JP7345332B2 - Regioregular self-doped poly(3,4-ethylenedioxythiophene) derivatives and their synthesis method - Google Patents

Description

This invention relates to a self-doped poly(3,4-ethylenedioxythiophene) derivative having head-to-tail bond regularity (regioregular) and a method for synthesizing the same.

Poly(3,4-ethylenedioxythiophene) (PEDOT) is one of the most widely used conductive polymers for applications such as flexible circuit boards, transparent electrodes, capacitors, and static electricity removers. PEDOT is usually complexed with polystyrene sulfonic acid (PSS) and provided as an aqueous dispersion, but dispersing this PEDOT:PSS complex in water is not easy, and in order to make a stable colloidal dispersion aqueous solution. requires excessive PSS. However, there is concern that using an excessive amount of PSS having a strongly acidic sulfonic acid group may have an adverse effect on electronic devices because it exhibits corrosivity or high water absorption. As one of the solutions, it has been proposed to use self-doped PEDOT derivatives. For example, Patent Documents 1 to 3 disclose that a self-doped PEDOT derivative can be obtained by oxidatively polymerizing a 3,4-ethylenedioxythiophene derivative having a sulfonic acid group in an aqueous solution. This has a chemical structure in which a sulfonic acid group is introduced into each repeating unit as a side chain of PEDOT via an alkyl chain. Since the monomers used to synthesize this are asymmetric, so-called head-to-head (or tail-to-tail) and head-to-tail bonds occur in the stereoregularity of the reaction positions during polymerization, but conventional methods control the stereoregularity. A PEDOT derivative with no regularity (regiorandom) is obtained.

On the other hand, in poly(3-hexylthiophene) (P3HT), various stereoregular (regioregular) polymers and regiorandom polymers have been synthesized. It has been reported that regioregular P3HT has longer wavelengths of ultraviolet-visible light absorption maximum in solutions or films, superior crystallinity, and increased charge mobility compared to regiorandom P3HT (Non-patent Literature 1, 2). Further, Patent Document 4 and Non-Patent Document 3 report the synthesis of PEDOT having an alkyl chain as a regioregular side chain. However, as shown in Comparative Example 1 herein, a regioregular self-doped poly(3,4-ethylene diethylene chloride) having a sulfonic acid group in the side chain was prepared using a method similar to those disclosed in these documents. However, there was a need for a method for synthesizing a regioregular self-doped poly(3,4-ethylenedioxythiophene) derivative having a sulfonic acid group in its side chain.

US Patent No. 5,111,327 International Publication No. 2014/007299 International Publication No. 2015/194657 Korean Publication No. 2011/105239

Journal of the American Chemical Society, Volume 117 (No. 1), Page 233 (1995). Nature, vol. 401, p. 685 (1999). Journal of Nanoscience and Nanotechnology, Volume 12 (No. 5), Page 4335 (2012).

An object of the present invention is to provide a regioregular self-doped PEDOT derivative exhibiting excellent electrical properties and an efficient method for synthesizing the same.

As a result of intensive studies to solve the above problems, the present inventors found that (7-Bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methanol is used as a key intermediate to form a novel sulfonate, and this product is further polymerized. It was discovered that a self-doped PEDOT derivative having head-to-tail bond regularity could be produced by the method, and furthermore, a self-doping type poly(3,4-ethylenedioxythiophene) having head-to-tail bond regularity (regioregular) could be produced. The present invention was completed based on the discovery that the derivative tends to exhibit higher electrical conductivity than a self-doped poly(3,4-ethylenedioxythiophene) derivative without regularity (regiorandom).

That is, the present invention is based on the following general formula (1)

(In the formula, a represents an integer of 2 or 3. R represents a hydrogen atom or a methyl group. X ¹ represents a chlorine atom or a bromine atom. X ² represents a hydrogen atom, a chlorine atom, a bromine atom. and an iodine atom, and represents an atom different from X ^1. Z represents a hydrocarbon group having 3 to 8 carbon atoms.)
A sulfonate having a 3,4-ethylenedioxythiophene structure represented by (hereinafter referred to as EDOT(X ¹ , X ² ) of the present invention), and the following general formula (2') derived therefrom

(In the formula, a and R represent the same meanings as above. Z' represents a hydrocarbon group having 3 to 8 carbon atoms, a hydrogen ion, an alkali metal ion, or an optionally substituted ammonium ion. However, When Z' is a hydrogen ion, an alkali metal ion, or an optionally substituted ammonium ion, the oxygen atom bonded to Z' has a negative charge.)
A head-to-tail bond type poly(3,4-ethylene diethylene chloride) having a sulfonate group in its side chain, which has at least two or more repeating units represented by oxythiophene) derivatives.

Furthermore, the present invention provides the following general formula (2) obtained by polymerizing the above EDOT (X ¹ , X ² ).

(In the formula, a and R represent the same meanings as above. Z represents a hydrocarbon group having 3 to 8 carbon atoms.)
A head-to-tail bond type poly(3,4-ethylene diethylene chloride) having a sulfonate group in its side chain, which has at least two or more repeating units represented by oxythiophene) derivative (hereinafter referred to as HT-PEDOT (2) of the present invention), and the following general formula (3) derived from HT-PEDOT (2) of the present invention.

(In the formula, a and R represent the same meanings as above. M ⁺ represents a hydrogen ion, an alkali metal ion, or an optionally substituted ammonium ion.)
A head-to-tail bond type poly(3,4-ethylene diethylene chloride) having a sulfonate group in its side chain, which has at least two or more repeating units represented by HT-PEDOT(3) of the present invention). The present invention also provides a conductive polymer (hereinafter referred to as the conductive polymer of the present invention) consisting of the above HT-PEDOT (2) and/or the above HT-PEDOT (3), and the above HT-PEDOT. (2) and/or a conductive polymer composition comprising a conductive polymer consisting of the above-mentioned HT-PEDOT (3), and further manufactured using the conductive polymer and/or the conductive polymer composition. The present invention relates to a conductive film, and an electrode or electronic device using the conductive polymer and/or the conductive polymer composition. Additionally, the present invention relates to a method for producing the above EDOT (X ¹ , X ² ), the above HT-PEDOT (2), and the above HT-PEDOT (3).

The conductive polymer of the present invention has a head-to-tail structure with high regioregularity, and can provide better conductivity than a regiorandom conductive polymer produced by a similar method. be.

The present invention will be explained in more detail below.

In the present invention, sulfonate represents a sulfonic acid ester or a salt of sulfonic acid, and the sulfonate group represents a sulfonic acid ester group or a sulfonic acid group forming a salt.

In EDOT (X ¹ , X ² ) of the present invention represented by general formula (1), a represents an integer of 2 or 3, and R represents a hydrogen atom or a methyl group. There is no particular restriction on the combination of a and R, but from the viewpoint of easy availability of raw materials, when a is 2, R is preferably a hydrogen atom or a methyl group, and when a is 3, R is a hydrogen atom. is preferable, and when a is 2, it is more preferable that R is a methyl group.

Examples of the hydrocarbon group having 3 to 8 carbon atoms for Z include straight-chain, branched, or cyclic hydrocarbon groups having 3 to 8 carbon atoms, and examples thereof include, but are not limited to, propyl group, isopropyl group, etc. group, cyclopropyl group, butyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, cyclobutyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclobutylmethyl group, cyclopentyl group, hexyl group, 1-methylpentyl group, 2-methyl Pentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, cyclohexyl group, heptyl group, 1-methylhexyl group, 1-ethylpentyl group, cyclohexylmethyl group, cycloheptyl group , octyl group, 1-methylheptyl group, or 2-ethylhexyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, benzyl group, 2-phenylethyl group, allyl group, 3-butenyl group , 4-pentenyl group, 5-hexenyl group, or propargyl group. Of these, isopropyl group and butyl group are preferred because they facilitate polycondensation of EDOT (X ¹ , X ² ) and control hydrolysis. , 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, pentyl group, 2,2-dimethylpropyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, or 2- Ethylhexyl is preferred, and 1-methylpropyl, 2-methylpropyl or 2,2-dimethylpropyl is particularly preferred.

In the EDOT (X ¹ , X ² ) of the present invention represented by the general formula (1), X ¹ represents a chlorine atom or a bromine atom. ^X2 is selected from a hydrogen atom, a chlorine atom, a bromine atom, and an iodine atom, and represents an atom different from ^X1 .

The combination of X ¹ and X ² is not particularly limited except that X ¹ and X ² are different as described above, but it is possible that X ¹ is a bromine atom and X ² is a hydrogen atom or an iodine atom. preferable.

In the HT-PEDOT (2) of the present invention represented by general formula (2), the definitions of a and R, the combination of a and R, and the definition of Z are the same as above.

In the HT-PEDOT (3) of the present invention represented by general formula (3), the definitions of a and R and the combination of a and R are the same as above. M ⁺ represents a hydrogen ion, an alkali metal ion, or an optionally substituted ammonium ion. The alkali metal ion in M ⁺ is not particularly limited, and examples thereof include lithium ion, sodium ion, potassium ion, and the like.

The ammonium ion that may be substituted in M ⁺ is not particularly limited, and examples thereof include ammonium ion (NH ₄ ⁺ ), trimethylammonium ion, tetramethylammonium ion, diethylammonium ion, triethylammonium ion, and tetraethyl. Ammonium ion, propylammonium ion, dipropylammonium ion, tripropylammonium ion, tetrapropylammonium ion, butylammonium ion, dibutylammonium ion, tributylammonium ion, tetrabutylammonium ion, bis(2-methylpropyl)ammonium ion, Tris (2-Methylpropyl) ammonium ion, pentylammonium ion, dipentylammonium ion, hexylammonium ion, dihexylammonium ion, octylammonium ion, dioctylammonium ion, trioctylammonium ion, dioctylmethylammonium ion, 2-ethylhexylammonium ion, bis (2-ethylhexyl) ammonium ion, decylammonium ion, didecylmethylammonium ion, dodecylammonium ion, dodecyldimethylammonium ion, didodecylammonium ion, didodecylmethylammonium ion, tetradecylammonium ion, hexadecyl ammonium ion, hexadecyl Examples include dimethyl ammonium ion, octadecyl ammonium ion, and dimethyl octadecyl ammonium ion. Among these, ammonium ion (NH ₄ ⁺ ), trimethylammonium ion, tetramethylammonium ion, diethylammonium ion, triethylammonium ion, tetraethylammonium ion, propylammonium ion, dipropylammonium ion, Tripropylammonium ion, tetrapropylammonium ion, butylammonium ion, dibutylammonium ion, tributylammonium ion, tetrabutylammonium ion, hexylammonium ion, dihexylammonium ion, octylammonium ion, dioctylammonium ion, 2-ethylhexylammonium ion, bis (2-ethylhexyl)ammonium ion, decylammonium ion, dodecylammonium ion, dodecyldimethylammonium ion, tetradecylammonium ion, hexadecylammonium ion, hexadecyldimethylammonium ion, octadecylammonium ion, or dimethyloctadecylammonium ion are preferred.

