JPS62168131A - Novel methine dye - Google Patents

Abstract

PURPOSE:To realize a dye which has excellent fastness and is effective as a filter dye and sensitizing dye and a dye laser having high energy conversion efficiency and high performance by synthesizing a methine dye expressed by the prescribed general formula. CONSTITUTION:The novel methine dye is expressed by the general formula, where n is 0 or 1, m is 0-2 integer, R1 is an alkyl group, R2 is an aryl group, heterocyclic group, R3-R5 are a hydrogen atom, alkyl group, alkoxy group, hydroxy group, amino group, halogen atom, R3 and R4, R3 and R5, R4 and R5 may form a condensed 6-membered ring. Z is a metallic atom group necessary for forming a 5- or 6-membered ring, X<-> is an anion, p is 1 or 2, p is 1 when the dye forms an inner salt. For example, 3-ethyl-2-{(4-methyl-2H- chromene-2-ylidene)methyl}benzolium perchlorate is subjected to heating reflux in an acetic anhydride and is cooled, by which the intended dye is deposited.

Description

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

(In the formula, n represents 0 or 1.m represents 0.1. or 2, R1 represents a substituted or unsubstituted alkyl group,
R2 represents a substituted or unsubstituted 7-aryl group or a heterocyclic group, and R3, Ra, and Rs may be the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a substituted or unsubstituted amino 7 group or a halogen atom, and R3 and R, R3 and R5 or R1 and R5 may form a fused 6-membered ring, Z is 5
It represents a group of nonmetallic atoms necessary to form a membered ring or a 6-membered ring, and these rings may have a substituent or be fused with another ring.

Here, other rings may be combined with R1 to further form a condensed ring, xe represents an anion, and p is! or 2
and p is l when the dye forms an inner salt. ) 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 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.) , or a substituted alkyl group (substituents include, for example, a carboxy group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), a hydroxy group,
Flucoxy groups having 8 or less carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxylcarbonyl group, etc.), alkoxy groups having 8 or less carbon atoms (e.g. methoxy group, ethoxy group, benzyloxy group, phenethyl group) oxy group, etc.),
Monocyclic 7-aryloxy groups having 10 or less carbon atoms (e.g. phenoxy group, P-)lyloxy group, etc.), acyloxy groups having 8 or less carbon atoms (e.g. acetyloxy group, propionyloxy group, etc.), acyloxy groups having 8 or less carbon atoms Acyl group (e.g. acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl group (e.g. carbamoyl group, N,
N-dimethylcarbamoyl group (1 morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (
For example, sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.), aryl group having 10 or less carbon atoms (for example, phenyl group, 4-chlorophenyl group).

An alkyl group having 18 or less carbon atoms substituted with a 4-methylphenyl group, an α-naphthyl group, etc.) is preferable.

It is also preferable that R1 be fused with a benzene ring fused to the 5- or 6-membered ring represented by Z to further form a 5- or 6-membered ring.

The 7-aryl group for R2 is a substituted or unsubstituted benzene ring group (e.g. phenyl group, 4-nitrophenyl group,
(4-chlorophenyl group, etc.), and substituted or unsubstituted naphthalene ring groups are preferred.

The substituted benzene ring group for R2 is represented by the following general formula (II)
A group represented by is more preferred.

In the formula, R11' R12, R13' R14 may be the same or different, and R11 to R14 have a carbon number of 1
12 unsubstituted alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group,
decyl group, dodecyl group, vinylmethyl group, etc.), or substituted alkyl group (substituents include carboxyl group, cyano group, hydroxy group, sulfo group, halogen atom (
(e.g., fluorine atom, chlorine atom, etc.), flukoxyl group having 8 or less carbon atoms (e.g., methoxycarbonyl group,
ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy groups having 8 or less carbon atoms (e.g. methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.), monocyclic aryl having 10 or less carbon atoms Oxy group (e.g. phenoxy group, p-)
lyloxy group, etc.), 7-syloxy group having 3 or less carbon atoms (
For example, acetyloxy group, propionyloxy group, etc.)
, an acyl group having 8 or less carbon atoms (eg, acetyl group, prohionyl group, benzoyl group, mesyl group, etc.).

