JPS62232461A - Cyanine dye - Google Patents

Abstract

NEW MATERIAL:Compds. of formula I, wherein R1 is H, Cl or Br; R2 is H or acetyl; n is 2 or 3; and X is an acid anion. EXAMPLE:1,1'-Di-beta-hydroxyethyl-3,3,3',3'-tetramethyl-5,5'-dichloroind otricarbocyanine perchlorate of formula II. USE:Cyanine dyes which are green and useful as a medium for recording and reproduction by laser beams and copying and printing photosensitive materials, etc. PREPARATION:A 2,3,3-trimethylindolenium derivative (A), of which the position 1 is substituted by a hydroxyalkyl group when R2 is H, and 1-anilino-5- anilinopenta-1,3-diene hydrochloride (B) are refluxed in the presence of sodium acetate or a tert. amine in an alcohol solvent for several hr. When R2 is an acetyl group, the component A is reacted with the component B in the presence of sodium acetate in acetic anhydride at 90-120 deg.C for several hr.

Description

Detailed Description of the Invention [Technical Field] The present invention relates to a novel cyanine dye having a maximum absorption wavelength in the near-infrared region. The present invention relates to dyes that are particularly useful as materials for optical information recording media.

[Prior art]

Conventionally, optical information recording media to which a thin layer of cyanine dye is applied as a recording layer are known (for example,
JP-A-59-85791). Recording media using this cyanine dye have a particularly large extinction coefficient compared to other dyes that absorb in the near-infrared region, so they have high sensitivity (recording/reproduction) and S/N, and they also have high storage capacity. It is a highly flexible optical information recording medium.

In addition, this recording medium can basically be formed by using various methods such as vapor deposition and coating to form a thin film containing a cyanine dye on a substrate. ! Although this method can be said to be industrially advantageous, it requires a step of dissolving the cyanine dye in an organic solvent to form a solution. However, conventionally known cyanine dyes have low solubility in organic solvents and lack stability, resulting in poor dispersibility and stability of cyanine dyes during the dissolution process, and recording media coated with this have poor recording reproducibility. Or the storage stability was insufficient.

〔the purpose〕

An object of the present invention is to provide a novel cyanine dye that has a maximum absorption wavelength in the near-infrared region and has excellent chemical stability and solubility in various organic solvents.

〔composition〕

According to the present invention, the general formula (1) (wherein R1 represents a hydrogen atom, a chlorine atom, or a bromine atom, R2 represents a hydrogen atom or an acetyl group, and n is 2 or 3
and X represents an acid anion. ) is provided.

Examples of the acid anion in the above general formula (I) include halogen, alkyl sulfate, arylsulfonyl group, verchlorate, and tetrafluoroborate.

The cyanine dye represented by the general formula (I) of the present invention is:
It has maximum wavelength absorption in the near-infrared region, and is a chemically stable substance, as well as methanol, ethanol,
Alcohols such as isopropanol, ketones such as acetone, methyl ethyl ketone, cyclohexanone,
Ethers such as ethyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate and n-butyl acetate; and chloroform, dioxane, and 2-dichloroethane.
Soluble in various organic solvents such as dimethylformamide and mixed solvents thereof.

Therefore, the cyanine dye of the present invention has the advantage that it can be used as a recording and reproducing medium using a laser beam, and can also be used as a sensitizing dye for photoreceptors or photoreceptors for copying and printing, and as a sensitizing dye for silver salt photography. It can also be used effectively as a material for optical filters, display materials, paints, etc.