In the head-to-tail poly(3,4-ethylenedioxythiophene) derivative of the present invention represented by general formula (2'), the definitions of a and R and the combination of a and R are the same as above. Z' represents a hydrocarbon group having 3 to 8 carbon atoms, a hydrogen ion, an alkali metal ion, or an optionally substituted ammonium ion. However, when Z' is a hydrogen ion, an alkali metal ion, or an optionally substituted ammonium ion, the oxygen atom bonded to Z' has a negative charge.

The definition and preferred version of the hydrocarbon group having 3 to 8 carbon atoms in Z' are the same as those for the hydrocarbon group having 3 to 8 carbon atoms in Z'.

The definition and preferred version of the alkali metal ion or optionally substituted ammonium ion in Z′ are the same as those of the alkali metal ion or optionally substituted ammonium ion in M ⁺ above.

Next, the method for producing EDOT (X ¹ , X ² ) of the present invention will be described in detail.

First, using 3,4-dihydroxythiophene-2,5-dicarboxylic acid dialkyl ester (hereinafter also referred to as dicarboxylic acid diester (6)) as a starting material, [Step 1] and [Step 2] are shown in the following general reaction formula. ] and [Step 3] to produce carboxylic acid ester (4).

(In the formula, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms.)
The hydrocarbon group having 1 to 8 carbon atoms represented by R ¹ may be a straight chain, branched or cyclic hydrocarbon group having 1 to 8 carbon atoms, and is not particularly limited, but for example, Methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, cyclobutyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclobutylmethyl group, cyclopentyl group, hexyl group , 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, cyclohexyl group, heptyl group, 1-methylhexyl group, 1-ethyl group Pentyl group, cyclohexylmethyl group, cycloheptyl group, octyl group, 1-methylheptyl group, 2-ethylhexyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, benzyl group, 2-phenylethyl Examples include methyl group, allyl group, 3-butenyl group, 4-pentenyl group, 5-hexenyl group, or propargyl group. Among these, methyl group, ethyl group, propyl group, or butyl group A group is preferred, and a methyl or ethyl group is more preferred.

The dicarboxylic acid diester (6) as a raw material can be produced with reference to known literature (for example, O. Stephan et al., Journal of Electroanalytical Chemistry, Vol. 443, pp. 217-226 (1998)). Each step will be described in detail below.

[Step 1] is a step in which dicarboxylic acid diester (6) is reacted with base 1 to hydrolyze one of the carboxylic acid esters, and then treated with acid 1 to produce dicarboxylic acid monoester (7).

The base 1 is not particularly limited as long as it can hydrolyze only one of the two carboxylic acid esters, but examples include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, and hydrogen carbonate. Examples include inorganic bases such as sodium and potassium bicarbonate, and organic bases such as ammonia, methylamine, dimethylamine, trimethylamine, hydrazine, methylhydrazine, 1,1-dimethylhydrazine, 1,2-dimethylhydrazine, piperazine, and guanidine. These can be used alone or in combination. Among these, lithium hydroxide, sodium hydroxide, or potassium hydroxide is preferred in terms of good yield. The hydrolysis reaction proceeds by stirring using an organic solvent and water at 0 to 120°C for several minutes to several tens of hours. Organic solvents that can be used include hydrocarbons such as hexane, cyclohexane, and toluene, ethers such as diethyl ether, tetrahydrofuran (THF), 1,4-dioxane (DOX), and cyclopentyl methyl ether (CPME), methanol, ethanol, and propanol. , alcohols such as 2-propanol and butanol, ketones such as acetone and 2-propanone (MEK), halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane, N,N-dimethylformamide (DMF), N, Examples include aprotic polar solvents such as N-dimethylacetamide (DMAc), 1-methylpyrrolidin-2-one (NMP), and dimethyl sulfoxide (DMSO), which may be used alone or in combination of two or more. be able to.

The acid 1 is not particularly limited as long as a dicarboxylic acid monoester (7) can be obtained by converting a carboxylate to a carboxylic acid, but examples include hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, and sulfuric acid. , sulfite, nitric acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, and the like. Hydrochloric acid is preferred because it is inexpensive and has good operability.

[Step 2] is a step of producing monocarboxylic acid ester (8) by decarboxylating the dicarboxylic acid monoester (7) obtained in [Step 1]. A general method of decarboxylation reaction will be described. Regarding the decarboxylation reaction, there is no particular restriction as long as the decarboxylation of the carboxylic acid proceeds to obtain the monocarboxylic acid ester (8), and known decarboxylation reaction conditions can be applied. A monocarboxylic acid ester (8) can be obtained by adding a catalyst and additives as necessary and heating at 120 to 300°C for several minutes to several tens of hours. The above-mentioned catalyst is not particularly limited, but for example, copper (II) oxide, copper (I) oxide, silver acetate, etc. are used in an amount of 0.001 to 0.5 equivalent to dicarboxylic acid monoester (7). be able to. In addition, the above-mentioned additives include, but are not particularly limited to, potassium bromide, potassium carbonate, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,10-phenanthroline, N,N , N',N'-tetramethylethylenediamine (TMEDA) or the like can be used in an amount of 0.001 to 10 equivalents based on the dicarboxylic acid monoester (7). The decarboxylation reaction can be carried out in a high boiling point solvent such as DMF, DMAc, NMP, quinoline, sulfolane, etc., and the reaction can be promoted by irradiating with ultrasound. After the reaction is completed, a highly pure monocarboxylic acid ester (8) can be produced by performing usual purification operations such as filtration, extraction, precipitation purification, and column chromatography purification.

[Step 3] is to produce carboxylic acid ester (4) by reacting monocarboxylic acid ester (8) obtained in [Step 2] with 2,3-dibromo-1-propanol in the presence of base 2. This is the process of The base 2 is not particularly limited as long as it can produce the carboxylic ester (4) by reacting the monocarboxylic ester (8) with 2,3-dibromo-1-propanol; for example, lithium hydroxide, Inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydride, sodium hydride, sodium methoxide, sodium ethoxide, sodium carbonate, potassium carbonate, cesium carbonate, etc. can be used for carboxylic acid ester (4). It is recommended to use 0.1 to 10 equivalents, preferably 1 to 3 equivalents in terms of good yield. The reaction proceeds by stirring at 30 to 120° C. for several minutes to several tens of hours using an organic solvent. Organic solvents that can be used include, but are not particularly limited to, hydrocarbons such as hexane, cyclohexane, and toluene, ethers such as diethyl ether, THF, DOX, and CPME, methanol, ethanol, propanol, and 2-propanol. , alcohols such as butanol, ketones such as acetone and MEK, halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane, and aprotic polar solvents such as DMF, DMAc, NMP, and DMSO. These can be used alone or in combination of two or more. After the reaction is completed, a highly pure carboxylic acid ester (4) can be produced by performing usual purification operations such as filtration, extraction, precipitation purification, and column chromatography purification.

Next, using the carboxylic acid ester (4) as a starting material, 7-halo-2,3-dihydrothieno[3 ,4-b][1,4]dioxin-2-yl)methanol (hereinafter referred to as alcohol (5)) is produced.

(In the formula, R ¹ and X ¹ represent the same meanings as above.)
Each step will be described in detail below.

[Step 4] is a step of producing a halogenated carboxylic ester (9) by allowing the halogenating agent 1 to act on the carboxylic ester (4). As the halogenating agent 1, there is no particular restriction as long as the halogenated carboxylic acid ester (9) is obtained, and any known chlorinating agent or brominating agent can be used. Specifically, N-chlorosuccinimide, N-chlorosuccinimide, N- - Examples include bromosuccinimide. The reaction between the carboxylic acid ester (4) and the halogenating agent 1 may be carried out in a solvent, and examples of the solvent include hydrocarbons such as hexane, cyclohexane, and toluene, and ethers such as diethyl ether, THF, DOX, and CPME. , halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane, carboxylic acids such as formic acid, acetic acid, and propionic acid, and amides such as DMAc and DMF, which may be used alone or in combination of two or more. It can be used as The reaction temperature can be selected as appropriate from the range of usually -50 to 100°C. The obtained halogenated carboxylic acid ester (9) can be purified using column chromatography or the like.

In [Step 5], the halogenated carboxylic acid ester (9) obtained in [Step 4] is treated with base 3 to hydrolyze the carboxylic ester, and then treated with acid 2 to form the halogenated carboxylic acid (10 ). Base 3 is not particularly limited as long as halogenated carboxylic acid (10) can be obtained by hydrolyzing the carboxylic ester and subsequent acid treatment, and it can be selected from the bases listed for base 1 above. The conditions for the hydrolysis reaction can also be selected from the conditions shown for the hydrolysis reaction using base 1 above. Acid 2 can be selected from the acids shown in acid 1 above.

[Step 6] is a step of performing a decarboxylation reaction of the halogenated carboxylic acid (10) obtained in [Step 5] to produce alcohol (5). The conditions for the decarboxylation reaction are not particularly limited as long as decarboxylation of the carboxylic acid proceeds and alcohol (5) is obtained, and known decarboxylation reaction conditions can be applied, as described in [Step 2] above. A method of decarboxylation reaction can be used.

Next, a method for producing EDOT (X ¹ , X ² ) of the present invention from alcohol (5) will be described. EDOT ( ^{X 1 ,} , H)) and a sulfonic acid ester having a 3,4-ethylenedioxythiophene structure ^represented by the general formula (1b) (hereinafter referred to as EDOT(X ¹ , It can be expressed separately.

(In the formula, a, R, X ¹ and Z have the same meanings as in the above general formula (1).)

(In the formula, a, R, X ¹ and Z represent the same meanings as in the above general formula (1). X ³ is selected from a chlorine atom, a bromine atom, or an iodine atom, and represents ^an atom different from .)
EDOT(X ¹ ,H) (1a) can be produced from alcohol (5) through [Step 7] as shown in the following general reaction formula.

As ^shown in the following general reaction formula, EDOT (X ¹ , and [Step 10].

[Step 7] is a step of producing EDOT (X ¹ , H) (1a) by sulfonic acid esterification reaction of alcohol (5). The sulfonic acid esterification reaction in [Step 7] further includes two steps: the alkyl sulfonic acid conversion reaction in [Step 7-1] and the esterification reaction in [Step 7-2].

