JPH06895B2 - 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].

In the formula, m and n may be the same or different, and 0 or 1, q represents 0, 1, 2 or 3.

R ₁ and R _{2, which} may be the same or different, each represents an unsubstituted alkyl group, or an alkyl group substituted with a phenyl group, an alkoxy group or a sulfo group. R ₃ , R
₄ , R ₅ may be the same or different and each is a hydrogen atom,
An alkyl group, an alkoxy group, a hydroxy group, a substituted or unsubstituted amino group or a halogen atom, and R ₃ and R ₄ , R ₄ and R ₅ , or R ₃ and R ₅ to form a condensed 6-membered ring. Good. R ₆ represents an unsubstituted alkyl group, a carboxy group, a hydroxy group, an alkyl group substituted with an alkoxy group or a phenyl group, or a phenyl group.

Z ₁ and Z ₂ may be the same or different from each other, and are thiazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, thiazoline,
3,3-dialkylindolenine, 2-pyridine, 4-
It represents a group of atoms necessary for forming a heterocyclic nucleus selected from pyridine, 2-quinoline, 4-quinoline, benzotellurazole or benzimidazole, and those rings may further have a substituent.

L ₁ and L ₂ represent a methine group or a methine group substituted with a methyl group or a benzyl group, and the substituents on these methine groups may be linked to each other to form a 6-membered carbocycle.

X Represents an anion.

P represents / or 2 and P is 1 when the compound forms an intramolecular salt.

Each substituent of the compound represented by the general formula [1] is preferably the following substituent.

That is, R ₁ and R ₂ may be the same or different, and may be 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). , A dodecyl group, an octadecyl group, a vinylmethyl group, a cyclohexyl group) or a sulfo group, an alkoxy group having a carbon number of 8 or less (eg, a methoxy group, an ethoxy group, a benzyloxy group, a phenethyloxy group, etc.) or a phenyl group. Carbon number 18
The following alkyl groups are preferred.

Examples of R ₆ include an unsubstituted alkyl group represented by R ₁ and R ₂ or an alkyl group substituted with an alkoxy group.

Z ₁ and Z ₂ may be the same or different from each other and represent a group of non-metal atoms necessary for forming the following heterocyclic nucleus,
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-methyl) Benzothiazole, 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, tetrahydrobenzothiazo Le, 5,6-dimethoxy-benzothiazole, 5-hydroxy-benzothiazole, 6-hydroxy-benzothiazole), naphthothiazole nucleus (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.), benzoxazole nucleus (for example, 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 nucleus (for example, naphtho [1,2-d] oxazole, naphtho [2,2].
1-d] oxazole, naphtho [2,3-d] oxazole, etc.), thiazoline nucleus (eg, thiazoline, 4-methylthiazoline, 4-phenylthiazoline, etc.), 3,3-
Dialkyl indolenine nucleus (eg 3,3-dimethyl indolenine, 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 (e.g. pyridine etc.), 2-quinoline nucleus (e.g. 6-ethoxyquinoline, 6-ethylquinoline, 6-cloquinoline, 8-fluoroquinoline etc.) , 4-quinoline nuclei (eg 8-methylquinoline, 8
-Fluoroquinoline, 6-chloroquinoline, etc.), a benzotellurazole nucleus (for example, benzotellurazole, 5-
Chlorobenzotellurazole, 5-methylbenzotellurazole, 5-methoxytellurazole and the like) are preferable.

As the ring formed by Z ₂ , the followings other than the above are also preferably used.

