JPH0583588B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel methine dye represented by the general formula [ ].

[Formula, n represents 0 or 1, m represents 1 or 2, R ₁ represents an unsubstituted alkyl group or an alkyl group substituted with an alkoxy group or a phenyl group, R ₂ represents the general formula [ ] represents a group. Z is thiazole, benzothiazole, naphthothiazole, oxazole, benzoxazole, naphthoxazole, benzoselenazole,
Represents a group of atoms necessary to form a heterocycle selected from tellurazole, 3,3-dialkylindolenine, 2-pyridine, 4-pyridine, and 2-quinoline, and these rings include a methyl group, a methoxy group, an ethoxy group, It may be substituted with a group selected from a trifluoromethyl group and a chlorine atom. X
represents an anion. p represents 1 or 2, and p is 1 when the dye forms an inner salt. )

[Formula] (In the formula, R ₁₁ and R ₁₂ are unsubstituted alkyl groups, or as substituents, an alkyl group with 18 or less carbon atoms substituted with a cyano group, a halogen atom, or an alkoxycarbonyl group with 8 or less carbon atoms. In addition, R ₁₁ and R ₁₂ may be linked to form a 5-membered ring or a 6-membered ring. R ₁₃ and R ₁₄ are a hydrogen atom, an unsubstituted alkyl group, a substituted or unsubstituted amino group, or a carboxyl group. , cyano group, hydroxy group, halogen atom, alkoxycarbonyl group having 8 or less carbon atoms,
It represents an alkoxy group having 2 to 8 carbon atoms, an acyloxy group having 8 or less carbon atoms, a carbamoyl group, or a sulfamoyl group, and R ₁₁ or R ₁₂ and R ₁₃ or R ₁₄
may be linked to form a 5-membered ring or a 6-membered ring. However, at least one of R ₁₃ and R ₁₄ is a substituted or unsubstituted amino group, carboxy group, cyano group, hydroxy group, halogen atom, alkoxycarbonyl group having 8 or less carbon atoms, an alkoxy group having 2 to 8 carbon atoms, Represents an acyloxy group, carbamoyl group, or sulfamoyl group having 8 or less carbon atoms. Each substituent of the compound represented by the general formula [] is preferably the substituent shown below. That is, R ₁ is an unsubstituted alkyl group having 18 or less carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, octyl group, decyl group, dodecyl group, octadecyl group, vinylmethyl group, cyclohexyl group, etc.). ), or an alkyl group having 18 or less carbon atoms substituted with an alkoxy group having 8 or less carbon atoms (eg, methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.). Preferred substituents in the group represented by the above general formula [] will be described. Examples of unsubstituted alkyl groups represented by R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ include unsubstituted alkyl groups having 1 to 12 carbon atoms, such as methyl group, ethyl group, pyropur group, butyl group, hexyl group, octyl group, and decyl group. A dodecyl group, a vinylmethyl group, and the like are preferred. Examples of the halogen atom as a substituent for the substituted alkyl group represented by R ₁₁ and R ₁₂ include fluorine atom and chlorine atom, and examples of the alkoxycarbonyl group having 8 or less carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, and phenoxycarbonyl group. Examples include carbonyl group and benzyloxycarbonyl group. The halogen atoms represented by R ₁₃ and R ₁₄ include, for example, a fluorine atom and a chlorine atom, and the alkoxycarbonyl groups having 8 or less carbon atoms include, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a phenoxycarbonyl group, a benzyloxycarbonyl group, etc. Also, alkoxy groups having 2 to 8 carbon atoms include, for example, ethoxy, benzyloxy, and phenethyloxy groups; and acyloxy groups having 8 or less carbon atoms include, for example, acetyloxy and propionyloxy groups;
Further, the carbamoyl group is, for example, a carbamoyl group,
N,N-dimethylcarbamoyl group, morpholinocarbamoyl group, piperidinocarbamoyl group, etc.;
The sulfamoyl group is, for example, a sulfamoyl group,
Examples include N,N-dimethylsulfamoyl group, morpholinosulfonyl group, and pyridinosulfonyl group. As unsubstituted or substituted amino groups for R ₁₃ and R ₁₄ ,

