JPS621754A - Novel methine dye - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [n is 0 or 1; m is 1 or 2; R1 is (substituted) alkyl; R2 is (substituted) aryl or heterocyclic ring; R3 and R4 are H, alkyl, alkoxy, OH, (substituted) amino or halogen; R3 and R4 may form a condensed six-membered ring; Z is atomic group required for formation of five- - six-membered ring; X<-> is anion; p is 1 or 2, and 1 when the dye forms an inner salt]. EXAMPLE:The compound expressed by formula II. USE:A dye or sensitizing dye for filters and photographic sensitive materials having improved fastness. PREPARATION:According to reaction formulas, the aimed compound can be obtained by condensation reaction of an intermediate (A) prepared by reacting a heterocyclic quaternary salt derivative having active methyl group with 2- methyl-4H-chromene-4-thione derivative with an aldehyde.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel methine dye represented by the general formula (1,1).

(Xe)p-1 In the formula, n represents O or /, m represents / or λ.

R1 represents a substituted or unsubstituted alkyl group, R2
represents a substituted or unsubstituted aryl group or a heterocyclic group, R3 and R4 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 It represents an atom, and R3 and R4 may form a fused membered ring.

Z! Represents a group of atoms necessary to form a membered ring or a membered ring, and these rings may have substituents or may be fused with other rings. X1→ represents an anion. p represents/or λ, and when the dye forms an internal salt, p is /.

Each substituent of the compound represented by the general formula [I] is preferably the substituent shown below.

That is, R1 is an unsubstituted alkyl group having carbon number/f or less (for example, 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, a carboxy group,
Sulfo group, cyano group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom), hydroxy group, alkoxycarbonyl group having less than 1 g of carbon atoms (for example, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxylcarbonyl group, etc.), an alkoxy group having a carbon number of g or less, (e.g., methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.), a monocyclic aryloxy group having a carbon number of 70 or less (e.g., phenoxy group, p -Tolyloxy group, etc.) Acyloxy group having 3 or less carbon atoms (e.g. acetyloxy group, propionyloxy group, etc.), Acyl group having 3 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, pyharidinocarbonyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, N,N-dimethylcarbamoyl group, morpholinosulfonyl group, pyphoridinosulfonyl group) base, etc.)
Aryl group having 10 or less carbon atoms (e.g. phenyl group, g-
Preferred is an alkyl group having a carbon number of less than or equal to 2, substituted with a chlorophenyl group, t-methylphenyl group, α-naphthyl group, etc.).

The aryl group for R2 includes a substituted or unsubstituted nohenzen ring group (e.g. phenyl group, t-nitrophenyl group, ≠
Preferred examples include (--(---)-(-------------------------------------------)-------------------------)-------------------------------------)-----------------------------O-----------(O---)---------(O-------------(O---)----------(O-------)------------------------------(--(--)--(--)-(--)-(O--)) naphthalene ring group;

The substituted benzene ring group for R2 is preferably a group represented by the following general formula (II).

RI3 RI4 In the formula, R11, R12, RI3, and R14 may be the same or different, and R11 to RI4 have a carbon number of / to /
2 unsubstituted alkyl groups (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, vinylmethyl group, etc.) or substituted alkyl groups (for example, carboxyl group, Cyano group, hydroxy group, sulfo group, halogen atom (e.g. fluorine atom, chlorine atom, etc.) Alkoxycarbonyl group with carbon number of g or less (e.g. methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.) Number of carbon atoms an alkoxy group (e.g., methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.), a monocyclic aryloxy group (e.g., phenoxy group, p-tolyloxy group, etc.) having less than 10 carbon atoms (e.g., phenoxy group, p-tolyloxy group), less than 3 carbon atoms Acyloxy groups (e.g., acetyloxy, propionyloxy, etc.), acyl groups with carbon number of g or less (e.g., acetyl, propionyl, benzoyl, mesyl, etc.), carbamoyl groups (e.g., carbamoyl, N,N-dimethylcarbamoyl) morpholinocarbonyl group, pyheridinocarbonyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, pi is lysinosulfonyl group, etc.) Aryl having 10 or less carbon atoms An alkyl group having a carbon number/♂ or less substituted with a group (eg, evaphenyl group, ≠-chlorophenyl group, Hiro-methylphenyl group, α-naphthyl group, etc.) is preferable.

