JP5649159B2 - NOVEL COMPOUND AND PROCESS FOR PRODUCING THE SAME - Google Patents

Description

  The present invention relates to a novel compound in which an azulene ring is condensed and a method for producing the same.

  Dye materials are applied in a wide range of fields such as pigments, dye-sensitized solar cells, organic thin film solar cells, photodynamic therapy, recording materials, or imaging applications. In particular, for the purpose of promoting the use of light in the near infrared region, development of a dye material having a property of absorbing the light (also referred to as a near infrared dye material) is being promoted.

  For example, phthalocyanine is known as a dye material that forms a complex with a metal and usually exhibits blue to green. In addition, a dye material called naphthalocyanine in which the benzene ring of phthalocyanine is replaced with a naphthalene ring has a relatively narrow main absorption band in the near-infrared region (for example, near a wavelength of 800 nm), and emits light (Patent Document 1 and Non-Patent Document 1). (See Patent Document 1).

JP 2009-29955 (filed on February 12, 2009)

B. L. Wheeler et al. J. Am. Chem. Soc. Vol.106, p7404-7410 (1984) (published November 1984)

  However, the light absorption characteristics required for near-infrared dye materials differ depending on the application. Therefore, development of a novel near-infrared dye material having light absorption characteristics different from naphthalocyanine dye materials is eagerly desired.

  This invention is made | formed in view of the said subject, and makes it a main objective to provide the novel compound which has the characteristic which absorbs the light of a near infrared region, and its manufacturing method.

  In order to solve the above problems, the compound according to the present invention, or an isomer thereof, has the following general formula (1),

(In the general formula (1), R1, R2, and R3 each independently represent a hydrogen atom, an aromatic ring group that may have a substituent, or a non-aromatic ring substituent having 0 to 20 carbon atoms, R1 and R2, R2 and R3 present in the same azulene ring may be bonded to form a ring, and R1s, R2 and R3 present in different azulene rings may be different from each other. M represents two hydrogen atoms or a divalent or higher cation atom, provided that when the cation atom is trivalent or higher, it may further have a counter anion having 20 or less carbon atoms.
It is characterized by being expressed.

  In the compound according to the present invention, or an isomer thereof, R1, R2, and R3 in the general formula (1) are independently of each other from a hydrogen atom; a nitro group; a cyano group; a chlorine atom, a bromine atom, a fluorine atom, and iodine. A halogen atom selected from the group consisting of: a chain alkyl group having 20 or less carbon atoms which may have a substituent; a cycloalkyl group having 20 or less carbon atoms which may have a substituent; An optionally substituted alkoxy group or aryloxy group having 20 or less carbon atoms; an optionally substituted alkylthio group or arylthio group having 20 or less carbon atoms; an optionally substituted acyl group; It is preferably an alkoxycarbonyl group having 20 or less carbon atoms which may have a group; or a heterocyclic group.

  The compound according to the present invention, or an isomer thereof, in the general formula (1), M is Mg, Al, Si, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y More preferably, any one selected from the group consisting of Zr, Nb, Ru, Sb, Pd, and Pt.

  The near-infrared light absorbing material according to the present invention includes the above-described compound according to the present invention or an isomer thereof.

  The solar cell element according to the present invention is characterized by including the above-described compound according to the present invention or an isomer thereof as a light-absorbing dye. The solar cell element also includes a photoelectric conversion member that converts light absorbed by the light-absorbing dye into electricity.

  The present invention also includes any one of the following general formulas (2) to (5):

(In the general formulas (2) to (5), R 1, R 2 and R 3 are each independently a hydrogen atom, an aromatic ring group which may have a substituent, or a non-aromatic ring substitution having 0 to 20 carbon atoms. Represents a group).

