JPH0617989B2 - New methine dye - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel methine dye represented by the general formula [I].

General formula [I] In the above general formula [I], each substituent is represented as follows. That is, n represents 0 or 1, and m represents 1 or 2. R
₁ represents a substituted or unsubstituted alkyl group, R ₂ ,
R ₃ and R ₄ may be the same or different from each other and represent a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a substituted or unsubstituted amino group or a halogen atom, and R ₂ and R ₃ , R ₃ And R ₄ or R ₂ and R ₄ may form a condensed 6-membered ring. Z ₁ represents an atomic group necessary for forming a 5-membered ring or a 6-membered ring, and those rings may have a substituent or may be condensed with another ring. Z ₂ represents an atomic group necessary for forming a 5-membered ring or a 6-membered ring, and those rings may have a substituent or may be condensed with another ring. L ₁ and L ₂ may be the same or different and each represents a methine group or a substituted methine group.

Each substituent of the compound represented by formula [I] is preferably the following substituent.

That is, R ₁ is an unsubstituted alkyl group having 18 or less carbon atoms (eg, 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 {for example, as a substituent, a carboxy group,
Sulfo group, cyano group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom), hydroxy group, alkoxycarbonyl group having 8 or less carbon atoms (for example, methoxycarbonyl group, ethoxycarbonyl group, phenylcarbonyl group, Benzyloxycarbonyl group, etc.), 8 carbon atoms
The following alkoxy groups (eg, methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.), Monocyclic aryloxy groups having 10 or less carbon atoms (eg, phenoxy group, p-tolyloxy group, etc.), Acyloxy having 3 or less carbon atoms Group (eg acetyloxy group, propionyloxy group etc.), acyl group having 8 or less carbon atoms (eg acetyl group, propionyl group, benzoyl group, mesyl group etc.)
Carbamoyl group (eg, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (eg, sulfamoyl group, N, N-dimethylsulfamoyl group,
Morpholinosulfonyl group, piperidinosulfonyl group, etc., aryl group having 10 or less carbon atoms (eg, phenyl group,
4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group and the like) and the like, an alkyl group having 18 or less carbon atoms} is preferable.

The alkyl group of R ₂ , R ₃ and R ₄ has 1 to 4 carbon atoms.
Up to lower alkyl groups (eg, methyl group, ethyl group, isopropyl group, butyl group, etc.) are preferred, and for alkoxy groups, alkoxy groups having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.) ) Is preferred.

The halogen atom of R _{2 to} R ₄ is preferably a fluorine atom, a chlorine atom or a bromine atom.

As the substituted or unsubstituted amino group of R _{2 to} R ₄ , And R ₁₁ and R ₁₂ may be the same or different and each is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, etc.), 2 carbon atoms. The acyl group of 8 to 8 (eg, acetyl group, propionyl group, benzoyl group, etc.) is preferable.

It is also preferable that R ₁₁ and R ₁₂ are connected to each other to form a 5-membered ring or a 6-membered ring.

Further, R ₁₁ and R ₁₂ may combine with the benzene ring of the benzopyran nucleus to form a condensed 5-membered or 6-membered ring.

