JP3438047B2 - Novel bispyrrolylazophenylene compound, method for producing the same, and polymer of the compound - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel bispyrrolylazophenylene compound and a method for producing the same. The present invention also relates to a novel poly (bispyrrolylazophenylene) compound and a battery using the poly (bispyrrolylazophenylene) compound.

[0002]

2. Description of the Related Art Many compounds having an azo group in the molecule have biological activity and are important as intermediates for the production of agricultural chemicals and pharmaceuticals.
Developer for heat-sensitive recording material, color former, photoconductive agent, EL material,
It is also useful as a diazonium salt or as an intermediate for the production thereof, and has been actively studied.

Since the above-mentioned azo compounds are extremely reactive, most of the conventional research subjects are those having a benzene ring structure which is easy to synthesize, and highly reactive hetero compounds containing nitrogen, oxygen or sulfur. Ring-containing compounds have been poorly synthesized. In particular, since pyrrole compounds having an electron-donating substituent at the α-position are very difficult to synthesize, pyrrole azo compounds have hardly been synthesized until now, and their properties have not been clarified.

By the way, in recent years, miniaturization of electronic equipment has progressed, and along with this, there has been a demand for development of a battery which is lightweight and exhibits excellent characteristics. Conductive polymers have attracted attention as electrode active materials for such batteries, and many polymers such as polyaniline, polypyrrole, and polythiophene have been developed so far. These polymers are generally synthesized from monomers by electrolytic oxidative polymerization or chemical oxidative polymerization. To date, most of the monomers are polyaniline, pyrrole, thiophene, and their derivatives, so the conjugated structure of the polymer backbone is composed of carbon-carbon double bonds except that polyaniline contains a nitrogen atom. It By introducing an azo group as a new structure into the main chain conjugated system composed of such a carbon-carbon double bond,
It was believed to improve stability and conductivity, and polyazophenylene was previously synthesized, but has not yielded better results than the carbon-carbon double bond system.

[0005]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a pyrrole azo compound having excellent properties as compared with conventional azo compounds and a method for producing the same.

It is another object of the present invention to provide a novel conductive polymer having an azo group in its main chain and a battery using the conductive polymer.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to achieve the above-mentioned object, and as a result, synthesized a bispyrrolylazophenylene compound for the first time, and obtained an excellent conductivity as a battery material from the compound. It was found that a hydrophilic polymer was obtained.

The present invention has the general formula (I):

[0009]

[Chemical 6]

The present invention provides a novel bispyrrolylazophenylene compound represented by the formula (wherein R, R ¹ and R ² are the same as above).

The present invention also has the following formula (II):

[0012]

[Chemical 7]

A pyrrole compound represented by the formula (wherein R, R ¹ and R ² are the same as above) is subjected to a coupling reaction with 1,4-bisdiazoniumphenylene. ):

[0014]

[Chemical 8]

The present invention provides a process for producing a novel bispyrrolylazophenylene compound represented by the formula (wherein R, R ¹ and R ² are the same as above).

Furthermore, the present invention provides the following general formula (III):

[0017]

[Chemical 9]

(In the formula, n represents an integer of 5 to 10000. R, R ¹ and R ² are the same as the above.) The poly (bispyrrolylazophenylene) compound is provided.

Furthermore, the present invention provides the following general formula (IV) obtained by doping a poly (bispyrrolylazophenylene) compound with an anion:

[0020]

[Chemical 10]

(In the formula, n, R, R ¹ and R ² are the same as above. X is an anion, m is 0.001 to 3, and a is 1, 2 or 3.) A poly (bispyrrolylazophenylene) compound is provided.

The compound of the present invention has an azo group,
Although cis-trans isomerism is conceivable at the azo group, cis type and trans type can be converted into each other, and the present invention includes both cis type and trans type.

The general formulas (I), (III) and (I
The compound of V) has R ¹ and R ² in two pyrrole residues, respectively, but these R ¹ and R ² may be the same group in the two pyrrole residues, and different substituents may be used. It may be a group.

Furthermore, the present invention provides the above general formula (III)
Alternatively, the present invention provides a battery characterized by using the poly (bispyrrolylazophenylene) compound of (IV) as an electrode active material. The battery of the present invention has the general formula (III)
One or more of the polymers of (IV) and (IV) can be used.

In the poly (bispyrrolylazophenylene) compound of the present invention represented by the general formulas (III) and (IV), the value of n is an integer of 5 to 10000, preferably 10
An integer of 1000 is good. In the poly (bispyrrolylazophenylene) compound of the present invention represented by the general formula (IV), the value of m is 0.002 to 3, preferably 0.01 to 2
Is good. The preferable value of a is 1.

As the anion represented by X, organic acid ions such as p-toluenesulfonate ion and trifluoromethanesulfonate ion, halogen ions such as fluorine ion, chlorine ion, bromine ion and iodine ion,
Examples thereof include inorganic acid ions such as perchlorate ion, tetrafluoroborate ion, fluoroarsenate ion, and sulfate ion.

In the present invention, the alkyl group represented by R is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group. Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, etc. The straight-chain or branched alkyl groups of the number 1 to 20 are mentioned.

In the present invention, the aralkyl group represented by R is-(CH ₂ ) ₁ --Ar (where l is 1 to 1).
5 represents an integer of 5, and Ar represents a phenyl group which may have a substituent, a biphenyl group which may have a substituent or a naphthyl group which may have a substituent). l is preferably an integer of 1 to 10, more preferably an integer of 1 to 5.

Examples of the aryl group represented by R include a phenyl group which may have a substituent, a biphenyl group which may have a substituent and a naphthyl group which may have a substituent. Can be mentioned.

Examples of the acyl group represented by R include acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, oleyl group, stearoyl group, eicosanoyl group. 2 to 20 carbon atoms such as groups
And an acyl group which may have a straight-chain or branched double bond.

The alkenyl group represented by R is an allyl group, a 2-butenyl group, a 3-butenyl group or a 2-methyl-group.
2-propenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonel group, decel group, undecel group, dodecel group, tridecel group, tetradecel group,
Examples thereof include a straight chain or branched alkenyl group having 3 to 20 carbon atoms, such as a pentadecel group, a hexadecel group, a heptadecell group, an octadecel group, a nonadecell group, and an eicocel group. The double bond does not directly bond to the nitrogen of pyrrole.