Carbamoyl group (e.g. carbamoyl group, N,N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidi7carbonyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group,
morpholinosulfonyl group, piperidinosulfonyl group, etc.), 7-aryl group having carbon number lθ or less (for example, phenyl group,
An alkyl group having 18 or less carbon atoms substituted with a 4-arylphenyl group, a 4-methylphenyl group, an α-naphthyl group, etc.) is preferable.

Furthermore, as R13 and R14, substituted or unsubstituted 7
Mino group, carboxyl group, cyano group, hydroxy group, sulfo group, halogen atom (for example, fluorine atom, chlorine atom, etc.), flukoxyluponyl group having 8 or less carbon atoms (for example, methoxycarbonyl group).

ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy groups with 8 or less carbon atoms (e.g. methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.), monocyclic groups with 10 or less carbon atoms. 7-aryloxy group (e.g. phenoxy group, p-
), 7-syloxy group having 8 or less carbon atoms (e.g. acetyloxy group, propionyloxy group, etc.), acyl group having 8 or less carbon atoms (e.g. acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl group groups (e.g. carbamoyl group, N,N-dimethylcarbamoyl 117 sulfolinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, N.

N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.) are also preferred.

Lower alkyl groups (eg, methyl, ethyl, propyl, butyl, etc.) and acyl groups having 2 to 8 carbon atoms (eg, acetyl, propionyl, benzoyl, etc.) are preferred.

Further, R1□ and R18 may form a ring.

Further, R13 and R14 may form a benzo-fused ring, and it is also preferable that R or R12 and R13 or R14 are connected to form a 5-membered ring or a 6-membered ring, and R1
It is also preferable that □ and R12 are linked to form a 5-membered ring or a 6-membered ring.

The alkyl group for R, R, R5 is preferably a lower alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, isopropyl group, butyl group, etc.), and the alkoxy group is preferably a lower alkyl group having 1 to 4 carbon atoms. Alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, etc.)
is preferred.

~4 lower alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, etc.), C2-8 acyl groups (e.g. acetyl group, propionyl group, benzoyl group, etc.)
is preferred.

It is also preferable that R15 and R16 are linked to each other to form a 5-membered ring or a 6-membered ring.

Furthermore, R15 and/or R1θ may be bonded to the benzene ring of the benzobyrylium nucleus to form a condensed ring.

Further, the heterocyclic group for R2 is a pyrazole nucleus.

Preferred examples include a 1,2-dihydro-1-7zazulene-2-one nucleus, a pyrrolo(5,1-b)quinazolin-9-one nucleus, an indole nucleus, a pyrrole nucleus, and a pyrrolo(2,3-b)pyridine nucleus.

Z represents an atomic group necessary to form a 5-membered or 6-membered ring,
The ring is, for example, a thiazole nucleus (e.g. thiazole, 4-
Methylthiazole, 4-2enylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4°5-diphenylthiazole, 4.
(2-chenylthiazole, etc.), benzothiazole nucleus (
For example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobezothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5.6 monodimethyl(nzothiazole, !-bromobenzothiazole, ti lomobe/soteazole, j-trifluoromethylbenzothiazole, !
-phenylbenzothiazole, g-methoxybenzothiazole, j-methoxybenzothiazole, b-methoxybenzothiazole,! -carboxybenzothiazole,
j-cyanobenzotheazole! -fluorobenzothiazole, j-ethoxybenzotheazole, tetrahydrobenzothiazole, j.

