JPH0528815B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel methine dye represented by the general formula []. (In the formula, n represents 0 or 1, m represents 0, 1, or 2. R ₁ represents a substituted or unsubstituted alkyl group, and R ₂ represents a substituted or unsubstituted aryl group or heterocyclic group. , R ₃ , R ₄ , and R ₅ may be the same or different from each other, and are hydrogen atoms, alkyl groups, alkoxy groups, hydroxy groups,
Represents a substituted or unsubstituted amino group or halogen atom, and also represents R ₃ and R ₄ , R ₃ and R ₅ or R ₄ and R ₅
may form a fused 6-membered ring. Z represents a group of nonmetallic atoms necessary to form a 5-membered ring or a 6-membered ring, and these rings may have a substituent or be fused with another ring. Here, other rings may be combined with R ₁ to further form a condensed ring. X represents an anion. p represents 1 or 2, and p is 1 when the dye forms an inner salt. ) 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 a substituted alkyl group {substituents include, for example, a carboxy group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), a hydroxy group, an alkoxycarbonyl group having 8 or less carbon atoms ( (e.g., methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxylcarbonyl group, etc.), alkoxy groups with 8 or less carbon atoms (e.g., methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.), 10 or less carbon atoms monocyclic aryloxy group (e.g. phenoxy group, p-
tolyloxy group, etc.), acyloxy group having 8 or less carbon atoms (e.g. acetyloxy group, propionyloxy group, etc.), acyl group having 8 or less carbon atoms (e.g. acetyl group, propionyl group, benzoyl group,
mesyl group, etc.), carbamoyl group (e.g. carbamoyl group, N,N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinocarbonyl group, etc.), sulfonyl group, piperidinosulfonyl group, etc.), an alkyl group having 18 or less carbon atoms substituted with an aryl group having 10 or less carbon atoms (e.g., phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group, etc.) group} is preferred. It is also preferable that R ₁ be fused with a benzene ring fused to the 5- or 6-membered ring represented by Z to further form a 5- or 6-membered ring. The aryl group for R ₂ is preferably a substituted or unsubstituted benzene ring group (eg, phenyl group, 4-nitrophenyl group, 4-chlorophenyl group, etc.), a substituted or unsubstituted naphthalene ring group, or the like. As the substituted benzene ring group for R ₂ , a group represented by the following general formula [] is more preferable. In the formula, R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ may be the same or different, and R ₁₁ to _{R 14} have a carbon number of 1 to
12 unsubstituted alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, vinylmethyl group, etc.) or substituted alkyl group {for example, carboxyl group as a substituent , cyano group, hydroxy group,
Sulfo group, halogen atom (e.g. fluorine atom, chlorine atom, etc.), alkoxycarbonyl group having 8 or less carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxylcarbonyl group, etc.), carbon number 8 The following alkoxy groups (e.g. methoxy group, ethoxy group,
benzyloxy group, phenethyloxy group, etc.),
Monocyclic aryloxy group having 10 or less carbon atoms (e.g. phenoxy group, p-tolyloxy group, etc.), acyloxy group having 3 or less carbon atoms (e.g. acetyloxy group, propionyloxy group, etc.), 8 carbon atoms
The following acyl groups (e.g. acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl group (e.g. carbamoyl group, N,N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group ( For example, sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.), aryl group having 10 or less carbon atoms (for example, phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α- An alkyl group having 18 or less carbon atoms substituted with a naphthyl group, etc.) is preferred. R ₁₃ and R ₁₄ are substituted or unsubstituted amino groups, carboxyl groups, cyano groups, hydroxy groups, sulfo groups, halogen atoms (e.g. fluorine atoms, chlorine atoms, etc.), and alkoxycarbonyl groups having 8 or less carbon atoms. (e.g. methoxycarbonyl group,
ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy groups with 8 or less carbon atoms (e.g. methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.), monocyclic groups with 10 or less carbon atoms. Aryloxy groups (e.g. phenoxy group, p-tolyloxy group, etc.), acyloxy groups having 8 or less carbon atoms (e.g. acetyloxy group, propionyloxy group, etc.),
Acyl group having 8 or less carbon atoms (e.g. acetyl group, propionyl group, benzoyl group, mesyl group, etc.),
Carbamoyl group (e.g. carbamoyl group, N,N
-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), and sulfamoyl groups (e.g., sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.) are also preferred. As unsubstituted or substituted amino groups for R ₁₃ and R ₁₄ ,

[Formula], and R ₁₇ and R ₁₈ may be the same or different, and include a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), and a carbon number Preferably, it has 2 to 8 acyl groups (eg, acetyl group, propionyl group, benzoyl group, etc.). Further, R ₁₇ and R ₁₈ may form a ring. Further, R ₁₃ and R ₁₄ may form a benzo-fused ring, and it is also preferable that R ₁₁ or R ₁₂ and R ₁₃ or R ₁₄ are connected to form a 5-membered ring or a 6-membered ring, It is also preferred that ₁₁ and R ₁₂ be linked to form a 5-membered ring or a 6-membered ring. The alkyl group for R ₃ , R ₄ , R ₅ is preferably a lower alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, isopropyl group, butyl group, etc.), and the alkoxy group is preferably a lower alkyl group having 1 to 4 carbon atoms. The alkoxy groups up to (eg, methoxy, ethoxy, propoxy, butoxy, etc.) are preferred. As unsubstituted or substituted amino groups for R ₃ , R ₄ , and R ₅ ,

[Formula], and R ₁₅ and R ₁₆ may be the same or different, and include a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), and a carbon number Preferably, it has 2 to 8 acyl groups (eg, acetyl group, propionyl group, benzoyl group, etc.). In addition, R ₁₅ and R ₁₆ are connected to each other, and a 5-membered ring or a 6-membered ring is formed.
It is also preferable to form a membered ring. Furthermore, R ₁₅ and/or R ₁₆ may combine with the benzene ring of the benzopyrylium nucleus to form a condensed ring. In addition, as the heterocyclic group for R ₂ , pyrazole nucleus,
1,2-dihydro-1-azaazulene-2-one nucleus, pyrrolo[5,1-b]quinazolin-9-one nucleus, indole nucleus, pyrrole nucleus, pyrrolo[2,3
-b] Pyridine core is preferred. Z represents an atomic group necessary to form a 5- or 6-membered ring, such as a thiazole nucleus (e.g., thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole). , 4,5-dimethylthiazole,
4,5-diphenylthiazole, 4,(2-thienylthiazole, etc.), benzothiazole core (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
-fluorobenzothiazole, 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 nuclei (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 nuclei (e.g. selenazole, 4-methylselenazole, 4-phenylselenazole, 4,5-diphenylselenazole, etc.),
benzoselenazole core (e.g. benzoselenazole, 5-chlorobenzoselenazole, 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. benzotellazole, 5
-Methylbenzotelllazole, 5,6-dimethylbenzotelllazole, naphtho[1,2-d]telllazole, naphtho[2,1-d]telllazole,
naphtho[2,3-d]tellazole, 6-methoxynaphtho[1,2-d]tellazole, etc.), thiazoline nuclei (e.g. thiazoline, 4-methylthiazoline, 4-phenylthiazoline, etc.), oxazoline nuclei, e.g. 5, 5-dimethyloxazoline, etc.),