The alkynyl group represented by R includes a propargyl group, a 3-butynyl group, a 2-butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group,
Having a straight or branched chain having 3 to 20 carbon atoms such as nonynyl group, decynyl group, undecynyl group, dodecynyl group, tridecynyl group, tetradecynyl group, pentadecynyl group, hexadecynyl group, heptadecynyl group, octadecynyl group, nonadecynyl group, eicosinyl group An alkynyl group may be mentioned. The triple bond does not directly bond to the nitrogen of pyrrole.

The alkylsulfonyl group represented by R is R
^a —SO ₂ — ( ^Ra is the same as the alkyl group represented by R above).

The arylsulfonyl group represented by R is R
^b —SO ₂ — (R ^b is the same as the aryl group represented by R above).

Among the aryl groups (Ar) of the above aryl group or aralkyl group, among the phenyl groups which may have a substituent, the phenyl group having a substituent means
A phenyl group having 1 to 5, preferably 1 to 3 substituents. As the substituent, a hydroxyl group, a methoxy group,
Ethoxy group, n-propoxy group, isopropoxy group, n
An alkoxy group having 1 to 4 carbon atoms such as a butoxy group, an isobutoxy group and a t-butoxy group, a methyl group, an ethyl group, n
An alkyl group having a straight chain or a molecule having 1 to 4 carbon atoms such as propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyano group, nitro group, carboxyl group, Methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group,
a lower alkoxycarbonyl group having a straight chain or molecule having 2 to 5 carbon atoms such as an n-butoxycarbonyl group and a t-butoxycarbonyl group, a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group,
Examples thereof include an alkylcarbonyloxy group having 2 to 5 carbon atoms such as an n-butylcarbonyloxy group and a t-butylcarbonyloxy group. When the substituent is a hydroxyl group, it is preferably protected with an appropriate protective group such as an acetyl group.

In the aryl group (Ar) of the above aryl group or aralkyl group, among the above-mentioned naphthyl groups which may have a substituent, the naphthyl group having a substituent is 1 to 7 It is preferably a naphthyl group having 1 to 5, and more preferably 1 to 3 substituents. Moreover, among the above-mentioned biphenyl groups which may have a substituent, the biphenyl group having a substituent has 1 to 9, preferably 1 to 5, more preferably 1 to 3 substituents. It has a biphenyl group. Examples of the substituent of the naphthyl group and the biphenyl group include the substituents of the above phenyl group.

1 to 20 carbon atoms represented by R ¹ or R ²
As the alkyl group of, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, Nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, alkyl groups having a branch such as eicosyl group, and the like,
Preferably, a hexyl group, a heptyl group and an octyl group which may have a branch are mentioned.

The compound represented by the general formula (I) is obtained by reacting the pyrrole compound represented by the formula (II) with 1,4-bisdiazoniumphenylene in a solvent as shown in the following reaction process formula (A). Obtained by coupling in the presence or absence of additives.

<Reaction Process Formula (A)>

[0040]

[Chemical 11]

[In the formula, X ¹ represents an anion. R, R ¹
And R ² are the same as above. In the above reaction process formula (A), the pyrrole compound (II) may be a single compound or a mixture of two or more pyrrole compounds.

The anion represented by X ¹ is C
l ⁻ , Br ⁻ , I ⁻ , HSO ₄ ⁻ , BF ₄ ⁻ or H ₂
PO ₄ ^- is mentioned.

As additives in the above reaction, sodium acetate, potassium acetate, lithium acetate, magnesium acetate, calcium acetate, sodium trifluoroacetate,
Examples thereof include alkali metal or alkaline earth metal salts of carboxylic acids such as sodium propionate and sodium benzoate. The additive is approximately 0.8 with respect to the pyrrole compound.
~ 1.2 molar equivalents are used. The additive is preferably used when R is an alkyl group, and need not be used when R is a phenyl group which may have a substituent.

Of the pyrroles which may have an alkyl group at the 3- and / or 4-position, 3-methylpyrrole, 3,4-dimethylpyrrole, 3-phenylpyrrole and 3,4-diphenylpyrrole are It is a known compound. Other pyrrole derivatives have the following reaction process formula (B)
And according to the reaction process formula (C).

<Reaction Process Formula (B)>

[0046]

[Chemical 12]

[In the formula, R ^c represents a linear or branched alkyl group having 1 to 19 carbon atoms. R ¹ has 2 to 2 carbon atoms
The alkyl group of 0 is shown. Ts represents a p-toluenesulfonyl group. <Reaction Process Formula (C)>

[0048]

[Chemical 13]

[In the formula, R ^c represents a linear or branched alkyl group having 1 to 19 carbon atoms. R ¹ and R ² represent an alkyl group having 2 to 20 carbon atoms or a phenyl group. T
s represents a p-toluenesulfonyl group. <Reaction Process Formula (D)>

[0050]

[Chemical 14]

[In the formula, R, R ¹ and R ² are the same as defined above. X represents a chlorine atom, a bromine atom or an iodine atom. ] N-p-toluenesulfonylpyrrole (3) is obtained by reacting pyrrole (1) and p-toluenesulfonyl chloride (TsCl) (2) in DMF in the presence of NaH. N-p-toluenesulfonyl pyrrole (3) in the presence of SnCl ₄ R ^c COCl and Fr
By carrying out the iedel-Crafts reaction, an acylated product of the general formula (4) is obtained. Next, the acylated product (4) is hydrolyzed in an aqueous sodium hydroxide solution to detosylate to obtain a compound (5). Compound (5) is TH
Reduction with LiAlH ₄ in F gives the 3-alkylpyrrole (6).

P-Toluenesulfonyl chloride (2)
And NaH are used in an amount of 1 to 1.2 equivalents based on 1 mol of pyrrole (1), the temperature is -10 to 0 ° C, and the reaction time is 1 to 5 hours. In the subsequent Friedel-Crafts reaction, an excessive amount of R ^c COCl was used, and about 0.4 to 0.5 equivalent of SnCl ₄ was used per 1 mol of the compound (3), the temperature was −10 to 50 ° C., and the reaction time was 1 Do it in about 5 hours. For the next hydrolysis, 0.5 equivalent or more of NaOH is used, the temperature is 30 to 50 ° C., and the reaction time is about 1 to 5 hours. In the next reduction reaction, Li
Using 1 to 1.1 equivalents of AlH ₄ , the temperature is 0 to 25 ° C., and the reaction time is 10 to 25 hours.

3,4-Dialkylpyrrole was reacted according to the following reaction process formula (C) using 3-alkylpyrrole (6) as a starting material under the same conditions as in the above reaction process formula (B). By carrying out, 3,4-di-substituted pyrrole (10) is obtained.

