agents include chlorine, bromine, iodine, N-chlorosuccinimide, N-bromosuccinimide, and N-iodinosuccinimide.

[0177] The compounds of the present invention can also be produced by appropriately combining known organic synthesis reactions. For example, they can be produced by referring to methods described in the literature (Journal of the American Chemical Society, Vol. 134, pp. 19254-19259, 2012, etc.). [Examples]

[0178] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0179] The compounds obtained in the examples are 1 Structural analysis was performed by 1H-NMR measurement. The molecular weight and molecular weight distribution of the polymers obtained in the polymerization reference examples were estimated by Gel Permeation Chlorography (GPC) measurement. Commercially available reagents were used.

[0180] <NMR measurement conditions> Measuring device: Bruker ASCEND TM ADVANCE III HD (400 MHz) Measuring solvent: deuterated chloroform (CDCl3), deuterated dimethyl sulfoxide (DMSO-d6), deuterated benzene (C6D6) Internal standard substance: tetramethylsilane (TMS)

[0181] <GPC measurement conditions> Measuring device: Tosoh Corporation High Speed GPC Device HLC-8320GPC EcoSEC Column: TSKgel SuperMultiporeHZ-H, TSKgel SuperHZ2000 Measuring solvent: THF Measuring temperature: 25 °C Calibration curve: polystyrene standard

[0182] <High temperature GPC measurement conditions Measuring device: Tosoh Corporation High Temperature GPC Device HLC-8321GPC / HT Column: TSKgel GMH HR -H(20)HT Measuring solvent: 1,2,4-trichlorobenzene (TCB) Measuring temperature: 140 °C Calibration curve: polystyrene standard

[0183] <TGA measurement conditions> Measuring device: SII Corporation EXSTAR6000 TGA / DTA6200<000128i>Sample container: aluminum pan Measurement atmosphere: nitrogen Flow rate: 50 mL / min Heating rate: 10 °C / min T d3 、T d5 and T d10 represent the 3%, 5% and 10% weight loss temperatures, respectively.

[0184] <DSC measurement conditions> Measurement device: SII Corporation EXSTAR6000 DSC6220 Sample container: Aluminum pan Measurement conditions: Nitrogen atmosphere, 10°C / min, 0-300°C. The results from the third HeatingScan were used.

[0185] [Reference example 1]

[0186] [ka]

[0187] A mixture of thieno[3,2-b]thiophene (500 mg, 3.56 mmol) and tetrahydrofuran (35 mL) was mixed with a hexane solution of n-butyllithium (2.3 mL, 3.56 mmol) at 0°C and stirred for 1 hour. Then, triisopropylsilyl chloride (0.83 mL, 756 mg, 3.92 mmol) was added and stirred at room temperature for 2 hours. Water was added to the reaction solution and extracted with hexane. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to obtain a colorless solid of 2-triisopropylsilylthieno[3,2-b]thiophene (924 mg, 88%). 1 H-NMR (CDCl3,400MHz) δ7.39(d,J=5.2Hz,1H),7.37(d,J=0.4Hz,1H),7.25(dd,J=5.2Hz,0.4Hz,2H),1.37(sep,J=7.6Hz,3H),1.13(d,J=7.6Hz,18H).

[0188] [Reference example 2]

[0189] [ka]

[0190] A mixture of 2-triisopropylsilylthieno[3,2-b]thiophene (1.00 g, 3.37 mmol) obtained in Reference Example 1 and THF (34 mL) was mixed with N-bromosuccinimide (660 mg, 3.71 mmol) and stirred at room temperature for 22.5 hours. Water was added to the resulting mixture and extracted with hexane. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to obtain colorless solid 2-bromo-5-triisopropylsilylthieno[3,2-b]thiophene (900 mg, 71%). 1 H-NMR (DMSO-d6, 400MHz) δ7.66 (s, 1H), 7.56 (s, 1H), 1.40-1.30 (m, 3H), 1.08 (d, J = 7.6Hz, 18H).

[0191] [Reference example 3]

[0192] [ka]

[0193] A mixture of 11-heneikosanone (12.9 g, 41.7 mmol) and tetrahydrofuran (83 mL) was mixed with ethynylmagnesium bromide (100 mL, 50.0 mmol) dropwise at 0°C and stirred at room temperature for 22.5 hours. The resulting mixture was mixed with saturated ammonium chloride aqueous solution and extracted with diethyl ether. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure to obtain a pale yellow liquid, 11-ethynyl-heneikosan-11-ol (14.0 g).

