JPS5851969B2 - Production method of polymethine dye - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polymethine dyes,
More specifically, using β-alkoxyacrolein,
The present invention relates to a method for producing pentamethine cyanine dye.

It is well known that by adding a cyanine dye to a silver halide photographic light-sensitive material, so-called spectral sensitization, which imparts photosensitivity to areas other than the intrinsic sensitivity range of the light-sensitive material, is possible.

*According to the present invention, a pentamethine cyanine dye represented by the following general formula (D) is provided in order to achieve the above object. isopropyl, butyl, etc.), aryl groups (e.g., phenyl), aralkyl groups (e.g., benzyl, phenethyl, etc.), and allyl groups, and these alkyl and aryl groups further contain halogen atoms (e.g., fluorine,
chlorine, bromine, iodine, etc.), hydroxy group, alkyl group, alkoxy group (e.g., methoxy, ethoxy, propoxy, isopropoxy, butoxy, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, impropoxycarbonyl,
butoxycarbonyl, etc.), a sulfo group, a carboxy group, etc.

However, substitution of halogen atoms and alkyl groups is limited to aryl groups.

Z represents a nonmetallic atomic group necessary to complete a 5- or 6-membered nitrogen-containing heterocyclic nucleus, and specific examples thereof include an oxazoline ring, an oxazole ring, a benzoxazole ring,
naphthoxazole ring, thiazoline ring, thiazole ring,
benzothiazole ring, naphthothiazole ring, selenazole ring, benzoselenazole ring, naphthoselenazole ring,
2-pyridine ring, 4-pyridine ring, 2-quinoline ring, 4
- There are quinoline rings, imidazole rings, benzimidazole rings, naphthothiazole rings, indolenine rings, etc., and these heterocycles, condensed benzenes, and naphthalenes further include halogen atoms, alkyl groups, aryl groups, aralkyl groups, and hydroxy groups. , an alkoxy group, an alkoxycarbonyl group, a carboxy group, a sulfo group, and the like.

and are 0 or 1, respectively.

The pentamethine cyan dye represented by the general formula (I) is used in silver halide photographic light-sensitive materials with a sensitivity wavelength range of from red to
It is known as a dye that extends into the near-infrared region.

According to the present invention, the pentamethine cyanine dye represented by the general formula (I) is a complex quaternary term having a β-alkoxyacrolein represented by the following general formula (n) and a reactive methyl group represented by the general formula (1). It can be produced by condensation from a salt compound in the presence or absence of a base.

General formula (n) R2-0-CH=CH-CHO General formula (I) In the formula, Rlp Z , X-, m and n represent the same meanings as described in general formula 〇).

R2 is an alkyl group (e.g. methyl, ethyl, propyl,
butyl, etc.).

The condensation reaction proceeds in the presence or absence of a solvent, but alcohols (e.g. methanol, ethanol, isopropanol, butanol, etc.), cellosolves (e.g. methyl cellosolve, ethyl cellosolve, etc.), amides (e.g. acetamide) , N,N-dimethylformamide, N,N-dimethylacetamide, etc.), dimethyl sulfoxide, acetonitrile, hexamethylphosphoramide, etc.), the condensation reaction proceeds more quickly and smoothly.Claim 1: General formula (II 1. A method for producing a polymethine dye represented by formula (1), which comprises condensing a compound represented by formula (1) with a compound represented by formula (I).

General formula (1) (wherein R0 is an alkyl group, an aryl group, an aralkyl group,
It represents an allyl group, and R2 represents an alkyl group.

Z represents a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocyclic nucleus.

X- represents an acid anion, and m and n are each O or 1.

)2 Claim 1 in which β-alkoxyacrolein of general formula (II) is represented by β-methoxyacrolein
The method for producing polymethine dyes described in Section.

3. The method for producing a polymethine dye according to claim 1, wherein the β-alkoxyacrolein of general formula (n) is represented by β-ethoxyacrolein.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polymethine dyes,
More specifically, using β-alkoxyacrolein,
Preparation of Pencumetine Cyanine Dye Instead of β-ethoxyacrolein used here, β-methoxyacrolein,
Dye (It) can be similarly obtained when β-propoxyacrolein or β-butoxyacrolein is used.

Moreover, if a nitrogen-containing 5- to 6-membered heterocyclic quaternary salt having another reactive methyl group is used in place of 3-ethyl-2-methyl-α-naphthothiazolium-P-toluenesulfonate, the corresponding A pentamethine cyanine dye is obtained.

Example 3 Synthesis of dye (I) * 3-ethyl-2-methyl-5-phenylbenzoxacilium-P-toluenesulfonate 4.7 g, β-
Add 30 g of triethylamine to a mixture of 0.4 J of propoxyacrolein and 10 ml of pyridine, and continue stirring at room temperature overnight.

After one night, a 10% sodium iodide aqueous solution was added to remove the precipitated crude dye.

After washing with warm water, wash with Ascent.

When recrystallized from methanol and dried, the melting point is 265.0°C.
2.1 g of blue crystalline powder (decomposition) is obtained.

Maximum absorption value of methanol solution: 592.560 mμ.

Instead of β-propoxyacrolein used here, β
-methoxyacrolein, β-ethoxyacrolein,
Alternatively, when β-butoxyacrolein is used,
Dye (I[) is obtained similarly.

