JPH0583587B2 - - Google Patents

Description

[Detailed description of the invention]

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

embedded image In the formula, m represents 0, 1 or 2. p and q represent 0 or 1. L represents a methine group or a methine group substituted with an alkyl group having 1 to 4 carbon atoms, a benzyl group, or a phenyl group, and these substituents on the methine group are linked to each other to form a 6-membered carbon ring. may be formed. R ₁ and R ₂ may be the same or different from each other and represent an unsubstituted alkyl group, an alkoxy group, a sulfo group, or an alkyl group substituted with a fluorine atom. Z and Z′ may be the same or different, and include thiazole, benzothiazole, naphthothiazole, oxazole, benzoxazole, benzoselenazole, benzimidazole, isoxazole,
Benzisoxazole, 3,3-dimethyl-indolenine, oxazoline, thiazoline, 2-pyridine, 4-pyridine, 2-quinoline, and 4
- Represents a group of nonmetallic atoms necessary to form a heterocyclic nucleus selected from quinoline, and these heterocycles are selected from a methyl group, a methoxy group, a trifluoromethyl group, a chlorine atom, a fluorine atom, and a phenyl group. may be substituted with a group. X ^- represents an anion. r represents 1 or 2, and r is 1 when the dye forms an inner salt. Examples of each substituent of the compound represented by the general formula [] are shown below. The unsubstituted alkyl group for R ₁ and R ₂ is preferably 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.), and the alkyl group substituted with an alkoxy group is preferably an alkoxy group having 8 or less carbon atoms (for example, methoxy group, ethoxy group, benzyloxy group, phenethyloxy group). ) is an alkyl group having 18 or less carbon atoms. As the substituent for the methine group represented by L,
Examples include alkyl groups having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, etc.). Furthermore, methylene groups can be crosslinked with trimethylene groups to form a 6-membered carbon ring on the methylene chain. The ring representing the nonmetallic atom group formed by Z is thiazole, such as thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-
Dimethylthiazole, 4,5-diphenylthiazole, 4,(2-thienyl)thiazole, etc., benzothiazole such as benzothiazole, 4,
-Chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromo Benzothiazole, 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 such as 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 such as 4-methyloxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4
-ethyloxazole, 4,5-dimedyloxazole, 5-phenyloxazole, etc.;
-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-methoxybenzoxazole, 5-ethoxybenzo Oxazole, 5-fluorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc. Examples of benzoselenazole include benzoselenazole, 5-chlorobenzoselenazole, 5-methylbenzoselenazole, 5-methoxybenzoselenazole, 5-methoxybenzoselenazole, 5-
phenylbenzoselenazole, etc., thiazoline such as thiazoline, 4-methylthiazoline, 4-methylthiazoline, etc.
- phenylthiazoline, etc., oxazoline such as 5,5-dimethyloxazoline, isoxazole such as 5-methylisoxazole, benzisoxazole such as benzisoxazole, 3,3-dimethylindolenine such as 3,3 -dimethylindolenine, 3,3,5-trimethylindolenine, 5-
Chloro-3,3-dimethylindolenine, 5-ethoxycarbonyl-3,3-dimethylindodine, etc., 2-pyridine such as pyridine, 5-methylpyridine, etc., 4-pyridine such as pyridine, 2-quinoline such as 6-ethoxyquinoline, 6-ethylquinoline, 6-chloroquinoline, 8-fluoroquinoline, etc. Examples of 4-quinoline include 8-methylquinoline, 8-fluoroquinoline, 6-chloroquinoline, etc. Z' may be the same as or different from Z, but
In addition to the examples listed above, the following rings are also preferred. That is, as benzimidazole, for example, 1,3-diethylbenzimidazole, 1,3-
Diethyl-5,6-dichlorobenzimidazole, 1,3-diethyl-5-trifluoromethyl-6-chlorobenzimidazole, 1,3-diethyl-5-cyano-6-chlorobenzimidazole, and the like. 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 2,6-dimethyl-4H- Piran-4
- It can be synthesized by reacting intermediate [A] obtained by reaction with thione and intermediate [B].

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[Chemical formula] In the above formula, Y represents a leaving group that is often used in dye synthesis, such as a halogen atom (e.g., chlorine atom), a substituted amino group (e.g., N-acetylanilino group, dimethylamino group, etc.). ), substituted mercapto groups (e.g., methylthio group, ethylthio group, 3-sulfopropylthio group, 4-sulfobutylthio group, etc.), sulfonate groups, alkoxy groups (e.g., methoxy group, ethoxy group, phenoxy group, etc.). . X ₁ and X ₂ represent anions. r ₁ , r ₂ and r ₃ represent 1 or 2, and are 1 when the molecule forms an inner salt. R ₁ , R ₂ , Z, Z', m, p, q are general formulas []
It has the same meaning as explained in. 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, by exciting these dyes with an excitation method such as an excimer laser or the second harmonic or third harmonic of a Nd:YAG laser, it is possible to obtain laser light in the near-infrared to infrared region.
It has good fastness and acts as a high-performance laser dye with high energy conversion efficiency. Specific examples of the compound represented by the general formula [ ] according to the present invention are shown below, but the invention is not limited thereto.

