JPH10237333A - Methine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new methine compound, excellent in solubility and useful for a colorant, a light absorber, a coloring matter for disks, a spectral coloring matter for silver halide photography, etc. SOLUTION: This methine compound is represented by formula I Z1 is an atomic group required to form a nitrogen-containing 5- or 6-membered heterocyclic ring; L1 and L2 are each methine; (p1 ) is 0 or 1; M1 is an electric charge balancing counterion; (m1 ) is a number of 0-10 required to neutralize the electric charge of a the molecule; Q is a group required to form a methine coloring matter; R1 is a group represented by formula II [La is methylene; A is a bivalent connecting group; V1 is a monovalent substituent group; (k1 ) is 0 or 1; (k2 ) is 0-4], etc.}, etc., e.g. a compound represented by formula III. The compound represented by formula I is obtained by reacting, e.g. a compound represented by formula IV with ethyl orthopropionate represented by formula V in the presence of pyridine, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a coloring agent, a light absorbing agent, a dye for optical disks, a spectral sensitizing dye for silver halide photography and electrophotography, and a methine compound useful as a medicine.

[0002]

2. Description of the Related Art A compound that absorbs light in the visible region exhibits various colors according to the wavelength of the absorbed light.
These compounds are called dyes or dyes. They are used for coloring various materials, and as more advanced uses, dyes for optical disc materials as high density information recording materials and silver halide photographs and It is used as a spectral sensitizing dye for photography and a dye for filters. Also,
In recent years, it has attracted attention as a medicine such as phototherapy.

[0003] Dyes used in these applications are often processed so as to form a desired state after being made into a solution, and are required to have excellent solubility. When used as a dye for an optical disk or a spectral sensitizing dye, it is in a solid state or an adsorbed state, so that unlike a solution state, the property as a molecular assembly greatly affects performance.

[0004]

An object of the present invention is to provide a novel methine compound.

[0005]

As a result of intensive studies on the object of the present invention, it has been found that the above object can be achieved by a methine compound represented by the following general formula (I). General formula (I)

[0006]

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In the formula (I), Z ₁ represents an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. L ₁ and L
₂ represents a methine group. p ₁ represents 0 or 1. M ₁ represents a charge balancing counter ion, and m ₁ represents a number from 0 to 10 required to neutralize the charge of the molecule. Q represents a group necessary for forming a methine dye. R ₁ is a group represented by the following Ra or Rb.

[0008]

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La represents a methylene group. A represents a divalent linking group. V represents a monovalent substituent. k ₁ is 0, or 1
Represents k ₂ represents 0, 1, ₂ , 3, or 4.

In the methine compound represented by the general formula (I), it is preferred that Q represents a group necessary for forming a cyanine dye.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds used in the present invention will be described below in detail. In the general formula (I), as the 5- or 6-membered nitrogen-containing heterocyclic ring represented by Z ₁ ,

Thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindone) Renin), imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, imidazo [4,5-b A quinoxaline nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, and a pyrimidine nucleus.

Preferred are a benzoxazole nucleus, a benzothiazole nucleus, a benzimidazole nucleus and a quinoline nucleus, and more preferred are a benzoxazole nucleus and a benzothiazole nucleus. Particularly preferred is a benzothiazole nucleus.

Assuming that the substituent on Z ₁ is V, the substituent represented by V is not particularly limited. Examples thereof include a halogen atom (eg, chlorine, bromine, iodine, fluorine), a mercapto group, a cyano group, and a carboxyl group. Group, phosphate group, sulfo group,
Hydroxy group, carbamoyl group (hereinafter, “carbamoyl group” is used in the meaning of carbamoyl group which may have a substituent), for example, having 1 to 10 carbon atoms, preferably 2 carbon atoms
To 8, more preferably a carbamoyl group having 2 to 5 carbon atoms (eg, methylcarbamoyl, ethylcarbamoyl, morpholinocarbonyl), a sulfamoyl group (optionally substituted), for example, having 0 to 10 carbon atoms, preferably 2 to 8 carbon atoms. More preferably a sulfamoyl group having 2 to 5 carbon atoms (eg, methylsulfamoyl, ethylsulfamoyl, piperidinosulfonyl), a nitro group,
Alkoxy group (optionally substituted), for example, an alkoxy group having 1 to 20, preferably 1 to 10, more preferably 1 to 8 carbon atoms (eg, methoxy, ethoxy, 2-methoxyethoxy, 2-phenyl Ethoxy), an aryloxy group (optionally substituted)
An aryloxy group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms (eg, phenoxy, p-methylphenoxy, p-chlorophenoxy, naphthoxy);