Isoxazole nucleus (e.g. 5-methylisoxazole etc.), benzisoxazole nucleus (e.g. benzisoxazole etc.), 3,3-dialkylindolenine nucleus (e.g. 3,3-dimethylindolenine, 3,3,5-trimethyl indolenine, 5-chloro-3,3-dimethylindolenine, 5-ethoxycarbonyl-3,3-dimethylindolenine, etc.), 2-pyridine nucleus (e.g. pyridine, 5-methylpyridine, etc.), 4-pyridine nucleus ( For example, pridine), 2-quinoline nucleus (for example, 6
-Ethoxyquinoline, 6-ethylquinoline, 6-
chloroquinoline, 8-fluoroquinoline, etc.),
4-quinoline nucleus (e.g. 8-methylquinoline, 8
-fluoroquinoline, 6-chloroquinoline, etc.),
1-isoquinoline nucleus (e.g. isoquinoline etc.),
is preferred. X represents an anion, and specifically preferred are chloride, bromide, iodide, thiocyanate, perchlorate, paratoluenesulfonate, and tetrafluoroborate. 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 4-methyl-2H-chromene- It can be obtained by a condensation reaction between intermediate [A] obtained by reaction with a 2-thione derivative and an aldehyde. In the above reaction formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , 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 N ^d :YAG laser, and can obtain laser light in the near-infrared to infrared region. It 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. Next, examples of synthesizing 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-{(4-methyl-2H-
chromen-2-ylidene)methyl}benzothiazolium perchlorate 3-ethyl-2-methylbenzothiazolium
17.5 g of p-toluenesulfonate and 4-methyl-
After heating 8.8 g of 2H-chromene-2-thione at 150° C. for 15 hours, 20 ml of methanol and 40 ml of acetone were added to the reaction mixture to form a homogeneous solution. After cooling to room temperature, 15.7 g of 60% perchloric acid was added and stirred at room temperature to precipitate crystals. The crystals were collected by filtration, washed with a small amount of acetone, then added to a mixed solvent of 20 ml of methanol and 40 ml of acetone at room temperature, stirred for 30 minutes, collected by filtration, and washed with acetone to obtain 8.5 g of the desired product. (Yield 40%) Brown crystal mp280℃ or higher (decomposition) 1-(2) 5-trifluoromethyl-3-ethyl-
2-{(4-Methyl-2H-chromen-2-ylidene)methyl}benzothiazolium p-toluenesulfonate 5-trifluoromethyl-3-ethyl-2-methylbenzothiazolium p-toluenesulfonate 2.37 After a heating reaction of 1.0 g of 4-methyl-2H-chromene-2-thione and 1.0 g of 4-methyl-2H-chromene-2-thione at 150° C. for 20 hours, 10 ml of methanol, followed by 10 ml of acetone and 20 ml of ethyl acetate were added to the reaction mixture to form a homogeneous solution. When cooled to room temperature, crystals precipitated. After filtering the crystals and washing with a small amount of acetone, add 10 ml of methanol at room temperature,
The crystals were added to a mixed solvent of 10 ml of acetone and 20 ml of ethyl acetate, stirred for 40 minutes, collected by filtration, and washed with acetone to obtain 1.47 g of the desired product. (Yield 46%) Brown crystals mp272-273℃ (decomposition) 1-(3) 5-chloro-3-ethyl-2-{(4-methyl-2H-chromen-2-ylidene)methyl}
Benzothiazolium p-toluenesulfonate 11.1 g of 5-chloro-3-ethyl-2-methylbenzothiazolium p-toluenesulfonate and 5.5 g of 4-methyl-2H-chromene-2-thione.
After heating the reaction at 150°C for 23 hours, add 25 ml of methanol to the reaction mixture, then 50 ml of acetone, and 150 ml of ethyl acetate.
ml was added and cooled to room temperature, crystals precipitated.
After filtering the crystals and washing with a small amount of acetone, add 25 ml of methanol, 50 ml of acetone, and ethyl acetate at room temperature.
Add the crystals to 150ml of mixed solvent and stir for 20 minutes.
It was collected by filtration and washed with acetone to obtain 7.9 g of the desired product. (Yield 52%) Brown crystal mp282-283℃ or higher (decomposition) 1-(4) 5-methyl-3-ethyl-2-{(4-methyl-2H-chromen-2-ylidene)methyl}
Benzothiazolium perchlorate 2.07 g of 5-methyl-3-ethyl-2-methylbenzothiazolium p-toluenesulfonate and 1.0 g of 4-methyl-2H-chromene-2-thione.
