JPH1060295A - Methine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new methine compound comprising a specific azamethine compound having an oxazole nucleus, having an absorption maximum within a UV region and useful as a UV absorber, a sensitizing coloring matter for a photograph, a dye, a coloring matter for a functional material, a pigment, a medicine, etc. SOLUTION: This methine compound is the new one of formula I (each of Z1 and Z2 represents a five- or six-membered heterocyclic ring including nitrogen with the proviso that at least one thereof is an oxazole nucleus; R1 and R2 are each an alkyl; M1 is an ion for neutralizing the charge), having an absorption maximum in the UV region and useful as a UV absorber, a sensitizing coloring matter for a photograph, a dye, a coloring matter for a functional material, a pigment, a medicine, etc. The compound of formula I is obtained by reacting 2-aminobenzoxazolium salt compound of formula II, etc., with 2 methylthiobenzoxazolium salt compound of formula III, etc., in a pyridine solution by heating and refluxing the compounds, adding a methanol solution of sodium iodide and ethyl acetate to the reaction product and filtering and separating the precipitated crystal.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel azamethine compound, and more particularly to an azamonomethine compound containing an oxazole nucleus.

[0002]

2. Description of the Related Art Azamethine compounds containing a nitrogen atom in a methine chain are sensitizing dyes for photographic purposes, dyes, dyes for functional materials,
Important as a pigment or pharmaceutical. Conventionally, as the azamonomethine compounds, those containing a thiazole nucleus or a quinoline nucleus as a heterocyclic ring are known as UK Patent 447,038, but the types thereof are limited, and the development of azamonomethine compounds having a novel structure has been desired. .

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an azamonomethine compound having a novel structure.

[0004]

The object of the present invention has been attained by a methine compound represented by the following general formula (1). General formula (1)

[0005]

Embedded image

In the formula, Z1 and Z2 each represent a 5- or 6-membered nitrogen-containing heterocyclic ring, at least one of which is an oxazole nucleus. R1 and R2 each represent an alkyl group. M1
Represents a charge neutralizing ion. In particular, among the general formula (1), a methine compound represented by the following general formula (2) is preferable. General formula (2)

[0007]

Embedded image

In the formula, R3 and R4 each represent an alkyl group. R5, R6, R7, R8, R9, R10, R11 and R12 each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a heterocyclic group, an alkenyl group, an alkynyl group, an alkylthio group, an arylthio group,
Represents a sulfo group, a hydroxy group, a halogen atom, a cyano group or a carboxy group. M2 represents a charge neutralizing ion.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the methine compounds represented by the general formulas (1) and (2) will be described in detail. Each of Z1 and Z2 is an oxazole nucleus having 3 to 25 carbon atoms (for example, 2-1-methyloxazolyl, 2-1-ethyloxazolyl, 2-1,3-diethyloxazolyl,
1-methylbenzoxazolyl, 2-1-ethylbenzoxazolyl, 2-1-sulfoethylbenzoxazolyl, 2-1-sulfopropylbenzoxazolyl, 2-
1-methylthioethylbenzoxazolyl, 2-1-methoxyethylbenzoxazolyl, 2-1-sulfobutylbenzoxazolyl, 2-1-methyl-β-naphthoxazolyl, 2-1-methyl- α-naphthoxazolyl, 2-1-sulfopropyl-β-naphthoxazolyl, 2-1-sulfopropyl-γ-naphthoxazolyl, 2-1- (1-naphthoxyethyl) benzoxazolyl, -1,5-dimethylbenzoxazolyl, 2-
6-chloro-1-methylbenzoxazolyl, 2-5-
Bromo-1-methylbenzoxazolyl, 2-1-ethyl-5-methoxybenzoxazolyl, 2-5-phenyl-1-sulfopropylbenzoxazolyl, 2-5-
(4-bromophenyl) -1-sulfobutylbenzoxazolyl, 2-1-dimethyl-5,6-dimethylthiobenzooxazolyl, etc.), having 3 to 25 carbon atoms.
A thiazole nucleus (for example, 2-1-methylthiazolyl,
2-1-ethylthiazolyl, 2-1,3-dimethylthiothiazolyl, 2-1-methylbenzothiazolyl, 2-1-ethylbenzothiazolyl, 2-1-butylbenzothiazolyl, 2-1 -Sulfopropylbenzothiazolyl, 2-1
-Sulfobutylbenzothiazolyl, 2-1-methyl-β
-Naphthothiazolyl, 2-1-sulfopropyl-γ-naphthothiazolyl, 2-1- (1-naphthoxyethyl) benzothiazolyl, 2-1, 5-dimethylbenzothiazolyl, 2-6-chloro-1-methylbenzothiazolyl , 2
-6-iodo-1-ethylbenzothiazolyl, 2-5-
Bromo-1-methylbenzothiazolyl, 2-1-ethyl-5-methoxybenzothiazolyl, 2-5-phenyl-
1-sulfopropylbenzothiazolyl, 2-5- (4-
Bromophenyl) -1-sulfobutylbenzothiazolyl, 2-1-dimethyl-5,6-dimethylthiobenzothiazolyl and the like; an imidazole nucleus having 3 to 25 carbon atoms (for example, 2-1; 3-diethylimidazolyl, 2-1, 3-dimethylimidazolyl, 2-1-methylbenzimidazolyl, 2-1, 3,4-triethylimidazolyl, 2-1, 3-diethylbenzimidazolyl, 2-1,3,5-trimethyl Benzimidazolyl,
2-6-chloro-1,3-dimethylbenzimidazolyl, 2-5,6-dichloro-1,3-diethylbenzimidazolyl, 2-1,3-disulfopropyl-5-cyano-6-chlorobenzimidazolyl and the like. ), A quinoline nucleus having 9 to 25 carbon atoms (for example, 2-1
Methylquinolyl, 2-1-ethylquinolyl, 2-1-methyl6-chloroquinolyl, 2-1,3-diethylquinolyl, 2-1-methyl-6-methylthioquinolyl, 2-1
-Sulfopropylquinolyl and the like), a selenazole nucleus having 3 to 25 carbon atoms (for example, 2-1-methylbenzoselenazolyl and the like), and 5 to 25 carbon atoms
(For example, 2-pyridyl and the like), and at least one of Z1 and Z2 is an oxazole nucleus.

