WO2011142329A1 - Complex compound and optical recording medium containing same - Google Patents

Abstract

Disclosed is a complex compound, and the like, comprising: the compound represented by formula (I) (wherein: R¹ and R³ are the same or different and represent a hydrogen atom, an alkyl group that may have a substituent group, an aryl group that may have a substituent group, or the like; R² represents an alkyl group that may have a substituent group, an aryl group that may have a substituent group, or the like; and R⁴ represents formula (III) (wherein ring A may further have a substituent group), or the like) used in an optical recording medium and having excellent resistance to moist heat and the like; a metal; and at least one ion selected from the group consisting of ammonium ions, quaternary ammonium ions, and ions generated by at least one proton being added to an amine.

Description

Complex compound and optical recording medium containing the same

The present invention relates to a complex compound used for an optical recording medium or the like.

In recent years, an optical recording medium capable of performing ultra-high density recording using a technique for increasing the numerical aperture NA of the objective lens, a technique for reducing the laser wavelength λ, and the like has been developed. For example, in order to record video information of HDTV (high definition television) for 2 hours or more, an optical recording medium having the same size as a DVD and a capacity of at least 23 GB is required. In order to meet these demands, a blue-violet laser beam is used, the NA of the objective lens is set to 0.85, and the laser spot diameter is reduced, so that an optical recording medium for recording higher density information, so-called Blu. -Ray Disc (BD) was developed.

A dye used for such an optical recording medium is required to have excellent characteristics such as heat and moisture resistance.
Known dyes for forming a recording layer of an optical recording medium include a complex composed of a hydrazide compound ligand and a transition metal cation (see Patent Document 1), a metal chelate complex compound composed of a hydrazide compound and a metal atom (see Patent Document 2), and the like. ing. However, these compounds have insufficient characteristics such as resistance to moist heat.

JP 2007-223289 A JP 2008-45092 A

An object of the present invention is to provide a complex compound or the like used for an optical recording medium having excellent moisture and heat resistance.

The present invention provides the following [1] to [14].
[1] Formula (I)

[Wherein, R ¹ and R ³ are the same or different and each has a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. Represents an aralkyl group which may have a substituent, an aryl group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent, R ² May have a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, an amino group which may have a substituent, an alkyl group which may have a substituent, or a substituent. An alkenyl group, an alkoxyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, an alicyclic ring which may have a substituent Represents a heterocyclic group optionally having a hydrocarbon group or a substituent, and R ⁴ is the formula (II)

(In the formula, R ⁵ has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aralkyl group which may have a substituent, and a substituent. An aryl group, an alicyclic hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent), or a formula (III)

(Wherein ring A may further have a substituent)], a metal, an ion generated by adding one or more protons to an amine, an ammonium ion, and a A complex compound comprising one kind selected from the group consisting of quaternary ammonium ions.
[2] The complex compound according to [1], wherein R ¹ is an aryl group which may have a substituent.
[3] The complex compound according to [1] or [2], wherein R ² is an alkyl group which may have a substituent or an aryl group which may have a substituent.
[4] The complex compound according to any one of [1] to [3], wherein R ³ is a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
[5] The complex compound according to any one of [1] to [4], wherein R ⁴ is formula (II).
[6] The complex compound according to [5], wherein R ⁵ is an aryl group which may have a substituent or a heterocyclic group which may have a substituent.
[7] The complex compound according to any one of [1] to [4], wherein R ⁴ is formula (III).
[8] Formula (III) is formula (IV)

(In the formula, R ⁶ has an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. The alicyclic hydrocarbon group or a heterocyclic group which may have a substituent).
[9] The complex compound according to any one of [1] to [8], wherein the metal is cobalt, rhodium, iridium, aluminum, gallium or iron.
[10] The complex compound according to any one of [1] to [8], wherein the metal is cobalt.
[11] Ion generated by adding one or more protons to an amine, one selected from the group consisting of an ammonium ion and a quaternary ammonium ion is an ion generated by adding one or more protons to an amine The complex compound according to any one of [1] to [10].
[12] The complex compound according to [11], wherein the amine is an aliphatic tertiary amine which may have a substituent.
[13] One selected from the group consisting of an ion generated by adding one or more protons to an amine, an ammonium ion and a quaternary ammonium ion is a quaternary ammonium ion [1] to [10] The complex compound in any one of.
[14] An optical recording medium containing the complex compound according to any one of [1] to [13].

According to the present invention, it is possible to provide a complex compound or the like used for an optical recording medium having excellent moisture and heat resistance.

Hereinafter, the compound represented by Formula (I) is referred to as Compound (I). The same applies to the compounds of other formula numbers.

In the definition of each group in the general formula, examples of the alkyl part of the alkyl group and the alkoxyl group include a linear or branched alkyl group having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, and the like. Propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, 1-methylbutyl group, 2-methylbutyl group, tert-pentyl group, hexyl group, heptyl group, A 1-isopropyl-2-methylpropyl group, an octyl group, a nonyl group, a decyl group, an eicosyl group and the like can be mentioned. Among them, those having 1 to 10 carbon atoms are preferable.

Examples of the alkenyl group include linear or branched alkenyl groups having 2 to 20 carbon atoms. Specific examples include a vinyl group, an allyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, 1 -Methyl-2-butenyl group, 1-ethyl-2-propenyl group, octenyl group, nonenyl group, decenyl group, eicocenyl group and the like.
Examples of the aralkyl group include aralkyl groups having 7 to 15 carbon atoms, and specific examples include a benzyl group, a phenethyl group, a phenylpropyl group, and a naphthylmethyl group.

Examples of the aryl group include aryl groups having 6 to 14 carbon atoms, and specific examples include a phenyl group, a naphthyl group, an anthryl group, and an azulenyl group.
Examples of the alicyclic hydrocarbon in the alicyclic hydrocarbon group include, for example, a cycloalkane having 3 to 8 carbon atoms, a cycloalkene having 3 to 8 carbon atoms, and a bicyclic or tricyclic condensed 3- to 8-membered ring. And alicyclic hydrocarbons.
Specific examples of the cycloalkane having 3 to 8 carbon atoms include, for example, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane and the like.
Specific examples of the C3-C8 cycloalkene include, for example, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene and the like.
Specific examples of the bicyclic or tricyclic alicyclic hydrocarbon condensed with a 3- to 8-membered ring include dihydropentalene, dihydroindene, tetrahydronaphthalene, hexahydrofluorene and the like.

Examples of the heterocyclic ring in the heterocyclic group include an aromatic heterocyclic ring and an alicyclic heterocyclic ring.
As the aromatic heterocyclic ring, for example, a 5- or 6-membered monocyclic aromatic heterocyclic ring containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom is condensed. Examples include bicyclic or tricyclic condensed aromatic heterocycles containing at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom. Specific examples include a pyridine ring, a pyrazine ring, and a pyrimidine ring. , Pyridazine ring, quinoline ring, isoquinoline ring, phthalazine ring, quinazoline ring, quinoxaline ring, naphthyridine ring, cinnoline ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, triazine ring, tetrazole ring, thiophene ring, furan ring, thiazole Ring, oxazole ring, isoxazole ring, indole ring, isoindole ring, indazole ring, benzimidazole Lumpur ring, benzothiophene ring, benzotriazole ring, benzothiazole ring, benzoxazole ring, purine ring, carbazole ring, acridine ring, phenazine ring, phenothiazine ring, a phenoxazine ring, a phenanthroline ring, and the like.

As the alicyclic heterocycle, for example, a 5- to 8-membered monocyclic alicyclic heterocycle containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom is condensed. A bicyclic or tricyclic condensed alicyclic heterocyclic ring containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, specifically, a pyrrolidine ring, a piperidine ring, Piperazine ring, morpholine ring, thiomorpholine ring, homopiperidine ring, homopiperazine ring, tetrahydropyridine ring, tetrahydroquinoline ring, tetrahydroisoquinoline ring, tetrahydrofuran ring, tetrahydropyran ring, dihydrobenzofuran ring, indoline ring, tetrahydrocarbazole ring, 1, And 8-diazabicyclo [5.4.0] undec-7-ene ring.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Ring A includes, for example, those having —CH═N— among the heterocyclic rings listed above, and specifically includes a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a quinoline ring, and an isoquinoline ring. , Phthalazine ring, quinazoline ring, quinoxaline ring, naphthyridine ring, cinnoline ring, pyrrole ring (2H-pyrrole ring, 3H-pyrrole ring), pyrazole ring, imidazole ring, triazole ring, triazine ring, tetrazole ring, thiazole ring, oxazole ring , Isoxazole ring, indole ring (3H-indole ring), isoindole ring, indazole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, purine ring, tetrahydropyridine ring (2,3,4,5-tetrahydropyridine) Ring) and the like.

Examples of the substituent of the amino group include one or two alkyl groups. Here, the alkyl group has the same meaning as described above. When the amino group has two alkyl groups, the two alkyl groups may be the same or different.

Examples of the substituent of the alkyl group and the alkoxyl group include 1 to 5 substituents that are the same or different, specifically, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a carbamoyl group, and a substituent. Amino group, alkoxyl group, alkoxyalkoxyl group, alkanoyl group, alkylcarbonyloxy group, alkoxycarbonyl group, aroyl group, aryloxy group, arylcarbonyloxy group, aryloxycarbonyl group, heterocyclic group and the like may be mentioned. . Here, the halogen atom, the amino group which may have a substituent, the alkoxyl group, and the heterocyclic group are as defined above. The alkyl portions of the alkanoyl group, alkylcarbonyloxy group and alkoxycarbonyl group are as defined above. The two alkoxy moieties of the alkoxyalkoxyl group have the same meaning as the above alkoxyl group, respectively. The aryl part of the aroyl group, aryloxy group, arylcarbonyloxy group and aryloxycarbonyl group has the same meaning as the above aryl group.

Examples of the substituent for the aralkyl group, aryl group, and alicyclic hydrocarbon group include the same or different 1 to 5 substituents, specifically, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a carbamoyl group. Group, amino group optionally having substituent, alkyl group optionally having substituent, alkoxyl group optionally having substituent, alkenyl group, aralkyl group, alkanoyl group, alkylcarbonyloxy Group, alkoxycarbonyl group, aryl group, aroyl group, aryloxy group, arylcarbonyloxy group, aryloxycarbonyl group, alicyclic hydrocarbon group, heterocyclic group and the like. Here, a halogen atom, an amino group which may have a substituent, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an alkenyl group, an aralkyl group, an alkanoyl group , Alkylcarbonyloxy group, alkoxycarbonyl group, aryl group, aroyl group, aryloxy group, arylcarbonyloxy group, aryloxycarbonyl group, alicyclic hydrocarbon group and heterocyclic group are as defined above.
Examples of the substituent for the alkenyl group include the groups listed above as the substituent for the alkyl group, and an aryl group which may have a substituent. Here, the aryl group which may have a substituent is as defined above.

Examples of the substituent of the heterocyclic group include the same or different 1 to 5 substituents, specifically, a hydroxyl group, an oxo group, a halogen atom, a nitro group, a cyano group, a carbamoyl group, and a substituent. An optionally substituted amino group, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkoxyl group, an aralkyl group, an alkanoyl group, Examples thereof include an alkylcarbonyloxy group, an alkoxycarbonyl group, an aryl group which may have a substituent, an aroyl group, an aryloxy group, an arylcarbonyloxy group, an aryloxycarbonyl group, and a heterocyclic group. Here, a halogen atom, an amino group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. Alkoxyl group, aralkyl group, alkanoyl group, alkylcarbonyloxy group, alkoxycarbonyl group, optionally substituted aryl group, aroyl group, aryloxy group, arylcarbonyloxy group, aryloxycarbonyl group and heterocyclic group Are as defined above.

Examples of the substituent when ring A further has a substituent include, for example, the same or different 1 to 5 substituents, specifically, a hydroxyl group, an oxo group, a halogen atom, a nitro group, a cyano group, A carbamoyl group, an amino group which may have a substituent, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aralkyl group which may have a substituent And an aryl group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, and the like. Here, it may have a halogen atom, an amino group which may have a substituent, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. The aralkyl group, the aryl group that may have a substituent, the alicyclic hydrocarbon group that may have a substituent, and the heterocyclic group that may have a substituent have the same meanings as described above.