Acyl group (optionally substituted), for example, an acyl group having 1 to 20, preferably 2 to 12, more preferably 2 to 8 carbon atoms (eg, acetyl, benzoyl, trichloroacetyl), acyloxy A group (optionally substituted), for example, having 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 carbon atoms
To 8 acyloxy groups (eg, acetyloxy, benzoyloxy), acylamino groups (optionally substituted)
For example, it has 1 to 20 carbon atoms, preferably 2 to 1 carbon atoms.
2, more preferably an acylamino group having 2 to 8 carbon atoms (eg, acetylamino), a sulfonyl group (which may be substituted), for example, 1 to 20 carbon atoms, preferably 1 carbon atom
To 10, more preferably a sulfonyl group having 1 to 8 carbon atoms (eg, methanesulfonyl, ethanesulfonyl, benzenesulfonyl, etc.), a sulfinyl group (optionally substituted), for example, 1 to 20 carbon atoms, preferably 1 carbon atom
To 10, more preferably a sulfinyl group having 1 to 8 carbon atoms (for example, methanesulfinyl, benzenesulfinyl), a sulfonylamino group (which may be substituted), for example, 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably Is a sulfonylamino group having 1 to 8 carbon atoms (for example, methanesulfonylamino, ethanesulfonylamino, benzenesulfonylamino, etc.),

Amino group, substituted amino group (optionally substituted), for example, a substituted amino group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms (eg, methylamino, dimethylamino Benzylamino, anilino, diphenylamino), ammonium group (optionally substituted), for example, an ammonium group having 0 to 15, preferably 3 to 10, more preferably 3 to 6 carbon atoms (eg, trimethylammonium Group, triethylammonium group), hydrazino group (optionally substituted), for example, a hydrazino group having 0 to 15, preferably 1 to 10, and more preferably 1 to 6 carbon atoms (eg, a trimethylhydrazino group) A ureido group (which may be substituted), for example, having 1 to 1 carbon atoms
5, preferably a ureido group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms (for example, ureido group, N, N
Dimethylureido group), imide group (which may be substituted), for example, an imide group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms (eg, succinimide group), an alkylthio group (Optionally substituted) For example, an alkylthio group having 1 to 20, preferably 1 to 12, and more preferably 1 to 8 carbon atoms (eg, methylthio, ethylthio, carboxyethylthio, sulfobutylthio, Arylthio group (optionally substituted), for example, having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, and more preferably 6 carbon atoms
To 10 arylthio groups (such as phenylthio) and alkoxycarbonyl groups (which may be substituted) such as alkoxycarbonyl groups having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms (eg, methoxy). Carbonyl, ethoxycarbonyl, benzyloxycarbonyl), an aryloxycarbonyl group (optionally substituted), for example, an aryloxycarbonyl group having 6 to 20, preferably 6 to 12, more preferably 6 to 8 carbon atoms (Eg phenoxycarbonyl),

An alkyl group (optionally substituted);
An unsubstituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methyl, ethyl, propyl, butyl), and 1 to 18 carbon atoms, preferably 1 carbon atom To 10, more preferably a substituted alkyl group having 1 to 5 carbon atoms (hydroxymethyl, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonylmethyl, acetylaminomethyl, and also preferably 2 to 18 carbon atoms, more preferably Represents that the substituted alkyl group also contains an unsaturated hydrocarbon group having 3 to 10 carbon atoms, particularly preferably 3 to 5 carbon atoms (eg, vinyl group, ethynyl group, 1-cyclohexenyl group, benzylidene group, benzylidene group). ), An aryl group (optionally substituted), for example, having 6 to 20 carbon atoms, preferably A substituted or unsubstituted aryl group having 6 to 15, more preferably 6 to 10 carbon atoms (for example, phenyl, naphthyl, p-carboxyphenyl, p-nitrophenyl, 3,5-dichlorophenyl, p-cyanophenyl, m- Fluorophenyl, p-
Toril),