[0194] A mixture of 2-bromo-5-triisopropylsilylthieno[3,2-b]thiophene (3.75 g, 10.0 mmol), 11-ethynyl-heneikosan-11-ol (3.70 g), and triethylamine (200 mL) obtained in Reference Example 2 was bubbling with argon for 30 minutes. To this mixture, copper(I) iodide (190 mg, 1.00 mmol) and Pd(PPh3)4 (578 mg, 0.500 mmol) were added under an argon stream, and the mixture was stirred at 100°C for 107 hours. After the resulting mixture was cooled to room temperature, saturated ammonium chloride aqueous solution was added, and the mixture was extracted with ethyl acetate. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 4 / 1 → 3 / 1 → 2 / 1) to obtain 11-(5-triisopropylsilyl-thieno[3,2-b]thiophene-2-ylethynyl)-heneikosan-11-ol, a pale yellow liquid (5.05 g, 80%). 1 H-NMR(CDCl3,400MHz)δ7.31(d,J=0.8Hz,1H),7.28(d,J=0.4Hz,1H),1.77-1.70(m,4 H),1.56-1.51(m,4H),1.43-1.27(m,31H),1.12(d,J=7.2Hz,18H),0.90-0.86(m,6H).

[0195] [Example 1]

[0196] [ka]

[0197] A mixture of 11-(5-triisopropylsilyl-thieno[3,2-b]thiophen-2-ylethynyl)-heneikosan-11-ol (2.71 g, 4.29 mmol) obtained in Reference Example 3 and dichloromethane (86 mL) was mixed with iodine (1.63 g, 6.44 mmol) at -15°C and stirred at -15°C for 5 hours. The resulting mixture was mixed with saturated sodium thiosulfate aqueous solution and extracted with ethyl acetate. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to obtain 2-triisopropylsilyl-5,6-diiodo-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene as a reddish-brown liquid (2.87 g, 77%). 1 H-NMR (CDCl3, 400MHz) δ7.40 (s, 1H), 1.94-1.86 (m, 2H), 1.68-1.61 (m, 2H), 1.43-1.11 (m, 47H), 0.90-0.84 (m, 10H), 0.61-0.55 (m, 2H).

[0198] [Example 2]

[0199] [ka]

[0200] To the mixture of 2-triisopropylsilyl-5,6-diiodo-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (551 mg, 0.636 mmol) obtained in Example 1 and tetrahydrofuran (6.4 mL), a hexane solution of n-butyllithium (0.40 mL, 0.636 mmol) was added at -78 °C and the mixture was stirred for 1.5 hours. Then, 11-heneicosanone (237 mg, 0.763 mmol) was added and the mixture was stirred at room temperature for 2 hours. The resulting mixture was extracted with ethyl acetate after adding an aqueous solution of saturated ammonium chloride. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 10 / 1 → 5 / 1 → 2 / 1 → 1 / 1) to obtain a colorless solid 2-triisopropylsilyl-5-(1-decyl-1-hydroxyundecyl)-6-iodo-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (431 mg, 64%). 1 H-NMR(CDCl3,400MHz)δ7.36(s,1H),2.39-2.32(m,2H),1.84-1.77(m,2H),1 .70-1.58(m,4H),1.47-1.10(m,81H),0.87-0.84(m,14H),0.57-0.48(m,2H).

[0201] [Example 3]

[0202] [ka]

[0203] The mixture of 2-triisopropylsilyl-5-(1-decyl-1-hydroxyundecyl)-6-iodo-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (2.04 g, 1.94 mmol) obtained in Example 2, thieno[3,2-b]thiophene-2-boronic acid (714 mg, 3.88 mmol), 1,2-dimethoxyethane (49 mL), and 2M potassium carbonate aqueous solution (19 mL, 38 mmol) was bubbling with argon for 30 minutes. (AMPHOS)2PdCl2 (69 mg, 97 μmol) was added to this mixture under an argon stream and stirred at 100°C for 37.5 hours. The resulting mixture was cooled to room temperature, and then saturated ammonium chloride aqueous solution was added and extracted with ethyl acetate. The collected organic layer was washed with water and saturated brine, then dried over anhydrous magnesium sulfate and filtered off, and the solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 10 / 1 → 5 / 1 → 2 / 1) to obtain the yellow solid 2-triisopropylsilyl-5-(1-decyl-1-hydroxyundecyl)-6-thieno[3,2-b]thiophene-2-yl-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (1.06 g, 52%). 1 H-NMR(CDCl3,400MHz)δ7.41(s,1H),7.38(d,J=5.2Hz,1H),7.27-7.26(m,1H),7.00(s,1H),1.93-1.83( m,4H),1.76-1.69(m,2H),1.64-1.57(m,2H),1.47-1.14(m,83H),0.88-0.84(m,12H),0.72-0.69(m,2H).