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embedded image Next, the method for synthesizing the compound 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, add 50ml of methanol to the reaction mixture.
Next, add 100ml of acetone and 300ml of ethyl acetate.
When the mixture was stirred at room temperature, crystals were precipitated. 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 13.4 g of 5-methyl-3-ethyl-2-methylbenzothiazolium p-toluenesulfonate and 2,6-dimethyl-4H-pyran-4-thione
After heating and reacting 5.6g at 150℃ for 15 hours, add 50ml of methanol, 60ml of acetone, and ethyl acetate to the reaction mixture.
When 120 ml of the mixture was added and stirred at room temperature, crystals were precipitated.
After collecting the crystals and washing them with a small amount of acetone, add 50 ml of methanol, 60 ml of acetone, and ethyl acetate at room temperature.
The crystals were added to 120 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 and reacting 12.9 g at 150° C. for 15 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 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 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 2,3-dimethylbenzoxazolium p-
1.5g of 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-27) 4-[{3-(2-methoxy)ethyl-2(3H)-
benzothiazolinylidene}methyl]-2,6-bis{(3-ethyl-2-benzothiazolinylidene)
-1,3-propenyl}pyrylium perchlorate 3-(2-methoxy)ethyl-2-{(2,6-
Dimethyl-4H-pyran-4-ylidene)methyl}
Benzothiazolium iodide 2.4g and 2-(2-
(vinyl acetanilide)-3-ethylbenzothiazolium iodide (7.4 g) and acetic anhydride (30 ml)
Add to 110ml of DMF and heat at 100℃ for 5 minutes, then 150℃
Then, 6 ml of triethylamine was added to the mixture, and the reaction was further heated for 5 minutes. After cooling to room temperature, diethyl ether 2 was added and left at room temperature for 2 hours. The precipitated crystals were mixed with methanol/chloroform = 2/8 (v/
Using the mixed solvent of v), the crystals were purified through a silica gel column, and the obtained crystals were added to 200 ml of methanol to make a homogeneous solution. 2 g of sodium perchlorate (100 ml of water solution) was added dropwise to this solution, and the mixture was stirred at room temperature for 1 hour to precipitate crystals. The crystals were collected and recrystallized (twice) from methanol-chloroform to obtain 2.6 g of the desired product. Dark green crystals Yield 61% Melting point 285°C or above (decomposition) λ ^MeoH _nax 609 nm, ε _nax = 1.86×10 ⁵ Example 3 The methine dye shown below was also synthesized in the same manner as the synthesis method shown in Examples 2 and 3. The λ ^MeoH _nax value and crystal color tone of the obtained compound are shown in Table 1.

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[Table] Example 4 The methine dye shown below was also synthesized in the same manner as the synthesis method shown in Examples 2 and 3, and the λ ^MeoH _nax value of the obtained compound and the color tone of the crystal are shown in Table 2.

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【table】

【table】

Claims (1)

[Claims] 1. A methine dye represented by the following general formula []. [Formula, m represents 0, 1 or 2; p and q represent 0 or 1; L represents a methine group, an alkyl group having 1 to 4 carbon atoms, a benzyl group, or a phenyl group; Represents a substituted methine group, and the substituents on these methine groups may be linked to each other to form a 6-membered carbon ring. R ₁ and R ₂ may be the same or different from each other, and Represents a substituted alkyl group, an alkoxy group, a sulfo group, or an alkyl group substituted with a fluorine atom.Z and Z' may be the same or different from each other; thiazole,
Benzothiazole, naphthothiazole, oxazole, benzoxazole, benzoselenazole, benzimidazole, isoxazole, benzisoxazole, 3,3-dimethyl-indolenine, oxazoline, thiazolidine, 2-pyridine, 4-pyridine, 2-quinoline, and 4
- Represents a group of nonmetallic atoms necessary to form a heterocyclic nucleus selected from quinoline, and these heterocycles are selected from a methyl group, a methoxy group, a trifluoromethyl group, a chlorine atom, a fluorine atom, and a phenyl group. may be substituted with a group. X represents an anion. r represents 1 or 2, and r is 1 when the dye forms an inner salt. )