Z ₁ represents an atomic group necessary for forming a 5- or 6-membered ring, and the ring is, for example, a thiazole nucleus (eg, thiazole,
4-methylthiazole, 4-phenylthiazole, 5-
Methylthiazole, 5-phenylthiazole, 4,5-
Dimethylthiazole, 4,5-diphenylthiazole,
4, (2-thienyl) thiazole, etc.), benzothiazole nucleus (eg, 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-methoxybenzo Thiazole, 6-
Methoxybenzothiazole, 5-carboxybenzothiazole, 5-cyanobenzothiazole, 5-fluorobenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5-hydroxybenzothiazole, 6-hydroxybenzo Thiazole, etc., naphthothiazole nucleus (for example, 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 (for example, 4-methyloxazole, 5-methyloxazole, 4-phenyloxazole, 4,5) -Diphenyloxazole, 4-ethyloxazole, 4,5-
Dimethyloxazole, 5-phenyloxazole, etc.), benzoxazole nucleus (for example, benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-)
Methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5
-Methoxybenzoxazole, 5-ethoxybenzoxazole, 5fluorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc., naphthoxazole nucleus (for example, naphtho [1,2-d] oxazole) , Naphtho [2,1-d] oxazole, naphtho [2,3-d] oxazole, etc.), selenazole nucleus (eg, selenazole, 4-methylselenazole, 4-phenylselenazole, 4,5-diphenylselenazole). Etc.), benzoselenazole nucleus (for example, benzoselenazole, 5-chlorobenzoselenazole, 5-methylbenzoselenazole, 5-methoxybenzoselenazole, 5-
Phenylbenzoselenazole, etc.), naphthoselenazole nucleus (eg, naphtho [1,2-d] selenazole, naphtho [2,1-d] selenazole, naphtho [2,3-d] selenazole, etc.), thiazoline nucleus (eg, Thiazoline, 4
-Methylthiazoline, 4-phenylthiazoline etc.), oxazoline nucleus (eg 5,5-dimethyloxazoline etc.), isoxazole nucleus (eg 5-methylisoxazole etc.), benzisoxazole nucleus (eg benzoisoxazole etc.), 3,3-dialkylindolenine nucleus (eg 3,3-dimethylindolenine, 3,3
3,5-trimethylindolenine, 5-chloro-3,3
-Dimethylindolenine, 5-ethoxycarbonyl-
3,3-dimethylindolenine etc.), 2-pyridine nucleus (eg pyridine, 5-methylpyridine etc.), 4-pyridine nucleus (eg pyridine etc.), 2-quinoline nucleus (eg 6-ethoxyquinoline, 6-ethylquinoline). , 6-chloroquinoline, 8-fluoroquinoline etc.), 4-quinoline nucleus (eg 8-methylquinoline, 8-fluoroquinoline, 6-chloroquinoline etc.), 1-isoquinoline nucleus (eg isoquinoline etc.), benzotellurazole nucleus (For example, benzotellurazole, 5-chlorobenzotellurazole, 5-methylbenzotellurazole, 5-methoxybenzotellurazole, etc.), naphthotelluazole nucleus (for example, naphtho [1,2-d] tellurazole, naphtho [2,2 1-d] tellurazole and the like) are preferable.

Z ₂ is preferably a rhodanine ring, a hydantoin ring, 2
-Thiohydantoin ring, oxazolidine-2,4-dione ring, 2-thiooxazolidine-2,4-dione ring, 2
-Thioselenazolidine-2,4-dione ring, 5-pyrazolone ring, indandione ring, 5 (4H) -isoxazolone ring, 2,4-chromandione ring, 4,6- (1H,
5H) an atomic group necessary for forming a pyridinedione ring, a barbituric acid ring, a 2-thiobarbituric acid ring, a 1,3-dioxane-4,6-dione ring, and a 3,5-pyrazolidinedione ring. Represent.

These heterocycles represented by Z ₂ may have a substituent.

