JPWO2010047341A1 - Metal complex of squarylium compound and optical recording medium containing the same - Google Patents

Abstract

The present invention provides a metal complex of a squarylium compound used in an optical recording medium having a highly sensitive photoresponsiveness to blue-violet laser light. The present invention provides a compound represented by formula (I) [wherein R1 is a heterocyclic group optionally having substituent (s), NR4R5 (wherein R4 and R5 may be the same or different, and may have substituent (s)). R2 represents an aryl group which may have a substituent, a heterocyclic group which may have a substituent, etc., and R3 represents a hydrogen atom etc.] And a metal complex of the squarylium compound represented.

Description

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

  In recent years, development of an optical recording medium that enables 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 progressing. For example, in order to record video information of HDTV (high definition television) for two 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, an optical recording medium that records higher density information by using a 405 nm blue-violet laser, setting the NA of the objective lens to 0.85, and reducing the laser spot diameter, so-called Blu-ray Disc (BD) has been developed.

The write-once Blu-ray Disc (BD-R) is required to have various excellent characteristics in terms of recording sensitivity, modulation degree, jitter (jitter), error rate, etc., in addition to the required performance that enables recording and reproduction. . However, those properties in BD-R using conventional organic dyes are not sufficient.
It is known that a metal complex of a squarylium compound having a pyrazole structure is useful as a dye used for a write-once digital versatile disk (DVD-R) (Patent Document 1). The dye is suitable for recording with a laser beam of about 650 nm used for DVD-R recording, but is not suitable for recording with a laser beam of 405 nm.

International Publication No. 2002/50190 Pamphlet

  An object of the present invention is to provide a metal complex of a squarylium compound used for an optical recording medium having a highly sensitive photoresponsiveness to blue-violet laser light.

The present invention provides the following [1] to [11].
[1] Formula (I)

[Wherein R ¹ represents an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or NR ⁴ R ⁵ (wherein R ⁴ and R ⁵ are the same or Differently, a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent Represents an alicyclic hydrocarbon group or a heterocyclic group which may have a substituent), and R ² may have an alkyl group which may have a substituent or a substituent. A good aralkyl group, 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, YR ⁶ (wherein , Y represents an oxygen atom or a sulfur atom, R ⁶ is an optionally substituted alkyl group, substituted Be aryl group, have also good alicyclic substituted hydrocarbon group or a substituent representing an even heterocyclic group) or NR 7 ^R 8 ^(wherein, R ⁷ and R ⁸ is the same or different and represents a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents an alicyclic hydrocarbon group which may have or a heterocyclic group which may have a substituent, and R ³ represents a hydrogen atom, an alkyl group which may have a substituent, 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 heterocycle which may have a substituent A metal complex of a squarylium compound represented by the formula:

[2] The metal complex of the squarylium compound according to [1], wherein R ¹ is a heterocyclic group which may have a substituent.
[3] The squarylium compound according to [1], wherein R ¹ is a heterocyclic group which may have a substituent, and the heterocyclic group is an aromatic heterocyclic group which may have a substituent. Metal complex.
[4] R ¹ is a heterocyclic group having a substituent, and the heterocyclic group having the substituent has the formula (X)

(In the formula, R ⁹ represents a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents an alicyclic hydrocarbon group which may have or a heterocyclic group which may have a substituent, and R ¹⁰ represents a hydrogen atom, a hydroxyl group, a carboxyl 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, an aralkyl group which may have a substituent, an aryl group which may have a substituent, a substituent; A alicyclic hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent.) A metal complex of a squarylium compound according to [1].

[5] R ¹⁰ may have an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. The metal complex of a squarylium compound according to [4], which is a good alicyclic hydrocarbon group or a heterocyclic group which may have a substituent.
[6] The metal complex of the squarylium compound according to [1], wherein R ¹ is NR ⁴ R ⁵ (wherein R ⁴ and R ⁵ are as defined above).
[7] ^{R 1} is ^NR 4 ^{R 5} (wherein, ^{R 4} and ^{R 5} are each the same meanings as defined above) and, ^{R 4} and ^{R 5} are the same or different, have a substituent The metal complex of the squarylium compound according to [1], which may be an aryl group or a heterocyclic group which may have a substituent.

[8] The metal complex of the squarylium compound according to any one of [1] to [7], wherein R ² is an aryl group which may have a substituent or a heterocyclic group which may have a substituent. .
[9] The metal complex of the squarylium compound according to any one of [1] to [8], wherein R ³ is a hydrogen atom.
[10] The metal complex of the squarylium compound according to any one of [1] to [9], wherein the metal is nickel, cobalt, aluminum, copper, zinc, or iron.
[11] An optical recording medium containing the metal complex of the squarylium compound according to any one of [1] to [10].

  According to the present invention, it is possible to provide a metal complex of a squarylium compound used for an optical recording medium having a highly sensitive photoresponsiveness to blue-violet laser light.

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 group include a linear or branched alkyl group having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, and an 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, 1-isopropyl-2- A methylpropyl group, an octyl group, a nonyl group, a decyl group, an eicosyl group, etc. are mentioned, Among them, those having 1 to 10 carbon atoms are preferable.

Examples of the aralkyl group include an aralkyl group having 7 to 15 carbon atoms, and specific examples include a benzyl group, a phenethyl group, a phenylpropyl group, and a naphthylmethyl group.
As an aryl group, a C6-C14 aryl group is mentioned, for example, A phenyl group, a naphthyl group, an anthryl group, an azulenyl group etc. are mentioned specifically ,.

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 C3-C8 cycloalkane 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 heterocycle, for example, a 5-membered or 6-membered monocyclic aromatic heterocycle containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and a 3- to 8-membered ring are 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 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, and a 3- to 8-membered ring are 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, Examples include 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, etc. It is done.

As an aromatic heterocyclic ring in an aromatic heterocyclic group, the same thing as the aromatic heterocyclic ring illustrated above is mentioned, for example.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the substituent of the amino group include one or two substituents, specifically, an alkyl group, an aralkyl group, an aryl group, an alicyclic hydrocarbon group, a heterocyclic group, and the like. Here, an alkyl group, an aralkyl group, an aryl group, an alicyclic hydrocarbon group, and a heterocyclic group have the same meanings as described above. When two substituents are present, each of the substituents may be the same or different.

  Examples of the substituent of the alkyl group include the same or different 1 to 5 substituents, specifically, hydroxyl group, carboxyl group, halogen atom, nitro group, cyano group, carbamoyl group, alkoxyl group, alkoxyalkoxyl. Group, alkanoyl group, alkylcarbonyloxy group, alkoxycarbonyl group, aroyl group, aryloxy group, arylcarbonyloxy group, aryloxycarbonyl group, heterocyclic group and the like. A halogen atom and a heterocyclic group are as defined above. The alkyl moiety of the alkoxyl group, alkanoyl group, alkylcarbonyloxy group and alkoxycarbonyl group has the same meaning as the above alkyl group. 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 carboxyl group, a halogen atom, a nitro group, a cyano group. Group, carbamoyl group, optionally substituted alkyl group, optionally substituted alkoxyl group, aralkyl group, alkanoyl group, alkylcarbonyloxy group, alkoxycarbonyl group, aryl group, aroyl group, Examples include an aryloxy group, an arylcarbonyloxy group, an aryloxycarbonyl group, an alicyclic hydrocarbon group, a heterocyclic group, and an amino group which may have a substituent. Here, halogen atom, optionally substituted alkyl group, alkoxyl group, aralkyl group, alkanoyl group, alkylcarbonyloxy group, alkoxycarbonyl group, aryl group, aroyl group, aryloxy group, arylcarbonyloxy group , An aryloxycarbonyl group, an alicyclic hydrocarbon group, a heterocyclic group and an amino group which may have a substituent are as defined above. As a substituent of an alkoxyl group, the same thing as the functional group illustrated above as a substituent of an alkyl group is mentioned, for example.

  Examples of the substituent of the aromatic heterocyclic group include the same or different 1 to 5 substituents, specifically, a hydroxyl group, an oxo group, a carboxyl group, a halogen atom, a nitro group, a cyano group, and a carbamoyl group. , An optionally substituted alkyl group, an optionally substituted alkoxyl group, an optionally substituted aralkyl group, an alkanoyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, a substituted group Aryl group optionally having a group, aroyl group, aryloxy group, arylcarbonyloxy group, aryloxycarbonyl group, alicyclic hydrocarbon group optionally having substituent (s), heterocyclic group, substituent And an amino group which may have. Here, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aralkyl group which may have a substituent, an alkanoyl group, an alkylcarbonyloxy group, An alkoxycarbonyl group, an optionally substituted aryl group, an aroyl group, an aryloxy group, an arylcarbonyloxy group, an aryloxycarbonyl group, an optionally substituted alicyclic hydrocarbon group, a heterocycle The cyclic group and the amino group which may have a substituent are as defined above.