Also, instead of 3-ethyl-2-methyl-5-phenylbenzoxacilium-Pt-luenesulfonate, another nitrogen-containing 5- to 6-membered heterocyclic quaternary salt having a reactive methyl group was used. For example, the corresponding pentamethine cyanine dye is obtained.

Example 4 Synthesis of dye (1) Anhydro-2,3,3-trimethyl-1-(3-sulfopropyl)indolenium hydroxide 2.8,9.
β-butoxyacrolein 1.3g, methanol 20r
2.5 g of N,N-dimethylcyclohexylamine was added to the mixture of rLl and heated under reflux for 30 minutes.

After the reaction, 1.5 g of sodium acetate is added as a methanol solution, and the precipitated crude dye is collected.

After washing with acetone and recrystallizing with methanol, 1.3 g of a dark blue crystalline powder with a melting point of 294.0° C. (decomposed) is obtained.

Maximum absorption value of methanol solution is 642.600 mμ.

Therefore, it is convenient.

As the base used in the condensation reaction, triethylamine, tributylamine, monoethanolamine, jetanolamine, triethanolamine, pyridine, piperidine, N-methylmorpholine, N,N-dimethylcyclohexylamine, etc. can be used.

Although the reaction often proceeds easily at room temperature, it can generally be carried out at a temperature ranging from 0° C. to the boiling point of the solvent used.

In addition, in the condensation reaction, the compound of general formula (1) can be used in a molar ratio of 0.5 to 3 mol to 1 mol of the compound of general formula (n), but it is preferable to use a 2 molar ratio or a slight excess. is advantageous.

β-alkoxyacrolein of general formula (I) is a known compound, and its production method is described in the β-carboalkoxyacrolein method (Zh, 0bshch) by V.T. Klimko et al.
.

Khim, 32.2961-6 (1962), method of reacting alcohol and propargyl aldehyde by A-P-8Koldino, etc. (Zh.Org-Khim-Sei, 183 (1968
)).

A.N. Staflovskaya (A, N, S ta
vr.

A method of treating 1-halogen-3,3-dialkoxy-1-propene such as Vskaya) with an ion exchange resin (Z
h-Org-Khim・45.1194-8 (196
8)), L.A. Yanovskaya (L, A, Yan)
ovskaya) et al. (Izv, Akad, Nauk, 5SSR, O
td, Khim, Nauk 1962.667-74), etc., but from the viewpoint of reactivity and yield in producing the dye of the present invention, one in which R2 is methyl ethyl is particularly advantageous.

Some of the compounds of general formula (1) are available as commercial products and also available from Pierre Graffkides.

Grafkides), Photographic Ch6mistry
) Vol. 2, pp. 768-772, Fountain Press, London.
It can be synthesized by the method described in the publication.

According to the present invention, polymethine dyes can be easily obtained under mild reaction conditions and in good yields.

The present invention will be discussed in more detail with reference to examples below.

Example 1 Synthesis of dye (I) 3-ethyl-3-methylbenzothiazolium iodide 6
．． 1g of triethylamine, 0.9g of β-methoxyacrolein, and 20ml of ethanol), 4.0g of triethylamine was added to the mixture, and the mixture was stirred at room temperature for 4 hours.

Ether is added and the precipitated crystals are collected in a furnace.

After washing with ether, recrystallization with methanol and drying yields 4.3 g of colored needle crystals with a metallic luster and a melting point of 253.0° C. (decomposed).

Maximum absorption value of methanol solution is 655.600 mμ.

When β-ethoxyacrolein, β-propoxyacrolein or β-butoxyacrolein is used instead of β-methoxyacrolein used here, dye (I) can be obtained in the same manner.

Further, if another nitrogen-containing 5- to 6-membered heterocyclic quaternary salt having an active methyl group is used in place of 3-ethyl-2-methylbenzothiazolium iodide, a corresponding pentamethine cyanine dye can be obtained.

Example 2 Synthesis of dye (n) 3-ethyl-2-methyl-α-naphthothiazolium-P
-4.0 g of toluenesulfonate and 1.0 g of β-ethoxyacrolein. Og is pyridine 2077271! Heat under reflux for 30 minutes.

After the reaction, a 10% potassium bromide aqueous solution is added, and the precipitated crude dye is removed from the oven while still warm.

Let's wash it with warm water and then wash it with acetone on the next page.

When recrystallized from methanol and dried, the melting point is 249.0℃ (
2.1 g of colored needle crystals with a metallic luster (decomposition) were obtained.

The maximum absorption value of methanol solution is 685.640 mμ.

Claims (1)

[Scope of Claims] 1. A method for producing a polymethine dye represented by general formula (I), which comprises condensing a compound represented by general formula (II) and a compound represented by general formula (I). General formula (I) (wherein R0 is an alkyl group, an aryl group, an aralkyl group,
It represents an allyl group, and R2 represents an alkyl group. Z represents a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocyclic nucleus. X- represents an acid anion, and m and n are each 0 or 1. )2 β-alkoxyacrolein of general formula (■) is β
A method for producing a polymethine dye according to claim 1, which is represented by methoxyacrolein. 3 β-alkoxyacrolein of general formula (II) is β
A method for producing a polymethine dye according to claim 1, which is represented by ethoxyacrolein.