JPS5980470A - Preparation of oxonol dye - Google Patents

Abstract

PURPOSE:To prepare the titled dye useful for the antihalation of a silver halide photographic material, in high yield and purity, with extremely little production of by-products, by condensing an alpha-ketomethylene compound with a specific compound. CONSTITUTION:The objective dye (e.g. the compound of formula IV) is prepared by condensing (A) an alpha-ketomethylene compound of formula I (Q is non-metallic atom group necessary to form a heterocyclic group) preferably the 5-pyrazolone ring of formula II [R6 is alkyl, aryl(oxy), OH, amino, etc.; R7 is alkyl, aryl or heterocyclic group] with (B) the compound of formula III (R1-R5 are H or electron-attracting group having positive Hammett's sigma-value, and at least one of R1-R5 is electron-attracting group; L is methine; n is 0-2), usually in the presence of a base such as pyridine, in an organic solvent such as DMF, preferably at 0 deg.C- room temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method for producing oxonol dyes.

In general, it is an oxonol dye, and is one of the dyes useful as a halogen (used in 11-Yoma photosensitive materials) rayon prevention, ylang rayon prevention, and as a filter monolayer phase.

Regarding the manufacturing method of this oxonol dye, for example, the specifications and publications of British Patent No. 506,385, Japanese Patent Publication No. 39-22069, Japanese Patent Publication No. 54-38129, Japanese Patent Publication No. 54-20967, and Japanese Patent Application Laid-Open No. 50-91627, etc. described and well known. That is, a methine chain supplier such as a q-ketomeethylene compound and orthoformic acid ester, diphenylformamidine, tetraalkoxypropane, malo/dialdehyde cyanyl, 2,4-dinitrobenzenepyridinium chloride, glutacondialtehyde dianyl, etc. It can be produced by condensing these in the presence of a base. When the above oxonol dyes are produced industrially, conventionally diphenylformamidine, malondialdehyde cyanyl and glutacondialdehyde cyanyl are used as monomethine, trimethine and pentamethine oxonol dyes as the methine chain suppliers. Fully manufactured.

However, it has been recognized that in the method for producing oxonol dyes as described above, by-products are produced during the reaction, reducing the purity and yield of the target product. In particular, in the case of pentamethine oxonol dye, it is unstable to heat, acidity, basicity, etc., and magenta-colored by-products are generated during the manufacturing process, so purification and isolation require many steps and are difficult. There are many things that happen.

Therefore, the object of the present invention is to provide a method for producing oxonol dyes of impurity in high yields and for general purposes, with extremely little generation of by-products as described above.

As a result of various studies by the present inventors, the above object was achieved by combining an α-ketomethylene compound represented by the following general formula [+1] and F
It has been found that this can be achieved by a method for producing an oxonol dye in which 4,444 4-oxonol dyes are produced by condensation with a compound represented by the general formula [111].

General formula (1) General formula (Ill In the formula, Q represents a group of nonmetallic atoms necessary to form a heterocycle, and RI * R2 * R3r R4 + R5 are hydrogen atoms or hydrogen atoms, respectively. represents an electron-withdrawing group in which is positive, and at least one position of RI-R5 is an electron-withdrawing group. Reed L represents a methine group, and niO
, l or 2.

3- The present invention will be explained in more detail below.

The production method of the present invention is characterized by condensing the ketomethylene compound represented by the above general formula El) and the compound represented by the general formula [11] in the presence of a base. For example, a 5-pyrazolone ring, )(rubituric acid, 'l-fobarbituric acid, 2-hir))'? /ring, 5-isoxacylone term, 1,3-thiazolidine-2,4-dione ring, 2-thio-1,3-thiazolidin-4-one ring, pyrazolidine-3,5-di, +7li, 4-hydroxy -2-
Quinolone ring, coumarin ring, 2-thio-1,3-oxazolidin-4-one ring, imitazolidine-2,4-dione ring, 2-thio-imidazolidin-4-one ring, benzo (R3-1 -: t phen-3-one ring, indole-3
-on ring etc., but preferably R5-
It is a pyrazolone ring, and has the following general formula (represented as a set: 4
- General formula (11 In the formula, R6 is an alkyl group, an aryl group, an alkoxy group,
It represents an aryloxy group, a hydroxy group, an amine group, an acylamino group, a carbamoyl group, a carboxy group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and R7 represents an alkyl group, an aryl group, and a heterocyclic group.

In more detail, the alkyl group represented by R0 above is preferably an alkyl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, t-
Butyl, octyl, hydroxyethyl, methoxyethyl, ethoxycarbonylmethyl, trifluoroethyl, pentafluoroethyl, 1 , 1 , 2 , 2 , 3 ,
Various groups such as 3-hexafluoropyropyl can be mentioned.

