JPH045069B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a novel methine dye with excellent fastness suitable for use as a dye for filters, a dye for photographic materials, a sensitizing dye, a dye for dyeing pulp, a laser dye, and the like. The present invention is a novel 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 an unsubstituted alkyl group having 7 or less carbon atoms or an alkoxy- or aryl-substituted alkyl group. Z is a benzothiazole nucleus , benzoxazole nucleus, benzoselenazole nucleus, 3,3-dialkylindolenine nucleus, thiazole nucleus, oxazole nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 2-pyridine nucleus, 4-pyridine nucleus, naphthothiazole nucleus,
Represents a group of nonmetallic atoms necessary to form a naphthoxazole nucleus, and these rings may have substituents or may be fused with other rings.
X ^- represents an anion. p represents 1 or 2, and p is 1 when the dye forms an inner salt. ) R ₂ is a 4-nitrophenyl group, 4-chlorophenyl group, 3-nitrophenyl group; must be closed with the following general formula []; (In the formula, R ₁₁ and R ₁₂ may be the same or different and represent an unsubstituted alkyl group or a substituted alkyl group having 1 to 6 carbon atoms, and R ₁₃ and R ₁₄ may be the same or different. , represents a hydrogen atom, a methyl group or a methoxy group. In addition, R ₁₃ and R ₁₄ may form a benzo-fused ring, or 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. In addition, R ₁₁ and R ₁₂ may be connected to form a 5-membered ring or a 6-membered ring.
It may form a membered ring. ) or 4-pyrazolyl group, pyrrolo[5,1-
b] Quinazolin-9-one-3-yl group, 3-indolyl group, 3-pyrrolyl group, 3-pyrrolo[2,
3-b] Pyridyl group or 1-azaazulene-2
-one-3-yl group. Hereinafter, the compound represented by the general formula [] of the present invention will be explained in detail. That is, R ₁ is an unsubstituted alkyl group having 7 or less carbon atoms (for example, a methyl group, ethyl group, propyl group, butyl group, pentyl group, etc.) or an alkoxy or aryl substituted alkyl group (the alkyl group has 7 or less carbon atoms). The alkoxy group as a substituent includes an alkoxy group with 8 or less carbon atoms (for example, methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.), and the aryl group as a substituent includes an aryl group with 10 or less carbon atoms ( For example, phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group, etc.). R ₂ is a 4-nitrophenyl group as described above,
4-chlorophenyl group, 3-nitrophenyl group,
A substituted aryl group represented by the general formula [],
Or, 4-pyrazolyl group, pyrrolo[5,1-
b] Quinazolin-9-one-3-yl group, 3-indolyl group, 3-pyrrolyl group, 3-pyrrolo[2,
3-b] Pyridyl group or 1-azaazulene-2
-one-3-yl group. In the general formula [] represented by R ₂ , R ₁₁ ,
R ₁₂ , R ₁₃ and R ₁₄ may be the same or different, and R ₁₁ to _{R 14} are unsubstituted alkyl groups having 6 or less carbon atoms (for example, methyl group, ethyl group, propyl group, hexyl group, etc.) or a substituted alkyl group {the number of carbon atoms in the alkyl group is 6 or less, the substituents are:
For example, cyano group, halogen atom (e.g. fluorine atom, chlorine atom, etc.), alkoxycarbonyl group having 4 or less carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group, etc.), alkoxy group having 2 or less carbon atoms (e.g. methoxy group, ethoxy groups, etc.), and sulfonamide groups (methanesulfonamide groups, etc.). 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 linked 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. Z represents a nonmetallic atomic group necessary to form a 5-membered or 6-membered hetero ring, and the ring is, for example, 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-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 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-methoxy benzoxazole,
(5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.), naphthoxazole nuclei (e.g. naphtho[1,2-d]oxazole, naphtho[2,1-d]oxazole, naphtho[2,3-d]oxazole, etc.) , benzoselenazole nucleus (e.g. benzoselenazole, 5-chlorobenzoselenazole, 5-methylbenzoselenazole, 5-methoxybenzoselenazole, 5-phenylbenzoselenazole, etc.), 3,3-dialkylindolenine nucleus (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.),
4-quinoline nucleus (e.g. 8-methylquinoline, 8
-fluoroquinoline, 6-chloroquinoline, etc.) are preferred. X represents an anion, and specifically preferred are chloride, bromide, iodide, auto, 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 obtained by a condensation reaction between intermediate [A] obtained by reaction with thione and aldehydes. 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 ground pulp and bleached sulphite pulp, as well as pure pulp, and are virtually completely dyed. In addition, these dyes can be used for excimer laser, Nd:YAG laser, second harmonic or third harmonic.
Laser light can be obtained in the near-infrared to infrared region by excitation using excitation methods such as harmonics.
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 [] 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-{(2,6-dimethyl-
4H-pyran-4-ylidene)methyl}benzothiazolium p-toluenesulfonate 3-ethyl-2-methylbenzothiazolium p
-24.4 g of toluenesulfonate and 10.6 g of 2,6-dimethyl-4H-pyran-4-thione were heated at 150℃ for 15 minutes.
