JP4728975B2 - Polymer compounds and their synthesis - Google Patents

Description

  The present invention relates to a novel compound, a benzodiimidazole compound, a polymer or oligomer containing the compound as a monomer component (hereinafter simply referred to as “polymer”), and a production method thereof. An object is to provide a polymer containing a benzodiimidazole unit, which is expected as a molecule, a light emitting material of an electroluminescence (EL) element, a charge injection material, a charge transport material, a charge transfer material of a fuel cell, and the like.

  Conventionally, benzimidazole having one imidazole structure in one molecule has been known in the skeleton of π-conjugated polymers (Non-Patent Documents 1 to 10), and is characterized by photoluminescence, acid-base behavior, electrical conductivity, and the like. have. However, there are no examples of a benzodiimidazole unit-containing polymer having two imidazole structures in one molecule, and functionality is expected as a novel polymer. Some benzodiimidazole compounds are known (Non-patent Document 11).

Grimmett MR. In: Katritzky AR, Rees CW, Potts KT, editors. Comprehensive cyclic chemistry, vol. 5. Oxford: Pergamon, 1984. P.345. J. Am. Chem. Soc. 1988, 110, 4105. Langmuir 1997, 13, 4807. J. Chem. Soc., Perkin Trans 2 1986, 1917. Macromol. Chem. Phys. 1998, 199, 1807. Inorg. Chem. Acta. 1999, 296, 254. Polymer 2002, 43, 1287-1293. Bull. Chem. Soc. Jpn. 1999, 72, 621. Macromol. Chem. Phys. 2001, 202, 2335-2340. Reactive & Functional Polymers 2000, 46, 49-53. Chimica Acta Turcica 1986, 14, 285-298.

  Accordingly, an object of the present invention is to provide a raw material for a polymer containing a novel benzodiimidazole unit, a polymer comprising the raw material, and a method for producing them.

（上式中のＲ₁およびＲ₂は、それぞれ独立に、Ｃ_1〜22の直鎖状または分岐鎖状アルキル基を表す。Ｒ₃およびＲ₄は、ｔ−ブトキシカルボニル基である。Ｘ₁およびＸ₂は、それぞれ独立に、水素原子、または塩素、臭素、ヨウ素のいずれかのハロゲン原子を表す。）
また本発明は、下記一般式（４）で表される化合物の窒素原子に結合している水素原子を、Ｒ₃およびＲ₄の基で置換することを特徴とする下記一般式（１）で表されるベンゾジイミダゾール化合物の製造方法を提供する。

（上式中のＲ₁およびＲ₂は、それぞれ独立に、Ｃ_1〜22の直鎖状または分岐鎖状アルキル基を表す。Ｒ₃およびＲ₄は、ｔ−ブトキシカルボニル基である。Ｘ₁およびＸ₂は、それぞれ独立に、水素原子、または塩素、臭素、ヨウ素のいずれかのハロゲン原子を表す。） The above object is achieved by the present invention described below. That is, the present invention provides a benzodiimidazole compound represented by the following general formula (1).

(R ₁ and R ₂ in the above formula each independently represent a C _1-22 linear or branched alkyl group. R ₃ and R ₄ are t-butoxycarbonyl groups. X ₁ And X ₂ each independently represents a hydrogen atom or a halogen atom of chlorine, bromine or iodine .)
Further, the present invention provides the following general formula (1), wherein a hydrogen atom bonded to a nitrogen atom of a compound represented by the following general formula (4) is substituted with R ₃ and R ₄ groups. A method for producing the represented benzodiimidazole compound is provided.

(R ₁ and R ₂ in the above formula each independently represent a C _1-22 linear or branched alkyl group. R ₃ and R ₄ are t-butoxycarbonyl groups. X ₁ And X ₂ each independently represents a hydrogen atom or a halogen atom of chlorine, bromine or iodine .)

（上式中のＲ₁およびＲ₂は、それぞれ独立に、Ｃ_1〜22の直鎖状または分岐鎖状アルキル基を表す。Ｘ₁およびＸ₂は、それぞれ独立に、水素原子、または塩素、臭素、ヨウ素のいずれかのハロゲン原子を表す。） The benzodiimidazole compound represented by the general formula (4) is reacted with 1,2,4,5-tetraaminobenzene and a compound represented by the following general formula (2) to give the following general formula (3 Benzodiimidazole compound represented by the following formula, and then halogenating the compound with a halogenating agent to halogenate the 3-position or 3,6-position of the benzene ring.

(R ₁ and R ₂ in the above formula each independently represent a C _1-22 linear or branched alkyl group. X ₁ and X ₂ are each independently a hydrogen atom, chlorine, (Represents a halogen atom of either bromine or iodine.)

（上式中のＲ₁およびＲ₂は、それぞれ独立に、Ｃ_1〜22の直鎖状または分岐鎖状アルキ基を表す。Ｘ₁およびＸ₂は、それぞれ独立に、水素原子、または塩素、臭素、ヨウ素のいずれかのハロゲン原子を表す。） Further, the benzodiimidazole compound represented by the general formula (4) is represented by a 1,2,4,5-tetraaminobenzene derivative represented by the following general formula (5) and the following general formula (2). It is obtained by reacting with a compound to be obtained.

(R ₁ and R ₂ in the above formula each independently represent a C _1-22 linear or branched alkyl group. X ₁ and X ₂ are each independently a hydrogen atom, chlorine, (Represents a halogen atom of either bromine or iodine.)