4-Dimethoxybenzothiazole! -hydroxybenzothiazole, 6-hydroxybenzothiazole, etc.),
naphthothiazole nucleus (e.g., 7-(/,, 2-d))
Thiazole, naphtho(z,/-d)thiazole, naphtho[λ, 3-d)thiazole,! -methoxynaphtho [λ,
/-d) Thiazole, j-ethoxynaf) (,2,/-
d) Thiazole, l-methoxynaphtho(/, 2-d)thiazole, 2-methoxynaphtho(/, J-d')thiazole, etc.), oxazole nuclei (e.g. goomethyloxazole, !-methyloxazole, cuphenyloxazole) , 4tl!-diphenyloxazole, couethyloxazole, !-dimethyloxazole, !-phenyloxazole, etc.), benzoxazole nuclei (e.g. benzoxazo-A/, j-chlorobenzoxazole, !-methylbenzoxazole, !-phenyl) Benzoxazole, 6-methylbenzoxazole!
6-dimethylbenzoxazole, 6-dimethylbenzoxazole,! -methoxybenzoxazole,
! -Ethoxybenzoxazole,! -Fluorobenzoxazole, O-Methoxybenzoxazole,! −
hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.), naphthoxazole core (e.g. naph) (/, 2-d]oxazole, nut(2,/
-d:l oxazole, nut (, z, 3.-d) oxazole, etc.), selenazole core (e.g. selenazole,
goomethylselenazole, gouphenylselenazole,
the law of nature.

! -diphenylselenazole, etc.), benzoselenazole core (e.g. benzoselenazole, !-chlorobenzoselenazole, !-methylbenzoselenazole, !-methoxybenzoselenazole, !-phenylbenzoselenazole, etc.), naphthoselenazole Nucleus (e.g. Nandos (/, 2
-d) selenazole, naphtho[λ,/-d) selenazole, naphtho[λ, j-d) selenazole, etc.), tellurazole core (e.g. penzotelllazole, !-methylbenzotelllazole, !, 6-dimethylbenzo Tellurazole,
Naft (/, J-d) Tellurazole, Naft (a, z-
d) Tellurazole, naphtho[2°3-d]tellazole, 6-methoxynaphtho[/.

J-d) Tellurazole, etc.), thiazoline nuclei (e.g. thiazoline, goomethylthiazoline, gouphenylthiazoline, etc.), oxazoline nuclei (e.g.!.

! -dimethyloxazoline, etc.), inoxazole core (
(e.g., methyl isoxazole, etc.), benzisoxazole core (e.g., benzoinoxazole, etc.), 3
．． 3-Dialkylindolenine nucleus (e.g. 3,3-dimethylindolenine, 3°3.3-1-I)ltylindolenine,! -chloroi, 3-dimethylindolenine,! -ethoxycarbonyl-3,3-dimethylindolenine, etc.), -pyridine nucleus (e.g. pyridine, j-methylpyridine, etc.), terpyridine nucleus (e.g. pyridine, etc.), λ-quinoline nucleus (e.g. 6-nitoxyquinoline, ethylquinoline, 6-chloroquinoline, /-fluoroquinoline, etc.), 9-quinoline nucleus (e.g.!-methylquinoline, l-fluoroquinoline, 6-chloroquinoline, etc.), /-inquinoline nucleus (e.g., isoquinoline, etc.),
is preferred.

Xe represents a=o/, and specifically, chloride, bromide, iosito, thiocyanate, /e-chlorate, paratoluenesulfonate, and tetrafluoroborate are preferable.

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 heterocyclic quaternary salt derivative having an active methyl group and a goomethyl-2H-chromene-corchion derivative and an aldehyde.

In the above reaction formula, R1, R2, R3, R4, R5, z,
p, n and m have the same meanings as those explained in the general formula (1)C. Also, X10, X2° and Xe 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 groundwood pulp and bleached sulphite pulp, as well as pure pulp, and are virtually completely dyed. Furthermore, these dyes can be excited with an excitation method such as the second or third harmonic of an excimer laser or 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 [Natsu] of the present invention are shown below, but the present invention is not limited thereto.