As a substituent of a heterocyclic group when R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ or R ¹⁰ is a heterocyclic group which may have a substituent Examples thereof include the same functional groups as those exemplified above as the substituent of the aromatic heterocyclic group.
Examples of the substituent of the heterocyclic group when R ¹ is an optionally substituted heterocyclic group include 1 to 5 substituents which are the same or different, specifically, a hydroxyl group, An oxo group, a carboxyl group, a halogen atom, a nitro group, a cyano group, a carbamoyl group, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent Good aralkyl group, alkanoyl group, alkylcarbonyloxy group, alkoxycarbonyl group, aryl group optionally having substituent, aroyl group, aryloxy group, arylcarbonyloxy group, aryloxycarbonyl group, having substituent Examples thereof include an alicyclic hydrocarbon group which may be present, a heterocyclic group which may have a substituent, and an amino group which may have a substituent. Here, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aralkyl group which may have a substituent, an alkanoyl group, 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, an alicyclic hydrocarbon group which may have a substituent, and The amino group which may have a substituent is as defined above. In addition, examples of the substituent of the heterocyclic group in the heterocyclic group which may have a substituent include the same functional groups exemplified above as the substituent of the aromatic heterocyclic group.

Examples of the metal in the metal complex include aluminum, ruthenium, osmium, iron, platinum, zinc, beryllium, copper, nickel, chromium, cobalt, manganese, iridium, vanadium, titanium, etc., among which nickel, cobalt, aluminum, Copper, zinc and iron are preferred.
R ¹ is preferably NR ⁴ R ⁵ (wherein R ⁴ and R ⁵ are as defined above) or an aromatic heterocyclic group which may have a substituent.

When R ¹ is NR ⁴ R ⁵ , R ⁴ and R ⁵ are the same or different and are an aryl group which may have a substituent or a heterocyclic group which may have a substituent. Is preferred. When R ⁴ or R ⁵ is an aryl group which may have a substituent, the aryl group is preferably a phenyl group, and R ⁴ or R ⁵ may have a substituent. When it is a group, the heterocyclic ring in the heterocyclic group is preferably a pyridine ring.

When R ¹ is a heterocyclic group which may have a substituent, the heterocyclic ring in the heterocyclic group is preferably an aromatic heterocyclic ring containing at least one nitrogen atom. Here, examples of the aromatic heterocycle containing at least one nitrogen atom include those containing at least a nitrogen atom among the aromatic heterocycles exemplified above, and more specifically, for example, Pyridine ring, pyrazine ring, 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, thiazole ring, oxazole ring, isoxazole ring, indole ring, isoindole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzothiazole ring, benzoxazole ring, purine ring, carbazole ring, acridine ring, phenazine ring, Phenothiazi Ring, phenoxazine ring, and among them, a pyrazole ring or indole ring.

When R ¹ is a group represented by the formula (X), R ⁹ has an alkyl group which may have a substituent, an aralkyl group which may have a substituent, and a substituent. It is preferably an aryl group, an alicyclic hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent.
Further, when R ¹ is a group represented by the formula (X), R ¹⁰ has an alkyl group which may have a substituent, an aralkyl group which may have a substituent, and a substituent. It is preferably 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, and may have a substituent. More preferably, it is an alkyl group.

R ² is preferably an aryl group which may have a substituent or a heterocyclic group which may have a substituent. When R ¹ is a group represented by the formula (X), R ² is more preferably an aryl group which may have a substituent.
When R ² is YR ⁶ (wherein R ⁶ is as defined above), Y is preferably an oxygen atom.

R ³ is preferably a hydrogen atom.
Next, the production method of compound (I) will be described with examples.
Compound (I) can be produced, for example, according to Reaction Schemes 1-3.
Reaction formula 1

Reaction formula 2

Reaction formula 3

(Wherein R ¹ , R ² and R ³ are as defined above, and W represents a chlorine atom, a bromine atom, an alkoxyl group having 1 to 4 carbon atoms, etc.)
As a C1-C4 alkoxyl group, a methoxy group, an ethoxy group, a butoxy group etc. are mentioned, for example.
Among compounds (III), those in which R ¹ is NR ⁴ R ⁵ (wherein R ⁴ and R ⁵ have the same meanings as described above) can be obtained as a commercial product or can be obtained by a known method, for example, an incorporated association The Chemical Society of Japan, “Experimental Chemistry Course (Volume 20)”, 4th edition, Maruzen Co., 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 produced according to the method described in 277-347.

The compound (III) in which R ¹ is a heterocyclic group which may have a substituent is obtained as a commercially available product, or is a known method such as the Japan Chemical Society, “Experimental Chemistry Course”. (Vol. 24) ", 4th edition, Maruzen Co., Ltd., 1991, p. 319-401, edited by Katritzky, “Handbook of Heterocycles”, Pergamon Press, 1985, p. 379-506, edited by Barton & Olis, “Comprehensive Organic Chemistry-Heterocyclic Compounds— (Volume 4)”, Pergamon Press, 1979, p. 1-246, p. 275-320, p. 411-492, p. 789-838, The Chemical Society of Japan, New Experimental Chemistry Course, Volume 14, “Synthesis and Reaction of Organic Compounds IV Heterocyclic Compounds”, Maruzen Co., Ltd., 1978, p. 2154, Chemistry, 1964, 26, p. 333, Journal of Organic Chemistry, 1957, Vol. 22, p. 780, Chemical & Pharmaceutical Bulletin, 1981, Vol. 29, No. 1, p. 244, Journal of Heterocyclic Chemistry, 1980, Vol. 17, No. 2, p. 389, Liebigs Annalen der Chemie, 1985, Vol. 1, p. 78, Journal of the Chemical Society. Perkin Transactions. 1, 1983, Volume 2, p. 325, Journal of the Indian Chemical Society, 1980, vol. 57, p. 1108, Journal of Organic Chemistry, 1979, vol. 44, p. It can be produced according to the method described in 4597.

The compound (III) in which R ¹ is an aryl group which may have a substituent is obtained as a commercially available product, or a known method such as “Chemical Chemistry Course” (edited by the Chemical Society of Japan). 19)), 4th edition, Maruzen Co., Ltd., 1991, p. 112-136, edited by Buehler & Pearson, “Survey of Organic Synthesis (Volume 1)”, Wiley-Interscience, 1970, p. 246-284, edited by Buehler & Pearson, “Survey of Organic Synthesis (Volume 2)”, Wiley-Interscience, 1977, p. It can manufacture and obtain according to the method of 391-460 description, etc.

  Compound (V) 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 of Organic Compounds II Synthesis of Diazo, Azo and Azoxy Compounds” "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 Nitrogen-containing Compounds”, 2nd Edition, Maruzen Co., Ltd., 1978, p. 1573-1584, Saul Patai ed., “The Chemistry of the hydrazo, azo, and azoxy group (Vol. 1)”, John Wiley & Sons, 1975, p. 69-107, Saul Pati ed., “The zheh”. group (Vol. 2) ", John Wiley & Sons, 1975, p. 599-723, edited by Gilman," Organic Synthesis Collective (Vol. 1) ", Shriner & Shrin. er, 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. 1108-1111.

Reaction formula 1
Compound (VII) can be obtained by a known method, for example, Journal of Organic Chemistry, 1977, Vol. 42, No. 7, p. 1126-1130, Dies and Pigments, 2001, Vol. 49, p. 161-179 and can be produced according to the method. Specifically, for example, compound (II) and 1 to 2 moles of compound (III) are optionally added in the presence of 1 to 2 moles of acid or 1 to 2 moles of base in a solvent. It can obtain by making it react at 0-100 degreeC for 1 to 20 hours.

  Examples of the solvent include halogenated hydrocarbon solvents such as chloroform, dichloromethane, 1,2-dichloroethane, ether solvents such as diethyl ether and tert-butyl methyl ether, aromatic hydrocarbon solvents such as toluene and benzene, Examples thereof include alcohol solvents such as methanol, ethanol and propanol, tetrahydrofuran, ethyl acetate, dimethylformamide, dimethyl sulfoxide (DMSO) and the like.

Examples of the acid include aluminum halides such as aluminum chloride and aluminum bromide, ferric halides such as ferric fluoride, ferric chloride and ferric bromide, and iron oxides such as ferric oxide. , Antimony halides such as antimony fluoride and antimony chloride, zinc chloride, ferric sulfate, trifluoromethanesulfonic acid, and fluorosulfonic acid.
Examples of the base include organic bases such as quinoline, triethylamine and pyridine, or potassium carbonate, potassium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, sodium hydroxide and the like.

Reaction formula 2
Compound (VI) can be obtained, for example, by treating compound (VII) in 40 to 90% by volume of acetic acid aqueous solution at 40 to 120 ° C. for 0.5 to 7 hours, or in 1 to 10% by weight of potassium carbonate aqueous solution. It can be obtained by treating at 40 to 120 ° C. for 0.5 to 20 hours.
Reaction formula 3
Compound (I) can be obtained, for example, by reacting compound (VI) with 1 to 5 moles of compound (V) in a solvent at 40 to 100 ° C. for 1 to 100 hours.