  The present invention is also a method for producing a compound represented by the above general formula (1), or an isomer thereof, wherein at least one selected from the compounds represented by the above general formula (2), the above general formula At least one selected from the compounds represented by (3), at least one selected from the compounds represented by the general formula (4), or at least selected from the compounds represented by the general formula (5) A method comprising the step of condensing one species is provided.

  According to the present invention, there is an effect that a novel compound having a property of absorbing light in the near infrared region and a method for producing the same are provided.

It is a figure which shows the light absorption spectrum of the compound (mixture of an isomer) which concerns on one Example of this invention.

[Embodiment 1]
(Compound according to the present invention)
The novel compound according to the present invention has the following general formula (1),

It is represented by

  Here, in the general formula (1), R1, R2, and R3 each independently represent a hydrogen atom, an aromatic ring group that may have a substituent, or a non-aromatic ring substituent having 0 to 20 carbon atoms. R1 and R2, R2 and R3 present in the same azulene ring may be bonded to each other to form a ring. Moreover, R1 which exists in a different azulene ring contained in General formula (1), R2 and R3 may mutually differ. However, from the viewpoint of easy synthesis, it is preferable that R1s, R2s, and R3s present in different azulene rings are the same.

<Aromatic ring group>
When R1, R2, and R3 are aromatic ring groups, the skeleton structure is not particularly limited. For example, as a 5-membered monocyclic ring, a furan ring, a thiophene ring, a pyrrole ring, an imidazole ring, a thiazole ring, an oxadiazole ring, Benzene ring, pyridine ring, pyrazine ring as 6-membered monocycle, naphthalene ring, phenanthrene ring, azulene ring, pyrene ring, quinoline ring, isoquinoline ring, quinoxaline ring, benzofuran ring, carbazole ring as 5- or 6-membered condensed ring , Dibenzothiophene ring, anthracene ring and the like. Among these, from the viewpoint of easier synthesis, a monocycle is preferable, a 6-membered monocycle is more preferable, and a benzene ring is particularly preferable.

  When R1, R2, and R3 are aromatic ring groups, the aromatic ring group may further have a substituent. The substituent is not particularly limited. For example, a chain alkyl group, a chain alkenyl group, a chain alkynyl group, a hydrocarbon ring group, a heterocyclic group, an alkoxy group, an alkylcarbonyl group, a (hetero) aryloxy group, ( Hetero) aralkyloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, or optionally substituted amino group, nitro group, cyano group, ester group, substituted group Good carbamoyl group, halogen atom, hydroxyl group and the like can be mentioned.

  Examples of chain alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, tert-butyl, hexyl, octyl, etc. A straight chain or branched chain having 20 or less, preferably 10 or less may be mentioned. The chain alkyl group may have a substituent such as a halogen atom.

  Examples of the chain alkenyl group include a vinyl group, a propenyl group, a butenyl group, a 2-methyl-1-propenyl group, a hexenyl group, an octenyl group, and the like. The thing of the shape is mentioned.

  Examples of the chain alkynyl group include straight chain or branched groups having 20 or less carbon atoms, preferably 10 or less, such as ethynyl group, propynyl group, butynyl group, 2-methyl-1-propynyl group, hexynyl group, and octynyl group. The thing of the shape is mentioned.

  Examples of the hydrocarbon ring group include a cyclopropyl group, a cyclohexyl group, a tetradecahydroanthranyl group, etc., having 3 or more carbon atoms, preferably 5 or more, and 20 or less carbon atoms, preferably 10 or less carbon atoms. A cycloalkyl group; a cycloalkenyl group such as a cyclohexenyl group having 3 or more, preferably 5 or more carbon atoms and having 20 or less, preferably 10 or less carbon atoms; phenyl group, anthranyl group, phenanthryl group, ferrocenyl Examples thereof include an aryl group having 6 or more carbon atoms and 18 or less, preferably 10 or less carbon atoms, such as a group. The hydrocarbon ring group may have a substituent such as a halogen atom.