Incidentally, R _1, R ₂ in the depicted Ru linear or branched alkyl group is preferably an alkyl group having 1 to 12 carbon atoms.

  According to the present invention, it is possible to synthesize a benzodiimidazole unit-containing polymer, which is a novel compound, and this polymer can be used as a proton sensor using the phenomenon that ultraviolet absorption and fluorescence change by protons, It can be used as a polymer, a light emitting material for an EL element, a charge injection material, and a charge transport material. It is soluble in a general-purpose organic solvent, and is characterized in that a thin film of nm unit can be easily formed on a transparent electrode substrate such as a glass substrate by a spin coating method or the like.

  Next, the present invention will be described in more detail with reference to preferred embodiments. The compound represented by the general formula (1) is a novel compound and can be produced by the following first method and second method.

（上式中のＲは、前記のＲ₁〜Ｒ₄と同じ意味である。一般式（３）中の同一分子上のＲは、同一でも異なってもよい。） [First method]
A method for producing a benzodiimidazole compound represented by the following general formula (3), comprising reacting 1,2,4,5-tetraaminobenzene and a compound represented by the following general formula (2) .

(R in the above formula has the same meaning as R _{1 to} R ₄ above. R on the same molecule in general formula (3) may be the same or different.)

As a typical example of the above method, the first method will be specifically described by taking the case where R ₁ and R ₂ are heptyl groups. Preferably, 1,2,4,5-tetraaminobenzene (hydrochloride or the like) and 2 equivalents of octyl aldehyde or octanoic acid are subjected to a condensation reaction under acidic conditions. More specifically, 1,2,4,5-tetraaminobenzene (1 mol) is reacted with octylaldehyde or octanoic acid (2 mol) in the presence of an acid (1 mmol to 50 mol). The crude product obtained by the reaction is purified by extraction, distillation, column chromatography, recrystallization or the like, if necessary. As the reaction solvent, an acid itself can be used, and methanol, benzene, toluene, xylene, and other general compounds can also be used as a solvent.

  As the acid used above, sulfuric acid, hydrochloric acid, methanesulfonic acid, p-toluenesulfonic acid, polyphosphoric acid, and other acids can be used. The reaction temperature is the amount of raw materials charged, the amount of solvent, the amount of solvent Although it varies depending on the type and the like, it must be at or above the temperature at which the reaction mixture solidifies and the reaction does not proceed, and it must be at or below the temperature at which the solvent, raw materials, etc. disappear in large quantities due to volatilization. Generally, it is in the range of 20 ° C to 180 ° C, preferably 50 ° C to 150 ° C. The reaction time is about 1 to 48 hours.

When at least one of X ₁ and X _{2 in} the general formula (1) is a halogen atom, the compound of the general formula (3) obtained above is reacted with a halogenating agent to effect halogenation. By doing so, hydrogen at the 3-position or 3,6-position of the benzene ring can be substituted with halogen. The dibromination with bromine will be described as an example. Dioctylbenzo [1,2-d, 4,5-d ′] diimidazole (compound of general formula (3)) (1 mol) into an organic solution or water Bromine (Br ₂ ) (1 to 100 mol) or bromine (Br ₂ ) -catalysts are added to the dispersion and reacted. The crude product obtained by the reaction is purified by extraction, distillation, column chromatography, recrystallization or the like, if necessary. As the reaction solvent, halogenated hydrocarbons, benzene, toluene, xylene, and other general compounds can be used as the solvent. In the bromination reaction, it is also preferable to use a catalyst or an additive in order to accelerate the reaction.

Examples of catalysts and additives include mineral acids such as sulfuric acid, hydrochloric acid and hydrobromic acid, Lewis acids such as iron chloride and zinc chloride, halogens other than bromine (Br ₂ ) such as iodine (I ₂ ), iron And heavy metals such as nickel, and oxidizing agents such as hydrogen peroxide and periodic acid. In the bromination reaction, hydrobromic acid is by-produced. In order to reduce the amount of bromine (Br ₂ ) used, this by-product hydrobromic acid is used as an oxidizing agent such as hydrogen peroxide in the system. It is also preferable to carry out the reaction while returning to bromine (Br ₂ ) by oxidation. The reaction temperature varies depending on the amount of raw materials charged, the amount of solvent, the type of solvent, etc., but it must be higher than the temperature at which the reaction mixture solidifies and the reaction does not proceed, and is below the temperature at which the solvent, raw materials, etc. disappear in large quantities due to volatilization Need to be. Generally, it is in the range of -20 ° C to 100 ° C, preferably 10 ° C to 80 ° C. The reaction time is about 1 to 48 hours. The above shows an example of halogenation with bromine, but halogenation with other general halogenating agents is also possible.

（上式中のＲは、前記のＲ₁〜Ｒ₄と同じ意味である。Ｘ₁またはＸ₂は、それぞれ独立に、水素原子、または塩素、臭素、ヨウ素などのハロゲン原子を表す。一般式（４）中の同一分子上のＲは、同一でも異なってもよい。） [Second method]
A 1,2,4,5-tetraaminobenzene derivative represented by the following general formula (5) is reacted with a compound represented by the following general formula (2). The manufacturing method of the benzodiimidazole compound represented by these.

(R in the above formula has the same meaning as R _{1 to} R ₄ above. X _{1 and} X ₂ each independently represent a hydrogen atom or a halogen atom such as chlorine, bromine, iodine, etc. (Rs on the same molecule in (4) may be the same or different.)

