JPS58157862A - Production of merocyanine dye - Google Patents

Abstract

PURPOSE:The condensation reaction between an aminoalkenyl cyclic amidinium compound and an active methylene compound is carried out in the presence of an inorganic base to produce a high-purity merocyanine dye that is used as a sensitizing dye for photographic materials and antihalation dye. CONSTITUTION:The objective dye is prepared by condensation reaction of an aminoalkenyl cyclic amidinium compound of formulaI Z is nonmetallic atom group required to form a 5-6 membered heterocyclic ring or condensed ring; L1-L4 are methin; l, m1, n are 0, 1, m1+m2 is 0-3; R is alkyl aryl, alkenyl, which may form a ring with L1; R1, R2 are lower alkyl, R1 and R2 may incorporate to form a ring; X is anion with an active methylene compound in the presence of an inorganic base such as sodium hydroxide or potassium hydroxide. For example, the reaction of a cyclic amidinium compound of formula II with an active methylene compound of formula III gives a dye of formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing merocyanine dyes. More specifically, the present invention relates to a method for producing an improved merocyanine dye by condensing an aminoalkenyl cyclic amidinium compound and an active methylene compound in the presence of an inorganic base.

Merocyanine dyes are extremely useful dyes as sensitizing dyes for photographic light-sensitive materials, or as anti-irradiation dyes and dyes for preventing smearing.

Alternatively, it is a compound that is also used as a raw material for synthetic intermediates such as complex cyanine dyes.

The method for synthesizing merocyanine dyes is described in U.S. Patent No. 2.165.
, No. 338, No. 2,170,803, British Pestle No. 4
No. 28,359, No. 466.244 or F.
Engineering A @ Marmar (F, M, Marmar)
Author [The cyanlne Dye El
and Related Compounds ) (1
964) Interscience Hazards Dictionary Wiley & Sons (Enter8ci@
nce pubxt8Mrs, yOhn Wiley
ASons), etc. That is, a method of heating an active mefL/n compound and a ketomethylene cyclic amidinium compound in acetic anhydride, a method of heating a thioether alkenyl cyclic amidinium compound in a suitable solvent in the presence of an organic base, or a method known as an ICI intermediate. It is produced by a method in which an anilinovinyl cyclic amidinium compound is reacted in the presence of an organic base.

Among them, a method using an ICI intermediate has been commonly used, a method of reacting in acetic anhydride in the presence of a base, and a method of reacting with an ICI intermediate, as disclosed in U.S. Pat. No. 2,170,804, etc. A method of isolating the WAM compound as an active N-acyl compound and heating it in an ethanol solvent in the presence of an organic amine has given relatively good results. However, this method cannot be applied to all anilinovinyl cyclic amidinium compounds, and therefore, for example, in the case of betaine-type anilinovinyl cyclic amidinium compounds substituted with acidic groups (°sulfonic acid groups), it is generally , 030゜584 and JP-A-55-45015, a method of carrying out the reaction at high temperature in a very pyridine solvent or without a solvent is used.

In the above method, since the reaction is carried out under high temperature conditions, it has been recognized that by-products are mixed into the reaction product, causing a decrease in yield or purity, especially when the sulfo group is substituted. The yield is significantly lower. 1 more
% warm reaction/reaction, the operating environment was deteriorated due to the presence of a marked amine odor and acetic acid odor, and it was necessary to take countermeasures against the odor, which was not desirable.

Therefore, an object of the present invention is to provide a method for producing a merocyanine dye with high yield and purity for general purposes.
Another object of the present invention is to provide a method for producing merocyanine dyes without polluting the environment.

The object of the present invention was achieved by the production method described below, that is, by condensing an aminoalkenyl cyclic amidinium compound represented by the following general formula (IJ) and a compound having an active methylene group in the presence of an inorganic base.