[0204] [Example 4]

[0205] [ka]

[0206] A mixture of 2-triisopropylsilyl-5-(1-decyl-1-hydroxyundecyl)-6-thieno[3,2-b]thiophene-2-yl-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (1.30 g, 1.22 mmol) obtained in Example 3 and tetrahydrofuran (24 mL) was mixed with a solution of tetrahydrofuran in 1 M tetrabutylammonium fluoride (1.5 mL, 1.5 mmol) and stirred at room temperature for 22 hours. Water was added to the resulting mixture and extracted with ethyl acetate. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 5 / 1 → 2 / 1) to obtain the yellow solid 5-(1-decyl-1-hydroxyundecyl)-6-thieno[3,2-b]thiophene-2-yl-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (0.995g, 90%). 1 H-NMR(CDCl3,400MHz)δ7.39(d,J=5.2Hz,1H),7.31(s,2H),7.27-7.26(m,1H),6.70( s, 1H), 1.89-1.60 (m, 8H), 1.51-1.13 (m, 60H), 0.88-0.84 (m, 14H), 0.74-0.63 (m, 2H).

[0207] [Example 5]

[0208] [ka]

[0209] In Example 4, a mixture of 5-(1-decyl-1-hydroxyundecyl)-6-thieno[3,2-b]thiophene-2-yl-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (300 mg, 0.330 mmol) and tetrahydrofuran (6.6 mL) was mixed with N-bromosuccinimide (129 mg, 0.727 mmol) at 0°C and stirred at room temperature for 23 hours. The resulting mixture was mixed with saturated sodium thiosulfate aqueous solution and extracted with ethyl acetate. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane / chloroform = 5 / 1 → 2 / 1) to obtain 2-bromo-5-(1-decyl-1-hydroxyundecyl)-6-(5-bromo-thieno[3,2-b]thiophen-2-yl)-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene as a yellow solid (268 mg, 76%). 1 H-NMR(C6D6,400MHz)δ7.00(s,1H),6.74(s,1H),6.67(s,1H),2.00-1.80(m,6H),1.69-1.47(m,8H),1.33-1.21(m,54H),0.92-0.89(m,16H).

[0210] [Reference example 4]

[0211] [ka]

[0212] A mixture of 7-tridecanone (2.00 g, 10.0 mmol) and tetrahydrofuran (20 mL) was mixed with ethynylmagnesium bromide (30.0 mL, 15.0 mmol) dropwise at 0°C and stirred at room temperature for 19 hours. The resulting mixture was mixed with saturated ammonium chloride aqueous solution and extracted with diethyl ether. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure to obtain a pale yellow liquid, 11-ethynyl-heneikosan-11-ol (1.51 g).

[0213] A mixture of 2-bromo-5-triisopropylsilylthieno[3,2-b]thiophene (2.30 g, 6.12 mmol) obtained in Reference Example 2, 7-ethynyl-tridecane-7-ol (1.51 g, 6.73 mmol), and triethylamine (123 mL) was bubbling with argon for 30 minutes. To this mixture, copper(I) iodide (116 mg, 612 μmol) and Pd(PPh3)4 (354 mg, 306 μmol) were added under an argon stream, and the mixture was stirred at 100°C for 65 hours. After the resulting mixture was cooled to room temperature, saturated ammonium chloride aqueous solution was added, and the mixture was extracted with ethyl acetate. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane → hexane / chloroform = 1 / 1) to obtain the yellow liquid 7-(5-triisopropylsilyl-thieno[2,3-d]thiophene-2-ylethinyl)-tridecane-7-ol (2.80 g, 88%). 1 H-NMR(CDCl3,400MHz)δ7.31(s,1H),7.28(s,1H),2.03(s,1H),1.76-1.71(m,4H), 1.58-1.51(m,4H),1.40-1.26(m,15H),1.12(d,J=7.4Hz,18H),0.91-0.88(m,6H).

[0214] [Example 6]

[0215] [ka]

[0216] A mixture of 7-(5-triisopropylsilyl-thieno[3,2-b]thiophen-2-ylethinyl)-tridecane-7-ol (2.65 g, 5.11 mmol) obtained in Reference Example 4 and dichloromethane (103 mL) was mixed with iodine (1.94 g, 7.66 mmol) at -15°C and stirred at -15°C for 5 hours. The resulting mixture was mixed with saturated sodium thiosulfate aqueous solution and extracted with ethyl acetate. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to obtain 2-triisopropylsilyl-5,6-diiodo-7,7-dihexyl-7H-cyclopenta[b]thieno[2,3-d]thiophene as a reddish-brown liquid (3.21 g, 83%). 1 H-NMR (CDCl3, 400MHz) δ7.40 (s, 1H), 1.95-1.85 (m, 2H), 1.68-1.61 (m, 2H), 1.43-1.11 (m, 31H), 0.90-0.75 (m, 10H), 0.61-0.52 (m, 2H).