  Examples of the solvent include alcohol solvents such as ethanol, propanol, 2-propanol, butanol, and octanol, or a mixed solvent of the alcohol solvent (20% by volume or more) and benzene, toluene, or xylene, acetonitrile, and the like. . 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.).

Among compounds (I), those in which R ¹ is NR ⁴ R ⁵ (wherein R ⁴ and R ⁵ have the same meanings as described above), for example, compound (IV) instead of compound (VI)

(In the formula, R ⁴ and R ⁵ have the same meanings as described above, respectively).
Compound (IV) can be produced and produced according to a known method, for example, the method described in JP-A No. 2002-131530. Specifically, for example, squalic acid and compound (III) in which R ¹ is NR ⁴ R ⁵ (wherein R ⁴ and R ⁵ are as defined above) in a solvent, 80 It can be obtained by reacting at ˜150 ° C. for 1 to 100 hours. Here, examples of the solvent include alcohol solvents such as ethanol, propanol, 2-propanol, butanol, and octanol, or a mixed solvent of the alcohol solvent (20% by volume or more) and benzene, toluene, or xylene. It is done. Of compound (III), R ¹ is NR ⁴ R ⁵ (wherein R ⁴ and R ⁵ have the same meanings as described above), and the amount used is 2 to 5 times mol of squaric acid. Is preferred. After the reaction, if necessary, the compound (IV) may be purified by methods usually used in organic synthetic chemistry (various chromatographic methods, recrystallization methods, distillation methods, etc.).

  The metal complex of compound (I) can be produced according to a known method, for example, the method described in WO 02/050190. Specifically, the organometallic compound or metal salt and the compound (I) are added in the presence of 1 to 5 moles of acetic acid, if necessary, in a solvent at a temperature of 25 to 120 ° C. at a temperature of 0.1 to 30. A metal complex of compound (I) can be produced by reacting for a period of time.

It is preferable that the usage-amount of compound (I) is 0.5-5 times mole amount with respect to an organometallic compound or a metal salt.
Examples of the organometallic compound include aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), aluminum isopropoxide, aluminum sec-butoxide, aluminum ethoxide, copper acetylacetonate, zinc acetylacetonate, iron tris. (2,4-pentanedionate), tris (carbonate) cobalt (III) acid sodium salt and the like.

Examples of the metal salt include aluminum chloride, copper chloride, copper acetate, nickel acetate, nickel chloride, cobalt acetate, cobalt chloride, and hydrates thereof.
Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, 2-propanol, butanol and isobutanol, halogen solvents such as chloroform and dichloromethane, aromatic solvents such as benzene, toluene and xylene, tetrahydrofuran and methyl. Examples 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, if necessary, the metal complex of compound (I) may be purified by methods usually used in organic synthetic chemistry (various column chromatography methods, recrystallization methods, washing with a solvent, etc.).
Specific examples of compound (I) are illustrated below. In the table, Me represents a methyl group, Et represents an ethyl group, ⁱ Pr represents an isopropyl group, ^t Bu represents a tert-butyl group, and ⁱ Bu represents an isobutyl group.

Hereinafter, the squarylium compound of Compound No. (1) is referred to as Compound (1). The same applies to the compounds with other compound numbers.
The metal complex of the compound (I) of the present invention comprises a dye for optical recording media, an ultraviolet absorber, a two-photon absorption dye as a three-dimensional recording material, and a sensitizing dye for short wavelength laser (for example, blue-violet laser). Can be used as etc. The metal complex of compound (I) is suitable as a dye for an optical recording medium because it has excellent light resistance, excellent weather resistance, excellent moisture and heat resistance, excellent coating properties, and excellent solubility.

Among the metal complexes of compound (I), those having particularly excellent light resistance include, for example, the following (1) and (2).
(1) In the formula (I), R ¹ is NR ⁴ R ⁵ , R ⁴ and R ⁵ are the same or different and each is a phenyl group which may have a substituent, and R ² is a substituent A cobalt or nickel complex of the compound (I), which may be a pyridyl group optionally having R ³ and a hydrogen atom.
(2) In Formula (I), R ¹ is a group represented by Formula (X), R ² is a phenyl group which may have a substituent, R ³ is a hydrogen atom, In Formula (X), R ⁹ is an optionally substituted alkyl group, an optionally substituted phenyl group, or an optionally substituted pyrimidinyl group, and R ¹⁰ is A cobalt or nickel complex of the compound (I) which is an alkyl group which may have a substituent.

  In the above (1) and (2), the alkyl group which may have a substituent is as defined above. Examples of the substituent of the phenyl group include the same functional groups exemplified above as the substituent of the aryl group. Examples of the substituent of the pyridyl group and the pyrimidinyl group include an aromatic heterocyclic group. Examples of the substituent include the same functional groups exemplified above.

The optical recording medium of the present invention contains a metal complex of compound (I) and has high sensitivity photoresponsiveness to blue-violet laser light, excellent recording signal quality, 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 a metal complex of compound (I). When the recording layer is formed using the metal complex of compound (I), the metal complex of compound (I) may be used alone or in admixture of two or more.

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

The recording layer may contain a binder as necessary. Examples of the binder include polyvinyl alcohol, polyvinyl pyrrolidone, ketone resin, nitrocellulose, cellulose acetate, polyvinyl butyral, and polycarbonate. You may use these individually or in mixture of 2 or more types.
Further, the recording layer may contain, for example, 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 (for example, chelate compounds of transition metal with acetylacetonate, bisphenyldithiol, salicylaldehyde oxime, bisdithio-α-diketone, etc.) and the like. 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 20 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 metal complex of compound (I) is adjusted to 0.3 to 2.5% by weight in order to obtain an appropriate film thickness. The number 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, a doctor blade method, a cast method, a spin coating method, a dipping method, etc.), the solvent of the solution may be on the substrate before applying the substrate and the recording layer. The solvent is not particularly limited 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 and ethyl cellosolve, n-hexane, n-octane, cyclohexane, methylcyclohexane, ethylcyclohexane , Hydrocarbon solvents such as dimethylcyclohexane, n-butylcyclohexane, tert-butylcyclohexane, cyclooctane, ether solvents such as diisopropyl ether and dibutyl ether, tetrafluoropropanol (TFP), octafluoropentanol, hexafluorobutanol, etc. And fluoroalkyl alcohol solvents, and ester solvents such as methyl lactate, ethyl lactate and methyl isobutyrate. You may use these individually or in mixture of 2 or more types.

  The substrate of the optical recording medium of the present invention preferably has a guide groove formed in a spiral shape on the surface for recording / reproduction with a laser beam. As the substrate, those that 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 a method for producing a 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.
The guide groove preferably has a height difference (groove depth) between the top and bottom surfaces of the irregularities of 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 reflectivity with respect to laser light having a wavelength of 550 nm or less and surface smoothness, an alloy mainly composed of silver or silver is used. preferable. The silver-based alloy preferably contains about 90% or more of silver, and as a component other than silver, a group of Cu, Pd, Nd, Ni, Si, Au, Al, Ti, Zn, Zr, Nb, 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. Examples of the material for the intermediate layer include metals, metal oxides, metal nitrides, and the like. The thickness of the reflective layer is preferably 5 to 300 nm, and more preferably 30 to 100 nm.

The transparent protective layer preferably has no or little absorption with respect to the laser beam used during 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. Examples of the material for 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).

  For the cover layer, for example, a polycarbonate sheet having a thickness of about 0.1 mm having an adhesive layer that is transparent to the recording / reproducing laser beam on the surface and has an adhesive force is used, and the sheet is transparently protected via the adhesive layer. By pressure-bonding to the 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.

Since the optical recording medium of the present invention contains a metal complex of compound (I), 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 laser light include, for example, blue-violet laser light having a center wavelength of 405 nm, 410 nm, etc., 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-state laser beam excited by the semiconductor laser beam and capable of continuous oscillation having a fundamental oscillation wavelength of 740 to 960 nm, etc. Light obtained by wavelength conversion by SHG) may be used. SHG may be any piezo element that lacks reflection symmetry, but KDP (KH ₂ PO ₄ ), ADP (NH ₄ H ₂ PO ₄ ), BNN (Ba ₂ NaNb ₅ O ₁₅ ), KN ( Preferred examples of SHG include KNbO ₃ ), LBO (LiB ₃ O ₅ ), and compound semiconductors.

Specific examples of light (second harmonic) obtained by wavelength conversion by SHG include, for example, 430 nm light obtained by wavelength conversion of semiconductor laser light having a fundamental oscillation wavelength of 860 nm, and semiconductor laser having a fundamental oscillation wavelength of 860 nm. Examples thereof include 430 nm light obtained by wavelength conversion of excitation solid-state laser light.
The optical recording medium of the present invention is preferably a BD. The BD is an optical recording medium that uses a blue-violet laser having a wavelength of 405 nm and records a higher density information by reducing the 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 a blue-violet laser beam from the cover layer side.