General formula (In the formula, 2 represents a nonmetallic atomic group necessary to form a 5- to 6-membered heterocycle. It's okay,
However, these rings can also have a substituent. The heterocycle may be of any type known in the field of cyanine dye chemistry, examples of which include: : Bilorin 3
1# (for example, 4-methyl-viroline ring, etc.); Oxazoline ring (for example, 4,4-dimethyloxazoline ring, etc.)
; thiazoline ring (for example, 5-methyl-thiazoline ring, etc.); selenazoline ring; indolenine destruction (for example, 3,3
-dimethylindolenine ring, 3.3-dimethyl-5-methoxyindolenine ring, 3゜3-dimethyl-5-chloroindolenine 1%, 3゜3-dimethyl-5-methylsulfonylindolenine 7m, 3? 3-dimethylbenzo[
benzimidazole ring (e.g. l-ethyl-5-trifluoromethyl-benzimidazole ring, 1-methyl-5-chlorobenzimidazole ring, 1-ethyl-s, 6-cyclo Penzimitazole term, l-ethyl-5-cyanobenzimidazole ring, dicarbonylbenzimidazole ring in 1-methyl-5-buto, 1-ethyl-5-7 cetylbenzimidazole, 1-methylbenzimidazole-5 -sulfonic acid pyrroliscito term, 1-king tilpenzimidazole-5-sulfonic acid dimethylamide ring, l-ethyl-5-7-ethylpenzimidazole term, l-methyl-5-methylthiobenzimidazole ring, 1-methyl -5-chloro-6-methylthiobenzimidazole ring, etc.) Nioxazole ring (such as Vi4-methyloxazole ring, 4,5-diphenyloxazole ring, 4-methyl-5-ethoxycarnioxazole term, benzoxazole ring, 5- 5-phenylbenzoxazole 31. 6-methoxybenzoxazole ring, 5-methoxybenzoxazole ring, 5-methyl-6-methoxybenzoxazole ring, 5-) romopenzoxazole destruction , 5-chloro-6-methylbenzoxazole ring, naphtho-[2,1-α]-oxazole ring, naphtho-
(1,2-α]-oxazole ring, naphtho-[2,3-
α]-oxazole ant, 4°5.6.7-titrahydrobenzoxazole product.

benzofuro (2,3-f)-benzoxazole ring, etc.); thiazole ring (e.g. 4-methyl-thiazole ring, 4-phenylthiazole ring, 4°5-diphenylthiazole ring, benzothiazole ring, 5-methylbenzo Thiazole, 6-methylbenzothiazole, 5-chlorobenzothiazole ring, 5-methoxy-benzothiazole ring, 6-medoxypenzothiazole, 5.6-dimethyl-penzothiazole, 5.6 -cymethoxybenzothiazole ring, 5-methyl-6-medoxybenzothiazole ring, 5-bromobenzothiazole 5-phenyl-ben If": fl-il, 6-methylthiobenzothiazole ring, 6-methyl-6-methoxybenzothiazole ring, 5-bromobenzothiazole Methylaminobenzothiazole term, 5-chloro-6-medoxybenzothiazole 3
jl, 5.6-methylenedioxybenzothiazole product,
6-β-cy7noethoxypenzothiazole ring, 5-ethoxycarbonyl-benzothiazole ring, 5-nitro-
Benzothiazole ring, 5-7 enylthiopenzothiazole ring, 5-f enylupenzothiazole It, 6
-Hydroxybenzothiazole iN, 4,5,6.7-
Titrahydrobenzothiazole, 4-oxo-4,
5,6,7-teto2hydro-benzothiazole ring, naphtho-[2,1-α]-thiazole term, na7)-[1,2
-α]-thiazole, 4゜5-dihydronaphtho-(1
,2-α]thiazole ring, 5-methoxynaphtho-[l,
2-α]-thiazole, 5,7.8-)rimethoxynaphtho[1,2-α]-thiazole, naphtho-[2
゜3-α)-thiazole ring, cheno-(4,5-1))
-thiazole ring, etc.); Selena pulley 19 and benzoselenazole ring, 5-methylbenzoselenazole ring, 5,
6-Simethyl-benzoselenazole 11.5-Methoxybenzoselenazole II, 5-methyl-6-medoxybenzoselenazole %5゜6-Simethoxybenzoselenazole II, 5.6-methylene Cyoxypenzoselenazole, 6-methyl-benzoselenazole, naphtho-(2゜l-α]-selenazole, etc.); l
*3e 4-oxadiazole ring (9 e.g. 5-methyl-1,3°4-oxadiazole ring, 5-phenyl-
1,3゜4-oxadiazole ring, etc.); 1,3.4-thiadiazole 1! (9 For example, 5-methyl-1,3,4-
Thiadiazole ring, 2,5-bis-methylthio-1,3
, 4-thiadiazole ring, 5-benzylthio-1,3,
4-thiadiazole ring, 2-mercapto-5-methylthio-1,3,4-thiadiazole ring, 5-methylthio-
1,3,4-thiadiazole ring, etc.); Pyridine ring; Quinoline ring (for example, 6-methylquinoline ring, 8-chloroquinoline ring, 6-nodoxyquinoline concentration, 5,6-benzoquinoline ring, etc.); Imidazolo- (4,5-b)-quinoxaline ring (e.g. l-ethylimidazolo-(4,5-b)
)-quinoxaline ring, etc.), LI + Ll +L, and TRI each represent a methine group, a lower alkyl group such as methyl or ethyl, a lower alkoxy group such as methoxy,
It may be substituted with a phenyl group, or a halogen atom such as a chlorine atom or a fluorine atom.

