JP7212220B2 - Compound, active material for storage battery, n-type semiconductor material, hydrogen storage material, and method for producing compound - Google Patents

Description

The present disclosure relates to compounds, active materials for storage batteries, n-type semiconductor materials, hydrogen storage materials, and methods of making compounds.

Currently, compounds are widely used in daily life, industrial activities, and the like.
Compounds can be broadly classified into organic compounds and inorganic compounds, and various types of each are known. Compounds are known to exhibit various functions depending on the elements, skeletons, substituents, etc. that constitute their structures. From this point of view, attempts have been made to control the elements, skeletons, substituents, etc. constituting the compound to produce a compound having a desired function, and to use the compound for the intended use.

As an example of the above application, there is an example of using the compound as an active material for a storage battery.
Patent Document 1 discloses a positive electrode chamber having a positive electrode, a negative electrode chamber having a negative electrode, a diaphragm separating the positive electrode chamber and the negative electrode chamber, an electrolytic solution filled in the positive electrode chamber and the negative electrode chamber, and the positive electrode. A redox flow battery comprising: a chamber, the negative electrode chamber, the diaphragm, and a housing that houses the electrolytic solution, wherein the electrolytic solution contains an active material that undergoes a reversible oxidation-reduction reaction by light energy. is disclosed.

JP 2017-50201 A

As described above, it is desired to produce new compounds having desired functions by controlling elements, skeletons, substituents, and the like.
The problem to be solved by the present disclosure is to provide novel compounds, active materials for storage batteries, n-type semiconductor materials, hydrogen storage materials, and methods for producing the novel compounds.

＜２＞ 上記環構造Ａ１は、下記式１ａ～下記式１ｅのいずれか１つで表される構造を有し、上記環構造Ａ２は、下記式１ｂ～下記式１ｅのいずれか１つで表される構造を有する＜１＞に記載の化合物である。

式１ａ～式１ｅ中、＊は環構造Ａ１又は環構造Ａ２に含まれる窒素原子との結合部位を表し、＊＊は環構造Ａ１又は環構造Ａ２との結合部位を表し、Ｒ_１～Ｒ_１１は、それぞれ独立に置換基を表し、隣接する置換基同士で環を構成してもよい。また、Ｘ１、Ｘ４～Ｘ６、及びＸ１１はそれぞれ独立に０～４の整数を表し、Ｘ２、Ｘ３、及び、Ｘ７～Ｘ１０はそれぞれ独立に０～３の整数を表す。
＜３＞ 上記環構造Ａ１及び上記環構造Ａ２は、下記式１ｂで表される構造を有する＜１＞又は＜２＞に記載の化合物である。

式１ｂ中、＊は環構造Ａ１又は環構造Ａ２に含まれる窒素原子との結合部位を表し、＊＊は環構造Ａ１又は環構造Ａ２との結合部位を表し、Ｒ_２及びＲ_３は、それぞれ独立に置換基を表し、隣接する置換基同士で環を構成してもよい。また、Ｘ２及びＸ３はそれぞれ独立に０～３の整数を表す。
＜４＞ 上記環構造Ａ１及び上記環構造Ａ２における芳香環の少なくとも１つは、アルキル基、アルケニル基、アルキニル基、アリール基、ホルミル基、アシル基、カルボキシ基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、シアノ基、アミノ基、アミド基、ニトロ基、ヒドロキシ基、アルコキシ基、アリールオキシ基、メルカプト基、スルファニル基、スルホ基及びハロゲノ基からなる群より選ばれる少なくとも１つの置換基を含む＜１＞～＜３＞のいずれか１つに記載の化合物である。
＜５＞ ＜１＞～＜４＞のいずれか１つに記載の化合物を含む蓄電池用活物質である。
＜６＞ ＜１＞～＜４＞のいずれか１つに記載の化合物を含むｎ型半導体材料である。
＜７＞ ＜１＞～＜４＞のいずれか１つに記載の化合物を含む水素貯蔵材料である。
＜８＞ 炭素数２～５の炭素鎖の一方の末端に脱離基を、他方の末端にアミノ基を、それぞれ有し、上記炭素鎖を構成する炭素は、水素原子と結合せず、かつ、芳香環を構成する化合物Ａを準備する工程と、準備した化合物Ａの脱離基が結合している部位においてカップリング反応を行って、下記式３で表される化合物を生成する工程と、下記式３で表される化合物について、環化反応を行って＜１＞～＜４＞のいずれか１つに記載の化合物を生成する工程と、を有する化合物の製造方法である。