Furthermore, R13 and RI4 are substituted or unsubstituted amino groups, carboxyl groups, cyan groups, hydroxy groups, sulfo groups, halogen atoms (e.g. fluorine atoms, chlorine atoms, etc.), alkoxycarbonyl groups having up to g carbon atoms (e.g. methoxycarbonyl (e.g., ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.) with a carbon number below (e.g., methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.)
Monocyclic aryloxy groups having up to 70 carbon atoms (e.g. phenoxy group, p-tolyloxy group, etc.), acyloxy groups having up to 3 carbon atoms (e.g. acetyloxy group, propionyloxy group, etc.), acyl groups having up to g carbon atoms ( For example, acetyl group, propionyl group, benzoyl group, mesyl group, etc.) Carbamoyl group (for example, carbamoyl group, N, N-
A dimethylcarbamoyl group, a morpholinocarbonyl group, a lysinocarbonyl group, etc.), a sulfamoyl group (for example, a sulfamoyl group, an N,N-dimethylcarbamoyl group, a morpholinosulfonyl group, a piperidinosulfonyl group, etc.) are also preferred.

R13, R14 may be combined with unsubstituted or substituted amine group, hydrogen atom, lower alkyl group with carbon number/~
For example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.) An acyl group having a carbon number of λ to g (for example, an acetyl group, a propionyl group, a benzoyl group, etc.) is preferable.

Further, R17 and R18 may form a ring.

Further, RJ3 and RI4 may form a benzo-fused ring, and it is also preferable that R11 or R12 and RI3 or RI4 are linked to form a j-membered ring or an o-membered ring,
It is also preferable that R11 and R12 are linked to form a j-membered ring or an o-membered ring.

Further, as the heterocyclic group for R2, pyrazole nucleus, /, 2-
dihydro-/-azaazulene-coon nucleus, pyrrolo(j
, /-b) A quinazoline-terion nucleus, an indole nucleus, a virol nucleus, a pyrrolo(,2,J-b)pyridine nucleus, and the like are preferred.

The alkyl group for R3 and R4 is preferably a lower alkyl group having a carbon number of / to ≠ (for example, methyl group, ethyl/L4'', isozolobyl group, butyl group, etc.), and the alkoxy group is preferably an alkoxy group having a carbon number of / to ≠. Groups (e.g. methoxy, ethoxy, propoxy, butoxy, etc.)
is preferred.

Z represents an atomic group necessary to form a j-membered ring,
The ring is, for example, a thiazole nucleus (e.g. thia7--/lz
, 4L-methylthiazole, t-phenylthiazole, j-methylthiazole, j-phenylthiazole, ≠
, j-dimethylthiazole, ri.