Compound-7 Compound −λ Compound-Hiroshi compound average −j Compound-6 Compound-7 Compound-g Compound-ta Compound-/l Compound-1 04e Compound-/3 Compound-/Hiroshi compound-/j Compound-17 compound-/ri Compound-20 compound-co/ e compound-,2- Compound-23 Compound - 1μ e Compound-2 Compound-26 Compound-, 27 ■0 Compound-,2,r Compound-1? Compound-30 re Compound-3/ Compound-32 Compound-33 Compound-3≠ Compound-3j Compound-3 Compound-37 Compound-3 Compound-32 Compound-Hiro O Compound-Hiroshi α04e Compound-1 Compound-4Zj Compound - Hirohiro Compound Kazuhiro 6 CI 04e Compound-μ7 Compound-Hiroshi! Compound-Hiroshi? cg04” Compound-s.

Compound-jl Compound-yo- αO4e Compound-53 c! ! 04e Compound-54 α04e Compound-55 Compound-56 Compound-57 Compound-59 104e Compound-60 Compound-61 α04e Compound-62 Compound-64 Compound-7139 Compound-73 CI! O4e Compound-74 Compound-75 Compound-76 Compound-77 e Compound-78 Compound-79 e Compound-80 Compound-81 re Compound-82 αO4e Compound-83 Compound-84 Next: Two synthesis examples of compounds according to the present invention This will be explained in detail with reference to the following examples.

Example-/(Synthesis of intermediate CA))/-(1) 3-ethyl-((4-methyl-2
H-chromene-ylidene)methyl)benzene/dithiazolium nomi-chlorate 3-ethyl-2-methylbenzothiazolium p-toluenesulfonate/2. tg! =41-methyl-cohychromene-corchion/, /g/! After a heating reaction at 0C for 13 hours, 20 ml of methanol and 4 tornl of acetone were added to the reaction mixture to form a homogeneous solution. After cooling to room temperature, 7 g of perchloric acid/j was added and stirred at room temperature to precipitate crystals. The crystals were collected by filtration, washed with a small amount of acetone, and then mixed with methanol (θml) and acetone <t□ at room temperature.
The crystals were added to a mixed solvent of tnl, stirred for 30 minutes, collected by filtration, and washed with acetone to obtain the target product ♂, jg. (yield rate
H) Brown crystals m921066 or higher (decomposition)/-(2) s-
) trifluoromethyl-3-ethyl-((gu-methyl-2H-chromene-koylidene)methyl) benzothiazolium p-toluenesulfonate-trifluoromethyl-3-ethyl-2-methylbenzothiazolium I)-toluene Sulfonate j, J7
g and goomethyl-coH-'chromene-2-thione/, O
After heating and reacting g at θ0C for 20 hours, the reaction mixture (;
io ml methanol, then 10 ml acetone,
20 ml of ethyl acetate was added to make a homogeneous solution. When cooled to room temperature, crystals precipitated. The crystals were collected by filtration, washed with a small amount of acetone, and then added with 10 ml of methanol at room temperature. The crystals were added to a mixed solvent of acetone/θ"ls 20ml of ethyl acetate, stirred for 4 minutes, collected by filtration, and washed with acetone to obtain 4t7g of the desired product. (Yield: 6%) Brown crystals.
9272～. 27 joC (decomposition)/-(3) J-
-chloro-3-ethyl-λ-((4t-methyl-2H-
chromene-yoylidene) methyl) benzothiazolium p-) luenesulfonate! -Chloro 3-Etelukometerbensochi 77”
IJ') Mu p-toluenesulfona)//, 7g and goomethyl-2H-chromene-corchion! .

