JP2003300981A - Method for producing acidic group-containing heterocyclic compound trimer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for industrially mass producing a high-purity acidic group-substituted heterocyclic compound trimer in a high yield. <P>SOLUTION: The method for producing the acidic group-substituted heterocyclic compound comprises reacting at least one kind of a compound (A) of a heterocyclic compound such as indole, benzo[b]thiophene, benzo[b]furan, etc., substituted with an acidic group such as a sulfonic acid group, a carboxy group, etc., its alkali metal salt, ammonium salt and substituted ammonium salt and, if necessary, a heterocyclic compound (D) with at least one kind of an oxidizing agent (C) in a solution containing a basic compound (B). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a heterocyclic compound trimer having an acidic group (hereinafter also referred to as an acidic group-substituted heterocyclic compound trimer). The composition containing the trimer as a main component is used for various antistatics, antistatics, capacitors, batteries, EMI shields, chemical sensors, display elements, organic EL materials, non-linear materials, rust preventives, adhesives, fibers, electrostatic charges. It can be applied to anti-corrosion paints, electrodeposition coatings, plating primers, conductive primers for electrostatic coatings, cathodic protection, etc.

[0002]

2. Description of the Related Art An indole polymerization reaction has been reported as an example of a polymerization reaction of a heterocyclic compound.
For example, as a chemical polymerization method of indole, Japanese Patent Laid-Open No. 5-1
Japanese Patent Laid-Open No. 48320 proposes a method of dropping an indole solution into an oxidant solution. This method is proposed only in the case of using an unsubstituted indole as a raw material, and nothing is described about an indole derivative having a substituent. Further, the product is a polymer having indole as a repeating unit, and nothing is described about the formation of a trimer.

On the other hand, as a method for producing a cyclic trimer of a heterocyclic compound, a reaction using indole as a monomer has been reported. For example, J. Electroanal. Ch
em., 414 (1996) p. 197, synthesis of polymers by electrolytic reaction of unsubstituted indoles, 4-nitroindoles, 5-nitroindoles is also described in J. Chem.
oc., Faraday Trans., 93 (1997)
On page 3791, the synthesis of a trimer by electrolytic reaction of unsubstituted indole and 5-cyanoindole is reported, respectively. When the redox test (cycle test) is performed on the unsubstituted indole and the substituted indole obtained by the methods described in these documents, the deterioration of the trimer progresses, and as a result, the cycle characteristics deteriorate and the conductive device Was difficult to apply to. Further, in the electrolytic reaction, it is difficult to synthesize a large amount of trimer at one time, and it is difficult to apply it as an industrial production method.

Heterocycles, 12 (197)
9) 471, Chem. Pharm. Bull. , 2
9, (1981) 3499, TiCl ₃ or F.
The synthesis of unsubstituted indole trimer using eSO ₄ and H ₂ O ₂ has been reported. However, as described in the report paper, there were many problems such as mixing of several kinds of by-products and low yield of the target trimer.

Similarly, J. Org. Chem. 199
On pages 8, 63, 7002, 5-acetylindole,
A method for synthesizing an indole trimer by reacting 5-methoxyindole with ammonium persulfate under acidic conditions has been reported. However, the obtained indole trimer has a low yield, and in addition, by-products such as a symmetric indole trimer (a trimer compound formed by all indole monomers bound in the same direction) as impurities. There are issues such as existing. In addition, there is no report of an acid group-substituted indole trimer.

[0006] In addition, Synthetic Metal
s, 80 (1996) p. 309 also reported the synthesis of an unsubstituted indole trimer by electrolytic reaction. Its physical properties are: layer spacing: 0.658 nm, conductivity: 0.03 S /
It is reported as cm.

On the other hand, Tetrahedoron, 36
(1980) p. 1451 reports the synthesis of a benzo [b] thiophene trimer from 3-acetoxybenzo [b] thiophene. This compound is also a trimer compound in which all monomers are bound in the same direction, and there is no report on an asymmetric compound.

As described above, the unsubstituted indole trimer and the substituted indole trimer obtained by the prior art have insufficient cycle characteristics and industrial application, and thus have high redox potential, high redox capacity, Development of an industrial production method of a heterocyclic compound trimer such as an indole derivative trimer having a high cycle property has been an important issue in this field.

[0009]

The object of the present invention is to:
Heterocyclic compound trimers such as indole derivative trimers having high conductivity, high redox potential, high redox capacity, and good cycle characteristics can be mass-produced in high yield and high purity. It is to provide an industrial manufacturing method.

[0010]

DISCLOSURE OF THE INVENTION The present inventors have found that trimeric heterocyclic compounds such as indole derivative trimers having high conductivity, high redox potential, high redox capacity, and good cycle characteristics. As a result of diligently studying the production method of the body, when an acidic group-substituted heterocyclic compound as a monomer is synthesized in a solution containing a basic compound using an oxidizing agent, the reactivity is particularly improved,
It was found that the reaction proceeds with high selectivity and high yield.
Moreover, the obtained acidic group-substituted heterocyclic compound trimer is
It showed high conductivity, high redox potential, high redox capacity, high cycle characteristics, good solubility in aqueous solution, and excellent solubility in organic solvent.

That is, the first aspect of the present invention is the following general formula (1):

[Chemical 6] (In the above formula, R₁~ R_FourIs hydrogen, a straight chain having 1 to 24 carbon atoms
Chain or branched alkyl group, straight chain having 1 to 24 carbon atoms,
Is a branched alkoxy group, a straight or branched chain having 2 to 24 carbon atoms
Various acyl groups, aldehyde groups, carboxyl groups, carbon numbers
2 to 24 linear or branched carboxylic acid ester groups,
Rufonic acid group, straight-chain or branched sulfo having 1 to 24 carbon atoms
Acid ester group, cyano group, hydroxyl group, nitro group, amino
Group, amide group, dicyanovinyl group, alkyl (carbon number 1
~ 8 linear or branched alkyl group) oxycarbonyl
Cyanovinyl group, nitrophenyl cyanovinyl group and Ha
Substituents independently selected from the group consisting of rogen groups
Indicates R₁~ R_FourAt least one of them is sulfonic acid
It is a group or a carboxyl group. Ht is NR
₂₈, S, O, Se and Te selected from the group consisting of
Terror atom group, R₂₈Is hydrogen and a straight chain having 1 to 24 carbon atoms.
Or a substituent selected from the group consisting of branched alkyl groups.
is there. ) An acidic group-substituted heterocyclic compound represented by
Lucari metal salt, ammonium salt and substituted ammonium
At least one compound (a) among the salts is combined with a basic compound.
At least one oxidizing agent in a solution containing
The following general formula characterized by reacting according to (C)
(2)

[Chemical 7] (In the above formula, R _{1 to} R ₄ and Ht are the same as those in the general formula (1).
And similar, also X ^a- is chloride, bromide,
Iodine ion, Fluorine ion, Nitrate ion, Sulfate ion, Hydrogen sulfate ion, Phosphate ion, Borofluoride ion, Perchlorate ion, Thiocyanate ion, Acetate ion, Propionate ion, Methanesulfonate ion, p
-At least one anion selected from a group of 1 to 3 valent anions consisting of a toluene sulfonate ion, a trifluoroacetate ion, and a trifluoromethane sulfonate ion, and a represents an ionic valence of X, 1 Is an integer of ˜3, m is a doping rate, and its value is 0 to 3.0. ) Is a heterocyclic compound trimer.

The second aspect of the present invention is the following general formula (1):

[Chemical 8] (In the above formula, R _{1 to} R ₄ are hydrogen, a straight-chain or branched alkyl group having 1 to 24 carbon atoms, a straight-chain or branched alkoxy group having 1 to 24 carbon atoms, and a straight-chain having 2 to 24 carbon atoms. Or branched acyl group, aldehyde group, carboxyl group, linear or branched carboxylic acid ester group having 2 to 24 carbon atoms, sulfonic acid group, linear or branched sulfonic acid ester group having 1 to 24 carbon atoms, cyano group , Hydroxyl group, nitro group, amino group, amide group, dicyanovinyl group, alkyl (carbon number 1
~ 8 linear or branched alkyl group) oxycarbonyl cyano vinyl group, a nitrophenyl cyano vinyl group, and a substituent independently selected from the group consisting of halogen groups, at least one of R _{1 to} R ₄ It is a sulfonic acid group or a carboxyl group. Ht is NR ₂₈ ,
A heteroatom group selected from the group consisting of S, O, Se and Te, R ₂₈ is a substituent selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 24 carbon atoms. ) At least one compound (a) selected from the group consisting of an acidic group-substituted heterocyclic compound, an alkali metal salt, an ammonium salt and a substituted ammonium salt thereof, and the following general formula (3):

[Chemical 9] (In the above formula, R _{5 to} R ₈ are hydrogen, a straight-chain or branched alkyl group having 1 to 24 carbon atoms, a straight-chain or branched alkoxy group having 1 to 24 carbon atoms, and a straight-chain having 2 to 24 carbon atoms. Or a branched acyl group, an aldehyde group, a linear or branched carboxylic acid ester group having 2 to 24 carbon atoms, a linear or branched sulfonic acid ester group having 1 to 24 carbon atoms, a cyano group, a hydroxyl group, a nitro group, amino A group, an amide group, a dicyanovinyl group, an alkyl (a linear or branched alkyl group having 1 to 8 carbon atoms) oxycarbonylcyanovinyl group, a nitrophenylcyanovinyl group, and a halogen group, each independently selected substituent Ht is NR
Heteroatom group selected from the group consisting of ₂₈ , S, O, Se and Te, and R ₂₈ is a substituent selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 24 carbon atoms. ), At least one heterocyclic compound (d) represented by the formula (4) is reacted with at least one oxidizing agent (c) in a solution containing the basic compound (b).