In each group of formula (I):
R ¹ is preferably an aryl group which may have a substituent.
R ² is preferably an alkyl group which may have a substituent and an aryl group which may have a substituent, and more preferably an alkyl group which may have a substituent.
R ³ is preferably a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent, and more preferably an aryl group which may have a substituent.
When R ⁴ is the formula (II), R ⁵ is preferably an aryl group which may have a substituent and a heterocyclic group which may have a substituent.
When R ⁴ is the formula (III), the ring A of the formula (III) is preferably a tetrazole ring or a benzoxazole ring, and more preferably a tetrazole ring.
When R ⁴ is the formula (III), the formula (III) is preferably the formula (IV). R ⁶ is preferably an aryl group which may have a substituent.
The compound (I) is preferably a compound in which the above-described preferred groups R ¹ , R ² , R ³ and R ⁴ are combined.
Examples of the metal include cobalt, rhodium, iridium, aluminum, gallium, iron and the like, and among these, cobalt is preferable.

An amine in an ion generated by adding one or more protons to an amine (hereinafter referred to as an amine cation) includes one having a basic nitrogen atom (monoamine) or a basic nitrogen atom. (Polyamine) having two or more can be used. Specific examples of amines include, for example, aliphatic primary amines which may have a substituent and those having 1 to 30 carbon atoms (for example, butylamine, ethanolamine, ethylenediamine, etc.), and those having a substituent. May be an aliphatic secondary amine having 2 to 30 carbon atoms (for example, dibutylamine, diethanolamine, etc.), and an aliphatic tertiary amine optionally having a substituent having 3 to 30 carbon atoms (for example, Triethylamine, triethanolamine, diisopropylethylamine and the like), an alicyclic amine having 3 to 30 carbon atoms which may have a substituent, an aromatic amine which may have a substituent, and a substituent. May be a basic nitrogen-containing heterocyclic compound (for example, pyridine, quinoline, indole, benzothiazole, bipyridine, phenanthroline, 1,8-diazabicyclo [5.4 .0] undec-7-ene), amines containing silicon (for example, heptamethyldisilazane, etc.).

Examples of the alicyclic amine include a 3- to 8-membered monocyclic alicyclic hydrocarbon ring, which may have an aliphatic chain on a basic nitrogen atom, or a basic nitrogen atom. And an amine which may have an aliphatic chain between the monocyclic alicyclic hydrocarbon ring and the like. Here, examples of the aliphatic chain that may be present on the basic nitrogen atom include the groups listed above as the alkyl group. Examples of the aliphatic chain that may be present between the basic nitrogen atom and the monocyclic alicyclic hydrocarbon ring include, for example, 1 hydrogen atom on carbon from the groups listed above as the alkyl group. The alkylene group etc. which arise by removing are illustrated. Specific examples of the alicyclic amine include cyclohexylamine and (cyclohexylmethyl) amine.

Examples of the aromatic amine include an aromatic hydrocarbon ring such as a benzene ring and a naphthalene ring, and may have an aliphatic chain on a basic nitrogen atom. And an amine which may have an aliphatic chain between the aromatic hydrocarbon ring. Here, the aliphatic chain which may be present on the basic nitrogen atom is as defined above. Examples of the aliphatic chain that may be present between the basic nitrogen atom and the aromatic hydrocarbon ring include, for example, between the basic nitrogen atom and the monocyclic alicyclic hydrocarbon ring. Examples of the aliphatic chain that may be included include the groups listed above. Specific examples of the aromatic amine include aniline, naphthylamine, benzylamine, tribenzylamine and the like.

Examples of the substituent of the aliphatic primary amine, aliphatic secondary amine, and aliphatic tertiary amine include, for example, the same or different substituents having 1 to 5 substituents, specifically a hydroxyl group, a halogen atom, and a nitro group. Cyano group, carbamoyl group, alkoxyl group, alkoxyalkoxyl group, alkanoyl group, alkylcarbonyloxy group, alkoxycarbonyl group and the like. Here, the halogen atom, the alkoxyl group, the alkoxyalkoxyl group, the alkanoyl group, the alkylcarbonyloxy group and the alkoxycarbonyl group are respectively as defined above.

Among the substituents of alicyclic amine and aromatic amine, examples of the substituent in the ring in alicyclic amine and ring in aromatic amine include, for example, aliphatic primary amine, aliphatic secondary amine, and aliphatic tertiary amine. Examples of the substituent of the amine include the groups listed above and an alkyl group which may have a substituent. Here, the alkyl group which may have a substituent is as defined above. Examples of the substituent of the aliphatic chain when the alicyclic amine and the aromatic amine have an aliphatic chain include, for example, the above-mentioned substituents of the aliphatic primary amine, aliphatic secondary amine, and aliphatic tertiary amine. And the like.

Examples of the substituent of the basic nitrogen-containing heterocyclic compound include the same or different 1 to 5 substituents, specifically, a hydroxyl group, an oxo group, a halogen atom, a nitro group, a cyano group, and a carbamoyl group. , An alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkoxyl group which may have a substituent, an aralkyl group, an alkanoyl group, an alkylcarbonyloxy group, an alkoxycarbonyl Group, an aryl group optionally having a substituent, an aroyl group, an aryloxy group, an arylcarbonyloxy group, an aryloxycarbonyl group, and the like. Here, a halogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkoxyl group which may have a substituent, an aralkyl group, an alkanoyl group, an alkylcarbonyl The oxy group, alkoxycarbonyl group, optionally substituted aryl group, aroyl group, aryloxy group, arylcarbonyloxy group and aryloxycarbonyl group have the same meanings as described above.

As a quaternary ammonium ion, for example, formula (X)

(Wherein L ¹ and L ² are the same or different and are each a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryl which may have a substituent) An oxy group, an optionally substituted amino group or an optionally substituted aroyl group; p and q are the same or different and each represents an integer of 0 to 5, and p is 2 to 5 Each of L ¹ may be the same or different, and two L ¹ and the two adjacent carbon atoms together form a benzene ring which may have a substituent. And when q is an integer of 2 to 5, each of L ² may be the same or different, and two L ² and the two adjacent carbon atoms together have a substituent. May form a benzene ring that may be It is below.

Here, the halogen atom, the alkyl group that may have a substituent, the alkoxyl group that may have a substituent, the aryloxy group, the amino group that may have a substituent, and the aroyl group, respectively, It is synonymous. Examples of the substituent for the aryloxy group, aroyl group and benzene ring include the groups listed above as the substituents for the aralkyl group, aryl group and alicyclic hydrocarbon group.

L ¹ and L ² are preferably a fluorine atom, a fluorine-substituted alkyl group or a fluorine-substituted alkoxyl group.
Examples of the fluorine-substituted alkyl group include groups in which 1 to 5 hydrogen atoms of the groups listed above as alkyl groups are substituted with fluorine atoms.
The fluorine-substituted alkyl part of the fluorine-substituted alkoxyl group has the same meaning as the above-mentioned fluorine-substituted alkyl group.

Specific examples of quaternary ammonium ions are shown below. In the formula, Ph represents a phenyl group.

Examples of the complex compound composed of the compound (I), a metal, and one selected from the group consisting of an amine cation, an ammonium ion, and a quaternary ammonium ion include, for example, the formula (Y)

(Wherein R ¹ , R ² , R ³ and R ⁴ are as defined above, M represents a metal, and Q ^{n +} represents a group consisting of an amine cation, an ammonium ion and a quaternary ammonium ion. And a compound represented by the formula (n represents an integer of 1 to 3). Here, a metal, an amine, and a quaternary ammonium ion are respectively synonymous with the above. n is preferably 1 or 2.

Next, an example is given and demonstrated about the manufacturing method of compound (I).
Compound (I) is represented, for example, by reaction formula (1)

(Wherein R ¹ , R ² , R ³ and R ⁴ are as defined above). Specifically, the compound (VII) and the compound (V) are added in a solvent at 10 to 100 ° C. in the presence of 0.1 to 10-fold mol of acetic acid, if necessary, relative to the compound (VII). The compound (I) can be produced by reacting for 5 to 30 hours.
The amount of compound (VII) to be used is preferably 0.5 to 5 times the molar amount of compound (V).

Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, isopropyl alcohol, butanol and octanol, hydrocarbon solvents such as hexane, decane, tetradecane, toluene and xylene, diethyl ether, dibutyl ether, methoxybenzene and diphenyl ether. Ether solvents such as dichloromethane, dichloroethane, chloroform, chlorobenzene, dichlorobenzene and other halogen solvents, N, N-dimethylformamide, amide solvents such as N, N-dimethylacetamide, sulfur-containing solvents such as dimethyl sulfoxide, Examples include acetonitrile.

Among the compounds (VII), R ³ has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aralkyl group which may have a substituent, and a substituent. An aryl group that may be substituted, an alicyclic hydrocarbon group that may have a substituent, or a heterocyclic group that may have a substituent may be obtained as a commercial product or publicly known Methods such as “Heterocycles”, 2006, Vol. 68, p. 1825-1835, “Journal of Organic Chemistry”, 2003, Vol. 68, No. 21, p. 7943-7950, “Journal of Medicinal Chemistry”, 1987, Vol. 30, No. 10, p. 1807-1812, “Journal of Medicinal Chemistry”, 2006, Vol. 49, No. 5, p. It can be obtained by manufacturing according to the method described in 1562-1575.
Among compounds (VII), those in which R ³ is a hydrogen atom can be obtained as a commercial product or can be obtained by a known method, for example, “Tetrahedron Letters”, 1999, Vol. 40, No. 18, p. 3535-3538, “Bioorganic and Medicinal Chemistry”, 2009, Vol. 17, No. 15, p. It can be obtained by manufacturing according to the method described in 5716-5721.

The compound (V) in which R ⁴ is the formula (III) can be obtained as a commercial product, or can be obtained by publicly known methods such as the Japan Chemical Society, “Experimental Chemistry Course (Volume 20)”, Vol. 4th edition, Maruzen Co., Ltd., 1991, p. 30-46, p. 112-185, p. 279-290, p. 338-342, The Chemical Society of Japan, “Experimental Chemistry Course (Vol. 13)”, 5th edition, Maruzen Co., Ltd., 1991, p. 374-416, The Chemical Society of Japan, “Experimental Chemistry Course (Vol. 14)”, 5th edition, Maruzen Co., Ltd., 2003, p. 289-320, edited by Buehler & Pearson, “Survey of Organic Synthesis (Volume 1)”, Wiley-Interscience, 1970, p. 411-512, edited by Buehler & Pearson, “Survey of Organic Synthesis (Volume 2)”, Wiley-Interscience, 1977, p. 812-853, edited by Saul Patai, “The Chemistry of the amino group”, John Wiley & Sons, 1968, p. It can be obtained by manufacturing according to the method described in 277-347 and the like.

The compound (V) in which R ⁴ is the formula (II) can be obtained as a commercial product, or can be obtained by publicly known methods such as the Japan Chemical Society, “Experimental Chemistry Course (Volume 20) Synthesis and Reaction II ”, first edition, Maruzen Co., Ltd., 1956, p. 347-389, edited by the Chemical Society of Japan, “New Experimental Chemistry Course (Vol. 14) Synthesis and Reaction of Organic Compounds III”, 2nd edition, Maruzen Co., Ltd., 1978, p. 1573-1584, edited by Saul Patai, “The Chemistry of the Hydro, azo, and azoxy group (Vol. 1)”, John Wiley & Sons, 1975, p. 69-107, edited by Saul Patai, “The Chemistry of the Hydro, azo, and azoxy group (Volume 2)”, John Wiley & Sons, 1975, p. 599-723, edited by Gilman, “Organic Synthesis Collective (Volume 1)”, Shriner & Shriner, 1932, p. 450-453, edited by Blatt, “Organic Synthesis Collective (Volume 2)”, Shriner & Shriner, 1943, p. 85-87, edited by Baumgarten, “Organic Synthesis Collective (Volume 5)”, Shriner & Shriner, 1973, p. 166-170, Bryan Li et al., “Organic Synthesis (Vol. 81)”, 2005, p. It can be obtained by manufacturing according to the method described in 1108-1111.
After the reaction, if necessary, the compound (I) may be purified by methods usually used in organic synthetic chemistry (various chromatographic methods, recrystallization methods, distillation methods, etc.).

Compound (I) wherein R ³ is a hydrogen atom [Compound (Ia)] is, for example, reaction formula (2)

(Wherein R ¹ , R ² and R ⁴ are as defined above, and R ⁷ and R ⁸ are the same or different and each represents an alkyl group having 1 to 4 carbon atoms, etc.) You can also. Specifically, the compound (V) and the compound (VI) are mixed at 0 to 100 ° C. in a solvent in the presence of 0.1 to 10-fold mol of acetic acid with respect to the compound (VI), if necessary. The compound (Ia) can be produced by reacting for 5 to 30 hours.