Hereinafter, the present invention will be described more specifically with reference to examples and reference examples.
Compounds (IV-1), (IV-2), (VI-1), (VI-2), (VI-3), (VI-4), (VI-5) used as raw materials for the squarylium compound, (VI-6) (VI-7) and (VI-8) are shown below. In the formula, Me represents a methyl group, ⁱ Pr represents an isopropyl group, and ^t Bu represents a tert-butyl group.

Reference Example 1 Compound (IV-1)
1-bromo-3,4-difluorobenzene 8.68 g, 3-fluoroaniline 5.00 g, bis (dibenzylideneacetone) palladium complex [Pd (dba) ₂ ] 128 mg, 1,1-bis (diphenylphosphino) ferrocene 125 mg of (dppf), 5.62 g of sodium tert-butoxide and 30 ml of toluene were mixed and stirred at 110 ° C. for 2 hours. After cooling the reaction solution, celite was added to the reaction solution, the mixture was filtered, the filtrate was washed with saturated brine, and the solvent was distilled off. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 9: 1) to obtain 6.82 g (68% yield) of 3,3 ′, 4-trifluorodiphenylamine.

3.5 g of 3,3 ′, 4-trifluorodiphenylamine and 0.72 g of squaric acid were reacted at 135 ° C. for 12 hours in a mixed solvent of 1.5 ml of toluene and 1.5 ml of butanol. After cooling the reaction solution, the precipitated solid was collected by filtration, washed with a methanol solvent, and dried to obtain 2.0 g of Compound (IV-1) (yield 61%).
Reference Example 2 Compound (IV-2)
The same operation as in Reference Example 1 was performed except that 4-fluoroaniline was used instead of 3-fluoroaniline to obtain 3,4,4′-trifluorodiphenylamine.

A squarylium compound (IV-2) was obtained in the same manner as in Reference Example 1 except that 3,4,4′-trifluorodiphenylamine was used instead of 3,3 ′, 4-trifluorodiphenylamine.
Reference Example 3. Compound (VI-1)
17.46 g of 4-methoxyphenylhydrazine hydrochloride, 10.12 g of triethylamine and 100 ml of chloroform were mixed and stirred at room temperature for 0.5 hour. The reaction solution was washed with 50 ml of water and the solvent was distilled off. To the residue were added 10 ml of xylene, 1.2 g of acetic acid and 18.8 g of ethyl trifluoroacetoacetate, and the mixture was stirred at 90 ° C. for 8 hours. The reaction solution was cooled to 5 ° C., 20 ml of octane was added to the reaction solution, the precipitated solid was collected by filtration, washed with a 2: 1 mixed solvent (volume ratio) of octane and xylene, and dried to give 1- ( 16.0 g (yield 58%) of 4-methoxyphenyl) -5-hydroxy-3-trifluoromethylpyrazole was obtained.

1- (4-Methoxyphenyl) -5-hydroxy-3-trifluoromethylpyrazole (12.9 g), 3,4-dimethoxycyclobutene-1,2-dione (7.11 g), potassium carbonate (6.9 g) and methanol (15 ml) were mixed. And stirred at 40 ° C. for 3 hours. After cooling the reaction solution, the precipitated solid was collected by filtration and washed with methanol. To the obtained solid, 3.46 g of potassium carbonate and 75 ml of water were added, and the mixture was stirred at 70 ° C. for 4 hours. After cooling the reaction solution, 100 ml of 3 mol / l hydrochloric acid was added to the reaction solution, the mixture was cooled to 30 ° C., the precipitated solid was collected by filtration, washed with diethyl ether, and dried to give compound (VI-1). 9.8 g (55% yield) was obtained.
Reference Example 4 Compound (VI-2)
13.21 g of ethyl 2,3,4,5-tetrafluorobenzoyl acetate, 0.6 g of acetic acid, 5.41 g of phenylhydrazine and 10 ml of xylene were mixed and stirred at 90 ° C. for 8 hours. After cooling the reaction solution to 5 ° C., 20 ml of octane is added to the reaction solution, and the precipitated solid is collected by filtration, washed with a 2: 1 mixed solvent (volume ratio) of octane and xylene, and then dried to give 5-hydroxy 13.35 g (yield 87%) of -1-phenyl-3- (2,3,4,5-tetrafluorophenyl) pyrazole was obtained.

  5-hydroxy-1-phenyl-3- (2,3,4,5-tetrafluorophenyl) pyrazole 9.25 g, 3,4-dimethoxycyclobutene-1,2-dione 4.26 g, potassium carbonate 4.15 g And 60 ml of methanol were mixed and stirred at 40 ° C. for 3 hours. After cooling the reaction solution, the precipitated solid was collected by filtration and washed with methanol. To the obtained solid, 2.07 g of potassium carbonate and 90 ml of water were added, and the mixture was stirred at 80 ° C. for 2 hours. After cooling the reaction solution, 50 ml of 3 mol / l hydrochloric acid was added to the reaction solution, the mixture was cooled to 50 ° C., the precipitated solid was collected by filtration, washed with water, and dried to give compound (VI-2) 8 .78 g (72% yield) was obtained.

Reference Example 5 Compound (VI-3)
To a mixture of 5.00 g of 3,4-dichlorocyclobutene-1,2-dione and 3.69 g of triethylamine, a mixture of 5.29 g of 1,2-dimethylindole and 160 ml of benzene was added dropwise at room temperature. Stir for 1 hour. The reaction solution was filtered, and the solvent of the filtrate was distilled off. The residue was recrystallized with 30 ml of a 1: 1 mixed solvent (volume ratio) of chloroform and ethyl acetate to obtain 4.6 g of a brown solid. 40 ml of a 1: 1 mixed solvent (volume ratio) of water and acetic acid was added to the obtained solid, and the mixture was heated at 110 ° C. for 5 hours. After cooling the reaction solution to 0 ° C., the precipitated solid was collected by filtration, washed with water, and dried to obtain 3.99 g (yield 50%) of compound (VI-3).

Reference Example 6 Compound (1)
0.50 g of compound (IV-1) and 0.14 g of 2-pyridinecarbohydrazide were reacted at 50 ° C. for 40 hours in 10 ml of acetonitrile. After cooling the reaction solution, the precipitated solid was collected by filtration and dried to obtain 0.39 g of Compound (1) (yield 88%).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 6.95-7.15 (4H, m), 7.40-7.50 (3H, m), 7.65-7.70 ( 1H, m), 8.01-8.07 (2H, m), 8.68-8.70 (1H, m), 11.62 (1H, s).

Reference Example 7 Compound (22)
0.50 g of compound (IV-2) and 0.13 g of isonicotinohydrazide were reacted in 20 ml of ethanol at 70 ° C. for 10 hours. After cooling the reaction solution, the precipitated solid was collected by filtration, washed with ethanol, and dried to obtain 0.37 g (yield 90%) of Compound (22).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 6.94-7.45 (7H, m), 7.71 (2H, d, J = 6.0 Hz), 8.77 (2H, d, J = 6.0 Hz), 11.61 (1H, bs).

Reference Example 8 Compound (64)
2.83 g of compound (VI-1) and 1.09 g of benzohydrazide were reacted for 40 hours at 70 ° C. in 32 ml of ethanol. After cooling the reaction solution, the precipitated solid was collected by filtration and dried to obtain 1.27 g (yield 34%) of Compound (64).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 3.81 (3H, s), 7.04-7.07 (2H, m), 7.53-7.65 (5H, m) , 7.79-7.81 (2H, m), 11.06 (1H, bs).

Reference Example 9 Compound (65)
1.77 g of compound (VI-1) and 0.69 g of 2-pyridinecarbohydrazide were reacted in 70 ml of ethanol at 70 ° C. for 3 hours. After cooling the reaction solution, the precipitated solid was collected by filtration and dried to obtain 2.15 g (yield 98%) of Compound (65).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 3.81 (3H, s), 4.05 (2H, bs), 7.06 (2H, d, J = 9.0 Hz), 7 .62-7.67 (3H, m), 8.02-8.12 (2H, m), 8.69 (1H, d, J = 2.2 Hz).

Reference Example 10 Compound (73)
1.61 g of compound (VI-2) and 0.55 g of nicotinohydrazide were reacted in ethanol 16 ml at 70 ° C. for 3 hours. After cooling the reaction solution, the precipitated solid was collected by filtration and dried to obtain 1.71 g of Compound (73) (98% yield).
¹ H-NMR (400 MHz) δ (CDCl ₃ ) ppm: 7.34 (1H, t, J = 7.4 Hz), 7.48-7.53 (3H, m), 7.82 (2H, d, J = 7.8 Hz), 7.90-7.93 (1 H, m), 8.55 (1 H, d, J = 8.1 Hz), 8.92 (1 H, d, J = 5.1 Hz), 9.12 (1H, m).