式３中、Ｒはそれぞれ独立に、化合物Ａから脱離基を除いた残基を表す。
＜９＞ 上記化合物Ａは、下記式２ａ～下記式２ｅから選択される少なくとも１つである＜８＞に記載の化合物の製造方法である。

式２ａ～式２ｅ中、Ｘは脱離基を表し、Ｒ_１～Ｒ_１１は、それぞれ独立に置換基を表し、隣接する置換基同士で環を構成してもよい。また、Ｘ１、Ｘ４～Ｘ６、及びＸ１１はそれぞれ独立に０～４の整数を表し、Ｘ２、Ｘ３、及び、Ｘ７～Ｘ１０はそれぞれ独立に０～３の整数を表す。 Means for solving the above problems include the following aspects.
<1> A compound represented by the following formula 1, wherein the ring structure A1 contains a nitrogen atom and has a ring structure with m carbon atoms, and the ring structure in the ring structure with m carbon atoms Carbons not constituting A2 are not bonded to hydrogen atoms and constitute an aromatic ring, ring structure A2 contains a nitrogen atom, has a ring structure having n carbon atoms, and the ring having n carbon atoms A compound in which the carbon atoms not constituting the ring structure A1 in the structure are not bonded to a hydrogen atom and constitute an aromatic ring, wherein m is an integer of 4 to 7 and n is an integer of 5 to 7 is.

<2> The ring structure A1 has a structure represented by any one of the following formulas 1a to 1e, and the ring structure A2 is represented by any one of the following formulas 1b to 1e. The compound according to <1> having a structure represented by

In formulas 1a to 1e, * represents a bonding site with a nitrogen atom contained in ring structure A1 or ring structure A2, ** represents a bonding site with ring structure A1 or ring structure A2, and R ₁ to R ₁₁ each independently represents a substituent, and adjacent substituents may form a ring. X1, X4 to X6 and X11 each independently represent an integer of 0 to 4, and X2, X3 and X7 to X10 each independently represent an integer of 0 to 3.
<3> The ring structure A1 and the ring structure A2 are compounds according to <1> or <2> having a structure represented by the following formula 1b.

In formula 1b, * represents a binding site to the nitrogen atom contained in ring structure A1 or ring structure A2, ** represents a binding site to ring structure A1 or ring structure A2, and R ₂ and R ₃ are each Each substituent may be independently represented, and adjacent substituents may form a ring. Also, X2 and X3 each independently represent an integer of 0 to 3.
<4> At least one of the aromatic rings in the ring structure A1 and the ring structure A2 is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a formyl group, an acyl group, a carboxy group, an alkoxycarbonyl group, and an aryloxycarbonyl group. , a carbamoyl group, a cyano group, an amino group, an amido group, a nitro group, a hydroxy group, an alkoxy group, an aryloxy group, a mercapto group, a sulfanyl group, a sulfo group and a halogeno group. The compound according to any one of <1> to <3>.
<5> A storage battery active material containing the compound according to any one of <1> to <4>.
<6> An n-type semiconductor material containing the compound according to any one of <1> to <4>.
<7> A hydrogen storage material containing the compound according to any one of <1> to <4>.
<8> A carbon chain having 2 to 5 carbon atoms has a leaving group at one end and an amino group at the other end, and the carbon atoms constituting the carbon chain are not bonded to a hydrogen atom, and , a step of preparing a compound A constituting an aromatic ring, and a step of performing a coupling reaction at the site where the leaving group of the prepared compound A is bonded to produce a compound represented by the following formula 3; A method for producing a compound, comprising: subjecting a compound represented by the following formula 3 to a cyclization reaction to produce a compound according to any one of <1> to <4>.