After heating reaction at 150℃ for 25 hours, add 10ml of methanol to the reaction mixture, then 10ml of acetone, and 20ml of ethyl acetate.
was added and cooled to room temperature, crystals precipitated. After the crystals were collected by filtration and washed with a small amount of acetone, 20 ml of methanol and then 40 ml of acetone were added to form a homogeneous solution at room temperature. Add 5g of 60% perchloric acid to this,
After stirring at room temperature for 30 minutes, the precipitated crystals were collected by filtration and washed with acetone to obtain 1.46 g of the desired product. (Yield 55%) Brown crystal mp270-275℃ or higher (decomposition) 1-(5) 5-methoxy-3-ethyl-2-{(4-
Methyl-2H-chromen-2-ylidene)methyl}benzothiazolium iodide 5-methoxy-3-ethyl-2-methylbenzothiazolium p-toluenesulfonate 2.15g
and 1.0 g of 4-methyl-2H-chromene-2-thione
After heating and reacting at 150° C. for 20 hours, 15 ml of methanol and 12 ml of acetone were added to the reaction mixture to make a homogeneous solution. 1.7 g of sodium iodide (5 ml solution in acetone) was added dropwise to this solution and stirred at room temperature to precipitate crystals. After collecting the crystals by filtration and washing them with a small amount of acetone, the crystals were added to 20 ml of room temperature sewage water and stirred for 15 minutes.
It was collected by filtration and washed with acetone to obtain 1.02 g of the target product.
(Yield 38%) Brown crystals mp273-274℃ (decomposition) 1-(6) 3-ethyl-2-{(4-methyl-2H-
chromen-2-ylidene)methyl}-naphtho[2,1-d]thiazolium iodide 3-ethyl-2-methylnaphtho[2,1-d]
Thiazolium p-toluenesulfonate 2.27g
and 1.0 g of 4-methyl-2H-chromene-2-thione
After heating and reacting at 150°C for 21 hours, 8 ml of methanol and then 12 ml of acetone were added to the reaction mixture to form a homogeneous solution. Add 1.7 g of sodium iodide (5 ml of water) to this solution.
ml solution) was added dropwise and stirred at room temperature for 1 hour to precipitate crystals. The crystals were collected by filtration and washed with a small amount of acetone, then added to a mixed solvent of 15 ml of sewage water and 15 ml of acetone at room temperature, stirred for 15 minutes, collected by filtration, and washed with acetone to obtain 0.8 g of the desired product. . (Yield 28%) Brown crystal mp280℃ or higher (decomposition) 1-(7) 3-(2-methoxyethyl)-2-{(4-
Methyl-2H-chromen-2-ylidene)methyl}benzothiazolium perchlorate 3-(2-methoxyethyl)-2-methylbenzothiazolium p-toluenesulfonate 4.3g and 4-methyl-2H-chromene 1.1 g of the target product was obtained from 1.0 g of -2-thione in the same manner as in 1-(1). (Yield 43%) Brown crystal mp280℃ or higher (decomposition) 1-(8) 5,6-dimethyl-3-ethyl-2-
{(4-methyl-2H-chromen-2-ylidene)
Methyl}benzothiazolium p-toluenesulfonate 5,6-dimethyl-3-ethyl-2-methylbenzothiazolium p-toluenesulfonate
26.0g and 4-methyl-2H-chromene-2-thione
After heating and reacting 13.2 g at 150° C. for 17 hours, 50 ml of methanol, then 100 ml of acetone and 300 ml of ethyl acetate were added to the reaction mixture, and upon cooling to room temperature, crystals were precipitated. After filtering the crystals and washing them with a small amount of acetone, add 50 ml of methanol, 100 ml of acetone,
Add the crystals to a mixed solvent of 300 ml of ethyl acetate, and add 20
After stirring for several minutes, filter it and wash with acetone to obtain the desired product.
Obtained 16.2g. (Yield 45%) Brown crystal mp201-203℃ or higher (decomposition) 1-(9) 3-methyl-2-{(4-methyl-2H-
chromen-2-ylidene)methyl}benzoxazolium perchlorate 2,3-dimethylbenzoxazolium p-
2.1g of toluenesulfonate and 4-methyl-2H-
After heating and reacting 1.2 g of chromene-2-thione at 150°C for 10 hours, 15 ml of methanol and acetone were added to the reaction mixture.