The N-substituted pyrrole compound (IIb) can be produced by a known method. Specifically, for example, it has a substituent at the 3-position and / or 4-position as shown in the reaction formula (D). By mixing strong pyrrole (IIa) with a strong base such as metallic potassium, metallic sodium, potassium t-butoxy, NaH, butyllithium, phenyllithium, sodium amide in a solvent with stirring, and then reacting with an alkyl halide. can get. The alkyl halide and the base are used in an amount of about 1 to 1.2 equivalents based on 1 mol of pyrrole (IIa) which may have a substituent at the 3- and / or 4-position, and the temperature is -10 to 0 ° C. The time is about 1 to 5 hours.

1,4-bisdiazoniumphenylene is
It can be obtained by tetrazotization according to a conventional method such as reacting 1,4-phenylenediamine in the presence of sodium nitrite, sulfuric acid and phosphoric acid. This tetrazotization reaction solution can be used as it is for the coupling reaction, but preferably, it is used after adding an aqueous solution of, for example, tetrafluoroboric acid, sodium tetrafluoroborate or the like to isolate it as a diazonium salt compound.

In the coupling reaction, the pyrrole compound (II) and, if necessary, an additive are dissolved in a solvent under an inert gas stream, and the solution is cooled in a dry ice-methanol bath to about a pyrrole content. The target bisdiazo compound (I) is obtained by gradually adding 0.5 molar equivalent of 1,4-bisdiazoniumphenylene. As the reaction solvent, alcohols such as methanol, ethanol and propanol, acetonitrile, dimethylformamide,
Examples thereof include polar solvents such as dimethyl sulfoxide, propylene carbonate and tetrahydrofuran, and halogen-based solvents such as methylene chloride and chloroform, and alcohols and dimethylformamide are preferable.

The concentration of the raw material pyrrole compound (II) was
About 0.01 to 0.5 mol / liter, preferably 0.1.
It is about 1 to 0.2 mol / liter. The reaction temperature is −
It is about 40 ° C to 0 ° C, preferably about -25 ° C to -5 ° C, and the reaction time is about 0.5 to 4 hours, preferably 1 to
It takes about 2 hours.

A red-brown bisdiazo compound is obtained by reacting under the conditions as described above and adding a large amount of water to the reaction solution after the reaction.

The poly (bispyrrolylazophenylene) compound of the present invention represented by the general formula (IV) has, for example, the general formula (I)

[0060]

[Chemical 15]

It can be obtained by chemically polymerizing bispyrrolylazophenylene represented by the formula (wherein R, R ¹ and R ² are the same as above) in a solvent using an oxidizing agent. Examples of the solvent for this polymerization reaction include alcohols such as methanol, ethanol and isopropanol, ethers such as tetrahydrofuran, carbonates such as propylene carbonate, nitro compounds such as nitrobenzene and nitromethane, and other acetonitrile, dimethylformamide, dimethyl sulfoxide and the like. , Preferably nitrobenzene, nitromethane, propylene carbonate or tetrahydrofuran. The solvent has a concentration of the bispyrrolylazophenylene of the general formula (I) of 0.01
The amount is about 1 to 1 mol / liter, preferably about 0.1 to 0.5 mol / liter.

As the oxidizing agent for polymerization, generally used oxidizing agents can be widely used. Specifically, ferric chloride,
Transition metal salts such as ferric perchlorate, silver chloride, silver perchlorate, cupric chloride, copper perchlorate, and copper tetrafluoroborate,
Examples thereof include hydrogen peroxide, quinones such as benzoquinone, and naphthoquinone. Iron compounds such as ferric chloride and ferric perchlorate and silver compounds such as silver chloride and silver perchlorate are preferable. The oxidizing agent is used in an amount of about 1 to 5 mol, preferably about 2 to 4 mol, per 1 mol of the raw material (monomer). The polymerization temperature is about 0 to 100 ° C, preferably 25 to 8
It is about 0 ° C., and the reaction time is about 1 to 30 hours, preferably about 2 to 24 hours.

A black poly (bispyrrolylazophenylene) compound powder is obtained by reacting under the conditions as described above, and purified by solvent washing.

The monomer to be subjected to the oxidative polymerization may be a purified one, or may be used as it is without isolating the reaction liquid state of the above reaction which is reacted with 1,4-bisdiazoniumphenylene. .

The poly (bispyrrolylazophenylene) compound represented by the general formula (IV) is obtained by electrolytically polymerizing the bispyrrolylazophenylene compound represented by the general formula (I) in an electrolytic solution containing a supporting electrolyte. It can also be obtained by doing.

The solvent for this electropolymerization is preferably one that dissolves the supporting electrolyte well, and specifically, alcohols such as methanol, ethanol and isopropanol, ethers such as tetrahydrofuran, carbonates such as propylene carbonate, nitrobenzene and nitromethane. And nitro compounds such as nitrobenzene, nitromethane, dimethylformamide, dimethylsulfoxide, etc., and preferably acetonitrile, propylene carbonate or tetrahydrofuran. The amount of the solvent is such that the concentration of the bispyrrolylazophenylene compound as a monomer is about 0.01 to 1 mol / liter, preferably about 0.1 to 0.5 mol / liter.

The supporting electrolyte used for this electrolytic oxidation is preferably a salt which is soluble in a solvent and easily dissociates ions, and specific examples thereof include tetrabutylammonium perchlorate, tetraethylammonium perchlorate and lithium perchlorate. Perchlorates, sodium tetrafluoroborate, lithium tetrafluoroborate, tetraethylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, etc., tetrafluoroborate, lithium iodide, etc., iodates, bromide Examples thereof include hydrobromide salts such as lithium, and tetrabutylammonium perchlorate, tetraethylammonium tetrafluoroborate and tetrabutylammonium tetrafluoroborate are preferable. The concentration of this supporting electrolyte is usually 0.01.
~ 1.0 mol / liter, preferably 0.05 ~
About 0.5 mol / liter is good.

The concentration of the bispyrrolylazophenylene compound of the general formula (I) is usually about 0.01 to 1.0 mol / liter, preferably 0.05 to 0.5 mol / liter.

The electrolysis method may be a constant potential method, a constant current method or a potential scanning method, and it may be a two-pole method or a three-pole method. The SCE or silver / silver chloride electrode is preferred as the reference electrode used when performing the three-electrode method. Also,
Conductive glass, Pt, carbon electrodes, etc. can be used for the electrodes. For example, the current density in the case of the constant current method is about 0.01 to 10 mA / cm ² , and preferably 0.1 to 10 mA / cm ^2.
It is about 1 mA / cm ² .