[Chemical 10] (In the above formula, R _{9 to} R ₁₂ , R _{13 to} R _16, and R ₁₇
To R ₂₀ are each a substituent of R ₁ to R ₁ in the general formula (1).
R ₄ or a substituent corresponding to R _{5 to} R ₈ in the general formula (3), and further R _{9 to} R ₁₂ , R _{13 to} R ₁₆ , R.
One or two of the three groups of _{17 to} R ₂₀ are substituents corresponding to R _{1 to} R ₄ in the general formula (1). Ht
Is the same as the general formula (1) and the general formula (3),
The X ^a- is, chlorine ion, bromine ion, iodine ion,
Fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methanesulfonate ion, p-toluenesulfonate ion, At least one anion selected from a group of 1 to 3 valent anions consisting of a trifluoroacetate ion and a trifluoromethanesulfonate ion, and a is X
Is an integer of 1 to 3, m is a doping rate, and its value is 0 to 3.0. ) Is a heterocyclic compound trimer.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method for producing the heterocyclic compound trimer having an acidic group according to the present invention will be described in detail.

The most representative compound (a) of at least one of the acidic group-substituted heterocyclic compound represented by the general formula (1), its alkali metal salt, ammonium salt and substituted ammonium salt used in the present invention. Specific examples of the acid group-substituted indoles include indole-4-carboxylic acid, indole-5-carboxylic acid, indole-6-carboxylic acid, indole-7-carboxylic acid, and other carboxyl group-substituted indoles, indole-4- Examples thereof include sulfonic acid group-substituted indoles such as sulfonic acid, indole-5-sulfonic acid, indole-6-sulfonic acid and indole-7-sulfonic acid. Specific examples of the acidic group-substituted benzo [b] thiophenes include benzo [b] thiophene-4-carboxylic acid, benzo [b] thiophene-5-carboxylic acid, benzo [b] thiophene-
Carboxyl group-substituted benzo [b] thiophenes such as 6-carboxylic acid, benzo [b] thiophene-7-carboxylic acid, benzo [b] thiophene-4-sulfonic acid, benzo [b] thiophene-5-sulfonic acid, benzo [B] Thiophene-6-sulfonic acid, benzo [b] thiophene-7
Examples thereof include benzo [b] thiophenes substituted with a sulfonic acid group such as sulfonic acid. Specific examples of the acidic group-substituted benzo [b] furans include benzo [b] furan-4-carboxylic acid, benzo [b] furan-5-carboxylic acid, benzo [b] furan-6-carboxylic acid and benzo [ b] benzo [b] furans substituted with a carboxyl group such as furan-7-carboxylic acid, benzo [b] furan-4-sulfonic acid, benzo [b] furan-5-sulfonic acid, benzo [b] furan-6- Sulfonic acid, benzo [b] furan-7-sulfonic acid and other sulfonic acid group-substituted benzo [b]
Furans and the like can be mentioned. Specific examples of the acidic group-substituted benzo [b] tellurophenes include benzo [b]
Tellurophen-4-carboxylic acid, benzo [b] tellurophene-5-carboxylic acid, benzo [b] tellurophene-6
-Carboxylic acid, benzo [b] -tellurophene 7-carboxylic acid and other carboxyl group-substituted benzo [b] tellurophenes, benzo [b] tellurophene-4-sulfonic acid, benzo [b] tellurophene-5-sulfonic acid, benzo [ Examples thereof include sulfonic acid group-substituted benzo [b] tellurophenes such as b] tellurophene-6-sulfonic acid and benzo [b] tellurophene-7-sulfonic acid.
Specific examples of the acidic group-substituted benzo [b] selenophenes include benzo [b] selenophene-4-carboxylic acid, benzo [b] selenophene-5-carboxylic acid, and benzo [b].
Carboxyl group-substituted benzo [b] selenophenes such as selenophene-6-carboxylic acid, benzo [b] -selenophene-7-carboxylic acid, benzo [b] selenophene-
4-sulfonic acid, benzo [b] selenophene-5-sulfonic acid, benzo [b] selenophene-6-sulfonic acid,
Examples thereof include sulfonic acid group-substituted benzo [b] selenophenes such as benzo [b] selenophene-7-sulfonic acid. Among these, acidic group-substituted indoles,
The acidic group-substituted benzo [b] thiophenes and the acidic group-substituted benzo [b] furans are practically preferably used, and the acidic group-substituted indoles are particularly preferably used.

Specific examples of the most representative indoles of the heterocyclic compound (d) represented by the general formula (3) used in the present invention include 4-methylindole, 5-methylindole and 6-methylindole. , 7-methylindole, 4-ethylindole, 5-ethylindole, 6
-Ethylindole, 7-ethylindole, 4-n-
Propylindole, 5-n-propylindole, 6
-N-propyl indole, 7-n-propyl indole, 4-iso-propyl indole, 5-iso-propyl indole, 6-iso-propyl indole,
7-iso-propyl indole, 4-n-butyl indole, 5-n-butyl indole, 6-n-butyl indole, 7-n-butyl indole, 4-sec-butyl indole, 5-sec-butyl indole, 6 -
Alkyl group-substituted indoles such as sec-butyl indole, 7-sec-butyl indole, 4-t-butyl indole, 5-t-butyl indole, 6-t-butyl indole, 7-t-butyl indole, 4-methoxy Indole, 5-methoxyindole, 6-methoxyindole, 7-methoxyindole, 4-ethoxyindole, 5-ethoxyindole, 6-ethoxyindole, 7-ethoxyindole, 4-n-propoxyindole, 5-n-propoxyindole , 6-n
-Propoxyindole, 7-n-propoxyindole, 4-iso-propoxyindole, 5-iso-
Propoxyindole, 6-iso-propoxyindole, 7-iso-propoxyindole, 4-n-butoxyindole, 5-n-butoxyindole, 6-
n-butoxyindole, 7-n-butoxyindole, 4-sec-butoxyindole, 5-sec-butoxyindole, 6-sec-butoxyindole,
Alkoxy group-substituted indoles such as 7-sec-butoxyindole, 4-t-butoxyindole, 5-t-butoxyindole, 6-t-butoxyindole, 7-t-butoxyindole, 4-acetylindole, 5-acetyl Acyl group-substituted indoles such as indole, 6-acetylindole and 7-acetylindole, aldehyde groups such as indole-4-carbaldehyde, indole-5-carbaldehyde, indole-6-carbaldehyde, indole-7-carbaldehyde Substituted indoles, indole-4-carboxylate, indole-5-carboxylate, indole
Carboxylic ester group-substituted indoles such as methyl 6-carboxylate and indole-7-methyl carboxylate, methyl indole-4-sulfonate, methyl indole-5-sulfonate, methyl indole-6-sulfonate,
Sulfonate-substituted indoles such as indole-7-methylsulfonate, indole-4-carbonitrile, indole-5-carbonitrile, indole-6-carbonitrile, indole-7-carbonitrile and other cyano group-substituted indoles Hydroxy group-substituted indoles such as 4-hydroxyindole, 5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole and the like, 4-nitroindole, 5-nitroindole, 6-nitroindole, 7-nitroindole and the like Amino group-substituted indoles such as nitro group-substituted indoles, 4-aminoindole, 5-aminoindole, 6-aminoindole, 7-aminoindole, 4-carbamoylindole, 5-carbamoylindole, 6 Amide group-substituted indoles, such as carbamoyl indole, 7-carbamoyl indole,
4-fluoroindole, 5-fluoroindole, 6
-Fluoroindole, 7-Fluoroindole, 4-
Chloroindole, 5-chloroindole, 6-chloroindole, 7-chloroindole, 4-bromoindole, 5-bromoindole, 6-bromoindole,
Halogen group-substituted indoles such as 7-bromoindole, 4-iodoindole, 5-iodoindole, 6-iodoindole, 7-iodoindole, 4-dicyanovinylindole, 5-dicyanovinylindole, 6-dicyanovinylindole, Dicyanovinyl group-substituted indoles such as 7-dicyanovinylindole, N-methylindole, N-ethylindole, N
-N-propyl indole, N-iso-propyl indole, N-n-butyl indole, N-sec-butyl indole, Nt-butyl indole, and other N-alkyl group-substituted indoles can be mentioned.