12 ml was added to make a homogeneous solution. 1.2 g of sodium perchlorate (5 ml of water solution) was added dropwise to this solution and stirred at room temperature to precipitate crystals. The crystals were collected by filtration, washed with a small amount of acetone, then added to 10 ml of sewage water, 10 ml of methanol, and 20 ml of ethyl acetate at room temperature, stirred for 15 minutes, collected by filtration, and washed with ethyl acetate to obtain 0.3 g of the desired product.
I got it. (Yield 12%) Brown crystals mp269-271℃ (decomposition) 1-(10) 3-ethyl-2-{(4-methyl-2H-
chromen-2-ylidene)methyl}naphtho[1,2-d]thiazolium iodide 3-ethyl-2-methylnaphtho[1,2-d]
Thiazolium p-toluenesulfonate 2.27g
and 1-(6) from 1.0 g of 4-methyl-2-thiocoumarin.
0.08g of the target product was obtained in the same manner as above. (Yield 3.5%) Brown crystal mp 140-142°C (decomposition) Example 2 (Synthesis of compound-1) 3-ethyl-2-{(4-methyl-2H-chromen-2-ylidene)methyl}benzothiazo 3.0 g of lium perchlorate and 1.1 g of 4-dimethylaminobenzaldehyde were added to 30 ml of acetic anhydride, and the mixture was heated to reflux on an oil bath at 150° C. for 45 minutes. After cooling to room temperature, the precipitated crystals were collected and washed with methanol. Recrystallization was performed five times from methanol-chloroform to obtain 0.4 g of the desired product. Green-black crystal mp209-211℃ λ ^MeOH _nax 594nm 〓 ^MeOH _nax = 3.83×10 ⁴ Example 3 (Synthesis of compound-2) 3-ethyl-2-{(4-methyl-2H-chromen-2-ylidene)methyl } 3.0 g of benzothiazolium perchlorate and 1.5 g of 4-dimethylaminocinnamaldehyde were added to 50 ml of acetic anhydride, and heated under reflux at 150° C. for 40 minutes on an oil bath. After cooling to room temperature, 100 ml of ethyl acetate was added, and stirring was continued at room temperature for 30 minutes. The precipitated crystals were purified through a silica gel column using a mixed solvent of methanol/chloroform = 1/9 (v/v), and then recrystallized twice in methanol/chloroform to obtain 0.4 g of the desired product. Dark green crystal mp195-196℃ (decomposition) λ ^MeOH _nax 606 nm 〓 ^MeOH _nax = 5.32×10 ⁴ Example 4 (Synthesis of compound-3) 3-ethyl-2-{(4-methyl-2H-chromene-2- ylidene) methyl}benzoxazolium perchlorate 2.5 g and 1,8-trimethylene-1,2,3,4-tetrahydroquinoline-6-
Add 1.5 g of aldehyde to 50 ml of acetic anhydride and place on oil bath.
The mixture was heated under reflux at 150°C for 45 minutes. After cooling to room temperature,
The precipitated crystals were collected, washed with methanol, and recrystallized three times from methanol-chloroform to obtain 2.1 g of the desired product. Dark green crystal mp265-268℃ (decomposed) λ ^MeOH _nax 678nm 〓 ^MeOH _nax = 5.23×10 ⁴ Example 5 (Synthesis of compound 46) 3-ethyl-5-trifluoromethyl-2-
{(4-methyl-2H-chromen-2-ylidene)
Add 6.5 g of methyl}benzothiazolium p-toluenesulfonate and 2.6 g of 4-dimethylaminocinnamaldehyde to 100 ml of acetic anhydride, and heat on an oil bath at 150°C.
The mixture was heated under reflux for 7 minutes. After cooling to room temperature, it was purified through a silica gel column using a mixed solvent of methanol/chloroform = 2/8 (v/v). The obtained crystals were dissolved in methanol and cooled to 0°C, then 2.8 g of sodium perchlorate (50 ml of water) was added.