A black film of a poly (bispyrrolylazophenylene) compound is deposited on the surface of the anode by applying a direct current between the electrodes under the above conditions.

The poly (bispyrrolylazophenylene) compound represented by the general formula (III) is obtained by electrolytically reducing the anion-doped poly (bispyrrolylazophenylene) compound represented by the general formula (IV). It can also be obtained. This reduction reaction can be carried out under the same conditions as in the above electrolytic oxidation polymerization.

The obtained poly (bispyrrolylazophenylene) compounds of the general formulas (III) and (IV) are purified by washing with a solvent.

By using a poly (bispyrrolylazophenylene) compound as a positive electrode and a conductive polymer such as polyacetylene, polyparaphenylene, or polypyridine carbon material as a negative electrode active material, a polymer secondary battery or Li A
A lithium secondary battery or the like can be manufactured by using an alloy with 1, Mg, Pb, Si, Ga, In.

Preferred compounds of the present invention are compounds in which R is an alkyl group or a phenyl group which may have a substituent.

[0075]

INDUSTRIAL APPLICABILITY The bisdiazo compound (I) of the present invention is useful as an intermediate for the production of agricultural chemicals, pharmaceuticals and dyes, and is also a developer for pressure and heat sensitive recording materials, a color former, a photoconductive agent and an EL material. It is also useful as a diazonium salt, or as an intermediate for the production thereof.

Since the compound (I) of the present invention has pyrrole residues at both ends, it can easily give a novel conductive polymer by electrolytic polymerization or chemical polymerization which is a conventional method.

Further, according to the production method of the present invention, the useful bisdiazo compound (I) can be obtained in a high yield.

Further, the poly (bispyrrolylazophenylene) (III) and (IV) compounds of the present invention are electrochemically active and have high stability, and this poly (bispyrrolylazophenylene) is used. As a result, a battery that is lightweight and exhibits excellent characteristics can be obtained.

[0079]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0080]

Example 1 2.16 g of p-phenylenediamine was dissolved in a phosphoric acid solution (d = 1.7) while heating in a three-necked flask equipped with a stirrer, a condenser and a thermometer, and this solution was dissolved. After cooling to about -5 ° C, 30 ml of concentrated sulfuric acid and nitrosylsulfuric acid synthesized from 2.88 g of sodium nitrite were added dropwise and reacted for 30 minutes. Further, 40 ml of a tetrafluoroboric acid solution (42%) was added to this solution, and the precipitated crystals were filtered, washed with methanol, and dried under reduced pressure to obtain 1,4-bisdiazoniumphenylene.

0.2 g of pyrrole (3
mmol) and 0.25 g of sodium acetate (3.6 m
mol) in 15 ml of methanol, 1,4-bisdiazonium phenylene tetrafluoroborate 0.7
1 g (1.5 mmol) was gradually added, and stirring was performed for 1.5 hours to carry out a coupling reaction. Next, this solution is filtered, and 50 ml of cold water is added to the filtrate to precipitate a bisazo compound, which is suction filtered and further washed with water.
By drying under reduced pressure at 0 ° C. for 5 hours, 0.38 g of the desired product, bispyrrolylazophenylene, was obtained.

The analytical data of the obtained bispyrrolylazophenylene are shown below.

FT-IR (KBr) ν (cm ^-1 ): 3
419, 1536, 1457, 1360, 12
54, 1104, 1078, 1038, 972
871, 855, 736, 568, 543
512 ¹ H-NMR ((CD ₃ ) ₂ CO) (ppm): 11.
5 (2H, s), 7.88 (4H, s), 7.15
(2H, m), 6.98 (2H, dd), 6.40
(2H, dd) ¹³ C-NMR ((CD ₃ ) ₂ CO) (ppm): 15
4.8, 147.8, 125.0, 124.7,
116.0, 112.9 UV (CH ₃ OH): max. 454.7 nm Elemental analysis C H N theoretical value (%) 63.64 4.54 31.82 measured value (%) 64.10 4.44 31.46 In addition, the following analytical instruments were used.

NMR: JNM-GX270 type (270M
Hz, manufactured by JEOL) IR: Nicolet 20SXC (manufactured by Nicolet) UV-VIS: U-3140 type (manufactured by Hitachi, Ltd.) ESCA: Shimadzu 850 Conductivity meter: Mitsubishi Petrochemical Loresta AP Elemental analysis: PERKIN ELMER 2400

[0085]

Example 2 0.30 g of bispyrrolylazophenylene was obtained in the same manner as in Example 1 except that the reaction solvent was changed to dimethylformamide.

[0086]

Example 3 A compound of the present invention in which R is a methyl group was obtained in the same manner as in Example 1 except that N-methylpyrrole was used instead of pyrrole.

Obtained bisazo (N-methylpyrrolyl)
The analytical data of phenylene is shown below.

FT-IR (KBr) ν (cm^-1): 1
511, 1498, 1358, 1326, 12
41, 1203, 1164, 1083, 104
5, 848, 710, 531, 416 ¹ H-NMR ((CD₃)₂CO) (ppm): 7.9
3 (4H, s), 7.20 (2H, m), 6.60
(2H, dd), 6.29 (2H, dd), 4.00
(6H, s) UV (CH₃CN): max. 473.4 nm

[0089]

Example 4 A compound of the present invention in which R is an n-octyl group was obtained in the same manner as in Example 1 except that N- (normal octyl) pyrrole was used instead of pyrrole. N- (Normal octyl) pyrrole was obtained by reacting pyrrole and metallic potassium in THF to form a potassium salt, and reacting the solution with n-octyl bromide.

The analytical data of the obtained bisazo (N-octylpyrrolyl) phenylene are shown below.

FT-IR (KBr) ν (cm ^-1 ): 3
103, 2926, 2854, 1508, 14
90, 1457, 1351, 1242, 119
8, 1147, 1111, 1063, 1024
849, 725, 611 ¹ H-NMR ((CD ₃ ) ₂ CO) (ppm): 7.9
2 (4H, s), 7.26 (2H, dd), 6.7
0 (2H, dd), 6.32 (2H, dd), 4.
46 (2H, t), 1.89 (2H, m), 1.4
2-1.10 (10H, m), 0.84 (3H, t) ¹³ C-NMR ((CD ₃ ) ₂ CO) (ppm): 15
4.8 147.2 128.0 123.3 11
1.2 100.946.9 32.4 32.3 2
9.9 29.7 27.3 23.2 14.6 UV (CH 3 CN): max. 478.8 nm

[0092]

Example 5 A compound of the present invention in which R is a stearyl group was obtained in the same manner as in Example 1 except that N-stearylpyrrole was used instead of pyrrole. N-stearylpyrrole was obtained in the same manner as in Example 4 except that 1-iodooctadecane was used instead of n-octyl bromide.