Reference Example 11 Compound (119)
0.28 g of compound (VI-3) and 0.12 g of ethyl carbamate were reacted in 70 ml of ethanol at 70 ° C. for 2.5 hours. After cooling the reaction solution, the precipitated solid was collected by filtration, washed with ethanol, and dried to obtain 0.33 g (yield: 85.6%) of Compound (119).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.23 (3H, t, J = 6.8 Hz), 3.01 (3H, s), 3.74 (3H, s), 4 .13 (2H, q, J = 6.8 Hz), 7.14 (1H, t, J = 7.2 Hz), 7.20 (1H, t, J = 7.2 Hz), 7.46 (1H, d, J = 8.0 Hz), 8.67 (1H, d, J = 7.6 Hz), 10.33 (1H, bs).

Reference Example 12. Compound (128)
0.50 g of compound (VI-3) and 0.31 g of phenylacetohydrazide were reacted in 15 ml of ethanol at 70 ° C. for 2 hours. After cooling the reaction solution, the precipitated solid was collected by filtration, washed with ethanol, and dried to obtain 0.71 g (yield 92%) of Compound (128).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 3.03 (3H, s), 3.58 (3H, s), 3.74 (3H, s), 7.13-7.35 (7H, m), 7.47 (1H, d, J = 8.0 Hz), 8.69 (1H, d, J = 7.6 Hz), 11.23 (1H, bs).

Reference Example 13 Compound (VI-4)
To a mixture of 8.73 g of 4-methoxyphenylhydrazine hydrochloride and 50 ml of chloroform was added 5.06 g of triethylamine, and the mixture was stirred at 25 ° C. for 0.5 hour. The reaction solution was washed with 30 ml of water, and then the solvent was distilled off. To the residue, 5 ml of xylene, 0.6 g of acetic acid and 13.21 g of ethyl 2,3,4,5-tetrafluorobenzoyl acetate were added, and the mixture was stirred at 90 ° C. for 7 hours. After cooling the reaction solution to 5 ° C., 20 ml of octane is added to the reaction solution, and the precipitated solid is collected by filtration, washed with a 2: 1 mixed solvent (volume ratio) of octane and xylene, and then dried to give 5-hydroxy There was obtained 10.77 g (yield 64%) of -1- (4-methoxyphenyl) -3- (2,3,4,5-tetrafluorophenyl) pyrazole.

  5-hydroxy-1- (4-methoxyphenyl) -3- (2,3,4,5-tetrafluorophenyl) pyrazole 8.46 g, 3,4-dimethoxycyclobutene-1,2-dione 3.55 g, 3.46 g of potassium carbonate and 25 ml of methanol were mixed and stirred at 40 ° C. for 3 hours. The reaction solution was cooled to 5 ° C., and the precipitated solid was collected by filtration and washed with methanol cooled to 5 ° C. To the obtained solid, 1.73 g of potassium carbonate and 65 ml of water were added, and the mixture was stirred at 80 ° C. for 2 hours. After cooling the reaction solution, 40 ml of 3 mol / l hydrochloric acid was added to the reaction solution, and the precipitated solid was collected by filtration, washed with water and dried to give 6.66 g (yield 61%) of compound (VI-4). Got.

Reference Example 14 Compound (VI-5)
To a mixture of 26.19 g of 2-chloro-4,6-dimethoxypyrimidine and 58 ml of pyridine, 75.09 g of hydrazine monohydrate was added dropwise at 5 ° C., and the mixture was stirred at 25 ° C. for 5 hours. 150 ml of water was added to the reaction solution, and the mixture was cooled to 5 ° C. The precipitated solid was collected by filtration, washed with water and dried to give 15.78 g of 2-hydrazino-4,6-dimethoxypyrimidine (yield 62 %).

  13.61 g of 2-hydrazino-4,6-dimethoxypyrimidine, 0.76 g of p-toluenesulfonic acid monohydrate and 80 ml of toluene were mixed and stirred at 50 ° C. for 0.5 hour. To the reaction solution was added 15.03 g of ethyl 4,4,4-trifluoroacetoacetate, and the mixture was refluxed for 7 hours in a reactor equipped with a Dean-Stark apparatus. To the reaction solution, 0.76 g of p-toluenesulfonic acid monohydrate was added, and the mixture was refluxed for 4 hours in a reactor equipped with a Dean-Stark apparatus. After cooling the reaction solution to 5 ° C., 80 ml of octane was added to the reaction solution, and the mixture was stirred at 5 ° C. for 1 hour. The precipitated solid was collected by filtration, washed with a 1: 1 mixed solvent (volume ratio) of octane and toluene, and then dried to give 5-hydroxy-1- (4,6-dimethoxy-2-pyrimidinyl) -3- 21.82 g (94% yield) of trifluoromethylpyrazole was obtained.

  5-hydroxy-1- (4,6-dimethoxy-2-pyrimidinyl) -3-trifluoromethylpyrazole 20.31 g, 3,4-dimethoxycyclobutene-1,2-dione 9.95 g, potassium carbonate 9.67 g And 75 ml of methanol were mixed and stirred at 40 ° C. for 4 hours. After cooling the reaction solution to 5 ° C., the precipitated solid was collected by filtration and washed with a 1: 1 mixed solvent (volume ratio) of methanol and toluene cooled to 5 ° C. To the obtained solid, 4.84 g of potassium carbonate and 140 ml of water were added, and the mixture was stirred at 80 ° C. for 4 hours. After cooling the reaction solution, 50 ml of 3 mol / l hydrochloric acid was added to the reaction solution, the mixture was cooled to 5 ° C., the precipitated solid was collected by filtration and cooled to 5 ° C. with 3 mol / l hydrochloric acid and 5 ° C. After sequentially washing with water and drying, 17.06 g (yield 63%) of compound (VI-5) was obtained.

Reference Example 15. Compound (VI-6)
37.5 g of tert-butylhydrazine hydrochloride, 39.95 g of ethyl acetoacetate, 30.75 g of triethylamine, 110 ml of xylene and 75 ml of methanol were mixed and refluxed in a reactor equipped with a Dean-Stark apparatus for 6 hours. The reaction mixture was cooled to room temperature, washed with 120 ml of water, concentrated under reduced pressure, and the precipitated solid was collected by filtration. The obtained solid was washed successively with 20 ml of xylene and 20 ml of methanol and then dried to obtain 33.7 g of 5-hydroxy-1-tert-butyl-3-methylpyrazole (yield 73%).

  A mixture of 10.0 g of 5-hydroxy-1-tert-butyl-3-methylpyrazole, 9.22 g of 3,4-dimethoxycyclobutene-1,2-dione, 8.96 g of potassium carbonate and 150 ml of methanol was mixed at 60 ° C. Stir for 4 hours. The reaction mixture was cooled to 0 ° C., and the precipitated solid was collected by filtration. To the obtained solid, 2.18 g of potassium carbonate and 75 ml of water were added, and the mixture was stirred at 75 ° C. for 2 hours. After cooling the reaction solution, 20 ml of 6 mol / l hydrochloric acid was added to the reaction solution, the mixture was cooled to room temperature, the precipitated solid was collected by filtration, washed with water and dried to give compound (VI-6) 11. 85 g (yield 73%) was obtained.

Reference Example 16. Compound (VI-7)
In a reactor equipped with 12.40 g 2-hydrazino-3-trifluoromethylpyridine, 0.69 g sulfuric acid, 10.09 g methyl 4-methyl-3-oxopentanoate and 21 ml toluene and equipped with a Dean-Stark apparatus. Refluxed for 5 hours. After cooling the reaction solution, the solvent was distilled off, and the residue was dried to obtain 19.91 g (yield 92%) of 5-hydroxy-1- (3-trifluoromethyl-2-pyridyl) -3-isopropylpyrazole. Obtained.

  5-hydroxy-1- (3-trifluoromethyl-2-pyridyl) -3-isopropylpyrazole 19.91 g, 3,4-dimethoxycyclobutene-1,2-dione 9.12 g, potassium carbonate 8.87 g, methanol 46 ml and 23 ml of toluene were mixed and stirred at 40 ° C. for 3 hours. After cooling the reaction solution to 5 ° C., the precipitated solid was collected by filtration and washed with a 1: 1 mixed solvent (volume ratio) of methanol and toluene cooled to 5 ° C. To the obtained solid, 4.44 g of potassium carbonate and 96 ml of water were added, and the mixture was stirred at 80 ° C. for 3 hours. After cooling the reaction solution, 64 ml of 3 mol / l hydrochloric acid was added to the reaction solution, the mixture was cooled to 5 ° C., the precipitated solid was collected by filtration, washed with water cooled to 5 ° C., and dried to give a compound ( VI-7) 16.62g (yield 71%) was obtained.