In formula 3, each R independently represents a residue obtained by removing a leaving group from compound A.
<9> The method for producing the compound according to <8>, wherein the compound A is at least one selected from the following formulas 2a to 2e.

In Formulas 2a to 2e, X represents a leaving group, R ₁ to R ₁₁ each independently represent a substituent, and adjacent substituents may form a ring. X1, X4 to X6 and X11 each independently represent an integer of 0 to 4, and X2, X3 and X7 to X10 each independently represent an integer of 0 to 3.

According to embodiments of the present disclosure, novel compounds, active materials for storage batteries, n-type semiconductor materials, hydrogen storage materials, and methods for producing novel compounds can be provided.

1 is a cyclic voltammogram showing reduction potentials measured in Examples. 1 is a graph showing absorption spectra and emission spectra of compounds synthesized in Examples.

In the present disclosure, a numerical range indicated using "to" means a range including the numerical values before and after "to" as lower and upper limits, respectively. In the numerical ranges described step by step in the present disclosure, upper or lower limits described in a certain numerical range may be replaced with upper or lower limits of other numerical ranges described step by step. In addition, in the numerical ranges described in the present disclosure, upper or lower limits described in a certain numerical range may be replaced with values shown in Examples.
In the present disclosure, the term "process" includes not only independent processes, but also processes that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.
In the present disclosure, combinations of preferred aspects are more preferred aspects.

≪Compound≫
The compound of the present disclosure is a compound represented by the following formula 1, wherein the ring structure A1 contains a nitrogen atom and has a ring structure with m carbon atoms, and the ring structure with m carbon atoms The carbons not constituting the ring structure A2 in are not bonded to a hydrogen atom and constitute an aromatic ring, the ring structure A2 contains a nitrogen atom, has a ring structure having n carbon atoms, and has the above-mentioned carbon number n The carbon atoms that do not constitute the ring structure A1 in each ring structure are not bonded to a hydrogen atom and constitute an aromatic ring, m is an integer of 4 to 7, and n is an integer of 5 to 7. is.

The compounds of the present disclosure have redox activity. Specifically, the compounds of the present disclosure are capable of undergoing a reduction reaction that receives electrons and an oxidation reaction that releases received electrons, and thus have redox activity.
As shown in the reaction scheme below, the compounds of the present disclosure can adsorb and store hydrogen molecules in the molecule through the reaction of compound I to compound II. In addition, the reaction from compound II to compound I can release hydrogen molecules stored in the molecule.
The compounds of the present disclosure have conjugated double bonds and therefore exhibit light absorption and fluorescence.

In addition, since the compound of the present disclosure has the structure represented by Formula 1 as described above, various chemical modifications can be performed. Accordingly, various functions can be imparted to the compound.
However, since redox-active sites and chemical modification methods of compounds are very limited, it has often been difficult to add desired functions to compounds.
The compound of the present disclosure is an organic compound having a novel redox-active site, and can be subjected to simple and diverse chemical modifications. This makes it possible to provide an organic compound having more diverse functions and redox activity.

<Compound Represented by Formula 1>
Formula 1 in the present disclosure includes ring structure A1 and ring structure A2.

The ring structure A1 contains a nitrogen atom and has a ring structure with m carbon atoms, and the carbon atoms not constituting the ring structure A2 in the ring structure with m carbon atoms are not bonded to a hydrogen atom and are aromatic rings and m is an integer from 4 to 7.
The number of carbon atoms m is preferably 4 to 6, more preferably 4 to 5, from the viewpoints of ease of compound synthesis and stability.
The aromatic rings include benzene, naphthalene and biphenyl. Among the above, benzene and naphthalene are preferred from the viewpoint of ease of compound synthesis and stability.