Specific examples of benzo [b] furans include:
4-methylbenzo [b] furan, 5-methylbenzo [b] furan, 6-methylbenzo [b] furan, 7-methylbenzo [b] furan, 4-ethylbenzo [b] furan, 5-ethylbenzo [b] furan, 6- Ethylbenzo [b] furan, 7-Ethylbenzo [b] furan, 4-n
-Propylbenzo [b] furan, 5-n-propylbenzo [b] furan, 6-n-propylbenzo [b] furan, 7-n-propylbenzo [b] furan, 4-iso
-Propylbenzo [b] furan, 5-iso-propylbenzo [b] furan, 6-iso-propylbenzo [b] furan, 7-iso-propylbenzo [b] furan, 4-n-butylbenzo [b] furan 5-n-butylbenzo [b] furan, 6-n-butylbenzo [b] furan, 7-n-butylbenzo [b] furan, 4-sec
-Butylbenzo [b] furan, 5-sec-butylbenzo [b] furan, 6-sec-butylbenzo [b] furan, 7-sec-butylbenzo [b] furan, 4-t-
Butylbenzo [b] furan, 5-t-butylbenzo [b] furan, 6-t-butylbenzo [b] furan, 7
Alkyl group-substituted benzo [b] furans such as -t-butylbenzo [b] furan, 4-methoxybenzo [b] furan, 5-methoxybenzo [b] furan, 6-methoxybenzo [b] furan, 7-methoxy Benzo [b] furan,
4-ethoxybenzo [b] furan, 5-ethoxybenzo [b] furan, 6-ethoxybenzo [b] furan, 7-
Ethoxybenzo [b] furan, 4-n-propoxybenzo [b] furan, 5-n-propoxybenzo [b] furan, 6-n-propoxybenzo [b] furan, 7-n-
Propoxybenzo [b] furan, 4-iso-propoxybenzo [b] furan, 5-iso-propoxybenzo [b] furan, 6-iso-propoxybenzo [b] furan, 7-iso-propoxybenzo [b] furan. Four
-N-butoxybenzo [b] furan, 5-n-butoxybenzo [b] furan, 6-n-butoxybenzo [b] furan, 7-n-butoxybenzo [b] furan, 4-se
c-butoxybenzo [b] furan, 5-sec-butoxybenzo [b] furan, 6-sec-butoxybenzo [b] furan, 7-sec-butoxybenzo [b] furan, 4-t-butoxybenzo [b] ] Alkoxy group-substituted benzo [b] furans such as furan, 5-t-butoxybenzo [b] furan, 6-t-butoxybenzo [b] furan, 7-t-butoxybenzo [b] furan, 4-acetyl Acyl group-substituted benzo [b] furans such as benzo [b] furan, 5-acetylbenzo [b] furan, 6-acetylbenzo [b] furan and 7-acetylbenzo [b] furan, benzo [b] furan- 4-carbaldehyde, benzo [b] furan-5-carbaldehyde, benzo [b]
Furan-6-carbaldehyde, benzo [b] furan-7
-Aldehyde group-substituted benzo [b] such as carbaldehyde
Furans, methyl benzo [b] furan-4-carboxylate, methyl benzo [b] furan-5-carboxylate, methyl benzo [b] furan-6-carboxylate, benzo [b]
Furan-7-carboxylic acid ester group-substituted benzo [b] furans such as methylcarboxylate, benzo [b] furan-
Sulfonate group-substituted benzo [such as methyl 4-sulfonate, methyl benzo [b] furan-5-sulfonate, methyl benzo [b] furan-6-sulfonate, methyl benzo [b] furan-7-sulfonate b] Furans, benzo [b] furan-4-carbonitrile, benzo [b]
Furan-5-carbonitrile, benzo [b] furan-6
-Cyano-substituted benzo [b] furans such as carbonitrile and benzo [b] furan-7-carbonitrile, 4-
Hydroxybenzo [b] furan, 5-hydroxybenzo [b] furan, 6-hydroxybenzo [b] furan, 7
-Hydroxy group-substituted benzo [b] furans such as hydroxybenzo [b] furan, 4-nitrobenzo [b] furan, 5-nitrobenzo [b] furan, 6-nitrobenzo [b] furan, 7-nitrobenzo [b] furan Such as nitro group-substituted benzo [b] furans, 4-aminobenzo [b] furan, 5-aminobenzo [b] furan, 6-aminobenzo [b] furan, 7-aminobenzo [b] furan, etc. b] Furans, 4-carbamoylbenzo [b] furan, 5-carbamoylbenzo [b] furan, 6-carbamoylbenzo [b] furan,
Amido group-substituted benzo [b] furans such as 7-carbamoylbenzo [b] furan, 4-fluorobenzo [b] furan, 5-fluorobenzo [b] furan, 6-fluorobenzo [b] furan, 7-fluoro Benzo [b] furan, 4-chlorobenzo [b] furan, 5-chlorobenzo [b] furan, 6-chlorobenzo [b] furan, 7-chlorobenzo [b] furan, 4-bromobenzo [b] furan, 5-bromobenzo [ b] furan, 6-bromobenzo [b] furan, 7-bromobenzo [b] furan, 4-iodobenzo [b] furan, 5-iodobenzo [b] furan, 6-iodobenzo [b] furan, 7-iodobenzo [b] Halogen group-substituted benzo [b] furans such as furan, 4-dicyanovinylbenzo [b] furan, 5-dicyanovinylbenzo [ ] Dicyanovinyl group-substituted benzo [b] furans such as furan, 6-dicyanovinylbenzo [b] furan, 7-dicyanovinylbenzo [b] furan, N-methylbenzo [b] furan, N-ethylbenzo [b] furan , N-n-propylbenzo [b] furan,
N-alkyl group-substituted benzo [b] such as N-iso-propylbenzo [b] furan, N-n-butylbenzo [b] furan, N-sec-butylbenzo [b] furan, Nt-butylbenzo [b] furan ] Furans, etc. can be mentioned.