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, and tert-butyl group.
The amount of compound (VI) used is preferably 0.5 to 5 times the molar amount of compound (V).
Examples of the solvent include those listed as solvents that can be used in the reaction formula (1).
Compound (VI) can be obtained as a commercial product or can be obtained by a known method, for example, “Heterocycles”, 2003, Vol. 61, p. 197-224, “Journal of Heterocyclic Chemistry”, 2001, Vol. 38, No. 4, p. It can be obtained by manufacturing according to the method described in 989-992.
After the reaction, if necessary, the compound (Ia) may be purified by methods usually used in organic synthetic chemistry (various chromatographic methods, recrystallization methods, distillation methods, etc.).

Next, the production method of the complex compound of the present invention will be described with examples.
The complex compound comprising compound (I), cobalt and an amine cation is, for example, compound (I), a cobalt salt or an organic cobalt compound, and an amine in a solvent in the presence of oxygen in the range of 0 to 120. It can be produced by reacting at a temperature of 0.degree. C. for 0.5 to 30 hours (this method is hereinafter referred to as Production Method 1).

Examples of the cobalt salt include cobalt acetate (II), cobalt chloride (II), cobalt bromide (II), cobalt iodide (II), cobalt fluoride (II), cobalt fluoride (II), and cobalt carbonate. (II), cobalt cyanide (II), hydrates thereof and the like.
Examples of the organic cobalt compound include sodium tris (carbonate) cobalt (III), cobalt (II) acetylacetonate hydrate, cobalt (III) acetylacetonate, and the like.

The amine can be obtained as a commercial product or can be obtained by a known method such as the Japan Chemical Society, “Experimental Chemistry Course (Volume 20) Synthesis and Reaction of Organic Compounds II”, 1st Edition, Maruzen Co., Ltd. Year, p. 391-582, edited by the Chemical Society of Japan, “New Experimental Chemistry Course (Volume 14) Synthesis and Reaction of Organic Compounds III”, 2nd edition, Maruzen Co., Ltd., 1978, p. 1332-1399, edited by The Chemical Society of Japan, “New Experimental Chemistry Course (Volume 20), Organic Synthesis II”, 4th edition, Maruzen Co., Ltd., 1992, p. 299-313, edited by the Chemical Society of Japan, “New Experimental Chemistry Course (Vol. 14) Synthesis of Organic Compounds II”, 5th Edition, Maruzen Co., Ltd., 2005, p. 351-377, edited by Buehler & Pearson, “Survey of Organic Synthesis (Volume 1)”, Wiley-Interscience, 1970, p. 411-512, edited by Buehler & Pearson, “Survey of Organic Synthesis (Volume 2)”, Wiley-Interscience, 1977, p. 391-459, edited by Saul Patai, “The Chemistry of the amino group”, John Wiley & Sons, 1968, p. 37-69, edited by Barton & Olis, “Comprehensive Organic Chemistry The Synthesis and Reactions of Organic Compounds (Volume 2)”, Pergamon Press, 79. 1-181, Katritzky & Rees, “Comprehensive Heterocyclic Chemistry”, Pergamon Press, 1984, p. It can be obtained by manufacturing according to the method described in 525-528.

The amount of compound (I) used is preferably 0.3 to 4 times the molar amount of the cobalt atom in the cobalt salt or organic cobalt compound.
When an amine having m basic nitrogen atoms is used, the amount of the amine used is 0.3 / m to 20 / m times the molar amount of the cobalt atom in the cobalt salt or organic cobalt compound. Is preferred.

Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, isopropyl alcohol, butanol and isobutanol, halogen solvents such as chloroform and dichloromethane, aromatic solvents such as benzene, toluene and xylene, tetrahydrofuran, methyl- Examples thereof include ether solvents such as tert-butyl ether, ester solvents such as ethyl acetate, ketone solvents such as acetone and methyl ethyl ketone, acetonitrile, and mixed solvents thereof.
After the reaction, the complex compound obtained by methods commonly used in organic synthetic chemistry (various column chromatography methods, recrystallization methods, washing with a solvent, etc.) may be purified as necessary.

In place of the cobalt salt or organocobalt compound, the same procedure as in Production Method 1 except that a metal salt other than cobalt or an organometallic compound wherein the metal is other than cobalt is used, compound (I) and A complex compound comprising a metal other than cobalt (for example, rhodium, iridium, aluminum, gallium, iron, etc.) and an amine cation can be produced (hereinafter, this method is referred to as Production Method 2).

Examples of the metal salt or organometallic compound other than cobalt and the metal other than cobalt include, for example, rhodium salt, organic rhodium compound, iridium salt, organic iridium compound, aluminum salt, organoaluminum compound, gallium Salts, organic gallium compounds, iron salts, organic iron compounds, and the like.

Examples of the rhodium salt include rhodium acetate (II) dimer, rhodium (III) chloride, and hydrates thereof.
Examples of the organic rhodium compound include rhodium (III) acetylacetonate and rhodium (II) hexanonate.
Examples of the iridium salt include iridium (III) chloride, iridium (III) bromide, and hydrates thereof.
Examples of the organic iridium compound include iridium (III) acetylacetonate.

Examples of the aluminum salt include aluminum acetate (III), aluminum chloride (III), aluminum chloride (III) = tetrahydrofuran complex, aluminum bromide (III), aluminum iodide (III), aluminum hydroxide (III), These hydrates can be mentioned.
Examples of the organoaluminum compound include aluminum (III) tris (acetylacetonate), aluminum (III) tris (ethylacetoacetonate), aluminum (III) isopropoxide, aluminum (III) ethylacetoacetonate = diiso Examples thereof include propoxide, aluminum (III) isopropoxide, aluminum sec-butoxide, and aluminum ethoxide.

Examples of the gallium salt include gallium chloride (III), gallium bromide (III), gallium iodide (III), and hydrates thereof.
Examples of the organic gallium compound include gallium (III) acetylacetonate.

Examples of iron salts include iron (II) chloride, iron (III) chloride, iron (II) fluoride, iron (III) fluoride, iron (II) bromide, iron (III) bromide, iron acetate (II), hydrates thereof and the like.
Examples of the organic iron compound include iron (II) acetylacetonate, iron (III) acetylacetonate, iron (III) ethoxide, and the like.

Of the complex compounds of the present invention, a complex compound composed of compound (I), cobalt and ammonium ions can be produced by operating in the same manner as in Production Method 1 except that ammonia is used instead of amine.
A complex compound composed of compound (I), a metal other than cobalt, and ammonium ions can be produced in the same manner as in Production Method 2, except that ammonia is used instead of amine.

The complex compound composed of compound (I), metal and quaternary ammonium ion is, for example, a complex compound composed of compound (I), metal and amine cation, and the corresponding quaternary ammonium salt in a solvent. It can be produced by reacting at 0 to 120 ° C. for 0.5 to 30 hours. Here, the complex compound which consists of compound (I), a metal, and the cation of an amine can be obtained by manufacturing according to the manufacturing method 1 or 2.
Examples of the anion in the quaternary ammonium salt include fluoride ion, chloride ion, bromide ion, iodide ion, and acetate ion.
The quaternary ammonium salt is obtained as a commercial product, or a known method, for example, Saul Patai ed., “The Chemistry of the amino group”, John Wiley & Sons, 1968, p. 161-199, edited by Katritzky & Rees, “Comprehensive Heterocyclic Chemistry”, Pergamon Press, 1984, p. 99-164 and p. It can be obtained by manufacturing according to the method described in 515-528 and the like.

A complex compound comprising compound (I), a metal and an amine cation (wherein the amine in the amine cation has m basic nitrogen atoms), and an n-valent quaternary ammonium salt. A quaternary ammonium ion contained in the n-valent quaternary ammonium salt used when producing a complex compound comprising the compound (I), a metal and an n-valent quaternary ammonium ion by reacting, and use The molar ratio of the compound (I) to the cation of the amine contained in the complex compound composed of the metal and the cation of amine is 0.3 m / n to 10 m / n (quaternary ammonium ion / amine cation). ) Is preferred.
Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, isopropyl alcohol, butanol and isobutanol, halogen solvents such as chloroform and dichloromethane, aromatic solvents such as benzene, toluene and xylene, tetrahydrofuran, methyl- Examples thereof include ether solvents such as tert-butyl ether, ester solvents such as ethyl acetate, ketone solvents such as acetone and methyl ethyl ketone, and mixed solvents thereof.
After the reaction, the complex compound obtained by methods commonly used in organic synthetic chemistry (various column chromatography methods, recrystallization methods, washing with a solvent, etc.) may be purified as necessary.

Specific examples of compound (I) are illustrated below. In the formula, Ph represents a phenyl group, i-Pr represents an isopropyl group, and n-Pr represents a propyl group.

Hereinafter, the compound of compound number (I-1) is referred to as compound (I-1). The same applies to the compounds with other compound numbers.
Specific examples of the complex compound of the present invention are shown in Tables 1 and 2.
In Tables 1 and 2, the cation represents an amine cation or a quaternary ammonium ion, and the molar ratio is the molar ratio of each component in the complex compound of the present invention [compound (I): metal: cation]. Represents.
In Tables 1 and 2, A1 and A2 represent the following amine cations. In the formula, Et represents an ethyl group, and i-Pr represents an isopropyl group.

The complex compound of the present invention can be used as a dye for optical recording media, an ultraviolet absorber, a two-photon absorbing dye as a three-dimensional recording material, a sensitizing dye for short wavelength laser (for example, blue-violet laser), etc. Can do. The complex compound of the present invention has properties such as excellent solubility, excellent coating properties, excellent light resistance, excellent water resistance, excellent moisture and heat resistance, and excellent storage stability in a solution.
The optical recording medium of the present invention contains the complex compound of the present invention and has excellent light resistance, excellent water resistance, excellent moisture and heat resistance, excellent recording / reproducing characteristics, and the like.

Examples of the optical recording medium of the present invention include a substrate, a reflective layer, a recording layer, a transparent protective layer, and a cover layer. The reflective layer, the recording layer, the transparent protective layer, and the cover are provided on the substrate. It is preferable that the layers are provided in this order. Examples of the optical recording medium of the present invention include those having a recording layer containing the complex compound of the present invention. When the recording layer is formed using the complex compound of the present invention, the complex compound of the present invention may be used alone or in admixture of two or more.

The complex compound of the present invention and other pigments may be used in combination. Other dyes preferably have absorption in the wavelength region of the recording laser light. Also, other dyes that do not hinder the formation of information recording (recording marks, etc. formed at the laser irradiation site due to thermal deformation in the recording layer, reflective layer or transparent protective layer, and cover layer) may be used. preferable. Other dyes include metal-containing azo dyes other than the complex compounds of the present invention, phthalocyanine dyes, naphthalocyanine dyes, cyanine dyes, azo dyes, squarylium dyes, metal-containing indoaniline dyes, triarylmethanes And dyes, merocyanine dyes, azurenium dyes, naphthoquinone dyes, anthraquinone dyes, indophenol dyes, xanthene dyes, oxazine dyes, and pyrylium dyes. You may use these individually or in mixture of 2 or more types. Among other dyes, a dye suitable for recording using a laser beam such as a near infrared laser beam of 770 to 830 nm, a red laser beam of 620 to 690 nm, etc., and the complex compound of the present invention are used in combination. An optical recording medium capable of recording with a laser beam can also be produced.

The recording layer may contain a binder as necessary. Examples of the binder include polyvinyl alcohol, polyvinyl pyrrolidone, nitrocellulose, cellulose acetate, polyvinyl butyral, ketone resin, polycarbonate resin, and silicone resin. You may use these individually or in mixture of 2 or more types.

Further, the recording layer may contain a singlet oxygen quencher, a recording sensitivity improver, or the like in order to improve the stability and light resistance of the recording layer.
Examples of the singlet oxygen quencher include transition metal chelate compounds (eg, chelate compounds of acetylacetonate, bisphenyldithiol, salicylaldehyde oxime, bisdithio-α-diketone, and the like and transition metals). You may use these individually or in mixture of 2 or more types.

As the recording sensitivity improver, a compound in which a metal such as a transition metal is contained in a compound in the form of atoms, ions, clusters, etc., for example, an ethylenediamine complex, an azomethine complex, a phenylhydroxyamine complex, a phenanthroline complex, And organic metal compounds such as dihydroxyazobenzene complex, dioxime complex, nitrosoaminophenol complex, pyridyltriazine complex, acetylacetonate complex, metallocene complex and porphyrin complex. You may use these individually or in mixture of 2 or more types.

The thickness of the recording layer of the optical recording medium of the present invention is preferably 1 nm to 5 μm, more preferably 5 to 100 nm, and further preferably 15 to 60 nm.
The recording layer can be formed by a known thin film forming method such as a vacuum deposition method, a sputtering method, a doctor blade method, a cast method, a spin coating method, or an immersion method, but the spin coating method is preferable from the viewpoint of mass productivity and cost. . When the recording layer is formed by spin coating, it is preferable to use a solution in which the concentration of the complex compound of the present invention is adjusted to 0.3 to 2.5% by weight in order to obtain an appropriate film thickness. The speed is preferably 500 to 10,000 rpm. After applying the solution by a spin coating method, treatment such as heating, drying under reduced pressure, or exposure to solvent vapor may be performed.