The second method will be specifically described with reference to the case where R is a heptyl group and at least one of X ₁ and X ₂ is a halogen atom. A compound in which the 3-position or 3,6-position of 1,2,4,5-tetraaminobenzene is previously halogenated is used as a raw material, and reacted with 2 equivalents of octyl aldehyde or octanoic acid under acidic conditions. More specifically, the presence of a halide (1 mol) such as 1,2,4,5-tetraamino-3,6-dibromobenzene and octylaldehyde or octanoic acid (2 mol) in the presence of an acid (1 mmol to 50 mol). Let it react below. The crude product obtained by the reaction is purified by extraction, distillation, column chromatography, recrystallization or the like, if necessary. As the reaction solvent, acid itself can be used, and methanol, benzene, toluene, xylene, and other general compounds can be used as the solvent. Usable acids and reaction conditions are the same as described in [0019].

（上式中のＲ₁〜Ｒ₄、Ｘ₁、Ｘ₂は、前記と同じ意味である。） Furthermore, a compound in which at least one of R ₃ and R ₄ in the general formula (1) is a group other than a hydrogen atom can be produced by the following method.
The hydrogen atom bonded to the nitrogen atom of the compound represented by the following general formula (4) is substituted with a group of R ₃ and / or R ₄ , which is represented by the following general formula (1) A method for producing a benzodiimidazole compound.

(R _{1 to} R ₄ , X ₁ and X ₂ in the above formula have the same meaning as described above.)

A typical example is a method in which R ₁ and R ₂ are heptyl groups, and amino protons are substituted with methyl groups. This method is a method in which a compound of the general formula (4) is reacted with an alkali and a methyl halide. More specifically, sodium hydride (2 mol) is added to a solution of the compound of general formula (4) (1 mol), and then methyl iodide is added and reacted. The crude product obtained by the reaction is purified by acid washing, extraction, distillation, column chromatography, recrystallization and the like, if necessary. As the reaction solvent, tetrahydrofuran, benzene, toluene, xylene, and other general compounds can be used as the solvent.

  In the above, the case where octyl aldehyde or octanoic acid is used as the compound of the general formula (2) used in the first and second methods has been described as a representative example. It is also possible to use a compound having an unsaturated hydrocarbon, an aromatic compound, or the like. Here, the alkyl group is an alkyl group having 1 to 22 carbon atoms. For example, in addition to the heptyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a nonyl group. Decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, docosyl group, isobutyl group, 2-ethylhexyl group and the like. Further, it is possible to use an alkyl group containing one or more hetero atoms such as nitrogen, oxygen or sulfur, or one containing an unsaturated bond. The reaction temperature varies depending on the amount of raw materials charged, the amount of solvent, the type of solvent, etc., but it must be higher than the temperature at which the reaction mixture solidifies and the reaction does not proceed, and is below the temperature at which the solvent, raw materials, etc. disappear in large quantities due to volatilization Need to be. Generally, it is in the range of 20 ° C to 180 ° C, preferably 50 ° C to 150 ° C. The reaction time is about 1 to 48 hours.

  The benzodiimidazole unit-containing polymer of the present invention can be produced as follows. That is, a benzodiimidazole unit-containing polymer represented by the following general formula (6) by reacting a compound represented by the following general formula (1) with a compound (comonomer) represented by the following general formula (7). Or a method of obtaining a benzodiimidazole unit-containing polymer represented by the following general formula (8) by polymerizing a compound represented by the following general formula (1) alone.

（上式中のＲ₁〜Ｒ₄、Ｙは前記と同じ意味である。ｍとｎとはそれぞれ１以上であり、ｍ＋ｎは２以上から、重量平均分子量（Ｍｗ）が１，０００，０００になる値であり、Ｘ₁〜Ｘ₄は、それぞれ独立に、塩素、臭素、ヨウ素などのハロゲン、ホウ素誘導体、メチン水素、スズ誘導体、グリニヤール試薬（マグネシウム−ハロゲン−）、リチウムなどのアルカリ金属およびその他の重合可能な基を表す。）

(R _{1 to} R ₄ and Y in the above formula have the same meanings as described above. M and n are each 1 or more, m + n is 2 or more, and the weight average molecular weight (Mw) is 1,000,000. X _{1 to} X ₄ are each independently a halogen such as chlorine, bromine or iodine, a boron derivative, a methine hydrogen, a tin derivative, a Grignard reagent (magnesium-halogen-), an alkali metal such as lithium, and others. Represents a polymerizable group.)

（上式中のＲ₁〜Ｒ₄およびＸ₁、Ｘ₂は前記と同じ意味であり、ｍは２以上の数である。重量平均分子量（Ｍｗ）が１，０００，０００になる値である。）

(In the above formula, R _{1 to} R ₄ and X ₁ and X ₂ have the same meaning as described above, and m is a number of 2 or more. The weight average molecular weight (Mw) is a value that results in 1,000,000. .)