Specific examples of benzo [b] thiophenes include 4-methylbenzo [b] thiophene, 5-methylbenzo [b] thiophene, 6-methylbenzo [b] thiophene, 7-methylbenzo [b] thiophene, 4-ethylbenzo. [B] Thiophene, 5-ethylbenzo [b] thiophene, 6-ethylbenzo [b] thiophene, 7-ethylbenzo [b] thiophene, 4-n-propylbenzo [b] thiophene, 5-n-propylbenzo [b] thiophene , 6-n-propylbenzo [b] thiophene, 7
-N-propylbenzo [b] thiophene, 4-iso-
Propylbenzo [b] thiophene, 5-iso-propylbenzo [b] thiophene, 6-iso-propylbenzo [b] thiophene, 7-iso-propylbenzo [b] thiophene, 4-n-butylbenzo [b] thiophene, 5-n-butylbenzo [b] thiophene, 6-n
-Butylbenzo [b] thiophene, 7-n-butylbenzo [b] thiophene, 4-sec-butylbenzo [b]
Thiophene, 5-sec-butylbenzo [b] thiophene, 6-sec-butylbenzo [b] thiophene, 7-
Alkyl such as sec-butylbenzo [b] thiophene, 4-t-butylbenzo [b] thiophene, 5-t-butylbenzo [b] thiophene, 6-t-butylbenzo [b] thiophene, 7-t-butylbenzo [b] thiophene Group-substituted benzo [b] thiophenes, 4-methoxybenzo [b] thiophene, 5-methoxybenzo [b] thiophene, 6-methoxybenzo [b] thiophene, 7-
Methoxybenzo [b] thiophene, 4-ethoxybenzo [b] thiophene, 5-ethoxybenzo [b] thiophene, 6-ethoxybenzo [b] thiophene, 7-ethoxybenzo [b] thiophene, 4-n-propoxybenzo [ b] thiophene, 5-n-propoxybenzo [b] thiophene, 6-n-propoxybenzo [b] thiophene, 7-n-propoxybenzo [b] thiophene, 4-
iso-propoxybenzo [b] thiophene, 5-is
o-propoxybenzo [b] thiophene, 6-iso-
Propoxybenzo [b] thiophene, 7-iso-propoxybenzo [b] thiophene, 4-n-butoxybenzo [b] thiophene, 5-n-butoxybenzo [b] thiophene, 6-n-butoxybenzo [b] thiophene ,
7-n-butoxybenzo [b] thiophene, 4-sec
-Butoxybenzo [b] thiophene, 5-sec-butoxybenzo [b] thiophene, 6-sec-butoxybenzo [b] thiophene, 7-sec-butoxybenzo [b] thiophene, 4-t-butoxybenzo [b] Thiophene, 5-t-butoxybenzo [b] thiophene, 6
Alkoxy group-substituted benzo [b] thiophenes such as -t-butoxybenzo [b] thiophene and 7-t-butoxybenzo [b] thiophene, 4-acetylbenzo [b] thiophene, 5-acetylbenzo [b] thiophene, 6-
Acyl group-substituted benzo [b] thiophenes such as acetylbenzo [b] thiophene and 7-acetylbenzo [b] thiophene, benzo [b] thiophene-4-carbaldehyde, benzo [b] thiophene-5-carbaldehyde, benzo Aldehyde group-substituted benzo [b] thiophenes such as [b] thiophene-6-carbaldehyde, benzo [b] thiophene-7-carbaldehyde, benzo [b] thiophene-4-carboxylate, benzo [b] thiophene- 5-carboxylate, benzo [b] thiophene-
Methyl 6-carboxylate, benzo [b] thiophene-7-
Carboxylic acid ester group-substituted benzo [b] thiophenes such as methyl carboxylate, benzo [b] thiophene-4-
Sulfonate group-substituted benzo [b] such as methyl sulfonate, methyl benzo [b] thiophene-5-sulfonate, methyl benzo [b] thiophene-6-sulfonate, and methyl benzo [b] thiophene-7-sulfonate Cyano groups such as thiophenes, benzo [b] thiophene-4-carbonitrile, benzo [b] thiophene-5-carbonitrile, benzo [b] thiophene-6-carbonitrile and benzo [b] thiophene-7-carbonitrile Substituted benzo [b] thiophenes, hydroxy group-substituted benzo [4- [benzobenzo [b] thiophene, 5-hydroxybenzo [b] thiophene, 6-hydroxybenzo [b] thiophene, 7-hydroxybenzo [b] thiophene, etc. b] Thiophenes, 4-nitrobenzo [b]
Thiophene, 5-nitrobenzo [b] thiophene, 6-
Nitro group-substituted benzo [b] thiophenes such as nitrobenzo [b] thiophene and 7-nitrobenzo [b] thiophene, 4-aminobenzo [b] thiophene, 5-aminobenzo [b] thiophene, 6-aminobenzo [b]
Amino group-substituted benzo [b] thiophenes such as thiophene and 7-aminobenzo [b] thiophene, 4-carbamoylbenzo [b] thiophene, 5-carbamoylbenzo [b] thiophene, 6-carbamoylbenzo [b] thiophene, 7- Amido group-substituted benzo [b] thiophenes such as carbamoylbenzo [b] thiophene, 4-fluorobenzo [b] thiophene, 5-fluorobenzo [b]
Thiophene, 6-fluorobenzo [b] thiophene, 7
-Fluorobenzo [b] thiophene, 4-chlorobenzo [b] thiophene, 5-chlorobenzo [b] thiophene, 6-chlorobenzo [b] thiophene, 7-chlorobenzo [b] thiophene, 4-bromobenzo [b] thiophene, 5- Bromobenzo [b] thiophene, 6-bromobenzo [b] thiophene, 7-bromobenzo [b] thiophene, 4-iodobenzo [b] thiophene, 5-iodobenzo [b] thiophene, 6-iodobenzo [b] thiophene, 7-iodobenzo [ b] halogen-substituted benzo [b] thiophenes such as thiophene, 4-dicyanovinylbenzo [b] thiophene, 5-dicyanovinylbenzo [b] thiophene, 6-dicyanovinylbenzo [b] thiophene, 7-dicyanovinylbenzo [B] Dicyano such as thiophene Sulfonyl group substituted benzo [b] thiophenes, N- methylbenzo [b] thiophene, N- ethylbenzo [b] thiophene, N-n-propyl-benzo [b] thiophene, N-an iso-propyl-benzo [b]
Thiophene, N-n-butylbenzo [b] thiophene,
N-sec-butylbenzo [b] thiophene, Nt-
Examples thereof include N-alkyl group-substituted benzo [b] thiophenes such as butylbenzo [b] thiophene.

Specific examples of benzo [b] selenophenes include 4-methylbenzo [b] selenophene, 5-methylbenzo [b] selenophene and 6-methylbenzo [b].
Selenophene, 7-methylbenzo [b] selenophene,
4-ethylbenzo [b] selenophene, 5-ethylbenzo [b] selenophene, 6-ethylbenzo [b] selenophene, 7-ethylbenzo [b] selenophene, 4-n
-Propylbenzo [b] selenophene, 5-n-propylbenzo [b] selenophene, 6-n-propylbenzo [b] selenophene, 7-n-propylbenzo [b] selenophene, 4-iso-propylbenzo [b] Selenophene, 5-iso-propylbenzo [b] selenophene, 6-iso-propylbenzo [b] selenophene,
7-iso-propylbenzo [b] selenophene, 4-
n-Butylbenzo [b] selenophene, 5-n-butylbenzo [b] selenophene, 6-n-butylbenzo [b] selenophene, 7-n-butylbenzo [b] selenophene, 4-sec-butylbenzo [b] selenophene, 5- sec-Butylbenzo [b] selenophene, 6
-Sec-butylbenzo [b] selenophene, 7-se
Alkyl such as c-butylbenzo [b] selenophene, 4-t-butylbenzo [b] selenophene, 5-t-butylbenzo [b] selenophene, 6-t-butylbenzo [b] selenophene, 7-t-butylbenzo [b] selenophene Group-substituted benzo [b] selenophenes, 4-
Methoxybenzo [b] selenophene, 5-methoxybenzo [b] selenophene, 6-methoxybenzo [b] selenophene, 7-methoxybenzo [b] selenophene, 4
-Ethoxybenzo [b] selenophene, 5-ethoxybenzo [b] selenophene, 6-ethoxybenzo [b] selenophene, 7-ethoxybenzo [b] selenophene,
4-n-propoxybenzo [b] selenophene, 5-n
-Propoxybenzo [b] selenophene, 6-n-propoxybenzo [b] selenophene, 7-n-propoxybenzo [b] selenophene, 4-iso-propoxybenzo [b] selenophene, 5-iso-propoxybenzo [b] Selenophene, 6-iso-propoxybenzo [b] selenophene, 7-iso-propoxybenzo [b] selenophene, 4-n-butoxybenzo [b] selenophene, 5-n-butoxybenzo [b] selenophene, 6-n- Butoxybenzo [b] selenophene, 7-
n-Butoxybenzo [b] selenophene, 4-sec-
Butoxybenzo [b] selenophene, 5-sec-butoxybenzo [b] selenophene, 6-sec-butoxybenzo [b] selenophene, 7-sec-butoxybenzo [b] selenophene, 4-t-butoxybenzo [b]
Selenophene, 5-t-butoxybenzo [b] selenophene, 6-t-butoxybenzo [b] selenophene, 7
-Alkoxy group-substituted benzo [b] selenophene such as t-butoxybenzo [b] selenophene, 4-acetylbenzo [b] selenophene, 5-acetylbenzo [b]
Acyl group-substituted benzo [b] selenophene such as selenophene, 6-acetylbenzo [b] selenophene, 7-acetylbenzo [b] selenophene, benzo [b] selenophene-4-carbaldehyde, benzo [b] selenophene-5- Carbaldehyde, benzo [b] selenophene-6-carbaldehyde, benzo [b] selenophene-
Aldehyde group-substituted benzo [b] selenophenes such as 7-carbaldehyde, benzo [b] selenophene-4
-Methyl carboxylate, benzo [b] selenophene-5-
Carboxylic acid ester group-substituted benzo [b] selenophenes such as methyl carboxylate, benzo [b] selenophene-6-carboxylate, benzo [b] selenophene-7-methylcarboxylate, and benzo [b] selenophene-4
-Methyl sulfonate, benzo [b] selenophene-5-
Sulfonate group-substituted benzo [b] selenophenes such as methyl sulfonate, benzo [b] selenophene-6-methyl sulfonate, benzo [b] selenophene-7-methyl sulfonate, and benzo [b] selenophene-4
Cyano group-substituted benzo [b] selenophenes such as carbonitrile, benzo [b] selenophene-5-carbonitrile, benzo [b] selenophene-6-carbonitrile, benzo [b] selenophene-7-carbonitrile,
4-hydroxybenzo [b] selenophene, hydroxy group-substituted benzo [b] selenophenes such as 5-hydroxybenzo [b] selenophene, 6-hydroxybenzo [b] selenophene, 7-hydroxybenzo [b] selenophene and 4-nitrobenzo Nitro group-substituted benzo [b] selenophenes such as [b] selenophene, 5-nitrobenzo [b] selenophene, 6-nitrobenzo [b] selenophene, 7-nitrobenzo [b] selenophene,
Amino group-substituted benzo [b] selenophenes such as 4-aminobenzo [b] selenophene, 5-aminobenzo [b] selenophene, 6-aminobenzo [b] selenophene, 7-aminobenzo [b] selenophene and 4-carbamoylbenzo [b] Selenophene, 5-carbamoylbenzo [b] selenophene, 6-carbamoylbenzo [b]
Ameno group-substituted benzo [b] selenophenes such as selenophene and 7-carbamoylbenzo [b] selenophene,
4-fluorobenzo [b] selenophene, 5-fluorobenzo [b] selenophene, 6-fluorobenzo [b]
Selenophene, 7-fluorobenzo [b] selenophene, 4-chlorobenzo [b] selenophene, 5-chlorobenzo [b] selenophene, 6-chlorobenzo [b] selenophene, 7-chlorobenzo [b] selenophene, 4
-Bromobenzo [b] selenophene, 5-bromobenzo [b] selenophene, 6-bromobenzo [b] selenophene, 7-bromobenzo [b] selenophene, 4-iodobenzo [b] selenophene, 5-iodobenzo [b]
Selenophene, 6-iodobenzo [b] selenophene,
Halogen group-substituted benzo [b] selenophene such as 7-iodobenzo [b] selenophene, 4-dicyanovinylbenzo [b] selenophene, 5-dicyanovinylbenzo [b] selenophene, 6-dicyanovinylbenzo [b]
Dicyanovinyl group-substituted benzo [b] selenophenes such as selenophene, 7-dicyanovinylbenzo [b] selenophene, N-methylbenzo [b] selenophene, N-
Ethylbenzo [b] selenophene, N-n-propylbenzo [b] selenophene, N-iso-propylbenzo [b] selenophene, N-n-butylbenzo [b] selenophene, N-sec-butylbenzo [b] selenophene, N- N such as t-butylbenzo [b] selenophene
-Alkyl group-substituted benzo [b] selenophenes and the like can be mentioned.