[Step 7-1] is to produce a sulfonate (13) by reacting a cyclic sultone compound (12) with an anionizing agent on the alcohol (5) to produce an alcoholate anion. It is a process.

(In the formula, a and R represent the same meanings as in the above general formula (1).)

(In the formula, a, R and X ¹ represent the same meanings as in the above general formula (1). (M ¹ ) ⁺ represents an allowable counter cation of the sulfonate.)
The anionizing agent used in [Step 7-1] is not particularly limited as long as it can anionize the alcohol and suppress side reactions, but specifically, lithium hydride, sodium hydride, phenyllithium, or lithium diisopropyl Examples include amides.

As the cyclic sultone compound (12), commercially available ones can be used, and specific examples include 1,3-propane sultone, 1,4-butane sultone, 1,3-(1-methyl)propane sultone, etc. .

The countercation (M ¹ ) ⁺ is naturally determined by the anionizing agent used, and is, for example, a lithium ion, a sodium ion, etc., but for solubility control or purification, the countercation (M ¹ ) ⁺ is converted into a sulfonate. It can be converted to other acceptable countercations by ion exchange treatment or the like. Other countercations that are acceptable as the sulfonate are not particularly limited, and include, for example, hydrogen ions, alkali metal ions, and optionally substituted ammonium ions. Examples are given above.

The reaction in [Step 7-1] proceeds smoothly in an organic solvent, and examples of the organic solvent include hydrocarbons such as hexane, cyclohexane, and toluene, ethers such as diethyl ether, THF, DOX, and CPME, DMAc, and DMF. Organic solvents such as amide and the like can be used alone or in combination of two or more kinds. The reaction temperature can usually be selected appropriately from the range of -80 to 100°C.

The obtained sulfonate (13) can be purified using extraction, concentration, precipitation purification, recrystallization purification, column chromatography, etc., but it can be directly subjected to the next esterification reaction in [Step 7-2]. It's okay.

[Step 7-2] is to react sulfonic acid salt (13) with a chlorinating agent to form sulfonic acid chloride (14), and then react with alcohol (15) to form EDOT(X ¹ ,H)( This is a process for manufacturing 1a).

(In the formula, a, R and ^X1 represent the same meanings as in the above general formula (1).)

(In the formula, Z represents the same meaning as in the above general formula (1).)
The chlorinating agent used in [Step 7-2] is not particularly limited as long as sulfonic acid chloride (14) can be obtained, but thionyl chloride, chlorinated dichloride, etc. Oxalyl chloride or phosphorus pentachloride is preferred, and oxalyl dichloride is particularly preferred. When the chlorinating agent is applied, the reaction can proceed smoothly by using an organic solvent. Examples of organic solvents include hydrocarbons such as hexane, cyclohexane, and toluene, ethers such as diethyl ether, THF, DOX, and CPME; Examples include ketones such as acetone and MEK, halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane, and these may be used alone or in combination of two or more. Additionally, a small amount of DMF may be added to accelerate the reaction. The reaction temperature can be selected as appropriate from the range of usually -20 to 150°C.

EDOT (X ¹ , H) (1a) of the present invention can be produced from sulfonic acid chloride (14) by adding alcohol (15) without purification. At this time, if an organic base such as triethylamine or pyridine is added, the reaction proceeds smoothly. The obtained EDOT(X ¹ , H) (1a) can be purified using column chromatography or the like.

[Step 8] is to add halogenating agent 2 to EDOT (X ¹ , H) (1a) and replace the hydrogen atom on the thiophene ring with a halogen atom selected from chlorine, bromine, and iodine atoms different from X ¹ . This is a process of manufacturing EDOT (X ¹ , X ³ ) (1b) by doing so.

As the halogenating agent 2 used in [Step 8], a known halogenating agent can be used, such as Cl ₂ , Br ₂ , I ₂ , sulfuryl dichloride, N-chlorosuccinimide, N-bromosuccinimide, N - Examples include iodosuccinimide or phosphorus pentachloride.

The esterification reaction in [Step 8] may be carried out in a solvent, and examples of the solvent include hydrocarbons such as hexane and cyclohexane, ethers such as diethyl ether, THF, DOX, and CPME, dichloromethane, chloroform, 1,2- Examples include halogenated hydrocarbons such as dichloroethane, and these can be used alone or in a mixture of two or more. Further, a catalytic amount of DMF may be added if necessary. The reaction temperature can usually be selected appropriately from the range of -20 to 100°C. The obtained EDOT (X ¹ , X ³ ) (1b) can be purified using column chromatography or the like.

<Route 2> is a route in which the order of [Step 7] and [Step 8] of <Route 1> is changed. That is, [Step 9] adds halogenating agent 2 to alcohol (5) and replaces the hydrogen atom on the thiophene ring with a halogen atom selected from chlorine atom, bromine atom, and iodine atom, which is different from ^X1 . (11) can be produced by the same method as [Step 8] except that the raw materials in [Step 8] are different. [Step 10] is ^a step for producing EDOT (X ¹ , ] Similarly, ^EDOT (X ¹ ,

The HT-PEDOT (2) of the present invention can be produced by polycondensing the EDOT (X ¹ , X ² ) (1) of the present invention as a raw material. When polycondensation is performed using EDOT(X ¹ , H) (1a) as a raw material, electrophilic substitution polymerization in the presence of a Lewis acid or Brønsted acid (publicly known literature: B. Bonillo et al., Journal of The American Chemical Society, Vol. 134) 18916-18919 (2012), A. Balasubramanian et al., Polymer Chemistry, Vol. 5, pp. 5928-5941 (2014)), or direct C-H arylation polycondensation using a palladium catalyst (known literature: A. Kumar et al. , Polymer Chemistry, Polymer Chemistry, Vol. 1, pp. 286-288 (2010), Q. Wang et al., Journal of The American Chemical Society, Vol. 132, pp. 11420-11421 ( 2010), Y. Fujinami et al., ACS Macro Letters, Vol. 1, pp. 67-70 (2012), H. Zhao et al., Macromolecules, Vol. 45, pp. 7783-7790 (2012), J. Kuwabara et al., Polymer Chemistry, Vol. 6, pp. 891-895 (2015), M. By applying known methods such as Wakioka et al., Macromolecules, Vol. 48, pp. 8382-8388 (2015), K. Fujita et al., Macromolecules, Vol. 49, pp. 1259-1269 (2016), the HT of the present invention - PEDOT (2) can be produced. Among these, direct C--H arylation polycondensation is preferably used because of its excellent polymer solubility.

A general method for producing HT-PEDOT (2) of the present invention from EDOT (X ¹ , H) (1a) directly through C--H arylation polycondensation will be described. General reaction formula below

(In the formula, a, R, X ¹ and Z have the same meanings as in the above general formula (1).)
As shown in Figure 2, a palladium catalyst, a phosphorus ligand, and a base 4 are used during the polymerization.

The palladium catalyst is not particularly limited, but palladium acetate, palladium chloride, etc. are preferably used, and it is generally added in an amount of 0.1 to 20 mol%, preferably 1 to 10 mol%, based on the substrate.

Examples of the phosphorus ligand include, but are not limited to, tri(tert-butyl)phosphine, tricyclohexylphosphine, triphenylphosphine, diphenyl(2-methoxyphenyl)phosphine, and tris(2-methoxyphenyl)phosphine. , tris(4-methoxyphenyl)phosphine, tris(o-tolyl)phosphine, tris(2-fluorophenyl)phosphine, tris(2-dimethylaminophenyl)phosphine, [2-(2-dimethylaminophenyl)phenyl]diphenyl Examples include phosphine, tris(2-methylsulfanylphenyl)phosphine, tricyclohexylphosphonium tetrafluoroborate, di(tert-butyl)methylphosphonium tetrafluoroborate, and the like. Triphenylphosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, and tris(o-tolyl)phosphine are preferred because they are inexpensive and easily available, and usually about 2 equivalents to the palladium catalyst. Good to add.

The base 4 is not particularly limited as long as it does not decompose the EDOT (X ¹ , H) (1a) of the present invention or inhibit polymerization, and includes, for example, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, An inorganic weak base such as sodium hydrogen carbonate is preferred, and is preferably added in an amount of about 0.5 to 4 equivalents, preferably about 1 to 2 equivalents, relative to the substrate. Direct C-H arylation polycondensation proceeds smoothly in a solvent, and the solvent is not particularly limited as long as it does not interfere with the reaction, such as hydrocarbons such as hexane, cyclohexane, toluene, diethyl ether, THF, DOX, etc. , ethers such as CPME, amides such as DMAc, DMF, and NMP, alcohols such as methanol, ethanol, propanol, 2-propanol, butanol, and water can be used alone or in combination of two or more. The reaction temperature can be appropriately selected from the range of usually 60 to 150°C, preferably 90 to 130°C.

^When polycondensation ^{is carried} out using EDOT (X ¹ , ^{There are no restrictions on the polymerization method, and it is not particularly limited, but for example, EDOT (X 1 ,} Stille, Angewandte Chemie, International Edition in English, Vol. 25 ^, pp. 508-524 (1986)) polymerization, EDOT (X ¹ , or A known method such as Grignard Metathesis (GRIM) polymerization using an exchange reaction between a Grignard reagent and a halogen atom (publicly known literature: R.S. Loewe et al., Advanced Materials, Vol. 11, pp. 250-253 (1999)). By applying the method, HT-PEDOT (2) of the present invention can be manufactured. Among them, GRIM polymerization is preferably used because of its high polymerization efficiency.

A general method for producing HT-PEDOT (2) of the present invention from EDOT (X ¹ , X ³ ) (1b) through GRIM polymerization will be described. General reaction formula below

(In the formula, a, R, X ¹ and Z have the same meanings as ⁱⁿ the above general formula ( ¹ ). ' represents an alkyl group having 6 or less carbon atoms. X represents a chlorine atom, a bromine atom, or an iodine atom.)
As shown in , a Grignard reagent (R'MgX) or a nickel catalyst is used during polymerization.

Examples of the alkyl group having 6 or less carbon atoms for R' include linear, branched, or cyclic alkyl groups having 1 to 6 carbon atoms, and examples thereof include, but are not limited to, methyl group, ethyl group, etc. , propyl group, isopropyl group, cyclopropyl group, butyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, cyclobutyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclobutylmethyl group, cyclopentyl group, hexyl group, 1-methylpentyl group 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, or cyclohexyl group.

The Grignard reagent described above can be prepared by reacting the corresponding alkyl halide with magnesium metal, but commercially available methylmagnesium iodide, ethylmagnesium chloride, ethylmagnesium bromide, propylmagnesium chloride, propylmagnesium bromide, isopropylmagnesium chloride, isopropyl Cyclohexane solution, toluene solution, diethyl ether solution, THF solution of magnesium bromide, butylmagnesium chloride, butylmagnesium bromide, sec-butylmagnesium bromide, tert-butylmagnesium chloride, tert-butylmagnesium bromide, cyclohexylmagnesium chloride, cyclohexylmagnesium bromide, etc. etc. may also be used.