[0217] [Example 7]

[0218] [ka]

[0219] To the mixture of 2-triisopropylsilyl-5,6-diiodo-7,7-dihexyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (3.06 g, 4.06 mmol) obtained in Example 6 and tetrahydrofuran (41 mL), a hexane solution of n-butyllithium (2.60 mL, 4.06 mmol) was added at -78 °C and the mixture was stirred for 1.5 hours. Then, 7-tridecanone (966 mg, 4.87 mmol) was added and the mixture was stirred at room temperature for 2 hours. The resulting mixture was extracted with ethyl acetate after adding an aqueous solution of saturated ammonium chloride. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 9 / 1) to obtain 2-triisopropylsilyl-5-(1-hexyl-1-hydroxyhepsyl)-6-iodo-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene as a brown liquid (2.04 mg, 61%). 1 H-NMR(CDCl3,400MHz)δ7.37(s,1H),2.40-2.33(m,2H),2.04(s,1H),1.85-1.77(m, 2H), 1.70-1.58(m, 4H), 1.46-1.09(m, 49H), 0.90-0.75(m, 14H), 0.52-0.48(m, 2H).

[0220] [Example 8]

[0221] [ka]

[0222] The mixture of 2-triisopropylsilyl-5-(1-hexyl-1-hydroxyhepsil)-6-iodo-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene (1.57 g, 1.90 mmol) obtained in Example 7, thieno[3,2-b]thiophene-2-boronic acid (699 mg, 3.80 mmol), 1,2-dimethoxyethane (47 mL), and 2M potassium carbonate aqueous solution (19 mL, 38 mmol) was bubbling with argon for 30 minutes. (AMPHOS)2PdCl2 (67.3 mg, 95.0 μmol) was added to this mixture under an argon stream and stirred at 100°C for 72 hours. After the resulting mixture cooled to room temperature, saturated ammonium chloride aqueous solution was added and extracted with ethyl acetate. The collected organic layer was washed with water and saturated brine, then dried over anhydrous magnesium sulfate and filtered off, and the solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 4 / 1 → 1 / 1) to obtain the yellow solid 2-triisopropylsilyl-5-(1-hexyl-1-hydroxyhepsil)-6-thieno[3,2-b]thiophene-2-yl-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene (1.34 g, 84%). 1 H-NMR(CDCl3,400MHz)δ7.41(s,1H),7.38(d,J=5.2Hz,1H),7.27-7.26(m,1H),7.00(s,1H),2.15(s,1H),1.94- 1.84(m,4H),1.76-1.69(m,2H),1.65-1.58(m,2H),1.48-1.14(m,50H),0.85-0.77(m,12H),0.75-0.68(m,3H).

[0223] [Example 9]

[0224] [ka]

[0225] A mixture of 2-triisopropylsilyl-5-(1-hexyl-1-hydroxyhepsil)-6-thieno[3,2-b]thiophene-2-yl-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene (1.42 g, 1.70 mmol) obtained in Example 8 and tetrahydrofuran (34 mL) was mixed with 1 M tetrabutylammonium fluoride tetrahydrofuran solution (2.2 mL, 2.2 mmol) and stirred at room temperature for 17 hours. Water was added to the resulting mixture and extracted with ethyl acetate. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 7 / 3) to obtain 5-(1-hexyl-1-hydroxyhepsyl)-6-thieno[3,2-b]thiophene-2-yl-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene as a yellowish-brown liquid (0.995 g, 90%). 1 H-NMR(CDCl3,400MHz)δ7.39(d,J=5.2Hz,1H),7.31(s,2H),7.27(d,J=5.2Hz,1H),7.00(s,1H),2.14(s,1H),1.9 2-1.71(m,6H),1.65-1.55(m,2H),1.49-1.44(m,2H),1.33-1.13(m,28H),0.85-0.78(m,12H),0.69-0.66(m,2H).

[0226] [Example 10]

[0227] [ka]

[0228] A mixture of 5-(1-hexyl-1-hydroxyhepsil)-6-thieno[3,2-b]thiophen-2-yl-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene (1.02 g, 1.51 mmol) obtained in Example 9 and tetrahydrofuran (31 mL) was mixed with N-bromosuccinimide (591 mg, 3.32 mmol) at 0°C and stirred at room temperature for 15 hours. The resulting mixture was mixed with saturated sodium thiosulfate aqueous solution and extracted with ethyl acetate. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 85 / 15 → 1 / 1) to obtain 2-bromo-5-(1-hexyl-1-hydroxyhepsyl)-6-(5-bromo-thieno[3,2-b]thiophen-2-yl)-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene, a yellow solid. 1 H-NMR(C6D6,400MHz)δ7.04(s,1H),6.81(s,1H),6.71(s,1H),2.04-1.83(m,6H),1.72-1.54(m,8H),1.40-1.18(m,26H),0.99-0.88(m,12H).