As a substituent, an unsubstituted alkyl group having 18 or less carbon atoms (eg, 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 (as a substituent, for example, a carboxy group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom or a bromine atom), a hydroxy group,
An alkoxycarbonyl group having 8 or less carbon atoms (eg, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.), an alkoxy group having 8 or less carbon atoms (eg, methoxy group, ethoxy group, benzyloxy group, Phenethyloxy group, etc.), a substituted alkoxy group having 12 or less carbon atoms (for example, hydroxymethoxy group, 2-hydroxyethoxy group, acetoxymethoxy group, 2-acetoxyethoxy group, 2-methoxyethoxy group, etc.) aryl group having 10 or less carbon atoms ( For example, phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group, etc.) Monocyclic aryloxy group having 10 or less carbon atoms (for example, phenoxy group, p-tolyloxy group, etc.), acyloxy having 3 or less carbon atoms. Groups (eg acetyloxy groups, groups Pionyloxy group etc.), acyl group having 8 or less carbon atoms (eg acetyl group, propionyl group, benzoyl group, mesyl group etc.), carbamoyl group having 12 or less carbon atoms (eg carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl) Group, piperidinocarbonyl group, N- (3-N, N-dimethylaminopropyl) carbamoyl group, N- (2-N, N-diethylaminoethyl) carbamoyl group, N- (3-morpholinopropyl) carbamoyl group, N- (3-piperidinopropylcarbamoyl group, N- (3-pyrrolidinopropyl) carbamoyl group, etc.), sulfamoyl group having 12 or less carbon atoms (eg, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl) Group, piperidinosulfonyl group, N- (3-N, N-dimethyl) Luaminopropyl) sulfamoyl group, N- (3-morpholinopropyl) sulfamoyl group, N- (3-piperidinopropyl) sulfamoyl group, etc., dialkylamino group having 12 or less carbon atoms (for example, dimethylamino group, diethylamino group, Piperidino group, morpholino group, etc.), carbon number 1
A heterocyclic group of 0 or less (for example, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-thiazole group, 2-benzothiazole group, tetrahydro-2-furanyl group, 2-furanyl group, etc.), etc. Substituted alkyl group having 18 or less carbon atoms, aryl group having 12 or less carbon atoms (for example, phenyl group, p-chlorophenyl group, p-methylphenyl group, p-methoxyphenyl group, p-carboxyphenyl group, p- Methoxycarbonylphenyl group, m-acetylaminophenyl group, m-dimethylaminophenyl group, p
-Dimethylaminophenyl group, etc.), a heterocyclic group having 10 or less carbon atoms (eg, 2-pyridyl group, 3-pyridyl group, 4
-Pyridyl group, thiazole group, 2-furanyl group, etc.) are preferred.

L ₁ and L ₂ represent a methine group or a substituted methine group, and as the substituent, an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), a carbon number 6
-10 aryl group (eg, phenyl group, 2-carboxyphenyl group, 4-methylphenyl group, 2-chlorophenyl group, etc.), substituted alkyl group having 1 to 9 carbon atoms (eg, chloromethyl group, benzyl group, 2-phenylethyl group) Base,
3-phenylpropyl group, methoxyethyl group, etc.) are preferred. It is also preferable that the substituents are linked to each other to form a 6-membered ring on the methine chain.

The compound represented by the general formula [I] can be synthesized by various synthetic methods. For example, as shown in the following reaction formula,
It can be obtained by the condensation reaction of the intermediate [A] and the intermediate [B] obtained by the reaction of the heterocyclic quaternary salt derivative having an active methyl group and the 4-methyl-2-thiocoumarin derivative.

In the reaction of the above formula, R ₁ , R ₂ , R ₃ , R ₄ , Z ₁ , Z ₂ , L
₁ , L ₂ , n and m have the same meanings as described in the general formula [I].

L ₃ , L ₄ and L ₅ represent a methine group or a substituted methine group.

X₁ , X_Two Represents an anion, specifically, black
Ride, bromide, iodide, thiocyanate, park
Lorate, paratoluene sulfonate, tetrafluorobo
Represents a rat etc.

p is 1 or 2, and p is 1 when the intermediate [A] forms an intramolecular salt.

Y represents a leaving group that is usually used in dye synthesis, and includes, for example, a substituted amino group (eg, dimethylamino group, N
—Methylanilino group, anilino group, N-acetylanilino group), alkoxy group (eg, methoxy group, ethoxy group), alkylthio group (eg, methylthio group, ethylthio group) and the like. In the condensation reaction, a base catalyst such as triethylamine, pyridine, 4-dimethyl, aminopyridine, sodium acetate, sodium hydroxide is usually used.