The ring structure A2 contains a nitrogen atom and has a ring structure with n carbon atoms, and the carbons not constituting the ring structure A1 in the ring structure with n carbon atoms are not bonded to a hydrogen atom and are aromatic rings and n is an integer from 5 to 7.
From the viewpoint of stability of the compound, the number of carbon atoms n is preferably 5 to 6, more preferably 5.
Examples of the aromatic ring include those similar to those of the ring structure A1, and preferred examples are also the same.

In the compound of the present disclosure, the ring structure A1 has a structure represented by any one of the following formulas 1a to 1e, and the ring structure A2 is any one of the following formulas 1b to 1e. It is preferred to have a structure represented by
From the viewpoint of ease of compound synthesis and stability, the ring structure A1 has a structure represented by any one of the following formulas 1a to 1c below, and the ring structure A2 has the following formula 1b or the following formula It is more preferable to have the structure represented by 1c, and it is further preferable that the ring structure A1 and the ring structure A2 have the structure represented by the following formula 1b.

In formulas 1a to 1e, * represents a bonding site with a nitrogen atom contained in ring structure A1 or ring structure A2, ** represents a bonding site with ring structure A1 or ring structure A2, and R ₁ to R ₁₁ each independently represents a substituent, and adjacent substituents may form a ring. X1, X4 to X6 and X11 each independently represent an integer of 0 to 4, and X2, X3 and X7 to X10 each independently represent an integer of 0 to 3.

In the present disclosure, the aromatic ring in ring structure A1 and ring structure A2 can contain a substituent. That is, the compounds of the present disclosure can contain substituents as R ₁ to R ₁₁ above.
The compounds of the present disclosure can have various functions depending on the types of substituents introduced as the above R ₁ to R ₁₁ that can be introduced into the aromatic rings in the ring structures A1 and A2.

Examples of the substituents include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, formyl groups, acyl groups, carboxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, cyano groups, amino groups, amido groups, nitro group, hydroxy group, alkoxy group, aryloxy group, mercapto group, sulfanyl group, sulfo group, halogeno group and the like.
Among the above, at least one of the aromatic rings in the ring structure A1 and the ring structure A2 preferably contains at least one substituent selected from the group consisting of an alkyl group, an alkenyl group, an aryl group, an alkoxy group, and a halogeno group. .

Examples of the above functions include improvement of redox activity, adjustment of redox potential, improvement of compound stability, improvement of solubility in organic solvents, improvement of water solubility, and the like.
From the viewpoint of improving the redox activity of the compound and adjusting the redox potential, R ₁ to R ₁₁ are preferably an alkenyl group, an alkynyl group, an aryl group, a cyano group, an amino group, a nitro group or an alkoxy group. It is preferred that the groups form a conjugated ring.
From the viewpoint of improving the stability of the compound, R ₁ to R ₁₁ are preferably alkyl groups, aryl groups, cyano groups, sulfanyl groups and halogeno groups.
From the viewpoint of improving the solubility of the compound in organic solvents, R ₁ to R ₁₁ are preferably an alkyl group, an aryl group, an alkoxy group, or an aryloxy group.
From the viewpoint of improving the water solubility of the compound, R ₁ to R ₁₁ are preferably carboxy, carbamoyl, amido, hydroxy, alkoxy and sulfo groups, more preferably carboxy, hydroxy, alkoxy and sulfo groups. preferable.

Examples of the ring composed of adjacent substituents in R ₁ to R ₁₁ include a cycloalkane ring, benzene ring, cyclopentadiene ring, cyclopentatriene ring, pyrrole ring, pyridine ring, furan ring, thiophene ring and the like. mentioned.
From the viewpoint of compound stability, the ring composed of adjacent substituents is preferably a benzene ring or a cyclopentadiene ring, more preferably a benzene ring.

Specific structures of compounds of the present disclosure include, for example, the structures shown below.