  Examples of the heterocyclic group include a heteroaryl group composed of a 5-6 membered monocyclic ring or a condensed ring formed by condensing 2-6 6-5 ring members, a 5-6 membered monocyclic ring, or a 5- A heterocycloalkyl group composed of a condensed ring formed by condensing 2 to 6 6-membered rings is exemplified, and examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. Specifically, a 5-membered monocyclic ring such as a thienyl group; a monocyclic 6-membered ring such as a pyridyl group, 2-piperidinyl group, 2-piperazinyl group; a benzothienyl group, a carbazolyl group, a quinolinyl group, an octahydroquinolyl group Examples include condensed rings formed by condensing 2 to 6 5- to 6-membered rings such as nyl groups.

  Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, iso-butoxy, sec-butoxy, tert-butoxy, hexyloxy, octyloxy, and the like. The number of carbon atoms is preferably 2 or more and 9 or less, preferably 8 or less. The alkoxy group may have a substituent such as a halogen atom.

  Examples of the alkylcarbonyl group include those having 18 or less carbon atoms, preferably 8 or less, such as a methylcarbonyl group, an ethylcarbonyl group, an isopropylcarbonyl group, a tert-butylcarbonyl group, and a cyclohexylcarbonyl group.

  Examples of (hetero) aryloxy groups include aryloxy groups having 6 to 18 carbon atoms, preferably 10 or less, such as phenoxy groups and naphthyloxy groups; 2-thienyloxy groups, 2-furyloxy groups, Examples thereof include heteroaryloxy groups such as a 2-quinolyloxy group having 5 or more and 18 or less, preferably 10 or less carbon atoms, including heteroatoms selected from a nitrogen atom, an oxygen atom, a sulfur atom, and the like. . The (hetero) aryloxy group may have a substituent such as a halogen atom.

  Examples of the (hetero) aralkyloxy group include an aralkyloxy group having 7 to 18 carbon atoms, preferably 12 or less, such as benzyloxy group, phenethyloxy group, and naphthylmethoxy group; 2-thienylmethoxy group, 2 A heteroaralkyloxy group having 6 or more and 18 or less, preferably 10 or less carbon atoms, such as a furylmethoxy group or a 2-quinolylmethoxy group, and a heteroatom selected from a nitrogen atom, an oxygen atom, a sulfur atom, and the like Group and the like.

  All of the alkylthio group, arylthio group, and alkoxycarbonyl group preferably have 20 or less carbon atoms, more preferably 10 or less, and may have a substituent such as a halogen atom.

  Examples of the amino group that may have a substituent include an amino group, an alkylamino group, and a (hetero) arylamino group.

  Examples of the alkylamino group include an ethylamino group, a dimethylamino group, a methylethylamino group, a dibutylamino group, a piperidyl group, etc., having 2 or more carbon atoms, preferably 3 or more, and 20 or less carbon atoms, Preferably the thing of 10 or less is mentioned.

  Examples of (hetero) arylamino groups include arylamino groups having 6 to 30 carbon atoms, preferably 15 or less carbon atoms, such as diphenylamino group, dinaphthylamino group, naphthylphenylamino group, and ditolylamino group; 2-thienyl) amino group, di (2-furyl) amino group, etc., having 5 or more carbon atoms, preferably 6 or more, and 30 or less, preferably 15 or less, nitrogen atoms and oxygen as heteroatoms Heteroarylamino group containing what is chosen from an atom, a sulfur atom, etc .; Carbon number is 11 or more, preferably 12 or more, and carbon number is 30 or less, preferably 16 or less, such as phenyl (2-thienyl) amino group Arylheteroarylamino group of the above.

  Examples of the carbamoyl group which may have a substituent include a carbamoyl group and an alkylcarbamoyl group.

  Examples of the alkylcarbamoyl group include those having 2 to 20 carbon atoms, preferably 10 or less, such as an N-methylcarbamoyl group, an N, N-dimethylcarbamoyl group, and an N-ethyl-N-cyclohexylcarbamoyl group. Can be mentioned.