[0229] Of the compounds obtained in Examples 1 to 10, the compounds of this embodiment obtained in Examples 5 and 10 are useful as intermediates for monomers used in the production of conjugated polymers that can be used as organic semiconductors, as shown in the monomer synthesis examples 1 to 3, polymer synthesis examples 1 to 6, and semiconductor property examples 1 to 3 below.

[0230] [Monomer Synthesis Example 1]

[0231] [ka]

[0232] A mixture of 2-bromo-5-(1-decyl-1-hydroxyundecyl)-6-(5-bromo-thieno[3,2-b]thiophen-2-yl)-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (114 mg, 0.107 mmol) and dichloromethane (4.3 mL) was freeze-degassed. To this mixture, a solution of tin tetrachloride in dichloromethane (1 M, 100 μL, 100 μmol) was added and the mixture was stirred at -15°C for 5 hours under an argon stream. The resulting mixture was extracted with saturated sodium bicarbonate aqueous solution and hexane. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to obtain a red solid monomer (mono-hal-28) (78 mg, 70%). 1 H-NMR (C6D6, 400MHz) δ6.69 (s, 2H), 2.11-2.03 (m, 8H), 1.28-1.08 (m, 62H), 0.91-0.87 (m, 14H).

[0233] [Monomer Synthesis Example 2]

[0234] [ka]

[0235] A mixture of (mono-hal-28) (200 mg, 0.191 mmol) obtained in monomer synthesis example 1 and tetrahydrofuran (3.8 mL) was mixed with a hexane solution of n-butyllithium (0.27 mL, 0.420 mmol) at 0°C and stirred for 3 hours. Then, trimethyltin chloride (91.3 mg, 0.458 mmol) was added and stirred at room temperature for 22 hours. Water was added to the reaction solution and extracted with hexane. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by reprecipitation (acetone) to obtain the red solid monomer (mono-Sn-28) (131 mg, 56%). 1H-NMR(C6D6,400MHz)δ6.87(s,2H),2.17-2.07(m,8H),1.28-1.23(m,4H),1.07-0.95(m,60H),0.69(t,J=7.0Hz,12H),0.07(s,18H).

[0236] [Monomer Synthesis Example 3]

[0237] [ka]

[0238] A mixture of 2-bromo-5-(1-hexyl-1-hydroxyhepsi)-6-(5-bromo-thieno[3,2-b]thiophen-2-yl)-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene (100 mg, 119 μmol) obtained in Example 10 and dichloromethane (4.8 mL) was freeze-degassed. To this mixture, 130 μL, 130 μmol, 1 M tin tetrachloride dichloromethane solution was added under an argon stream and stirred at -15°C for 1 hour. The resulting mixture was extracted with saturated sodium bicarbonate aqueous solution and hexane. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to obtain a red solid monomer (mono-hal-16) (85 mg, 87%). 1 H-NMR (C6D6, 400MHz) δ6.67 (s, 2H), 2.09-1.98 (m, 8H), 1.28-1.03 (m, 32H), 0.79-0.75 (m, 12H).

[0239] [Polymer Synthesis Example 1]

[0240] [ka]

[0241] The mixture of (mono-hal-28) (100 mg, 95.5 μmol) obtained in monomer synthesis example 1, 4,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,1,3-benzothiadiazole (37.0 mg, 68.3 μmol), one drop of tri(n-octylmethyl)ammonium chloride (PTC), toluene (3.1 mL), and 1 M sodium carbonate aqueous solution (0.64 mL, 0.64 mmol) was bubbled with argon for 30 minutes. To this mixture, Pd2(dba)3·CHCl3 (2.0 mg, 1.9 μmol) and tri(o-tolyl)phosphine (2.3 mg, 7.6 μmol) were added and the mixture was stirred at 120 °C for 60 hours. The resulting mixture was cooled to room temperature and then precipitated in a methanol / concentrated hydrochloric acid mixture (150 mL / 15 mL). The precipitated solid was filtered. The obtained solid was extracted using Soxhlet extraction with methanol, acetone, and hexane to remove components soluble in these solvents. Furthermore, the residue on the filter was dissolved in n-decane. The resulting mixture was concentrated under reduced pressure and precipitated in methanol. The precipitated solid was filtered. The obtained solid was washed with methanol and then dried under reduced pressure at 90°C to obtain a black solid conjugated polymer (3-10) (65.3 mg, 67%). GPC(THF): Mn=10500g / mol, Mw=17800g / mol, PDI=1.69. GPC (TCB, 120℃): Mn=3800g / mol, Mw=13000g / mol, PDI=3.3. T d3 =396℃,T d5 =403℃,T d10 = 417℃. No phase transition was observed using DSC.