The novel methine dye of the present invention has excellent fastness and is effective as a dye for filters, and is also effective as a dye and a sensitizing dye for photographic light-sensitive materials. These dyes also dye mixtures from groundwood and bleached sulphite pulps as well as pure pulp and are virtually completely dyed. Further, these dyes can obtain laser light in the near infrared to infrared region by being excited by an excitation method such as excimer laser, argon laser, second harmonic or third harmonic of Nd: YAG laser, It acts as a high-performance laser dye with good robustness and high energy conversion efficiency.

Specific examples of the compound represented by formula (I) of the present invention are shown below, but the invention is not limited thereto.

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43. Next, examples of the compound according to the present invention will be described in detail below.

Example-1 (Synthesis of Intermediate [A]) 1- (1) 3-Ethyl-2-{(4-methyl-2H-chromene-2-ylidene) methyl} benzothiazolium
p-Toluene sulfonate 3-ethyl-2-methylbenzothiazolium 27 g of p-toluene sulfonate and 15 g of 4-methyl-2-thiocoumarin were heated and reacted at 150 ° C. for 15 hours, and then the reaction mixture was mixed with 40 ml of methanol and 80 ml of acetone. 200 ml of ethyl acetate was added to make a homogeneous solution. Crystals precipitated upon stirring at room temperature. The crystals were collected and washed with a small amount of acetone, and then the crystals were added to a mixed solvent of 20 ml of methanol and 40 ml of acetone at room temperature, and 200 ml of ethyl acetate was further added to the mixture.
After stirring for a minute, it was collected and washed with acetone to obtain 15.3 g of the desired product. (Yield 40%) Brown crystals mp 280 ° C. or higher (decomposition) 1- (2) 5-trifluoromethyl-3-ethyl-2-
1. {(4-Methyl-2H-chromen-2-ylidene) methyl} -benzothiazolium p-toluenesulfonate 5-trifluoromethyl-3-ethyl-2-methylbenzothiazolium p-toluenesulfonate 2. 37 g
After heating and reacting 1.0 g of 4-methyl-2-thiocoumarin at 150 ° C. for 20 hours, 10 ml of methanol was added to the reaction mixture,
Next, 10 ml of acetone and 20 ml of ethyl acetate were added to make a uniform solution. Crystals precipitated upon cooling to room temperature. The crystals were collected and washed with a small amount of acetone, and then the crystals were added to a mixed solvent of 10 ml of methanol, 10 ml of acetone and 20 ml of ethyl acetate at room temperature, stirred for 40 minutes, collected, and washed with acetone to obtain 1.47 g of the desired product. Got (Yield 46%) Brown crystals mp 272 to 273 ° C. (decomposition) 1- (3) 5-chloro-3-ethyl-2-{(4-methyl-2H-chromene-2-ylidene) methyl} -benzothiazo Lithium p-toluenesulfonate 5-chloro-3-ethyl-2-methylbenzothiazolium 11.1 g of p-toluenesulfonate and 5.5 g of 4-methyl-2-thiocoumarin were heated at 150 ° C. for 23 hours, and then reacted. To the reaction mixture were added 25 ml of methanol, 50 ml of acetone and 150 ml of ethyl acetate, and the mixture was cooled to room temperature to precipitate crystals. Crystals were collected and washed with a small amount of acetone, then at room temperature methanol 25 ml, acetone 50 m
Crystals were added to a mixed solvent of l and 150 ml of ethyl acetate, and 2
After stirring for 0 minutes, it was taken and washed with acetone to obtain 7.9 g of the desired product.
Got (Yield 52%) Brown crystals mp 282-283 ° C. (decomposition) 1- (4) 5-methyl-3-ethyl-2-{(4-methyl-2H-chromene-2-ylidene) methyl} benzothiazolium , Perchlorate 5-methyl-3-ethyl-2-methylbenzothiazolium p-toluenesulfonate 2.07 g and 4-methyl-2-thiocoumarin 1.0 g were reacted by heating at 150 ° C. for 25 hours, and then methanol was added to the reaction mixture. 10 ml, then 10 ml of acetone and 20 ml of ethyl acetate were added, and the mixture was cooled to room temperature to precipitate crystals. The crystals were collected and washed with a small amount of acetone, and then 20 ml of methanol and then 40 ml of acetone were added at room temperature to obtain a uniform solution. 60% perchloric acid here 5