(S-diphenylthiazole, ≠, (l-thenyl)thiazole, etc.), benzothiazole nuclei (e.g. benzothiazole, μm chlorobenzothiazole, !-chloropenzotheasol, O-chlorobenzotheasol, 7-chlorobenzo Theasol, ≠-methylbenzothiazole, ohmethylbenzothiazole, O-methylbenzothiazole, j, A-dimethylbenzotheasole, terbromobenzothiazole, O-bromobenzothiazole,
J”-trifluoromethylbenzothiazole, 5-phenylbenzothiazole, ≠-methoxybenzothiazole, j-methoxybenzothiazole, O-methoxybenzothiazole, j-carboxybenzothiazole, j-cya/benzothiazole, !-fluorobenzo Thiazole, j-ethoxybenzotheazole, tetrahydrobenzothiazole, j-ethoxybenzotheazole
, j-hydroxy (nzothiazole, 6-hydroxybenzotheazole, etc.), naphthothiazole core (e.g. naphtho-(/,,2-d)thiazole, naphtho-lj,
/-d] thiazole, naphtho[, 3-d) thiazole, j-methoxynaphtho(,2,/-d) thiazole,
j-ethoxynaphtho(:,2./-d)thiazole, za-methoxynaphtho(/,2-d)thiazole, 7-methoxynaphtho(/,rd, lthiazole, etc.), oxazole core (e.g. μm methyl Oxazole, j-methyloxazole, ≠-phenyloxazole, Hiroshi, j-diphenyloxazole, ≠-ethyloxazole, μI!
-dimethyloxazole,! - phenyloxazole, etc.), benzoxazole nucleus (e.g. ninzoxazole/--
Lu,! -chlorobenzoxazole, j-methylbenzoxazole,! -phenylbenzoxazole, 6-
Methylbenzoxazole! , 6-dimethylbenzoxazole, g, O-dimethylbenzoxazole, j
-Nodoxybenzoxasol! -Ethoxybenzoxazole, j-fluorobenzoxazole, 6-nodoxybenzoxazole,! -hydroxybenzoxazole, -hydroxybenzoxazole, etc.),
Naphthoxazole nucleus (e.g. naphtho(/,,2-d)
Oxazole, naphtho [λ,/-d) oxazole, naphtho (t2, 3-d, l oxazole, etc.), selenazole nucleus (e.g. selenazole, 4L-methylselenazole, ≠-phenylselenazole, "+1 diphenylselenazole" etc.), benzoselenazole core (e.g. benzoselenazole, j-chlorobenzoselenazole, j-methylbenzoselenazole, !-methoxybenzoselenazole, t-phenylbenzoselenazole, etc.), naphthoselenazole core (e.g. naphthoselenazole ) (/, 2-d) selenazole, naphtho [2,/-d) selenazole, naphtho (!
, 3-d] selenazole etc.], tellurazole core (e.g. penzotelllazole, j-methylbenzotelllazole,
j, O-dimethylbenzotellurazole, naphtho(/,-
2-d) Tellulazole, naphtho lj, /-d) Tellulazol, naphtho [co.

3-d] Tellurazole, 6-nodoxynaphtho [/.

2-d] tellurazole, etc.), thiazoline nuclei (e.g. thiazoline, ≠-methylthiazoline, ≠-phenylthiazoline, etc.), oxazoline nuclei (e.g.!).

j-dimethyloxazoline, etc.), isoxazole core (
(e.g., methyl isoxazole, etc.), benzisoxazole core (e.g., benzisoxazole, etc.),
3.3-dialkylindolenine nucleus (e.g. 3,3-dimethylindolenine, 3゜3,j-toIJmethylindolenine, J'-10rho3,3-dimethylindolenine, J'-ethoxycarbonyl-3 , 3-dimethylindolenine, etc.), 2-pyridine nuclei (e.g., pyridine, !-methylpyridine, etc.), ≠-pyridine nuclei (e.g., pyridine, etc.).

λ-quinoline nucleus (e.g. O-ethoxyquinoline, 6-ethylquinoline, O-chloroquinoline, f-fluoroquinoline, etc.), t-quinoline nucleus (e.g. g-methylquinoline, male-fluoroquinoline, O-chloroquinoline, etc.)
, /-isoquinoline nucleus (eg, isoquinoline, etc.) are preferred.

R3, R4 may have an unsubstituted or substituted amino group, a hydrogen atom, a lower alkyl group with carbon number/~μ (e.g. methyl group, ethyl group, propyl group, butyl group, etc.), carbon number λ~g Acyl groups (eg, acetyl, propionyl, benzoyl, etc.) are preferred.

It is also preferable that RI5 and R16 are linked to each other to form a j-membered ring or a 6-membered ring.

Furthermore, R15 and/or RI6 may combine with the benzene ring of the benzobyrylium nucleus to form a condensed ring.

Xe represents an anion, specifically chloride, bromide, iosito, thiocyanate, perchlorate,
Paratoluenesulfonate and tetrafluoroborate are preferred.