  Examples of the ester group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a tert-butoxycarbonyl group, an acetyloxy group, a benzoyloxy group, and the like. Is 10 or less.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

<Non-aromatic ring substituent>
When R1, R2, or R3 is a non-aromatic ring substituent having 0 to 20 carbon atoms, specific examples thereof include a substituent that may be further present when R1, R2, or R3 is an aromatic ring group. Among the specific examples described above, examples of the group include substituents other than the aromatic ring group.

<Ring structure>
In the general formula (1), R1 and R2 existing in the same azulene ring may be bonded to each other to form a ring. Further, R2 and R3 present in the same azulene ring may be bonded to each other to form a ring structure. The ring structure may further have a substituent having 20 or less carbon atoms. Specific examples of the substituent include the same substituents as the above-described specific examples as the substituent that may further be present when R1, R2, or R3 is an aromatic ring group.

<Preferable combination of R1, R2 and R3>
In general formula (1), R 1, R 2 and R 3 are independently of each other hydrogen atom; nitro group; cyano group; halogen atom selected from the group consisting of chlorine atom, bromine atom, fluorine atom and iodine; An optionally substituted alkyl group having 20 or less carbon atoms; an optionally substituted cycloalkyl group having 20 or less carbon atoms; an optionally substituted alkoxy group having 20 or less carbon atoms or an aryl group An oxy group; an optionally substituted alkylthio group or arylthio group having 20 or less carbon atoms; an optionally substituted acyl group having 20 or less carbon atoms; an optionally substituted carbon It is preferably any one selected from the group consisting of an alkoxycarbonyl group having a number of 20 or less; and a heterocyclic group.

  In the general formula (1), R1, R2, and R3 are independently of each other a hydrogen atom; a nitro group; a cyano group; a halogen atom selected from the group consisting of a chlorine atom, a bromine atom, a fluorine atom, and iodine; More preferably, it is any one selected from the group consisting of an alkyl group having 5 or less carbon atoms which may have a substituent. More specifically, R2 is a hydrogen atom, and R1 and R3 are independently selected from the group consisting of a hydrogen atom; a nitro group; a cyano group; a chlorine atom, a bromine atom, a fluorine atom, and iodine. More preferably, it is any one selected from the group consisting of an atom and an alkyl group having 5 or less carbon atoms which may have a substituent.

  In the general formula (1), R 1 s, R 2 s, and R 3 s present in different azulene rings may be different from each other, but they are present in different azulene rings from the viewpoint of easy synthesis. R1s, R2s and R3s are preferably the same.

<M in general formula (1)>
In the general formula (1), M represents two hydrogen atoms or a divalent or higher cation atom. When M is a cation atom, the type thereof is not particularly limited as long as it can be bonded to the nitrogen atom of the condensed azulene ring skeleton. Specific examples thereof include Be, B, Mg, Al, Si, P, Ca, Ti, V, Cr, Fe, Ni, Co, Cu, Zn, Ga, Ge, Y, Zr, Nb, Ru, Sb, Pd, Pt, etc. are mentioned, More preferably, Mg, Al, Si, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Ru, Sb, Pd , And Pt.

  In addition, when M is a cation atom and the cation atom is trivalent or more, it may further have a counter anion (axial ligand) having 20 or less carbon atoms. Specific examples of the counter anion include water, alcohol, phenol, carboxylic acid, phosphonic acid, halogen, perchloric acid, periodic acid, cyanic acid, isocyanic acid, isothiocyanic acid, azide, nitric acid, carbonic acid, bicarbonate, Substituted or unsubstituted sulfuric acid (sulfuric acid, hydrosulfuric acid, methylsulfuric acid, etc.), methanesulfonic acid, trifluoromethanesulfonic acid, tosylic acid, substituted or unsubstituted phosphoric acid (phosphoric acid, hydrophosphoric acid, dihydrogen phosphate) Acid, phenylphosphoric acid, etc.), phosphorus hexafluoride, antimony hexafluoride, substituted or unsubstituted phosphinic acid (phosphinic acid, methylphosphinic acid, etc.), substituted or unsubstituted boronic acid (tetraphenylboronic acid etc.), Examples include anionized compounds such as benzenesulfonic acid, acetic acid, and trifluoroacetic acid. Among these, from the viewpoint of ease of synthesis and the like, it is preferable to have anionized water, alcohol or phenol.