g was added, the mixture was stirred at room temperature for 30 minutes, and the precipitated crystals were collected and washed with acetone to obtain 1.46 g of the desired product. (Yield 55%) Brown crystals mp 270-275 ° C. (decomposition) 1- (5) 5-methoxy-3-ethyl-2-{(4-methyl-2H-chromen-2-ylidene) methyl} benzothiazolium After heating and reacting iodide 5-methoxy-3-ethyl-2-methylbenzothiazolium 2.15 g and 4-methyl-2-thiocoumarin 1.0 g for 20 hours at 150 ° C., the reaction mixture contains 15 ml of methanol. , Acetone 1
2 ml was added to make a homogeneous solution. Sodium iodide (1.7 g, acetone 5 ml solution) was added dropwise to this solution, and the mixture was stirred at room temperature to precipitate crystals. The crystals were taken, washed with a small amount of acetone, added to 20 ml of water at room temperature, stirred for 15 minutes, taken, and washed with acetone to obtain 1.02 g of the desired product. (Yield 38%) Brown crystals mp 273 to 274 ° C. (decomposition) 1- (6) 3-ethyl-2-{(4-methyl-2H-chromene-2-ylidene) methyl} -naphtho [2,1-
d] thiazolium iodide 3-ethyl-2-methylnaphtho [2,1-d] thiazolium p-toluenesulfonate 2.27 g and 4-methyl-2-thiocoumarin 1.0 g were heated at 150 ° C. for 21 hours, and then the reaction mixture was added. To the solution, 8 ml of methanol and then 12 ml of acetone were added to make a uniform solution. 1.7 g of sodium iodide (5 ml of water solution) was added dropwise to this solution and stirred at room temperature for 1 hour to precipitate crystals. The crystals were collected and washed with a small amount of acetone, and then the crystals were added to a mixed solvent of water (15 ml) and acetone (15 ml) at room temperature. After stirring for 15 minutes, the crystals were collected and washed with acetone to obtain 0.8 g of the desired product. (Yield 28%) Brown crystal mp 280 ° C. or higher (decomposition) 1- (7) 3-ethyl-2-{(4-methyl-2H-chromene-2-ylidene) methyl} naphtho [1,2-d]
Thiazolium iodide 3-ethyl-2-methylnaphtho [1,2-d] thiazolium p-toluenesulfonate (2.27 g) and 4-methyl-2-thiocoumarin (1.0 g) were used in the same manner as in 1- (6) to obtain the target compound 0. 0.08 g was obtained. (Yield 3.5%) Brown crystals mp 140 to 142 ° C. (decomposition) 1- (8) 5,6-dimethyl-3-ethyl-2-{(4
-Methyl-2H-chromene-2-ylidene) methyl}-
Benzothiazolium p-toluenesulfonate 5,6-dimethyl-3-ethyl-2-methylbenzothiazolium p-toluenesulfonate 26.0 g and 4-
Methyl-2-thiocoumarin 13.2g at 150 ℃ 17
After the reaction under heating for 50 hours, 50 ml of methanol, 100 ml of acetone and 300 ml of ethyl acetate were added to the reaction mixture, and the mixture was cooled to room temperature to precipitate crystals. The crystals are taken out and washed with a small amount of acetone, then the crystals are 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 20 minutes, taken and washed with acetone to obtain 16.2 g of the desired product. Obtained. (Yield 45%) Brown crystals mp 201 to 203 ° C. (decomposition) 1- (9) 3-methyl-2-{(4-methyl-2H-chromene-2-ylidene) methyl} benzoxazolium perchlorate 2,3 2.1 g of dimethylbenzoxazolium p-toluenesulfonate and 1.2 g of 4-methyl-2-thiocoumarin were heated and reacted at 150 ° C. for 10 hours, and then 15 ml of methanol and 12 ml of acetone were added to the reaction mixture to form a uniform solution. . 1.2 g of sodium perchlorate (water 5
(ml solution) was added dropwise and the mixture was stirred at room temperature to precipitate crystals.
The crystals were collected and washed with a small amount of acetone, and then the crystals were added at room temperature to 10 ml of water, 10 ml of methanol and 20 ml of ethyl acetate, stirred for 15 minutes, collected and washed with ethyl acetate to obtain 0.3 g of the desired product. . (Yield 12%) Brown crystals mp269-271 ° C (decomposition) Example 2 (Synthesis of compound 1) 3-Ethyl-2-{(4-methyl-2H-chromene-2)
-Ylidene) methyl} -benzothiazolium p-toluenesulfonate 1.50 g and 5- (N-acetylanilinomethylene) -3-ethylrhodanine 0.93 g
In addition to 30 ml of MF, after heating to 100 ° C. on an oil bath, 3.0 ml of triethylamine was added.