The compound represented by general formula (1) can be synthesized by various synthetic methods, but for example, as shown in the reaction formula below,
It can be obtained by a condensation reaction between an intermediate (A) obtained by the reaction of a bicyclic quaternary salt conductor having an active methyl group and an 11-methyl-μH-chromene-≠-thione derivative and an aldehyde.

In the above reaction formula, R,, R2, R3, R4, Z, P, and m have the same meanings as explained in general formula [I]. Also, x,
x2 and x represent an anion.

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 with an excimer laser, such as the second harmonic or third harmonic of a 1Nd:YAG laser, to obtain laser light in the near-infrared to infrared region, and their fastness is improved. It often acts as a high-performance laser dye with high energy conversion efficiency.

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

Compound-/ Compound = 2 Compound-3 Compound −≠ Compound-! Compound-6 Compound-7 Compound-g Compound-ta Compound-70 Compound-/l α04e Compound-72 Compound-73 Compound-/ll.

Compound-/yoα04e Compound-76 Compound-77 Compound-/za compound-/ri compound-λO Compound-, 2/ ■e Compound-2,! le Compound-13 104e Compound-2lA Engineering 6 Compound-,! ! Compound-2 Compound-27 e Compound-2g Compound-22 Compound-50 Br” Compound-3/ Compound-32 Compound-33 Compound-54L Compound-3! Compound-36 Compound-37 α04e Compound-3g Compound-57 ClO4 (:1 Compound-≠0 Compound-≠7 αo4e Compound-4L, 2 H2 go 4e Compound-q3 Compound-≠≠ Compound-month! Compound-≠6 CI!04e Compound-μ7 clo, e Compound-ψg clO40 Compound- ≠α04” Compound-jO (JO4” Compound-j/ Compound-j2 Compound-53 α04e Compound-j≠ 104e Compound-jS ClO4e Compound-! Otsu compound-37 CI!, Oa ” Compound-jlr Compound-jri compound -OtsuO Compound-6/α04e Next, examples of synthesizing the compound according to the present invention will be explained in detail with reference to the following examples.

Example-7 (Synthesis of intermediate (A)) / -(1) 3-ethyl-λ-((2-methyl-≠
H-chromene-Hiro-ylidene) methyl) benzothiazolium chlorate 3-ethyl! -Methylbenzothiazolium p-+-luenesulfonate/7. j-no and 2-methyl-μH-chromene-hiro-theone 1. After reacting IP by heating at /jO0C for lj hours, 20t1 of methanol and 4tOd of acetone were added to the reaction mixture to form a homogeneous solution. After cooling to room temperature 6
0% perchloric acid ir.

7F was added and 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 20 m methanol and acetone UOW at room temperature, and after stirring for 30 minutes, collected and washed with acetone, the desired product was obtained.
I got p. (Yield Hiro 0%) Brown crystal mp, 2g00C
Above (decomposition)/-(2)j-)lifluoromethyl-3-
Ethyl-2-l(2-methyl-H-chromene≠-yritene)methyl)-benzothiazolium pt-luenesulfonate! -Trifluoromethyl-3-ethyl-λ-methylbenzothiazolium p-toluenesulfonate, 37y
After heating and reacting 760 g of 2-methyl-4LH-chromene-≠-thione at 0°C for 20 hours, 10 td of methanol, then 10 d of acetone, and 2 d of ethyl acetate were added to the reaction mixture.
0 we was added to make a homogeneous solution. When cooled to room temperature, crystals precipitated.

After collecting the crystals and washing with a small amount of acetone, add iowt of methanol, 10d of acetone, 20d of ethyl acetate at room temperature.
Add the crystals to a mixed solvent of
After washing with acetone, the desired product/t71 was obtained. (Yield Hirotochi) Brown crystal mpu♂0°C or higher (decomposition) / -(,1
) j-chloro-3-ethyl-1(,!-methyl-1AH-chromene-hiro-ylidene)methyl)-benzothiazolium p~toluenesulfonate! -Kuroro 3-Ethyl! -Methylbenzothiazolium p-toluenesulfonate//, /y and 2-methyl-μH-diO-men-t-thionej.