1 and n represent an integer of 0 or 1, and m is
0 or 1, m, +- represents an integer selected from 0 to 3. R represents an alkyl group, an aryl group, or an alkenyl group (for example, an allyl group), and may be substituted (or may be bonded with L to form a ring. R1*
``* each represents a lower alkyl group, which may be bonded to each other to form a base. -Represents toluenesulfonate, etc.

The alkyl group represented by R1 includes, for example, linear and branched alkyl groups such as methyl, ethyl, n-propyl, and 1sO-propyl; alkyloxy groups such as hydroxy; methoxy; and ethoxy; and alkylthio groups such as methylthio and ethylthio. : Alkoxycarbonyl group such as ethoxycarbonyl and methoxycarbonyl; Aryloxycarbonyl group; Carbamoyl group, i) group, sulfo, sulfonamide group, phenyl group, halogen atom such as fluorine atom or chlorine atom, trimethylsilyl group , substituted alkyl groups such as carboxy, etc.

The aryl group represented by R is preferably an it phenyl group, and examples of substituents include hydroxy, methoxy, acyl, sulfo-carboxy, ethoxycarbonyl, carno (moyls, aminos, halogen atoms,
These include sulfonamide groups.

Among these aminoalkenyl amidinium compounds, the compounds represented by the general formula are particularly good.

In the formula, Z, Ll + LHr R'HR" p
m'' has the same meaning as described in the general formula (month), and A represents a divalent aliphatic group or a divalent aromatic group.

The divalent aliphatic group represented by A includes linear and branched alkylene groups such as methylene, ethylene, fluoropylene, and 1-methyl-propylene; ...may be substituted with a rogone atom, etc., and may also be substituted with an ether bond such as 3-oxahexylene or 4-+7 hexylene (
Represents an alkylene group (including a thioether bond, etc.). The divalent aromatic group represented by A is, for example, a phenylene group, and may have, for example, a hydroxy, nodoxy, acyl group, sulfo, or halogen atom as a substituent.

Preferred inorganic bases used in the present invention are selected from alkali metals, and specific examples include sodium hydroxide, potassium hydroxide, sodium alcoholade, potassium alcoholade, and the like.

The active methylene compound of the present invention has the following general formula tl),
Includes compounds shown in [1].

General Formula El) General Formula In the above general formula, Q represents a 5- or 6-membered AA or a group of nonmetallic atoms necessary to complete the condensed product, such as 9, benzo[]thiophene -5(2H)-one ring, benzoToJthiophene-5(2H)-one-1,1
-dioxide term, 2H-indene-1,3-dione,
imidazo[1゜2-α]pyridine-2(5)1)-one ring, imidazo[1,2-α]pyridine-5(2)1)-
on ring, 1,3-dihydro-2H-indol-2-one term, IH-quinolin-2-one ring, coumarin ring, 3B
-imidazo[4,2-α]viridinium-2-one term,
3H-imidazo[4,2-α]viridinic mu-3-one ring, 5,6,7.8-nato2hydroimidazo[l,2
-α]Pyridine-2(5-imidazol-5(2H)-one ring, barbituric acid ring, 2-thiobarbital acid ring,
α-pyridone ring, r-pyridone ring, pyrazolidine-3,
5-dione ring, 5(4H)-pyrazolo/yellow, 2,1°3
-Thiadiazolidin-4-one I! , 1,3-thiazolidine-2,4-dione ring, 2-thio-1°3-thiazolidin-4-one ring, 4(5H)-1°3-thiazolone ring, 2-thio-1,3-selenazolidine -4-on 3J
l, 5(4B)-isoxacylone ring, 2-thio-1,3
-oxazolidin-4-one ring, imidazolidine-2,
These are acidic rings such as 4-dione rings, 2-thio-imidazolidin-4-one rings, and cyclohexanone rings. Substituents include straight chain, branched, or cyclic alkyl groups such as methyl, ethyl, inglovir, and cyclohexyl ( (However, it may be substituted with, for example, hydroxy, methoxy, sulfo, carboxy, phenyl group, halogen atom such as 79 atoms); phenyl group (however).