  The group represented by Y in the general formula (7) is an aromatic group or an aliphatic group, and particularly preferably these groups are conjugated groups. Preferable specific examples include, for example, aromatic groups such as benzene ring, biphenyl ring, naphthalene ring, anthracene ring, pyrene ring, terphenyl ring, carbazole ring, triphenylene ring, chrysene ring, benzanthracene ring, bipyridine ring, terpyridine. Ring, bithiophene ring, terthiophene ring, pentacene ring, benzofuran ring, dibenzothiophene ring, dibenzofuran ring, benzimidazole ring, indene ring, quinoline ring, phenanthroline ring, benzothiazole ring, benzothiophene ring, fluorene ring, 9,9- Examples thereof include a diarylfluorene ring and a 9,9-dialkylfluorene ring. As the aliphatic group, a group having a polyacetylene structure such as ethylene, butadiene, or hexatriene is preferable. In particular, a benzene ring, a fluorene ring, and a substituted derivative thereof such as a benzene ring, a fluorene ring, a 9,9-diarylfluorene ring, and a 9,9-dialkylfluorene ring are preferable. The above compounds are examples of preferred compounds, and the present invention is not limited to the groups exemplified above.

  The benzodiimidazole unit-containing polymer of the present invention is a compound of the above general formula (1) and the compound of the above general formula (7) at an equimolar ratio or in an arbitrary ratio in an appropriate solvent at about 20 ° C to 120 ° C. The reaction product (polymer) represented by the general formula (6) is produced by reacting at the reaction temperature of about 1 to 96 hours, and the desired product is obtained by separating the reaction product. In the above reaction, the compound of the general formula (1) and the compound of the general formula (7) may be used singly or as a mixture of plural kinds. Further, without using the compound of the general formula (7), the reaction product (polymer) represented by the general formula (8) can be generated by polymerization of the compound of the general formula (1) alone or by a plurality of types. It is.

The method for producing the polymer represented by the general formula (6) or (8) using the compound of the general formula (1) of the present invention is referred to as “N, N′-di-t-butoxycarbonyl-2,6- “Diheptyl-4,8-dibromobenzodiimidazole” (in formula (1), R ₁ , R ₂ = heptyl group, R ₃ , R ₄ = t-butoxycarbonyl group, X ₁ , X ₂ = bromine group) is used. The method will be described as a representative example.

  The first method is a copolymerization or homopolymerization of “N, N′-di-t-butoxycarbonyl-2,6-diheptyl-4,8-dibromobenzodiimidazole” with a boronic acid ester or a tin compound using a metal catalyst. This is a polymerization method. More specifically, in an inert gas atmosphere, “N, N′-di-t-butoxycarbonyl-2,6-diheptyl-4,8-dibromobenzodiimidazole” (1 mol) and an aromatic or heterocyclic compound, etc. A diboronic acid ester or ditin compound (1 mol) of a metal catalyst (0.1 mmol to 1 mol) such as a palladium zero-valent complex and an alkali reagent (1 mol to 100 mol) such as sodium carbonate, potassium carbonate or sodium hydroxide. Is obtained as a reaction reagent in a solvent.

  As the solvent, compounds such as toluene, tetrahydrofuran, and acetone can be used, and two-phase reaction with an aqueous alkali solution, one-phase reaction, and polymerization in a system to which a phase transfer catalyst is added are possible. The reaction temperature varies depending on the amount of raw material charged, the amount of solvent, the type of solvent, etc., but it must be higher than the temperature at which the reaction mixture solidifies and the reaction does not proceed, and is below the temperature at which the solvent or raw material disappears in large quantities due to volatilization Need to be. Generally, it is in the range of 30 ° C to 130 ° C, preferably 50 ° C to 110 ° C. The reaction time is about 1 to 80 hours. Polymerization quenching, post-treatment, and polymer purification can be performed by general methods. In addition, “N, N′-di-t-butoxycarbonyl-2,6-diheptyl-4,8-dibromobenzodiimidazole” itself is converted into a boronic acid ester or a tin compound, and coupling polymerization with a dihalogenated compound is performed. It is also possible to do this. In addition, a complex copolymer (oligomer) can be synthesized by combining with other plural kinds of dihalogenated comonomers or boronic esters.

  The second method is a polymerization method of “N, N′-di-t-butoxycarbonyl-2,6-diheptyl-4,8-dibromobenzodiimidazole” using a nickel coupling reaction. More specifically, in an inert gas atmosphere, “N, N′-di-t-butoxycarbonyl-2,6-diheptyl-4,8-dibromobenzodiimidazole” (1 mol) and nickel (1,5-cyclohexane) This is a method in which an octadiene) 2 complex (1 to 20 mol) is reacted in a solvent.

  As the solvent, toluene, dimethylformamide, tetrahydrofuran or the like can be used. The reaction temperature varies depending on the amount of raw material charged, the amount of solvent, the type of solvent, etc., but it must be higher than the temperature at which the reaction mixture solidifies and the reaction does not proceed, and is below the temperature at which the solvent or raw material disappears in large quantities due to volatilization Need to be. Generally, it is in the range of 20 ° C to 110 ° C, preferably 50 ° C to 100 ° C. The reaction time is about 1 to 72 hours. Polymerization quenching, post-treatment, and polymer purification can be performed by general methods. In addition, a random copolymer (oligomer) can be synthesized by a combination with other plural kinds of dihalogenated monomers.

  Coupling polymerization methods other than using nickel (1,5-cyclooctadiene) 2 complex include nickel complex, zinc, and phosphine compound (triphenylphosphine) in an inert gas atmosphere and in a polar solvent in a catalytic amount or more. Etc.) to produce an active nickel zero-valent catalyst and react with “N, N′-di-t-butoxycarbonyl-2,6-diheptyl-4,8-dibromobenzodiimidazole”. As the reaction solvent, dimethylformamide, dimethylacetamide, toluene, tetrahydrofuran and the like can be used. Random copolymers (oligomers) can also be synthesized in combination with other dihalogenated comonomers.