After reacting by heating at 1jo0c for 23 hours, 21ml of methanol was added to the reaction mixture. Next, 0ml of acetone and 10ml of ethyl acetate were added, and when the mixture was cooled to room temperature, crystals were precipitated. The crystals were collected by filtration, washed with a small amount of acetone, and then mixed with methanol, acetone, and ethyl acetate at room temperature. The crystals were added to Oml of a mixed solvent, stirred for -0 minutes, collected by filtration, and washed with acetone to obtain 2.9 g of the desired product.

(Yield j2chi) Brown crystal mp212-213°C or higher (decomposition)/-
(4) z-Methyl-3-ethyl-yo((4-monomethyl-λH-chromene-ylidene)methyl)benzothiazolium perchloratej-methyl-3-ethyl-yomethylbenzothiazolium p-toluene 2.07 g of sulfonate/thiru, 2H-chromene-corchion/.

After heating and reacting og with tjo'C for 2 hours, 10 ml of methanol was added to the reaction mixture. Next, add 10 ml of acetone and ethyl acetate, and cool to room temperature.

Then, crystals precipitated. The crystals were collected by filtration, washed with a small amount of acetone, and then 20 ml of methanol and then 10 ml of acetone were added to form a homogeneous solution at room temperature. 40% here
After adding 1 g of perchloric acid and stirring at room temperature for 3 g, the precipitated crystals were collected by filtration and washed with acetate to obtain 4 g of the desired product. (Yield 21@) Brown crystal mpx2o-x2t'
C or higher (decomposition) / -(5)
Ylidene) Methyl) Benzothiazolium Yosito! -Methoxy-3-ethyl-comethylbenzotheazolium p-toluenesulfonate, /! g and comethyl-2H-chromene-corchion/, θg 1ro0c
After heating reaction for 2g hours, methanol/jm was added to the reaction mixture.
1 and acetone/2 ml were added to make a homogeneous solution. Add sodium iodide to this solution, 7g (73ml acetate solution)
was added dropwise and stirred at room temperature to precipitate crystals. After collecting the crystals by filtration and washing with a small amount of acetone, add 20 ml of room temperature sewage water.
Add crystals inside! After stirring for several minutes, it was collected by filtration and washed with acetone to obtain 02 g of the desired product. (Yield 3!) Brown crystals mp273~27'l-°C (decomposition)/-(
6) j-ethyl-yo((4t-methyl-2H-chromen-2-ylidene)methyl)-naphtho[co,/-d
) Thiazolium iosito 3-ethyl-yomethylnaphtho [x, t-d) Thiazolium p-toluenesulfonate, 27 g and u-methyl-2H-chromene-cochion/, Og to 1jO0C
After heating reaction for 2j hours, methanol ♂m was added to the reaction mixture.
1 and then acetone/λml to form a homogeneous solution. 7.2 g of sodium iodide (6 ml of water solution) was added dropwise to this solution, and the mixture was stirred at room temperature for 7 hours to precipitate crystals. The crystals were collected by filtration, washed with a small amount of acetone, and then washed with sewage water at room temperature.
ml, add the crystals to acetone/jml mixed solvent,
! After stirring for several minutes, it was collected by filtration and washed with acetone.
I got g. (Yield, 2j%) Brown crystal mp2tro
'C or higher (decomposition)/-(force 3-(iomethoxyethyl)-yo((4t-methyl-2H-riramen-ylidene)methyl)penzothiazolium perchlorate J-(,2- methoxyether)-comethylbensoteasolium p-toluenesulfof-)&.

3g and goomethyl-JH-chromene-cochion/, O
The target product /, /g was obtained from /-g in the same manner as in (1). (Yield: 4tJ) Brown crystal m922000 or more (decomposition)/-(a)t+
a-dimethyl-3-ethylrouyo((4t-methyl-2
H-chromene-yoylidene)methyl)benzothiazolium p-)luenesulfonate! , O-dimethyl-3-ethyl-comethylbenzotheazolium p-toluenesulfonate-t,og and goo-methyl-coheychromene-2-thione/j,, 2g to 7
! After heating reaction at θ0C for 72 hours, 60 ml of methanol was added to the reaction mixture. Then 100 ml of acetone 3 s of ethyl acetate
00ml was added, and when the mixture was cooled to room temperature, crystals were precipitated.