Each of R1, R2, R3 and R4 is an alkyl group (herein, it is used in a sense including a group having a substituent), preferably an alkyl group having 1 to 20 carbon atoms. , N-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-
Nonyl, i-propyl, i-butyl, i-pentyl, t
-Butyl and the like. These may be substituted.
Examples of the substituent include a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom), a nitro group,
Alkoxy groups (eg, methoxy, ethoxy), aryl groups (eg, phenyl), aryloxy groups (eg,
Phenoxy), an amide group, a carbamoyl group, a sulfo group,
Examples include a hydroxy group, a carboxy group, an alkylthio group, and a cyano group. Hereinafter, these are referred to as a substituent group X. Preferred substituent groups are a sulfo group, a carboxy group, an alkoxy group, an alkenyl group, and an amide group. When the substituent is a sulfo group, examples of the counter ion include alkali metals and quaternary ammonium compounds, such as sodium, potassium, pyridinium,
1-ethylpyridinium, triethylammonium and the like. Preferably as R1, R2, R3 and R4,
A methyl group, an ethyl group, a propyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a carboxyethyl group, and a methoxyethyl group.

R5, R6, R7, R8, R9, R10,
R11 and R12 each represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (eg, methyl, ethyl, n-propyl, n
-Butyl, n-pentyl, n-hexyl, n-heptyl, n-nonyl, i-propyl, i-butyl, i-pentyl, t-butyl and the like, which may be substituted.
Examples of the substituent include the substituent group X described above. ), An aryl group having 6 to 20 carbon atoms (for example, phenyl, 1-naphthyl, 2-naphthyl, etc., which may be substituted. Examples of the substituent include the above-mentioned substituent group X or an alkyl group. ), An alkoxy group having 1 to 20 carbon atoms (for example, methoxy, ethoxy, n-propoxy, n-butoxy, etc., which may be substituted. Examples of the substituent include the above-mentioned substituent group X). An aryloxy group having 6 to 20 carbon atoms (e.g., phenoxy, 1-naphthoxy, 2-naphthoxy, etc., which may be substituted. Examples of the substituent include the above-described substituent group X or an alkyl group). A heterocyclic group having 3 to 20 carbon atoms (for example,
2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyridyl, 4-pyridyl, 4-quinolinyl, 7
-Quinolinyl, 2-thiazolyl, 2-imidazolyl and the like, which may be substituted. Examples of the substituent include the above-described substituent group X or an alkyl group. ), Carbon number 2
-20 alkenyl groups (e.g., ethenyl and the like;
It may be substituted. Examples of the substituent include the substituent group X described above. ), An alkynyl group having 2 to 20 carbon atoms (for example, ethynyl and the like, which may be substituted. Examples of the substituent include the above-described substituent group X), and an alkylthio group having 1 to 20 carbon atoms ( Examples thereof include methylthio, ethylthio, etc., which may be substituted. Examples of the substituent include the above-described substituent group X), and arylthio groups having 6 to 20 carbon atoms (for example, phenylthio, etc., and are substituted). Examples of the substituent include the above-described substituent group X or an alkyl group.), A sulfo group, a hydroxy group, a halogen atom (eg, chlorine, bromine, iodine, fluorine), a cyano group, and a carbon atom having 2 carbon atoms. And 20 to 20 acyl groups (for example, acetyl, benzoyl, etc., which may be substituted. Examples of the substituent include the above-mentioned substituent group X) or a carboxy group. . R5, R6, R7, R8, R9, R10, R11 and R12 are preferably a hydrogen atom, an alkyl group, an alkylthio group, an aryl group, a 1-thienyl group, an alkoxy group, and a halogen atom. Particularly preferably, R6 and / or
Or R10 is chlorine, methylthio, phenyl, p-
A bromophenyl group and a 1-thienyl group.