Heterocyclic group (optionally substituted) For example, an optionally substituted heterocyclic group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 to 6 carbon atoms (eg, pyridyl, 5-methylpyridyl, thienyl, furyl, morpholino, tetrahydrofurfuryl). Further, a structure in which a benzene ring, a naphthalene ring, or an anthracene ring is condensed can be employed. Further, V may further substitute on these substituents.

Preferred substituents on Z ₁ are the above-mentioned alkyl group, aryl group, alkoxy group, halogen atom, acyl group, cyano group, sulfonyl group and benzene ring condensed, more preferably alkyl group, aryl group Groups, a halogen atom, an acyl group, a sulfonyl group, and a benzene ring condensation, and particularly preferably a methyl group, a phenyl group, a methoxy group, a chlorine atom, a bromine atom, an iodine atom, and a benzene ring condensation. Most preferably, a phenyl group,
These are chlorine atom, bromine atom, iodine atom and benzene ring condensation.

The methine groups represented by L ₁ and L ₂ may have a substituent, and examples of the substituent include the substituents represented by V described above. Preferably it is an unsubstituted methine group.
p ₁ is 0 or 1, preferably 0.

Q represents a methine group or a polymethine group necessary for forming a methine dye. The number of methines in the polymethine group is preferably from 0 to 7, more preferably from 1 to 5, particularly preferably from 1 to 3. (When a methine group is incorporated into a heterocycle, the methine group may be apparently 0. For example, simple merocyanine (zero methine merocyanine) may be mentioned.)

The methine group and polymethine group of Q may be any as long as they form a methine dye, but are preferably substituted methine groups or polymethine groups necessary for forming a methine dye. Examples of the substituent include an aromatic group, a heterocyclic group, an amino group, a cyano group, an alkoxycarbonyl group, an alkylsulfonyl group, and an acyl group. Specifically, examples of the aromatic group include a substituted or unsubstituted aromatic group (for example, 4-dimethylaminophenyl, 4-methoxyphenyl, phenyl, 4-dimethylaminonaphthyl) and the like. Examples of the heterocyclic ring of the heterocyclic group include known basic nuclei and acidic nuclei when forming a dye, and include a heterocyclic ring of Z ₂ described later. As the amino group, a substituted or unsubstituted amino group (for example, amino,
Dimethylamino). Examples of the alkoxycarbonyl group include a substituted or unsubstituted alkoxycarbonyl group (for example, ethoxycarbonyl). Examples of the alkylsulfonyl group include a substituted or unsubstituted alkylsulfonyl group (for example, methanesulfonyl).
Examples of the acyl group include a substituted or unsubstituted acyl group (for example, acetyl).

With Q, any methine dye can be formed, but preferred are cyanine dyes, merocyanine dyes, rhodacyanine dyes, trinuclear merocyanine dyes, allopolar dyes, hemicyanine dyes, styryl dyes, styryl base dyes and the like. Can be Preferred are cyanine dyes. For more information on these dyes, see FM Harmer, Heterocyclic Compounds-Cyanine Soybeans and Related Compounds.
Dyes and Related Compounds), John Willie
John Wiley & Sons, New York, London, 1964, D.M.
(DMSturmer), Heterocyclic Compounds-Special Topics in Heterocyclic Compounds-Special topi
cs in heterocyclic chemistry) ", Chapter 18, Chapter 14
Sections 482-515. The general formulas of the cyanine dye, merocyanine dye and rhodacyanine dye are preferably those shown in (XI), (XII) and (XIII) of U.S. Pat. No. 5,340,694, Nos. 21 and 22. In the general formula (III), Q
For example, when a cyanine dye is formed by the above method, it can be represented by the following resonance formula.