[0242] [Polymer Synthesis Example 2]

[0243] [ka]

[0244] The mixture of (mono-Sn-28) (100 mg, 82.3 μmol) obtained in monomer synthesis example 2, 4,7-dibromo-2,1,3-benzothiadiazole (24.2 mg, 82.3 μmol), and tetralin (2.5 mL) was bubbling with argon for 30 minutes. To this mixture, Pd2(dba)3·CHCl3 (1.7 mg, 1.6 μmol) and tri(o-tolyl)phosphine (2.0 mg, 6.6 μmol) were added and the mixture was stirred at 180°C for 2 hours using a microwave reactor. Subsequently, 2-(tributylstannyl)thiophene (0.23 mL, 276 mg, 0.74 mmol) was added to the reaction solution and the mixture was stirred at 180°C for 10 minutes using a microwave reactor. Furthermore, 2-bromothiophene (0.08 mL, 134 mg, 0.82 mmol) was added and the mixture was stirred at 180°C for 10 minutes using a microwave reactor. The resulting mixture was cooled to room temperature and then precipitated in a methanol / concentrated hydrochloric acid mixture (150 mL / 15 mL), and the precipitated solid was filtered. The obtained solid was extracted using Soxhlet extraction with methanol, acetone, and hexane to remove components soluble in these solvents. The residue on the filter was then dissolved in chloroform. The resulting mixture was concentrated under reduced pressure and precipitated in methanol, and the precipitated solid was filtered. The obtained solid was washed with methanol and then dried under reduced pressure at 90°C to obtain a black solid conjugated polymer (3-10) (60 mg, 71%). GPC(THF): Mn=21000g / mol, Mw=34000g / mol, PDI=1.62. T d3 =364℃,T d5 =381℃,T d10 = 397℃. No phase transition was observed using DSC.

[0245] [Polymer Synthesis Example 3]

[0246] [ka]

[0247] The mixture of (mono-hal-28) (100 mg, 95.5 μmol) obtained in Monomer Synthesis Example 1, 2,5-bis(2-octyldodecyl)-3,6-bis[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophen-2-yl]pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (106 mg, 95.5 μmol), tetrahydrofuran (1.9 mL), and 2M potassium carbonate aqueous solution (1.0 mL, 2.0 mmol) was bubbling with argon for 30 minutes. Bis(tri-t-butylphosphine)palladium(0) (2.4 mg, 4.8 μmol) was added to this mixture and stirred at 80°C for 62 hours. Then, 2-thiopheneboronic acid (110 mg, 860 μmol) was added to the reaction solution and stirred at 80°C for 4 hours. Furthermore, 2-bromothiophene (92 μL, 950 μmol) was added and the mixture was stirred at 80°C for 4 hours. After the resulting mixture was cooled to room temperature, it was precipitated in a methanol / concentrated hydrochloric acid mixture (150 mL / 15 mL), and the precipitated solid was filtered. The obtained solid was removed from components soluble in methanol, acetone, and hexane by Soxhlet extraction. Furthermore, the residue on the filter was dissolved in chloroform. The resulting mixture was concentrated under reduced pressure, and the precipitated solid was filtered after precipitation in methanol. The obtained solid was washed with methanol and then dried under reduced pressure at 90°C to obtain a black solid conjugated polymer (3-650) (105 mg, 63%). GPC(THF): Mn=24400g / mol, Mw=41500g / mol, PDI=1.70.

[0248] [Polymer Synthesis Example 4]

[0249] [ka]

[0250] The mixture of (mono-hal-16) (100 mg, 121 μmol) obtained in monomer synthesis example 3, 4,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,1,3-benzothiadiazole (47.0 mg, 121 μmol), one drop of tri(n-octylmethyl)ammonium chloride (PTC), toluene (3.9 mL), and 1 M sodium carbonate aqueous solution (0.81 mL, 0.81 mmol) was bubbled with argon for 30 minutes. To this mixture, Pd2(dba)3·CHCl3 (2.5 mg, 2.4 μmol) and tri(o-tolyl)phosphine (2.9 mg, 9.7 μmol) were added and the mixture was stirred at 120°C for 64 hours. The resulting mixture was cooled to room temperature and then precipitated in a methanol / concentrated hydrochloric acid mixture (150 mL / 15 mL). The precipitated solid was filtered. The obtained solid was extracted using Soxhlet extraction with methanol, acetone, and hexane to remove components soluble in these solvents. Furthermore, the residue on the filter was dissolved in chloroform. The resulting mixture was concentrated under reduced pressure and precipitated in methanol. The precipitated solid was filtered. The obtained solid was washed with methanol and then dried under reduced pressure at 90°C to obtain a black solid conjugated polymer (3-166) (47 mg, 49%). GPC(THF): Mn=5200g / mol, Mw=11800g / mol, PDI=2.27.