Examples of the aryl group represented by R6 include evaphenyl, tolyl, cyanophenyl, nitrophenyl, hydroxyphenyl, methoxyphenyl, chlorophenyl, 3,5-disulfophenyl, and naphthyl.

Next, examples of the alkoxy group represented by R6 include t[
Examples of the aryloxy group include methoxy, ethoxy, propoxy and the like, and examples of the aryloxy group include phenoxy, chlorophenoxy and nitrophenoxy. Furthermore, examples of the acylamino group include acetamide, globionamide, succinimide, benzamide, chlorobenzamide, and nitrobenzamide. Subsequent carbamoyl groups include, for example, evacarbamoyl, methylcarbamoyl, ethylcarbamoyl, hydroxyethylcarbamoylphenylcarbamoyl, chlorophenylcarbamoyl, hydroxyphenylcarbamoyl, nitrophenylcarbamoyl, cyanophenylcarbamoyl, and the like.

Furthermore, as an alkoxycarbonyl group, for example, each group such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, hydroxyethoxycarbonyl, methoxyethoxycarbonyl, etc. can be used, and aryloxycarbonyl group can be used as h%. [11] Examples include groups such as phenoxycarbonyl and chlorophenoxycarbonyl.

Next, the alkyl group represented by R7 in the above general formula II [J is preferably an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, n-butyl, 2-hydroxyethyl,
-methoxyethyl, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, carboxyethyl, 2-carboxyethyl, 3-carboxyethyl, and the like.

Further, examples of the aryl group represented by R2 include evaphenyl, 4-chlorophenyl, 4-sulfophenyl, 3-
Sulfophenyl, 2-1 thyl-4-sulfophenyl, 2
-Chloro-4-sulfophenyl, 4-chloro-3-sulfophenyl, 2-meth7-toxy4-sulfophenyl, 2-hydroxy-4-sulfophenyl, 2.5-cyclo-4-sulfophenyl, 3.5 -disulfophenyl, 2゜5-disulfophenyl, 4-phenoxy-3-sulfophenyl, 2-chloro-6-meth-4-sulfophenyl, 3-carboxy-
2-hydroxy-5-sulfophenyl, 4-hydroxy-3-sulfophenyl, 4-carboxyphenyl, 3-
Examples of the heterocyclic group represented by R9 include carboxyphenyl, 3,6-disulfo-α-naphthyl, 6,8-disulfo-β-naphthyl, and the like. or 6)-sulfo-2-benzthiazolyl and other groups.

Next, the above general formula (RI*R1+R9 in nJ
+ The electron-withdrawing group represented by R4 and R6 and having a positive ζ value is defined in "Journal of Organism.
Chemistry, Vol. 5, p. 425, (1'95
8th grade) and New Experimental Chemistry Course, Volume 14, 2608
Hameut's a in the table published in Page, (1978) etc.
. , am and a substituent having a positive value, 8- Specifically, halokene atoms (fluorine, chlorine, bromine, etc.),
Examples include trifluoromethyl group, cyanogen group, alkoxycarbonyl group (ethoxycarbonyl group, etc.), nitro group, acyl group (acetyl group, globionyl group, pivaloyl group, etc.), acetoxy group, methylsulfonyl group, carbamoyl group, sulfamoyl group, etc. be able to. In the present invention, compounds in which the meta-position of the phenyl group of the general formula (IIJ), that is, R7, R4, or para-position, that is, Rs, are electron-withdrawing groups are particularly preferred.

In addition, the methine group in the general formula +÷machi is, for example, an alkyl group (methyl group, ethyl group, etc.)
, may be substituted with an aryl group (such as a phenyl group).

Furthermore, the compounds represented by the general formula may form salts with various acids, such as hydrochloric acid,
Examples include hydrobromic acid, perchloric acid, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, and ethanesulfonic acid.

In the production method of the present invention, a method for producing a pentamethine oxonol dye by condensation of a pyrazolone derivative represented by the general formula - with a compound represented by the general formula The most preferred method is to produce a pentamethine oxonol dye using the above pyrazolone derivative having an alkyl group.

In the production method of the present invention described above, a base is used during the condensation reaction. Examples of the above bases used in the present invention include pyridine, piperidine, triethylamine,
Examples include jetanolamine, triethanolamine, and ammonia.