When a recording layer is formed by applying a solution (for example, doctor blade method, cast method, spin coating method, dipping method, etc.), the solvent of the solution used on the substrate before applying the substrate and the recording layer is as follows. There is no particular limitation as long as it is a solvent that does not attack the formed layer (for example, a reflective layer). For example, ketone alcohol solvents such as diacetone alcohol and 3-hydroxy-3-methyl-2-butanone, cellosolv solvents such as methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, n-hexane, n-octane, cyclohexane, Hydrocarbon solvents such as methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, n-butylcyclohexane, tert-butylcyclohexane, cyclooctane, ether solvents such as diisopropyl ether and dibutyl ether, 2,2,3,3-tetrafluoropropanol (TFP), fluoroalkyl alcohol solvents such as octafluoropentanol, hexafluorobutanol, methyl lactate, ethyl lactate, methyl isobutyrate, propylene glycol mono Ester solvents such as chill ether acetate. You may use these individually or in mixture of 2 or more types.

The substrate of the optical recording medium of the present invention is preferably such that a guide groove formed in a spiral shape is formed on the surface for recording / reproduction with a laser beam. As the substrate, those which can easily form fine grooves having a narrow track pitch are preferable, and specific examples thereof include glass and plastic. Examples of plastics include acrylic resin, methacrylic resin, polycarbonate resin, vinyl chloride resin, vinyl acetate resin, nitrocellulose, polyester resin, polyethylene resin, polypropylene resin, polyimide resin, polystyrene resin, epoxy resin, and alicyclic polyolefin resin. However, a polycarbonate resin is preferable from the viewpoint of high productivity, cost, moisture absorption resistance, and the like.

The substrate is preferably produced by injection molding the plastic. Examples of the method for producing the substrate by injection molding include a method using a stamper made of a metal such as Ni in which a guide groove is formed.
The master for producing the stamper is produced, for example, as follows. Polish the surface of the disk-shaped glass substrate to be smooth. A photoresist whose thickness is adjusted according to a desired groove depth is applied on the substrate. Next, the photoresist is exposed using a laser beam or an electron beam having a wavelength shorter than that of the blue-violet laser beam and developed, thereby producing a master having a guide groove.
Next, a conductive film such as Ni is vacuum-deposited on the surface of the master, and a stamper made of a metal such as Ni in which a guide groove is formed is produced through a plating process. A substrate having guide grooves formed on the surface is produced by injection molding the plastic using this stamper.

As the guide groove, the height difference (groove depth) between the top and bottom surfaces of the irregularities is preferably 15 to 80 nm, and more preferably 25 to 50 nm. The ratio of the width of the convex portion to the concave portion is preferably in the range of 40%: 60% to 60%: 40% (convex portion: concave portion).
The reflective layer is preferably a metal. Examples of the metal include gold, silver, aluminum, and alloys thereof. From the viewpoint of reflectance with respect to laser light having a wavelength of 550 nm or less and surface smoothness, silver or an alloy containing silver as a main component is preferable. The alloy containing silver as a main component preferably contains about 90% or more of silver, and as a component other than silver, a group of Cu, Pd, Ni, Si, Au, Al, Ti, Zn, Zr, Nb, Bi and Mo What contains 1 or more types chosen from is preferable. The reflective layer can be formed on the substrate by, for example, vapor deposition, sputtering (eg, DC sputtering), ion plating, or the like. An intermediate layer may be provided between the reflective layer and the recording layer for the purpose of improving the recording / reproducing characteristics or adjusting the reflectance. Specific examples of the intermediate layer include metals, metal oxides, and metal nitrides. The thickness of the reflective layer is preferably 5 to 300 nm, more preferably 20 to 100 nm.

The transparent protective layer preferably has no or only slight absorption with respect to the laser beam used at the time of recording and reproduction, and the real part of the refractive index is relatively large, about 1.5 to 2.0. What has the value of is preferable. Specific examples of the transparent protective layer include metal oxides, metal nitrides, metal sulfides, and mixtures thereof.
The thickness of the transparent protective layer is preferably 5 to 50 nm. When the thickness of the protective layer is 5 nm or more, a recording signal formed by deforming the recording layer can be clearly separated from an unrecorded portion between the recording marks, so that a better signal can be obtained. Further, when the thickness of the protective layer is 50 nm or less, the transparent protective layer is easily deformed, so that a better signal can be obtained. The transparent protective layer can be formed on the recording layer by sputtering (for example, RF sputtering). Examples of the target material used when forming the transparent protective layer by the sputtering method include ZnS—SiO ₂ and indium tin oxide (ITO).

The cover layer is made of, for example, a polycarbonate resin sheet having a thickness of about 0.1 mm and having an adhesive layer that is transparent to the recording / reproducing laser beam on the surface, and the sheet is transparent through the adhesive layer. By pressure-bonding to the protective layer, it can be formed on the transparent protective layer. The adhesive layer is preferably one that does not hinder the deformation of the recording layer and the transparent protective layer during information recording. The cover layer can also be formed using an ultraviolet curable resin, and the ultraviolet curable resin is preferably one that does not hinder the deformation of the recording layer and the transparent protective layer during information recording, like the adhesive layer.
It is preferable to form a hard coat on the cover layer.

Since the optical recording medium of the present invention contains the complex compound of the present invention, the wavelength of the laser beam used during recording is preferably 350 to 530 nm. In general, the shorter the wavelength of laser light used for recording, the higher the density recording possible.
Specific examples of the laser light include, for example, blue-violet laser light having a center wavelength of 405 nm, 410 nm, etc., a blue-green high-power semiconductor laser light having a center wavelength of 515 nm, and the center wavelength is 405 nm. Blue-green high-power semiconductor laser light is preferred.
A semiconductor laser beam capable of continuous oscillation having a fundamental oscillation wavelength of 740 to 960 nm, a solid laser beam capable of continuous oscillation having a fundamental oscillation wavelength of 740 to 960 nm that is excited by the semiconductor laser beam, etc. Light obtained by wavelength conversion by SHG) may be used. As SHG, any piezoelectric element lacking reflection symmetry may be used, but KDP (KH ₂ PO ₄ ), ADP (NH ₄ H ₂ PO ₄ ), BNN (Ba ₂ NaNb ₅ O ₁₅ ), KN ( KNbO ₃ ), LBO (LiB ₃ O ₅ ), compound semiconductors and the like are preferable.

Specific examples of light (second harmonic) obtained by wavelength conversion by SHG include 430 nm light obtained by wavelength conversion of semiconductor laser light having a fundamental oscillation wavelength of 860 nm, and semiconductor laser excitation with fundamental oscillation wavelength of 860 nm. Examples thereof include 430 nm light obtained by wavelength conversion of solid laser light.
The optical recording medium of the present invention is preferably a BD. BD is an optical recording medium that uses a blue-violet laser with a wavelength of 405 nm and records NA with a smaller laser spot diameter by setting the NA of the objective lens to 0.85. In the BD-R, a reflective layer, a recording layer, a transparent protective layer, and a cover layer thinner than the substrate are sequentially laminated on the substrate. Recording and reproduction is performed by irradiating the cover layer side with a blue-violet laser beam.

Hereinafter, the present invention will be described more specifically with reference to examples and test examples.
The abbreviations are described below.
TFP: 2,2,3,3-tetrafluoropropanol DMSO: dimethyl sulfoxide DBU: 1,8-diazabicyclo [5.4.0] undec-7-ene

[Production of raw material for compound (I)]
“Bioorganic and Medicinal Chemistry Letters”, 2007, Vol. 17, p. In accordance with the method described in 1189-1192, phenylhydrazine and ethyl 4-methoxybenzoyl acetate were reacted to obtain 3- (4-methoxyphenyl) -1-phenyl-5-pyrazolone. In the same manner as in the production method of 3- (4-methoxyphenyl) -1-phenyl-5-pyrazolone, 1-phenyl-3- (trifluoromethyl) -5-pyrazolone, 3-methyl-1-phenyl-5- Pyrazolone, 3-isopropyl-1-phenyl-5-pyrazolone, 1,3-diphenyl-5-pyrazolone and 1-phenyl-3-propyl-5-pyrazolone were obtained.

“Heterocycles”, 2006, Vol. 68, p. In accordance with the method described in 1825-1835, 4-acetyl-3- (4-methoxyphenyl) -1 was obtained by reacting 3- (4-methoxyphenyl) -1-phenyl-5-pyrazolone with trimethyl orthoacetate. -Phenyl-5-pyrazolone was obtained. In the same manner as in the production method of 4-acetyl-3- (4-methoxyphenyl) -1-phenyl-5-pyrazolone, 4-acetyl-1-phenyl-3- (trifluoromethyl) -5-pyrazolone, 4- Acetyl-3-methyl-1-phenyl-5-pyrazolone, 4-acetyl-3-isopropyl-1-phenyl-5-pyrazolone, 4-acetyl-1,3-diphenyl-5-pyrazolone and 4-acetyl-1- Phenyl-3-propyl-5-pyrazolone was obtained.

“Heterocycles”, 2003, Vol. 61, p. In accordance with the method described in 197-224, 4- (N, N-dimethylaminomethylene) -1,3-reacted by reacting N, N-dimethylformamide dimethyl acetal with 1,3-diphenyl-5-pyrazolone. Diphenyl-5-pyrazolone was obtained. In the same manner as the production method of 4- (N, N-dimethylaminomethylene) -1,3-diphenyl-5-pyrazolone, 4- (N, N-dimethylaminomethylene) -3- (4-methoxyphenyl)- 1-Phenyl-5-pyrazolone was obtained.

“Journal of Organic Chemistry”, 1999, Vol. 64, p. 2-Hydrazinopyrimidine was obtained by reacting 2-chloropyrimidine with hydrazine hydrate according to the method described in 5644-5649. In the same manner as the production method of 2-hydrazinopyrimidine, 5-hydrazino-1-phenyl-1H-tetrazole was obtained.

"Journal of the American Chemical Society", 1953, Vol. 75, p. 2-Hydrazinobenzoxazole was obtained by reacting 2-chlorobenzoxazole with hydrazine hydrate according to the method described in 712.

“Bioorganic and Medicinal Chemistry”, 2003, Vol. 11, p. 4- (N, N-dimethylamino) benzohydrazide was obtained by reacting ethyl 4- (N, N-dimethylamino) benzoate with hydrazine hydrate according to the method described in 1381-1387. 3- (1-Propylindole) carbohydrazide was obtained in the same manner as the production method of 4- (N, N-dimethylamino) benzohydrazide.

[Production of quaternary ammonium salt]
“Journal of Materials Chemistry”, 2006, Vol. 16, p. In accordance with the method described in 345-347, 1,1′-bis (2,4-dinitrophenyl) -4,4′-bipyridinium dichloride is reacted with 4-phenoxyaniline. (4-Phenoxyphenyl) -4,4′-bipyridinium dichloride was obtained. In the same manner as the method for producing 1,1′-bis (4-phenoxyphenyl) -4,4′-bipyridinium dichloride, 1,1′-bis [4- (N, N-dimethylamino) phenyl] -4, 4′-bipyridinium dichloride, 1,1′-bis (4-methoxyphenyl) -4,4′-bipyridinium dichloride, 1,1′-bis (4-benzoylphenyl) -4,4′-bipyridinium dichloride, 1, 1'-bis (3-fluorophenyl) -4,4'-bipyridinium dichloride, 1,1'-bis [4- (trifluoromethoxy) phenyl] -4,4'-bipyridinium dichloride, and 1,1'- Bis (3-methoxyphenyl) -4,4′-bipyridinium dichloride was obtained.

[Production of Compound (I)]
Synthesis Example 1: Production of Compound (I-1) 4-Benzoyl-3-methyl-1-phenyl-5-pyrazolone (Tokyo Chemical Industry Co., Ltd.) 1.00 g, 4- (N, N-dimethylamino) benzo 0.71 g of hydrazide, 0.22 g of acetic acid and 15 ml of methanol were mixed and stirred at 50 ° C. for 1 hour. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 1.36 g (yield 86%) of compound (I-1).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.41 (3H, s), 2.92 (6H, s), 6.62 (2H, d, J = 8.7 Hz), 7 .13-7.68 (10H, m), 7.98 (2H, d, J = 8.7 Hz), 10.56 (1H, s).