The cyanine dye of the present invention can be synthesized by applying various production methods conventionally known in this field. That is, when producing a cyanine dye in which R2 in the general formula is one hydrogen atom, a 2,3,3-trimethylindolenium salt derivative substituted with a hydroxyalkyl group at the 1-position and a 1-anilino-5-aniline It can be produced by boiling and refluxing linopentane-1,3-diene hydrochloride with sodium acetate or a tertiary amine in an alcoholic solvent for several hours. Also,
Another method is to produce a 2,3,3-trimethylindolenium salt derivative substituted with a hydroxyalkyl group at the 1-position by boiling and refluxing 2,4-dinitrophenylpyridium chloride in pyridine for several hours. I can do it. In addition, when producing a cyanine dye in which R2 in the general formula is an acetyl group, a 2,3,3-trimethylindolenium salt derivative substituted with a hydroxyalkyl group at the 1-position and 1-anilino-5-anilinopenta-1, 3-
By reacting diene hydrochloride with sodium acetate in acetic anhydride at 90 to 120°C for several hours, a cyanine dye is formed, and at the same time, the hydroxyl group of the hydroxyalkyl group substituted at the 1-position of the indolenine nucleus is reacted with acetic anhydride. is acetylated by

The 2,3,3-trimethylindolenium salt derivative in which the 1-position is substituted with a hydroxyalkyl group, which is the starting material compound, can be synthesized by the method described below. A hydrochloride of a phenylhydrazine derivative which is unsubstituted or substituted with a chlorine atom or a bromine atom at the 4-position and 3-methyl-2-butanone is boiled and refluxed in an ethanol solvent under acidic sulfuric acid to add chlorine to the unsubstituted or 5-position. A 2,3,3-trimethylindolenine derivative substituted with an atom or a bromine atom is synthesized. Next, the synthesized 2,3,3-trimethylindolenine derivative and 2-bromoethanol or 3-bromo-1-propanol were heated at 90 to 110°C for several hours to substitute a hydroxyalkyl group at the 1-position. 2, 3.3
- A trimethylindolenium salt derivative is synthesized.

Also, 1-anilino-5-anilinopentane-1゜3-
Diene hydrochloride is described in the literature of Ogata et al.
.

Phys, Chem, Res, (Tokyo),
13. P511. (1934)).

To create an optical information recording medium using the cyanine dye of the present invention, the cyanine dye is dissolved in the above-mentioned solvent or mixed solvent, and the solution is applied to a base plate to form a thin film containing the cyanine dye. Form. The substrate material may be a commonly used recording material support such as glass, quartz, ceramic, plastic, paper, plate-shaped or foil-shaped metal. Moreover, as a method of application, conventional coating methods such as spraying, roller coating, dipping, and spinning can be used.

〔effect〕

The novel cyanine dye represented by the general formula (1) obtained by the present invention has a maximum wavelength in the near-infrared region and has excellent chemical stability and solubility in various organic solvents.

Therefore, the cyanine dye of the present invention has the advantage that it can be used as a recording and reproducing medium using a laser beam, and also as a sensitizing dye for photoreceptors or photoreceptors for copying and printing, and as a sensitizing dye for silver salt photography. Furthermore, it can be effectively used as a material for optical filters, display materials, paints, etc.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to Examples.

Example 1 1.1'-di-β-hydroxyethyl-3,3,3'
, Production of 3'-tetramethyl-5,5'-dichloroindotricarbocyanine verchlorate] One of the raw materials, 1-β-hydroxyethyl-2゜3.
3-)-Dimethyl-5-chloroindolenium bromide 2H40H was synthesized as follows.

60.9 g of 4-chlorophenylhydrazine hydrochloride and 3-
35.1g of methyl-2-butanone and 450c of ethanol
37.5 cc of concentrated sulfuric acid was added thereto, and the mixture was boiled and refluxed for 1 hour. After removing the solvent, the mixture was made alkaline with a 10% aqueous sodium hydroxide solution, and then extracted with ether.

The product was then purified by vacuum distillation to obtain 2,3°3-trimethyl-5-chloroindolenine. Boiling point 103℃/2
mmHg, yield 50.1g.