The crystals were collected by filtration, washed with a small amount of acetone, and then washed with methanol at room temperature. θml, acetone/θomls vinegar R ethyl J
Add the crystals to the mixed solvent of OOmlj, and after stirring for 20 minutes,
It was collected by filtration and washed with acetone to obtain 76.2 g of the desired product. (
Yield %) Brown crystals m p 20 / ~20 °C or higher (decomposition) / -(9) J-Methylamino ((gumethyl-2H-chromene-ylidene) methyl) (nzoxazolium・G-chloratoco, 3-dimethylbenzoxacilium p-toluenesulfonate 2.1g
Upper 4t-) fk-JH-chromene-cochion/, 2g
of/! After a heating reaction at 00C for 7θ hours, methanol/jml and a7ton/2ml were added to the reaction mixture to form a homogeneous solution. Add 2g of sodium perchlorate to this solution (6 ounces of water)
ml solution) was added dropwise and stirred at room temperature to precipitate crystals. The crystals were collected by filtration, washed with a small amount of acetone, and then mixed with room temperature sewage/θml and methanol 70ml. Ethyl acetate-0ml
Crystals were added thereto and after stirring for 1 minute, the mixture was collected by filtration and washed with ethyl acetate to obtain 0.3 g of the desired product. (Yield/flathead) Brown crystal mpat q ~, 27/'C (min%)/
-(lo) J-ethyl-2-((4'-methyl-coH-chromene-coylidene)methyl)nut[/,2
-d] Thiazolium iosito 3-ethyl-2-methylnaphtho(/, J-d”) Thiazolium p-toluene 2.27f and 4-methyl-2-thiocoumarin/, 02 to/- Same as (6) the object o, or in a way
I got e. (Yield J, j) Brown crystals mp t po
~/tax 'C (Decomposition) Example 2 (Synthesis of Compound-7) 3-Ethylruyo((gumethyl-j H-chromene-ylidene) methyl 1-benzothiazolium perchlorate 3.02 and ≠-dimethylaminobe /zoaldehyde/, /S' was added to acetic anhydride JOtnl on an oil bath/!
Heat to reflux at O'C for ≠j minutes. After cooling to room temperature, P was collected from the precipitated crystals.

Washed with methanol. Recrystallization was performed 5 times from methanol and 90 roform to obtain the desired product, 0.119.

Green-black crystal mp20~, 21/0Cmax
, max Example 3 (synthesis of compound -) yo-ethyl-J-((<=-methyl-λH-chromene-coylidene)methyl)benzothiazolium perchlorado, 01 and gauge methylaminocinnamaldehyde/ , j7 to acetic anhydride romt; 1. On the oil bath
The mixture was heated to reflux at oC.

After cooling to room temperature, 100 ml of ethyl acetate was added, and stirring was continued for 3Q minutes at room temperature. The precipitated crystals were purified by passing through a silica gel column using a mixed solvent of methanol/chloroform = liter/liter (V/V), and then recrystallized twice from methanol/chloroform to obtain the desired product. I got IIt.

Dark green crystal mp/9j-/? A°C (decomposition) max
rnax Examples Synthesis of Example Component-3) 3-ethyl-2-((Hiro-methyl-2H-chromene-ylidene)methyl)benzothiazolium perchlorate, sy and/, f-)rimethyle 7-/, J, j, 4
Add t-tetrahydroquinoline-t-aldehyde/, j2 to acetic anhydride romt and place on oil bath/! Heated to reflux at O'C for ≠j minutes. After cooling to room temperature, the precipitated crystals were collected, washed with methanol, and recrystallized three times from methanol-chloroform to obtain the desired product. I got it.