After heating for 25 minutes and cooling, 50 ml of isopropanol
Was added. The precipitated crystals were collected, washed with isopropanol, and recrystallized from methanol / chloroform to obtain 1.0 g of the desired product.

Dark green crystal Melting point 287 ℃ (decomposition) λ _max 698nm (methanol / chloroform = 9/1 vol)
/ vol) ε = 1.07 × 10 ⁵ Example 3 (Synthesis of Compound 2) 3-Ethyl-5,6-dimethyl-2-{(4-methyl-
2H-chromene-2-ylidene) methyl} benzothiazolium p-toluenesulfonate 2.0 g and 5- (N
-Acetylanilinomethylene) -3-ethylrhodonine (1.2 g) was used in the same manner as in Synthesis Example 2 to obtain the desired compound (0.
5 g was obtained.

Dark green crystal Melting point 300 ° C or higher λ _max 710nm (methanol / chloroform = 9/1 vol
/ vol) ε = 1.44 × 10 ⁵ Example 4 (Synthesis of Compound 11) 3-Ethyl-5,6-dimethyl-2-{(4-methyl-
2H-chromene-2-ylidene) methyl} benzothiazolium p-toluenesulfonate 1.0 g and 5- (N
-Acetylanilinomethylene) -1,3-dimethylthiohydantoin (0.6 g) was added to DMF (20 ml), and the mixture was placed on an oil bath to give 1
After heating to 00 ° C, 1 ml of triethylamine was added.

After heating for 20 minutes and cooling, the reaction mixture is purified by passing through a silica gel column chromatography (eluent: ethyl acetate) and then recrystallized from methanol-chloroform to give the desired product 3
0 mg was obtained.

Dark green crystal Melting point 275-278 ° C (decomposition) λ _max 668 nm (chloroform) ε = 6.25 × 10 ⁴ Example 5 The following compounds were synthesized in the same manner as in Examples 2-4.
The color tone of crystals of the obtained compound and the maximum absorption wavelength in a methanol solution were determined and are shown in the table below.

Claims (1)

[Claims] 1. A methine dye represented by the following general formula [I]. General formula [I] (In the formula, n represents 0 or 1, m represents ₁ or 2. R ₁
Represents a substituted or unsubstituted alkyl group, R ₂ , R
₃ , R ₄ may be the same or different from each other and represent a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a substituted or unsubstituted amino group or a halogen atom,
Also, condensed with R ₂ and R ₃ , R ₃ and R ₄ or R ₂ and R ₄ 6
You may form a member ring. Z ₁ represents an atomic group necessary for forming a 5-membered ring or a 6-membered ring, and those rings may have a substituent or may be condensed with another ring. Z ₂ represents an atomic group necessary for forming a 5-membered ring or a 6-membered ring, and those rings may have a substituent,
It may also be condensed with another ring. L ₁ and L ₂ represent a methine group or a substituted methine group. )