[0093]

Example 6 A compound of the present invention in which R is a phenyl group was obtained in the same manner as in Example 1 except that N-phenylpyrrole was used instead of pyrrole.

The analytical data of the obtained bisdiazo (N-phenylpyrrolyl) phenylene are shown below.

UV (CH ₃ CN): max. 445.8
nm

[0096]

Example 7 R was the same as in Example 1 except that N- (2-methoxyphenyl) pyrrole was used instead of pyrrole.
A compound of the present invention having a 2-methoxyphenyl group was obtained.

[0097]

Example 8 A compound of the present invention in which R is a 2,4-dimethylphenyl group is obtained in the same manner as in Example 1 except that N- (2,4-dimethylphenyl) pyrrole is used instead of pyrrole. It was

[0098]

Example 9 A compound of the present invention in which R is an acetyl group was obtained in the same manner as in Example 1 except that N-acetylpyrrole was used instead of pyrrole.

[0099]

Example 10 A compound of the present invention in which R is a palmityl group was obtained in the same manner as in Example 1 except that N-palmitylpyrrole was used instead of pyrrole. N-palmitylpyrrole was obtained in the same manner as in Example 4 except that palmitoyl chloride was used instead of n-octyl bromide.

[0100]

Example 11 A compound of the present invention in which R is a benzyl group was obtained in the same manner as in Example 1 except that N-benzylpyrrole was used instead of pyrrole.

[0101]

[Example 12] The same procedure as in Example 1 except that N- (p-methoxybenzyl) pyrrole was used instead of pyrrole.
A compound of the present invention in which R is a p-methoxybenzyl group was obtained. N- (p-methoxybenzyl) pyrrole was obtained in the same manner as in Example 4 except that p-methoxybenzyl bromide was used instead of n-octyl bromide.

[0102]

Example 13 R was the same as Example 1 except that N- (2-phenylethyl) pyrrole was used instead of pyrrole.
A compound of the present invention having a 2-phenylethyl group was obtained.
N- (2-phenylethyl) pyrrole was obtained in the same manner as in Example 4 except that 2-phenylethyl bromide was used instead of n-octyl bromide.

[0103]

Example 14 A compound of the present invention in which R is an allyl group was obtained in the same manner as in Example 1 except that N-allylpyrrole was used instead of pyrrole.

[0104]

Example 15 R was the same as in Example 1 except that N- (phenylsulfonyl) pyrrole was used instead of pyrrole.
To obtain a compound of the present invention in which is a phenylsulfonyl group.

[0105]

Example 16 A compound of the present invention in which R ¹ is a methyl group was obtained in the same manner as in Example 1 except that 3-methylpyrrole was used instead of pyrrole.

[0106]

Example 17 R ¹ and R were prepared in the same manner as in Example 1 except that 3,3-dimethylpyrrole was used instead of pyrrole.
A compound of the invention in which ² is a methyl group is obtained.

[0107]

Example 18 A compound of the present invention in which R ¹ is a phenyl group was obtained in the same manner as in Example 1 except that 3-phenylpyrrole was used instead of pyrrole.

[0108]

Example 19 A compound of the present invention in which R ¹ is an octyl group was obtained in the same manner as in Example 1 except that 3-octylpyrrole was used instead of pyrrole.

[0109]

Example 20 A compound of the present invention in which R ¹ is a stearoyl group was obtained in the same manner as in Example 1 except that 3-stearoylpyrrole was used instead of pyrrole.

[0110]

Example 21 A solution of 0.26 g of bispyrrolylazophenylene in which R is a hydrogen atom dissolved in 5 cc of acetonitrile was cooled to 0 ° C. and 0.28 g of ferric chloride (1.8 mm)
ol) was added dropwise to a suspension of 5 cc of acetonitrile. Then, the mixture was reacted for 3 hours to obtain a black powder. Further, this powder was washed with methanol and acetone, and then dried under reduced pressure at 100 ° C. to give poly (bispyrrolylazophenylene) at 0.
20 g was obtained. The product was pelletized and the conductivity was measured. As a result, it was 10 ^-2 S / cm. After the pellets were left in the air for several months, the conductivity was measured again, but the measured values did not change.

The FT-IR and elemental analysis data of the product obtained as a result of the above polymerization reaction are shown below.

FT-IR (KBr) ν (cm ^-1 ):
1590, 1541, 1492, 1457, 1
428, 1330, 1233, 1164, 112
3, 1036, 945, 836, 783, 6
69 From these values, it is found that the polymer has bisazopyrrolylphenylene as a repeating unit.

Further, as shown in the following table, from the elemental analysis values, carbon / nitrogen (molar ratio) = 2.39 (theoretical value 2.
The result of 33) was obtained, and it was confirmed that this product was a polymer having the desired product, bisazopyrrolylphenylene, as a repeating unit.

[0114] However, the theoretical value is a value when X: dopant is present in 20.1% of the whole.

[0115]

[Example 22] 0.50 g (1.3 mmo) of copper perchlorate was added to a nitromethane solution (5 cc) of 0.13 g (0.5 mmol) of bispyrrolylazophenylene in which R is a hydrogen atom.
1) was added and the mixture was reacted at 25 ° C. for 24 hours to obtain a black solid. Next, this powder was washed with methanol and acetone, and then dried under reduced pressure at 100 ° C. to obtain 0.16 g of poly (bispyrrolylazophenylene).

FT-IR (KBr) ν (cm ^-1 ):
1577, 1540, 1506, 1496, 1
334, 1306, 1254, 1227, 112
0, 1109, 1046, 949, 843,
768 However, the theoretical value is the value when X: dopant is present at 18.9% of the total.

The obtained product was pelletized and the conductivity was measured. As a result, it was 10 ^-6 S / cm. Further, by doping the pellets with sulfuric acid, the conductivity becomes 10 ^-3 S
/ Cm.

[0118]

Example 23 The target poly (bispyrrolylazophenylene) (0.05 g) was obtained in the same manner as in Example 21 except that iron perchlorate was used instead of copper perchlorate. The obtained product was pelletized and the conductivity was measured. As a result, 10
It was ^-6 S / cm.