[Formula] may be different and include a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, etc.), an acyl group having 2 to 8 carbon atoms (e.g. acetyl group) , propionyl group, benzoyl group, etc.) are preferred. Further, R ₁₇ and R ₁₈ may form a ring. The heterocycle formed by Z has a thiazole nucleus (e.g. thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole,
4,5-diphenylthiazole, 4,(2-thienyl)thiazole, etc.), benzothiazole nuclei (e.g. benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole) , 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole,
5,6-dimethylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-trifluoromethylbenzothiazole,
5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-carboxybenzothiazole, 5-cyanobenzothiazole, 5-fluoromenzothiazole, 5-ethoxybenzothiazole, Tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole,
5-hydroxybenzothiazole, 6-hydroxybenzothiazole, etc.), naphthothiazole nuclei (e.g. naphtho-[1,2-d]thiazole, naphtho[2,1-d]thiazole, naphtho[2,3-
d] Thiazole, 5-methoxynaphtho[2,1-
d] Thiazole, 5-ethoxynaphtho[2,1-
d] Thiazole, 8-methoxynaphtho[1,2-
d] Thiazole, 7-methoxynaphtho[1,2-
d] thiazole, etc.), oxazole nucleus (e.g. 4
-Methyloxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole,
4,5-dimethyloxazole, 5-phenyloxazole, etc.), benzoxazole nuclei (e.g. benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5, 6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-
methoxybenzoxazole, 5-ethoxybenzoxazole, 5-fluorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.), naphthoxazole core (e.g. naphtho[1,2-d]oxazole) , naphtho[2,1-d]oxazole, naphtho[2,3-
d] Oxazole, etc.), selenazole core (e.g. selenazole, 4-methylselenazole, 4-phenylselenazole, 4,5-diphenylselenazole, etc.), benzoselenazole nucleus (e.g. benzoselenazole, 5-chlorobenzo selenazole, 5-methylbenzoselenazole, 5-methoxybenzoselenazole, 5-phenylbenzoselenazole, etc.), naphthoselenazole core (e.g. naphtho[1,2-d]selenazole, naphtho[2,
1-d]selenazole, naphtho[2,3-d]selenazole, etc.), tellurazole core (e.g. benzotelllazole, 5-methylbenzotelllazole,
5,6-dimethylbenzotellazole, naphtho[1,2-d]telllazole, naphtho[2,1-
d] tellurazole, naphtho[2,3-d]tellazole, 6-methoxynaphtho[1,2-d]tellazole, etc.), 3,3-dialkylindolenine core (e.g. 3,3-dimethylindolenine,
3,3,5-trimethylindolenine, 5-chloro-3,3-dimethylindolenine, 5-ethoxycarbonyl-3,3-dimethylindolenine, etc.), 2-pyridine nucleus (e.g. pyridine, 5-methylpyridine, etc.) ), 4-pyridine nucleus (e.g. pyridine etc.), 2-quinoline nucleus (e.g. 6-ethoxyquinoline, 6-ethylquinoline, 6-chloroquinoline, 8-fluoroquinoline etc.), X represents an anion, specifically: , chloride, bromide, iodide, thiocyanate, perchlorate, paratoluenesulfonate, and tetrafluoroborate are preferred. The compound represented by the general formula [] can be synthesized by various synthetic methods. For example, as shown in the reaction formula below, a heterocyclic quaternary salt derivative having an active methyl group and 2,6-dimethyl-4H- Piran-4
- It can be obtained by a condensation reaction between intermediate [A] obtained by reaction with thione and aldehydes.

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embedded image In the above reaction formula, R ₁ , R ₂ , Z, P, n and m have the same meanings as explained in the general formula [ ]. Moreover, X ₁ , X ₂ , and X represent anions. The novel methine dye of the present invention has excellent fastness and is effective as a dye for filters, and also as a dye for photographic materials and a sensitizing dye. These dyes also dye mixtures from groundwood pulp and bleached sulphite pulp, as well as pure pulp, and are virtually completely dyed. Furthermore, these dyes can be excited by excitation methods such as excimer laser, second harmonic or third harmonic of Nd:YAG laser, etc., to obtain laser light in the near-infrared to infrared region, and their fastness is improved. It often acts as a high-performance laser dye with high energy conversion efficiency. Specific examples of the compound represented by the general formula [] of the present invention are shown below, but the invention is not limited thereto.