Specific examples of benzo [b] tellurophenes include 4-methylbenzo [b] tellurophene, 5-methylbenzo [b] tellurophene, 6-methylbenzo [b].
Tellurophen, 7-methylbenzo [b] tellurophene,
4-ethylbenzo [b] tellurophene, 5-ethylbenzo [b] tellurophene, 6-ethylbenzo [b] tellurophene, 7-ethylbenzo [b] tellurophene, 4-n
-Propylbenzo [b] tellurophene, 5-n-propylbenzo [b] tellurophene, 6-n-propylbenzo [b] tellurophene, 7-n-propylbenzo [b] tellurophene, 4-iso-propylbenzo [b] Tellurophene, 5-iso-propylbenzo [b] tellurophene, 6-iso-propylbenzo [b] tellurophene,
7-iso-propylbenzo [b] tellurophene, 4-
n-Butylbenzo [b] tellurophene, 5-n-butylbenzo [b] tellurophene, 6-n-butylbenzo [b] tellurophene, 7-n-butylbenzo [b] tellurophene, 4-sec-butylbenzo [b] tellurophene, 5- sec-Butylbenzo [b] tellurophene, 6
-Sec-butylbenzo [b] tellurophene, 7-se
Alkyl such as c-butylbenzo [b] tellurophene, 4-t-butylbenzo [b] tellurophene, 5-t-butylbenzo [b] tellurophene, 6-t-butylbenzo [b] tellurophene, 7-t-butylbenzo [b] tellurophene Group-substituted benzo [b] tellurophenes, 4-
Methoxybenzo [b] tellurophene, 5-methoxybenzo [b] tellurophene, 6-methoxybenzo [b] tellurophene, 7-methoxybenzo [b] tellurophene, 4
-Ethoxybenzo [b] tellurophene, 5-ethoxybenzo [b] tellurophene, 6-ethoxybenzo [b] tellurophene, 7-ethoxybenzo [b] tellurophene,
4-n-propoxybenzo [b] tellurophene, 5-n
-Propoxybenzo [b] tellurophene, 6-n-propoxybenzo [b] tellurophene, 7-n-propoxybenzo [b] tellurophene, 4-iso-propoxybenzo [b] tellurophene, 5-iso-propoxybenzo [b] Tellurophene, 6-iso-propoxybenzo [b] tellurophene, 7-iso-propoxybenzo [b] tellurophene, 4-n-butoxybenzo [b] tellurophene, 5-n-butoxybenzo [b] tellurophene, 6-n- Butoxybenzo [b] tellurophene, 7-
n-Butoxybenzo [b] tellurophene, 4-sec-
Butoxybenzo [b] tellurophene, 5-sec-butoxybenzo [b] tellurophene, 6-sec-butoxybenzo [b] tellurophene, 7-sec-butoxybenzo [b] tellurophene, 4-t-butoxybenzo [b]
Tellurophene, 5-t-butoxybenzo [b] tellurophene, 6-t-butoxybenzo [b] tellurophene, 7
-Alkoxy group-substituted benzo [b] tellurophene such as t-butoxybenzo [b] tellurophene, 4-acetylbenzo [b] tellurophene, 5-acetylbenzo [b]
Acyl group-substituted benzo [b] tellurophenes such as tellurophene, 6-acetylbenzo [b] tellurophene, 7-acetylbenzo [b] tellurophene, benzo [b] tellurophene-4-carbaldehyde, benzo [b] tellurophene-5- Carbaldehyde, benzo [b] tellurophene-6-carbaldehyde, benzo [b] tellurophene-
Aldehyde group-substituted benzo [b] tellurophenes such as 7-carbaldehyde, benzo [b] tellurophene-4
-Methyl carboxylate, benzo [b] tellurophene-5-
Carboxylic ester group-substituted benzo [b] tellurophenes such as methyl carboxylate, benzo [b] tellurophene-6-carboxylate, benzo [b] tellurophene-7-methylcarboxylate, and benzo [b] tellurophene-4
-Methyl sulfonate, benzo [b] tellurophene-5-
Sulfonate group-substituted benzo [b] tellurophenes such as methyl sulfonate, benzo [b] tellurophene-6-methyl sulfonate, benzo [b] tellurophene-7-methyl sulfonate, and benzo [b] tellurophene-4
Cyano group-substituted benzo [b] tellurophenes such as carbonitrile, benzo [b] tellurophene-5-carbonitrile, benzo [b] tellurophene-6-carbonitrile, benzo [b] tellurophene-7-carbonitrile,
4-Hydroxybenzo [b] tellurophene, hydroxy group-substituted benzo [b] tellurophene such as 5-hydroxybenzo [b] tellurophene, 6-hydroxybenzo [b] tellurophene, 7-hydroxybenzo [b] tellurophene, 4-nitrobenzo Nitro group-substituted benzo [b] tellurophenes such as [b] tellurophene, 5-nitrobenzo [b] tellurophene, 6-nitrobenzo [b] tellurophene, 7-nitrobenzo [b] tellurophene,
Amino group-substituted benzo [b] tellurophenes such as 4-aminobenzo [b] tellurophene, 5-aminobenzo [b] tellurophene, 6-aminobenzo [b] tellurophene, 7-aminobenzo [b] tellurophene and 4-carbamoylbenzo [b] Tellurophene, 5-carbamoylbenzo [b] Tellurophene, 6-carbamoylbenzo [b]
Amido group-substituted benzo [b] tellurophenes such as tellurophen and 7-carbamoylbenzo [b] tellurophene,
4-fluorobenzo [b] tellurophene, 5-fluorobenzo [b] tellurophene, 6-fluorobenzo [b]
Tellurophene, 7-fluorobenzo [b] tellurophene, 4-chlorobenzo [b] tellurophene, 5-chlorobenzo [b] tellurophene, 6-chlorobenzo [b] tellurophene, 7-chlorobenzo [b] tellurophene, 4
-Bromobenzo [b] tellurophene, 5-bromobenzo [b] tellurophene, 6-bromobenzo [b] tellurophene, 7-bromobenzo [b] tellurophene, 4-iodobenzo [b] tellurophene, 5-iodobenzo [b]
Tellurophen, 6-iodobenzo [b] tellurophene,
Halogen group-substituted benzo [b] tellurophene such as 7-iodobenzo [b] tellurophene, 4-dicyanovinylbenzo [b] tellurophene, 5-dicyanovinylbenzo [b] tellurophene, 6-dicyanovinylbenzo [b]
Tellurophene, dicyanovinyl group-substituted benzo [b] tellurophenes such as 7-dicyanovinylbenzo [b] tellurophene, N-methylbenzo [b] tellurophene, N-
Ethylbenzo [b] tellurophene, N-n-propylbenzo [b] tellurophene, N-iso-propylbenzo [b] tellurophene, N-n-butylbenzo [b] tellurophene, N-sec-butylbenzo [b] tellurophene, N- N such as t-butylbenzo [b] tellurophene
-Alkyl group-substituted benzo [b] tellurophenes and the like can be mentioned.

Among these, indoles, benzo [b]
Thiophenes and benzo [b] furans are practically preferably used, and indoles are particularly preferably used. Among the indoles, cyano group-substituted indoles, nitro group-substituted indoles, amide group-substituted indoles, halogen group-substituted indoles and the like are practically preferable, and cyano group-substituted indoles are particularly preferable.

The basic compound (b) used when synthesizing the acidic group-substituted heterocyclic compound trimer is a compound which forms a salt with the acidic group-substituted heterocyclic compound (a). It is not particularly limited as long as it is, for example, ammonia, aliphatic amines, cyclic saturated amines,
Cyclic unsaturated amines, ammonium compounds thereof,
And inorganic bases are preferably used.