Reference Example 17. Compound (VI-8)
9.09 g of 2-hydrazino-4,6-dimethoxypyrimidine obtained by the same method as in Reference Example 14, 24 ml of toluene, 0.52 g of concentrated sulfuric acid, and 7.07 g of ethyl 4-methyl-3-oxopentanoate were obtained. Mix and reflux for 8 hours in a reactor equipped with a Dean-Stark apparatus. After cooling the reaction solution to 40 ° C., 48 ml of octane was added to the reaction solution, and the mixture was cooled to 5 ° C. and stirred at 5 ° C. for 1 hour. The precipitated solid was collected by filtration, washed with a 2: 1 mixed solvent (volume ratio) of octane and toluene, and then dried to give 5-hydroxy-1- (4,6-dimethoxy-2-pyrimidinyl) -3- 11.81 g (84% yield) of isopropylpyrazole was obtained.

  5-hydroxy-1- (4,6-dimethoxy-2-pyrimidinyl) -3-isopropylpyrazole 10.57 g, 3,4-dimethoxycyclobutene-1,2-dione 5.68 g, potassium carbonate 5.53 g, methanol 20 ml and 100 ml of toluene were mixed and stirred at 40 ° C. for 3 hours. After cooling the reaction solution to 5 ° C., the precipitated solid was collected by filtration and washed with a 1: 2 mixed solvent (volume ratio) of methanol and toluene cooled to 5 ° C. To the obtained solid, 2.76 g of potassium carbonate and 100 ml of water were added, and the mixture was stirred at 80 ° C. for 3 hours. After cooling the reaction solution, 55 ml of 3 mol / l hydrochloric acid was added to the reaction solution, the mixture was cooled to 5 ° C., the precipitated solid was collected by filtration, washed with water cooled to 5 ° C., and dried to give a compound ( VI-8) 15.97 g (79% yield) was obtained.

Reference Example 18. Compound (81)
0.50 g of compound (VI-4) and 0.14 g of 2-pyridinecarbohydrazide were reacted in 10 ml of acetonitrile at 50 ° C. for 40 hours. After cooling the reaction solution, the precipitated solid was collected by filtration and dried to obtain 0.39 g (yield 88%) of Compound (81).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 3.78 (3H, s), 6.98 (2H, bd, J = 9.1 Hz), 7.30-7.32 (1H, m), 7.51-7.71 (1H, m), 7.84 (2H, bd, J = 9.1 Hz), 8.03-8.10 (2H, m), 8.70 (1H, bd, J = 4.9 Hz), 11.24 (1H, bs), 11.37 (1H, bs).

Reference Example 19. Compound (148)
Compound (VI-5) 0.50 g and 2,4,6-trimethylbenzohydrazide 0.13 g were reacted in ethanol 20 ml at 70 ° C. for 10 hours. After cooling the reaction solution, the precipitated solid was collected by filtration, washed with ethanol, and dried to obtain 0.37 g (yield 90%) of Compound (148).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 2.14 (3H, s), 2.21 (3H, s), 2.25 (3H, s), 3.94 (6H, s ), 6.30 (1H, s), 6.85 (1H, s), 6.89 (1H, s), 10.18 (1H, s), 10.31 (1H, s).

Reference Example 20. Compound (149)
2.83 g of compound (VI-5) and 1.09 g of 2,6-difluorobenzohydrazide were reacted at 70 ° C. for 40 hours in 32 ml of ethanol. After cooling the reaction solution, the precipitated solid was collected by filtration and dried to obtain 1.27 g (yield 34%) of Compound (149).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 3.94 (6H, s), 6.30 (1H, s), 7.19 (2H, dt, J = 2.4, 8. 1 Hz), 7.51-7.60 (1 H, m), 10.57 (1 H, s), 11.04 (1 H, s).

Reference Example 21. Compound (150)
0.73 g of compound (VI-6) and 0.61 g of 2,4,6-trimethylbenzohydrazide were reacted at 70 ° C. for 3 hours in 6 ml of ethanol. After cooling the reaction solution, 10 ml of diethyl ether was added to the reaction solution. The precipitated solid was collected by filtration, washed with diethyl ether and dried to obtain 0.49 g (yield 37%) of compound (150).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.51 (9H, bs), 2.26 (6H, bs), 2.32 (3H, bs), 2.51 (3H, bs ), 6.90 (2H, bs), 10.15 (1H, s), 11.16 (1H, s).

Reference Example 22. Compound (151)
1.47 g of compound (VI-7) and 0.54 g of benzohydrazide were reacted in 5 ml of ethanol at 70 ° C. for 4 hours. After cooling the reaction solution, the precipitated solid was collected by filtration, washed with diethyl ether, and dried to obtain 1.39 g of Compound (151) (yield 72%).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.08 (3H, d, J = 6.8 Hz), 1.28 (3H, d, J = 6.8 Hz), 3.49- 3.54 (1H, m), 7.50-7.62 (3H, m), 7.77-7.89 (3H, m), 8.41-8.53 (1H, m), 8. 86-8.97 (1H, m), 10.46 (1H, s), 11.09 (1H, s).

Reference Example 23. Compound (152)
1.47 g of compound (VI-7) and 0.71 g of 2,4,6-trimethylbenzohydrazide were reacted in 10 ml of ethanol at 70 ° C. for 4 hours. After cooling the reaction solution, the precipitated solid was collected by filtration, washed with ethanol, and dried to obtain 1.50 g (yield 71%) of Compound (152).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.20 (6H, d, J = 6.8 Hz), 2.26 (9H, bs), 3.40-3.57 (1H, m), 6.91 (2H, bs), 7.80-7.85 (1H, m), 8.41-8.49 (1H, m), 8.85-8.90 (1H, m) , 10.15 (1H, s), 11.25 (1H, s).

Reference Example 24. Compound (153)
1.44 g of compound (VI-8) and 0.82 g of 3-trifluoromethylbenzohydrazide were stirred at 70 ° C. for 3 hours in 16 ml of ethanol. After cooling the reaction solution, the precipitated solid was collected by filtration, washed with ethanol, and dried to obtain 1.52 g (yield 70%) of Compound (153).
¹ H-NMR (400 MHz) δ (DMSO-d ₆ ) ppm: 1.19 (3H, d, J = 6.8 Hz), 1.31 (3H, d, J = 7.0 Hz), 3.48− 3.57 (1H, m), 3.86 (3H, s), 3.91 (3H, s), 6.16 (1H, s), 7.77-7.83 (1H, m), 7 .95-8.20 (3H, m), 10.51 (1H, s), 11.27 (1H, s).

(Production of metal complexes of squarylium compounds)
By performing thermogravimetric analysis under the following conditions using TG / DTA6200 manufactured by Seiko Instruments Inc., the decomposition start temperature of the metal complex of the squarylium compound obtained in the following examples was determined. The temperature at which a weight loss of 0.05% by weight / ° C. or more was observed was taken as the decomposition start temperature. A compound having a decomposition start temperature of 300 ° C. or lower is preferred because high-sensitivity photoresponsiveness to blue-violet laser light or the like is expected.

  Measurement temperature: 40 to 400 ° C., temperature rising temperature: 10 ° C./min, atmosphere; nitrogen aeration (300 ml / min), sample container: 15 μl (open) made of aluminum, sample: 1 to 1.5 mg

2: 1 complex of compound (1) and nickel [compound (1-N)]
150 mg of compound (1) and 42 mg of nickel (II) acetate tetrahydrate were reacted in 5 ml of ethanol at 70 ° C. for 7 hours. The precipitated solid was collected by filtration, washed with ethanol, and dried to give 142 mg (yield 96%) of compound (1-N).
Absorption maximum wavelength (CHCl ₃ ): 415 nm
Molar extinction coefficient (CHCl ₃ ): 59100 (mol / l) ⁻¹ · cm ⁻¹
Absorption maximum wavelength (TFP): 410 nm
Decomposition temperature: 228 ° C
Molecular weight: 932 [FAB-MS: m / z 933 (M + H) ⁺ ]

2: 1 complex of compound (1) and cobalt [compound (1-CO)]
150 mg of compound (1) and 42 mg of cobalt (II) acetate tetrahydrate were reacted in 70 ml of ethanol in 5 ml of ethanol for 7 hours. The precipitated solid was collected by filtration, washed with ethanol, and dried to obtain 135 mg (yield 85%) of compound (1-CO).
Absorption maximum wavelength (CHCl ₃ ): 422 nm
Molar extinction coefficient (CHCl ₃ ): 40400 (mol / l) ⁻¹ · cm ⁻¹
Absorption maximum wavelength (TFP): 408 nm
Molecular weight: 933 [FAB-MS: m / z 934 (M + H) ⁺ ]

2: 1 complex of compound (22) and nickel [compound (22-N)]
150 mg of compound (22) and 40 mg of nickel (II) acetate tetrahydrate were reacted in 3 ml of ethanol at 70 ° C. for 2 hours. The precipitated solid was collected by filtration, washed with ethanol, and dried to obtain 0.13 g (yield 83.8%) of compound (22-N).
Absorption maximum wavelength (CHCl ₃ ): 414.5 nm
Molar extinction coefficient (CHCl ₃ ): 40500 (mol / l) ⁻¹ · cm ⁻¹
Absorption maximum wavelength (TFP): 403.5 nm
Decomposition start temperature: 265 ° C