~ Properties of compounds ~
(Redox activity)
Since the compound of the present disclosure is an electron-accepting compound that exhibits reversible reducing properties as described above, it has redox activity. Therefore, the compound of the present disclosure can be used as an active material for storage batteries (particularly a negative electrode active material), an n-type semiconductor material, and the like.

(solubility)
The compounds of the present disclosure exhibit good solubility in organic solvents (eg THF).
Therefore, the compounds of the present disclosure can be applied to applications that require solubility in organic solvents. Applications that require solubility in organic solvents include, for example, the above active materials for storage batteries.

(Light Absorbing and Fluorescent)
The compounds of the present disclosure have light absorption and fluorescence emission properties.
Therefore, the compound of the present disclosure can be used as an optical functional material.

(Hydrogen storage capacity)
The compounds of the present disclosure exhibit chemisorption of molecular hydrogen as described above.
Therefore, the compounds of the present disclosure can be used as hydrogen storage materials, reduction catalysts, and the like.

<Method for producing compound>
In the method for producing a compound of the present disclosure, a carbon chain having 2 to 5 carbon atoms has a leaving group at one end and an amino group at the other end, and the carbon atoms constituting the carbon chain are hydrogen atoms and A step of preparing compound A that does not bond and constitutes an aromatic ring (preparation step), and performing a coupling reaction at the site where the leaving group of prepared compound A is bonded, represented by the following formula 3 and a step of cyclizing the compound represented by Formula 3 below to produce the compound of the present disclosure (cyclization step).

式３中、Ｒはそれぞれ独立に、化合物Ａから脱離基を除いた残基を表す。

In formula 3, each R independently represents a residue obtained by removing a leaving group from compound A.

(Preparation process)
In the preparation step in the present disclosure, a carbon chain having 2 to 5 carbon atoms has a leaving group at one end and an amino group at the other end, and the carbons constituting the carbon chain are bonded to hydrogen atoms. It is a step of preparing a compound A which does not need to be removed and which constitutes an aromatic ring.

The method for preparing compound A is not particularly limited, and compound A can be synthesized by appropriately selecting from known methods.

-Compound A-
Compound A in the present disclosure has a leaving group at one end of a carbon chain having 2 to 5 carbon atoms and an amino group at the other end, and the carbon atoms constituting the carbon chain are bonded to hydrogen atoms. and constitutes an aromatic ring.
Examples of the leaving group include a chloro group, a bromo group, and an iodo group.
Among the above, a bromo group and an iodo group are preferred, and a bromo group is particularly preferred.

Compound A may be, for example, a compound represented by Formula 2 below.

In Formula 2, X represents a leaving group, R represents a carbon chain having 2 to 5 carbon atoms, and A3 represents an aromatic ring. Further, the carbons constituting the carbon chain do not bond to hydrogen atoms and constitute the aromatic ring A3.

The number of carbon atoms in the carbon chain represented by R is preferably 2 to 4, more preferably 2 to 3, from the viewpoints of ease of compound synthesis and stability.

Examples of the aromatic ring A3 include benzene, naphthalene and biphenyl. Among the above, benzene and naphthalene are preferable as the aromatic ring A3 from the viewpoint of ease of compound synthesis and stability.

Compound A is preferably at least one selected from Formulas 2a to 2e below.

In Formulas 2a to 2e, X represents a leaving group, R ₁ to R ₁₁ each independently represent a substituent, and adjacent substituents may form a ring. X1, X4 to X6 and X11 each independently represent an integer of 0 to 4, and X2, X3 and X7 to X10 each independently represent an integer of 0 to 3.

In Formulas 2a to 2e, specific examples and preferred aspects of the substituents are the same as in Formulas 1a to 1e above, and preferred aspects are also the same.

Specific methods for synthesizing compound A include, for example, the following methods.
As a method for synthesizing compound A, as shown in the following reaction formula, 1,8-diaminonaphthalene and a nitrite (e.g., isoamyl nitrite) are reacted, and then hydrobromic acid is reacted to obtain compound A. (Compound III in the following reaction formula) can be obtained.