[0119]

Example 24 0.14 g of the target poly (bispyrrolylazophenylene) was prepared in the same manner as in Example 21 except that copper tetrafluoroborate was used instead of copper perchlorate and acrylonitrile was used instead of nitromethane. Obtained. The obtained product was pelletized and the conductivity was measured. As a result, it was 10 ⁻⁷ S / cm.

[0120]

Example 25 0.17 g of the target poly (bispyrrolylazophenylene) was obtained in the same manner as in Example 21 except that the reaction conditions were 60 ° C. and 3 hours. The obtained product was pelletized and the conductivity was measured. As a result, 10 ⁻⁶ S / c
It was m. Further, by doping the pellet with sulfuric acid, the conductivity was increased to 10 ^-1 S / cm.

[0121]

Example 26 The reaction was carried out at 60 ° C. for 3 hours, and the target poly (bispyrrolylazophenylene) was prepared in the same manner as in Example 21 except that copper tetrafluoroborate was used instead of copper perchlorate. 0.15 g was obtained. The obtained product was pelletized and the conductivity was measured. As a result, 10 ⁻⁵ S / c
It was m. Further, by doping the pellet with sulfuric acid, the conductivity was increased to 10 ⁻³ S / cm.

[0122]

[Example 27] 0.50 g of copper perchlorate was added to 5 cc of a nitromethane solution containing 0.17 g of bispyrrolylazophenylene having a methyl group as R and reacted at 60 ° C for 6 hours to obtain a black solid. Next, this powder was washed with methanol and acetone and dried under reduced pressure at 100 ° C.
0.06 g of poly (bispyrrolylazophenylene) having a methyl group was obtained. The obtained product was pelletized and the conductivity was measured. As a result, it was 10 ⁻⁷ S / cm. Further, by doping the pellet with sulfuric acid, the conductivity becomes 10
It rose to ^-3 S / cm.

[0123]

Example 28 0.09 g of the intended poly (bispyrrolylazophenylene) in which R was a methyl group was obtained in the same manner as in Example 27 except that the reaction conditions were 100 ° C. and 4 hours.
The obtained product was pelletized and the conductivity was measured. As a result, it was 10 ⁻⁷ S / cm. Further, by doping the pellet with sulfuric acid, the conductivity was increased to 10 ⁻³ S / cm.

[0124]

Example 29 To a mixed solution of 0.21 g of bispyrrolylazophenylene in which R is a phenyl group, 2 cc of nitromethane and 3 cc of nitrobenzene, 0.50 g of copper perchlorate was added, and the mixture was reacted at 60 ° C. for 6.5 hours. A black solid was obtained. Next, after washing this powder with methanol and acetone, 1
By drying under reduced pressure at 00 ° C., 0.08 g of poly (bispyrrolylazophenylene) in which R was a phenyl group was obtained.
The obtained product was pelletized and the conductivity was measured. As a result, it was 10 ⁻⁷ S / cm. Further, by doping the pellets with sulfuric acid, the conductivity increased to 10 ⁻⁵ S / cm.

[0125]

Example 30 0.17 g of the intended poly (bispyrrolylazophenylene) in which R was a phenyl group was obtained in the same manner as in Example 24 except that the reaction conditions were 100 ° C. and 3 hours. The obtained product was pelletized and the conductivity was measured. As a result, it was 10 ⁻⁷ S / cm. Further, by doping the pellet with sulfuric acid, the conductivity was increased to 10 ⁻³ S / cm.

[0126]

Example 31 To a mixed solution of 0.24 g of bispyrrolylazophenylene in which R is an octyl group, 2 cc of nitromethane and 3 cc of nitrobenzene, 0.50 g of copper perchlorate was added and reacted at 25 ° C. for 24 hours to give a black mixture. A solid was obtained. Next, after washing this powder with methanol and acetone, 1
By drying under reduced pressure at 00 ° C., 0.27 g of poly (bispyrrolylazophenylene) in which R was an octyl group was obtained.
The obtained product was pellet-molded and the conductivity was measured. As a result, it was 10 ^-6 S / cm.

[0127]

Example 32 0.23 g of the target poly (bispyrrolylazophenylene) in which R was an octyl group was obtained in the same manner as in Example 26 except that the reaction conditions were 100 ° C. and 3 hours. The obtained product was pelletized and the conductivity was measured. As a result, it was 10 ^-7 S / cm.

..

Example 33 A bispyrrolylazophenylene solution in which R is a stearyl group obtained in the same manner as in Example 5 was used in place of the bispyrrolylazophenylene solution in which R was a hydrogen atom used in Example 21. As a result of carrying out polymerization in the same manner as in Example 21, a polymer of the present invention in which R was a stearyl group was obtained.

[0129]

[Example 34] A bispyrrolylazophenylene solution in which R is a 2-methoxyphenyl group obtained in the same manner as in Example 7 in place of the bispyrrolylazophenylene solution in which R is a hydrogen atom used in Example 21 As a result of carrying out polymerization in the same manner as in Example 21 using the solution, a polymer of the present invention in which R was a 2-methoxyphenyl group was obtained.

[0130]

[Example 35] A bispyrrolylazophenylene solution in which R is a hydrogen atom used in Example 21 was replaced by a procedure similar to that in Example 8 in which R was a 2,4-dimethylphenyl group bispyrrolyl group. Polymerization was performed in the same manner as in Example 21 using an azophenylene solution, and as a result, a polymer of the present invention in which R was 2,4-dimethylphenyl group was obtained.

[0131]

Example 36 A bispyrrolylazophenylene solution in which R is an acetyl group obtained in the same manner as in Example 9 is used in place of the bispyrrolylazophenylene solution in which R is a hydrogen atom used in Example 21. As a result of carrying out polymerization in the same manner as in Example 21, a polymer of the present invention in which R was an acetyl group was obtained.

[0132]

Example 37 A bispyrrolylazophenylene solution in which R is a palmityl group obtained in the same manner as in Example 10 was used in place of the bispyrrolylazophenylene solution in which R was a hydrogen atom used in Example 21. As a result of carrying out polymerization in the same manner as in Example 21, a polymer of the present invention in which R was a palmityl group was obtained.

[0133]

Example 38 A bispyrrolylazophenylene solution in which R is a benzyl group obtained in the same manner as in Example 11 is used in place of the bispyrrolylazophenylene solution in which R is a hydrogen atom used in Example 21. As a result of carrying out polymerization in the same manner as in Example 21, a polymer of the present invention in which R was a benzyl group was obtained.

