JPH08127582A - Methine compound - Google Patents

Abstract

PURPOSE: To obtain a new methine compound useful for a cyanine coloring matter, especially a photographic sensitizing coloring matter, a filter dye, etc., having strong light absorbing sensitivity in a prescribed wavelength region without extending the methine chain. CONSTITUTION: A methine compound of formula I [V is an aromatic group which may be substituted; R1 and R2 are each independently a 1-4C alkyl that may be substituted; Z is an atomic group required for forming benzene ring or naphthalene ring which may be substituted; X is a counter ion; (n) is a number required to keep the equilibrium of charges in the whole molecule]. The compound of formula I is obtained by reacting, e.g. a compound of formula II with a compound of formula III. For example, 3-(2-methyl-6-phenylquinolinio) propanesufonate and 3-[2-(3-sulfopropylthio)benzothiazolio] propanesulfonate are dissolved in ethyl alcohol and water and triethylamine is then added to the resultant solution. The reactional mixture is refluxed under heating and returned to the ambient temperature. Ethyl acetate is added thereto to collect a formed crude crystal by filtration and the resultant crystal is further recrystallized to provide the compound of formula I.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel methine compound used as a sensitizing dye for photography, a filter dye, a dye for optical recording materials and the like.

[0002]

2. Description of the Related Art Conventionally, monomethinecyanine compounds having quinoline and benzothiazole as their cores are as follows:
F.M.Harmer, "Heterocyclic Compounds-Cyanine Soybean and Related Compounds" (John Wheelie & Sons, Inc.)
Known are those described in Chapter 2 (New York, London, 1964). These compounds have a maximum absorption wavelength near 500 nm and are useful as sensitizing dyes for photography, filter dyes, and dyes for optical recording materials. It is considered that the improvement of the light absorption sensitivity and the reduction of the usage amount are achieved by increasing the light absorption efficiency. As a method of increasing the light absorption efficiency, a method of increasing the absorption coefficient of a cyanine compound by increasing the number of methine chains is known. However, by increasing the number of methine chains, the absorption maximum wavelength was significantly lengthened, and it was difficult to obtain one having an absorption maximum wavelength of 550 nm or less.

[0003]

An object of the present invention is to provide a compound useful as a cyanine dye having a strong light absorption sensitivity in a desired wavelength range without extending a methine chain.

[0004]

The above-mentioned objects have been achieved by the following means. (1) A methine compound represented by the general formula (I).

[0005]

Embedded image

In the general formula (I), V represents an aromatic group which may be substituted. R ₁ and R ₂ each independently have 1 carbon atom
To 4 represent an optionally substituted alkyl group. Z represents an atomic group necessary for forming an optionally substituted benzene ring or naphthalene ring. X represents a counter ion, and n represents the number necessary for maintaining the balance of charges in the entire molecule.

(2) V in the general formula (I) represents an optionally substituted aryl group, and R ₁ and R ₂ each independently represent an alkyl group having 1 to 4 carbon atoms which may be substituted with a sulfo group. The methine compound according to (1) above, which is represented.

Preferably, the methine compound described in (2) above, wherein V in the general formula (I) represents an optionally substituted phenyl group.

The compound (I) will be specifically described below. In general formula (I), V represents an aromatic group which may be substituted. The optionally substituted aromatic group refers to an optionally substituted aryl group (aromatic hydrocarbon ring) or an optionally substituted aromatic heterocycle. Preferably, it has 6 to 10 carbon atoms.
Optionally substituted aryl groups (eg, phenyl, naphthyl, p-methoxyphenyl, p-methylphenyl), 2-pyridyl group, 2-thienyl group, 2-furanyl group, barbituric acid group, benzothiazole nucleus, benzoxazole nucleus , A benzoselenazole nucleus, a benzoterrazole nucleus, a quinoline nucleus, a benzimidazole nucleus, a thiazoline nucleus, an indoline nucleus, an oxadiazole nucleus, a thiazole nucleus or an imidazole nucleus, and more preferably a C 6-10 substituted group. It is a good aryl group, particularly preferably an optionally substituted phenyl group, and most preferably an unsubstituted phenyl group.