For example, halogen atoms such as hydroxy and chlorine atoms; These include aryloxycarbonyl group, sulfonyl, sulfo, carbamoyl group, sulfonamido group, nitro group, and the like.

In the present invention, the reaction is preferably carried out at a temperature below (a)°C, and in order to suppress side reactions, it is particularly preferable that K is also carried out at a temperature below 30°C.

The reaction solvent can be any solvent that is inert to the reaction except for water and dissolves the reactants, but preferred examples include alcohols such as methanol, ethanol, methylcellosolve, phenol, and cresol. Can be mentioned.

In the present invention, aminoalkenyl cyclic amidini represented by general formula 113? : Mu compounds can be registered using known methods.

For example, a method using diethyl acetal of dimethylformamide is described by H. Bredereck et, a.
l.

Argew, eh@1m, 73493 (1961)
A method using dimethyl acetal of dimethylformamide is described by HoMeerwein, et. al., An.
n 641 1 (1961), the synthesis method using the Wills-Meyer reaction is described in US Pat. No. 2,155,447 and US Pat. No. 3,723,419, respectively.

In addition, U.S. Patent No. 2,166.736, U.S. Patent No. 2.
No. 263,749, G, RoBrooker,
F.L.

White at, al, J, Am+Ohem+S
It can also be synthesized by a method in which an anilinoalkenylamidinium compound is substituted with an alkylamine under acylation conditions, as described in J. oc., 53 3192-3203 (1941).

Although typical aminoalkenyl cyclic amidinium compounds are shown above, the present invention is not limited thereto.

■-■ I-■ I-■ ■-■ 1-(5ri r-■ ■-■ ■-■ 1-■ I-(91-01(,
3 Luo ■ -〇e
Summer −〇! −0■ ■−[phase]
, e′4°L″ stand) C81-(c) ■-[Phase] 1-Φli 1-0F91-J mark
1-(t)l-@H@ In the present invention, the aminoflukenyl loamy amidinium compound and the active methylene compound represented by the general formula [IJ]
Molar ratio of 1.5 to 1.0 to 1. The molar ratio of the amine vinyl cyclic amidinium compound and the inorganic base is preferably at least 1.0, and is preferably from 1.0 to 2.
．． A range of 0 is preferred. There is no limit to the solvent cap used in this reaction, and any amount can be used in order to carry out a uniform reaction.

In the method of the present invention, it is desirable to avoid the presence of excess water in the reaction system. This is rounding to avoid hydrolysis of the aminoalkenyl group.

The fact that the ami-7 group reacts as a leaving group is shown in U.S. Pat.
, No. 166.736. However, J.
Am, Ohem, Soe, 63, 3192
3203 (1941) and the implementation (p. 46), the yield was extremely low and inferior to other methods of synthesizing merocyanine dyes.

With the method of the present invention, small yields and high purity have been achieved for the first time, and yet it has been possible to achieve significant advantages over other known methods. That is, (1) the reaction operation is simple, (2) the reaction is carried out at low temperature, (3) there is no release of significant amine odor or acetic acid odor, and (4) the yield is high, especially for merocyanine dyes having a sulfo group. In the case of (5), significantly better yields can be obtained compared to conventionally known methods.The production of by-products is suppressed and the purity of the crude crystals is high. .

Merocyanine dyes produced by the present flJ(7) method include, for example, the following, but the present invention is not limited thereto.