[0024]

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M ₁ is included in the formula to indicate the presence of a cation or an anion when necessary to neutralize the ionic charge of the dye. Typical cations include hydrogen ions (H ⁺ ), inorganic cations such as alkali metal ions (eg, sodium ion, potassium ion, lithium ion), alkaline earth metal ions (eg, calcium ion), and ammonium ions (eg, Organic ions such as ammonium ion, tetraalkylammonium ion, pyridinium ion, and ethylpyridinium ion. The anion may be either an inorganic anion or an organic anion,
Halogen anions (for example, fluorine ions, chlorine ions,
Iodine ion), substituted aryl sulfonate ion (for example, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion), aryl disulfonate ion (for example, 1,3-benzene sulfonate ion, 1,5-naphthalenedi sulfone) Acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (eg, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethane Sulfonate ions. Further, another dye having a charge opposite to that of the ionic polymer or the dye may be used. m ₁ represents the number necessary to balance the charges, and is 0 when a salt is formed in the molecule. Preferably, 0, 1, 2, 3, or 4
And more preferably 0 and 1.

A may be any divalent linking group, but preferably comprises an atom or atomic group containing at least one of carbon, nitrogen, sulfur and oxygen. Preferably, an alkylene group (eg, methylene, ethylene, propylene, butylene, pentylene), an arylene group (eg, phenylene, naphthylene), an alkenylene group (eg, ethenylene, propenylene), an alkynylene group (eg, ethinylene, propynylene), amide Group, ester group, sulfoamide group, sulfonic ester group, ureido group, sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, -N (Ra)-(Ra is a hydrogen atom, a substituted or unsubstituted alkyl group , Represents a substituted or unsubstituted aryl group), a heterocyclic divalent group (for example, 6-chloro-1,
3,5-triazine-2,4-diyl group, pyrimidine-
2,4-diyl group, quinoxaline-2,3-diyl group)
Represents a divalent linking group having 1 or more and 20 or less carbon atoms, which is constituted by combining one or more. These divalent linking groups may be further substituted, and examples of the substituent include the aforementioned V.

More preferably, an alkylene group having 1 to 4 carbon atoms (for example, methylene, ethylene, propylene, butylene), an arylene group having 6 to 10 carbon atoms (for example, phenylene, naphthylene), and 1 to 4 carbon atoms
A divalent linkage having 1 to 10 carbon atoms formed by combining one or more of the following alkenylene groups (eg, ethenylene, propenylene) and alkynylene groups having 1 to 4 carbon atoms (eg, ethynylene, proopinylene). Group. k ₁ is preferably 0.

La is a methylene group (in the present invention, "methylene group" is used to mean a methylene group which may be substituted), for example, an unsubstituted methylene group or a substituted methylene group (for example, when V is substituted, Specific examples include a methylene group substituted with a methyl group, a methylene group substituted with an ethyl group, a methylene group substituted with a phenyl group, a methylene group substituted with a hydroxy group, and a methylene group substituted with a halogen atom (for example, a chlorine atom or a bromine atom). Are mentioned.). Preferably, it is an unsubstituted methylene group.

V ₁ may be any substituent as long as it is a monovalent substituent, but preferably includes the substituents represented by V described above.

K ₂ is preferably 0, 1, 2, more preferably 0, 1 and particularly preferably 0.
It is. When k ₂ is 2 or more, although V ₁ is repeated need not be the same.

The boric acid group in R ₁ of the present invention changes its state depending on pH, and reacts with a diol compound.
It easily becomes an ester. For example, Angewandte Chemie Interview English
national Edition Englis
h), (35), 1910 Tribute (1996), and the like.

Ra and Rb are particularly preferably as follows.