R ₁ and R ₂ preferably have 1 to 1 carbon atoms.
4 unsubstituted alkyl group (methyl, ethyl, propyl, butyl), or a substituted alkyl group having 1 to 4 carbon atoms in the alkyl moiety (eg, a carboxy group, a sulfo group, a cyano group, a halogen atom (eg, fluorine) ,chlorine,
It is bromine. ), A hydroxy group, an alkoxycarbonyl group having 2 to 8 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl), an alkoxy group having 1 to 8 carbon atoms (eg, methoxy, ethoxy, benzyloxy, phenethyloxy). , A C 2-8 acyloxy group (eg acetyloxy, propionyloxy), a C 2-8 acyl group (eg acetyl, propionyl, benzoyl, mesyl), a C 1-8 carbamoyl group (eg carbamoyl, N , N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl) and a sulfamoyl group having 0 to 8 carbon atoms (for example, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl). Preferably, an unsubstituted alkyl group having 1 to 4 carbon atoms (for example, methyl, ethyl, n-propyl), a carboxyalkyl group having 1 to 8 carbon atoms (for example, 2-carboxyethyl, carboxymethyl), and 1 carbon atom.
8 sulfoalkyl groups (eg, 2-sulfoethyl,
3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl), most preferably a sulfoalkyl group having 1 to 4 carbon atoms.

Z represents an atomic group necessary for forming an optionally substituted benzene ring or naphthalene ring. As a substituent, a halogen atom (for example, a chlorine atom, a fluorine atom,
Bromine atom), an unsubstituted alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl), a substituted alkyl group having 1 to 10 carbon atoms (for example, benzyl, α-naphthylmethyl, 2-phenylethyl, trifluoromethyl), C2-C10 acyl group (eg acetyl, benzoyl, mesyl), C2-C10 acyloxy group (eg acetoxy), C2-C10 alkoxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl) ), A substituted or unsubstituted carbamoyl group having 1 to 10 carbon atoms (eg, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), a substituted or unsubstituted sulfamoyl group having 0 to 10 carbon atoms (eg, Sulfamoyl, N, N-dimethylsulfamoyl, Le morpholino, piperidinosulfonyl), a carboxy group, a cyano group, hydroxy group,
Amino group, acylamino group having 2 to 8 carbon atoms (eg acetylamino), alkoxy group having 1 to 10 carbon atoms (eg methoxy, ethoxy, benzyloxy), 6 to 1 carbon atoms
0 aryl group (eg phenyl, tolyl), 1 carbon atoms
A heterocyclic group having 10 to 10 (eg, 2-pyridyl, 2-thiazolyl), an alkylthio group having 1 to 10 carbon atoms (eg, methylthio, ethylthio), and the like are preferable, and an aryl group having 6 to 10 carbon atoms is most preferable It is preferably an unsubstituted phenyl group.

(X) n is included in the formula to indicate the presence or absence of a cation or anion when required to neutralize the ionic charge of the compound. Typical cations are inorganic or organic ammonium and alkali metal ions, while the anion may be either an inorganic or organic anion, for example a halogen anion (eg a fluoride ion, (Chlorine ion, bromine ion, iodine ion), substituted aryl sulfonate ion (for example, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion), aryl disulfonate ion (for example, 1,3-benzene disulfonate ion, 1, 5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion,
Examples thereof include acetate ion and trifluoromethanesulfonate ion. Of these, ammonium ion, iodine ion and p-toluenesulfonate ion are preferable.

When the compound included in the present invention is represented by C, C
Is generally synthesized by the method shown in the scheme below.