The nickel catalyst is not particularly limited, but includes, for example, [1,3-bis(diphenylphosphino)ethane]nickel(II) dichloride (Ni(dppe)Cl ₂ ), [1,3-bis (diphenylphosphino)propane]nickel(II) dichloride (Ni(dppp)Cl ₂ ) and the like are preferably used.

GRIM polymerization proceeds smoothly in a solvent, and there are no particular restrictions on the solvent as long as it does not interfere with the reaction, and solvents such as hydrocarbons such as hexane, cyclohexane, and toluene, and ethers such as diethyl ether, THF, DOX, and CPME may be used alone. Alternatively, two or more types can be used in combination. The reaction temperature can be appropriately selected from the range of usually 0 to 120°C, preferably 0 to 100°C.

The HT-PEDOT (2) of the present invention obtained by various polycondensations is easily agglomerated because the doping progresses under the influence of oxygen in the air. In such cases, HT-PEDOT (2) soluble in organic solvents can be obtained by dedoping, for example by adding a reducing agent such as hydrazine to the highly doped dispersion solution of HT-PEDOT (2). can be obtained.

The molecular weight of HT-PEDOT (2) of the present invention can be indicated depending on the measuring method such as weight average molecular weight, number average molecular weight, viscosity average molecular weight, etc. Regarding the weight average molecular weight (Mw), it is preferably 1,000 to 1,000,000, and more preferably 2,000 to 500,000 from the viewpoint of controlling the properties of the polymer and processability. . The molecular weight distribution (Mw·Mn ⁻¹ ) is not particularly limited, but it is preferably in the range of approximately 1 to 20, and more preferably in the range of 1 to 5 from the viewpoint of uniformity of the polymer. As a method for calculating the molecular weight, known methods such as size exclusion chromatography (SEC) method, viscosity method, and light scattering method, which are converted based on a standard sample such as polystyrene or polyethylene glycol, can be used.

The HT-PEDOT (2) of the present invention is purified by a combination of methods such as solvent washing, precipitation purification, centrifugal sedimentation, ultrafiltration, dialysis, dedoping treatment, and ion exchange resin treatment, and then the sulfonic acid ester group is purified. Although HT-PEDOT (3) can be obtained by performing a hydrolysis treatment, HT-PEDOT (3) may also be obtained by performing the hydrolysis treatment without purifying HT-PEDOT (2).

The hydrolysis treatment will be explained. The hydrolysis method is not particularly limited as long as side reactions other than the hydrolysis reaction of the sulfonic acid ester group can be suppressed, but specifically, the HT-PEDOT (2) of the present invention is treated with a Lewis acid such as AlBr ₃ or TiCl ₄ . A method of acting with an alkali halide salt such as LiI, LiBr, LiCl, NaI, NaBr, NaCl, KI, KBr, KCl (Public literature: For example, Florian M. Koch et al., Chemistry-A European Journal, 17 Vol., pp. 3679-3692 (2011), Mori Hideharu et al., Macromolecules, Vol. 43, pp. 7021-7032 (2010), Christopher C. Kotoris et al., The Journal of Organic Che mistry, vol. 63, pp. 8052-8057 (1998 2003)), methods of using acids such as hydrochloric acid, sulfuric acid, nitric acid, trifluoroacetic acid, etc., butyldimethylamine, hexyldimethylamine, triethylamine, N,N'-dimethylpiperazine, 1,8-diazobicyclo [5.4. 0]-7-undecene, 1,4-diazobicyclo[2.2.2]octane, and other tertiary amines (known literature: for example, J.F. King et al., Journal of the American Chemical Society , Vol. 104, pp. 7108-7122 (1982); Maria Mahrova et al., Journal of Chemical & Engineering Data, Vol. 57, pp. 241-248 (2012)); , a method in which a halogenated alkali salt is used, and a method in which a tertiary amine is used are preferred.

When performing hydrolysis using a halogenated alkali salt or tertiary amine, there is no particular restriction on the amount of the halogenated alkali salt or tertiary amine used, and the amount to be added is determined as appropriate, taking into account the chemical structure and the rate of hydrolysis. However, it is sufficient to use 0.1 to 100 equivalents based on the molar amount of the sulfonic acid ester group of HT-PEDOT (2) of the present invention, and from 0.5 to 100 in terms of easy control of the hydrolysis ratio. Preferably, 50 equivalents are used. The production method of the present invention may be carried out in a solvent. Examples of the solvent include hydrocarbon solvents such as hexane, cyclohexane, and toluene, ether solvents such as diethyl ether, THF, DOX, and CPME, amide solvents such as DMF and DMAc, dichloromethane, chloroform, and 1,2-dichloroethane. Examples include halogen solvents, acetone, ketone solvents such as MEK, and water, and these can be used alone or in combination of two or more. There is no limit to the amount of reaction solvent.

The reaction temperature when hydrolyzing the HT-PEDOT (2) of the present invention can usually be appropriately selected from the range of 0 to 150°C, and is preferably room temperature to 120°C in terms of reaction efficiency.

The method for purifying the HT-PEDOT (3) of the present invention obtained by hydrolyzing the HT-PEDOT (2) of the present invention is not particularly limited, but examples include solvent washing, precipitation purification, centrifugal sedimentation, Examples include filtration, dialysis, dedoping treatment, ion exchange resin treatment, etc., and each can be used alone or in combination.

The conductive polymer of the present invention may contain the above HT-PEDOT (2) and/or the above HT-PEDOT (3). ) alone or by mixing the above HT-PEDOT (2) and the above HT-PEDOT (3) in any ratio. Alternatively, the conductive polymer of the present invention can also be obtained by converting some of the repeating units of the above HT-PEDOT (2) into the above HT-PEDOT (3). The ratio of mixing the above HT-PEDOT (2) and the above HT-PEDOT (3), and the ratio of converting some repeating units of the above HT-PEDOT (2) to the above HT-PEDOT (3) There is no particular restriction on the amount, and it may be appropriately determined in consideration of the conductivity, solubility, dispersibility, hygroscopicity, acidity, film-forming property, coating property, etc. of the conductive polymer of the present invention.

In addition, if necessary, the sulfonate (when M ⁺ is not a hydrogen ion in -SO ₃ ^- M ⁺ ) can be converted to the acid form (-SO ₃ H) by treating it with an ion exchange resin and provided. .

In order to control conductivity, dispersibility in solvents, film formability, hygroscopicity, acidity, etc., additives are added to the above HT-PEDOT (2) and the above HT-PEDOT (3) to form the present invention. It can be a conductive polymer composition. The additives are not particularly limited, but include, for example, polyacrylic acid, polymethacrylic acid, polyvinylphosphonic acid, polyvinylsulfonic acid, polystyrene sulfonic acid, Nafion (TM), polyvinyl alcohol and its derivatives, poly( 1-vinylpyrrolidin-2-one), poly(3-vinyl-1,3-oxazolidin-2-one), poly(1-vinyl-1,3-imidazolidin-2-one), polyacrylic acid, poly Methacrylic acid, polyvinylphosphonic acid, polyvinylsulfonic acid, polyacrylamide, poly(alkylacrylamide), cellulose, fullerenes, carbon nanotubes, dimethyl sulfoxide, DMF, ethylene glycol, oligo(poly)ethylene glycol, butanediol, oligo Examples include (poly)tetramethylene glycol, methyl cellosolve, and butyl cellosolve, which may be used alone or in combination. The (total) amount of the additives is preferably 50% by weight or less based on the weight of the above HT-PEDOT (2) and/or the above HT-PEDOT (3). ) and/or the above characteristics of HT-PEDOT (3), the content is preferably 10% by weight or less. The conductive polymer or conductive polymer composition of the present invention can be dissolved or dispersed in a solvent to form a conductive polymer solution. Solvents that can be used include, but are not particularly limited to, hydrocarbons such as hexane, cyclohexane, and toluene, ethers such as diethyl ether, THF, DOX, and CPME, amides such as DMF and DMAc, dichloromethane, and chloroform. , halogenated hydrocarbons such as 1,2-dichloroethane, acetone, ketones such as MEK, and water, and these may be used alone or in combination of two or more. The concentration of the conductive polymer in the conductive polymer solution is not particularly limited, but is usually preferably 50% by weight or less, and preferably 20% by weight or less in terms of ease of handling.

When preparing a conductive polymer solution by dissolving or dispersing the conductive polymer or conductive polymer composition of the present invention in a solvent, mixing can be performed using a magnetic stirrer tip or a stirring blade of a mechanical stirrer. In addition to ultrasonic irradiation, mixing can be performed by appropriately combining treatments using a mechanical homogenizer, an ultrasonic homogenizer, a high-pressure homogenizer, or the like. The temperature during preparation is preferably approximately 100°C or less.

When the conductive polymer, conductive polymer composition, or conductive polymer solution of the present invention is used for an electrode or an electronic device, there are no particular restrictions on the shape, such as a film that adheres to a substrate, a film, particles, fibers, etc. It can be selected according to need. When molding into a film, the conductive polymer solution is applied to a base material and dried. There are no particular restrictions on the material or shape of the base material as long as it can form a film, but examples of the base material include glass, ceramics, silica, inorganic base materials such as alumina, polystyrene, polyester, polyacrylate, polycarbonate, Examples include polymer base materials such as polyurethane, polyamide, polyimide, and cellulose, and resin base materials such as epoxy resins, phenol resins, and urea resins. The shape of the base material can be freely selected from dense membranes, compression molded membranes, porous membranes, particles, woven fabrics, nonwoven fabrics, etc. There are no particular limitations on the coating method, but examples include casting, dipping, bar coating, roll coating, gravure coating, flexographic printing, spray coating, and inkjet printing. There is no particular limit to the film thickness, but it is usually about 0.01 to 200 μm. Drying of the film can be carried out in the atmosphere or in an inert gas atmosphere such as nitrogen gas, under normal pressure or reduced pressure, and the drying temperature can be generally in the range of room temperature to 100°C over several hours to several days. can. The electrical conductivity of the formed film is not particularly limited and can be controlled widely depending on the application, but the electrical conductivity is approximately 0.001 to 1000 S·cm ^-1 .

The conductive polymer, conductive polymer composition, or conductive polymer solution of the present invention, as well as electrodes and electronic devices made from them, can be used, for example, as antistatic materials, transparent electrodes for displays, electrodes for photoelectric conversion elements, solid electrolyte It can be applied to solid electrolytes for capacitors, separators for aluminum solid electrolytic capacitors, organic semiconductors, etc.