[0033]

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In a methine compound represented by the general formula (I) and Q represents a group necessary for forming a cyanine dye, when the compound is a compound selected from the following general formula (II): More preferred. General formula (II)

[0035]

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In the formula (II), Z ₁ , R ₁ , L ₁ , L ₂ ,
p ₁ , M ₁ , and m ₁ have the same meanings as in formula (I). L ₃ ,
L ₄ , L ₅ , L ₆ and L ₇ represent a methine group. p2 represents 0 or 1. n ₁ represents 0, 1, 2, or 3. Z
₂ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. R ₂ represents an alkyl group.

In the general formula (II), Z ₂ has the same meaning as Z ₁ ;
L ₆ and L ₇ have the same meanings as L ₁ and L _2, and are preferably the same.

R ₂ represents an alkyl group, for example, 1 to 18, preferably 1 to 7, particularly preferably 1 to 1 carbon atoms.
To 4 unsubstituted alkyl groups (eg, methyl, ethyl,
Propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), 1 carbon atom
To 18, preferably 1 to 7, particularly preferably 1 to 4 substituted alkyl groups {for example, a heterocyclic group substituted by V mentioned as a substituent such as Z ₁ described above. Preferably, an aralkyl group (eg, benzyl, 2-phenylethyl), an unsaturated hydrocarbon group (eg, an allyl group), a hydroxyalkyl group (eg, 2-hydroxyethyl, 3-hydroxypropyl), a carboxyalkyl group (eg,
2-carboxyethyl, 3-carboxypropyl, 4-
Carboxybutyl, carboxymethyl), alkoxyalkyl groups (eg, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), aryloxyalkyl groups (eg, 2-phenoxyethyl, 2- (1-naphthoxy) ethyl), Alkoxycarbonylalkyl group (for example, ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl), aryloxycarbonylalkyl group (for example, 3-phenoxycarbonylpropyl), acyloxyalkyl group (for example, 2-acetyloxyethyl), acylalkyl group (for example, 2 -Acetylethyl), a carbamoylalkyl group (eg, 2-morpholinocarbonylethyl), a sulfamoylalkyl group (eg, N, N-dimethylcarbamoylmethyl), a sulfoalkyl group (eg, 2-sulfoethyl) , 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-
Sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl),
A sulfoalkenyl group (for example, a sulfopropenyl group),
A sulfatoalkyl group (eg, 2-sulfatoethyl group, 3-sulfatopropyl, 4-sulfatobutyl), a group represented by R ₁ of the present invention, a heterocyclic-substituted alkyl group (eg, 2- (pyrrolidine- 2-on-1-yl) ethyl, tetrahydrofurfuryl), alkylsulfonylcarbamoylmethyl group (for example, methanesulfonylcarbamoylmethyl group)}.

Preferred are the above-mentioned carboxyalkyl group, sulfoalkyl group, sulfoalkenyl group, unsubstituted alkyl group and R ₁ of the present invention, and more preferred are the sulfoalkyl group and R ₁ of the present invention.

L ₃ , L ₄ and L ₅ each independently represent a methine group. These methine groups may have a substituent. Examples of the substituent include a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. (Eg, methyl, ethyl, 2-carboxyethyl), substituted or unsubstituted, having 6 to 20 carbon atoms, preferably 6 to 1 carbon atoms.
5, more preferably an aryl group having 6 to 10 carbon atoms (eg, phenyl, o-carboxyphenyl), substituted or unsubstituted 3 to 20 carbon atoms, preferably 4 carbon atoms
To 15, more preferably a heterocyclic group having 6 to 10 carbon atoms (for example, N, N-, diethylbarbituric acid group), a halogen atom (for example, chlorine, bromine, fluorine, iodine), and having 1 to 15 carbon atoms, preferably C1 to C10, more preferably C1 to C5 alkoxy group (for example, methoxy, ethoxy), C1 to C15, preferably C1 to C10, more preferably C1 to C5 alkylthio group ( For example, methylthio, ethylthio), carbon number 6
To 20, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms, for example, phenylthio, 0 to 15 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 to 10 carbon atoms. Amino groups (eg, N, N-diphenylamino, N-methyl-N
-Phenylamino, N-methylpiperazino) and the like. Further, a ring may be formed with another methine group, or a ring may be formed together with Z ₁ , Z ₂ and R ₂ .