The structural formulas of amines used as the basic compound (b) of the present invention are shown below.

[Chemical 11] In the formula, R _{21 to} R ₂₃ are each independently selected from hydrogen, an alkyl group having 1 to 4 carbon atoms (C _{1 to} C ₄ ), CH ₂
OH, CH ₂ CH ₂ OH, CONH ₂ or NH ₂ .

The structural formulas of the ammonium compounds used as the basic compound (b) of the present invention are shown below.

[Chemical 12] In the formula, R _{24 to} R ₂₇ are each independently selected hydrogen, an alkyl group having 1 to 4 carbon atoms (C _{1 to} C ₄ ), CH ₂
OH, CH ₂ CH ₂ OH, CONH ₂ or NH ₂ ; Y ⁻ is OH ⁻ , 1/2 · SO ₄ ²⁻ , NO ₃ ⁻ , 1
/ 2CO ₃ ²⁻ , HCO ₃ ⁻ , 1/2 · (COO) ₂
^2, or R'COO ^- [wherein, R 'is 1 to 3 carbon atoms
(It is an alkyl group of (C ₁ -C ₃ )].

The cyclic saturated amines include piperidine,
Pyrrolidine, morpholine, piperazine, derivatives having these skeletons, and ammonium hydroxide compounds thereof are preferably used.

Examples of the cyclic unsaturated amines include pyridine,
α-picoline, β-picoline, γ-picoline, quinoline, isoquinoline, pyrroline, derivatives having these skeletons, and ammonium hydroxide compounds thereof are preferably used.

As the inorganic base, metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide are preferably used.

The concentration of these basic compounds (b) is 0.0
5 mol / l or more and 15 mol / l or less, preferably 0.1-10.0 mol / l, more preferably 0.2-
Used in the range of 8.0 mol / l. At this time, if the amount of the basic compound is too small, the yield of the polymer obtained will decrease, and if it is too large, the conductivity will tend to decrease. The basic compounds may be mixed and used in arbitrary proportions.

The weight ratio of the acidic group-substituted heterocyclic compound (a) to the basic compound (b) is (a) :( b) = 1:
100-100: 1, preferably 10: 90-90: 1
0 is used. Here, if the ratio of the basic compound is too low, the reactivity may decrease and the conductivity may also decrease. On the contrary, when the ratio is too high, the ratio of the acidic group and the basic compound in the obtained polymer to form a salt becomes high, and the conductivity may decrease.

Further, the equivalent ratio of the acidic group in the acidic group-substituted heterocyclic compound (a) to the basic compound (b) is 1: 100 to 100: 1, preferably 1: 0.25.
It can be used at 1:20, more preferably 1: 0.5 to 1:15. Here, if the ratio of the basic compound is too low, the reactivity decreases and the conductivity also decreases. On the other hand, if the ratio is too high, the ratio of the acidic group and basic compound in the trimer obtained to form a salt increases, and the conductivity tends to decrease.

The reaction is carried out by an oxidizing reaction with an oxidizing agent (c) in the presence of these basic compounds (b).

The oxidizing agent (c) used in the method for synthesizing the above-mentioned acidic group-substituted heterocyclic compound trimer is not particularly limited,
For example, ferric chloride hexahydrate, anhydrous ferric chloride, ferric nitrate nonahydrate, ferric sulfate n-hydrate, ferric ammonium ammonium dodecahydrate, perchloric acid second Iron n-hydrate, ferric tetrafluoroborate, cupric chloride, ferric nitrate, cupric sulfate, cupric tetrafluoroborate, nitrosonium tetrafluoroborate, ammonium persulfate, sodium persulfate , Potassium persulfate, potassium periodate, hydrogen peroxide, ozone, potassium hexacyanoferrate, tetraammonium cerium (IV) sulfate dihydrate ferric chloride hexahydrate, and the like. Preferably, ferric chloride hexahydrate, anhydrous ferric chloride, ferric nitrate nonahydrate, ferric sulfate n-hydrate, ferric ammonium sulfate dodecahydrate, perchloric acid Ferric iron n-hydrate, ferric tetrafluoroborate, cupric chloride, ferric nitrate, cupric sulfate, cupric tetrafluoroborate, nitrosonium tetrafluoroborate, ammonium persulfate, persulfate Sodium sulfate, potassium persulfate,
Mention may be made of potassium periodate, hydrogen peroxide and ozone. More preferably, ferric chloride hexahydrate, anhydrous ferric chloride, ferric nitrate nonahydrate, ferric sulfate n-hydrate, ferric ammonium ammonium dodecahydrate, perchlorine Ferric acid n-hydrate, ferric tetrafluoroborate, cupric chloride, ferric nitrate, cupric sulfate, cupric tetrafluoroborate, ammonium persulfate, ozone, among them, , Ferric chloride hexahydrate, anhydrous ferric chloride, ferric nitrate nonahydrate, ferric sulfate n-hydrate, ferric ammonium ammonium dodecahydrate, perchloric acid second Iron n-hydrate, ferric tetrafluoroborate, ammonium persulfate, and ozone are most practically preferable. These oxidizing agents may be used alone or in combination of two or more at an arbitrary ratio.

The molar ratio of the monomer such as (a) or the mixture of (a) and (d) used in the above-mentioned method for synthesizing the trimer of the acidic group-substituted heterocyclic compound to the oxidizing agent (c) is , Monomer:
Oxidizing agent = 1: 0.5 to 100, preferably 1: 1 to 50
Used in. Here, if the proportion of the oxidant is low, the reactivity is lowered and the raw material remains. On the contrary, if the proportion is too high, the produced trimer may be peroxidized to cause deterioration of the product.

Water or an organic solvent can be used as the solvent used in the above-mentioned method for producing a trimer of an acidic group-substituted heterocyclic compound. The organic solvent is not particularly limited, but includes methanol, ethanol, isopropanol, acetone, acetonitrile, propionitrile, tetrahydrofuran, 1,4-dioxane, methyl isobutyl ketone, methyl ethyl ketone,
γ-butyl lactone, propylene carbonate, sulfolane, nitromethane, N, N-dimethylformamide,
N-methylacetamide, dimethyl sulfoxide, dimethyl sulfone, N-methylpyrrolidone, benzene, toluene, xylene, methylene chloride, chloroform, dichloroethane and the like are used. These solvents may be used alone, or two or more kinds may be mixed and used at an arbitrary ratio. Among these solvents, water, acetone, acetonitrile, 1,4-dioxane, γ-butyl lactone, N, N-dimethylformamide and the like are preferable, and acetonitrile is most preferable for practical use.

An acidic compound can be added to these solvents. Examples of the acidic compound include inorganic acids such as sulfuric acid, hydrochloric acid and nitric acid, p-toluenesulfonic acid, acetic acid and methanesulfonic acid.

In the above-mentioned method for producing a trimer of an acidic group-substituted heterocyclic compound, the acidic group-substituted heterocyclic compound (a) during the reaction is used.
When used together with the heterocyclic compound (d), the molar ratio (i) :( d) is 10:90 to 99: 1, and preferably 20:80 to 99: 1. .

In the above-mentioned method for producing an acidic group-substituted heterocyclic compound trimer, the acidic group-substituted heterocyclic compound (a) at the time of reaction is used.
Or the concentration of the mixture of the acidic group-substituted heterocyclic compound (a) and the heterocyclic compound (d) is 0.
It is in the range of 01 mass% or more, preferably 0.1 to 50 mass%, more preferably 1 to 30 mass%.

The reaction temperature in the production method of the present invention is -2.
It is preferably carried out in the range of 0 to 120 ° C, more preferably in the range of 0 to 100 ° C. At −20 ° C. or lower, the progress of the oxidation reaction is extremely slow, and X a ^{− serving as a} dopant may not be efficiently doped into the trimer.
The conductivity may decrease. If the temperature is 120 ° C. or higher, the structure of the trimer is deteriorated and the conductivity tends to decrease.

The reaction method in the production method of the present invention can be arbitrarily selected. For example, a solution of an acidic group-substituted heterocyclic compound (a) and a basic compound (b), or an acidic group-substituted heterocyclic compound (a) and a heterocyclic compound (d)
A method of adding the solution of the oxidant (ha) to the solution of the mixture of the basic compound (ii) and the solution of the basic compound (ii) is also possible, and the reverse method is also applicable. The addition time of the oxidizing agent (C) solution is not particularly limited, but is usually 15 minutes or more,
Preferably 30-720 minutes, more preferably 30-18
0 minutes.