(Coupling process)
The coupling step in the present disclosure is a step of performing a coupling reaction at the site where the leaving group of the prepared compound A is bonded to produce a compound represented by Formula 3 below.

式３中、Ｒはそれぞれ独立に、化合物Ａから脱離基を除いた残基を表す。

In formula 3, each R independently represents a residue obtained by removing a leaving group from compound A.

The coupling step can be performed using a known method, but a method using the Sonogashira coupling reaction is preferred.
The coupling step can be performed, for example, as follows.
As shown in the reaction formula below, the compound III obtained above is reacted with, for example, trimethylsilylacetylene to obtain a compound IV, and then the trimethylsilyl group in the obtained compound IV is eliminated to obtain a compound V.
Next, a copper catalyst (e.g., copper iodide) and a palladium catalyst (dichlorobis(triphenylphosphine)palladium) are added to the compound III, the compound V, and a base (e.g., triethylamine) to carry out a coupling reaction to give the following compound VI. (Compound represented by Formula 3 above) can be obtained.

(Cyclization step)
The cyclization step in the present disclosure is a step of subjecting the compound represented by Formula 3 above to a cyclization reaction to produce the compound of the present disclosure.
The cyclization reactions can include cycloisomerization reactions, oxidative cyclization reactions, and the like.

The cyclization step is not particularly limited as long as it is a method capable of producing the compounds of the present disclosure, and known methods may be used.
The cyclization step can be performed, for example, by the method shown below.
As shown in the reaction formula below, palladium chloride is used as a catalyst, and compound VI is cycloisomerized with THF (tetrahydrofuran) to obtain compound VII below.
Compound VII is then oxidatively cyclized to give compound VIII using compound VII below and bis(trifluoroacetoxy)iodobenzene.

The method for producing the compound of the present disclosure is not limited to the method shown in the specific reaction scheme, and for example, compounds represented by formulas 2a to 2e other than compound III may be synthesized and used. Further, when producing the compound represented by Formula 3, the reaction of trimethylsilylacetylene and the coupling reaction via the elimination reaction of the trimethylsilyl group are not limited, and a coupling reaction via other reactions may be performed. good.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

(Example 1)
[Synthesis of compound]
-Synthesis of compound III-
First, compound III (compound A described above) was synthesized by the following procedure.
The following compound I (1,8-diaminonaphthalene, 2.00 g, 12.7 mmol) was dissolved in a mixed solution of ethanol (20 mL) and acetic acid (4.0 mL) and cooled to 0° C. under a nitrogen atmosphere. Isoamyl nitrite (1.7 mL, 12.7 mmol) was added, warmed to room temperature (25° C.) and stirred for 1 hour. The following compound II (2.02 g, 11.9 mmol, yield 94%) was obtained by washing the solid obtained by filtering the precipitate formed after stirring with ethanol.

Hydrobromic acid (48%, 10 mL) was added to a flask containing compound II (507 mg, 3.0 mmol) obtained above and copper shavings (38 mg, 0.60 mmol) under a nitrogen atmosphere, and the mixture was stirred for 16 hours. bottom. After that, 50 mL of water was added, and after heating at 100° C. and stirring for 1 hour, the resulting precipitate was filtered, and the filtrate was neutralized with aqueous ammonia. After the filtrate was extracted with ethyl acetate, the extract was washed with saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate. Compound III (460 mg, 2.1 mmol, yield 69%) was obtained by alumina column chromatography (ethyl acetate/hexane=1/10 (by volume)).

-Synthesis of compound VI-
Next, compound VI was synthesized by the following procedure.
A Schlenk tube containing compound III obtained above (491 mg, 2.21 mmol), copper iodide (13 mg, 0.066 mmol) and dichlorobis(triphenylphosphine) palladium (14 mg, 0.020 mmol) under a nitrogen atmosphere. , triethylamine 6.0 mL and trimethylsilylacetylene (0.35 mL, 2.5 mmol) were added, heated to 50° C. and stirred for 3 hours. After that, the reaction solution was extracted with dichloromethane, washed with a saturated sodium chloride aqueous solution, and dried with anhydrous sodium sulfate. Purification by silica gel column chromatography (ethyl acetate/hexane=1/20 to 1/10 (by volume)) gave compound IV (502 mg, 2.10 mmol, yield 95%).