  The third method is a method in which “N, N′-di-t-butoxycarbonyl-2,6-diheptyl-4,8-dibromobenzodiimidazole” is monoglynarized and a metal catalyst is used. More specifically, in an inert gas atmosphere, “N, N′-di-t-butoxycarbonyl-2,6-diheptyl-4,8-dibromobenzodiimidazole” (1 mol) and magnesium metal (1 mol) This is a method in which a reaction is carried out to form a monogrillial and polymerize using a halide such as nickel, palladium, iron, chromium (0.1 mmol to 1 mol), a zero-valent complex, a bivalent complex (halogen-free) or the like as a catalyst.

As the solvent, ethers such as tetrahydrofuran, dioxane and dialkyl ether can be used. The reaction temperature varies depending on the amount of raw material charged, the amount of solvent, the type of solvent, etc., but it must be higher than the temperature at which the reaction mixture solidifies and the reaction does not proceed, and is below the temperature at which the solvent or raw material disappears in large quantities due to volatilization It needs to be. Generally it is 0 degreeC or more. The reaction time is about 1 to 72 hours. Polymerization quenching, post-treatment, and polymer purification can be performed by general methods. In addition, a random copolymer (oligomer) can be synthesized by a combination with other plural kinds of dihalogenated monomers.
The method for producing the above polymer has been described for the case where R ₁ , R ₂ = heptyl group, R ₃ , R ₄ = t-butoxycarbonyl group, X ₁ , X ₂ = bromine, but R _{1 to} R ₄ , The same applies when X ₁ and X ₂ are other groups.

  Specific examples of the comonomer (general formula (7)) include 2,7-dibromo-9,9-diarylfluorene, 2,7-diiodo-9,9-diarylfluorene, 2,7-dibromo-9,9. -Dialkylfluorene, 2,7-diiodo-9,9-dialkylfluorene, 2,5-dibromothiophene, 2,5-diiodothiophene, 2,5-dibromo-3-hexylthiophene, 2,5-diiodo-3 -Methylthiophene, dibromobithiophene, diiodobithiophene, dibromoterthiophene, diiodoterthiophene, dibromobipyridine, diiodobipyridine, dibromoterpyridine, diiodoterpyridine, dibromopyridine, diiodopyridine, 1,4-dibromo Benzene, 1,4-dibromo-2,5-dialkoxybenzene, 1 4-diiodobenzene, dibromobenzothiadiazole, diiodobenzothiadiazole, dibromocarbazole, diiodocarbazole, dibromonaphthalene, diiodonaphthalene, dibromoanthracene, diiodoanthracene, dibromoquinoline, diiodoquinoline, dibromobiphenyl, diiodobiphenyl, Dibromoterphenyl, diiodoterphenyl, dibromophenanthroline, diiodophenanthroline or boronic ester substituted compounds, tin substituted compounds, Grignard reagents and alkali metal substituted compounds of the above compounds, 1,4-divinylbenzene (polymerized by Heck reaction) ) And acetylene derivatives (polymerizable by Sonogashira reaction). The above compounds are exemplary, and the present invention is not limited to the above exemplary compounds.

  The content of the benzodiimidazole unit in the polymer of the present invention is 100% by mass when only the raw material represented by the general formula (1) is used, but when the polymer contains a comonomer unit (Y). The proportion of the comonomer unit (Y) in the copolymer is 0.01 to 99.9% by mass, preferably 10 to 80% by mass, except for special cases such as alternating copolymerization.

  In the above three methods, a carbon-carbon bond is newly formed using a benzodiimidazole compound as a homopolymer or copolymer raw material. The benzodiimidazole unit is a conjugated unit. The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resulting polymer vary depending on the raw material species and reaction conditions used, but in the present invention, the weight average molecular weight (Mw) is about 1,000 to 1,000,000. , Preferably 1,000 to 500,000, more preferably 1,000 to 200,000, and Mw / Mn is 1 to 4.0, preferably 1 to 3.0, more preferably 1 to 2.0. It is.

  The benzodiimidazole unit-containing polymer of the present invention obtained as described above can be used as a proton sensor using a phenomenon in which an ultraviolet absorption wavelength or a fluorescence wavelength changes depending on acidity, or a light emitting device of a conductive polymer or an EL element. They can be used as materials, charge injection materials, charge transport materials, charge transfer materials for fuel cells, and the like. Further, the benzodiimidazole unit-containing polymer of the present invention is soluble in general-purpose organic solvents such as chloroform, tetrahydrofuran, and chlorobenzene, and a thin film of nm unit is formed on a transparent electrode substrate such as a glass substrate by a spin coating method or the like. It can also be easily formed.

EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this invention is not necessarily limited to these Examples.
<Example 1> Synthesis of benzodiimidazole derivative 1 (1)
In a 100 ml eggplant-shaped flask, 1.3 g (4.6 mmol) of 1,2,4,5-tetraaminobenzene hydrochloride and 2.34 g (18.2 mmol) of octyl aldehyde 40 ml of methanol were placed at 50 ° C. After heating and dissolving, a catalytic amount of p-toluenesulfonic acid was added, and the mixture was stirred and reacted at 70 ° C. for 24 hours. After the reaction, the reaction solution was mixed with water and washed, and the target product was extracted with chloroform. The extract was dried and then washed with methanol to recover insolubles and dried to obtain 0.25 g (15% yield) of white powder. The analysis results of this powder are as follows, and it was confirmed that the powder had the following structure.