[0134]

[Example 39] A bispyrrolylazophenylene solution in which R is a p-methoxybenzyl group obtained in the same manner as in Example 12 instead of the bispyrrolylazophenylene solution in which R is a hydrogen atom used in Example 21. As a result of carrying out polymerization in the same manner as in Example 21 using the solution, a polymer of the present invention in which R was a p-methoxybenzyl group was obtained.

[0135]

[Example 40] A bispyrrolylazophenylene having R is a 2-phenylethyl group obtained in the same manner as in Example 13 instead of the bispyrrolylazophenylene solution in which R is a hydrogen atom used in Example 21. As a result of carrying out polymerization in the same manner as in Example 21 using the solution, a polymer of the present invention in which R was a 2-phenylethyl group was obtained.

[0136]

Example 41 A bispyrrolylazophenylene solution in which R is an allyl group obtained in the same manner as in Example 14 is used in place of the bispyrrolylazophenylene solution in which R is a hydrogen atom used in Example 21. As a result of carrying out polymerization in the same manner as in Example 21, a polymer of the present invention in which R was an allyl group was obtained.

[0137]

Example 42 A solution of bispyrrolylazophenylene in which R is a phenylsulfonyl group obtained in the same manner as in Example 15 in place of the solution of bispyrrolylazophenylene in which R is a hydrogen atom obtained in Example 21. As a result of carrying out polymerization in the same manner as in Example 21, a polymer of the present invention in which R was a phenylsulfonyl group was obtained.

[0138]

Example 43 A solution of bispyrrolylazophenylene in which R ¹ is a methyl group, obtained in the same manner as in Example 16, instead of the solution of bispyrrolylazophenylene in which R is hydrogen atom obtained in Example 21. As a result of carrying out polymerization in the same manner as in Example 21, a polymer of the present invention in which R ¹ was a methyl group was obtained.

[0139]

Example 44 A bispyrrolylazophenylene solution in which R is a hydrogen atom obtained in Example 21 is replaced with a bispyrrolyl group in which R ¹ and R ² are methyl groups, which are obtained by the same operation as in Example 17. Polymerization was carried out in the same manner as in Example 21 using an azophenylene solution, and as a result, a polymer of the present invention in which R ¹ and R ² were methyl groups was obtained.

[0140]

Example 45 A solution of bispyrrolylazophenylene in which R ¹ is a phenyl group obtained in the same manner as in Example 18 in place of the solution of bispyrrolylazophenylene in which R is a hydrogen atom As a result of carrying out polymerization in the same manner as in Example 21, a polymer of the present invention in which R ¹ was a phenyl group was obtained.

[0141]

Example 46 A solution of bispyrrolylazophenylene in which R ¹ is an octyl group, which is obtained in the same manner as in Example 19, instead of the solution of bispyrrolylazophenylene in which R is a hydrogen atom obtained in Example 21 As a result of carrying out polymerization in the same manner as in Example 21, a polymer of the present invention in which R ¹ was an octyl group was obtained.

[0142]

Example 47 A bispyrrolylazophenylene solution in which R ¹ is a stearoyl group obtained in the same manner as in Example 20 in place of the bispyrrolylazophenylene solution in which R is a hydrogen atom obtained in Example 21 Was polymerized in the same manner as in Example 21 to obtain a polymer of the present invention in which R ¹ is a stearoyl group.

[0143]

Example 48 The electrode was produced by pelletizing the poly (bispyrrolylazophenylene) obtained in the above Example 21. This electrode was dipped in an acetonitrile solution containing 0.1 M LiClO ₄ and then under an argon atmosphere at -0.1.
The polybispyrrolylazophenylene compound in the neutral state represented by the general formula (I) was obtained by reduction with mA / cm ² . FT-IR of the compound thus obtained
The spectrum showed a pattern similar to that of the polymer of Example 1. Moreover, when ESCA measurement was performed, a chlorine peak derived from the dopant was not observed.

From the elemental analysis values, the result of carbon / nitrogen (molar ratio) = 2.39 (theoretical value 2.33) was obtained, and this product was the desired product, bispyrrolylazo. It was confirmed that the polymer was in a neutral state having phenylene as a repeating unit.

[0145]

[Example 49] The poly (bispyrrolylazophenylene) obtained in Example 21 was pelletized to prepare an electrode. This electrode was immersed in an acetonitrile solution containing 0.1 M LiClO _4, and the atmosphere was heated to 0 V-
As a result of scanning the potential at 1.3 V (vs. Ag / AgCl) and 0.1 v / s, a redox peak was observed at around 0.6 V, and it was confirmed that this polymer was electrochemically active. From this result, it was confirmed that the poly (bispyrrolylazophenylene) of the present invention can be applied as an electrode active material of a secondary battery.

[0146]

[Example 50] A working electrode ITO plate and a counter electrode Pt plate were immersed in a propylene carbonate solution in which tetrabutylammonium tetrafluoroammonium 0.2M and R was hydrogen atom bispyrrolylazophenylene 0.01M were dissolved.
Electrolytic oxidation was performed at a constant current of 0.05 mA / cm ^{2 in} an argon atmosphere. After 0.2 coulomb was energized, the working electrode was taken out and a blue precipitate was deposited on the surface. After washing with methanol and drying under reduced pressure, the target R was poly (bis (bis) bis (bis) bis (bis) bis (vinyl))). 1 mg of pyrrolylazophenylene) was obtained. The conductivity of this polymer was measured and found to be 10 ^-2 S / cm. The electrode on which the black precipitate was deposited was immersed in a 0.2 M tetrabutylammonium tetrafluoroborate / propylene carbonate solution, and a cyclic voltammogram was measured at a sweep rate of 50 mV / s. The result is shown in FIG.
As is clear from FIG. 12, 0.65 to 0.70 V (v
s. Ag / Ag), which shows a redox peak, indicating that this polymer is electrochemically active. As is clear from this result, the polymer of the present invention is useful as an electrode active material for batteries.

[0147]

Example 51 A working electrode ITO plate and a counter electrode Pt plate are immersed in a propylene carbonate solution in which tetrabutylammonium tetrafluoroborate 0.2M and R is hydrogen atom bispyrrolylazophenylene 0.01M are dissolved.
Electrolytic oxidation was performed at a constant potential of 1.2 V in an argon atmosphere. After 0.2 coulomb was energized, the working electrode was taken out and a blue precipitate was deposited on the surface. The precipitate was washed with methanol and dried under reduced pressure to obtain the target R
Is a hydrogen atom of poly (bispyrrolylazophenylene) 1
mg was obtained. When the conductivity of this polymer was measured, it was 3
It was S / cm.

