JPH03103476A - Metal-containing indoaniline based compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [M is metal ion capable of chelating; R<1> is alkyl or aryl; R<2> and R<3> are halogen or monovalent organic group; X is -OR<6> (R<6> is alkyl), hydroxy, etc.; Z<-> is anion; m and n are 0-3]. USE:A pigment useful for optical recording media. The compound expressed by formula I has high solubility in organic solvents, enable coating, is high in reflectance and excellent in storage stability and has long wavelength as wavelength of spectral absorption. PREPARATION:A starting compound expressed by formula II such as 5-chloro-8- quinolinol is nitrated and then the nitrated compound is reacted with sodium hydrosulfite to afford a compound expressed by formula III. Then the compound expressed by formula III is reacted with a compound expressed by the formula RCOCl (R is R<1>) to give a compound expressed by formula IV, which is then reacted with a compound expressed by formula V. Finally, the resultant compound expressed by formula VI is reacted with a compound expressed by the formula M<+> Z<->.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to metal-containing indoaniline compounds useful for optical recording.

[Background of the Invention] Optical recording using laser light has been particularly developed in recent years because it enables high-density information recording and reproduction.

Examples of optical recording methods include recording on an optical disc and recording on a recording material for infrared image formation.

Generally, recording on an optical disk is performed by irradiating a thin recording layer provided on a circular base with a laser beam focused to about 1 lIm. When the recording layer is irradiated with laser light, the recording layer absorbs the energy of the irradiated laser light, and thermal changes such as decomposition, evaporation, and melting occur at that location, and information is recorded. In addition, recording on an infrared image-forming recording material involves forming a dye that can be imagewise chelated with specific light, reacting this with a metal donor, and
This is done by enabling reading with laser light.

Since these records are generally reproduced by laser light, it is necessary for the optical recording medium to efficiently absorb or reflect the energy of the laser light having a specific wavelength.

Various configurations of this type of optical recording medium are known. ．． For example, JP-A-55-97033 discloses a method in which a single layer of phthalocyanine dye is provided on a substrate. However, phthalocyanine dyes have problems such as low sensitivity, high decomposition point, and difficulty in evaporating.
Furthermore, since the solubility in organic solvents is extremely low, it also has the problem that it cannot be dissolved in organic solvents and coated.

Further, JP-A-58-83344 discloses a recording layer in which a phenalene dye is provided, and JP-A-58-224793 discloses a recording layer in which a naphthoquinone dye is provided.

However, while these dyes have the advantage of being easily evaporated, they also have the problem of low reflectance. If the reflectance is low, there will be no difference in the intensity of the laser beam reflected from the portion recorded by the laser beam and the unrecorded portion, making it difficult to reproduce the recorded information. Furthermore, organic dyes generally have a problem of poor storage stability.

Further, JP-A No. 83-227589 discloses a metal-containing indoaniline compound that has improved the above-mentioned problems, but the spectral absorption wavelength of the disclosed metal-containing indoaniline compound is short wavelength. However, the storage stability was still insufficient.

[Objective of the Invention] Therefore, the object of the present invention is to provide light that has high solubility in organic solvents, can be coated by coating, has high reflectance, has excellent storage stability, and has a long spectral absorption wavelength. An object of the present invention is to provide a metal-containing indoaniline compound useful for recording purposes.

[Structure of the Invention] The above objects of the present invention have been achieved by a metal-containing indoaniline compound represented by the following general formula [I].

General formula [■] In the formula, M represents a chelatable metal ion, and R! represents an alkyl group or an aryl group, R2 and R3 represent a halogen atom or a monovalent organic group, 2- represents an anion, R4, R
S and R6 represent an alkyl group, m and n represent integers of O to 3, and when m and n are 2 or more, R2 and R3 may be the same or different.

The compound of the present invention causes a state change by a laser beam and is used in an optical recording medium for recording and reproducing the state change, and a dye that can be imagewise chelated by a specific light is formed, and this is transferred to a metal. It reacts with a donor substance to form a metal-containing indoaniline compound, which is useful as a dye for use in optical recording media that enables near-infrared reading.