(Isomers of compounds according to the present invention)
The compound represented by the general formula (1) according to the present invention has an isomer represented by the following general formula (6). The compound according to the present invention or an isomer thereof may be a mixture containing at least two isomers shown below. Or when preparing what contains only one type of compound or its isomer shown in the said General formula (1), what is necessary is just to refine | purify only a specific isomer from a mixture, for example. Although a refinement | purification process is not specifically limited, For example, it can carry out using in-phase or reverse phase HPLC.

(Agglomerates in which the compounds or isomers according to the present invention are accumulated)
In the compound represented by the above general formula (1) or an isomer thereof, when M is a trivalent or higher cation atom and has the above counter anion having 20 or less carbon atoms, the general formula is represented via the counter anion. One or more of the compounds shown in (1) or isomers thereof may be further bonded. That is, it can be a so-called sandwich type aggregate in which two or more compounds represented by the above general formula (1) or isomers thereof are bonded through one counter anion.

(Synthetic intermediate)
The present invention also provides a novel compound represented by the following general formula (2), (3), (4), or (5). These novel compounds can be used as synthetic intermediates for producing the compound represented by the general formula (1) or an isomer thereof as described later.

  In the general formulas (2), (3), (4), and (5), R1, R2, and R3 are each independently a hydrogen atom, an aromatic ring group that may have a substituent, or carbon. Represents a non-aromatic ring substituent of 0-20. Here, the definitions of “optionally substituted aromatic ring group” and “non-aromatic ring substituent having 0 to 20 carbon atoms” are the same as in the case of the compound represented by the general formula (1). .

(Compound according to the present invention, and method for producing isomer)
The compound represented by the general formula (1) or an isomer thereof is selected from, for example, at least one selected from the compounds represented by the general formula (2), from the compounds represented by the general formula (3). In addition, it is produced by condensing at least one selected from the compounds represented by the general formula (4) or at least one selected from the compounds represented by the general formula (5).

<Production Example of Compound Represented by General Formula (2)>
A dihalogenated azulene (for example, 5,6-dibromoazulene) in which hydrogens at the 5th and 6th positions of the 7-membered ring constituting azulene are substituted with a halogen atom is used as a reference (Y. Lu et al. J. Am. Chem). Soc. Vol.122, p.2440-2445 (2000)).

  Next, a cyanating agent (for example, copper cyanide) is reacted with the obtained dihalogenated azulene to obtain 5,6-dicyanoazulene. Furthermore, if necessary, the compound represented by the general formula (2) is obtained by reacting the reagent for introducing R1, R2 and R3 with 5,6-dicyanoazulene in one step or multiple steps. . For example, when R1, R2 and R3 are alkyl groups, an alkylating agent (a combination of an alkyl halide and aluminum trichloride or the like) is reacted. When a halogen atom is used, a halogenating agent is reacted. The reaction conditions such as the amount of the reagent for introducing R1, R2 and R3, the reaction temperature, the reaction solvent and the like are not particularly limited as long as the compound represented by the general formula (2) is obtained. Good. In addition, in the production, the description of Examples described later is also referred to.