[0251] [Polymer Synthesis Example 5]

[0252] [ka]

[0253] The mixture of (mono-hal-16) (100 mg, 121 μmol) obtained in monomer synthesis example 3, 2,5-bis(2-octyldodecyl)-3,6-bis[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophen-2-yl]pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (135 mg, 121 μmol), one drop of tri(n-octylmethyl)ammonium chloride (PTC), toluene (3.9 mL), and 1 M sodium carbonate aqueous solution (0.81 mL, 0.81 mmol) was bubbling with argon for 30 minutes. To this mixture, Pd2(dba)3·CHCl3 (2.5 mg, 2.4 μmol) and tri(o-tolyl)phosphine (2.9 mg, 9.7 μmol) were added and the mixture was stirred at 120°C for 66 hours. After the resulting mixture was cooled to room temperature, it was precipitated in a methanol / concentrated hydrochloric acid mixture (150 mL / 15 mL), and the precipitated solid was filtered. The obtained solid was removed from components soluble in methanol, acetone, and hexane by Soxhlet extraction. Furthermore, the residue on the filter was dissolved in chloroform. The resulting mixture was concentrated under reduced pressure, and the precipitated solid was filtered after precipitation in methanol. The obtained solid was washed with methanol and then dried under reduced pressure at 90°C to obtain a black solid conjugated polymer (3-646) (12 mg, 7%). GPC(THF): Mn=14800g / mol, Mw=30000g / mol, PDI=2.03.

[0254] [Polymer Synthesis Example 6]

[0255] [ka]

[0256] The mixture of (mono-hal-16) (100 mg, 121 μmol) obtained in monomer synthesis example 3, 2,5-bis(2-decyltetradecyl)-3,6-bis[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophen-2-yl]pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (148 mg, 121 μmol), one drop of tri(n-octylmethyl)ammonium chloride (PTC), toluene (3.9 mL), and 1 M sodium carbonate aqueous solution (0.81 mL, 0.81 mmol) was bubbling with argon for 30 minutes. To this mixture, Pd2(dba)3·CHCl3 (2.5 mg, 2.4 μmol) and tri(o-tolyl)phosphine (2.9 mg, 9.7 μmol) were added and the mixture was stirred at 120°C for 65 hours. After the resulting mixture was cooled to room temperature, it was precipitated in a methanol / concentrated hydrochloric acid mixture (150 mL / 15 mL), and the precipitated solid was filtered. The obtained solid was removed from components soluble in methanol, acetone, and hexane by Soxhlet extraction. Furthermore, the residue on the filter was dissolved in chloroform. The resulting mixture was concentrated under reduced pressure, and the precipitated solid was filtered after precipitation in methanol. The obtained solid was washed with methanol and then dried under reduced pressure at 90°C to obtain a black solid conjugated polymer (3-666) (78 mg, 40%). GPC(THF): Mn=5500g / mol, Mw=8400g / mol, PDI=1.53.

[0257] [Semiconductor Characteristics Example 1] A composition for forming organic thin films was prepared by heating a 0.5 wt% o-DCB solution of the conjugated polymer (3-10) synthesized in Polymer Synthesis Example 1 in a glove box under a nitrogen atmosphere.

[0258] After cooling to room temperature, the solution was filtered through a 0.22 μm filter, confirming that the compound maintained its solution state and was suitable for film formation.

[0259] Next, parylene C was deposited on a glass substrate as a base layer by CVD. Then, a shadow mask with a channel length of 100 μm and a channel width of 500 μm was placed on the parylene C layer, and the source and drain electrodes were attached by depositing gold under vacuum. The solution prepared above was spin-coated in a glove box under a nitrogen atmosphere. This was heated to 150°C and held for 15 minutes to create an organic thin film of a conjugated polymer (3-10). Parylene C was deposited as a gate insulating film by CVD, and then a silver electrode was created by deposition to create a top-gate-bottom contact type organic thin-film transistor element (gate electrode is silver, gate insulating layer is parylene C, source and drain electrodes are gold).

[0260] Under atmospheric pressure, the organic thin-film transistor element was connected to a semiconductor parameter analyzer (Keithley, 4200A-SCS model), and the transfer characteristics were evaluated by scanning the gate voltage (Vg) from +10 to -100V in 1V increments at a drain voltage (Vd = -100V). The organic thin-film transistor element exhibited p-type characteristics, and its hole carrier mobility was 0.046 cm². 2 The value was / Vs. Furthermore, after annealing at 150°C for 15 minutes, the hole carrier mobility was 0.043 cm². 2 The value was / Vs. This confirmed that carrier mobility did not decrease even after heat treatment.

[0261] [Example of semiconductor characteristics 2]

[0262] The same procedure as in Semiconductor Characteristics Example 1 was repeated, except that the source and drain electrodes were surface-treated with pentafluorobenzenethiol. The resulting organic thin-film transistor device exhibited p-type characteristics, and its hole carrier mobility was 0.078 cm⁻¹. 2 The value was / Vs. Furthermore, after annealing at 150°C for 15 minutes, the hole carrier mobility was 0.074 cm². 2 The value was / Vs. This confirmed that carrier mobility did not decrease even after heat treatment.