A + B → C In this scheme, A represents a compound represented by the general formula (IV), and B represents a compound represented by the general formula (V). General formula (IV)

[0015]

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In the general formula (IV), V, R ₁ , X and n have the same meanings as in the general formula (I). General formula (V)

[0017]

[Chemical 4]

In general formula (V), Z, R ₂ X and n have the same meanings as in general formula (I).

The reaction conditions will be described in detail. In general, this reaction is carried out without solvent or in a solvent, and the solvent is preferably a hydrogen-donating solvent, more preferably an alcohol having 1 to 4 carbon atoms (for example, methanol, ethanol, isopropyl alcohol), 1 to 1 carbon atoms. 8 amides (eg, dimethyl sulfonamide), 2 to 8 carbon atoms
(For example, dimethylsulfoxide), nitriles having 2 to 4 carbon atoms (for example, acetonitrile), most preferably ethanol or acetonitrile. A base is used to accelerate the reaction, and the base can be selected from organic bases (eg, tertiary amines such as triethylamine, aromatic heterocyclic amines such as pyridine, and tetramethylguanidine), and particularly bases such as triethylamine. Aromatic heterocyclic amines such as tertiary amines and pyridine are preferred. Reaction temperature is -20 ° C to 200
It can be selected from the range of ° C. The range of 0 ° C to 180 ° C is preferable, and the range of 10 ° C to 160 ° C is more preferable. Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

[0020]

[Table 1]

[0021]

[Table 2]

[0022]

[Table 3]

In Tables 1 to 3, Ph means a phenyl group, MeO means a methoxy group, and 4,5-benzo means that the benzene ring is condensed at the 4,5-position in the benzothiazole nucleus. , 6-benzo represents that the benzene ring is condensed at the 5th and 6th positions in the benzothiazole nucleus.

[0024]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these. Example 1 1.6 g of 3- (2-methyl-6-phenylquinolinio) propane sulfonate and 3.2 g of 3- [2- (3-sulfopropylthio) benzothiazolio] propane sulfonate
Dissolved in 30 ml of ethyl alcohol and 1 ml of water,
Add 3.2 ml of triethylamine. The reaction solution was heated to reflux for 1 hour and then allowed to cool to room temperature, and ethyl acetate 100 was added.
ml is added and the resulting crude crystals are collected by filtration. This was recrystallized from methanol to obtain 1.7 g of compound (1). λmax (MeOH) = 496nm, εmax (MeOH) = 5.5x10 ⁴ , mp> 250
℃ (dec.)

Example 2 1.6 g of 4- (2-methyl-6-phenylquinolinio) butanesulfonate and 3.3 g of 4- [2- (4-sulfobutylthio) benzothiazolio] butanesulfonate were combined with 32 ml of ethyl alcohol and Dissolve in 1 ml of water and add 3.2 ml of triethylamine. The reaction solution is heated under reflux for 1 hour, allowed to cool to room temperature, 100 ml of ethyl acetate is added, and the resulting crude crystals are collected by filtration. By recrystallizing this from methanol, 1.8 g of compound (2) was obtained. λmax (MeOH) = 496nm, εmax (MeOH) = 5.5x10 ⁴ , mp> 250
℃ (dec.)

Example 3 1.6 g of 1-methyl-3- (2-methyl-6-phenylquinolinio) propane sulfonate and 1-methyl-3-
[2- (3-sulfopropylthio) benzothiazolio]
Propane sulfonate 3.3g in ethyl alcohol 32ml
And dissolved in 1 ml of water, 3.2 ml of triethylamine are added. The reaction solution was heated to reflux for 1 hour and then allowed to cool to room temperature,
100 ml of acetic acid ethyl ester was added and the resulting crude crystals were collected by filtration. By recrystallizing this from methanol, 1.8 g of compound (3) was obtained. λmax (MeOH) = 496nm, εmax (MeOH) = 5.5x10 ⁴ , mp> 250
℃ (dec.)