Synthesis Example 2: Production of Compound (I-2) 4-benzoyl-3-methyl-1-phenyl-5-pyrazolone (Tokyo Chemical Industry Co., Ltd.) 5.00 g, 5-hydrazino-1-phenyl-1H-tetrazole 3.16 g, 1.08 g of acetic acid and 50 ml of methanol were mixed and stirred at 50 ° C. for 4 hours. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 6.68 g (yield 85%) of compound (I-2).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.70 (3H, s), 7.15-8.00 (15H, m), 9.85 (1H, s).

Synthesis Example 3: Production of Compound (I-3) 4-acetyl-3- (4-methoxyphenyl) -1-phenyl-5-pyrazolone 2.00 g, 5-hydrazino-1-phenyl-1H-tetrazole 1.14 g Then, 0.39 g of acetic acid and 20 ml of methanol were mixed and stirred at 50 ° C. for 3 hours. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 1.81 g (yield 62%) of compound (I-3).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 2.08 (3H, s), 3.82 (3H, s), 7.05 (2H, d, J = 8.5 Hz), 7 .18 (1H, t, J = 7.6 Hz), 7.41-7.70 (9H, m), 8.02 (2H, d, J = 7.8 Hz), 10.02 (1H, s) .

Synthesis Example 4: Production of Compound (I-4) 4-acetyl-3-methyl-1-phenyl-5-pyrazolone 0.50 g, 2-hydrazinobenzothiazole (Tokyo Chemical Industry Co., Ltd.) 0.38 g, acetic acid 1 ml and 15 ml of methanol were mixed and stirred at 50 ° C. for 1 hour. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.52 g (yield 62%) of compound (I-4).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 2.35 (3H, s), 2.54 (3H, s), 7.05-7.15 (3H, m), 7.29 (1H, t, J = 7.3 Hz), 7.40 (2H, t, J = 7.6 Hz), 7.73 (1H, d, J = 7.8 Hz), 8.01 (2H, d, J = 8.8 Hz), 11.98 (1 H, bs).

Synthesis Example 5 Production of Compound (I-5) 4-acetyl-1-phenyl-3- (trifluoromethyl) -5-pyrazolone 1.00 g, 4- (N, N-dimethylamino) benzohydrazide 0.66 g , Acetic acid 0.22 g and methanol 15 ml were mixed and stirred at 50 ° C. for 1 hour. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 1.30 g (yield 82%) of compound (I-5).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 3.02 (6H, s), 3.18 (3H, s), 6.79 (2H, d, J = 8.8 Hz), 7 .29 (1H, t, J = 7.3 Hz), 7.47-7.51 (2H, m), 7.80 (2H, d, J = 8.8 Hz), 7.95 (2H, d, J = 7.8 Hz), 11.26 (1H, bs).

Synthesis Example 6 Production of Compound (I-6) 1.00 g of 4-acetyl-3-isopropyl-1-phenyl-5-pyrazolone, 0.73 g of 4- (N, N-dimethylamino) benzohydrazide, 0. 25 g and 10 ml of methanol were mixed and stirred at 50 ° C. for 1 hour. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 1.15 g (yield 69%) of compound (I-6).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.29 (6H, d, J = 6.6 Hz), 2.45 (3H, s), 3.15-3.22 (1H, m), 3.31 (6H, s), 6.78 (2H, d, J = 9.0 Hz), 7.14 (1H, t, J = 7.3 Hz), 7.38-7.43 ( 2H, m), 7.79 (2H, d, J = 9.0 Hz), 8.01 (2H, d, J = 7.6 Hz), 10.86 (1H, s), 12.84 (1H, bs).

Synthesis Example 7 Production of Compound (I-7) 1.00 g of 4-acetyl-1,3-diphenyl-5-pyrazolone, 0.65 g of 4- (N, N-dimethylamino) benzohydrazide, 0.22 g of acetic acid and 10 ml of methanol was mixed and stirred at 50 ° C. for 1.5 hours. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.92 g of Compound (I-7) (yield 58%).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 2.05 (3H, s), 3.00 (6H, s), 6.76 (2H, d, J = 9.0 Hz), 7 .18 (1H, t, J = 7.3 Hz), 7.41-7.45 (2H, m), 7.49-7.56 (5H, m), 7.77 (2H, d, J = 9.0 Hz), 8.05 (2H, d, J = 7.6 Hz), 10.93 (1 H, s), 12.82 (1 H, bs).

Synthesis Example 8 Production of Compound (I-8) 4- (N, N-dimethylaminomethylene) -1,3-diphenyl-5-pyrazolone 1.00 g, 2-hydrazinobenzoxazole 0.52 g, acetic acid 0. 21 g and 10 ml of methanol were mixed and stirred at 50 ° C. for 1 hour. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.88 g of Compound (I-8) (yield 64%).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 7.07-7.12 (1H, m), 7.19-7.21 (2H, m), 7.44-7.53 ( 7H, m), 7.79 (2H, d, J = 6.8 Hz), 8.11 (2H, d, J = 8.1 Hz), 8.29 (1H, s), 11.92 (1H, bs).

Synthesis Example 9 Production of Compound (I-9) 4- (N, N-dimethylaminomethylene) -1,3-diphenyl-5-pyrazolone 0.70 g, 2-hydrazinopyrimidine 0.27 g, acetic acid 0.15 g And 7 ml of methanol were mixed and stirred at 50 ° C. for 1 hour. The reaction mixture was cooled to room temperature, 14 ml of water was added to the reaction mixture, and the precipitated solid was collected by filtration, washed with a mixed solvent of water and methanol (volume ratio 2: 1), and dried to give compound (I-9). ) 0.77 g (yield 90%) was obtained.
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 7.39-7.53 (7H, m), 7.73-7.76 (2H, m), 8.09 (2H, d, J = 7.8 Hz), 8.21 (1 H, s), 8.51 (2 H, d, J = 4.9 Hz), 10.52 (1 H, bs).

Synthesis Example 10 Production of Compound (I-10) 1.00 g of 4-acetyl-3- (4-methoxyphenyl) -1-phenyl-5-pyrazolone, 4- (N, N-dimethylamino) benzohydrazide 58 g, 0.20 g of acetic acid and 7 ml of methanol were mixed and stirred at 50 ° C. for 1 hour. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.94 g (yield 62%) of Compound (I-10).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 2.07 (3H, s), 3.00 (6H, s), 3.82 (3H, s), 6.76 (2H, d , J = 9.0 Hz), 7.05 (2H, d, J = 8.5 Hz), 7.15-7.19 (1H, m), 7.40-7.45 (2H, m), 7 .47 (2H, d, J = 8.5 Hz), 7.77 (2H, d, J = 9.0 Hz), 8.04 (2H, d, J = 7.6 Hz), 10.90 (1H, s), 12.81 (1H, bs).

Synthesis Example 11 Production of Compound (I-11) 4- (N, N-dimethylaminomethylene) -3- (4-methoxyphenyl) -1-phenyl-5-pyrazolone 1.00 g, 2-hydrazinopyrimidine 0 .34 g, acetic acid 0.19 g and methanol 7 ml were mixed and stirred at 50 ° C. for 1 hour. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to give 0.88 g (yield 73%) of compound (I-11).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 6.89-6.93 (1H, m), 7.04-7.09 (2H, m), 7.17 (1H, t, J = 7.3 Hz), 7.40-7.46 (2H, m), 7.68 (2H, d, J = 8.8 Hz), 8.04-8.09 (2H, m), 8. 16 (1H, s), 8.50-8.52 (2H, m), 10.43 (1H, bs).

Synthesis Example 12 Production of Compound (I-12) 0.80 g of 4-acetyl-1-phenyl-3-propyl-5-pyrazolone, 0.59 g of 4- (N, N-dimethylamino) benzohydrazide, 0. 20 g and 7 ml of methanol were mixed and stirred at 50 ° C. for 1 hour. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.98 g (yield 73%) of Compound (I-12).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.00 (3H, t, J = 7.4 Hz), 1.67-1.73 (2H, m), 2.41 (3H, s), 2.70 (2H, t, J = 7.6 Hz), 3.00 (6H, s), 6.76 (2H, d, J = 8.8 Hz), 7.11-7.14 ( 1H, m), 7.37-7.41 (2H, t, J = 7.6 Hz), 7.78 (2H, d, J = 8.8 Hz), 7.99 (2H, d, J = 7) .8 Hz), 10.86 (1 H, s), 12.64 (1 H, bs).

Synthesis Example 13 Production of Compound (I-13) 1.00 g of 4-acetyl-1-phenyl-3-propyl-5-pyrazolone, 0.89 g of 3- (1-propylindole) carbohydrazide, 0.25 g of acetic acid and 10 ml of methanol was mixed and stirred at 50 ° C. for 2 hours. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to give 1.45 g (yield 80%) of compound (I-13).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 0.88 (3H, t, J = 7.3 Hz), 1.01 (3H, t, J = 7.3 Hz), 1.68- 1.74 (2H, m), 1.80-1.86 (2H, m), 2.46 (3H, s), 2.71 (2H, t, J = 7.3 Hz), 4.23 ( 2H, t, J = 7.1 Hz), 7.11-7.15 (1H, m), 7.14-7.26 (2H, m), 7.37-7.42 (2H, m), 7.61 (1H, d, J = 8.0 Hz), 8.00 (2H, d, J = 7.6 Hz), 8.10 (1H, d, J = 7.6 Hz), 8.19 (1H , S), 10.69 (1H, s), 12.71 (1H, bs).

[Production of complex compounds]
Example 1
To a mixture of 1.00 g of compound (I-1), 0.69 g of DBU and 10 ml of methanol was added 0.28 g of cobalt (II) acetate tetrahydrate, and the mixture was stirred at 50 ° C. for 3 hours in an air atmosphere. The reaction mixture was cooled to room temperature, 10 ml of water was added to the reaction mixture, the precipitated solid was collected by filtration, washed with a mixed solvent of water and methanol (volume ratio 1: 1), and dried to give the complex compound (1). 1.09 g (yield 88%) was obtained.
Absorption maximum wavelength (TFP): 374.5nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.51 (6H, s), 1.56-1.87 (3H, m), 1.87 (1H, m), 2.59 (1H, s), 2.82 (12H, s), 3.20-3.49 (11H, m), 6.46 (4H, d, J = 8.8 Hz), 7.02 (2H, t , J = 7.3 Hz), 7.23 (4H, t, J = 7.8 Hz), 7.44 (4H, d, J = 8.8 Hz), 7.59-7.76 (14H, m) .

(Example 2)
0.30 g of complex compound (1), 0.08 g of 1,1′-bis (4-phenoxyphenyl) -4,4′-bipyridinium dichloride and 9 ml of methanol were mixed and stirred at 50 ° C. for 3 hours. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.26 g of complex compound (2) (yield 80%).
Absorption maximum wavelength (TFP): 376.5 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.50 (12H, s), 2.82 (24H, s), 6.45 (8H, d, J = 8.8 Hz), 7 .02 (4H, t, J = 7.6 Hz), 7.16-7.32 (14H, m), 7.44 (8H, d, J = 8.8 Hz), 7.52-7.74 ( 36H, m), 7.96 (4H, bs), 9.01 (4H, bs), 9.62 (4H, bs).

(Example 3)
Complex compound (1) 0.50 g, 1,1′-bis [4- (N, N-dimethylamino) phenyl) -4,4′-bipyridinium dichloride 0.11 g and methanol 15 ml were mixed and mixed at 50 ° C. with 3 Stir for hours. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.48 g of complex compound (3) (yield 92%).
Absorption maximum wavelength (TFP): 375.0 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.50 (12H, s), 2.82 (24H, s), 3.00 (12H, s), 6.45 (8H, d , J = 9.0 Hz), 7.02 (8H, m), 7.21-7.25 (8H, m), 7.44 (8H, d, J = 9.0 Hz), 7.60-7 .75 (32H, m), 8.61 (4H, bs), 9.20 (4H, bs).

Example 4
To a mixture of 2.50 g of compound (I-2), 1.48 g of diisopropylethylamine and 25 ml of acetonitrile was added 0.71 g of cobalt (II) acetate tetrahydrate, and the mixture was stirred at 70 ° C. for 3 hours in an air atmosphere. The reaction mixture was cooled to room temperature, 37 ml of water was added to the reaction mixture, the precipitated solid was collected by filtration, washed with a mixed solvent of water and acetonitrile (volume ratio 3: 2), and dried to give a complex compound (4). 2.84 g (94% yield) was obtained.
Absorption maximum wavelength (TFP): 359.0 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.22-1.25 (15H, m), 1.52 (6H, s), 3.12 (2H, m), 3.59 (2H, m), 7.06 (2H, t, J = 7.6 Hz), 7.18 (2H, t, J = 7.6 Hz), 7.25-7.35 (8H, m), 7 .62-7.78 (18H, m), 8.13 (1H, bs).