To a flask containing compound IV (561 mg, 2.34 mmol) obtained above and potassium fluoride (546 mg, 9.40 mmol), 12 mL of methanol was added under a nitrogen atmosphere, heated to 40° C., and stirred for 5 hours. After that, water was added to the reaction solution, and the mixture was extracted with ethyl acetate, washed with a saturated aqueous sodium chloride solution, and dried with anhydrous sodium sulfate. Purification by silica gel column chromatography (ethyl acetate/hexane=1/20 (by volume)) gave compound V (386 mg, 2.31 mmol, yield 99%).

Compound III above (91 mg, 0.41 mmol), Compound V above (76.1 mg, 0.45 mmol), copper iodide (3.0 mg, 0.016 mmol) and dichlorobis(triphenylphosphine)palladium (8.6 mg, 0 012 mmol), 2.0 mL of triethylamine was added in a nitrogen atmosphere, heated to 50° C., and stirred for 5 hours. After that, water was added to the reaction solution, and after extraction with dichloromethane, the extract was washed with a saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate. Then, reprecipitation was performed using a chloroform/hexane mixed solution to obtain compound VI (90 mg, 0.29 mmol, yield 72%).

-Synthesis of Compound VIII-
Finally, compound VIII was synthesized by the following procedure.
THF (tetrahydrofuran, 6.4 mL) was added to a Schlenk tube containing the above compound VI (97 mg, 0.31 mmol) and palladium chloride (11 mg, 0.062 mmol) under a nitrogen atmosphere, heated to 60°C and stirred for 2 hours. bottom. After that, the reaction solution was concentrated and purified by silica gel column chromatography (ethyl acetate/hexane=1/10 (by volume)) to obtain compound VII (83 mg, 0.27 mmol, yield 86%).

Bis(trifluoroacetoxy)iodobenzene (154 mg, 0.36 mmol) was added to a solution of compound VII (50 mg, 0.16 mmol) in dichloromethane (22 mL), and the mixture was stirred at room temperature for 1 hour. After that, water was added to the reaction solution, and the mixture was extracted with dichloromethane, washed with a saturated aqueous sodium chloride solution, and dried with anhydrous sodium sulfate. After purification by silica gel column chromatography (toluene/hexane = 2/1 (by volume)), reprecipitation was performed using a chloroform/hexane mixed solution to obtain compound VIII (19 mg, 0.061 mmol, yield 38%). .

〔evaluation〕
(Reduction potential measurement (cyclic voltammetry))
The reduction potential was measured by the following measuring method.
The compound VIII obtained above was dissolved in THF containing 0.1 M tetrabutylammonium hexafluorophosphate as an electrolyte, and argon bubbling was performed to obtain a measurement solution. A silver/silver chloride electrode was used as a reference electrode, and a platinum wire was used as a working electrode and a counter electrode, respectively, and measurements were made at a sweep rate of 0.1 V/s. The potential was calculated using ferrocene/ferrocenium ion as a reference material.
As a measurement result, as shown in FIG. 1, a two-step reversible reduction was observed at −1.33 V and −1.83 V.

(Measurement of absorption spectrum and emission spectrum)
Using a spectrophotometer V-630 and a spectrofluorophotometer FP-6200 (manufactured by JASCO Corporation) as measurement devices, the absorption spectrum and emission spectrum of a chloroform solution of compound VIII were measured using excitation light of 568 nm. It was measured.
As a measurement result, an absorption spectrum and an emission spectrum as shown in FIG. 2 were obtained.
Further, the molar extinction coefficient at the maximum absorption wavelength of 568 nm was 30000 M ⁻¹ cm ⁻¹ and the fluorescence quantum yield was 0.123.
In addition, 1 in FIG. 2 represents an absorption spectrum and 2 represents an emission spectrum.