Benzimidazole nuclei (eg 1-methylbenzimidazole, 1-ethylbenzimidazole, 1-benzylbenzimidazole, 5,6-dimethyl-1-ethylbenzimidazole, 5,6-dichloro-1- (2-methoxyethyl) benzo Imidazole, 5-chloro-1-ethyl-6-methylbenzimidazole, 5,6-dichloro-1- (2-phenylethyl) benzimidazole,
6-chloro-1-ethyl-5-trifluoromethylbenzimidazole, 6-chloro-5-cyano-1-ethylbenzimidazole, 1,7-trimethylenebenzimidazole, 1- (2-chloroethyl) benzimidazole, 1 -(2,2,2-trifluoroethyl) -5,6
-Dichlorobenzimidazole, 5-phenoxy-1-
Ethylbenzimidazole, etc.) As the unsubstituted or substituted amino group of R ₃ and R ₄ , And R ₁₅ and R ₁₆ may be the same or different,
A hydrogen atom and a lower alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, etc.) are preferable.

It is also preferable that R ₁₅ and R ₁₆ are connected to each other to form a 5-membered ring or a 6-membered ring.

Further, it is also preferable that R ₁₅ and / or R ₁₆ is bonded to the benzene ring of the benzopyrylium nucleus to form a condensed 5- or 6-membered ring.

The alkyl group of R ₃ , R ₄ and R ₅ 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.

In addition to the above, a hydroxy group and a benzo-fused ring are also preferable as R ₃ , R ₄ , and R ₅ .

X Represents an anion, specifically, chloride or bromine.
Lomid, iodide, thiocyanate, perchlorate,
Paratoluene sulfonate, methyl sulfate, ethi
Rusulfate and tetrafluoroborate are preferred.

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 synthesized by a condensation reaction of an intermediate [A] and an intermediate [B] obtained by reacting a heterocyclic quaternary salt derivative having an active methyl group with a 4-methyl-2-thiocoumarin derivative in the presence of a base. it can.

In the above reaction formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
R ₆ , Z ₁ , Z ₂ , P, m, n and q are represented by the general formula [I].
It has the same meaning as described in.

X ₁ and X ₂ represent anions and have the same meanings as X, P ₁ and P ₂
Is the same as P.

R ₇ represents a substituted or unsubstituted lower alkyl group.

As the base used for the condensation reaction, an inorganic base (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, etc.) and an organic base (for example, pyridine, 4-dimethylaminopyridine, triethylamine, etc.) usually used for organic synthesis are used.

As the method for synthesizing the intermediate [A], in addition to the method described above, for example, Research Dice Closure (Research D
isclosure) 16325 (163, page 29)
1977), JP-A-60-78444, and 60.
The method of Japanese Patent No. 78445 is cited.

The novel methine dye of the present invention has excellent fastness, and is a dye for filters, laser recording material (optical disc, etc.).
It is effective as a dye for photographic use, 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 settled. Further, these dyes can obtain laser light in the near infrared to infrared region by being excited by an excitation method such as second harmonic or third harmonic of excimer laser or Nd: YAG laser, and have good robustness. , Acts as a high-performance laser dye with 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.