Next, 18.8 g of 2,3,3-1-dimethyl-5-chloroindolenine and 12.1 g of 2-bromoethanol were added to 10
The mixture was heated and stirred at 0° C. for 1.5 hours. The precipitated and solidified crystals were washed with ethyl acetate and then recrystallized with ethanol to obtain 1-β.
-Hydroxy-2,3,3-trimethyl-5-chloroindolenium bromide was obtained. Melting point 215℃, yield 1
8.2g.

3.50 g of 1-β-hydroxy-2,3,3-trimethyl-5-chloroindolenium bromide obtained above and 1-anilino-5-anilinopent-1,3-diene (
(melting point: 137-139°C) was mixed with 20 cc of n-butanol, 0.82 g of sodium acetate was added, and the mixture was heated and stirred at 100-110°C for 2 hours. After cooling, pour into 70 cc of an aqueous solution of 1.35 g of sodium perchlorate, add 40 cc of toluene, and stir while heating to precipitate crystals. The precipitated perchlorate of the dye was collected by filtration and purified by recrystallization several times with methanol to obtain green crystals. Yield: 1.21 g, melting point: 217.5-219°C, maximum absorption wavelength in ethanol: 753 nm.

Example 2 1.1'-di-β-ace1-oxyethyl-3,3,
Production of 3-3'-tetramethyl-5,5'-dichloroindotricarbocyanine verchlorate] 1-β-hydroxyethyl-2,3 synthesized in Example 1
, 18.2 g of 3-trimethyl-5-chlorof-nodorenium bromide, 1-anilino-5-anilinopenta-
1,3-diene hydrochloride 8.3g, sodium acetate 4.7
1.5g in 100cc of acetic anhydride at 100-110℃
Time reacted. After cooling, 6.98 g of sodium perchlorate
The mixture was poured into 500 cc of an aqueous solution and stirred for a while while heating to precipitate crystals. After filtering the crystals, methanol], 00
It was washed with cc and dissolved under heating in 70 cc of 1,2-dichloroethane. After removing insoluble matter, ethanol was added little by little. The precipitated green crystals were collected by filtration and washed with methanol. Yield: 15.0 g, melting point: 209°C, maximum absorption wavelength in ethanol: 750 nm.

Infrared absorption spectra of cyanine dyes of Examples 1 and 2 (
KBr tablet), the spectrum of Example 1 showed a broad absorption band of 0-11 stretching vibration at 3'400 cm-', but the spectrum of Example 2 did not have such an absorption band. Instead, a sharp absorption band indicating ester was observed at 1.140 cm-''.

Example 3 1.1'-di-twohydroxypropyl-3,,3,
3'.

Production of 3'-tetramethyl-5,5'-dichloroindotricarbocyanine verchlorate] One of the raw materials, 1-γ-hydroxypropyl 2.3
．． 3-Trimethyl-5-chloroindolenium verchlorate 3H60H was synthesized as follows.

2.3.3- Trimethyl-5-chloroindolenine 1
9.4 g, 3-bromo-1-propertool], 3.9 g
, 1.2.2 g of sodium perchlorate for 1.5 hours 100
Reacted at ~110°C. After cooling, the solidified crystals were washed with ethyl acetate and dissolved in acetone. After removing the insoluble matter, the solvent is distilled off. Recrystallize the crystals with ethanol,
1-γ-hydroxypropyl-3,3-dimethyl-5-
Chlorindolenium verchlorate was obtained.

Yield: 16.1 g, melting point: 140.5-142°C.

1-γ-human p-xypropyl-2.3.3- obtained above
5.0 g of trimethyl-5-chloroindolenium verchlorate and 2,4-dinitrophenylpyridium.
, -11-muchloride (melting point 200-202°C)2. 'Og was boiled and refluxed for 2 hours in 200 cc of pyridine. After cooling, pour into 500cc of water,
A slightly viscous solid was obtained. After drying, it was washed with 1,2-dichloroethane and recrystallized with methanol to obtain green crystals. Yield 0.25g, melting point 218-219°C, maximum absorption wavelength of ethanol 752nm.