(solubility)
The solubility of the compound was measured by the following method.
A solvent (density d) was added to compound VIII to prepare a saturated solution (with undissolved residue). Next, the saturated solution was filtered and the weight _W1 of the filtrate was measured. _The solvent was completely distilled off and the weight W2 of the remaining compound VIII was measured. Then, it was calculated as solubility (mg/mL)=W ₂ ×d/W ₁ .

As a measurement result, the solubility of Compound VIII was 2.5 mg/mL when THF (tetrahydrofuran, d=0.89) was used as the solvent. Further, when CHCl ₃ (chloroform, d=1.49) was used as a solvent, the solubility of compound VIII was 4.1 mg/mL.

The compounds of the present disclosure have oxidation-reduction activity and can be used for various purposes by performing various chemical modifications. Examples of the above applications include active materials for storage batteries, n-type semiconductor materials, hydrogen storage materials, and the like.

Claims (8)

A compound represented by the following formula 1,
When the ring structure A1 has the following formula 1a, the ring structure A2 has the following formula 1b, the following formula 1d or the following formula 1e and the following formula 1b, the substituent R ₂ or the substituent R ₃ is an adjacent substituent do not form a ring with each other,
Alternatively, a compound in which the ring structure A1 has any one of the following formulas 1b to 1e and the ring structure A2 has any one of the following formulas 1b to 1e .

In formulas 1a to 1e, * represents a bonding site with a nitrogen atom contained in ring structure A1 or ring structure A2, ** represents a bonding site with ring structure A1 or ring structure A2, and R ₁ to R ₁₁ each independently represents a substituent, and adjacent substituents may form a ring. X1, X4 to X6 and X11 each independently represent an integer of 0 to 4, and X2, X3 and X7 to X10 each independently represent an integer of 0 to 3. The compound according to claim 1, wherein the ring structure A1 and the ring structure A2 have a structure represented by the following formula 1b.

In formula 1b, * represents a binding site to the nitrogen atom contained in ring structure A1 or ring structure A2, ** represents a binding site to ring structure A1 or ring structure A2, and R ₂ and R ₃ are each Each substituent may be independently represented, and adjacent substituents may form a ring. Also, X2 and X3 each independently represent an integer of 0 to 3. At least one of the aromatic rings in the ring structure A1 and the ring structure A2 is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a formyl group, an acyl group, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, and a carbamoyl group. , cyano group, amino group, amido group, nitro group, hydroxyl group, alkoxy group, aryloxy group, mercapto group, sulfanyl group, sulfo group and halogeno group. Or a compound according to claim 2 . A storage battery active material comprising the compound according to any one of claims 1 to 3 . An n-type semiconductor material comprising the compound according to any one of claims 1 to 3 . A hydrogen storage material comprising a compound according to any one of claims 1-3 . A carbon chain having 2 to 5 carbon atoms has a leaving group at one end and an amino group at the other end, and the carbon atoms constituting the carbon chain are not bonded to hydrogen atoms and are aromatic rings providing a compound A comprising
a step of performing a coupling reaction at the site where the leaving group of the prepared compound A is bound to produce a compound represented by the following formula 3;
A step of subjecting a compound represented by the following formula 3 to a cyclization reaction to produce the compound according to any one of claims 1 to 3 ;
A method for producing a compound having

In formula 3, each R independently represents a residue obtained by removing a leaving group from compound A. 8. The method for producing a compound according to claim 7 , wherein the compound A is at least one selected from the following formulas 2a to 2e.

In Formulas 2a to 2e, X represents a leaving group, R ₁ to R ₁₁ each independently represent a substituent, and adjacent substituents may form a ring. X1, X4 to X6 and X11 each independently represent an integer of 0 to 4, and X2, X3 and X7 to X10 each independently represent an integer of 0 to 3.

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