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

Example-1 (Synthesis of Intermediate [A]) 1- (1) 3-Ethyl-2-{(4-methyl-2H-chromene-2-ylidene) methyl} benzothiazolium
Perchlorate 3-Ethyl-2-methylbenzothiazolium 17.8 g of p-toluenesulfonate and 8.8 g of 4-methyl-2-thiocoumarin were heated and reacted at 150 ° C. for 15 hours, and then 20 ml of methanol and 40 ml of acetone were added to the reaction mixture. Then, a uniform solution was prepared. After cooling to room temperature 60% perchloric acid 1
When 5.7 g was added and stirred at room temperature, crystals were precipitated. The crystals were collected by filtration, washed with a small amount of acetone, and then added to a mixed solvent of 20 ml of methanol and 40 ml of acetone at room temperature,
After stirring for 30 minutes, the product is collected by filtration and washed with acetone.
Got (Yield 40%) Brown crystals mp 280 ° C. or higher (decomposition) 1- (2) 5-trifluoromethyl-3-ethyl-2-
{(4-Methyl-2H-chromene-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 by filtration 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 by filtration and washed with acetone to obtain the desired product 1. 0.47 g was obtained. (Yield 46%), brown crystal, 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-trienesulfonate and 5.5 g of 4-methyl-2-thiocoumarin were heated and reacted at 150 ° C. for 23 hours, 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. The crystals were collected by filtration, washed with a small amount of acetone, and then 25 ml of methanol and 50 m of acetone at room temperature.
Crystals were added to a mixed solvent of l and 150 ml of ethyl acetate, and 2
After stirring for 0 minutes, the product was collected by filtration and washed with acetone to give the desired product 7.9.
g was obtained. (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 2.07 g of p-toluenesulfonate and 1.0 g of 4-methyl-2-thiocoumarin are heated at 150 ° C. for 25 hours, and then the reaction mixture is mixed with 10 ml of methanol. 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 by filtration 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 give a uniform solution. To this was added 5 g of a 60% aqueous solution of perchloric acid, the mixture was stirred at room temperature for 30 minutes, and the precipitated crystals were collected by filtration 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 2.15 g of iodo-5-methoxy-3-ethyl-2-methylbenzothiazolium p-toluenesulfonate and 1.0 g of 4-methyl-2-thiocoumarin were heated and reacted at 150 ° C. for 20 hours, and methanol was added to the reaction mixture. 15 ml and 12 ml of acetone were added to make a uniform 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 collected by filtration, washed with a small amount of acetone, and then added to 20 ml of water at room temperature to add 1
After stirring for 5 minutes, the product of interest is 1.02 when collected by filtration and washed with acetone.
g was obtained. (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 by filtration and washed with a small amount of acetone, then the crystals were added to a mixed solvent of water (15 ml) and acetone (15 ml) 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 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 iodide 2.27 g and 4-methyl-2-thiocoumarin 1.0 g from the target compound 0.0 in the same manner as 1- (6)
8 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 collected by filtration and washed with a small amount of acetone, and 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, filtered, and washed with acetone to obtain the desired product 16 Obtained 0.2 g. (Yield 45%) Brown crystals mp 201 to 203 ° C. (decomposition) 1- (9) 3-methyl-2 {(4-methyl-2H-chromene-2-ylidene) methyl} benzoxolium 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 obtain a uniform solution. 1.2 g of sodium perchlorate (water 5
(ml solution) was added dropwise and stirred at room temperature to precipitate crystals.
The crystals were collected by filtration and washed with a small amount of acetone. 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 by filtration and washed with ethyl acetate to obtain 0.3 g of the desired product. It was (Yield 12%) Brown crystals mp269-271 ° C (decomposition) Example 2 (synthesis of compound) 5-chloro-3-ethyl-2-{(4-methyl-2H-
Chromene-2-ylidene) methyl} -benzothiazolium p-trienesulfonate 2.6 g and 3-ethyl-
4-oxo-5- (3-methylbenzothiazoline-2-
2.5 g of (ylidene) -2-methylthio-4,5-dihydrothiazolium p-toluenesulfonate and 3 ml of triethylamine were added to 100 ml of acetonitrile, and the mixture was heated and reacted on a steam bath for 30 minutes.