Hereinafter, the present invention will be explained in more detail with reference to Examples, Reference Examples, and Comparative Examples, but the present invention is not limited thereto.

The molecular weight of the obtained polymer was determined from the results of size exclusion chromatography (SEC). The SEC system was GL-7400 manufactured by GL Sciences (detector: GL-7456, columns (4): TSKgel SuperH5000, H4000x2, H2000, column temperature: 40°C, developing solvent: 0.01M LiCl DMF solution , standard polystyrene equivalent) was used.

Reference example-1
Synthesis of ethyl 2-hydroxymethyl-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-carboxylate

Under an argon atmosphere, diethyl 3,4-dihydroxythiophene-2,5-dicarboxylate (33.9 g, 130 mmol) and lithium hydroxide (15.6 g, 651 mmol) were dissolved in 240 mL of DMSO and stirred at 90°C for 24 hours. . The reaction solution was acidified with 6N hydrochloric acid while cooling in an ice bath, and the resulting precipitate was filtered and dried to obtain 21.0 g of 5-(ethoxycarbonyl)-3,4-dihydroxythiophene-2-carboxylic acid as a colorless solid. (yield: 69.5%). ^1H -NMR (400MHz, DMSO-d ₆ , ppm), δ: 1.27 (3H, t, J = 7.1Hz), 4.26 (2H, q, J = 7.1Hz), 10.28 (3H, bs).
Under an argon atmosphere, 5-(ethoxycarbonyl)-3,4-dihydroxythiophene-2-carboxylic acid (21.0 g, 90.5 mmol) and copper(II) oxide (1.50 g, 18.8 mmol) were added to 400 mL of DMF. The mixture was dissolved and heated under reflux for 6 hours. DMF was distilled off, and the residue was dissolved in ethyl acetate and washed with water. The organic layer was dehydrated with magnesium sulfate and concentrated to obtain 8.74 g (yield: 51.3%) of ethyl 3,4-dihydroxythiophene-2-carboxylate as a brown viscous liquid. ^1H -NMR (400MHz, CDCl ₃ , ppm), δ: 1.38 (3H, t, J = 7.1Hz), 4.37 (2H, q, J = 7.1Hz), 5.40 (1H , bs), 6.56 (1H, s), 9.48 (1H, bs).
Under an argon atmosphere, ethyl 3,4-dihydroxythiophene-2-carboxylate (8.74 g, 46.4 mmol) was dissolved in DMF, and 2,3-dibromo-1-propanol (8.90 mL, 70.1 mmol) was dissolved in DMF. ), potassium iodide (159 mg, 0.959 mmol) and cesium carbonate (33.6 g, 103 mmol) were added, and the mixture was stirred at 90°C for 24 hours. DMF was distilled off, chloroform was added to the residue, insoluble matter was filtered off, and the filtrate was washed with water. The organic layer was dehydrated with magnesium sulfate, concentrated, and purified by silica gel column chromatography (developing solution: 1% triethylamine (TEA) solution in hexane/ethyl acetate = 1/2) to obtain 2-hydroxymethyl as a colorless liquid. 4.01 g (yield: 35.6%) of ethyl -2,3-dihydrothieno[3,4-b][1,4]dioxin-5-carboxylate was obtained. This product contained 24% ethyl 2-hydroxymethyl-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-carboxylate. ^1H -NMR (400MHz, CDCl ₃ , ppm), δ: 1.35 (3H, t, J = 7.1Hz), 3.85 to 3.93 (2H, m), 4.10 to 4.37 (4H, m), 4.45 (1H, d, J=10.6Hz), 6.58 (1H, s).
Reference example-2
Synthesis of (7-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methanol

Ethyl 2-hydroxymethyl-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-carboxylate (4.01 g, 16.5 mmol) synthesized by the method of Reference Example-1 was placed in an argon atmosphere. The mixture was dissolved in 75 mL of THF, and N-bromosuccinimide (3.27 g, 18.3 mmol) was added thereto, followed by stirring at 0° C. for 3 hours. The reaction solution was diluted with ethyl acetate and washed with water, and the organic layer was dried over magnesium sulfate and concentrated. By purifying this with silica gel column chromatography (developing solution: 1% TEA solution of hexane/ethyl acetate = 3/1), a colorless liquid of 7-bromo-2-hydroxymethyl-2,3-dihydrothieno[3, Ethyl 4-b][1,4]dioxin-5-carboxylate (this one is 7-bromo-3-hydroxymethyl-2,3-dihydrothieno[3,4-b][1,4]dioxin- 4.48 g (yield: 83.0%) of ethyl 5-carboxylate (presumed to contain ethyl 5-carboxylate as an impurity) was obtained. ^1H -NMR (400MHz, CDCl ₃ , ppm), δ: 1.34 (3H, t, J = 7.1Hz), 3.85 to 4.00 (2H, m), 4.25 (1H, dd , J=8.1, 11.3Hz), 4.28-4.35 (1H, m), 4.31 (2H, q, J=7.1Hz), 4.46 (1H, dd, J= 1.7, 11.3Hz).
Ethyl 7-bromo-2-hydroxymethyl-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-carboxylate (4.48 g, 13.9 mmol) synthesized above was added under an argon atmosphere. , was dissolved in 14 mL of ethanol, 14 mL of an aqueous solution of sodium hydroxide (8.36 g, 209 mmol) was added thereto, and the mixture was stirred at 80° C. for 2 hours. After concentrating the reaction solution to about half, it was acidified with 12N hydrochloric acid while cooling in an ice bath, and the formed precipitate was collected by filtration and dried to obtain 7-bromo-2-hydroxymethyl-2,3- as a colorless solid. Dihydrothieno[3,4-b][1,4]dioxin-5-carboxylic acid (this one is 7-bromo-3-hydroxymethyl-2,3-dihydrothieno[3,4-b][1,4 ] 4.04 g (yield: 98.6%) of dioxin-5-carboxylic acid was obtained. ^1H -NMR (400MHz, DMSO-d ₆ , ppm), δ: 3.65 (2H, m), 4.13 (1H, dd, J = 7.7, 11.8Hz), 4.27 (1H , m), 4.43 (1H, dd, J=2.1, 11.8Hz), 5.20 (1H, t, J=5.4Hz).
7-bromo-2-hydroxymethyl-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-carboxylic acid (4.04 g, 13.7 mmol) synthesized above and copper (II oxide) ) (218 mg, 2.74 mmol) was dissolved in 50 mL of DMF under an argon atmosphere and stirred at reflux temperature for 6 hours. DMF was distilled off, and the residue was dissolved in chloroform and washed with water. The organic layer was dehydrated with magnesium sulfate, concentrated, and purified by silica gel column chromatography (developing solution: 1% TEA solution in hexane/ethyl acetate = 3/1) to obtain 7-bromo-2,3 as a colorless liquid. 1.33 g (yield: 38.7%) of -dihydrothieno[3,4-b][1,4]dioxin-2-yl)methanol was obtained. This product contained 4% of 5-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methanol. ^1H -NMR (400MHz, CDCl ₃ , ppm), δ: 2.01 (1H, bs), 3.87 (1H, dd, J = 4.9, 12.2Hz), 3.94 (1H, dd , J=4.4, 12.2Hz), 4.11 (1H, dd, J=7.9, 11.8Hz), 4.25 (1H, dd, J=2.3, 11.8Hz), 4.27-4.32 (1H, m), 6.35 (1H, s).
Example-1
Synthesis of 2,2-dimethylpropyl 4-[(7-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonate

Under an argon atmosphere, 215 mg (118 mg, 4.88 mmol) of sodium hydride (55%) was washed with hexane, dried in vacuum, suspended in 4 mL of THF solution containing 120 μL of TEA, and added to it by the method of Reference Example-2. Slowly add 4 mL of a THF solution containing synthesized 7-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methanol (1.11 g, 4.42 mmol) and 120 μL of TEA. The mixture was added dropwise, stirred for 15 minutes in an ice bath, and then stirred at room temperature for 1 hour. Thereafter, the mixture was placed in an ice bath again, and a solution of 2,4-butanesultone (470 μL, 4.52 mmol) in THF (4 mL) was slowly added dropwise, followed by stirring at room temperature for 2 hours. After the reaction, THF was distilled off under reduced pressure to obtain a brown viscous solid of 4-[(7-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane. Sodium -2-sulfonate was obtained. This was used in the next reaction without any particular purification. ¹ H-NMR (400 MHz, D ₂ O, ppm), δ: 1.14 (3 H, d, J = 6.9 Hz), 1.52 (1 H, m), 2.08 (1 H, m), 2 .83 (1H, m), 3.51 to 3.71 (4H, m), 3.99 (1H, dd, J = 6.3, 12.1Hz), 4.15 (1H, dd, J = 1.8, 12.1Hz), 4.36 (1H, m), 4.62 (1H, s).
The sodium 4-[(7-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonate synthesized above was dissolved in THF/ It was dissolved in 12 mL of a mixed solvent of chloroform (=1/1 volume ratio), 5 drops of DMF were added, and the mixture was cooled in an ice bath. 380 μL (4.65 mmol) of oxalyl dichloride was slowly added thereto, and the mixture was stirred for 1 hour. The reaction solution was concentrated to obtain 4-[(7-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonic acid chloride. ¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 1.64 (3H, d, J=6.7Hz), 1.93 (1H, m), 2.55 (1H, m), 3. 62-3.80 (4H, m), 3.86 (1H, m), 4.06 (1H, m), 4.22 (1H, dd, J=2.3, 11.8Hz), 4. 33-4.39 (1H, m), 6.35 (1H, s).
Under an argon atmosphere, 474 mg (5.38 mmol) of 2,2-dimethyl-1-propanol and 930 μL (6.67 mmol) of TEA were dissolved in 18 mL of chloroform, and 18 mL of the chloroform solution of the sulfonic acid chloride synthesized above was slowly added thereto. The mixture was added dropwise and stirred in an ice bath for 2 hours. The reaction solution was washed with water, and the organic layer was dried over magnesium sulfate and then concentrated. This was purified by silica gel column chromatography (developing solution: 1% TEA solution in hexane/ethyl acetate = 3/1), resulting in a colorless liquid of 4-[(7-bromo-2,3-dihydrothieno[3,4 1.33 g (yield: 65.7%) of 2,2-dimethylpropyl-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonate was obtained. ¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 0.99 (9H, s), 1.45 (3H, d, J=6.9Hz), 1.82 (1H, m), 2. 37 (1H, m), 3.38 (1H, m), 3.60 to 3.79 (4H, m), 3.88 (2H, s), 4.05 (1H, m), 4.22 (1H, dd, J=2.3, 11.8Hz), 4.35 (1H, m), 6.41 (1H, s).
Example-2
2,2-dimethylpropyl 4-[(7-bromo-5-iodo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonate synthesis