[0148]

[Example 52] Example 52 was carried out except that bispyrrolylazophenylene in which R was a hydrogen atom was used as a monomer, bispyrrolylazophenylene in which R was a methyl group was used as a monomer, and a carbon plate was used instead of an ITO plate as a working electrode. In the same manner as in Example 51, 1 mg of poly (bispyrrolylazophenylene) in which R was a methyl group was obtained. The conductivity of this polymer was measured and found to be 1 S / cm. Further, the electrode on which the black precipitate was deposited was immersed in a 0.2M tetrabutylammonium tetrafluoroborate / propylene carbonate solution, and a cyclic voltammogram was measured at a sweep rate of 10 mV / s. The result is shown in FIG. As is clear from FIG. 13, 0.43 to 0.53 V (vs. Ag /
A redox peak is shown near Ag), indicating that the polymer is electrochemically active.

[0149]

Example 53 Example 53: Bispyrrolylazophenylene in which R is a hydrogen atom is used as a monomer, bispyrrolylazophenylene in which R is a phenyl group is used as a monomer, and a carbon plate is used instead of an ITO plate as a working electrode. In the same manner as in Example 52, 0.8 g of poly (bispyrrolylazophenylene) in which R was a phenyl group was obtained. The conductivity of this polymer was measured and found to be 10 ⁻⁵ S / cm. Further, the electrode on which the black precipitate was deposited was immersed in a 0.2M tetrabutylammonium tetrafluoroborate / propylene carbonate solution, and a cyclic voltammogram was measured at a sweep rate of 10 mV / s. The result is shown in FIG.
As is clear from FIG. 14, 0.36 to 0.45 V (v
s. Ag / Ag), which shows a redox peak, indicating that this polymer is electrochemically active.

[0150]

Example 54 Bispyrrolylazophenylene in which R is an n-octyl group is used in place of bispyrrolylazophenylene in which R is a hydrogen atom as a monomer, and ITO is used as a working electrode.
In the same manner as in Example 52 except that a carbon plate was used instead of the plate, 0.9 g of poly (bispyrrolylazophenylene) in which R was a phenyl group was obtained. The conductivity of this polymer was measured and found to be 10 ⁻⁴ S / cm. The electrode on which the blue precipitate was deposited was immersed in a 0.2 M tetrabutylammonium tetrafluoroborate / propylene carbonate solution, and a cyclic voltammogram was measured at a sweep rate of 10 mV / s. The results are shown in FIG. As is clear from FIG. 15, 0.30 to 0.46V
A redox peak is shown near (vs. Ag / Ag), indicating that this polymer is electrochemically active.

[Brief description of drawings]

FIG. 1 ¹ H—N of a compound of the present invention in which R is a hydrogen atom.
The chart of MR is shown.

FIG. 2 is ¹³ C—N of the compound of the present invention in which R is a hydrogen atom.
The chart of MR is shown.

FIG. 3 FT-I of the compound of the present invention in which R is a hydrogen atom.
The chart of R is shown.

FIG. 4 shows a UV chart of a compound of the present invention in which R is a hydrogen atom.

FIG. 5 ¹ H—N of compounds of the present invention where R is a methyl group.
The chart of MR is shown.

FIG. 6 is an FT-I of the compound of the present invention in which R is a methyl group.
The chart of R is shown.

FIG. 7 shows a UV chart of a compound of the present invention in which R is a methyl group.

FIG. 8 ¹ H— of a compound of the present invention in which R is an octyl group.
An NMR chart is shown.

FIG. 9: ¹³ C- of the compound of the present invention in which R is an octyl group
An NMR chart is shown.

FIG. 10: UV of the compound of the present invention in which R is an octyl group
Shows a chart of.

FIG. 11: FT of a compound of the present invention in which R is an octyl group
-IR chart is shown.

FIG. 12 shows a chart of a cyclic voltammogram of the compound of the present invention in which R is a hydrogen atom.

FIG. 13 shows a cyclic voltammogram chart of a compound of the present invention in which R is a methyl group.

FIG. 14 shows a chart of a cyclic voltammogram of a compound of the present invention in which R is a phenyl group.

FIG. 15 shows a cyclic voltammogram chart of a compound of the present invention in which R is an octyl group.

Front page continuation (58) Fields surveyed (Int.Cl. ⁷ , DB name) C07D 207/34 C08G 61/12 H01M 4/02 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] 1. A compound represented by the general formula (I): (Wherein, R are the same or different, .R ¹ and R ² represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an acyl group, an alkenyl group, an alkynyl group, an alkylsulfonyl group or an arylsulfonyl group, The same or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a phenyl group.) A new bispyrrolylazophenylene compound. 2. The following formula (II): (In the formula, R is a hydrogen atom, an alkyl group, an aralkyl group,
Aryl group, acyl group, alkenyl group, alkynyl group,
An alkylsulfonyl group or an arylsulfonyl group is shown. R ¹ and R ² are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a phenyl group. ) 1,4-bisdiazoniumphenylene is subjected to a coupling reaction with a pyrrole compound represented by the following general formula (I): (In the formula, R, R ¹ and R ² are the same as above.) A method for producing a novel bispyrrolylazophenylene compound. 3. General formula (III): (In the formula, n represents an integer of 5 to 10000, R is the same or different, and is a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an acyl group, an alkenyl group, an alkynyl group, an alkylsulfonyl group or an arylsulfonyl group. R ¹ and R ² are the same or different and each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a phenyl group.), A poly (bispyrrolylazophenylene) compound. 4. A compound represented by the following general formula (I) prepared by doping a poly (bispyrrolylazophenylene) compound with an anion.
V): [Chemical 5] (In the formula, X represents an anion, n represents an integer of 5 to 10000, m is 0.001 to 3, a is 1, 2 or 3, and R is the same or different and is a hydrogen atom or an alkyl. Base,
An alkalkyl group, an aryl group, an acyl group, an alkenyl group, an alkynyl group, an alkylsulfonyl group or an arylsulfonyl group is shown. R ¹ and R ² are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a phenyl group. ) The poly (bispyrrolyl azophenylene) compound represented by these. 5. A battery using the poly (bispyrrolylazophenylene) compound according to claim 3 or 4 as an electrode active material.