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embedded image Next, synthesis examples of the compounds according to the present invention will be explained in detail with reference to the following examples. Example 1 (Synthesis of intermediate [A]) 1-(1) 3-ethyl-2-{(2,6-dimethyl-
4H-pyran-4-ylidene)methyl}benzothiazolium p-toluenesulfonate 3-ethyl-2-methylbenzothiazolium
24.4 g of p-toluenesulfonate and 10.6 g of 2,6-dimethyl-4H-pyran-4-thione at 150℃
After heating reaction for 15 hours, methanol 50% was added to the reaction mixture.
ml, then 100 ml of acetone and 300 ml of ethyl acetate were added and stirred at room temperature to precipitate crystals. After collecting the crystals and washing them with a small amount of acetone, the crystals were added to a mixed solvent of 50 ml of methanol, 100 ml of acetone, and 300 ml of ethyl acetate at room temperature, stirred for 30 minutes, collected, and washed with acetone to obtain 12.7 g of the desired product. . (Yield 40%) Brown crystals, mp160-165℃ (decomposition) 1-(2) 5-methyl-3-ethyl-2-{(2,6
-dimethyl-4H-pyran-4-ylidene)
Methyl}benzothiazolium p-toluenesulfonate 5-methyl-3-ethyl-2-methylbenzothiazolium p-toluenesulfoner 13.4g and 2,
5.6 g of 6-dimethyl-4H-pyran-4-thione
After heating the reaction at 150°C for 15 hours, add 50 ml of methanol to the reaction mixture, then 60 ml of acetone, and 120 ml of ethyl acetate.
ml and stirred at room temperature to precipitate crystals. After taking the crystals and washing them with a small amount of acetone, add 50 ml of methanol, 60 ml of acetone, and 120 ml of ethyl acetate at room temperature.
The crystals were added to ml of mixed solvent, stirred for 30 minutes, collected, and washed with acetone to obtain 3.5 g of the desired product. (yield
20%) Brown crystals, mp244-246℃ (decomposition) 1-(3) 5-chloro-3-ethyl-2-{(2,6
-dimethyl-4H-pyran-4-ylidene)
Methyl}benzothiazolium p-toluenesulfonate 31.7 g of 5-chloro-3-ethyl-2-methylbenzothiazolium p-toluenesulfonate and 2,6-dimethyl-4H-pyran-4-thione
After heating reaction of 12.9 g at 150° C. for 15 hours, 50 ml of methanol, then 100 ml of acetone and 300 ml of ethyl acetate were added to the reaction mixture, and the mixture was stirred at room temperature to precipitate crystals. After collecting the crystals and washing them with a small amount of acetone, the crystals were added to a mixed solvent of 50 ml of methanol, 100 ml of acetone, and 30 ml of ethyl acetate at room temperature, stirred for 30 minutes, and washed with acetone to obtain 23.5 g of the desired product. .
(Yield 58%) Brown crystals, mp265-268℃ (decomposition) 1-(4) 3-ethyl-2-{(2,6-dimethyl-
4H-pyran-4-ylidene)methyl}-naphtho[2,1-d]thiazolium perchlorate 3-ethyl-2-methylnaphtho[2,1-d]
Thiazolium p-toluenesulfonate 1.9g and 2,6-dimethyl-4H-pyran-4-thione
After heating and reacting 0.7 g at 150° C. for 10 hours, 8 ml of methanol and then 12 ml of acetone were added to the reaction mixture to form a homogeneous solution. 1.2g of sodium perchlorate in this solution
(20 ml of water solution) was added dropwise and stirred at room temperature for 1 hour to precipitate crystals. After collecting the crystals and washing them with a small amount of acetone, the crystals were added to a mixed solvent of 15 ml of sewage water and 15 ml of acetone at room temperature, stirred for 15 minutes, and then collected.
After washing with acetone, 0.4 g of the target product was obtained. (yield 19
%) Brown crystals, mp245-250℃ (decomposition) 1-(5) 3-ethyl-2-{(2,6-dimethyl-
4H-pyran-4-ylidene)methyl}naphtho[1,2-d]thiazolium perchlorate 3-ethyl-2-methylnaphtho[1,2-d]
Thiazolium p-toluenesulfonate 1.9g and 2,6-dimethyl-4H-pyran-4-thione
From 0.7g, 0.55g of the target product was obtained in the same manner as in 1-(4). (Yield 27%) Brown crystals, mp228-230℃ (decomposition) 1-(6) 3-Methyl-2-{(2,6-dimethyl-
4H-pyran-4-ylidene)methyl}benzoxazolium perchlorate 1.5 g of 2,3-dimethylbenzoxazolium p-toluenesulfonate and 2,6-dimethyl-
After a heating reaction of 0.7 g of 4H-pyran-4-thione at 150° C. for 10 hours, 15 ml of methanol and then 12 ml of acetone were added to the reaction mixture to form a homogeneous solution. Add 1.2 g of sodium perchlorate (20 ml of water solution) to this solution,
After stirring for 1 hour at room temperature, crystals were precipitated. After taking the crystals and washing them with a small amount of acetone, place them under water at room temperature.
Add the crystals to a mixed solvent of 15 ml and acetone,
After stirring for 15 minutes, remove and wash with acetone to obtain the desired product.
Obtained 0.24g. (Yield 15%) Brown crystals, mp280℃ or higher (decomposition) Example 2 (Compound-1) 3-ethyl-2-{(2,6-dimethyl-4H-
Add 4.0 g of pyran-4-ylidene)methyl benzothiazolium p-toluenesulfonate and 4.2 g of 2-amino-4-dimethylaminobenzaldehyde to 150 ml of acetic anhydride, and heat under reflux on an oil bath at 100°C for 60 minutes. I let it happen. After cooling to room temperature, using a mixed solvent of methanol/chloroform = 1/5 (V/V),
The crystals obtained by purification through a silica gel column were added to 200 ml of ethanol to form a homogeneous solution. 2 g of sodium perchlorate (50 ml of water solution 5) was added dropwise to this solution and stirred for 1 hour at room temperature to precipitate crystals. The crystals were collected and recrystallized three times from ethanol-isopropanol to obtain 1.7 g of the desired product. Brown crystals, mp 270℃ or higher (decomposed) λ ^MeOH _nax 608 nm, ε ^MeOH _nax = ^4.80 The compound was synthesized in the same manner as the synthesis method, and the λ ^MeOH _nax value and crystal color tone of the obtained compound are shown in Table 1.