4-[(7-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonic acid 2, synthesized by the method of Example-1. 2-Dimethylpropyl (1.37 g, 3.00 mmol) was dissolved in 15 mL of THF under an argon atmosphere, and N-iodosuccinimide (709 mg, 3.15 mmol) and acetic acid 2.5 mL were added thereto under an ice bath, and the mixture was heated to room temperature. The mixture was stirred for 2 hours. After diluting the reaction solution with ethyl acetate and washing with water, the organic layer was dehydrated with magnesium sulfate. After concentration, the residue was purified by silica gel column chromatography (developing solution: 1% TEA solution of hexane/ethyl acetate = 3/1) to obtain colorless liquid 4-[(7-bromo-5-iodo-2, 1.35 g (yield: 77.2%) of 2,2-dimethylpropyl 3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonate was obtained. . ¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 0.99 (9H, s), 1.46 (3H, d, J=6.9Hz), 1.82 (1H, m), 2. 37 (1H, m), 3.38 (1H, m), 3.61 to 3.78 (4H, m), 3.88 (2H, s), 4.11 (1H, m), 4.24 ~4.37 (2H, m).
Example-3
4-[(7-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfone using PPh ₃ as a ligand for palladium acetate C-H direct arylation polymerization of 2,2-dimethylpropyl acid

4-[(7-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2- synthesized by the method of Example-1 under an argon atmosphere. 2,2-dimethylpropyl sulfonate (664 mg, 1.45 mmol) was dissolved in 1.5 mL of DMF, and palladium acetate (Fuji Film Wako Pure Chemical Industries, Ltd., 65.2 mg, 0.290 mmol) and triphenylphosphine (153 mg, 0.0 .582 mmol) and cesium carbonate (473 mg, 1.45 mmol) were added, and the mixture was stirred at 100°C for 48 hours. The reaction solution was poured into an excess amount of methanol/water (=1/1 (v/v)) mixed solvent, and the generated precipitate was collected by filtration to obtain 332 mg of black powder.

Under an argon atmosphere, the black powder (204 mg) obtained above was suspended in 2 mL of ethanol, 2 mL of hydrazine monohydrate was added thereto, and the mixture was stirred at room temperature for 24 hours. The precipitate was collected by filtration and washed with ethanol. 184 mg of a black powdered head-to-tail poly(3,4-ethylenedioxythiophene) derivative was obtained. As a result of SEC measurement, the number average molecular weight (Mn) was 7,750 and the weight average molecular weight (Mw) was 13,600.

Example-4
Synthesis of self-doped poly(3,4-ethylenedioxythiophene) derivatives with head-to-tail bond regularity by hydrolysis of sulfonic acid esters

Under an argon atmosphere, the head-to-tail poly(3,4-ethylenedioxythiophene) derivative (154 mg) synthesized by the method of Example 3 was suspended in 10 mL of degassed 2-butanone, and lithium bromide (693 mg) was suspended in 10 mL of degassed 2-butanone. , 7.98 mmol) and stirred at 90°C for 4 days. The generated precipitate was collected by filtration and washed with acetone to obtain 152 mg of a self-doped poly(3,4-ethylenedioxythiophene) derivative having head-to-tail bond regularity in the form of a black powder.

Example-5
4-[(7-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy] using P(o-Tol) ₃ as a ligand for palladium acetate C-H direct arylation polymerization of 2,2-dimethylpropyl butane-2-sulfonate

4-[(7-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2- synthesized by the method of Example-1 under an argon atmosphere. Dissolve 2,2-dimethylpropyl sulfonate (665 mg, 1.45 mmol) in 1.5 mL of DMF, palladium acetate (65.5 mg, 0.292 mmol), tri(o-tolyl)phosphine (178 mg, 0.585 mmol) and 473 mg (1.45 mmol) of cesium carbonate were added thereto, and the mixture was stirred at 100°C for 48 hours. The reaction solution was poured into an excess amount of methanol/water (=1/1 (v/v)) mixed solvent, the resulting precipitate was collected by filtration, and a black solid head-to-tail bond type poly(3,4-ethylene diethylene chloride) was obtained. 332 mg of oxythiophene) derivative was obtained. As a result of SEC measurement, Mn was 9,380 and Mw was 16,400.

Example-6
₄ -[(7-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy] using P(2-MeOPh) as a ligand for palladium acetate C-H direct arylation polymerization of 2,2-dimethylpropyl butane-2-sulfonate (HT-PEDOT(2)-1)

4-[(7-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2- synthesized by the method of Example-1 under an argon atmosphere. Dissolve 2,2-dimethylpropyl sulfonate (637 mg, 1.39 mmol) in 1.5 mL of DMF, and add palladium acetate (64.2 mg, 0.286 mmol) and tris(2-methoxyphenyl)phosphine (197 mg, 0.559 mmol). ) and cesium carbonate (453 mg, 1.39 mmol) were added, and the mixture was stirred at 100°C for 48 hours. The reaction solution was poured into an excess amount of methanol/water (=1/1 (v/v)) mixed solvent, the resulting precipitate was collected by filtration, and a black solid head-to-tail poly(4-[(2, 582 mg of 3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonic acid (2,2-dimethylpropyl) (HT-PEDOT(2)-1) was obtained. .

HT-PEDOT (2)-1 (200 mg) was suspended in 2 mL of ethanol under an argon atmosphere, 2 mL of hydrazine monohydrate was added thereto, and the mixture was stirred at room temperature for 24 hours. After adding 200 mL of ethanol to the reaction solution, the precipitate was collected by filtration and washed with ethanol. 142 mg of black powder (dedoped HT-PEDOT (2)-1) was obtained. As a result of SEC measurement, Mn was 20,100 and Mw was 42,900.

Example-7
Synthesis of HT-PEDOT(3)-1 (Li ⁺ salt form)

Under an argon atmosphere, dedoped HT-PEDOT (2)-1 (137 mg) synthesized by the method of Example 6 was suspended in 10 mL of degassed 2-butanone, and lithium bromide (925 mg, 10.7 mmol) was suspended in 10 mL of degassed 2-butanone. was added and stirred at 90°C for 4 days. The precipitate was collected by filtration and washed with 2-butanone to obtain 115 mg of black powder HT-PEDOT(3)-1 (Li ⁺ salt).

Example-8
₄ -[(7-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy] using P(2-MeOPh) as a ligand for Hermann catalyst C-H direct arylation polymerization of 2,2-dimethylpropyl butane-2-sulfonate (HT-PEDOT(2)-2)

4-[(7-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2- synthesized by the method of Example-1 under an argon atmosphere. 2,2-dimethylpropyl sulfonate (519 mg, 1.13 mmol) was dissolved in 1.5 mL of DMAc, and Hermann's catalyst (Sigma-Aldrich, 112 mg, 0.115 mmol) and tris(2-methoxyphenyl)phosphine (80 mg, 1.13 mmol) were dissolved in 1.5 mL of DMAc. 0 mg, 0.227 mmol) and cesium carbonate (370 mg, 1.14 mmol) were added, and the mixture was stirred at 100°C for 48 hours. The reaction solution was poured into a methanol/water (=1/1 (v/v)) mixed solvent, the resulting precipitate was collected by filtration, and a black solid head-to-tail poly(4-[(2,3- 518 mg of dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonic acid (2,2-dimethylpropyl) (HT-PEDOT(2)-2) was obtained.

Under an argon atmosphere, HT-PEDOT (2)-2 (502 mg) obtained above was suspended in 5 mL of ethanol, 5 mL of hydrazine monohydrate was added thereto, and the mixture was stirred at room temperature for 24 hours. After adding 200 mL of ethanol to the reaction solution, the precipitate was collected by filtration and washed with ethanol. 399 mg of black powder (dedoped HT-PEDOT (2)-2) was obtained. As a result of SEC measurement, Mn was 38,100 and Mw was 95,200.

Example-9
Synthesis of HT-PEDOT(3)-2 (Li ⁺ salt form)

Under an argon atmosphere, dedoped HT-PEDOT (2)-2 (203 mg) synthesized by the method of Example 8 was suspended in 13 mL of degassed 2-butanone, and lithium bromide (928 mg, 10.7 mmol) was suspended in 13 mL of degassed 2-butanone. was added and stirred at 90°C for 4 days. After the reaction, the generated precipitate was collected and washed with acetone to obtain 182 mg of HT-PEDOT(3)-2 (Li salt).

Example-10
2,2-dimethylpropyl 4-[(7-bromo-5-iodo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonate GRIM polymerization (HT-PEDOT(2)-3)

4-[(7-bromo-5-iodo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy] synthesized by the method of Example-2 under argon atmosphere 2,2-dimethylpropyl butane-2-sulfonate (413 mg, 708 μmol) was dissolved in 1.4 mL of THF, 2M tert-butylmagnesium chloride-diethyl ether solution (355 μL, 710 μmol) was added, and the solution was dissolved in an ice bath. Stir for 30 minutes. After further stirring at room temperature for 1 hour, [1,3-bis(diphenylphosphino)propane]nickel(II) dichloride (Ni(dppp)Cl ₂ ) (4.00 mg, 7.08 μmol) was added, and the mixture was heated at 50°C. Stirred for 24 hours. The reaction solution was poured into methanol, and the generated precipitate was collected by filtration to obtain a black powder.

The black powder obtained above was suspended in 2 mL of ethanol under an argon atmosphere, 2 mL of hydrazine monohydrate was added thereto, and the mixture was stirred at room temperature for 24 hours. By adding water to the reaction solution and collecting the generated precipitate by filtration, dedoped head-to-tail poly(4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin 140 mg of 2,2-dimethylpropyl-2-yl)methoxy]butane-2-sulfonate (HT-PEDOT(2)-3) was obtained. As a result of SEC measurement, Mn was 21,600 and Mw was 42,300.

Example-11
Synthesis of HT-PEDOT(3)-3 (Li ⁺ salt form)

Under an argon atmosphere, dedoped HT-PEDOT (2)-3 (95 mg) synthesized by the method of Example 10 was suspended in 20 mL of degassed 2-butanone, and lithium bromide (419 mg, 4.82 mmol) was suspended in 20 mL of degassed 2-butanone. was added and stirred at 90°C for 4 days. The precipitate was collected by filtration and washed with 2-butanone to obtain 90 mg of HT-PEDOT(3)-3 (Li salt).