¹ H NMR (DMSO-d ₆ , ppm) /7.9 (2H, ArH); 3.1 (4H, —CH ₂ —); 1.9 (4H, —CH ₂ —); 1.1-1 _{.5 (16H, -CH 2 -)} ; 0.9 (6H, -CH 3) ( Figure 1)
Elemental analysis / calcd. for C ₂₂ H ₃₄ N ₄ · CHCl ₃ · 0.5H ₂ O
: C = 57.20, H = 7.51, N = 11.60
found: C = 57.73, H = 7.91, N = 12.11
Melting point / 280 ° C. or higher Mass Spectrometry / 353 (EI)

<Example 2> Synthesis of benzodiimidazole derivative 1 (2)
In a 100 ml eggplant-shaped flask, 2.6 g (9.2 mmol) of 1,2,4,5-tetraaminobenzene hydrochloride and 50 g of polyphosphoric acid were added, heated and stirred at 80 ° C., and n-octanoic acid was added. Stir and react at 140 ° C. for 24 hours under nitrogen. After the reaction, the reaction solution was poured into 300 ml of water and washed. The washing of the product was repeated until the aqueous solution became transparent, then washed with chloroform and methanol, and the insoluble matter was collected by filtration and dried to obtain 0.678 g (49% yield) of white powder. From the analysis result of this powder, it was confirmed that it had the same structure as Example 1.

<Example 3> Synthesis of benzodiimidazole derivative 2 In a 300 ml eggplant-shaped flask, 2.9 g (8.2 mmol) of derivative 1 obtained in Example 2, 3.6 g of sodium acetate trihydrate (27 Mmol) and 40 ml of acetic acid were added, 3.3 g (21 mmol) of bromine was added, and the mixture was stirred and reacted at room temperature for 2 days. After the reaction, a sodium bicarbonate aqueous solution was added to the reaction solution to neutralize it, and the produced solid was collected by filtration. The obtained solid was washed with water and washed with chloroform, and then recrystallized from a methanol-chloroform mixed solvent, and recovered by filtration and dried to obtain 2.1 g (50% yield) of a white powder. The analysis results of this powder are as follows, and it was confirmed that the powder had the following structure.

¹ H NMR (DMSO-d ₆ , ppm) /12.4 (2H, NH); 2.8 (4H, —CH ₂ —); 1.8 (4H, —CH ₂ —); 1.1-1 .4 (16H, —CH ₂ —); 0.8 (6H, —CH ₃ ) (FIG. 2)
Elemental analysis / calcd. for C ₂₂ H ₃₂ N ₄ Br ₂
: C = 51.58, H = 6.30, N = 10.94,
Br = 31.39
found: C = 51.51, H = 6.29, N = 10.97,
Br = 31.20
Melting point / 280 ℃ or more

<Example 4> Synthesis of benzodiimidazole derivative 3 Into a 50 ml Schlenk tube substituted with an inert gas, 0.0774 g (0.15 mmol) of derivative 2 obtained in Example 3, 5.5 mg of dimethylaminopyridine was obtained. (0.045 mmol) and 30 ml of dehydrated tetrahydrofuran were added, 0.10 g (0.45 mmol) of di-t-butyl dicarbonate was added, and the mixture was stirred and reacted at 80 ° C. After the reaction, the solvent was distilled off from the reaction solution, and the obtained solid was purified by column chromatography (silica gel-chloroform). After distilling off the solvent, recrystallization was performed from a mixed solvent of hexane-chloroform, and 0.064 g (60% yield) of white powder was obtained by filtration and collection and drying. The analysis results of this powder are as follows, and it was confirmed that the powder had the following structure.

¹ H NMR (CDCl ₃ , ppm) /3.0 (4H, —CH ₂ —); 1.8 (4H, —CH ₂ —); 1.7 (9H, t-Bu); 1.6 (9H , t-Bu); 1.2-1.5 ( 16H, -CH 2 -); 0.9 (6H, -CH 3) ( Fig. 3)
Elemental analysis / calcd. for C ₃₂ H ₄₈ N ₄ O ₄ Br ₂
: C = 53.94, H = 6.79, N = 7.86,
O = 8.98, Br = 22.43
found: C = 54.12, H = 6.75, N = 7.85,
O = 9.02 and Br = 22.82.

<Example 5> Synthesis of benzodiimidazole derivative 4 Into a 50 ml Schlenk tube substituted with an inert gas, 0.40 g (0.56 mmol) of derivative 3 obtained in Example 4, a catalytic amount of tetrakis (tri Phenylphosphine) palladium (valence 0), deaerated aqueous sodium carbonate solution (2 mol / liter) 5 ml, phenylboronic acid 0.17 g (1.4 mmol), degassed toluene 30 ml were added and stirred at 80 ° C. for 20 hours. And reacted. After the reaction, the target product was extracted from the reaction solution with chloroform, washed with water, and purified by column chromatography (silica gel-chloroform). After distilling off the solvent, the t-butoxycarbonyl group was removed by heating at 200 ° C., and the resulting product was recrystallized from a methanol-chloroform mixed solvent, and recovered by filtration and dried to obtain 0.27 g (93 % Yield) of white powder. The analysis results of this powder are as follows, and it was confirmed that the powder had the following structure.