After a heating reaction for an hour, 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. take the crystal,
After washing with a small amount of acetone, wash with methanol at room temperature.
The crystals were added to a mixed solvent of 50 ml of acetone (100 ml) and ethyl acetate (300 ml), 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 13.4 g of p-toluenesulfonate and 2,6-dimethyl -4H-pyran-4-thione 5.6
After heating reaction 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 5-chloro-3-ethyl-2-methylbenzothiazolium 31.7 g of 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. Sodium perchlorate 1.2 to this solution
g (20 ml of water solution) was added dropwise and stirred at room temperature for 1 hour to precipitate crystals. After taking the crystals and washing them with a small amount of acetone, add 15 ml of room temperature sewage water and 15 ml of acetone.
The crystals were added to the mixed solvent, stirred for 15 minutes, taken out, and washed with acetone to obtain 0.4 g of the desired product. (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]
1.9 g of thiazolium p-toluenesulfonate and 0.7 g of 2,6-dimethyl-4H-pyran-4-thione
0.55 g of the target product was obtained from g 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. 1.2 g of sodium perchlorate (20 ml of water solution) was added dropwise to this solution, and the mixture was stirred at room temperature for 1 hour to precipitate crystals.
After taking 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, taken out, and washed with acetone.
0.24 g of the target product was obtained. (Yield 15%) Dry color crystals, mp280°C or higher (decomposition) Example 2 (Compound-1) 4-{(3-ethyl-2(3H)-benzothiazolinylidene)methyl}-2,6- Bis {2-(4-
dimethylaminophenyl)vinyl}pyrylium perchlorate 3-ethyl-2-{(2,6-dimethyl-4H-
Add 4.0 g of benzothiazolium p-toluenesulfonate, 3.9 g of 4-dimethylaminobenzaldehyde, and 2 g of ammonium acetate to 150 ml of ethanol,
The mixture was heated to reflux on an oil bath at 100°C for 60 minutes. After cooling to room temperature, methanol/chloroform = 1/5
Using a mixed solvent of (V/V), purification was carried out through a silica gel column, and the obtained crystals were purified using ethanol.
200ml to make a homogeneous solution. 2 g of sodium perchlorate (50 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 four times from ethanol-isopropanol to obtain 1.8 g of the desired product. (Yield 32%) Brown crystals, mp 290°C or higher (decomposition) λ ^MeOH _nax 614 nm, ε ^MeOH _nax = 4.90×10 ⁴ Example 3 (Compound-22) 4-{(5-chloro-3-ethyl-2- (3H)−
benzothiazolinidene)methyl}-2,6-bis{2-(2-methyl-4-diethylaminophenyl)byl}pyrylium perchlorate 5-chloro-3-ethyl-2-{(2,6 -dimethyl-4H-pyran-4-ylidene)methyl}benzothiazolium p-toluenesulfonate
Add 6.0 g and 5.5 g of 2-methyl-4-diethylaminobenzaldehyde to 100 ml of acetic anhydride, and place on an oil bath.
The mixture was heated under reflux at 150°C for 40 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 =
The crystals were purified through a silica gel column using a 2/8 (V/V) mixed solvent, and the obtained crystals were added to 200 ml of ethanol to form 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 three times from ethanol-isopropanol to obtain 2.3 g of the desired product. (yield 25
%) Brown crystals mp232-235°C (decomposition) λ ^MeOH _nax 596 nm ε ^MeOH _nax =1.14×10 ⁵ Example 4 The methine dye shown below was also synthesized using the general synthesis method described above and the synthesis shown in Examples 1 to 3. The λ ^MeOH _nax value and crystal color tone of the obtained compound are shown in Table 1.

【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 an unsubstituted alkyl group having 7 or less carbon atoms or an alkoxy- or aryl-substituted alkyl group. Z is a benzothiazole nucleus , benzoxazole nucleus, benzoselenazole nucleus, 3,3-dialkylindolenine nucleus, thiazole nucleus, oxazole nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 2-pyridine nucleus, 4-pyridine nucleus, naphthothiazole nucleus,
Represents a group of nonmetallic atoms necessary to form a naphthoxazole nucleus, and these rings may have substituents or may be fused with other rings.
X ^- represents an anion. p represents 1 or 2, and p is 1 when the dye forms an inner salt. ) R ₂ is a 4-nitrophenyl group, 4-chlorophenyl group, 3-nitrophenyl group; a group closed by the following general formula []; (In the formula, R ₁₁ and R ₁₂ may be the same or different and represent an unsubstituted alkyl group or a substituted alkyl group having 1 to 6 carbon atoms, and R ₁₃ and R ₁₄ may be the same or different. , represents a hydrogen atom, a methyl group or a methoxy group. In addition, R ₁₃ and R ₁₄ may form a benzo-fused ring, or 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. In addition, R ₁₁ and R ₁₂ may be connected to form a 5-membered ring or a 6-membered ring.
It may form a membered ring. ) or 4-pyrazolyl group, pyrrolo[5,1-
b] Quinazolin-9-one-3-yl group, 3-indolyl group, 3-pyrrolyl group, 3-pyrrolo[2,
3-b] Pyridyl group or 1-azaazulene-2
-one-3-yl group.