N ₁ is preferably 0, 1, 2;
More preferably, it is 0 or 1, and particularly preferably 1. When n ₁ is 2 or more, the methine group is repeated but need not be the same.

Specific examples of the compound represented by the general formula (I) (including the subordinate concept (II)) of the present invention are shown below.
This does not limit the invention.

[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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The reaction conditions for synthesizing the compound of the present invention will be described in detail. The quaternizing agent (B) as a raw material for introducing R ₁ into the basic nucleus represented by Z ₁ can be synthesized, for example, by the following route.

[0049]

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Further, as shown below, (D) as a raw material for the dyeing reaction can be synthesized.

[0051]

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The reaction conditions are as follows: azoles (nitrogen-containing heterocycle)
(C) and (B) are performed. Reaction temperature is from 0 ° C to 270
Can be selected from the range of ° C. The range is preferably from 80 ° C to 230 ° C, more preferably from 100 ° C to 200 ° C. N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMS)
Any solvent may be used, from polar solvents such as O) and sulfolane to non-polar solvents such as anisole and xylene, except those that undergo alkylation by (B) and those that decompose (B). Further, no solvent may be used. The raw material charging ratio ((B) / (C)) can be selected from the range of 0.5 to 20. The range is preferably from 0.75 to 7, more preferably from 1 to 4. In the reaction, an acid or a base may or may not be used as a catalyst.

The compound represented by the general formula (I) is represented by the formula (D)
Can be synthesized by using the compound represented by the formula as a raw material and reacting with a combination of other raw materials according to the structure of the target compound. Regarding the selection of raw materials to be used in combination, generally speaking, FM Harmer, `` Heterocyclic Compounds-Cyanine Soybeans and Related Compounds (Heterocyclic Compounds)
ounds-Cyanine Dyes and Related Compounds), John Wiley & Sons, New York, London, 1964, DMSturmer, Heterocyclic
Heterocyclic Compounds- Special Topics in Heterocyclic Compounds
Specialtopics in heterocyclic chemistry)
Chapter 8, Section 14, 482-515, John Wiley & Sons, New York, London, 1977, "Rodd's Chemistr.
y of Carbon Compounds) '' 2nd.Ed.vol.IV, partB, 197
Seventh Edition, Chapter 15, Chapters 369-422, Elsevier
Science Public Company, Inc. (Elsevie
r Science Publishing Company Inc.), New York, and the like.

The reaction conditions will be described in detail. The reaction temperature can be selected from the range of -20 ° C to 200 ° C. The temperature range is preferably from 0 ° C to 180 ° C, and from 15 ° C to 1 ° C.
A range of 60 ° C. is more preferred. As the reaction solvent,
From polar solvents such as water, N, N-dimethylformamide (DMF), and dimethylsulfoxide (DMSO),
It can be selected from any range up to non-polar solvents such as benzene and hexane. Polar solvents such as DMF and DMSO, alcohols such as methanol and ethanol, nitriles such as acetonitrile and benzonitrile, esters such as ethyl acetate, tetrahydrofuran and 1,2
Ethers such as -dimethoxyethane are preferable, and polar solvents, alcohols and nitriles are more preferable, and a mixed solvent thereof can be used. In the reaction, an acid or a base can be used. In some cases, it is preferable to use a mixture of both an acid and a base. The acid can be selected from inorganic acids and organic acids, and organic acids are preferred. Particularly, carboxylic acids such as acetic acid and propionic acid, and phenols such as phenol and m-cresol are preferable. The base can be selected from inorganic bases and organic bases, and organic bases are preferred. Particularly, a tertiary amine such as triethylamine and an aromatic heterocyclic amine such as pyridine are preferable.

[0055]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Synthesis of Compound (1) Compound (1) was synthesized according to the following scheme.