[0263] [Example of semiconductor characteristics 3] The same procedure as in Semiconductor Properties Example 1 was repeated, except that the conjugated polymer (3-10) synthesized in Polymer Synthesis Example 2 was used. The resulting organic thin-film transistor device exhibited p-type characteristics, and its hole carrier mobility was 0.077 cm⁻¹. 2 The value was / Vs. Furthermore, after annealing at 150°C for 15 minutes, the hole carrier mobility was 0.075 cm². 2 The value was / Vs. This confirmed that carrier mobility did not decrease even after heat treatment. [Industrial applicability]

[0264] The compounds of this embodiment can be suitably used as intermediates for organic semiconductors, fluorescent probes, fillers, pharmaceuticals and agrochemicals, low molecular weight intermediates for organic semiconductors, and monomer intermediates for polymers used in organic semiconductors.

Claims

1. A compound represented by the following general formula (int-1). 【Chemistry 1】 (wherein, R １ and R ２ each independently represent an alkyl group having 1 to 50 carbon atoms. R １ and R ２ may be combined together to form a ring together with the carbon atom to which they are attached, and examples of the ring include a cyclopropane-1,1-diyl group, a cyclobutane-1,1-diyl group, a cyclopentane-1,1-diyl group, a cyclohexane-1,1-diyl group, a cycloheptane-1,1-diyl group, a cyclooctane-1,1-diyl group, an indene-1,1-diyl or a fluorene-9,9-diyl group. R ３ represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 50 carbon atoms. J １ and J ２ each independently represent a chalcogen atom. M １ represents one group selected from the group consisting of a hydrogen atom, a halogen atom, a trialkylsilyl group, a dialkylarylsilyl group, an alkyldiarylsilyl group and a triarylsilyl group. Y １ represents one group selected from the group consisting of a hydrogen atom, a halogen atom, and an aromatic group represented by the following general formula (Y arom). Y ２ represents one group selected from the group consisting of an alkyl group having from 3 to 50 carbon atoms which may be substituted with a hydroxyl group, a hydrogen atom and a halogen atom, and when the alkyl group is selected, the alkyl group has a hydroxyl group at the carbon atom at the 1-position (the carbon atom of Y ２ which forms a bond with the tricyclic structure having J １ and J ２ ).) 【Chemistry 2】 (In the formula, R ４ J represents a hydrogen atom or a fluorine atom. ３ and J ４ Each of these independently represents a chalcogen atom. ２ (This represents one group selected from the group consisting of a hydrogen atom, a halogen atom, a trialkylsilyl group, a dialkylarylsilyl group, an alkyldiarylsilyl group, and a triarylsilyl group.)

2. R １ and R ２ Each of these is an alkyl group having 1 to 34 carbon atoms, R １ and R ２ These may combine to form a ring with the carbon atom to which they are bonded, and the ring may be a cyclopropane-1,1-diyl group, a cyclobutane-1,1-diyl group, a cyclopentane-1,1-diyl group, a cyclohexane-1,1-diyl group, a cycloheptane-1,1-diyl group, a cyclooctane-1,1-diyl group, an indene-1,1-diyl group, or a fluorene-9,9-diyl group. R ３ is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 34 carbon atoms. J １ and J ２ Each of these is independently an oxygen atom, a sulfur atom, or a selenium atom. M １ is a hydrogen atom, a bromine atom, an iodine atom, a trialkylsilyl group, a dialkylarylsilyl group, an alkyldiarylsilyl group, or a triarylsilyl group, Y １ This is an aromatic group or halogen atom represented by the general formula (Yarom), Y ２ A C3-C50 alkyl group (if an alkyl group is selected, the C1 atom of the alkyl group may be substituted with a hydroxyl group) ２ J １ and J ２ The compound according to claim 1, wherein the carbon atom having a tricyclic structure and forming a bond with it has a hydroxyl group on it, or is a halogen atom.

3. R ３ That is a hydrogen atom, J １ and J ２ This is a sulfur atom, M １ is a hydrogen atom, a bromine atom, a trialkylsilyl group, a dialkylarylsilyl group, an alkyldiarylsilyl group, or a triarylsilyl group, Y １ This is an aromatic group or halogen atom represented by the general formula (Yarom), Y ２ A C3-C3 alkyl group (if an alkyl group is selected, the C3-C3 alkyl group may have a hydroxyl group substituted on its carbon atom at position 1 (Y) ２ J １ and J ２ The compound according to claim 1 or 2, wherein the carbon atom having a tricyclic structure and a bond with it has a hydroxyl group on it, or is a halogen atom.

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