Reference example-3
Synthesis of 2,2-dimethylpropyl 4-[(5,7-dibromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonate

Under an argon atmosphere, sodium hydride (55%) (793 mg, 18.0 mmol) was washed with hexane, dried in vacuo, and 15 mL of DMF was added. ,4]dioxin-2-yl)methanol (2.58 g, 15.0 mmol) in DMF (15 mL) was slowly added, and the mixture was stirred at room temperature for 15 minutes. The temperature was raised to 60°C, and after stirring for 1 hour, a DMF solution (15 mL) of 1-methyl-1,3-propane sultone (1.60 mL, 15.0 mmol) was slowly added, and the mixture was stirred at 60°C for 2 hours. After the reaction, DMF was distilled off under reduced pressure to obtain a brown solid of 4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonic acid. Obtained sodium. ¹ H-NMR (400 MHz, D ₂ O, ppm), δ: 1.20 (3 H, d, J = 6.9 Hz), 1.60 (1 H, m), 2.14 (1 H, m), 2 .89 (1H, m), 3.56 to 3.73 (4H, m), 4.02 (1H, dd, J = 12.0, 6.8Hz), 4.21 (1H, dd, J = 12.0, 2.3Hz), 4.36 (1H, m), 6.43 (2H, s).
Next, sodium 4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonate synthesized above was added to THF/sulfonate under an argon atmosphere. It was dissolved in chloroform (=1/1 volume ratio) mixed solvent (45 mL), and 2 drops of DMF were added. Oxalyl dichloride (1.47 mL, 18.0 mmol) was slowly added to the mixture in an ice bath, and the mixture was stirred for 2 hours. The reaction solution was concentrated to obtain 4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonic acid chloride. ¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 1.63 (3H, d, J=6.8Hz), 1.92 (1H, m), 2.55 (1H, m), 3. 63-3.78 (4H, m), 3.84 (1H, m), 4.05 (1H, ddd, J = 11.7, 7.2, 5.8Hz), 4.22 (1H, dd , J=11.7, 2.2Hz), 4.31 (1H, m), 6.34 (2H, s).
Subsequently, under an argon atmosphere, 2,2-dimethylpropanol (1.59 g, 18.0 mmol) and triethylamine (3.14 mL, 22.5 mmol) were dissolved in 30 mL of chloroform, and the above-synthesized 4-[( A chloroform solution (30 mL) of 2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonic acid chloride was slowly added dropwise in an ice bath for 2 hours. Stirred. The organic layer was washed with water, dried over magnesium sulfate, and then concentrated. This was purified by silica gel column chromatography (developing solution: 1% TEA solution of hexane/ethyl acetate = 3/1) to obtain a colorless liquid 4-[(2,3-dihydrothieno[3,4-b][ 4.73 g (yield: 83.4%) of 2,2-dimethylpropyl 1,4]dioxin-2-yl)methoxy]butane-2-sulfonate was obtained. ¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 0.99 (9H, s), 1.45 (3H, d, J=6.9Hz), 1.81 (1H, m), 2. 37 (1H, m), 3.32-3.42 (4H, m), 3.64 (1H, m), 3.87 (2H, s), 4.05 (1H, ddd, J=11. 7, 7.4, 4.3Hz), 4.22 (1H, dd, J=11.7, 2.2Hz), 4.30 (1H, m), 6.33 (2H, s).
Under an argon atmosphere, 2,2-dimethylpropyl 4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonate (2,2-dimethylpropyl) synthesized above N-bromosuccinimide (4.68 g, 26.3 mmol) was added to a THF solution (60 mL) of N-bromosuccinimide (4.73 g, 12.5 mmol), and the mixture was stirred in an ice bath for 2 hours. 100 mL of ethyl acetate was added, and the mixture was washed with saturated brine, and the organic layer was dried over magnesium sulfate and concentrated. This was purified by silica gel column chromatography (developing solution: 1% TEA solution of hexane/ethyl acetate = 3/1), and a colorless liquid 4-[(5,7-dibromo-2,3-dihydrothieno[3 ,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonic acid 2,2-dimethylpropyl was obtained in an amount of 6.39 g (yield: 95.3%). ¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 0.99 (9H, s), 1.45 (3H, d, J=6.9Hz), 1.82 (1H, m), 2. 37 (1H, m), 3.37 (1H, m), 3.60 to 3.79 (4H, m), 3.88 (2H, s), 4.12 (1H, m), 4.29 ~4.37 (2H, m).
Reference example-4
4-[(5-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonic acid 2,2-dimethylpropyl/4-[( Synthesis of 2,2-dimethylpropyl 7-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonic acid mixture

4-[(5,7-dibromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane synthesized by the method of Reference Example-3 under an argon atmosphere. 2,2-dimethylpropyl 2-sulfonate (1.94 mg, 3.62 mmol) was dissolved in 4 mL of THF, and a 2M tert-butylmagnesium chloride-diethyl ether solution (2.0 mL, 4.0 mmol) was added thereto. Stirred at room temperature for 2 hours. Thereafter, water was added, and after stirring at room temperature for 12 hours, the reaction solution was extracted with ethyl acetate, and the organic layer was dried over magnesium sulfate and concentrated. This was purified by silica gel column chromatography (developing solution: 1% TEA solution in hexane/ethyl acetate = 3/1), resulting in a colorless liquid of 4-[(5-bromo-2,3-dihydrothieno[3,4 -b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonic acid 2,2-dimethylpropyl/4-[(7-bromo-2,3-dihydrothieno[3,4-b][ 1.33 g (yield: 80.3%) of a 50/50 (%) mixture of 2,2-dimethylpropyl 1,4]dioxin-2-yl)methoxy]butane-2-sulfonate was obtained.

Reference example-5
2,2-dimethylpropyl 4-[(5-bromo-7-iodo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonate/ 2,2-dimethylpropyl 4-[(7-bromo-5-iodo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonic acid mixture synthesis of

4-[(5-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonic acid 2, synthesized by the method of Reference Example-4. 2-dimethylpropyl/2,2-dimethylpropyl 4-[(7-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonate A 50/50 (%) mixture of (3.24 g, 7.09 mmol) was dissolved in 38 mL of THF under an argon atmosphere, and to this was added N-iodosuccinimide (1.68 g, 7.46 mmol) and 6 mL of acetic acid under an ice bath. was added and stirred at room temperature for 2 hours. After diluting the reaction solution with ethyl acetate and washing with water, the organic layer was dehydrated with magnesium sulfate. After concentration, the residue was purified by silica gel column chromatography (developing solution: 1% TEA solution of hexane/ethyl acetate = 3/1) to obtain colorless liquid 4-[(5-bromo-7-iodo-2, 2,2-dimethylpropyl 3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonate/4-[(7-bromo-5-iodo-2, 4.73 g (yield :66.7%).

Comparative example-1
4-[(7-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfone carried out with reference to the prior art document Patent Document 4 Synthesis study of 2,2-dimethylpropyl acid

Under an argon atmosphere, 2,2-dimethylpropyl 4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonate (379 mg, 1. 00 mmol) was dissolved in 1 mL of DMF, and N-bromosuccinimide (160 mg, 0.899 mmol) was added thereto under an ice bath, followed by stirring for 2 hours under an ice bath. The reaction solution was diluted with ethyl acetate and washed with water, and then the organic layer was dehydrated with magnesium sulfate. After concentrating this, purification was attempted using silica gel column chromatography (developing solution: 1% TEA solution of hexane/ethyl acetate = 3/1). 362 mg of colorless liquid was obtained. From the integral value of the hydrogen atom on the thiophene ring in the ¹ H-NMR spectrum, 4-[(7-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy] 2,2-dimethylpropyl butane-2-sulfonate/4-[(5-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2- It was a 45/55 (%) mixture of 2,2-dimethylpropyl sulfonate.

Comparative example-2
₄ -[(5-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy] using P(2-MeOPh) as a ligand for palladium acetate 2,2-dimethylpropyl butane-2-sulfonate/4-[(7-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2- Synthesis of redioundum (R)-PEDOT (2)-1) by C-H direct arylation polymerization of a 50/50 (%) mixture of 2,2-dimethylpropyl sulfonate and by hydrolysis of the sulfonic acid ester Synthesis of R-PEDOT(3)-1 (Li ⁺ salt form)

4-[(5-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2- synthesized by the method of Reference Example-4 under argon atmosphere 2,2-dimethylpropyl sulfonate/4-[(7-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonic acid 2, A 50/50 (%) mixture of 2-dimethylpropyl (690 mg, 1.51 mmol) was dissolved in 1.5 mL of DMF, palladium acetate (68.5 mg, 305 μmol), tris(2-methoxyphenyl)phosphine (215 mg, 609 μmol) ) and cesium carbonate (491 mg, 1.51 mmol) were added, and the mixture was stirred at 100°C for 48 hours. The reaction solution was poured into an excess amount of methanol/water (=1/1 (v/v)) mixed solvent, the generated precipitate was collected by filtration, and a black solid regiorandom poly(4-[(2,3- 655 mg of dihydrothieno[3,4-b][1,4]dioxin-2(or 3)-yl)methoxy]butane-2-sulfonic acid 2,2-dimethylpropyl) (R-PEDOT(2)-1) Obtained.

Under an argon atmosphere, R-PEDOT (2)-1 (302 mg) obtained above was suspended in 3 mL of ethanol, 3 mL of hydrazine monohydrate was added thereto, and the mixture was stirred at room temperature for 24 hours. The reaction solution was poured into 200 mL of ethanol. The precipitate was collected by filtration and washed with ethanol. 213 mg of black powder (dedoped R-PEDOT (2)-1) was obtained. As a result of SEC measurement, Mn was 16,800 and Mw was 34,800.

Under an argon atmosphere, the dedoped R-PEDOT (2)-1 (150 mg) synthesized above was suspended in 10 mL of degassed 2-butanone, lithium bromide (867 mg, 9.98 mmol) was added, and the mixture was heated at 90°C. The mixture was stirred for 4 days. The generated precipitate was collected by filtration and washed with acetone to obtain 168 mg of black powder R-PEDOT(3)-1 (Li salt).

Comparative example-3
4-[(5-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy] using P(2-MeOPh) as a _ligand for Hermann catalyst 2,2-dimethylpropyl butane-2-sulfonate/4-[(7-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2- Synthesis of regiorandom polymer (R-PEDOT(2)-2) by C-H direct arylation polymerization of a 50/50 (%) mixture of 2,2-dimethylpropyl sulfonate and by hydrolysis of sulfonic acid ester Synthesis of R-PEDOT(3)-2 (Li ⁺ salt form)

4-[(5-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2- synthesized by the method of Reference Example-4 under argon atmosphere 2,2-dimethylpropyl sulfonate/4-[(7-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonic acid 2, A 50/50 (%) mixture of 2-dimethylpropyl (812 mg, 1.78 mmol) was dissolved in 1.5 mL of DMAc, Hermann's catalyst (172 mg, 177 μmol), tris(2-methoxyphenyl)phosphine (125 mg, 384 μmol) and Cesium carbonate (579 mg, 1.78 mmol) was added and stirred at 100°C for 48 hours. The reaction solution was poured into a methanol/water (=1/1 (v/v)) mixed solvent, the resulting precipitate was collected by filtration, and a black solid regiorandom poly(4-[(2,3-dihydrothieno[ 877 mg of 3,4-b][1,4]dioxin-2(or 3)-yl)methoxy]butane-2-sulfonic acid 2,2-dimethylpropyl) (R-PEDOT(2)-2) was obtained. .