The acidic group-substituted heterocyclic compound trimer represented by the general formula (2) or (4) obtained by the production method of the present invention is a self-doping type trimer with an acidic group in the molecule. Although it has performance such as conductivity even when no external dopant is present, an external dopant can be added.
X ^a- is in the general formula (2) or (4) is an external dopant is the anion of a protonic acid derived from the oxidation agent in the reaction. Specifically, chlorine ion, bromine ion,
Iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, borate ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, p-toluenesulfonate ion, trifluoro It is a 1 to 3 valent anion such as acetate ion and trifluoromethanesulfonate ion, preferably 1 such as chloride ion, sulfate ion and borofluoride ion.
~ A divalent anion. Most preferred are monovalent anions such as chloride and divalent anions such as sulfate. For example, if the reaction was carried out to select the anhydrous ferric chloride as an oxidant, external dopant X ^a- is a heterocyclic compound trimer becomes chloride ions, in the case of performing the reaction using ammonium persulfate, External dopant X
^a- becomes sulfate ion.

The acidic group-substituted heterocyclic compound trimer obtained by the production method of the present invention is a doped heterocyclic compound trimer except when hydrogen peroxide or ozone is used as an oxidizing agent. External dopant X ^a- for the repeating unit
The molar ratio (dope ratio) m is 0.001 to 3.0.
When hydrogen peroxide or ozone is used as an oxidant, m = 0
Becomes

The N-alkylated acidic group-substituted heterocyclic compound trimer may be trimerized by using the N-alkyl group-substituted heterocyclic compound trimer as a raw material, or the trimer may be It is also possible to synthesize using a known alkylating agent after the synthesis.

When the acidic group-substituted heterocyclic compound trimer of the present invention is used for electrodes of batteries, capacitors, etc., good cycle characteristics are indispensable. The cycle characteristics may be affected by the superiority or inferiority depending on the type of the external dopant ^Xa- . The external dopant ^Xa-, which gives an acidic group-substituted heterocyclic compound trimer having good cycle characteristics, is
It is a monovalent to monovalent anion, preferably a monovalent to divalent anion, and most preferably a monovalent anion, a chloride ion, and a divalent anion, a sulfate ion.

The externally doped acidic group-substituted heterocyclic compound trimer obtained by the reaction method of the present invention in the presence of the ^Xa- component has been conventionally used for dedoping of various conductive polymers and charge transfer complexes. known methods as steps, i.e., aqueous ammonia, sodium hydroxide, can be removed outside dopant X ^a- and trimer was Nigosa Ken the alkaline solution such as lithium hydroxide.

Further, it is possible to add an arbitrary external dopant at an arbitrary doping rate by treating again with an arbitrary kind and an arbitrary amount of a doping agent. That is, by performing the doping treatment on the acidic group-substituted heterocyclic compound trimer produced after the completion of the reaction using an acidic solution, the doping rate can be improved and the conductivity can be improved. The acidic solution is specifically an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid, or p
-Organic acids such as toluenesulfonic acid, camphorsulfonic acid, benzoic acid and derivatives having these skeletons, polystyrenesulfonic acid, polyvinylsulfonic acid, poly (2-acrylamido-2-methylpropane) sulfonic acid, polyvinylsulfuric acid and these It is an aqueous solution containing a polymeric acid such as a derivative having a skeleton, or a mixed solution of water and an organic solvent. In addition, these inorganic acids, organic acids, and polymeric acids may be used alone or as a mixture of two or more kinds at an arbitrary ratio.

Further, the acidic group-substituted heterocyclic compound trimer obtained by the method of the present invention is used as a conductive composition of an acidic group-substituted heterocyclic compound trimer alone or as a conductive auxiliary agent of various carbons. Alternatively, it can be used as a conductive composition of an acidic group-substituted heterocyclic compound trimer complex by kneading and compounding with colloidal silica as an additive and various binders. Among them, especially the particle size 0.1-5
Conductive compositions using 0 μm particles are preferred. The method of adjusting the particle size is not particularly limited, but generally, it is carried out by spray-drying after washing the slurry or by pulverizing the powder after drying with a mortar, a ball mill, a blender, an ultrasonic vibration treatment or the like. When the above conductive composition is molded using an acidic group-substituted heterocyclic compound trimer having a particle size of more than 50 μm, the mechanical strength of the molded product tends to become brittle.

Further, the acidic group-substituted heterocyclic compound trimer of the present invention exhibits a conductive function due to having a laminated structure. In particular, it is preferable to have a laminated structure with a layer interval of 0.1 to 0.6 nm. In general, a compound having an ultrafine laminated structure has good physical properties such as rigidity, strength and heat resistance. However, if the layer spacing is less than 0.1 nm, the laminated structure tends to be unstable. If the layer spacing is wider than 0.6 nm, the electron hopping conduction between the trimers is adversely affected and the conductivity tends to decrease.

Since the purity of these acidic group-substituted heterocyclic compound trimers affects the conductive performance, after the synthesis,
It is preferable to highly purify using a purification method such as recrystallization, reprecipitation purification, and sublimation purification.

..

EXAMPLES The present invention will be described in more detail with reference to examples, but the following examples do not limit the scope of the present invention.

In the production example of the indole derivative trimer, elemental analysis was carried out by EA11 manufactured by Thermoquest Co.
It was measured at 10. The electrical conductivity was measured with a Mitsubishi Chemical Lorester meter MCP-T350 (4 terminal method: distance between electrodes 1 mm). Furthermore, X-ray diffraction analysis (XRD) was performed by Rigaku Denki Co., Ltd. RINT-1100 (tube: CuK _α X
Line).

Example 1 Synthesis of Indole-5-carboxylic acid trimer 20 ml of water was placed in a 200 ml three-necked flask and 1.52 g of triethylamine and 2.42 g of indole-5-carboxylic acid were dissolved. On the other hand, the oxidant solution was prepared by adding 50.54 g of water to 20.54 g of ammonium persulfate
Was dissolved and stirred for 10 minutes. Next, Indore-5
The prepared oxidizing agent solution was added dropwise to the carboxylic acid aqueous solution over 30 minutes, and the mixture was stirred at 20 ° C. for 5 hours. The reaction solution changed from pale yellow to pale green with some heat generation.
After completion of the reaction, the mixture was suction filtered with a Kiriyama funnel, washed with acetonitrile and then with methanol, and dried to obtain 2.06 g (yield 85%) of a pale green indole-5-carboxylic acid trimer. The obtained trimer was pressure-molded with a tablet molding machine, cut into a shape with a diameter of 10 mm and a thickness of 1 mm, and the conductivity was measured by the four-terminal method, and it was 0.41 S / cm. As a result of X-ray diffraction crystal analysis, the layer spacing was 0.48.
was nm. 5 parts by mass of the indole-5-carboxylic acid trimer and 1 part by mass of ammonia were dissolved in 100 parts by mass of water with stirring at room temperature to prepare a conductive composition. The solution thus obtained was applied on a glass substrate by spin coating and dried at 80 ° C. A colorless transparent film having a smooth surface resistance value of 2.0 × 10 ⁶ Ω having a film thickness of 3.5 μm was obtained.

Example 2 Synthesis of indole-5-sulfonic acid trimer 10 ml of water and 10 ml of acetonitrile were placed in a 200 ml three-necked flask, and aqueous ammonia (27%) 1.50 was added.
g and indole-5-sulfonic acid 2.42 g were dissolved. On the other hand, in the preparation of the oxidizing agent solution, 20.54 g of ammonium persulfate was dissolved in 50 ml of water and stirred for 10 minutes. Next, add 3 parts to the indole-5-sulfonic acid aqueous solution.
After adding the prepared oxidant solution dropwise over 0 minutes, 20
The mixture was stirred at 0 ° C for 5 hours. The reaction solution changed from pale yellow to pale green with some heat generation. After completion of the reaction, the mixture was suction filtered with a Kiriyama funnel, washed with acetonitrile and then with methanol, and dried to obtain 2.13 g (yield 85%) of a pale green indole-5-sulfone "acid trimer." The trimer was pressure-molded with a tablet molding machine and had a diameter of 10 mm and a thickness of 1
When it was cut into a shape of mm and the conductivity was measured by the four-terminal method, it was 0.56 S / cm. The indole
3 parts by mass of 5-sulfonic acid trimer, acrylic emulsion "Dianal MX-1708" (manufactured by Mitsubishi Rayon Co., Ltd.)
20 parts by mass and 0.4 parts by mass of ammonia were dissolved in 100 parts by mass of water with stirring at room temperature to prepare a conductive composition. The solution thus obtained was applied on a glass substrate by spin coating and dried at 80 ° C. A colorless transparent film having a smooth surface resistance value of 2.7 × 10 ⁷ Ω having a film thickness of 2.0 μm was obtained.