¹ H NMR (CDCl ₃ , ppm) /9.0 (2H, NH); 7.9 (4H, ArH); 7.6 (4H, ArH); 7.4 (2H, ArH); 2.9 ( 4H, —CH ₂ —); 1.8 (4H, —CH ₂ —); 1.1-1.5 (16H, —CH ₂ —); 0.9 (6H, —CH ₃ ) (FIG. 4)
Elemental analysis / calcd. for C ₃₄ H ₄₂ N ₄ · 0.04CHCl ₃
: C = 79.93, H = 8.28, N = 10.95,
Cl = 0.83
found: C = 79.63, H = 8.23, N = 10.86,
Cl = 0.78

<Example 6> Production of polymer 1 To 50 ml of Schlenk substituted with an inert gas, 30.7 mg (0.0266 mmol) of tetrakis (triphenylphosphine) palladium (zero valent), 9,9-dioctylfluorene-2 , 7-di (propyleneboronate) 0.495 g (0.887 mmol), 0.632 g (0.887 mmol) of derivative 3 obtained in Example 4, 16.6 ml of degassed toluene, degassed carbonic acid A potassium aqueous solution (2 mol / liter) (8.9 ml, 17.8 mmol) and a phase transfer catalyst 0.07 g (0.17 mmol) were added, and the mixture was stirred and reacted at 85 ° C. for 79 hours. After the reaction, the reaction solution was put into a methanol-water mixture (4: 1) to terminate the polymerization. The product was collected by filtration, dissolved in chloroform, and then subjected to usual polymer purification operations such as water washing and chelate washing. After the solvent was distilled off, it was dried to obtain 0.835 g (> 99% yield) of a light green powder. The analysis results of this powder are as follows, and it was confirmed that the powder had the following structure.

GPC (CHCl ₃ ) / Mn = 1,000, Mw = 6,700
(Small because it contains monomer and oligomer)
Mw / Mn (polydispersity) = 6.6
Elemental analysis / calcd. for C ₆₁ H ₈₈ N ₄ O ₄
: C = 77.83, H = 9.42, N = 5.95
O = 6.80
found: C = 76.05, H = 9.40, N = 5.96
O = 6.55
Fluorescence spectrum (CHCl ₃ ) / 430 nm (excitation wavelength: 375 nm)
UV spectrum (CHCl ₃ ) / λ _max = 380 nm (FIG. 7)
Fluorescence quantum yield (CHCl ₃ solution) = 37%

<Example 7> Production of polymer 2 0.1215 g of the polymer 1 obtained in Example 6 was placed in a 10-ml glass container and dried under reduced pressure at 190 ° C for 1 hour to remove substituents. The product was transferred to a 300 ml eggplant-shaped flask, stirred with 50 ml of methanol, washed and dried to obtain 0.0625 g of an ocher powder. The analysis results of this powder are as follows, and it was confirmed that the powder had the following structure.

¹ H NMR (CDCl ₃ , ppm) /9.0 (2H, NH); 8.0 (6H, ArH); 3.0 (4H, —CH ₂ —); 2.1 (4H, —CH ₂ — _{); 1.9 (4H, -CH 2} -); 1.0-1.5 (36H, -CH 2 -); 0.9 (6H, -CH 3); 0.8 (10H, -CH 2 -, - CH ₃₎ (FIG. 8)
GPC (CHCl ₃ ) / Mn = 8,700, Mw = 26,300
Mw / Mn (polydispersity) = 3.0
Elemental analysis / calcd. _{for H- (C 51 H 72 N} 4 · H 2 O) 12 -B (OH) 2
: C = 80.28, H = 9.81, N = 7.35
O = 2.45
found: C = 79.21, H = 9.67, N = 7.20
O = 2.04
Fluorescence spectrum (CHCl ₃ ) / 446 nm (excitation wavelength: 391 nm)
UV spectrum (CHCl ₃ ) / λ _max = 396 nm (FIG. 7)
Fluorescence quantum yield (CHCl ₃ solution) = 28%

<Example 8> Production of polymer 3 To 50 ml of Schlenk substituted with an inert gas, tetrakis (triphenylphosphine) palladium (zero valent), 2,5-hexoxybenzene-1,4-di (propylene boronate) was prepared. ), Derivative 3 obtained in Example 4, degassed toluene, and degassed potassium carbonate aqueous solution (2 mol / liter) were added, and the mixture was stirred and reacted at 80 ° C. for 3 days. After the reaction, the reaction solution was put into a methanol-water mixture to terminate the polymerization. The product was recovered by filtration, and subjected to usual polymer purification operations such as washing with water and reprecipitation (chloroform-methanol). This polymer was dried under reduced pressure at 200 ° C. for 1 hour, subjected to a purification operation, and then dried to obtain a light yellow powder having the following structure.

<Example 9> Production of polymer 4 In 50 ml of Schlenk substituted with an inert gas, 0.87 g (3.2 mmol) of biscyclooctadienyl nickel (zero valent), dehydrated toluene 40 ml, 2,2 ′ -Bipyridyl (0.46 g, 2.9 mmol) was added, stirred for 15 minutes at room temperature, 1,5-cyclooctadiene (0.32 g, 2.9 mmol), and 0.71 g (1) obtained in Example 4 0.0 mmol) of derivative 3 was added and the resulting mixture was stirred and reacted at 60 ° C. for 96 hours. After the reaction, the reaction solution was put into an aqueous ammonia solution to stop the polymerization. The product is recovered by filtration, dissolved in chloroform, and subjected to normal polymer purification operations such as aqueous ammonia washing, water washing, chelate washing, and the like, and then the solvent is distilled off and washed with methanol. Drying gave an ocher powder. When the obtained powder was dried under reduced pressure at 200 ° C. for 1 hour to remove the substituent, the color of the polymer changed from ocher to red. The analysis results of the obtained polymer are as follows, and it was confirmed that the polymer had the following structure.