Further, an organic solvent is used during the above condensation reaction. Examples of organic solvents include alcohols (methanol, ethanol, etc.), ethylene glycol, ethylene glycol monoalkyl ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.), acetonitrile, dimethyl sulfoxide, amides (dimethyl Formamide, dimethylacetamide, acetamide, etc.) are commonly used, but in the method for producing pentamethine oxonol dye according to the present invention, daughter, @
Preferably used are compounds having an electrical conductivity of ~40°C (90°C to 5°C), such as dimethylformamide, dimethylacetamide, acetonitrile, and ethylene glycol.

The above condensation reaction according to the invention can be carried out at a temperature varying from 0° C. to the boiling point of the solvent used. Particularly, since the pentamethine oxonol dye is unstable to linear heat, it is preferable to carry out the reaction in the range of 0.000 to room temperature. In addition, in the above reaction, it is appropriate to use the pyrazolone derivative group represented by the above general formula, which is a reaction reagent, in an amount equivalent to twice the mole of the compound represented by the general formula [nJ].

Next, typical examples of the phenyl group that carries the electron-withdrawing group in the compound represented by the general formula tI[1 will be described, but the present invention is not limited to these.

〔Concrete example〕

+134-fluorophenyl group 1l- (2)3. fi-difluorophenyl group (312,4,
6-1 Lifluorophenyl group (4) 4-chlorophenyl group (5) 3-chlorophenyl group (6) 2-chlorophenyl group (7) 3.4-dichlorophenyl group (8) 3.5-dichlorophenyl group (9J2 , 4.6-1lichlorophenyl group ([Q 4-
Bromophenyl group α1) 3-bromophenyl group α23,5-dibromophenyl group L32,4.6-dribromophenyl group a413-)lifluoromethylphenyl group (154-trifluoromethylphenyl group the 2-cyanophenyl group α73 -Cyanophenyl group α84-Cyanophenyl group (192-ethoxycarbonylphenyl group (a) 4-
Ethoxycarbonylphenyl group 9υ 4-methoxycarbonylphenyl group 12- (a) 2-nitrophenyl group 3-nitrophenyl group t24 4-nitrophenyl group i3-acetylphenyl group Uq 4-acetoxyphenyl group 4-4-sulfonamidophenyl A group (44-carbamoylphenyl group (212-10) fluoromethylphenyl group (304-fluoro-3-oo phenyl group) represented by the general formula ITII having a group as shown in the above specific examples. The compound is described in Chemical Abstracts, Volume 41.
41 Sada, (1957), By Ruthstein Hand 7'Tsuk der Organik Hemi-1 Volume 12, 6
04 pages, 610 pages, 611 pages, 634 Sada, 691 pages, 7
03 pages, 718 pages, Berichte der Deutschen Hemitschen Gesellschaft, Volume 102, 260
9 pages (1969) or Journal of the Photographic Society of Japan, Vol. 33,
It is generally easily synthesized by reacting an aniline derivative with an orthoformic acid ester, a tetraalkoxypuff, or 2,4-dinitrobenzenepyridinium chloride, respectively. I can do it.

Furthermore, typical examples of the pyrazolone derivatives represented by the general formula - are shown below, but the present invention is not limited by these.

〔Concrete example〕

(1) +23 80,H (31(41 (7) (8)(91(
IQ 15- (tllaa (L3 (L4 So, H5o3H αQ (IQ = 16- a71 a8 (194) , a sulfo group) may form salts with alkali metals such as IJum and Kaliwam, organic bases such as triethylamine and pyridine, or bases such as ammonia, and generally sodium salts or potassium salts are suitable. .

Typical specific examples of the -1' +4↓↓ oxonol dye produced in the above manner will be described below, but the present invention is not limited thereto.

[Exemplary compounds]

M L%K 20 S O, niF
The present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.

Example 1 [Synthesis of compound represented by general formula (11)]
(11 Glutacondialdehyde di(m-chloroanyl)
Synthesis of Hydrochloride In 100 mA of ethanol, 17.7 % of K 2 , 4-1 nitrobenzene pyridinium chloride was added, and 23.0.9 ml of m-chloroaniline was further added, and the mixture was stirred at room temperature for 5 hours. The contents are once dissolved in the bath, but as the reaction progresses, red crystals precipitate. Take f of this, wash with 50 ml of ethanol, thoroughly wash with 150 ml of acetone, dry, and remove 17 ml of water.
．． The desired product (red crystal) with a yield of 0.9 was obtained.

Synthesis of (m-chloroanyl) hydrochloride 28.19+ m-chloroaniline is added to a mixed solvent of 40 ml of water and 60 ml of methanol, and further 40 ml of concentrated hydrochloric acid is stirred manually.Contents The mixture became homogeneous, and 5.4 times of tetramethoxyzorononol was added thereto, stirred at room temperature for 5 hours, and then incubated overnight.