[0057]

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(E) 2.3 g (0.014 mol),
(F) 3 g (0.014 mol) of the mixture was heated and stirred at an external temperature of 100 ° C. for 2 hours, and then 100 ml of acetone was added thereto and allowed to cool. The obtained crystals are separated by suction filtration to give a colorless powder (G).
(3.73 g, yield 71%, melting point 195-200 ° C.). (G) 3 g (0.0079 mol), orthopropionic acid ethyl ester 6.8 ml (0.0337 mol)
l), 2.3 ml of acetic acid and 9 ml of pyridine at 110 ° C.
The mixture was heated and stirred on an oil bath for 1 hour. The reaction solution was cooled with water while stirring, 150 ml of 1N hydrochloric acid was further added, and the mixture was stirred for 30 minutes, and the obtained crystals were separated by suction filtration. The obtained crystals were dissolved in 30 ml of dimethylacetamide by heating, and after natural filtration, 100 ml of ethyl acetate was added to the filtrate. After standing, the precipitated crystals were separated by suction filtration and dried. (1) (purple powder, yield 0.97 g, yield 37%,
λmax = 560 nm, ε = 98000 (methanol)
(Melting point: 245 to 250 ° C.) Application Example—Application to Optical Recording Material A 2% methanol solution of the compound (1) was spin-coated on a glass substrate. 300 rpm for coating, 15 for drying
The rotation was performed at a rotation speed of 00 rpm. The thickness of the obtained dye thin film was 100 nm. The semiconductor laser pumped YAG
SHG device (Amoco Laser (Amoco Laser)
Co. 1) light intensity, beam diameter 100μ
m, light having a wavelength of 532 nm was applied for 10 seconds at 10 mm intervals. After irradiation, when observed with an optical microscope, destruction of the dye film was observed at the irradiated site. From the above, it can be seen that this dye film functions as an optical disk.

[0059]

According to the present invention, a novel methine compound can be obtained.

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[Procedure amendment]

[Submission date] August 22, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 1

[Correction method] Change

[Correction contents]

Embedded image In the formula (I), Z ₁ represents an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. L ₁ and L ₂ represent a methine group. p ₁ represents 0 or 1. M ₁ represents a charge balancing counter ion, and m ₁ represents a number from 0 to 10 required to neutralize the charge of the molecule. Q represents a group necessary for forming a methine dye. R ₁ is a group represented by the following Ra or Rb.

Embedded image La represents a methylene group. A represents a divalent linking group. V
₁ represents a monovalent substituent. k ₁ represents 0 or 1. k
₂ represents 0, 1, ₂ , 3 or 4.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction contents]

[0008]

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[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction contents]

La represents a methylene group. A represents a divalent linking group. V ₁ represents a monovalent substituent. k ₁ represents 0 or 1. k2 represents 0, 1, ₂ , 3, or 4.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction contents]

The reaction is carried out with azoles (nitrogen-containing heterocycle)
(C) and (B) are performed. Reaction temperature is from 0 ° C to 270
Can be selected from the range of ° C. The range is preferably from 80 ° C to 230 ° C, more preferably from 100 ° C to 200 ° C. N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMS)
Any solvent may be used, from polar solvents such as O) and sulfolane to non-polar solvents such as anisole and xylene, except those that undergo alkylation by (B) and those that decompose (B). Further, no solvent may be used. The raw material charging ratio ((B) / (C)) can be selected from the range of 0.5 to 20. The range is preferably from 0.75 to 7, more preferably from 1 to 4. In the reaction, an acid or a base may or may not be used as a catalyst.

Claims (2)

[Claims] 1. A methine compound represented by the following general formula (I). General formula (I) In the formula (I), Z ₁ represents an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. L ₁ and L ₂ represent a methine group. p ₁ represents 0 or 1. M ₁ represents a charge balancing counter ion, and m ₁ represents a number from 0 to 10 required to neutralize the charge of the molecule. Q represents a group necessary for forming a methine dye. R ₁ is a group represented by the following Ra or Rb. Embedded image La represents a methylene group. A represents a divalent linking group. V
Represents a monovalent substituent. k ₁ represents 0 or 1. k ₂
Represents 0, 1, 2, 3 or 4. 2. The methine compound according to claim 1, wherein in the compound represented by the general formula (I) according to claim 1, Q represents a group necessary for forming a cyanine dye.