2: 1 complex of compound (22) and cobalt [compound (22-CO)]
150 mg of compound (22) and 40 mg of cobalt (II) acetate tetrahydrate were reacted in 3 ml of ethanol at 70 ° C. for 4.5 hours. The precipitated solid was collected by filtration, washed with ethanol, and dried to obtain 90 mg (yield 56%) of compound (22-CO).
Absorption maximum wavelength (CHCl ₃ ): 415.0 nm
Molar extinction coefficient (CHCl ₃ ): 44400 (mol / l) ⁻¹ · cm ⁻¹
Absorption maximum wavelength (TFP): 403.5 nm
Decomposition temperature: 275 ° C

2: 1 complex of compound (64) and nickel [compound (64-N)]
470 mg of the compound (64) and 120 mg of nickel (II) acetate tetrahydrate were reacted in 5 ml of ethanol at 70 ° C. for 4 hours. The precipitated solid was collected by filtration, washed with ethanol, and dried to obtain 490 mg of Compound (64-N) (yield 98%).
Absorption maximum wavelength (TFP): 397 nm
Molar extinction coefficient (TFP): 43100 (mol / l) ⁻¹ · cm ⁻¹
Decomposition start temperature: 282 ° C
Molecular weight: 1000 [FAB-MS: m / z 1001 (M + H) ⁺ ]

2: 1 complex of compound (64) and cobalt [compound (64-CO)]
470 mg of the compound (64) and 120 mg of cobalt (II) acetate tetrahydrate were reacted in 5 ml of ethanol at 70 ° C. for 4 hours. The precipitated solid was collected by filtration, washed with ethanol, and dried to obtain 490 mg of Compound (64-CO) (yield 98%).
Absorption maximum wavelength (TFP): 382 nm
Molar extinction coefficient (TFP): 42400 (mol / l) ⁻¹ · cm ⁻¹
Decomposition temperature: 276 ° C
Molecular weight: 1001 [FAB-MS: m / z 1002 (M + H) ⁺ ]

2: 1 complex of compound (65) and nickel [compound (65-N)]
950 mg of compound (65) and 250 mg of nickel (II) acetate tetrahydrate were reacted in 70 ml of ethanol at 70 ° C. for 4 hours. The precipitated solid was collected by filtration, washed with ethanol, and dried to obtain 950 mg (yield 90%) of compound (65-N).
Absorption maximum wavelength (TFP): 372 nm
Decomposition temperature: 291 ° C

2: 1 complex of compound (65) and cobalt [compound (65-CO)]
950 mg of compound (65) and 280 mg of cobalt (II) acetate tetrahydrate were reacted in 15 ml of ethanol at 70 ° C. for 4 hours. The precipitated solid was collected by filtration, washed with ethanol, and dried to obtain 970 mg (yield 97%) of compound (65-CO).
Absorption maximum wavelength (TFP): 382 nm
Decomposition start temperature: 290 ° C

2: 1 complex of compound (73) and nickel [compound (73-N)]
750 mg of compound (73) and 170 mg of nickel (II) acetate tetrahydrate were reacted in 15 ml of ethanol at 70 ° C. for 4 hours. The precipitated solid was collected by filtration, washed with ethanol, and dried to obtain 730 mg of Compound (73-N) (yield 92%).
Absorption maximum wavelength (TFP): 385 nm
Decomposition start temperature: 257 ° C

2: 1 complex of compound (73) and cobalt [compound (73-CO)]
750 mg of the compound (73) and 170 mg of cobalt (II) acetate tetrahydrate were reacted in 15 ml of ethanol at 70 ° C. for 4 hours. The precipitated solid was collected by filtration, washed with ethanol, and dried to obtain 720 mg (yield 90%) of compound (73-CO).
Absorption maximum wavelength (TFP): 380 nm
Decomposition start temperature: 253 ° C

2: 1 complex of compound (119) and cobalt [compound (119-CO)]
Compound (119) (200 mg) and cobalt (II) acetate tetrahydrate (76 mg) were reacted in ethanol (2 ml) at 70 ° C. for 0.5 hour. The precipitated solid was collected by filtration, washed with ethanol, and dried to obtain 206 mg (yield 93%) of compound (119-CO).
Absorption maximum wavelength (CHCl ₃ ): 413.5 nm
Molar extinction coefficient (CHCl ₃ ): 79100 (mol / l) ⁻¹ · cm ⁻¹
Absorption maximum wavelength (TFP): 404.5 nm
Decomposition start temperature: 192 ° C

2: 1 complex of compound (128) and nickel [compound (128-N)]
200 mg of compound (128) and 67 mg of nickel (II) acetate tetrahydrate were reacted in 3 ml of ethanol at 70 ° C. for 4.5 hours. The precipitated solid was collected by filtration, washed with ethanol, and dried to obtain 218 mg (yield 100%) of compound (128-N).
Absorption maximum wavelength (CHCl ₃ ): 433.0 nm
Molar extinction coefficient (CHCl ₃ ): 105300 (mol / l) ⁻¹ · cm ⁻¹
Absorption maximum wavelength (TFP): 427.5 nm
Decomposition start temperature: 186 ° C

2: 1 complex of compound (128) and cobalt [compound (128-CO)]
200 mg of compound (128) and 67 mg of cobalt (II) acetate tetrahydrate were reacted in 3 ml of ethanol at 70 ° C. for 4.5 hours. The precipitated solid was collected by filtration, washed with ethanol, and dried to obtain 227 mg (yield 100%) of compound (128-CO).
Absorption maximum wavelength (CHCl ₃ ): 432.0 nm
Molar extinction coefficient (CHCl ₃ ): 92200 (mol / l) ⁻¹ · cm ⁻¹
Absorption maximum wavelength (TFP): 424.5 nm
Decomposition start temperature: 175 ° C

2: 1 complex of compound (81) and nickel [compound (81-N)]
150 mg of compound (81) and 42 mg of nickel (II) acetate tetrahydrate were reacted in 5 ml of ethanol at 70 ° C. for 7 hours. The precipitated solid was collected by filtration, washed with ethanol, and dried to obtain 142 mg of Compound (81-N) (yield 96%).
Absorption maximum wavelength (TFP): 445.0 nm
Decomposition start temperature: 238 ° C

2: 1 complex of compound (81) and cobalt [compound (81-CO)]
150 mg of compound (81) and 42 mg of cobalt (II) acetate tetrahydrate were reacted in 5 ml of ethanol at 70 ° C. for 7 hours. The precipitated solid was collected by filtration, washed with ethanol, and dried to give 135 mg (yield 85%) of compound (81-CO).
Absorption maximum wavelength (TFP): 451.0 nm
Decomposition start temperature: 234 ° C

2: 1 complex of compound (148) and cobalt [compound (148-CO)]
150 mg of compound (148) and 40 mg of cobalt (II) acetate tetrahydrate were reacted in 3 ml of ethanol at 70 ° C. for 4.5 hours. The precipitated solid was collected by filtration, washed with ethanol, and dried to obtain 90 mg (yield 56%) of compound (148-CO).
Absorption maximum wavelength (TFP): 372.0 nm
Decomposition start temperature: 261 ° C
Molecular weight: 1149 [FAB-MS: m / z 1150 (M + H) ⁺ ]

2: 1 complex of compound (149) and cobalt [compound (149-CO)]
470 mg of compound (149) and 120 mg of cobalt (II) acetate tetrahydrate were reacted in 5 ml of ethanol at 70 ° C. for 4 hours. The precipitated solid was collected by filtration, washed with ethanol, and then dried to obtain 490 mg (yield 98%) of compound (149-CO).
Absorption maximum wavelength (TFP): 380.0 nm
Decomposition temperature: 248 ° C
Molecular weight: 1137 [FAB-MS: m / z 1138 (M + H) ⁺ ]

2: 1 complex of compound (150) and cobalt [compound (150-CO)]
440 mg of the compound (150) and 130 mg of cobalt (II) acetate tetrahydrate were reacted in 3 ml of ethanol at 70 ° C. for 3 hours. After cooling the reaction solution, 10 ml of diethyl ether was added to the reaction solution, the mixture was stirred, the precipitated solid was collected by filtration, washed with diethyl ether and dried to give 320 mg of compound (150-CO) (yield 46%). )
Absorption maximum wavelength (TFP): 389.0 nm
Decomposition start temperature: 233 ° C
Molecular weight: 877 [FAB-MS: m / z 878 (M + H) ⁺ ]

2: 1 complex of compound (151) and cobalt [compound (151-CO)]
970 mg of the compound (151) and 250 mg of cobalt (II) acetate tetrahydrate were reacted in 3 ml of ethanol at 70 ° C. for 3 hours. After cooling the reaction solution, 10 ml of diethyl ether was added to the reaction solution, the mixture was stirred, the precipitated solid was collected by filtration, washed with diethyl ether, and dried to give 850 mg of compound (151-CO) (yield 83%). )
Absorption maximum wavelength (TFP): 385.0 nm
Decomposition start temperature: 244 ° C
Molecular weight: 1027 [FAB-MS: m / z 1028 (M + H) ⁺ ]