Example 4 1.1'-di-γ-acetoxypropyl-3,3,3
S3'-tetramethyl-5,5'-dichloroindolicarbosia converter chlorate, 2,7S-'to, s゛methyl-5-chloroindolenium bar'? E] rate 7.8 g, 1-anilino-
5-anilinobenter 1,3-diene hydrochloride3. -2g
,, 1.8 g of sodium acetate in 50 cc of acetic anhydride, 1
The reaction was carried out at 00 to 110°C for 1.5 hours. After cooling, the mixture was poured into 200 cc of water and stirred for a while while heating to precipitate crystals. The crystals were collected by filtration and recrystallized several times with methanol to obtain green crystals.

Yield: 5.7 g, melting point: 198°C, maximum absorption wavelength in ethanol: 750 nm.

Comparing the infrared absorption spectra (KBr tablets) of the cyanine dyes of Examples 3 and 4, it was found that the spectrum of Example 3 had a broad 0-11 stretching vibration absorption band at 3400c+n-''; In the spectrum of Example 4, there was no such absorption band, but instead a sharp absorption band indicating ester was observed at 1730 cm-1.

Example 5 1.1'-di-γ-acetoxypropyl-3,3,3
23'-tetramethyl-5,5'-dibromoindo 1-
Production of lycarbocyanine perchlorate] 1-β-hydroxyethyl-2,3,3-trimethyl in place of 1-β-hydroxyethyl-2,3,3-trimethyl-5-chloroindolenium bromide in Example 2 -5-bromoindolenium promy 1.1
The same procedure was carried out except that 200° C. (melting point: 208° C.) was used.

Melting point 226-228℃, maximum absorption wavelength in ethanol 7
52r+m.

Example 6 1.1'-di-β-hydroxyace1-oxyethyl-
Production of 3,3,3',3'-tetramethylindotricarbocyanine verchlorate] Instead of 1-β-hydroxychochotyl-2,3,3trimethyl-5-chloroindolenium bromide in Example 1 1-β-hydroxyethyl-2,3,3-trimethylindolenium bromide (melting point 198-199°C)
The procedure was the same except that . Melting point 144-146
°C, maximum absorption wavelength in ethanol 751 nm.

Next, in order to specifically demonstrate that the cyanine dye of the present invention is excellent as a material for optical information recording media, application examples will be described below.

Application Example 1 The cyanine dye of Example 1 was dissolved in methanol to make a 1% by weight solution. The solution was spin-coated onto an acrylic base plate and dried to obtain a recording layer with a thickness of 450 mm.

A semiconductor laser with a wavelength of 700 nm is used for these recording media, and a beam diameter of 1. ．． Linear speed to 54μm], 2m/sec
A 0.7 MHz signal was recorded. When this recording section was irradiated with a weak laser beam and the signal was reproduced, the initial c/N was:
) Yayuya body. . . . After leaving it in the engine for 40 days, the signal was regenerated.1.
The C value was 48 dB.

Application Example 2 The cyanine dye of Example 3 was dissolved in 1,2-dichloroethane, and the experiment was carried out in the same manner as in Application Example 1. The initial value of C/N is 54 dB, and the C/N value after the storage test is 5 ], d
It was B.

151 Application Example 3 The cyanine dye of Example 6 was dissolved in ethanol, and the experiment was carried out in the same manner as in Application Example 1. The initial value of C/N is 56d
B. The C/N value after the storage test was 52 dB, 't-.

As described above, the cyanine dye of the present invention has significantly superior properties as a material for optical information recording media compared to conventional dyes, and has many industrial advantages.

Claims (1)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 represents a hydrogen atom, chlorine atom, or bromine atom, R_2 represents a hydrogen atom or an acetyl group,
n represents 2 or 3, and X represents an acid anion. ) A cyanine dye represented by