After cooling, the precipitated crystals were collected by filtration and washed with acetone. Then, methanol / chloroform = 2/8 (Vol./Vo
l. After purification through silica gel column chromatography using the mixed solution of 1), recrystallization was performed from a mixed solvent of notanol / chloroform to obtain 1.1 g of the desired product. (Yield 2
7.5%) Dark reddish brown crystals, melting point 245-250 ° C (decomposition) Example 3 (Synthesis of Compound 3) 3-Ethyl-5,6-dimethyl-2-{(4-methyl-
2H-chromene-2-ylidene) methyl} benzothiazolium p-toluenesulfonate 2.5 g and 3-ethyl-4-oxo-5- (5-methoxy-3-methylbenzothiazoline-2-ylidene) -2
2.4 g of -ethylthio-4,5-dihydrothiazolium ethanesulfate and 8 ml of triethylamine were added to 150 ml of acetonitrile and reacted for 30 minutes on a steam bath. After cooling, the precipitated crystals were collected by filtration and subjected to silica gel column chromatography (opening solvent methanol / chloroform = 3/17
(Vol / Vol)). The product was dissolved in methanol, 1.0 g of sodium iodide was added thereto, and the precipitated crystals were collected by filtration and washed with methanol to obtain the desired product 1.8.
g was obtained. (Yield 48%) Dark brown crystals Melting point 235-240 ° C Decomposition Example (Compound 18) 5-chloro-3-ethyl-2-{(4-methyl-2H-
Chromene-2-ylidene) methyl} benzothiazolium p-toluenesulfonate 1.8 g and 3-ethyl-4
-Oxo-5- {2- (3-ethylnaphtho [1,2-
d] Thiazoline-2-ylidene) ethylidene} -2-methylthio-4,5-dihydrothiazolium p-trienesulfonate (1.95 g) and triethylamine (5 ml) were added to acetonitrile (150 ml) and heated on a steam bath for 30 minutes. . After cooling, the precipitated crystals were collected by filtration and recrystallized from methanol-acetonitrile to give the desired product 1.55
g was obtained. (Yield 51%) Dark reddish brown crystals, melting point 280 ° C or higher Example 5 (Compound 19) 3-Ethyl-5,6-dimethyl-2-{(4-methyl-
2.0 g of 2H-chromene-2-ylidene) methyl} -benzothiazolium p-toluenesulfonate and 3-ethyl-4-oxo-5- {2- (3-ethylbenzothiazoline-2-ylidene) ethylidene} 2.1 g of 2-methylthio-4,5-dihydrothiazolium p-toluenesulfonate and 8 ml of triethylamine were added to 100 ml of acetonitrile and heated and reacted on a steam bath for 30 minutes. After cooling, the reaction mixture was chromatographed on silica gel (eluent methanol / chloroform = 3/17 (Vol / Vo
After purification through l)), recrystallization from methanol-acetonitrile was carried out to obtain 0.6 g of the desired product. (Yield 19
%) Dark reddish brown crystals, melting point 267-9 ° C. Example 6 The compounds shown below were also synthesized in the same manner as in Examples 2-5.

Claims (1)

[Claims] 1. A methine dye represented by the following general formula [I]:
Fee. General formula [I](In the formula, m and n may be the same or different from each other.
Alternatively, 1 and q represent 0, 1, 2 or 3. R₁, R_TwoMay be the same or different, but not placed
If an alternative alkyl group, phenyl group, or alkoxy group
Represents an alkyl group substituted with a sulfo group. R_Three, R_Four, R₅May be the same or different
Elementary atom, alkyl group, alkoxy group, hydroxy group, position
Represents a substituted or unsubstituted amino group or halogen atom
And R_ThreeAnd R_Four, Or R_ThreeAnd R₅With a fused 6-membered ring
You may form. R₆Is an unsubstituted alkyl group,
Si group, hydroxy group, alkoxy group or phenyl group
Represents an alkyl group substituted with or a phenyl group. Z₁, Z_TwoThey may be the same or different,
Azole, benzothiazole, naphthothiazole, ben
Zoxazole, naphthoxazole, thiazoline,
3,3-dialkylindolenine, 2-pyridine, 4-
Pyridine, 2-quinoline, 4-quinoline, benzotellurium
Heterocycle selected from azole or benzimidazole
Represents the group of atoms necessary to form a nucleus, whose rings are
Methyl group, methoxy group, ethoxy group, trifluoro
Substituted with a group selected from chill group, chlorine atom and phenyl group
It may have been done. L₁, L_TwoIs a methine group or a methyl group or benzyl
Represents a methine group substituted with a
The substituents of may combine with each other to form a 6-membered carbocycle.
Yes. X Represents an anion. P represents 1 or 2, and the compound forms an intramolecular salt.
Then P is 1. )