<Production Example of Compound Represented by General Formula (3), (4), or (5)>
For the derivative represented by the general formula (3), for example, a nitrogen source (ammonia, urea, etc.) and a metal alkoxide may be reacted with the compound represented by the general formula (2). For the derivative represented by the general formula (4) and the derivative represented by the general formula (5), for example, the derivative represented by the general formula (3) may be oxidized stepwise. In addition, in the production, the description of Examples described later is also referred to.

<Production Example of Compound Represented by General Formula (1) or its Isomer>
The compound represented by the general formula (1) or an isomer thereof is obtained by condensing four molecules of at least one selected from the compound represented by the general formula (2) or in the general formula (3). By condensing four molecules of at least one selected from the compounds represented, or by condensing four molecules of at least one selected from the compounds represented by the general formula (4), or It is produced by condensing four molecules of at least one selected from the compound represented by (5).

  Said condensation is performed in a solvent as needed. As a solvent, what does not react with the compound represented by the said General formula (2), (3), (4) or (5) can be utilized suitably. Although not particularly limited, the solvent is, for example, an aliphatic hydrocarbon such as hexane, heptane, or octane; an alicyclic hydrocarbon such as cyclohexane; an aromatic hydrocarbon such as benzene or toluene; methanol, ethanol, propanol, or hexanol. And alcohols such as cyclohexanol; various ethers such as tetrahydrofuran; dimethylformamide; and the like.

  If necessary, a catalyst and cocatalyst are used for the above condensation. The catalyst and the cocatalyst are not particularly limited as long as the above condensation can be performed, and specific examples include alkali metal alkoxides, alkaline earth metal alkoxides, ammonium molybdate, dimethylaminoethanol, and the like. It is done.

  In addition, when condensing the compound represented with the said General formula (4) or (5), it is necessary to coexist nitrogen-containing compounds, such as ammonia and urea, for example.

  The introduction of M in the general formula (1) is carried out by allowing the compound containing M to coexist during the condensation, or further reacting with the compound containing M after the condensation. This can be done. Further, after the introduction of M, the counter anion can be introduced by allowing the counter anion to coexist if necessary.

(Use)
The compound of the present invention represented by the general formula (1) or an isomer thereof exhibits strong absorption in near infrared light. Therefore, the compound or its isomer can be used as a near infrared light absorbing material. Near-infrared absorbers include, for example, light-absorbing dyes for dye-sensitized solar cell elements or organic thin-film solar cell elements, light-absorbing dyes (light beams) used for photodynamic therapy (laser therapy, etc.), especially for photodynamic therapy targeting cancer. It is used as a light-sensitizing agent (recording material or the like) used for molecular imaging or optical recording.

  It is known that light in the near-infrared light region (mainly having a wavelength of 700 nm to 1100 nm) is relatively excellent in cell tissue permeability. Therefore, if the compound of the present invention or an isomer thereof (may be a mixture) is used as a sensitizer in photodynamic therapy, for example, treatment of a deeper lesion can be performed or it is on the surface layer. It shows the effect that the possibility of giving side effects to normal cells can be reduced.

  In addition, as can be seen from the examples, the compound of the present invention or its isomer has an advantage that it is more excellent in chemical stability than, for example, naphthalocyanine.

  In addition, the compound of the present invention or an isomer thereof can be used as a near-infrared light absorbing material in a solution state or a solid phase state (for example, in a film-formed state). Further, the method for bringing the compound or its isomer into a solution state or a solid phase state is not particularly limited, and a known method can be adopted.

  Hereinafter, the present invention will be described specifically by way of examples.

[Example 1: Production of synthetic intermediate]
The following compound a (1.83 mmol) and CuCN (5.5 mmol) were added to dimethylformamide (DMF) sufficiently substituted with argon, and the mixture was stirred and reacted for 17 hours under heating and reflux. The temperature was returned to room temperature, an aqueous sodium thiosulfate solution was added to the reaction solution, the product was extracted with ethyl acetate, dried, the solvent was evaporated, and the residue was purified with a silica gel column to obtain compound b. The yield of compound b was 83%. The reaction formula is shown below.