2: 1 complex of compound (152) and cobalt [compound (152-CO)]
1060 mg of compound (152) and 250 mg of cobalt (II) acetate tetrahydrate were reacted in 6 ml of ethanol at 70 ° C. for 3 hours. After cooling the reaction solution, 10 ml of diethyl ether was added, the mixture was stirred, the precipitated solid was collected by filtration, washed with diethyl ether and dried to obtain 970 mg of compound (152-CO) (yield 87%). It was.
Absorption maximum wavelength (TFP): 375.0 nm
Decomposition temperature: 245 ° C
Molecular weight: 1111 [FAB-MS: m / z 1112 (M + H) ⁺ ]

2: 1 complex of compound (153) and cobalt [compound (153-CO)]
980 mg of compound (153) and 220 mg of cobalt (II) acetate tetrahydrate were reacted at 70 ° C. for 3 hours in 12 ml of ethanol. After cooling the reaction solution, the precipitated solid was collected by filtration, washed with ethanol, and dried to obtain 630 mg of compound (153-CO) (61% yield).
Absorption maximum wavelength (TFP): 371.0 nm
Decomposition start temperature: 257 ° C
Molecular weight: 1149 [FAB-MS: m / z 1150 (M + H) ⁺ ]

(Solubility test)
Compounds (1-N), (1-CO), (22-CO), (64-N), (64-CO), (148-CO), (149-CO), (150-CO), ( 151-CO), (152-CO) and (153-CO) were examined for solubility in TFP.

Each of the above-mentioned squarylium compound metal complexes and TFP were mixed, and after applying ultrasonic vibration for 30 minutes at room temperature, the mixture was visually observed. The results are shown in Tables 1 and 2. In Tables 1 and 2, the solubility test 1 was carried out using 10 mg of the squarylium compound metal complex and 990 mg of TFP, and the solubility test 2 was used of 20 mg of the squarylium compound metal complex and 980 mg of TFP. The compounds (1-N), (1-CO), (22-CO), (64-N), (64-CO), (148-CO), (149-CO), It can be seen that (150-CO), (151-CO), (152-CO) and (153-CO) each have excellent solubility in TFP.

(Coating property test)
As a metal complex of a squarylium compound, the compounds (1-N), (1-CO), (22-CO), (64-N), (64-CO), (148-CO), (149-CO), (150-CO), (151-CO), (152-CO) and (153-CO) were used.
20 mg of the metal complex of each of the above squarylium compounds was dissolved in 980 mg of TFP, and the solution was filtered through a Teflon (registered trademark) filter (manufactured by Whatman, pore size: 0.45 μm) to obtain a metal complex solution of the squarylium compound. . As the substrate, polycarbonate resin (manufactured by Dazai Equipment Co., Ltd .; 5 cm × 5 cm, thickness 1 mm) was used. The solution was applied onto a substrate by spin coating (3,000 rpm, 30 seconds, amount of solution used: 10 to 15 drops) using 1H-SX manufactured by Mikasa, and dried in an oven at 70 ° C. for 30 minutes. And a thin film of a metal complex of a squarylium compound, respectively. It was visually confirmed that each thin film had no unevenness and was formed uniformly.

(Light resistance test)
Compounds (1-N), (1-CO), (22) in the same manner as in the coating property test, except that glass (made by Taiko Equipment Co., Ltd .; 2 cm × 2 cm, thickness 2 mm) is used as the substrate instead of polycarbonate resin. -CO), (64-N), (64-CO), (148-CO), (149-CO), (150-CO), (151-CO), (152-CO) and (153-CO) ) Were obtained. Using a Suga Test Instruments Dew panel / light control weather meter DPWL-5R type equipped with an ultraviolet fluorescent lamp (SUGA-FS40 manufactured by Suga Test Instruments Co., Ltd .: peak wavelength 313 nm, illuminance distribution 282 to 373 nm) Irradiated with light of / m ² at 45 ° C. for 10 hours. Before and after the light resistance test, the absorbance at the absorption maximum wavelength was measured using a spectrophotometer. Table 3 shows the absorbance (I) at the absorption maximum wavelength after the light resistance test with respect to the absorbance (I ₀ ) at the absorption maximum wavelength before the light resistance test. A larger I / I ₀ represents an excellent light resistance. Compounds (1-N), (1-CO), (22-CO), (64-N), (64-CO), (148-CO), (149-CO), (150-CO) and ( 153-CO) have excellent light resistance.

(Photoresponsiveness test)
In the same manner as in the coating property test, compounds (1-N), (1-CO), (22-CO), (64) on a substrate of polycarbonate resin (manufactured by Dazai Equipment Co., Ltd .; 5 cm × 5 cm, thickness 1 mm). -N), (64-CO), (148-CO), (149-CO), (150-CO), (151-CO), (152-CO) and (153-CO) thin films were obtained. . A nano-processing device (NEO-1000 manufactured by Pulstec Industrial Co., Ltd.) having a pickup head having a wavelength of 405 nm and a numerical aperture NA of 0.85 was used for the recording test. As the recording mark interval, the dot interval (track pitch) in the radial direction was set to 0.32 μm, and the dot interval in the rotation direction was set to 0.50 μm. After the thin film was placed on the nano-processing apparatus, the thin film was irradiated with a laser beam having an output of 3 mW at a linear velocity of 9.84 m / sec. When the surface of the thin film after irradiation with laser light was observed with a scanning microscope (SEM), it was confirmed that a recording mark was formed on the surface of the thin film due to thermal deformation of the thin film.

  Compounds (1-N), (1-CO), (22-CO), (64-N), (64-CO), (148-CO), (149-CO), (150-CO), ( It can be seen that the thin films of (151-CO), (152-CO) and (153-CO) each have a highly sensitive photoresponsiveness to blue-violet laser light.

  According to the present invention, it is possible to provide a metal complex of a squarylium compound used for an optical recording medium having a highly sensitive photoresponsiveness to blue-violet laser light.

Claims (11)

Formula (I)

[Wherein R ¹ represents an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or NR ⁴ R ⁵ (wherein R ⁴ and R ⁵ are the same or Differently, a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent Represents an alicyclic hydrocarbon group or a heterocyclic group which may have a substituent), and R ² may have an alkyl group which may have a substituent or a substituent. A good aralkyl group, 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, YR ⁶ (wherein , Y represents an oxygen atom or a sulfur atom, R ⁶ is an optionally substituted alkyl group, substituted Be aryl group, have also good alicyclic substituted hydrocarbon group or a substituent representing an even heterocyclic group) or NR 7 ^R 8 ^(wherein, R ⁷ and R ⁸ is the same or different and represents a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents an alicyclic hydrocarbon group which may have or a heterocyclic group which may have a substituent, and R ³ represents a hydrogen atom, an alkyl group which may have a substituent, 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 heterocycle which may have a substituent A metal complex of a squarylium compound represented by the formula: The metal complex of a squarylium compound according to claim 1, wherein R ¹ is a heterocyclic group which may have a substituent. The metal complex of a squarylium compound according to claim 1, wherein R ¹ is a heterocyclic group which may have a substituent, and the heterocyclic group is an aromatic heterocyclic group which may have a substituent. R ¹ is a heterocyclic group having a substituent, and the heterocyclic group having the substituent has the formula (X)

(In the formula, R ⁹ represents a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents an alicyclic hydrocarbon group which may have or a heterocyclic group which may have a substituent, and R ¹⁰ represents a hydrogen atom, a hydroxyl group, a carboxyl 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, an aralkyl group which may have a substituent, an aryl group which may have a substituent, a substituent; The metal complex of a squarylium compound according to claim 1, wherein the alicyclic hydrocarbon group optionally having a substituent or a heterocyclic group optionally having a substituent is represented. R ¹⁰ may have an alkyl 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 The metal complex of a squarylium compound according to claim 4, which is a heterocyclic group optionally having a formula hydrocarbon group or a substituent. The metal complex of a squarylium compound according to claim 1, wherein R ¹ is NR ⁴ R ⁵ (wherein R ⁴ and R ⁵ are as defined above). R ¹ is ^NR 4 ^{R 5} (wherein, ^{R 4} and ^{R 5} are each the same meanings as defined above) and, ^{R 4} and ^{R 5} are the same or different, aryl which may have a substituent The metal complex of a squarylium compound according to claim 1, which is a heterocyclic group which may have a group or a substituent. The metal complex of a squarylium compound according to any one of claims 1 to 7, wherein R ² is an aryl group which may have a substituent or a heterocyclic group which may have a substituent. Metal complexes of squarylium compound according to any one of claims 1 to 8 R ³ is a hydrogen atom.   The metal complex of a squarylium compound according to any one of claims 1 to 9, wherein the metal is nickel, cobalt, aluminum, copper, zinc or iron.   The optical recording medium containing the metal complex of the squarylium compound in any one of Claims 1-10.