Dark green crystal mp2Gj, 24r'C (decomposition) ma
x max Synthesis of Example Compound Hiro 6) 3-Ethyl-! -trifluoromethyl-co((ψ-methyl-2H-chromene-2-ylide/)mer)
Benzothiazolium p-)luenesulfonate 11
9 and 2.62 μm dimethylaminocinnamaldehyde were added to 100 ml of acetic anhydride, and the mixture was heated under reflux for 7 minutes on an oil bath using IZO'C. After cooling to room temperature, it was purified through a silica gel column using a mixed solvent of methanol/chloroform = 2/j (v/v). The obtained crystals were dissolved in methanol and cooled to 0.6C, whereupon sodium perchlorate 2. I? (Water jOmt) Aqueous solution was added. The precipitated crystals were collected and recrystallized three times from methanol-chloroform to obtain the desired product 3. I got j2.

Dark green crystal mpco3/'C (decomposition) max
max Example 6 The methine dyes shown below are also used in Examples 2~! It was synthesized in the same manner as described.

a　X The key is shown below.

Example 7 (Synthesis of Compound-53) 3-Ethyl-2-((leemeter-2H-chromene-mooylidene)methyl)benzothiazolium nochlorate J, Og and 7.3 g of 11-amino-cu-dimethylaminobenzaldehyde The mixture was added to 30 ml of acetic anhydride and heated under reflux on an oil bath/zo0c for 30 minutes. After cooling to room temperature, the precipitated crystals were collected by filtration and washed with methanol. Recrystallize from methanol-chloroform! Non-rotating object Q
- Obtained rg.

Green-black crystal mp, 220-2210C Example 8 (synthesis of compound-55) 3-ethyl-co-((4t-methyl-co-H-chromene-coylidene)methyl)benzothiazolium perchlorate 3.0 g and no-hydroxy-goodiethylamino Add benzaldehyde/, jg to acetic anhydride, jOml,
The mixture was heated to reflux on an oil bath/jo0C for 90 minutes. After cooling to room temperature, ioml of ethyl acetate was added, and stirring was continued at room temperature for 30 minutes.

The precipitated crystals were mixed with methanol/chloroform = //9 (v
/v) was purified through a silica gel column, and then recrystallized once from methanol-chloroform to obtain 0.7 g of the desired product.

Dark green crystal mpλ3/~ko 33°C (decomposition) Example 9
(Synthesis of Compound-61) 3-Ether-yo-chloro-2-((<z-methyl-2H
-Chromen-2-ylidene) methyl) benzothiazolium perchloratoco, jg and! -Methoxy/? −
) Rimethylene/, 2. ! .

Gutetrahydroquinoline-6-aldehyde/.

Add jg to jOml of acetic anhydride and heat on oil bath/at 5o0C for 4 hours.
The mixture was heated to reflux for tj minutes. After cooling to room temperature, the precipitated crystals were collected by filtration, washed with methanol, and then recrystallized three times from methanol-chloroform to obtain the desired product.

Dark green crystal mp, 27j-27/'C (decomposition) Example 10 The methine dye shown below was also synthesized in the same manner as shown in Examples 5-9.

eOH For the obtained compound, λ and crystal color ax The key is shown below.

Table 2-/ Table 2-2

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 0, 1, or 2. R_1 represents a substituted or unsubstituted alkyl group, and R_2 represents a substituted or unsubstituted alkyl group. R_3R_4R_5 may be the same or different 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_4, R_
3 and R_5 or R_4 and R_5 may form a fused 6-membered ring. Z represents a group of nonmetallic atoms 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. Here, the other ring may be combined with R_1 to further form a condensed ring, and X^■ represents an anion. p represents 1 or 2, and when the dye forms an inner salt, p is 1
It is. )