Example 4 1.7 g of 3- (2-methyl-6-phenylquinolinio) propane sulfonate and 4- [2- (4-sulfobutylthio) -5-phenylbenzothiazolio] butanesulfonate 2.6 g is dissolved in 20 ml of ethyl alcohol and 1.4 ml of triethylamine is added. The reaction solution is heated under reflux for 1 hour, allowed to cool to room temperature, 300 ml of acetone is added, and the resulting crude crystals are collected by filtration. This was recrystallized from methanol to obtain 1.4 g of compound (4). λmax (MeOH) = 506nm, εmax (MeOH) = 5.8x10 ⁴ , mp> 250
℃ (dec.)

Example 5 1.7 g of 1-methyl-3- (2-methyl-6-phenylquinolinio) propane sulfonate and 1-methyl-3-
2.6 g of [2- (4-sulfobutylthio) -5-phenylbenzothiazolio] propanesulfonate are dissolved in 20 ml of ethyl alcohol, and 1.4 ml of triethylamine is added. The reaction solution is heated under reflux for 1 hour, allowed to cool to room temperature, 300 ml of acetone is added, and the resulting crude crystals are collected by filtration. By recrystallizing this from methanol, compound (5) 1.
I got 4g. λmax (MeOH) = 506nm, εmax (MeOH) = 5.8x10 ⁴ , mp> 250
℃ (dec.)

Example 6 1.6 g of 3- (2-methyl-6-phenylquinolinio) propanesulfonate and 3- [2- (3-sulfopropylthio) -3- [1,2-d] naphthothiazolio] 3.2 g of propane sulfonate is dissolved in 30 ml of ethyl alcohol and 1 ml of water, and 3.2 ml of triethylamine is added. The reaction solution is heated under reflux for 1 hour, allowed to cool to room temperature, 100 ml of ethyl acetate is added, and the resulting crude crystals are collected by filtration. This was recrystallized from methanol to obtain 1.7 g of compound (6). λmax (MeOH) = 516nm, εmax (MeOH) = 5.2x10 ⁴ , mp> 250
℃ (dec.)

Example 7 Gelatin is dissolved in distilled water so that the concentration of gelatin will be 70 g / liter. Keep 50g of this gelatin solution at 40 ℃,
0.0005 of the compounds of the present invention or control compounds shown in Table 4
Add a methanol solution containing mol / liter. The mixture thus obtained is referred to as solution I. On a substrate formed of polyethylene terephthalate, 5 ml of the liquid I is coated in a circle so that the gelatin density on the substrate becomes 30 g / m ² . This was dried at 25 ° C and 60% for 12 hours to give a gelatin dry film (10
0) to (107) were obtained. This gelatin dry film sample (10
Hitachi's UV absorption spectrum of 0) to (107)
Measured at -3100, the value obtained by integrating the absorption intensity in the main absorption with the horizontal axis (eV) is S.

When the value of S for the sample (100) was set to 1, S'of each sample was represented by S '.

[0032]

[Table 4]

[0033]

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It can be seen from Table 4 that the compounds of the present invention have increased coating film absorption as compared to the control compound.

[0035]

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a methine compound having a high light absorption intensity and useful as a sensitizing dye for photography, a filter dye, a dye for optical recording materials and the like.

Claims (2)

[Claims] 1. A methine compound represented by the general formula (I). Embedded image In general formula (I), V represents an aromatic group which may be substituted. R ₁ and R ₂ each independently represent an optionally substituted alkyl group having 1 to 4 carbon atoms. Z represents an atomic group necessary for forming an optionally substituted benzene ring or naphthalene ring. X represents a counter ion, and n represents the number necessary for maintaining the balance of charges in the entire molecule. 2. A group represented by general formula (I) in which V may be substituted.
Reel group, R ₁And R₂Each independently
Represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a group.
The methine compound according to claim 1.