Next, compound b (0.1 mmol) and tert-butyl chloride (0.6 mmol) were dissolved in CH ₃ NO ₂ , and AlCl ₃ (0.3 mmol) was added, followed by stirring at room temperature. After 6 hours, water was added to the reaction solution, and the product was extracted with ethyl acetate. After drying, the solvent was distilled off and the residue was purified with a silica gel column to obtain compound c. The yield of compound c was 49%. The reaction formula is shown below.

[Example 2]
After adding Li (4.1 mmol) to n-hexanol sufficiently substituted with argon, the mixture was stirred at 80 ° C. to dissolve Li (generation of metal alkoxide). Subsequently, the compound c (0.68 mmol) obtained in Example 1 was added thereto, and the mixture was refluxed and stirred for 4 hours. After the reaction, the obtained reaction solution was dropped into a methanol solution to which several drops of 2N hydrochloric acid was added, and then insolubles were collected. After drying, purification was performed using a silica gel column and BioBead SX-8 (trade name, manufactured by Bio-Rad) to obtain a black compound d as a mixture of isomers according to the present invention. The yield of compound d was 12%. The reaction formula is shown below.

  Compound d was soluble in various organic solvents such as benzene, toluene, chloroform, methylene chloride, tetrahydrofuran (THF), dioxane and the like. That is, the compound d exhibits a property that it is easily dissolved in an organic solvent as compared with, for example, a naphthalocyanine-based material, and is excellent in handleability.

Compound d had an absorption band in a wide range from the ultraviolet visible region to the near infrared region, and λ _max in chloroform was 1085 nm (see FIG. 1). As shown by comparison in FIG. 1, compound d has a main absorption band on the longer wavelength side (900 nm to 1100 nm) than naphthalocyanine. Therefore, the compound d can be used as a very excellent near infrared light absorbing material. Furthermore, since the main absorption band of compound d covers the near-infrared region widely, for example, when used as a light-absorbing dye for a solar cell element, a solar cell element with excellent near-infrared light utilization efficiency is provided It becomes possible.

  Furthermore, as a result of electrochemical measurement of the compound d by cyclic voltammetry, the first oxidation potential was +0.4 V vs. Ag / AgCl, and the first reduction potential was -0.6 V vs. Ag / AgCl. . In the case of naphthalocyanine shown in FIG. 1, under the same measurement conditions, the first oxidation potential is +0.5 V vs. Ag / AgCl, and the first reduction potential is −0.9 V vs. Ag / AgCl. It was found that the absorption band in the near-infrared region was obtained by lowering the LUMO energy level without significantly changing the level. That is, compound d is a novel near-infrared light dye that is highly resistant to oxidation and stable.

Example 3
A synthetic reaction is carried out according to the method described in Example 2 except that the compound b shown in Example 1 is used in place of the compound c. As a result, a compound according to the present invention is obtained in which the tert-butyl group in compound d is a hydrogen atom. The reaction formula is shown below.

[Example 4: Production of metal complex]
The compound d (0.019 mmol) obtained in Example 2 and nickel acetate tetrahydrate (0.19 mmol) are dissolved in dimethylformamide sufficiently substituted with argon, and the reaction is carried out with stirring for 9 hours while heating under reflux. went. After returning the reaction solution to room temperature, the solvent was distilled off, and purification was performed with a silica gel column to obtain Compound e. The yield of compound e was 35%. The reaction formula is shown below. Λ _max of compound e in chloroform was 1059 nm.

[Example 5: Production of other metal complexes]
Except that nickel acetate tetrahydrate was replaced with zinc acetate, a synthesis reaction was performed according to the description in Example 4 above, thereby synthesizing a compound in which the central metal of compound e was replaced with nickel from zinc. The yield of this compound was 78%. The reaction formula is shown below. In addition, λ _max of this compound in chloroform was 1056 nm.