As the reaction progresses, brown crystals will precipitate. Add 1fi (nu) of water along the reaction, and add the crystallized IJ" water ioo
After washing with TNB, washing with 300 mJ of acetone and drying, the desired product 20.59 (yellow-orange crystals) was obtained.

(31(m-chlorophenyl)formamidine σ)
14.8 & of synthetic ethyl ortho-acid and 25.5 & of m-chloroaniline are mixed and reacted for 4 hours while ethanol produced at 100° C. is distilled off at atmospheric pressure.

The contents were cooled to about 50°C, and 120% methanol was added to this.
! Add ILt. Pour out the white crystals or heat it further to melt it and let it cool. One liter of precipitated crystals was collected, washed with 50 portions of methanol, and dried to obtain the desired product 19.311 (white crystals).

-%- Compounds represented by other general formulas can also be easily synthesized by carrying out the same reaction as above using a compatible aniline conductor.

Example 2 [Synthesis of Exemplified Compound 1] 30.8 g of fluoromethyl-1-(4'-sulfophenyl)-5-pyrazolone and 20.2 # of triethylamine were placed in 300 mA of dimethylformamide and heated. Lend. This is combined with glutacondialdehydochide (m
-chloroanil) hydrochloride '17. '/1/ added, 2
Stir at 0'C. After 3 hours reaction, 300ml of ethanol
After adding 19.69 g of potassium acetate and stirring for a while, 120 g of acetonitrile was added and left overnight. One of the precipitated crystals was taken, washed with 100 g of ethanol, washed vertically with 200 g of acetone, and dried to obtain 27.8 g of oxonol dye. This dye did not require further purification and was a highly pure dye.

The λmax h of the water M solution of this dye was 627 nm.

In addition, the same reaction was carried out using geltacondialdehyde di(m-chloroanyl) hydrochloride as a specific softener instead of glutacondialdehyde di(m-chloroanyl) hydrochloride.
As a result, the dye was contaminated with magenta-colored by-products, and in order to obtain a highly pure dye, salting-out purification had to be performed, resulting in a significant decrease in yield.

Furthermore, a similar reaction was carried out using curtacondialdehyde di(m-chloroanyl) hydrochloride, dimethylformamide as the electric medium, and methanol.
Since a large amount of magenta dye was produced, the desired pentamethine oxonol dye could not be purified and isolated.

When a similar reaction was carried out using glutacondialdehyde cyanyl phosphate in methanol, magenta dye was the main product, and the desired pentamethine dye was hardly obtained.

Example 3 [Synthesis of Exemplified Compound 2] 3-carbamoyl-1-(4'-sulfophenyl)-5
-Pyrazolone 28.3# and triethylamine 20.2.
9 and dissolved in 4001 U of dimethylformamide. To this was added 21.09 g of glutacondialdehyde di(m-trifluoromethylanyl) hydrochloride, and the mixture was stirred at room temperature. After reacting for 3 hours, 800 IILh of methanol was added, followed by 19.69 kg of potassium acetate, and after stirring for a while, the mixture was left to stand overnight. The precipitated crystals were collected, thoroughly washed with 200 times of ethanol, and dried to give an oxonol dye of 28.
．． 5.9 was obtained.

The λfox X of the aqueous solution of this dye was 635 nm, indicating that it was a highly pure dye.

For comparison, glutacondialdehyde cyanyl hydrochloride was used instead of glutacondialdehyde di(m-trifluoromethylanyl) hydrochloride in methanol.
When a similar reaction was carried out, a larger amount of magenta-colored by-products was produced, and the resulting dye L was a dye with low purity.

Example 4 [Synthesis of Exemplified Compound 3] 3-Calfoxy 1-(4'-sulfophenyl)-5-
Pyrazolone 28.49 and triethylamine 18.2.9
and are dissolved in dimethylformamide 300a.

In this, glutacondialdehyde di(m-bromoanil)
Add 22.1.9 of the hydrochloride and stir at room temperature. After 2 hours of reaction, add 30% of ethanol and 6.0% of glacial acetic acid, and further add 14.7% of potassium acetate. Stir for hours. The precipitated crystals were collected and diluted with ethanol 150
After washing with mA and further washing with 200 mA of acetone, it was dried to obtain oxonol dye 30.2.9. The λmax of this dye in a water bath was 635 nff1, indicating that it was a hot dye of high purity.

For comparison, when the same reaction was carried out in methanol with glutacondialdehyde cyanyl hydrochloride instead of glutacondialdehyde di(m-bromoanil) hydrochloride, a larger amount of magenta-colored by-products were produced. However, the resulting dye had low purity.