(Example 5)
0.30 g of complex compound (4), 0.06 g of 1,1′-bis (4-methoxyphenyl) -4,4′-bipyridinium dichloride and 9 ml of methanol were mixed and stirred at 50 ° C. for 3 hours. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.28 g of complex compound (5) (yield 82%).
Absorption maximum wavelength (TFP): 356.5 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.50 (12H, s), 3.32 (6H, bs), 7.04 (4H, t, J = 7.3 Hz), 7 .17 (4H, t, J = 7.3 Hz), 7.23-7.34 (16H, m), 7.61-7.76 (40H, m), 7.95 (4H, bs), 9 .04 (4H, bs), 9.68 (4H, bs).

(Example 6)
0.30 g of complex compound (4), 0.08 g of 1,1′-bis (4-benzoylphenyl) -4,4′-bipyridinium dichloride and 9 ml of methanol were mixed and stirred at 50 ° C. for 3 hours. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.30 g of complex compound (6) (yield 90%).
Absorption maximum wavelength (TFP): 355.5 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.51 (12H, s), 7.06 (4H, t, J = 7.3 Hz), 7.18 (4H, t, J = 7.3 Hz), 7.25-7.34 (16 H, m), 7.63-7.83 (50 H, m), 8.13 (4 H, bs), 9.09 (4 H, bs), 9 .77 (4H, bs).

(Example 7)
0.30 g of Complex Compound (4), 0.06 g of 1,1′-bis (3-fluorophenyl) -4,4′-bipyridinium dichloride and 9 ml of ethanol were mixed and stirred at 70 ° C. for 3 hours. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.26 g of complex compound (7) (yield 85%).
Absorption maximum wavelength (TFP): 357.0 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.51 (12H, s), 7.05 (4H, t, J = 7.3 Hz), 7.18 (4H, t, J = 7.3 Hz), 7.25-7.35 (16H, m), 7.62-7.93 (44H, m), 9.08 (4H, bs), 9.70 (4H, bs).
FAB-MS [matrix: m-nitrobenzyl alcohol]: (+) 346, (−) 927
Elemental analysis: measured value (%) C: 64.0, H: 3.9, N: 21.6

(Example 8)
To a mixture of 0.50 g of compound (I-3), 0.28 g of diisopropylethylamine and 5 ml of acetonitrile was added 0.13 g of cobalt (II) acetate tetrahydrate, and the mixture was stirred at 70 ° C. for 3 hours in an air atmosphere. The reaction mixture was cooled to room temperature, 8 ml of water was added to the reaction mixture, the precipitated solid was collected by filtration, washed with a mixed solvent of water and acetonitrile (volume ratio 3: 2), and dried to give the complex compound (8). 0.58 g (yield 96%) was obtained.
Absorption maximum wavelength (TFP): 350.0 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.22-1.25 (15H, m), 2.75 (6H, s), 3.12 (2H, m), 3.60 (2H, m), 3.87 (6H, s), 7.04-7.22 (12H, m), 7.52-7.63 (12H, m), 8.04-8.10 (5H , M).

Example 9
0.30 g of complex compound (8), 0.08 g of 1,1′-bis (4-phenoxyphenyl) -4,4′-bipyridinium dichloride and 10 ml of ethanol were mixed and stirred at 70 ° C. for 3 hours. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.31 g of complex compound (9) (yield 98%).
Absorption maximum wavelength (TFP): 357.0 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 2.74 (12H, s), 3.86 (12H, s), 7.02-7.30 (34H, m), 7.49 −7.54 (20H, m), 7.62 (8H, d, J = 7.8 Hz), 8.03 to 8.05 (12H, m), 9.01 (4H, bs), 9.62 (4H, bs).

(Example 10)
0.07 g of cobalt (II) acetate tetrahydrate was added to a mixture of 0.20 g of compound (I-4), 0.17 g of DBU and 4 ml of methanol, and the mixture was stirred at 50 ° C. for 3 hours in an air atmosphere. The reaction mixture was cooled to room temperature, 8 ml of water was added to the reaction mixture, and the precipitated solid was collected by filtration, washed with a mixed solvent of water and methanol (volume ratio 2: 1), and dried to give a complex compound (10). 0.22 g (yield 86%) was obtained.
Absorption maximum wavelength (TFP): 375.0 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.59-1.63 (6H, m), 1.88-191 (2H, m), 2.40 (6H, s), 2 .60-2.63 (2H, m), 3.11 (6H, s), 3.23 (2H, t, J = 5.6 Hz), 3.45 (2H, t, J = 5.6 Hz) 3.51-3.54 (2H, m), 6.60-6, 63 (2H, m), 6.78 (2H, d, J = 8.0 Hz), 6.92-6.96 ( 2H, m), 6.99-7.03 (2H, m), 7.15 (2H, d, J = 7.6 Hz), 7.24 (4H, t, J = 8.0 Hz), 7. 65 (4H, d, J = 8.5 Hz).

(Example 11)
Complex compound (10) 0.20 g, 1,1′-bis [4- (trifluoromethoxy) phenyl) -4,4′-bipyridinium dichloride 0.06 g and methanol 6 ml were mixed and stirred at 50 ° C. for 3 hours. . The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.19 g of complex compound (11) (yield 82%).
Absorption maximum wavelength (TFP): 374.5nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 2.39 (12H, s), 3.10 (12H, s), 6.58-6.62 (4H, m), 6.76 (4H, d, J = 7.8 Hz), 6.90-6.95 (4H, m), 6.97-7.02 (4H, m), 7.14 (4H, d, J = 7. 6 Hz), 7.20-7.24 (8 H, m), 7.64 (8 H, d, J = 7.8 Hz), 7.85 (4 H, bs), 8.10 (4 H, bs), 9 .07 (4H, bs), 9.68 (4H, bs).

(Example 12)
0.14 g of cobalt (II) acetate tetrahydrate was added to a mixture of 0.50 g of compound (I-5), 0.35 g of DBU and 7 ml of methanol, and the mixture was stirred at 50 ° C. for 3 hours in an air atmosphere. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.42 g (yield 79%) of the complex compound (12).
Absorption maximum wavelength (TFP): 363.0 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.60-1.64 (6H, m), 1.88-1.92 (2H, m), 2.60-2.63 ( 2H, m), 2.88 (12H, s), 3.19 (6H, s), 3.24 (2H, t, J = 5.8 Hz), 3.46 (2H, t, J = 5. 8Hz), 3.52-3.54 (2H, m), 6.56 (4H, d, J = 8.8 Hz), 7.15-7.22 (6H, m), 7.32 (4H, d, J = 8.1 Hz), 7.69 (4H, d, J = 8.8 Hz).

(Example 13)
0.25 g of Complex Compound (12), 0.06 g of 1,1′-bis (4-methoxyphenyl) -4,4′-bipyridinium dichloride and 7 ml of methanol were mixed and stirred at 50 ° C. for 3 hours. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.24 g of complex compound (13) (yield 78%).
Absorption maximum wavelength (TFP): 364.0 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 2.88 (24H, s), 3.18 (12H, s), 3.91 (6H, bs), 6.55 (8H, d , J = 9.0 Hz), 7.14-7.22 (12H, m), 7.31-7.33 (12H, m), 7.69 (8H, d, J = 9.0 Hz), 7 .92 (4H, bs), 8.98 (4H, bs), 9.60 (4H, bs).

(Example 14)
Complex compound (12) 0.30 g, 1,1′-bis [4- (trifluoromethoxy) phenyl] -4,4′-bipyridinium dichloride 0.09 g and methanol 9 ml were mixed and stirred at 50 ° C. for 3 hours. . The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.30 g (yield 75%) of the complex compound (14).
Absorption maximum wavelength (TFP): 360.5 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 2.88 (24H, s), 3.18 (12H, s), 6.55 (8H, d, J = 8.8 Hz), 7 .14-7.22 (12H, m), 7.32 (8H, d, J = 7.3 Hz), 7.69 (8H, d, J = 8.8 Hz), 7.88 (4H, bs) , 8.12 (4H, bs), 9.08 (4H, bs), 9.70 (4H, bs).

(Example 15)
0.15 g of cobalt (II) acetate tetrahydrate was added to a mixture of 0.50 g of compound (I-6), 0.37 g of DBU and 7 ml of methanol, and the mixture was stirred at 50 ° C. for 3 hours in an air atmosphere. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.57 g (yield 93%) of the complex compound (15).
Absorption maximum wavelength (TFP): 366.5 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.35 (6H, d, J = 6.8 Hz), 1.38 (6H, d, J = 6.6 Hz), 1.59— 1.64 (6H, m), 1.86-1.90 (2H, m), 2.50-2.59 (2H, m), 2.87 (12H, s), 3.22 (2H, t, J = 5.6 Hz), 3.26 (6H, s), 3.44 (2H, t, J = 5.8 Hz), 3.50-3.55 (4H, m), 6.54 ( 4H, d, J = 9.0 Hz), 6.93-6.97 (2H, m), 7.10-7.14 (4H, m), 7.53 (4H, d, J = 7.8 Hz) ), 7.68 (4H, d, J = 9.0 Hz).

(Example 16)
Complex compound (15) 0.30 g, 1,1′-bis [4- (trifluoromethoxy) phenyl] -4,4′-bipyridinium dichloride 0.08 g and methanol 9 ml were mixed and stirred at 50 ° C. for 3 hours. . The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.30 g (yield 90%) of the complex compound (16).
Absorption maximum wavelength (TFP): 365.0 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.34-1.38 (24H, m), 2.86 (24H, s), 3.25 (12H, s), 3.51 −3.55 (4H, m), 6.53 (8H, d, J = 9.0 Hz), 6.92-6.96 (4H, m), 7.09-7.14 (8H, m) 7.52 (8H, d, J = 7.6 Hz), 7.67 (8H, d, J = 9.0 Hz), 7.86 (4H, bs), 8.11 (4H, bs), 9 .04 (4H, bs), 9.67 (4H, bs).

(Example 17)
0.08 g of cobalt (II) acetate tetrahydrate was added to a mixture of 0.30 g of compound (I-7), 0.31 g of DBU and 5 ml of methanol, and the mixture was stirred at 50 ° C. for 4 hours in an air atmosphere. The reaction mixture was cooled to room temperature, 2 ml of water was added to the reaction mixture, the precipitated solid was collected by filtration, washed with a mixed solvent of water and methanol (volume ratio 1: 2), and then dried to give the complex compound (17). 0.32 g (yield 86%) was obtained.
Absorption maximum wavelength (TFP): 366.5 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.59-1.66 (6H, m), 1.87-1.91 (2H, m), 2.60-2.63 ( 2H, m), 2.74 (6H, s), 2.87 (12H, s), 3.23 (2H, t, J = 5.8 Hz), 3.45 (2H, t, J = 5. 6 Hz), 3.51-3, 53 (2H, m), 6.54 (4H, d, J = 9.0 Hz), 7.00-7.05 (2H, m), 7.19-7. 23 (4H, m), 7.49-7.53 (2H, m), 7.54-7.58 (4H, m), 7.61-7.63 (8H, m), 7.68 ( 4H, d, J = 9.0 Hz).

(Example 18)
0.30 g of Complex Compound (17), 0.08 g of 1,1′-bis (4-phenoxyphenyl) -4,4′-bipyridinium dichloride and 9 ml of methanol were mixed and stirred at 50 ° C. for 3 hours. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.24 g of complex compound (18) (yield 73%).
Absorption maximum wavelength (TFP): 367.0 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 2.73 (12H, s), 2.85 (24H, s), 6.52 (8H, d, J = 9.0 Hz), 7 .00-7.04 (4H, m), 7.14-7.22 (12H, m), 7.26-7.30 (6H, m), 7.47-7.61 (32H, m) 7.66 (8H, d, J = 9.0 Hz), 7.95 (4H, bs), 8.98 (4H, bs), 9.56 (4H, bs).

(Example 19)
0.25 g of complex compound (17), 0.06 g of 1,1′-bis [4- (N, N-dimethylamino) phenyl] -4,4′-bipyridinium dichloride and 7 ml of methanol were mixed and mixed at 50 ° C. with 3 Stir for hours. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.21 g (yield 79%) of the complex compound (19).
Absorption maximum wavelength (TFP): 366.0 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 2.72 (12H, s), 2.85 (24H, s), 3.05 (12H, bs), 6.52 (8H, d , J = 8.3 Hz), 6.95 (4H, bs), 7.00-7.21 (4H, m), 7.17-7.21 (8H, m), 7.49-7.61. (28H, m), 7.66 (8H, d, J = 8.3 Hz), 7.73 (4H, bs), 8.80 (4H, bs), 9.44 (4H, bs).