Under an argon atmosphere, R-PEDOT (2)-2 (807 mg) obtained above was suspended in 8 mL of ethanol, 8 mL of hydrazine monohydrate was added thereto, and the mixture was stirred at room temperature for 24 hours. After adding 300 mL of ethanol to the reaction solution, the precipitate was collected by filtration and washed with ethanol. 604 mg of black powder (dedoped R-PEDOT (2)-2) was obtained. As a result of SEC measurement, Mn was 23,500 and Mw was 61,200.

Under an argon atmosphere, the dedoped R-PEDOT (2)-2 (203 mg) obtained above was suspended in 13 mL of degassed 2-butanone, lithium bromide (924 mg, 10.6 mmol) was added, Stirred at ℃ for 4 days. After the reaction, the generated precipitate was collected and washed with acetone to obtain 171 mg of R-PEDOT(3)-2 (Li salt).

Comparative example-4
2,2-dimethylpropyl 4-[(5-bromo-7-iodo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonate/ 2,2-dimethylpropyl 4-[(7-bromo-5-iodo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonate GRIM polymerization of 50/50 (%) mixture (R-PEDOT(2)-3) and synthesis of R-PEDOT(3)-3 (Li ⁺ salt form) by hydrolysis of sulfonic acid ester

4-[(5-bromo-7-iodo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy] synthesized by the method of Reference Example-5 under argon atmosphere 2,2-dimethylpropyl butane-2-sulfonate/4-[(7-bromo-5-iodo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy] A 50/50 (%) mixture of 2,2-dimethylpropyl butane-2-sulfonate (938 mg, 1.61 mmol) was dissolved in 3.1 mL of THF, and a 2M tert-butylmagnesium chloride diethyl ether solution (805 μL) was dissolved in 3.1 mL of THF. , 1.61 mmol) and stirred for 30 minutes in an ice bath. After further stirring at room temperature for 1 hour, Ni(dppp)Cl ₂ (8.83 mg, 16.2 μmol) was added, and the mixture was stirred at 50° C. for 24 hours. The reaction solution was poured into methanol, and the generated precipitate was collected by filtration to obtain a black powder.

The black powder obtained above was suspended in 5 mL of ethanol under an argon atmosphere, 5 mL of hydrazine monohydrate was added thereto, and the mixture was stirred at room temperature for 24 hours. By adding water to the reaction solution and collecting the generated precipitate by filtration, dedoped regiorandom poly(4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2 500 mg of 2,2-dimethylpropyl (or 3)-yl)methoxy]butane-2-sulfonate) (R-PEDOT(2)-3) was obtained. As a result of SEC measurement, Mn was 21,300 and Mw was 38,500.

Under an argon atmosphere, the dedoped R-PEDOT (2)-3 (206 mg) obtained above was suspended in 14 mL of degassed 2-butanone, lithium bromide (929 mg, 10.7 mmol) was added, and the mixture was heated at 90°C. The mixture was stirred for 4 days. The precipitate was collected by filtration and washed with 2-butanone to obtain 161 mg of R-PEDOT(3)-3 (Li ⁺ salt).

Test Example 50 mg of each polymer (Li salt) obtained in Examples 7, 9, 11 and Comparative Examples 2, 3, and 4 was weighed out, 5.0 mL of pure water was added, and the mixture was stirred overnight. Ultrasonic treatment was performed using an ultrasonic homogenizer (UH-150, 20 kHz) for 20 minutes to ensure uniform dissolution. 1.0 g of a cation exchange resin (Lewatit MonoPlus S 100, acid type) was added to each polymer aqueous solution, stirred for 6 hours, and the cation exchange resin was filtered out using a membrane filter (10 μm). The filtrate was concentrated to approximately 4 mL. 500 μL of the solution was placed in a microtube, 25 μL of ethylene glycol (EG) or diethylene glycol (DEG) was added thereto, and the tube was sonicated for 10 minutes. Five drops of this were dropped onto a glass plate using a Pasteur pipette and applied in a circular shape with a diameter of about 1.2 cm. Dry at 60 °C for 10 minutes, at 120 °C for 10 minutes, then at 160 °C for 10 minutes in the case of EG addition/200 °C for 10 minutes in the case of DEG addition, and then immediately dry under vacuum for 30 minutes to form a circular shape. A thin film was obtained.

The thickness of the obtained thin film was determined by measuring the thickness of the glass plate before and after film formation using a digital micrometer (MDC-25PJ, Mitutoyo), and subtracting the measured thickness. The conductivity was measured by the four-probe method using a resistivity meter (Lorestar GP, Mitsubishi Chemical). The electrical conductivity is summarized in the table below.

In the table, HT-PEDOT(3)-1 and R-PEDOT(3)-1, HT-PEDOT(3)-2 and R-PEDOT(3)-2, and HT-PEDOT(3)-3 and R -PEDOT(3) -3 are head-to-tail (regioregular) type and regiorandom self-doped poly(3,4-ethylenedioxythiophene) derivatives synthesized by the same polymerization method, respectively. When compared using the same polymerization method, it can be seen that the head-to-tail (regioregular) type self-doped poly(3,4-ethylenedioxythiophene) derivative exhibits superior conductivity compared to the regiorandom type.

Claims (14)

General formula (1) below
(In the formula, a represents an integer of 2 or 3. R represents a hydrogen atom or a methyl group. X ¹ represents a chlorine atom or a bromine atom. X ² represents a hydrogen atom, a chlorine atom, a bromine atom. and an iodine atom, and represents an atom different from X ^1. Z represents a hydrocarbon group having 3 to 8 carbon atoms.)
A sulfonate having a 3,4-ethylenedioxythiophene structure. 3,4-ethylene according to claim 1, characterized in that a is 2 and R is a hydrogen atom or a methyl group, or a is 3 and R is a hydrogen atom A sulfonate with a dioxythiophene structure. The sulfonate having a 3,4-ethylenedioxythiophene structure according to claim 1 or 2, wherein X ¹ is a bromine atom and X ² is a hydrogen atom or an iodine atom. General formula (2') below
(In the formula, a represents an integer of 2 or 3. R represents a hydrogen atom or a methyl group. Z' represents a hydrocarbon group having 3 to 8 carbon atoms, a hydrogen ion, an alkali metal ion, or a substituted (However, when Z' is a hydrogen ion, an alkali metal ion, or an optionally substituted ammonium ion, the oxygen atom bonded to Z' has a negative charge.)
A head-to-tail bond type poly(3,4-ethylene diethylene chloride) having a sulfonate group in its side chain, which has at least two or more repeating units represented by oxythiophene) derivatives. The head-to-tail type poly(3,4-ethylenedioxythiophene) derivative having a sulfonate group in the side chain according to claim 4, which has the following general formula (2):
(In the formula, a represents an integer of 2 or 3. R represents a hydrogen atom or a methyl group. Z represents a hydrocarbon group having 3 to 8 carbon atoms.)
A head-to-tail bond type poly(3,4-ethylene diethylene chloride) having a sulfonate group in its side chain, which has at least two or more repeating units represented by oxythiophene) derivatives. A sulfonate group in the side chain according to claim 5, wherein a is 2 and R is a hydrogen atom or a methyl group, or a is 3 and R is a hydrogen atom. A head-to-tail type poly(3,4-ethylenedioxythiophene) derivative having the following. The head-to-tail type poly(3,4-ethylenedioxythiophene) derivative having a sulfonate group in the side chain according to claim 4, which has the following general formula (3):
(In the formula, a represents an integer of 2 or 3. R represents a hydrogen atom or a methyl group. M ⁺ represents a hydrogen ion, an alkali metal ion, or an optionally substituted ammonium ion.) A head-to-tail type poly(3,4-ethylenedioxy thiophene) derivatives. A sulfonate group in the side chain according to claim 7, wherein a is 2 and R is a hydrogen atom or a methyl group, or a is 3 and R is a hydrogen atom. A head-to-tail type poly(3,4-ethylenedioxythiophene) derivative having the following. A conductive polymer composition comprising the head-to-tail poly(3,4-ethylenedioxythiophene) derivative having a sulfonate group in a side chain according to claim 7 or 8. A conductive film comprising the conductive polymer composition according to claim 9. General formula (1) below
(In the formula, a represents an integer of 2 or 3. R represents a hydrogen atom or a methyl group. X ¹ represents a chlorine atom or a bromine atom. X ² represents a hydrogen atom, a chlorine atom, a bromine atom. and an iodine atom, and represents an atom different from X ^1. Z represents a hydrocarbon group having 3 to 8 carbon atoms.)
The following general formula (2) is characterized by polycondensing a sulfonate having a 3,4-ethylenedioxythiophene structure represented by
(In the formula, a, R and Z are as defined above.)
Head-to-tail type poly(3,4-ethylenedioxythiophene) having at least two or more repeating units represented by the formula, and having a sulfonate group in the side chain where the repeating units form a head-to-tail type Method for producing derivatives. The production method according to claim 11 , characterized in that X ² is a hydrogen atom and the polycondensation is direct C-H arylation polycondensation. The manufacturing method according to claim 11 , wherein ^X2 is a chlorine atom, a bromine atom, or an iodine atom (provided that ^X2 is a different atom from ^X1 ), and the polycondensation is Grignard Metathesis polymerization. . General formula (2) below
(In the formula, a represents an integer of 2 or 3. R represents a hydrogen atom or a methyl group. Z represents a hydrocarbon group having 3 to 8 carbon atoms.)
The following general formula (3) is characterized by hydrolyzing the sulfonate of a head-to-tail poly(3,4-ethylenedioxythiophene) derivative having a sulfonate group in the side chain having a repeating unit represented by
(In the formula, a and R are as defined above. M ⁺ represents a hydrogen ion, an alkali metal ion, or an optionally substituted ammonium ion.)
A self-doped poly(3,4-ethylenedioxythiophene) having at least two repeating units represented by the formula, and having a head-to-tail bond regularity characterized in that the repeating units are head-to-tail bonded. ) Method for producing derivatives.