Aqueous solution was added. The precipitated crystals were collected and recrystallized three times from methanol-chloroform to obtain 3.5 g of the desired product. Dark green crystal mp 231°C (decomposed) λ ^MeOH _nax 624 nm ^MeOH _nax = 5.63×10 ⁴ Example 6 The methine dye shown below was also synthesized in the same manner as shown in Examples 2-5. The λ ^MeOH _nax and crystal color tone of the obtained compound are shown below.

[Table] Example 7 (Synthesis of compound-53) 3-ethyl-2-{(4-methyl-2H-chromen-2-ylidene)methyl}benzothiazolium perchlorate 3.0 g and 2-amino-4-dimethyl 1.3 g of aminobenzaldehyde was added to 30 ml of acetic anhydride, and the mixture was heated to reflux on an oil bath at 150° C. for 30 minutes.
After cooling to room temperature, the precipitated crystals were collected by filtration and washed with methanol. Recrystallization was performed five times from methanol-chloroform to obtain 0.8 g of the desired product. Dark black crystal mp220-225℃ λ ^MeOH _nax 588nm 〓 ^MeOH _nax = 3.80×10 ⁴ Example 8 (Synthesis of compound-55) 3-ethyl-2-{(4-methyl-2H-chromen-2-ylidene)methyl }Add 3.0 g of benzothiazolium perchlorate and 1.5 g of 2-hydroxy-4-diethylaminobenzaldehyde to 50 g of acetic anhydride.
ml and heated under reflux on an oil bath at 150°C for 40 minutes. After cooling to room temperature, add 100ml of ethyl acetate and stir at room temperature.
Stirring was continued for 30 minutes. The precipitated crystals are mixed with methanol/
The product was purified through a silica gel column using a mixed solvent of chloroform = 1/9 (v/v), and then recrystallized twice from methanol-chloroform to obtain 0.7 g of the target product. Dark green crystal mp231-233℃ (decomposition) λ ^MeOH _nax 598nm 〓 ^MeOH _nax = 4.02×10 ⁴ Example 9 (Synthesis of compound-61) 3-ethyl-5-chloro-2-{(4-methyl-
2.5 g of 2H-chromen-2-ylidene)methyl}benzothiazolium perchlorate and 1.5 g of 5-methoxy-1,8-trimethylene-1,2,3,4-tetrahydroquinoline-6-aldehyde were added to 50 ml of acetic anhydride. and heated to reflux on an oil bath at 150°C for 45 min. After cooling to room temperature, the precipitated crystals were collected by filtration,
After washing with methanol, recrystallization was performed three times from methanol-chloroform to obtain 2.1 g of the desired product. Dark green crystal mp 275-278°C (decomposed) λ ^MeOH _nax 670 nm ^MeOH _nax =5.21×10 ⁴ Example 10 The methine dye shown below was also synthesized in the same manner as shown in Examples 5-9. The λ ^MeOH _nex and crystal color tone of the obtained compound are shown below.

【table】

【table】

Claims (1)

[Claims] 1. A methine dye represented by the following general formula []. (In the formula, n represents 0 or 1, m represents 0, 1, or 2. R ₁ represents a substituted or unsubstituted alkyl group, and R ₂ represents a substituted or unsubstituted aryl group or heterocyclic group. , R ₃ , R ₄ , and R ₅ may be the same or different from each other, and are hydrogen atoms, alkyl groups, alkoxy groups, hydroxy groups,
Represents a substituted or unsubstituted amino group or halogen atom, and also represents R ₃ and R ₄ , R ₃ and R ₅ or R ₄ and R ₅
may form a fused 6-membered ring. Z represents a group of nonmetallic atoms necessary to form a 5-membered ring or a 6-membered ring, and these rings may have a substituent or be fused with another ring. Here, other rings may be combined with R ₁ to further form a condensed ring. X represents an anion. p represents 1 or 2, and p is 1 when the dye forms an inner salt. )