[Exemplary dye]

2 4 6 78 10 122 324 526 27 28 c,)'I-
132 334 536 3738 0H, OH, 8Q, H Below, the present invention will be specifically explained along with a synthesis example of a dialkylaminoalkenyl cyclic amidiecum compound represented by the general formula [IJ and a comparative synthesis example of a merocyanine dye.

Reference Example II-Synthesis of ■ (Starting Material) 2.4-) Add 23.4 jl of iodoethyl to 11:M of 4-)limethyloxazoline at room temperature, and heat to 90'C.
After stirring for 2 hours in an oil bath, 30°C of nitromethane is added and the mixture is reacted again for 4 hours in a ~90'C oil bath.

Meanwhile, 36.5 # of dimethyl formamide and 4 Jl of dimethyl sulfate were mixed and stirred in an oil bath at 70-80°C for 3 hours. Thereafter, metallic sodium 11.51 was dissolved in dehydrated methanol 150117KII, cooled on ice, and the above reaction solution was added dropwise while maintaining the temperature at 0°C. After finishing dropping, 70~80″C
After stirring for 2 hours in an oil bath,! f! The L-form substance is distilled off and the distillate is distilled using a column packed with metal shafts.

Distillate was added to the above nitromethane reaction solution, and after refluxing for 1 hour, it was concentrated, dissolved in 200d of 180-glopanol, and cooled.

Collect the precipitated crystals. Yield: 18.61, recrystallized with methanol and amethane.

Reference example 2 Synthesis of l-■ (starting material) anhydro-
200 g of ethanol was added to 59 g of 2-(2-ethoxy-1-butenyl')-(5-phenyl-3-2-sulfoethyl)penzoxazoliwam hydroxide, and the mixture was suspended and stirred during addition. Then add 2.49 piperidine,
Stir for 1 hour. Concentrate to dryness and mix water and ethanol fl! If&2DILt(1: 1 O
! 1JO) Melt and heat under heat. After cooling, the precipitated crystals are collected.

Yield 3.3g Reference Example 3 Synthesis of I-■ (Starting material) Anhydro-
2-(β-anilinovinyl 3-3-(3-sulfopropyl)-2-thiazolium hydroxide 131 and piperidine 8.59 are stirred and cooled on ice. Washed with 1so-propyl ether and the supernatant liquid The residue is ground, washed with 1so-propyl ether, and treated with F.

Yield 1i12.3.9 Other starting material compounds represented by the general formula (!) can also be synthesized in the same manner as above.

Reference Example 4 (Comparative Example 1) 4-(2-anilinovinyl-3-benzoxazolio)
butane-1=sul7honor) 71.6# and l-and droxyethyl-3-phenyl-2-thiohydantoin 47.
211 is mixed, pyridine 300I is added, and the mixture is suspended and stirred. Add piperidine 17# to this and heat and stir in an oil bath at 120 to 110°C for 75 minutes. Thereafter, the reaction solution was allowed to cool, and 16.69 ml of sodium acetate was dissolved in 3001 ml of ethanol, and 9#l was added thereto, stirred, and allowed to cool. The precipitate was collected and washed with ethanol and 77 tons. Yield 40.5I
i. Recrystallize with methanol and water.

With this synthesis method, L has low crude crystal purity and low yield.

Reference Example 5 (Comparative Example 2) 4-(2-anilinovinyl-3-penzoxazolio)
1-Hydroxyethyl-3-7enyl-2-thiohydantoy y2B, 81 to 34 g of phytane-1-sulfonate
and morpholine 90s+j, and in an oil bath at 90'C,
After heating for an hour, ethyl acetate 2001 was added and left at room temperature. After decanting the supernatant liquid, add a small amount of methanol to the residue, dissolve it, and add hot acetone 501.
was added and left at room temperature, the precipitate was collected, and methanol 2
DydlfC and a solution of 161 potassium acetate dissolved in 50 methanol were added and heated for 10 minutes, then left at room temperature and collected.

Yield: 2 g The synthesis method described in JP-A No. 55-45015 requires complicated operations and has a low yield.

