JP2579228B2 - Cyanine compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel dye which can be used as a dye, a sensitizing dye for photography, a dye for recording on an optical information recording medium, a stain for biological samples such as cells, or a medicine. Related to various cyanine compounds.

[Conventional technology]

Cyanine dyes having a heterocyclic ring as a terminal group in which a naphthoquinone skeleton and an imidazole skeleton are fused are described in Chemical Abstracts, vol. 71.
22892K, Vol. 62, p. 11942, and Vol. 58, p. However, these dyes have a structure of a substituent or a structure of a conjugated methine chain limited to a specific structure, and are not suitable for various uses.

[Problems to be solved by the invention]

The present invention provides a novel cyanine dye having various structural changes so as to be suitable for various uses and having the above-mentioned specific heterocyclic structure.

[Means for solving the problem]

The above problem has been solved by a compound represented by the following general formula (I).

General formula (I) [Wherein T ¹ and T ² independently represent an atomic group necessary for forming a fused benzene ring, and L ³ is formed by connecting 1, 3, 5, or 7 methine groups with a conjugated double bond. R ²¹ , R ²² , R ²³ and R ²⁴ independently represent an optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted phenyl group Y represents an anion, and q represents a number necessary to neutralize a positive charge. However, if L ³ is 1,3, or of five methine ^{groups, R 21, R 22, R} 23, and at least one of R ²⁴ is an alkyl group having 3 or more carbon atoms. Among the compounds represented by the general formula (I), the compound represented by the following general formula (II) is more preferable in view of easy synthesis.

General formula (II) [Wherein X is ^{Cl -, Br -, I -} , ClO 4 -, H 2 PO 4 -, HSO 4 -, HPO 4
_{^{2-, PO 4 3-, SO 4}} 2-, CH 3 SO 3 -, _{^{p-toluenesulfonate, BF 4 -, PF 6 -}} , perfluoroalkanesulfonic acid ion, Monovalent or divalent carboxylate ions (eg CH
₃ CO ₂ ^-, (CO ₂ ^-) _2, Wherein R ¹ represents an alkyl group having 3 or more carbon atoms, R ² represents an alkyl group having 1 to 18 carbon atoms which may be substituted, a phenyl group which may be substituted, and L ³ represents It represents a group having the same meaning as L ^{3 in} formula (I). Next, specific examples of the compound represented by formula (I) of the present invention will be given, but the scope of the present invention is not limited only to these.

The compound represented by the general formula (I) of the present invention can be synthesized according to a conventional method for synthesizing a cyanine dye.
The compound can be synthesized with reference to the description in Chemical Abstracts, Vol. 71, 22892k.

〔Example〕

 Next, the synthesis method will be specifically described with reference to synthesis examples.

Example 1 Synthesis of Compound I-2 1,4-Diisobutyl-4,9-dioxo-
0.23 g of 2-methylnaphtho [2,3-d] imidazolium 4-methylbenzenesulfonate and 1 ml of ethyl orthoformate were added, and the mixture was heated under reflux for 6.5 hours. The solvent was distilled off under reduced pressure, and after adding 3 ml of methanol, 0.3 g of tetrabutylammonium perchlorate dissolved in 3 ml of methanol was added.
The precipitated crystals were collected by filtration and washed with methanol to give Compound I.
-2 blue-green crystals were obtained.

Yield 86mg, Example 2 Synthesis of Compound I-3 1,4-Diisobutyl in 4 ml of N, N-dimethylformamide
0.9 g of 4,9-dioxo-2-methylnaphtho [2,3-d] imidazolium 4-methylbenzenesulfonate and 1,5-
Add 180 mg of diaza-1,5-diphenyl-1,3-pentadiene to dissolve, then add 0.18 ml of acetic anhydride and 0.27 ml of 1,8-diazabicyclo [5,4,0] -7-undecene for 2 hours at room temperature. Stirred. The reaction solution was poured into 150 ml of water, and the resulting solid was collected by filtration and washed with water. This solid was dissolved in methanol (20 ml), and tetrabutylammonium perchlorate (1 g) dissolved in methanol (2 ml) was added. The precipitated crystals are collected by filtration,
After washing with methanol, green crystals of the compound I-3 were obtained.

Yield 210mg, melting point 225-226 ° C (decomposition), Example 3 Synthesis of Compound I-7 1,3-Dibutyl-4,30 ml in 30 ml of N, N-dimethylformamide
9-dioxo-2-methylnaphtho [2,3-d] imidazolium 4-methylbenzenesulfonate 5 g and 1,5-diaza-1,5-diphenyl-1,3-pentadiene 1,1 g, acetic anhydride
1 ml, 1,8-diazabicyclo [5,4,0] -7-undecene
2.2 ml was added and the mixture was stirred at room temperature for 2 hours.

The reaction mixture was poured into a solution prepared by dissolving 5 g of tetrabutylammonium perchlorate in 150 ml of methanol. The resulting crystals were collected by filtration and washed with methanol to obtain 0.5 g of a yellowish-green metallic luster crystal of Compound I-7. Melting point 215-2
16 ° C (decomposition).

Next, examples using the compound of the present invention as a dye for an optical filter will be described below.

Example 4 An optical filter composition was prepared by using the compound I-2 synthesized in Synthesis Example 1 to prepare an optical filter: that is, each component was mixed with the composition shown in parts by weight below and mixed well. Then, after filtration, the composition was applied onto a metal support by a casting method, peeled off after film formation, and an intended optical filter was obtained.
Several types of optical filters were obtained in which the dry film thickness was varied between 0.02 and 0.3 mm. The optical filter (25 microns thick) thus obtained absorbed light near 500-750 nm.

Composition example (Example 5) A solution having a composition shown in parts by weight below was spin-coated on a PMMA support at 1000 rpm using the compound I-7 synthesized in Synthesis Example 3.

composition The optical density of the thus obtained optical filter having a smooth surface is shown in FIG.

As is clear from FIG. 1, it can be seen that the use of the compound I-7 of the present invention makes it possible to obtain an optical filter having a smooth surface which absorbs light of about 500 nm to 750 nm.

(Comparative Example) Instead of compound I-7 used in Example 5, Chemic
Using the following comparative compounds described in al Abstracts, Vol. 58, p. 6818, an attempt was made to produce an optical filter with the same formulation as in Example 5, but the surface was not smooth but roughened. A good optical filter could not be made. Probably because the number of carbon atoms of the alkyl group bonded to the nitrogen atom in the compound of the comparative example was less than that of the compound of the present invention, the degree of freedom of the conformation of the dye molecule was small, and the amorphous film of the dye crystallized. It is considered easier.

[Effects of the Invention] The cyanine compound of the present invention is useful as a dye, a sensitizing dye for photography, a dye for a recording layer of an optical information recording medium, a stain for biological samples such as cells, a medicine, and the like.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a curve of the wavelength dependence of the absorbance of an optical filter.

Claims (1)

(57) [Claims] 1. A cyanine compound represented by the following general formula (I). General formula (I) [Wherein T ¹ and T ² independently represent an atomic group necessary for forming a fused benzene ring, and L ³ is formed by connecting 1, 3, 5, or 7 methine groups with a conjugated double bond. R ²¹ , R ²² , R ²³ and R ²⁴ independently represent an optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted phenyl group Y represents an anion, and q represents a number necessary to neutralize a positive charge. However, when L ³ comprises 1, 3 or 5 methine groups, at least one of R ²¹ , R ²² , R ²³ and R ²⁴ is an alkyl group having 3 or more carbon atoms which may be substituted. It is. ]