After heating reaction at 750°C for 23 hours, 2! of methanol was added to the reaction mixture. ;Ml, then acetone! Ott.

Ether acetate/jO- was added and the mixture was cooled to room temperature to precipitate crystals. After the crystals were collected and washed with a small amount of acetone, they were mixed with methanol 2 j d, acetone jOd, acetic ether/! at room temperature. The crystals were added to a mixed solvent of Od, stirred for 20 minutes, collected, and washed with acetone to obtain the desired product 7. Got the tag.

(Yield j2%) Brown crystal mp2IO'C or higher (decomposition)/-(4)j-methyl-3-ethyl-2-+(!-methyl-μH-chromene-hiro-ylidene)methyl)benzothiazolium perchloratej -Methyl-3-ether-comethylbenzotheasorium p-toluenesulfonate 2, 071 and 2-methyl-4CH-chromene-≠-thione/.

After heating and reacting Oy at 1so0c for 2j hours, 10xl of methanol was added to the reaction mixture, followed by 0mg of acetone.

After adding 20 ml of ethyl acetate and cooling to room temperature, crystals precipitated. After collecting the crystals and washing with a small amount of acetone, at room temperature, methanol was added for 20 minutes, then acetone was added.
1 was added to make a homogeneous solution. To this, 60 g of perchloric acid was added, and after stirring at room temperature for 30 minutes, the precipitated crystals were collected by FI.
When washed with acetone, the target object / , <41. I got f. (Yield SS) Brown crystal mp2g00c or more (decomposition)/
-(5) s-methoxy-3-ethyl-j-((,
2-Methyl-1AH-chromen-4-ylidene)methyl)benzothiazolium iositoj-methoxy-3-ethyl-λ-methylbenzthiazolium p-toluenesulfonate2. /! ip and 2-
Methyl=≠H-chromene-Hiro-theon/, Of/! O
After heating reaction at 0C for 20 hours, methanol/
! ;mt, acetone/2 times was added to make a homogeneous solution.

To this solution was added l-IJium iodide/, 7F (acetone
We solution) was added dropwise and stirred at room temperature to precipitate crystals. The crystals were taken out and washed with a small amount of acetone, then added to 20 td of sewage water at room temperature, stirred for 71 minutes, taken out as F, and washed with acetone to obtain the desired product/02p. (Yield 3g%
) Brown crystal mp2g00c (decomposition) / -(6) 3-ethyluno((,2-methyl-
gH-chromene-Hiro-ylidene)methyl)-naphtho(,
2,/-d) Thiazolium iosito 3-ethyl-no-methylnaphtho Ij, /-d) Thiazolium iosito 2.271 and 1-methyl=≠H-chromene-t-thione/, Oy/! After heating reaction at O0C for 2 hours, methanol was added to the reaction mixture. rt, and then acetone/1 m was added to make a homogeneous solution. To this solution, 7.7 g of sodium iodide (water j m! bath solution) was added dropwise and stirred at room temperature for 7 hours to precipitate crystals. d, acetone/
The crystals were added to a mixed solvent of JD, stirred for 75 minutes, filtered, and washed with acetone to obtain 00 g of the desired product.

(Yield 2g%) Brown crystals mp, more than 2 oz (decomposition)/-(7
)3-(2-methoxyethyl)-! -((!-Methyl-≠H-chromene-≠-ylidene)methyl)benzothiazolium perchlorate 3-C2-methoxyethyl)-2-methylbenzothiazolium p-toluenesulfonate 4.3 and 2- Methyl-≠H-chromene-hiro-thione/.

The target product /, /1 was obtained from O in the same manner as /-(1). (Yield≠3%) Brown crystals mp,! 10'C or more (decomposition)/-(8
) j, A-dimethyl-3-ethyl-2-((2-methyl-H-chromene-gooylidene)methyl)benzothiazolium p-toluenesulfonate s, b-dimethyl-3-ethyl-! -Methylbenzothiazolium p-1 luenesulfonate 6.0y and 2-
After heating and reacting methyl-4'H-chromene-≠-thione/3.21 with isooC for 77 hours, methanol was added to the reaction mixture. Oxl, then 100 tt of acetone, and 300 ytl of ethyl acetate were added, and upon cooling to room temperature, crystals were precipitated. After collecting the crystals and washing with a small amount of acetone, the crystals were added to a mixed solvent of methanol, 100 yt of acetone, and 300 scraps of ethyl acetate at room temperature. After stirring for 1.20 minutes, the crystals were collected and washed with acetone. After washing, the desired product/A, 29 was obtained.