Reference 916 (Comparative Example 3) Compound 1-■ 1B21 and 1-hydroxyethyl-3-
11.89 g of phenyl-2-thiohydantoin was dissolved in 2501111 JKl of ethanol, 59 g of triethylamine was added thereto, and the mixture was heated under reflux for 1 hour. The reaction solution did not change in appearance,
Merocyanine dye #1 is rarely produced. Reference 7 (Comparative Example 4) Dissolve 2-(2-7nilinovinyl)-3-ethylbenzoxazoliumethylsulfurine) 19.5.9 in methanol 100ml .

A solution of 11.8# of 1-hydroxyethyl-3-phenyl-2-thiohydantoin dissolved in 1001 LtK of methanol is added and stirred. A solution of 5.69 ml of potassium hydroxide in 30 dl of methanol was added dropwise, and the mixture was stirred for 1 hour. After stirring, the mixture is cooled in thick ice, the precipitate is washed with ethanol, and F is collected. Yield: 4 gEven in the presence of an inorganic base, the yield is low in the case of the reaction of the anilinovinyl cyclic amidinicum compound and the active methylene compound.

Synthesis of the following dye (Exemplary Dye-1O) Compound I-■15.91 3-Hydroxyethyl-2
-thio-1,3-oxazolidine-2,4-dione8.
1 g of ethanol is dissolved in 200 mK of ethanol, and tS, which is a solution of 3 g of potash hydroxide dissolved in ml of methanol, is added dropwise while stirring under water cooling.

After 2 hours, the precipitated crystals are collected. Yield 14g water,
Recrystallization is performed using a mixed solvent of methanol. Yield 9
．． 9g Example 2 Synthetic compound ■-■181 of the following dye (exemplary dye-17) and 1-human tetraxyethyl-3-phenyl-2-thiohydantoin 121i were mixed with methanol 30
Stir and dissolve in 01. A solution of 5 g of hydrogen oxidizing power dissolved in methanol 5017 is added dropwise to the reaction solution. After the completion of the droplet F, it is cooled, and the precipitate is washed with ethanol and collected. Yield: 31. Recrystallize with a mixed solvent of water and methanol. Yield 21
g.

Example 3 Synthesis of the following dye (Exemplary Dye-19) 35 g of compound l-■ and 22 g of 1-(2-(2-hydroxyethyloxy)ethyl)-3-methyl-2-thiohydantoin were mixed with 3 ow Lt of m-cresol and methanol. 1
Add to the mixture of 50- and stir at room temperature, S0 potassium hydroxide 119 dissolved in methanol 50 s
Add the liquid dropwise and continue stirring for an additional hour. Immediately before the end of stirring, acetone 1001 was added and cooled in thick ice, and the precipitate was washed with acetone and removed. Yield: 41.51 Recrystallization is performed with a mixed solvent of water and methanol.

Yield: 31.3 #0 Example 4 Synthesis of the following dye (Exemplary Dye-13): 25 g of Ibi-extractant 1-1 and 1-(2-(2-hydroxyethyloxy)ethyl)-3-phenyl-2-thiohytintoin Mix 209, add ethanol 2001, and stir at room temperature. A solution of sodium hydroxide 5II dissolved in methanol 1001 was added dropwise, and stirring was continued for an additional hour. After stirring, the mixture is cooled in thick ice, and the precipitate is washed with acetone and collected.

Yield (material): 39 Recrystallize with methanol.

Yield Sae, 31! .

Example 5 Synthetic compound 1-018g of the following dye (exemplary dye-23) and 3-(2-methoxyethyl)-2
-thio-1,3-thiazolidine-2,4-dione tO9
Suspend and stir in ethanol 20011j, add dropwise a solution of 3Ii of potassium hydroxide dissolved in 1 part of methanol under water cooling, and stir for 1 hour.

After stirring, cool in ice field, take one precipitate and pour into ethanol.
, wash with water. Yield: 179 Recrystallize from acetonitrile. Yield 15.3 #o-Example 6 Synthetic compound of the following dye (Exemplary Dye-29)! -■η, 2 g was dissolved in 300,114 K of ethanol, 11.9 g of 3-ethyl-1-phenyl-2-thia-hydantoin was added, and the mixture was stirred on ice-cooled F. A solution of potassium hydroxide 39 dissolved in methanol 20 iK was added dropwise and stirred for 1 hour. Cool in an ice field, wash the precipitate with ethanol, and collect. The yield was 23.5 g. Recrystallization was performed using a mixed solvent of water and methanol.