In the general formula [I], M represents a chelatable metal ion. Examples of these metal ions that can be chelated include nickel ions, copper ions, cobalt ions, iron ions, and zinc ions. Particularly preferred among these are nickel ions and copper ions.

R1 represents an alkyl group or an aryl group. These alkyl groups and aryl groups include those having substituents.

Examples of substituents include halogen atoms, (fluorine atoms,
chlorine atom, etc.), alkyl group, aryl group, heterocyclic group, nitro group, cyano group, alkoxy group, aryloxy group, alkylthio group, arylthio group, keto group, sulfonamide group, sulfamoyl group, acylamino group, carbamoyl group , a sulfonyl group, a sulfinyl group, a hydroxy group, a carboxy group, an amino group, or a primary or secondary amino group.

The alkyl group is preferably a linear or branched alkyl group having 1 to zG carbon atoms, and the aryl group is preferably a phenyl group.

R2 and Rff represent a halogen atom or a monovalent organic group.

The halogen atom is preferably a chlorine atom or a fluorine atom. In addition, monovalent organic groups include alkyl groups that may have substituents (e.g., methyl group, ethyl group), alkoxy groups that may have substituents (e.g., methoxy group, ethoxy group), -CONR'R' -NHCO
R9-NHCO2R9-NHSO2R9-NHSO
2NR'R'-COOR'-So,R' -N
HCONR'R' or the 7/ group is preferred. Here, R7 and R6 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and R9 represents a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, a heterocyclic group, or an amino group. Each group may have a substituent.

Examples of substituents include halogen atoms, (fluorine atoms,
chlorine atom, etc.), alkyl group, aryl group, heterocyclic group, nitro group, cyano group, alkoxy group, aryloxy group, alkylthio group, arylthio group, keto group, sulfonamide group, sulfamoyl group, acylamino group, carbamoyl group , a sulfonyl group, a sulfinyl group, a hydroxy group, a carboxy group, an amino group, or a primary or secondary amino group.

The alkyl group of R4, R5 and R6 has 1 to 1 carbon atoms.
Particularly preferred are four alkyl groups (eg methyl, ethyl, n-propyl, n-butyl).

These alkyl groups include those having substituents.

Substituents include hydroxy group, alkoxy group (e.g. methoxy group, ethoxy group), alkylsulfonamide group (
For example, preferred examples include a methanesulfonamide group), a sulfo group, a carboxy group, a sulfamoyl group, and a carbamoyl group.

Examples of the anion represented by 2- include commonly known anions.

Examples of anions represented by Z- include! -(R')
．． (R'). (R2) lm Yes.

The metal-containing indoaniline compound represented by the general formula CI] exhibits absorption in a wavelength band of 750 ns to 900 nm, and has a molecular absorption coefficient of 10 4 to 10 cm.

The metal-containing indoaniline compound represented by the general formula [I] of the present invention can be synthesized by the following route.

(R') a Specific examples of the metal-containing indoaniline compounds of the present invention are listed below, but the present invention is not limited thereto.

Margin below [Example] Examples of the present invention will be described below.

Example 1 (Synthesis of Compound 3) Synthesis of 5-chloro-7-nitro-8-quinolinol or 5-chloro-8-quinolinol 25. Glacial acetic acid 2 3
Add to 0 cc and cool with ice water under dispersion stirring, 20
After lowering the temperature to below ℃, add nitric acid (d = 1.42)9.
8 ml was added dropwise. After the dropwise addition was completed, the mixture was stirred at the same temperature for 1 hour, then 230 cc of water was added, and the mixture was further stirred for 1 hour. The precipitated crystals are filtered, washed with water, then washed with methanol, dried,
25.8 g of orange crude crystals were obtained. Yield is 81.
It was 8%.

Synthesis of 7-amino-5-chloro-8-quinolinol 5-chloro-7-nitro-8--1-/IJ
/ - Le 25. Of, 60 cc of ethanol, 8 cc of water
It was added to 0 cc of the mixed solution and stirred for t hours. 1 more water
After adding 00 cc of sodium hydrosulfite and cooling with ice water to 20°C or less, sodium hydrosulfite 8B. 'l. was added little by little.