[Example 6: Production of other synthetic intermediates]
Compound a (1.46 mmol) and sodium methoxide (1.80 mmol) described in Example 1 were fed into sufficiently dried methanol and stirred at 70 ° C. for 7 hours while blowing NH ₃ gas. . After completion of the reaction, the reaction mixture was cooled to room temperature, the solvent was distilled off, and the residue was washed with water to obtain compound x. The reaction formula is shown below. The yield of compound x was 91%.

  The obtained compound x can be used, for example, as a synthesis intermediate for synthesizing the compound obtained in Example 3.

[Example 7: Production of other synthetic intermediates]
Compound a (0.10 mmol) and N-bromosuccinimide (0.60 mmol) are dissolved in benzene and reacted with stirring for 2 days while heating under reflux. After returning the reaction solution to room temperature, the solvent was distilled off, and purification was performed with a silica gel column to obtain Compound y. The reaction formula is shown below. The yield of compound y was 82%.

  The obtained compound y can be subjected to a condensation reaction according to the methods described in Examples 2 and 3.

  ADVANTAGE OF THE INVENTION According to this invention, the novel compound which has the characteristic which absorbs the light of a near infrared region, and its manufacturing method are provided.

Claims (7)

The following general formula (1) , (11), (21) or (31),

(Formula (1), (11), (21) and (in 31) in each, R1, R2, R3, independently of one another, a hydrogen atom, which may have a substituent aromatic ring group, or a carbon Represents a non-aromatic ring substituent of 0 to 20, and R1 and R2, R2 and R3 present in the same azulene ring may be bonded to each other to form a ring.
R 1 s, R 2 s, and R 3 s present in different azulene rings may be different from each other.
M represents two hydrogen atoms or a divalent or higher cation atom. However, when the cation atom is trivalent or more, it may further have a counter anion having 20 or less carbon atoms. )
A compound represented by the formula: Formula (1), (11), (21) and in (31) in each, R1, R2, R3, independently of one another, a hydrogen atom; a nitro group; a cyano group; a chlorine atom, a bromine atom, a fluorine atom, iodine A halogen atom selected from the group consisting of: a chain alkyl group having 20 or less carbon atoms which may have a substituent; a cycloalkyl group having 20 or less carbon atoms which may have a substituent; An optionally substituted alkoxy group or aryloxy group having 20 or less carbon atoms; an optionally substituted alkylthio group or arylthio group having 20 or less carbon atoms; an optionally substituted acyl group; The compound according to claim 1 , which is an alkoxycarbonyl group having 20 or less carbon atoms which may have a substituent; or a heterocyclic group . Formula (1), (11), in each in (21) and (31), M is, Mg, Al, Si, Ti , V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Ge, The compound according to claim 1 or 2, wherein the compound is any one selected from the group consisting of Y, Zr, Nb, Ru, Sb, Pd, and Pt . Near-infrared light absorbing material, characterized in it to contain a compound according to any one of claims 1 to 3. Solar cell element which comprises a compound according to any one of claims 1 to 3 as Hikari吸 yield dye. Any of the following general formulas (2) to (5),

(In the general formulas (2) to (5), R 1, R 2 and R 3 are each independently a hydrogen atom, an aromatic ring group which may have a substituent, or a non-aromatic ring substitution having 0 to 20 carbon atoms. Represents a group.)
A compound represented by the formula: A method for producing the compound according to any one of claims 1 to 3,

(In the general formulas (2) to (5), R 1, R 2 and R 3 are each independently a hydrogen atom, an aromatic ring group which may have a substituent, or a non-aromatic ring substitution having 0 to 20 carbon atoms. Represents a group.)
At least one selected from the compound represented by the general formula (2), at least one selected from the compound represented by the general formula (3), and a compound represented by the general formula (4) And a method of condensing at least one selected from the compounds represented by the general formula (5).

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