Implementation vAJfi [Synthesis of water compound 4] 3-amino-
1-(3'-sulfophenyl)-5-pyrazolone25.
511 and 20.2 g of triethylamine were placed in dimethylformamide 30oIILt, and glutacondialdehyde di(3,4-dichloroanyl) hydrochloride 19.
Add 4 g and stir at room temperature. After reacting for 5 hours, methanol 1501 was added, and sodium acetate 16.4.9 was further added, and after stirring for IFWf, it was left to stand overnight. The precipitated Oshima was collected, washed twice with ethanol 100 parts, dried, and treated with oxonol dye 30 parts.
．． I got 8.9. λmax h of the aqueous solution of this dye, 6
02 nm, and was a highly pure dye.

For comparison, when a reaction was carried out using glutacondialdehyde di(3,4-dichloroanyl) hydrochloride and glutacondialdehyde cyanyl hydrochloride in methanol, a magenta dye was produced as a by-product. However, the dye obtained was a dye with low purity.

Example 6 [Synthesis of Exemplified Compound 5] 1-(4'-sulfophenyl)-3-)lifluoromethyl-5-pyrazolone 30.8.9 and triethylamine 2
0.29 and ethanol 4! ' mOIRt and further malondialdehyde di(m-bromoanil) 19.
Add 09 and heat, under reflux 1. The reaction was carried out for Fi time.

After the reaction, 30.0 g of potassium acetate was added to [0-A].
After being refluxed for - minutes, it was cooled and one of the precipitated crystals was taken, thoroughly washed with ethanol 200 Inb and dried to obtain oxonol dye 30.711. λma of the aqueous solution of this dye
x il, 538 nm, and the dye was of high purity.

Example 7 (Plateau of compound 6 shown in 1+lI) 14.2.9 of 3-carbamoyl-1-(4'-sulfophenyl)-5-pyrazolone and 15.2 g of triethylamine were added to 200 mt of methanol and a glass of malon. 8.211 g of dialtehyde di(m-chloroanyl) hydrochloride was added, heated and reacted under reflux for 1 hour.After the reaction, 14.7 g of potassium acetate was added and kept in the refrigerator for 10 minutes. The precipitated crystals were collected, thoroughly washed with 150 ml of ethanol, and dried to obtain oxonol dye 14.5.9. there were.

Example 8 [Synthesis of -j water compound 7] 15.39 of 3-methyl-1-(3'-sulfophenyl)-5-pyrazolone and 12.19 of triethylamine were placed in 150 mA of dimethyl formaldehyde, and further di(
8.09 g of m-chlorophenyl)formamidine was added, heated, and reacted at 80° C. for an addition period. After the reaction, cool, add 70% of methanol, and add 11.8% of potassium acetate.
9 was added and stirred for 1 hour, 20ON of acetonitrile was added and the precipitated crystals were taken out and washed with 1QQmJ of methanol. The crude crystals were dissolved in 45 mA of pure water, 360 mA of methanol was added, and the precipitated crystals were collected, washed with 100 ml of methanol, and dried. I got it. λ of the aqueous solution of this dye
The max was 420 nm, and the dye was of high purity.

Example 9 [Synthesis of listed compound 8] 12.8 g of Barbir m was dissolved in dimethylformamide 18
Put it in 0ffiJ and comb it. Furthermore, glutacondialtehyde di(m-trifluoromethylanyl) hydrochloride 21.
Add 09 and stir. After the reaction became uniform, 15.2 g of triethylamine was added and stirred at room temperature. 2
After reacting for an hour, 9.0 g of glacial acetic acid was added, and further 180 m/V of ethanol was added, followed by stirring for 1 hour. The precipitated crystals were collected, washed with 200 ml of ethanol, and dried to obtain 15.1 # of oxonol dye. The aqueous solution of this dye had a λmax of 582 nm and was a pure dye.

Agent Ryo Sakae Sen Moxibustion-3- -4- Attachment Claims An oxonol dye is produced by condensing an α-ketomethylene compound represented by the following general formula CI) and a compound represented by the following general formula (n). A method for producing an oxonol dye, characterized in that:

General formula CI) General formula [”II]

Claims (1)

[Scope of Claims] An oxonol dye characterized in that an oxonol dye is obtained by condensing an α-ketomethylene compound represented by the following general formula (II) with a compound represented by the general formula [11J]. Manufacturing method. General formula represents a positive electron-withdrawing group, and at least one of R1"" R11 is a linear electron-withdrawing group.L represents a methine group,
nho represents an integer of 1 or 2. ]