Yield: 16.2.9゜Example 7 Synthesis of the following dye (Exemplary Dye-6) 4.49 ml of sodium methoxide was dissolved in 50 ml of methanol, and 9.89 ml of N-n-octyl nitrile acetic acid amide was added. , stir. Compound I-■16.
A solution of No. 39 dissolved in 2 AJd of methanol is added, and after stirring in a circular motion, the mixture is cooled on ice and the precipitated inorganic matter is collected.

Pl& is removed under reduced pressure and the residue is extracted with 90 su of ethyl acetate. Add n-hexane to the extract. Take 1 portion of the precipitate. Yield 13-91.

Example 8 Synthetic compound of the following dye (exemplary dye-25) ■-016 & and 3-(2-methoxyethyl)-2
-thio-1,3-thiazolidine-2,4-dione IOg
Suspend and stir in ethanol 3001 and cool on ice. A solution of 3I potassium hydroxide dissolved in 20ajK methanol is added dropwise and stirred. After stirring, it is cooled in an ice field, and the precipitated 7 substances are washed with ethanol and collected.

The yield was 19 g, and recrystallization was performed using a mixed solvent of water and methanol. Yield: 15g.

Various merocyanine dyes were obtained in the same manner.

The results are shown in the table below.

6 (Exemplary Dye-30) (Exemplary Dye-53) (Exemplary Dye-54) (Exemplary Dye-3) OH, OH, OH, 80, K (Exemplary Dye-7) Based on the merocyanine dye having a nisulfo group, A table comparing the yields of the known method and the method of the present invention is shown.

(Exemplified Dye-17) (Exemplified Dye-1O) (Exemplified Dye-29) (Exemplified Dye-25) (Exemplified Dye-1l) C Exemplified Dye-+8) (C Peng), So, K (Exemplified Dye-7) (Al Method of Reference 2 Example 4 (b) #5〃 (C1 Method of Japanese Patent Publication No. 47-13424 9) In the case of merocyanine dyes substituted with sulfo groups, the method according to the present invention has a significantly higher yield than the known method. It is clear that the rate is improved.

Attorney Atsushi Kuwa, Patent 1J Commissioner, Atsushi Kuwa, Case Indication Showa M Year Patent Application No. 400! $7 No. 2, Name of the invention Method for producing merocyanine dye 3 Relationship to the case of Supplementary IE Nagisa “T” Patent author Address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (1st Tsukasa Konishiroku) Photo Industry Co., Ltd. Address: 1-6 Sakura-cho, Hino-shi, Tokyo Column 7 of ``Detailed Description of the Invention 11J'' of the specification to be amended Contents of the amendment (1) Detailed description of the invention 1! Father-in-law as follows: to correct.

Claims (3)

[Claims] (1) A method for producing a merocyanine dye characterized by condensing an aminoalkenyl cyclic amidinium compound represented by the general formula [1] and a compound having an active methylene group in the presence of an inorganic base. ←)
, L□Ls and L4 each represent a methine group. ! and n each represent an integer of 0 or l,
m represents Ol or 1s'1''% represents an integer selected from 0 to 3. R represents an alkyl group, an aryl group or an alkenyl group, and may be combined with L to form a ring. , R1+R1 each represents a lower alkyl group and may be bonded to each other to form a group. X represents an anion.] (2) The method for producing a merocyanine dye according to claim 11, characterized in that the compound having an active methylene group is represented by the following general formula [IJ or IJ]. General formula (1) General formula, drama υ [In the formula, Q represents a group of nonmetallic atoms necessary to form a 5- or 6-membered ring (which may form a condensed ring).V
, W represent electron-withdrawing groups which may be different or the same. ] (3) The method for producing a merocyanine dye according to claim (1), wherein the aminoalkenyl cyclic amidinium compound is represented by the general formula shown below. General formula
, Llfi% each represent a methine group. rl;l:0
Further, 扛1 represents an integer, and m represents an integer selected from 0 to 3. R1 and R1 each represent a lower alkyl group,
They may be combined with each other to form a product. A represents a divalent aliphatic group or a divalent aromatic group. ]