(Yield: 4tj) Brown crystal m p 2♂o 0C or more (decomposition) / -
(9) j-methyl-2((l-methyl-≠H-chromene-ψ-ylidene)methyl)benzoxacilium
Nomi-chlorate 2.3-dimethylbenzoxacilium p-toluenesulfonate 2. After heating reaction of jp and nometer≠H-chromene≠-thione/, 29 at /JO°C for 10 hours, methanol/j- and acetone were added to the reaction mixture.
d was added to make a homogeneous solution.

Add sodium perchlorate/2 to this solution (water/d solution)
was added dropwise and stirred at room temperature to precipitate crystals. f the crystal
After washing with a small amount of acetone, 10 d of room temperature sewage,
The crystals were added to 10 d of methanol, 20 d of ethyl acetate, and after stirring for j minutes, P was removed and washed with ethyl acetate to obtain the desired product.
3y- was obtained. (Yield/2%) Brown crystal mpj Otori~27/0C (Decomposition) Example 2 (Synthesis of compound -/) 3-Ethyl-((2-methyl-≠H-chromene!)
-ylidene)methyl)benzothiazolium perchlorate3. Of and≠-dimethylaminobenzaldehyde/
, /ノ was added to acetic anhydride and placed on an oil bath. The mixture was heated to reflux at 0°C for 30 minutes. After cooling to room temperature, precipitated crystalline P was collected and washed with methanol. Recrystallization from methanol-chloroform was performed j times to obtain 1 g of the target product O.

Green-black crystal mpr,? o-a2r 0Cmax
max Example 3 (synthesis of compound-2) 3-ethyl-,! -[(,2-Methyl-≠H-chromene-μm ylidene)methyl)benzothiazolium Bartalorade 3.0y and t-dimethylaminocinnamaldehyde/,j were added with acetic anhydridejOtdK on an oil bath/60
The mixture was heated to reflux at °C for ≠0 minutes.

After cooling to room temperature, ethyl acetate/00 d was added and stirring was continued for 30 minutes at room temperature. Using a mixed solvent of precipitated crystalline methanol/chloroform//de (v/v),
Passed through a silica gel column, then methanol-
The desired product 01j1 was obtained by recrystallizing twice from chloroform.

Dark green crystal mp, 2//~2/3°C (decomposition) max
max example ti
-(Synthesis of compound-3) 3-ethyl-,2-1(,2-methyl-4tH-chromene-gooylidene)methyl)benzothiazolium perchlorate2. jp and 7. Z-trimethylene-/, 2,
3,4t-tetrahydroquinoline-6-aldehyde i,
sy is acetic anhydride! ;In addition to 0 trt, on an oil bath/! 0°C
The mixture was heated under reflux for 4 Lj minutes. After cooling to room temperature, precipitated crystal P was collected, washed with methanol, and then washed with methanol.
Recrystallize from chloroform three times to obtain the desired product 2. /9'
I got it.

Dark green crystal mp 265~. 2 Otsu, r'c (disassembly)
Examples The methine dyes shown below were also synthesized in the same manner as shown in Examples λ to t.

The color tones are shown below.

Table 1-/ Table 1-2 Table 1-3 Table 1 - μ Procedural amendment 1985 is 7.3 days a month

Claims (1)

[Claims] A methine dye represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [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
represents a substituted or unsubstituted aryl group or a heterocyclic group, 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 It represents an atom, and R_3 and R_4 may form a fused 6-membered ring. Z represents an atomic group 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. X^■ represents an anion. p represents 1 or 2, and P is 1 when the dye forms an inner salt. )