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Claims (1)

[Claims] 1. A methine dye represented by the following general formula []. [Formula, n represents 0 or 1, m represents 1 or 2, R ₁ represents an unsubstituted alkyl group or an alkyl group substituted with an alkoxy group or a phenyl group, R ₂ represents the general formula [ ] represents a group. Z is thiazole, benzothiazole, naphthothiazole, oxazole, benzoxazole, naphthoxazole, benzoselenazole,
Represents a group of atoms necessary to form a heterocycle selected from tellurazole, 3,3-dialkylindolenine, 2-pyridine, 4-pyridine, and 2-quinoline, and these rings include a methyl group, a methoxy group, an ethoxy group, It may be substituted with a group selected from a trifluoromethyl group and a chlorine atom. X
represents an anion. p represents 1 or 2, and p is 1 when the dye forms an inner salt. ) [Formula] (In the formula, R ₁₁ and R ₁₂ are unsubstituted alkyl groups, or alkyl groups having 18 or less carbon atoms substituted with a cyano group, a halogen atom, or an alkoxycarbonyl group having 8 or less carbon atoms as a substituent. and R ₁₁ and R ₁₂ may be linked to form a 5- or 6-membered ring. R ₁₃ and R ₁₄ are hydrogen atoms, unsubstituted alkyl groups, substituted or unsubstituted amino groups, carboxyl group, cyano group, hydroxy group, halogen atom, alkoxycarbonyl group having 8 or less carbon atoms,
Represents an alkoxy group having 2 to 8 carbon atoms, an alkoxy group having 8 or less carbon atoms, a carbamoyl group, or a sulfamoyl group, and R ₁₁ or R ₁₂ and R ₁₃ or R ₁₄ are linked to form a 5- or 6-membered ring. You may.
However, at least one of R ₁₃ and R ₁₄ is a substituted or unsubstituted amino group, carboxy group, cyano group, hydroxy group, halogen atom, alkoxycarbonyl group having 8 or less carbon atoms, an alkoxy group having 2 to 8 carbon atoms, Represents an acyloxy group, carbamoyl group, or sulfamoyl group having 8 or less carbon atoms.