(Example 20)
0.25 g of the complex compound (17), 0.07 g of 1,1′-bis [4- (trifluoromethoxy) phenyl] -4,4′-bipyridinium dichloride and 8 ml of methanol were mixed and stirred at 50 ° C. for 3 hours. . The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.21 g of complex compound (20) (yield 75%).
Absorption maximum wavelength (TFP): 357.0 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 2.74 (12H, s), 2.86 (24H, s), 6.54 (8H, d, J = 8.3 Hz), 7 .01-7.05 (4H, m), 7.19-7.23 (8H, m), 7.48-7.62 (28H, m), 7.67 (8H, d, J = 8. 3 Hz), 7.84 (4H, bs), 8.09 (4H, bs), 9.05 (4H, bs), 9.67 (4H, bs).

(Example 21)
To a mixture of 0.50 g of compound (I-8), 0.58 g of DBU and 8 ml of methanol was added 0.16 g of cobalt (II) acetate tetrahydrate, and the mixture was stirred at 50 ° C. for 3 hours in an air atmosphere. The reaction mixture was cooled to room temperature, 4 ml of water was added to the reaction mixture, the precipitated solid was collected by filtration, washed with a mixed solvent of water and methanol (volume ratio 1: 2), and dried to give a complex compound (21). 0.59 g (yield 93%) was obtained.
Absorption maximum wavelength (TFP): 368.5 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.58 (6H, m), 1.88 (2H, m), 2.59 (2H, m), 3.22 (2H, m ), 3.43 (2H, m), 3.50 (2H, m), 6.66 (2H, m), 6.74 (2H, d, J = 6.8 Hz), 6.92 (2H, m), 6.97 (2H, d, J = 7.1 Hz), 7.06 (2H, m), 7.27 (4H, m), 7.50-7.53 (2H, m), 7 .61 (4H, m), 7.78-7.84 (8H, m), 8.71 (2H, s).

(Example 22)
0.25 g of the complex compound (21), 0.06 g of 1,1′-bis (3-methoxyphenyl) -4,4′-bipyridinium dichloride and 7 ml of methanol were mixed and stirred at 50 ° C. for 4 hours. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.21 g of complex compound (22) (yield 78%).
Absorption maximum wavelength (TFP): 368.0 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 3.91 (6H, s), 6.66 (4H, t, J = 7.6 Hz), 6.74 (4H, d, J = 7.8 Hz), 6.89-6.93 (4H, m), 6.97 (4H, d, J = 7.8 Hz), 7.03-7.08 (4H, m), 7.24- 7.29 (8H, m), 7.36 (4H, bs), 7.48-7.52 (4H, m), 7.58-7.62 (8H, m), 7.70 (4H, bs), 7.78 (8H, d, J = 7.8 Hz), 7.82 (8H, d, J = 7.1 Hz), 8.71 (4H, s), 9.04 (4H, bs) , 9.69 (4H, bs).

(Example 23)
To a mixture of 0.30 g of compound (I-9), 0.38 g of DBU and 5 ml of methanol was added 0.10 g of cobalt (II) acetate tetrahydrate, and the mixture was stirred at 50 ° C. for 3 hours in an air atmosphere. The reaction mixture was cooled to room temperature, 10 ml of water was added to the reaction mixture, the precipitated solid was collected by filtration, washed with a mixed solvent of water and methanol (volume ratio 2: 1), and dried to give a complex compound (23). 0.33 g (yield 86%) was obtained.
Absorption maximum wavelength (TFP): 358.5 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.59 (6H, m), 1.87 (2H, m), 2.58 (2H, m), 3.22 (2H, m ), 3.42 (2H, m), 3.48 (2H, m), 5.86 (2H, bs), 7.04 (4H, m), 7.23 (4H, m), 7.50 (2H, m), 7.60 (4H, m), 7.72-7.74 (4H, m), 7.84 (6H, m), 8.63 (2H, s).

(Example 24)
0.30 g of Complex Compound (23), 0.10 g of 1,1′-bis (4-phenoxyphenyl) -4,4′-bipyridinium dichloride and 10 ml of methanol were mixed and stirred at 50 ° C. for 3 hours. The reaction mixture was cooled to room temperature, 5 ml of water was added to the reaction mixture, the precipitated solid was collected by filtration, washed with a mixed solvent of water and methanol (volume ratio 2: 1), and dried to give a complex compound (24). 0.26 g (yield 75%) was obtained.
Absorption maximum wavelength (TFP): 358.5 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 5.86 (4H, s), 7.03 (8H, m), 7.17 (4H, d, J = 7.8 Hz), 7 .22 (8H, t, J = 8.0 Hz), 7.28-7.36 (6H, m), 7.48-7.54 (8H, m), 7.57-7.60 (8H, m), 7.73 (8H, d, J = 7.8 Hz), 7.84 (12H, d, J = 6.8 Hz), 7.95 (4H, bs), 8.64 (4H, s) 9.03 (4H, s), 9.65 (4H, s).

(Example 25)
0.19 g of cobalt (II) acetate tetrahydrate was added to a mixture of 0.70 g of compound (I-10), 0.69 g of DBU and 7 ml of methanol, and the mixture was stirred at 50 ° C. for 3 hours in an air atmosphere. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.75 g of complex compound (25) (yield 87%).
Absorption maximum wavelength (TFP): 362.0 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.59-1.67 (6H, m), 1.88-1.92 (2H, m), 2.60-2.63 ( 2H, m), 2.76 (6H, s), 2.87 (12H, s), 3.24 (2H, t, J = 5.8 Hz), 3.46 (2H, t, J = 5. 8Hz), 3.52-3.55 (2H, m), 3.88 (6H, s), 6.54 (4H, d, J = 9.3 Hz), 7.02 (2H, t, J = 7.3 Hz), 7.12 (4H, d, J = 8.8 Hz), 7.20-7.22 (4H, m), 7.52 (4H, d, J = 8.8 Hz), 7. 61 (4H, d, J = 7.6 Hz), 7.67 (4H, d, J = 9.3 Hz).

(Example 26)
0.30 g of the complex compound (25), 0.07 g of 1,1′-bis [4- (trifluoromethoxy) phenyl] -4,4′-bipyridinium dichloride and 8 ml of methanol were mixed and stirred at 50 ° C. for 3 hours. . The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.29 g (yield 92%) of the complex compound (26).
Absorption maximum wavelength (TFP): 363.5 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 2.77 (12H, s), 2.86 (24H, s), 3.88 (12H, s), 6.54 (8H, d) , J = 9.0 Hz), 7.02 (4H, t, J = 7.1 Hz), 7.12 (8H, d, J = 9.0 Hz), 7.19-7.21 (8H, m) 7.51 (8H, d, J = 9.0 Hz), 7.60 (8H, d, J = 7.6 Hz), 7.67 (8H, d, J = 9.0 Hz), 7.98 ( 8H, bs), 9.04 (4H, bs), 9.64 (4H, bs).

(Example 27)
To a mixture of 0.70 g of compound (I-11), 0.82 g of DBU and 5 ml of methanol was added 0.22 g of cobalt (II) acetate tetrahydrate, and the mixture was stirred at 50 ° C. for 3 hours in an air atmosphere. The reaction mixture was cooled to room temperature, 25 ml of water was added to the reaction mixture, the precipitated solid was collected by filtration, washed with a mixed solvent of water and methanol (volume ratio 4: 1), and dried to give the complex compound (27). 0.86 g (yield 97%) was obtained.
Absorption maximum wavelength (TFP): 358.5 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.58 (6H, m), 1.87 (2H, m), 2.58 (2H, m), 3.22 (2H, m ), 3.42 (2H, m), 3.48 (2H, m), 3.86 (6H, s), 5.85 (2H, s), 7.01-7.21 (12H, m) , 7.70-7.82 (10H, m), 8.60 (2H, s).

(Example 28)
0.30 g of Complex Compound (27), 0.08 g of 1,1′-bis (4-phenoxyphenyl) -4,4′-bipyridinium dichloride and 9 ml of methanol were mixed and stirred at 50 ° C. for 3 hours. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.27 g (yield 83%) of the complex compound (28).
Absorption maximum wavelength (TFP): 359.0 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 3.86 (12H, s), 5.82-5.85 (4H, m), 6.98-7.03 (8H, m) 7.12-7.22 (20H, m), 7.28-7.30 (6H, m), 7.49-7.52 (4H, m), 7.69 (8H, d, J = 8.0 Hz), 7.75 (8H, d, J = 8.8 Hz), 7.81 (4H, m), 7.95 (4H, bs), 8.58 (4H, s), 9.01 (4H, bs), 9.64 (4H, bs).

(Example 29)
To a mixture of 0.80 g of compound (I-12), 0.61 g of DBU and 6 ml of methanol, 0.25 g of cobalt (II) acetate tetrahydrate was added, and the mixture was stirred at 50 ° C. for 3 hours. The reaction mixture was cooled to room temperature, 10 ml of water was added to the reaction mixture, the precipitated solid was collected by filtration, washed with a mixed solvent of water and methanol (volume ratio 1: 1), and then dried to give the complex compound (29). 0.98 g (99% yield) was obtained.
Absorption maximum wavelength (TFP): 364.0 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.05 (6H, t, J = 7.3 Hz), 1.58-1.64 (6H, m), 1.75-1. 82 (4H, m), 1.84-1.88 (2H, m), 2.58 (2H, m), 2.78-2.93 (16H, m), 3.21 (8H, m) 3.41-3.43 (2H, m), 3.49 (2H, m), 6.53 (4H, d, J = 9.0 Hz), 6.92-6.96 (2H, m) 7.12 (4H, d, J = 7.6 Hz), 7.51 (4H, d, J = 7.6 Hz), 7.66 (4H, d, J = 9.0 Hz).

(Example 30)
The complex compound (29) (0.30 g), 1,1′-bis [4- (N, N-dimethylamino) phenyl] -4,4′-bipyridinium dichloride (0.07 g) and methanol (9 ml) were mixed and mixed at 50 ° C. with 3 Stir for hours. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.24 g (yield 75%) of the complex compound (30).
Absorption maximum wavelength (TFP): 364.0 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.04 (12H, t, J = 7.3 Hz), 1.74-1.82 (8H, m), 2.76-2. 94 (32H, m), 3.05 (12H, bs), 3.29 (12H, s), 6.52 (8H, d, J = 9.0 Hz), 6.92-6.95 (8H, m), 7.09-7.13 (8H, m), 7.50 (8H, d, J = 7.6 Hz)), 7.66 (8H, d, J = 9.0 Hz), 7.73 (4H, bs), 8.81 (4H, bs), 9.43 (4H, bs).

(Example 31)
0.30 g of complex compound (29), 0.08 g of 1,1′-bis [4- (trifluoromethoxy) phenyl] -4,4′-bipyridinium dichloride and 9 ml of methanol were mixed and stirred at 50 ° C. for 3 hours. . The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.25 g of complex compound (31) (yield 75%).
Absorption maximum wavelength (TFP): 361.0 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.04 (12H, t, J = 7.3 Hz), 1.74-1.82 (8H, m), 2.80-2. 91 (32H, m), 3.20 (12H, s), 6.52 (8H, d, J = 9.0 Hz), 6.92-6.96 (4H, m), 7.09-7. 13 (8H, m), 7.50 (8H, d, J = 7.6 Hz), 7.66 (8H, d, J = 9.0 Hz), 7.85 (4H, bs), 8.10 ( 4H, bs), 9.03 (4H, bs), 9.67 (4H, bs).

(Example 32)
To a mixture of 1.00 g of compound (I-13), 0.69 g of DBU and 7 ml of methanol was added 0.28 g of cobalt (II) acetate tetrahydrate, and the mixture was stirred at 50 ° C. for 3 hours in an air atmosphere. The reaction mixture was cooled to room temperature, 5 ml of water was added to the reaction mixture, the precipitated solid was collected by filtration, washed with a mixed solvent of water and methanol (volume ratio 1: 1), and dried to give a complex compound (32). 1.16 g (94% yield) was obtained.
Absorption maximum wavelength (TFP): 352.5 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 0.71 (6H, t, J = 7.3 Hz), 1.07 (6H, t, J = 7.3 Hz), 1.59− 1.68 (10H, m), 1.78-1.90 (6H, m), 2.59-2.62 (2H, m), 2.85-2.96 (4H, m), 3. 23 (2H, t, J = 5.6 Hz), 3.32 (6H, s), 3.44 (2H, t, J = 5.6 Hz), 3.50-3.53 (2H, m), 4.02 (4H, t, J = 6.8 Hz), 6.91-6.94 (2H, m), 7.09-7.16 (8H, m), 7.39 (2H, d, J = 7.3 Hz), 7.56-7.58 (6H, m), 8.44 (2H, d, J = 6.6 Hz).