¹ H NMR (DMSO-d ₆ , ppm) /11.6 (2H, NH); 7.7-8.1 (0.3H, ArH); 2.5-3.1 (4H, —CH ₂ — _{); 1.7-2.0 (4H, -CH 2} -); 1.0-1.6 (16H, -CH 2 -); 0.7-1.0 (6H, -CH 3) ( FIG. 9)
GPC (DMF) / Mn = 980, Mw = 1,400
Mw / Mn (polydispersity) = 1.4
Elemental analysis / calcd. _{for Br- (C 22 H 32 N} 4) 3 -H · 4H 2 O
: C = 65.48, H = 8.74, N = 13.89,
O = 5.29
found: C = 65.48, H = 7.73, N = 13.39,
O = 5.18
UV spectrum (CHCl ₃ ) / λ _max = 295 nm
Mass spectrometry (FAB +) /
708 Dimer (M + 1) = H (C ₂₂ H ₃₂ N ₄ ) ₂ H
And tetramer (M + 2) / 2 = H (C ₂₂ H ₃₂ N ₄ ) ₄ H
1,060 trimer (M + 1) = H (C ₂₂ H ₃₂ N ₄ ) ₃ H

<Usage example>
When an acid or a base is added to the solution of each polymer obtained as described above, the polymer can be used as a proton sensor due to the phenomenon that the ultraviolet absorption spectrum, the fluorescence spectrum, and the fluorescence quantum yield change. As a specific example, the DMF-methanol mixed solution of polymer 4 obtained in Example 9 showed absorption at λmax = 300 nm. However, when a base was added to the solution, a phenomenon that a shoulder peak appears around 430 nm occurred.
Moreover, the obtained polymer can be formed into a film and has a feature that it can be used as a thin film. The polymer 1 obtained in Example 6 was dissolved in chloroform so as to have a concentration of 30 mg / ml, and applied to a glass substrate (anode) coated with indium / tin oxide by a spin coating method and dried to obtain a uniform layer. Formed. At this time, no polymer was precipitated and a uniform thin film was formed. The same was true for the polymers of the other examples.

  According to the present invention, it is possible to synthesize a benzodiimidazole unit-containing polymer, which is a novel compound, and this polymer can be used as a proton sensor using a phenomenon in which ultraviolet absorption and fluorescence change by protons, It can be used as a molecule, a light emitting material of an EL element, a charge injection material, and a charge transport material. It is soluble in a general-purpose organic solvent, and is characterized in that a thin film of nm unit can be easily formed on a transparent electrode substrate such as a glass substrate by a spin coating method or the like.

¹ H NMR spectrum of benzodiimidazole derivative 1 of Example 1. ¹ H NMR spectrum of benzodiimidazole derivative 2 of Example 3. ¹ H NMR spectrum of benzodiimidazole derivative 3 of Example 4. ¹ H NMR spectrum of benzodiimidazole derivative 4 of Example 5. Infrared spectra of the products of Examples 1, 3, 4, 9 Infrared spectrum of benzodiimidazole derivative 4 of Example 5. The ultraviolet absorption spectrum of the polymer of Examples 6 and 7. ¹ H NMR spectrum of polymer 2 of Example 7. ¹ H NMR spectrum of polymer 4 of Example 9.

Claims (4)

A benzodiimidazole compound represented by the following general formula (1):

(R ₁ and R ₂ in the above formula each independently represent a C _1-22 linear or branched alkyl group. R ₃ and R ₄ are t-butoxycarbonyl groups. X ₁ And X ₂ each independently represents a hydrogen atom or a halogen atom of chlorine, bromine or iodine .) A benzodi group represented by the following general formula (1), wherein a hydrogen atom bonded to a nitrogen atom of a compound represented by the following general formula (4) is substituted with a group of R ₃ and R ₄ A method for producing an imidazole compound.

(R ₁ and R ₂ in the above formula each independently represent a C _1-22 linear or branched alkyl group. R ₃ and R ₄ are t-butoxycarbonyl groups. X ₁ And X ₂ each independently represents a hydrogen atom or a halogen atom of chlorine, bromine or iodine .) The benzodiimidazole compound represented by the general formula (4) is reacted with 1,2,4,5-tetraaminobenzene and a compound represented by the following general formula (2) to give the following general formula (3 The benzodiimidazole compound represented by formula (1) is then obtained by reacting the compound with a halogenating agent to halogenate the 3-position or 3,6-position of the benzene ring. The manufacturing method of the benzodiimidazole compound represented by General formula (1).

(R ₁ and R ₂ in the above formula each independently represent a C _1-22 linear or branched alkyl group. X ₁ and X ₂ are each independently a hydrogen atom, chlorine, (Represents a halogen atom of either bromine or iodine.) The benzodiimidazole compound represented by the general formula (4) is represented by the 1,2,4,5-tetraaminobenzene derivative represented by the following general formula (5) and the following general formula (2). The method for producing a benzodiimidazole compound represented by the general formula (1) according to claim 2, which is obtained by reacting a compound.

(R ₁ and R ₂ in the above formula each independently represent a C _1-22 linear or branched alkyl group. X ₁ and X ₂ are each independently a hydrogen atom, chlorine, (Represents a halogen atom of either bromine or iodine.)

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