Example 3 Synthesis of co-trimer of indole-5-carbonitrile and indole-5-carboxylic acid 20 ml of water was placed in a 200 ml three-necked flask, 1.52 g of triethylamine and 1. 61 g and indole-5-carbonitrile 0.
71 g was dissolved. On the other hand, the oxidizer solution is prepared with 50 m of water.
20.54 g of ammonium persulfate was dissolved in 1 and stirred for 10 minutes. Next, the prepared oxidizing agent solution was added dropwise to the indole-5-carboxylic acid and indole-5-carbonitrile aqueous solution over 30 minutes, followed by stirring at 20 ° C. for 5 hours. The reaction solution changed from pale yellow to pale green with some heat generation. After completion of the reaction, suction filtration with a Kiriyama funnel, washing with acetonitrile and then methanol,
After drying, 1.92 g (yield: 83%) of a co-trimer of light green indole-5-carboxylic acid and indole-5-carboxylic acid was obtained. The obtained trimer was pressure-molded with a tablet molding machine, cut into a shape with a diameter of 10 mm and a thickness of 1 mm, and the conductivity was measured by the four-terminal method.
It was m. A conductive composition was prepared by stirring and dissolving 0.3 part by mass of the co-trimer of indole-5-carbonitrile and indole-5-carboxylic acid in 100 parts by mass of N-methylpyrrolidone at room temperature. The solution thus obtained was applied onto a glass substrate by spin coating to form 100
It was dried at ° C. A colorless transparent film having a smooth surface resistance value of 5.4 × 10 ⁸ Ω and a film thickness of 0.1 μm was obtained.

Comparative Example 1 Synthesis of indole-5-carboxylic acid trimer 20 ml of water was placed in a 200 ml three-necked flask, and 2.42 g of indole-5-carboxylic acid was suspended and dispersed. On the other hand, in the preparation of the oxidizing agent solution, 20.54 g of ammonium persulfate was dissolved in 50 ml of water and stirred for 10 minutes. Then add 3 parts of indole-5-carboxylic acid
After adding the prepared oxidant solution dropwise over 0 minutes, 20
The mixture was stirred at 0 ° C for 5 hours. The reaction solution generated little exotherm and changed from pale yellow to black. After completion of the reaction, suction filtration with a Kiriyama funnel, washing with acetonitrile and then methanol, and drying were carried out to obtain a black indole-5-carboxylic acid trimer 0.3.
6 g (yield 15%) was obtained. The obtained trimer was pressure-molded with a tablet molding machine, cut into a shape having a diameter of 10 mm and a thickness of 1 mm, and the conductivity was measured by the four-terminal method.
It was 08 S / cm.

[0054]

INDUSTRIAL APPLICABILITY As described above, according to the present invention, it is possible to produce an acidic group-substituted heterocyclic compound trimer having a conductive redox capacity and good cycle characteristics with high purity and high yield. It is easily possible. The chemical oxidation method of the present invention is capable of mass production, can obtain a large amount of trimer at one time, and is very suitable for industrial production. On the other hand, in conventional electrolytic oxidation, mass production is difficult to achieve due to the peculiarities of the equipment. Also, unlike the electrolytic reaction, in the chemical oxidation reaction, the last cyclization reaction is an oxidative cyclization reaction under mild conditions and does not peroxidize the trimer itself, so there are few impurities and good conductivity. It is possible to obtain a new trimer. These acidic group-substituted heterocyclic compound trimers are various antistatic agents, electrostatic agents, capacitors, batteries, EMI shields, chemical sensors, display elements,
It can be widely applied to organic EL materials, non-linear materials, rust preventives, adhesives, fibers, antistatic paints, plating primers, bases for electrostatic coating, galvanic protection and the like.

Claims (3)

[Claims] 1. The following general formula (1) [Chemical 1] (In the above formula, R₁~ R_FourIs hydrogen, a straight chain having 1 to 24 carbon atoms
Chain or branched alkyl group, straight chain having 1 to 24 carbon atoms,
Is a branched alkoxy group, a straight or branched chain having 2 to 24 carbon atoms
Various acyl groups, aldehyde groups, carboxyl groups, carbon numbers
2 to 24 linear or branched carboxylic acid ester groups,
Rufonic acid group, straight-chain or branched sulfo having 1 to 24 carbon atoms
Acid ester group, cyano group, hydroxyl group, nitro group, amino
Group, amide group, dicyanovinyl group, alkyl (carbon number 1
~ 8 linear or branched alkyl group) oxycarbonyl
Cyanovinyl group, nitrophenyl cyanovinyl group and Ha
Substituents independently selected from the group consisting of rogen groups
Indicates R₁~ R_FourAt least one of them is sulfonic acid
It is a group or a carboxyl group. Ht is NR
₂₈, S, O, Se and Te selected from the group consisting of
Terror atom group, R₂₈Is hydrogen and a straight chain having 1 to 24 carbon atoms.
Or a substituent selected from the group consisting of branched alkyl groups.
is there. ) An acidic group-substituted heterocyclic compound represented by
Lucari metal salt, ammonium salt and substituted ammonium
At least one compound (a) among the salts is combined with a basic compound.
At least one oxidizing agent in a solution containing
The following general formula characterized by reacting according to (C)
(2) [Chemical 2] (In the above formula, R₁~ R_FourAnd Ht are represented by the general formula (1)
Is the same as^a-Is chlorine ion, bromine ion,
Iodine ion, fluorine ion, nitrate ion, sulfate ion
Ion, hydrogen sulfate ion, phosphate ion, borofluoride ion
Ion, perchlorate ion, thiocyanate ion, acetate ion
Ion, propionate ion, methanesulfonate ion, p
-Toluenesulfonate ion, trifluoroacetate ion
And trifluoromethanesulfonate ion
At least one anion selected from a group of 1 to 3 valent anions
Is an ion, a represents the ionic valence of X, and has an integer of 1 to 3
Is a number, m is a doping rate, and the value is 0 to 3.0.
is there. ] The manufacturing method of the heterocyclic compound trimer shown by these. 2. The following general formula (1): (In the above formula, R _{1 to} R ₄ are hydrogen, a straight-chain or branched alkyl group having 1 to 24 carbon atoms, a straight-chain or branched alkoxy group having 1 to 24 carbon atoms, and a straight-chain having 2 to 24 carbon atoms. Or branched acyl group, aldehyde group, carboxyl group, linear or branched carboxylic acid ester group having 2 to 24 carbon atoms, sulfonic acid group, linear or branched sulfonic acid ester group having 1 to 24 carbon atoms, cyano group , Hydroxyl group, nitro group, amino group, amide group, dicyanovinyl group, alkyl (carbon number 1
~ 8 linear or branched alkyl group) oxycarbonyl cyano vinyl group, a nitrophenyl cyano vinyl group, and a substituent independently selected from the group consisting of halogen groups, at least one of R _{1 to} R ₄ It is a sulfonic acid group or a carboxyl group. Ht is NR ₂₈ ,
A heteroatom group selected from the group consisting of S, O, Se and Te, R ₂₈ is a substituent selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 24 carbon atoms. ) A heterocyclic compound substituted with an acidic group, at least one compound (a) selected from alkali metal salts, ammonium salts and substituted ammonium salts thereof, and the following general formula (3): (In the above formula, R _{5 to} R ₈ are hydrogen, a straight-chain or branched alkyl group having 1 to 24 carbon atoms, a straight-chain or branched alkoxy group having 1 to 24 carbon atoms, and a straight-chain having 2 to 24 carbon atoms. Or a branched acyl group, an aldehyde group, a linear or branched carboxylic acid ester group having 2 to 24 carbon atoms, a linear or branched sulfonic acid ester group having 1 to 24 carbon atoms, a cyano group, a hydroxyl group, a nitro group, amino A group, an amide group, a dicyanovinyl group, an alkyl (a linear or branched alkyl group having 1 to 8 carbon atoms) oxycarbonylcyanovinyl group, a nitrophenylcyanovinyl group, and a halogen group, each independently selected substituent Ht is NR
Heteroatom group selected from the group consisting of ₂₈ , S, O, Se and Te, and R ₂₈ is a substituent selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 24 carbon atoms. ), At least one heterocyclic compound (d) represented by the formula (4) is reacted with at least one oxidizing agent (c) in a solution containing the basic compound (b). [Chemical 5] (In the above formula, R _{9 to} R ₁₂ , R _{13 to} R _16, and R ₁₇
To R ₂₀ are each a substituent of R ₁ to R ₁ in the general formula (1).
R ₄ or a substituent corresponding to R _{5 to} R ₈ in the general formula (3), and further R _{9 to} R ₁₂ , R _{13 to} R ₁₆ , R.
One or two of the three groups of _{17 to} R ₂₀ are substituents corresponding to R _{1 to} R ₄ in the general formula (1). Ht
Is the same as the general formula (1) and the general formula (3),
The X ^a- is, chlorine ion, bromine ion, iodine ion,
Fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methanesulfonate ion, p-toluenesulfonate ion, At least one anion selected from a group of 1 to 3 valent anions consisting of a trifluoroacetate ion and a trifluoromethanesulfonate ion, and a is X
Is an integer of 1 to 3, m is a doping rate, and its value is 0 to 3.0. ] The manufacturing method of the heterocyclic compound trimer shown by these. 3. The method for producing a heterocyclic compound trimer according to claim 1, wherein the heterocyclic compound trimer has a laminated structure.