M1 and M2 each represent a charge neutralizing ion. Whether a compound is a cation, an anion, or has a net ionic charge depends on its substituents. Typical cations are ammonium and alkali metal ions, while anions can be either inorganic or organic. Examples of the cation include sodium ion, potassium ion, triethylammonium ion, pyridinium ion, and 1-ethylpyridinium ion. Examples of the anion include halogen anion (eg, chloride ion, bromide ion, fluorine ion, Iodine ion), substituted aryl sulfonate ion (eg, paratoluene sulfonate ion), alkyl sulfate ion (eg, methyl sulfate ion), sulfate ion, perchlorate ion, tetrafluoroborate ion, acetate ion and the like. .

Next, preferred combinations will be described. A preferred combination is that R1 to R4 are alkyl groups, R5 to R12
Is a hydrogen atom, R1 to R4 are an alkyl group, and R6 and / or R10 are a chloro group, a methylthio group, a phenyl group, a p-bromophenyl group or a 1-thienyl group.

The specific examples of the compounds represented by formulas (1) and (2) of the present invention are shown below, but the present invention is not limited thereto.

[0015]

Embedded image

[0016]

Embedded image

[0017]

Embedded image

[0018]

Embedded image

The compounds of the present invention can be carried out, for example, according to the methods described in the following documents. Dee
M. Hammer, Heterocyclic Compounds-
Special Topics in Heterocyclic Chemistry, Chapter 8, John Wiley and Sons, New York (1977). UK Patent 447-6
No. 38.

Specifically, a method of reacting a 2-aminooxazolium compound with an azolium compound having a leaving group (eg, a halogen atom, an alkylthio group, a sulfo group) substituted at the 2-position under basic conditions or Examples include a method of reacting an aminooxazolium compound with 2,4-dinitrochlorobenzene.

[0021]

Next, the present invention will be described in more detail with reference to examples.

Example 1 (Synthesis of Compound No. 2)

[0023]

Embedded image

0.25 g of the compound (C-1) and the compound (C
-2) 1 ml of a 0.30 g pyridine solution was refluxed for 3 hours, cooled, then a methanol solution of sodium iodide and ethyl acetate were added, and the precipitated crystals were separated by filtration. The obtained crude crystals were crystallized from methanol / ethyl acetate to give 0.11 g of the desired compound (No. 2). λmax = 335nm (MeOH)

Embodiment 2 FIG. (Synthesis of Compound No. 21)

[0026]

Embedded image

Compound (C-1) (1.0 g) and compound (C-
3) 5 ml of a 1.2 g pyridine solution was refluxed for 3 hours, and after cooling, a methanol solution of sodium iodide and ethyl acetate were added, and the precipitated crystals were separated by filtration. The obtained crude crystals were crystallized from methanol / ethyl acetate to give 0.32 g of the desired compound (No. 21). λmax = 355nm (MeOH)

Embodiment 3 FIG. The absorption maximum wavelengths of the compounds (No. 1) and (No. 21) of the present invention and the conventional compounds (M1), (M2) and (M3) in a solution were compared (Table 1). As a result, it was found that the compound of the present invention absorbs light of shorter wavelength side than the conventional compound.

[0029]

Embedded image

[0030]

[Table 1]

The results show that the compounds of the present invention are excellent as UV absorbers.

[0032]

The methine compound of the present invention has an absorption maximum in the UV region and can be used as an absorbent.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 20, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction contents]

[0016]

Embedded image

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction contents]

[0017]

Embedded image

Claims (2)

[Claims] 1. A methine compound represented by the following general formula (1). General formula (1) In the formula, Z1 and Z2 each represent a 5- or 6-membered nitrogen-containing heterocyclic ring, at least one of which is an oxazole nucleus. R
1 and R2 each represent an alkyl group. M1 represents a charge neutralizing ion. 2. The methine compound according to claim 1, represented by the following general formula (2). General formula (2) In the formula, R3 and R4 each represent an alkyl group. R5, R
6, R7, R8, R9, R10, R11 and R12 each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group,
Represents an aryloxy group, a heterocyclic group, an alkenyl group, an alkynyl group, an alkylthio group, an arylthio group, a sulfo group, a hydroxy group, a halogen atom, a cyano group or a carboxy group. M2 represents a charge neutralizing ion.