(Example 33)
0.30 g of Complex Compound (32), 0.08 g of 1,1′-bis (4-phenoxyphenyl) -4,4′-bipyridinium dichloride and 9 ml of methanol were mixed and stirred at 50 ° C. for 3 hours. The reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with methanol, and dried to obtain 0.27 g (yield 86%) of the complex compound (33).
Absorption maximum wavelength (TFP): 355.0 nm
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 0.69 (12H, t, J = 7.3 Hz), 1.07 (12H, t, J = 7.3 Hz), 1.60- 1.67 (8H, m), 1.76-1.87 (8H, m), 2.81-2.96 (8H, m), 3.33 (12H, s), 4.00 (8H, t, J = 6.8 Hz), 6.90-6.94 (4H, m), 7.09-7.18 (20H, m), 7.29-7.33 (6H, m), 7. 38 (4H, d, J = 7.6 Hz), 7.51-7.57 (16H, m), 7.93 (4H, bs), 8.43 (4H, d, J = 7.4 Hz), 8.93 (4H, bs), 9.57 (4H, bs).

(Test Example 1)
-Solubility test-
980 mg of TFP was added to each of 20 mg of the complex compounds (1) to (33), and ultrasonic vibration was applied at room temperature for 3 minutes. It was visually confirmed that 20 mg of complex compounds (1) to (33) were completely dissolved in 980 mg of TFP.

(Test Example 2)
-Coating property test-
Each of 20 mg of the complex compounds (1) to (33) was dissolved in 980 mg of TFP, and filtered through a Teflon (registered trademark) filter (Whatman, pore size 0.20 μm) to obtain the complex compounds (1) to (33). ) Solution was obtained. Using a plate made of polycarbonate resin (made by Dazai Equipment Co., Ltd .; diameter 2 inches, thickness 1 mm) as a substrate, spin coating method (3000 rpm, 30 seconds, amount of solution used) using Mikasa 1H-SX; The solution was applied onto a substrate at 25 to 0.30 g), and the substrate was dried in an oven at 70 ° C. for 30 minutes to obtain complex compound thin films, respectively. It was confirmed by visual observation that the thin films of the obtained complex compounds (1) to (33) were uniform and formed uniformly.

(Test Example 3)
-Light resistance test-
The complex compounds (2), (5), (5), (5), (5) and (5) were used in the same manner as in the coating property test except that a glass plate (manufactured by Dazai Equipment Co., Ltd .; 2 cm × 2 cm, thickness 2 mm) was used instead of the polycarbonate resin plate. 6), (7), (9), (19), (20), (26), (30), and (33) thin films were obtained, respectively. Using a Dew panel light control weather meter DPWL-5R manufactured by Suga Test Instruments Co., Ltd. equipped with an ultraviolet fluorescent lamp (Suga Test Instruments Co., Ltd., SUGA-FS40: peak wavelength 313 nm, illuminance distribution 282 to 373 nm) Irradiated with light of / m ² at 45 ° C. for 10 hours. In the thin film before and after the light resistance test, an ultraviolet-visible absorption spectrum was measured using a spectrophotometer. Table 3 shows the ratio (I ^a / I ^a ₀ ) of the absorbance (I ^a ) at the absorption maximum wavelength after the light resistance test to the absorbance (I ^a ₀ ) at the absorption maximum wavelength before the light resistance test. Here, the absorption maximum wavelength after the light resistance test represents the absorption maximum wavelength in the absorption spectrum after the light resistance test. A larger _{value of} I ^a / I ^a ₀ represents better light resistance.
The thin films of the complex compounds (2), (5), (6), (7), (9), (19), (20), (26), (30) and (33) have excellent light resistance, respectively. It can be seen that

(Test Example 4)
-Water resistance test-
Similar to the coating property test, the complex compounds (2), (5), (6), (7), (9), (19), (20), (26), (30) and (33) Each thin film was obtained. The thin film was immersed in 75 ° C. water for 30 minutes. In the thin film before and after the water resistance test, an ultraviolet-visible absorption spectrum was measured using a spectrophotometer. Absorbance at the absorption maximum wavelength before water resistance test ratio (I ^{b ₀₎} the absorbance at the absorption maximum wavelength after the water resistance test for ^{(I b) (I b /} I b 0), and the absorption maximum wavelength before and after the water resistance test Table 4 shows the change [Δλmax (b)]. Here, the absorption maximum wavelength after the water resistance test represents the absorption maximum wavelength in the absorption spectrum after the water resistance test. As those ^{I _b} / I ^b ₀ is close to 1, also as those Δλmax (b) is small, indicating that it has excellent water resistance.
The thin films of the complex compounds (2), (5), (6), (7), (9), (19), (20), (26), (30) and (33) have excellent water resistance, respectively. It can be seen that

(Test Example 5)
-Moist heat resistance test-
Similar to the coating property test, the complex compounds (2), (5), (6), (7), (9), (19), (20), (26), (30) and (33) Each thin film was obtained. Using a constant temperature and humidity chamber KHWII-40HP manufactured by Satake Chemical Machinery Co., Ltd., the thin film was exposed to an atmosphere having a temperature of 80 ° C. and a relative humidity of 80% for 100 hours. In the thin film before and after the wet heat resistance test, the ultraviolet-visible absorption spectrum was measured using a spectrophotometer. Absorbance at the absorption maximum wavelength before moist heat resistance test ratio (I ^{C ₀₎} absorbance at the absorption maximum wavelength after wet heat resistance test for ^{(I c) (I C /} I C 0), and wet heat resistance test maximum absorption wavelength around Table 5 shows the change [Δλmax (c)]. Here, the absorption maximum wavelength after the moist heat resistance test represents the absorption maximum wavelength in the absorption spectrum after the moist heat resistance test. As I ^C / I ^C ₀ is closer to 1 and Δλmax (c) is smaller, it indicates that the heat and heat resistance is excellent.
The thin films of the complex compounds (2), (5), (6), (7), (9), (19), (20), (26), (30), and (33) each have excellent moisture and heat resistance. It can be seen that

(Test Example 6)
-Storage stability test in solution-
13 mg of each of the complex compounds (2), (5), (6), (7), (9), (19), (20), (26), (30) and (33) was added to 1 ml of TFP. Dissolved and filtered through a Teflon (registered trademark) filter (Whatman, pore size 0.20 μm), and complex compounds (2), (5), (6), (7), (9), (19) , (20), (26), (30) and (33) were obtained, respectively. Each of the resulting solutions was transferred to a brown bottle with a lid and stored at 25 ° C. for 3 days. Before and after the storage stability test, the complex compounds (2), (5), (6), (7), (9), (19), (20), (26), (30) were measured using a spectrophotometer. ) And (33) were diluted 1250 times, and an ultraviolet-visible absorption spectrum was measured. The ratio of the absorbance (I ^d ) at the absorption maximum wavelength after the storage stability test (I ^d / I ^d ₀ ) to the absorbance (I ^d ₀ ) at the absorption maximum wavelength before the storage stability test, and before and after the storage stability test Table 6 shows the change [Δλmax (d)] of the absorption maximum wavelength. Here, the absorption maximum wavelength after the storage stability test represents the absorption maximum wavelength in the absorption spectrum after the storage stability test. As ^{I _d} / I ^d ₀ is close to 1, also, as the Δλmax (d) is small, indicating that it has excellent storage stability in solution.
Complex compounds (2), (5), (6), (7), (9), (19), (20), (26), (30) and (33) are excellent in solution, respectively. It can be seen that it has storage stability.

(Example 34)
-Production of recording media-
As a substrate, a polycarbonate resin disk having an outer diameter of 120 mm and a thickness of 1.1 mm having a guide hole having a through hole in the center and a track pitch of 0.32 μm, a groove width of 180 nm, and a groove depth of 32 nm on the surface is used. It was. On the surface of the substrate on which the guide groove was formed, an Ag alloy reflective layer having a thickness of 40 to 60 nm was formed by sputtering.
20 mg of complex compound (2) was dissolved in 1980 mg of TFP, and filtered through a Teflon (registered trademark) filter (Whatman, pore size 0.20 μm) to obtain a solution of complex compound (2). The solution was applied onto the reflective layer by spin coating (1200 rpm to 5000 rpm, 10 seconds, amount of solution used: 1 ml) using Mikasa 1H-SX, and the solution was applied in an oven at 70 ° C. for 30 minutes. The substrate was dried to form a recording layer. Next, a transparent protective film having a thickness of 10 to 15 nm is formed on the recording layer by RF sputtering using ZnS—SiO ₂ (composition ratio: ZnS / SiO ₂ = 80 wt% / 20 wt%) as a target material. A layer was formed. Next, a recording medium (2) was produced by attaching a cover film (D-900) manufactured by the company using a cover film applying apparatus (Opteria MODEL 300m / ST) manufactured by Lintec Corporation on the protective layer.
Other than using complex compound (5), (6), (7), (9), (19), (20), (26), (30) or (33) instead of using complex compound (2) Is the same as the manufacturing method of the recording medium (2), and the recording medium (5), (6), (7), (9), (19), (20), (26), (30) or (30) 33) was produced.

(Test Example 7)
-Test of recording / reproduction characteristics of recording media-
Recording / reproducing apparatus (Pulstec Industrial Co., Ltd.) for recording media (2), (5), (6), (7), (9), (19), (20), (26), (30) and (33) The dependence of jitter on the recording power was measured when the recording power of the recording laser light was in the range of 3 to 8 mW (measurement conditions: wavelength 405 nm, numerical aperture (NA) 0. 85, recording speed 4.92 m / s]. With regard to the dependency of the obtained recording power on jitter, the minimum jitter in the range of 3 to 8 mW of recording power was defined as bottom jitter. Table 7 shows the obtained bottom jitter. The smaller the bottom jitter, the better the recording / reproducing characteristics.
Recording media (2), (5), (6), (7), (9), (19), (20), (26), (30), and (33) each have excellent recording / reproduction characteristics. It turns out that it has. Among these, it can be seen that the recording media (5), (6), (7), (9), (20) and (26) have more excellent recording / reproducing characteristics.

According to the present invention, it is possible to provide a complex compound or the like used for an optical recording medium having excellent moisture and heat resistance.

Claims (14)

1. Formula (I)
   

   

   [Wherein, R ¹ and R ³ are the same or different and each has a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. Represents an aralkyl group which may have a substituent, an aryl group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent, R ² May have a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, an amino group which may have a substituent, an alkyl group which may have a substituent, or a substituent. An alkenyl group, an alkoxyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, an alicyclic ring which may have a substituent Represents a heterocyclic group optionally having a hydrocarbon group or a substituent, and R ⁴ is the formula (II)
   

   

   (In the formula, R ⁵ has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aralkyl group which may have a substituent, and a substituent. An aryl group, an alicyclic hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent), or a formula (III)
   

   

   (Wherein ring A may further have a substituent)], a metal, an ion generated by adding one or more protons to an amine, an ammonium ion, and a A complex compound comprising one kind selected from the group consisting of quaternary ammonium ions.
2. The complex compound according to claim 1, wherein R ¹ is an aryl group which may have a substituent.
3. The complex compound according to claim 1, wherein R ² is an alkyl group which may have a substituent or an aryl group which may have a substituent.
4. The complex compound according to any one of claims 1 to 3, wherein R ³ is a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
5. The complex compound according to any one of claims 1 to 4, wherein R ⁴ is the formula (II).
6. The complex compound according to claim 5, wherein R ⁵ is an aryl group which may have a substituent or a heterocyclic group which may have a substituent.
7. The complex compound according to any one of claims 1 to 4, wherein R ⁴ is the formula (III).
8. Formula (III) is formula (IV)
   

   

   (In the formula, R ⁶ has an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. The complex compound of Claim 7 represented by the alicyclic hydrocarbon group which may be sufficient, or the heterocyclic group which may have a substituent.
9. The complex compound according to any one of claims 1 to 8, wherein the metal is cobalt, rhodium, iridium, aluminum, gallium or iron.
10. The complex compound according to any one of claims 1 to 8, wherein the metal is cobalt.
11. One selected from the group consisting of an ion generated by adding one or more protons to an amine, an ammonium ion and a quaternary ammonium ion is an ion generated by adding one or more protons to the amine Item 11. The complex compound according to any one of Items 1 to 10.
12. The complex compound according to claim 11, wherein the amine is an aliphatic tertiary amine which may have a substituent.
13. The quaternary ammonium ion is one selected from the group consisting of an ion generated by adding one or more protons to an amine, an ammonium ion, and a quaternary ammonium ion. Complex compounds.
14. An optical recording medium containing the complex compound according to any one of claims 1 to 13.