The precipitated crystals were filtered, washed with water, washed with acetonitrile, and dried to obtain beige crude crystals with a weight of 22.0 mm. I got it. Yield is 86. It was B%.

Synthesis of 5-kuoo-7-1so-butanamido-8-quinolinol 15.0 g of 7-amino-5-chloro-8-quinolinol
ethyl acetate 100ee, sodium acetate trihydrate 13
．． 7 g, added to 40 cc of water, cooled with ice water,
℃ or below, and 10.7 g of isobutyric acid chloride was added dropwise. After completion of the dropwise addition, the mixture was stirred at the same temperature for 3 hours, and the precipitated crystals were filtered, washed with water, washed with ethyl acetate, and dried. Recrystallization was performed from ethanol to obtain 11.9 g of crystals. Yield is 58. It was 1%. The structure was confirmed by NMR and MASS.

Synthesis of compound NllL3 2-Amino-5-(N-ethyl-N-methoxyethyl)
9.9 g of aminotoluene●p-toluenesulfonate was added to 100 Cc of water, Q. fl, 9 g of caustic soda, 1.58 g of caustic soda, cooled with ice water, brought to 5°C, and added 1.04 g of caustic soda, 65 c of water.
After adding the c solution, 3.4 g of 5-chloro-7-lso-butanamido-8-quinolinol was added. After stirring at the same temperature for 30 minutes, 40 ml of 5% sodium hypochlorite aqueous solution was slowly added dropwise. After the addition was completed, the mixture was stirred at the same temperature for 1 hour, extracted with ethyl acetate, and washed with water. The oil layer was separated, concentrated to dryness, and purified using silica gel column chromatography to obtain 2.5 g of blue crystals.

yield. 44.2%, λmax; 645nm
(dichloromethane), εmax; 1.95
It was xlO'.

0.87 g of the obtained dye was dissolved in 435 cc of ethanol, and nickel perchlorate t. A solution of gg in 435 cc of pure water was added dropwise over 3 hours. After the dropwise addition was completed, the reaction was continued at the same temperature for 1 hour, and then ethanol was distilled off under reduced pressure. The precipitated crystals were filtered, washed with water, and dried.

yield. 0.9. (79%) λmaxH 82
0nm (dichloromethane), εmax; 1.7
1 XLG'.

The light resistance and heat resistance of the compounds of the present invention were investigated as follows.

15. Applying polyvinyl chloride (n-1.100, manufactured by Wako Pure Chemical Industries, Ltd.) mixed with the compound NLL3 of the present invention on photographic baryta paper. A sample sample 1 was prepared by coating the sample in such a manner that it was or/rrr. In the above, Compound Hiroshi 3 of the present invention was added so that the D wax of the coating film was 2.0.

Samples k2 to k6 were prepared in the same manner except that the compound NllL3 of the present invention was replaced with the compounds shown in Table 1.

These samples 1 to 6 were irradiated with a xenon lamp for 24 hours, the concentration before irradiation (Do) and after irradiation (D) was measured, and the value of (D/Do)xtoo was taken as the residual rate (%), and the light resistance was evaluated. Further, the sample was left for 7 days at a relative temperature of 70% and a temperature of 60° C., and the residual rate was similarly measured from the maximum concentration before and after being left to evaluate heat resistance. The results are shown in Table 1.

Comparison Compound 1 A: Table 1 Compounds Described in JP-A No. 63-227569 As is clear from Table 1, all of the compounds of the present invention have improved light resistance and are excellent in storage stability. ing.

Further, Compound Hiroshi 3 of the present invention and Comparative Compound-A were dissolved in methylene chloride, and the absorbance was measured.

The absorbance of compound k3 of the present invention is shown in FIG. 1, and the absorbance of comparative compound 1A is shown in FIG.

In the figure, the vertical axis represents absorbance and the horizontal axis represents wavelength (nm).

From FIG. 1 and FIG. 2, it can be seen that the spectral absorption wavelength of the compound k3 of the present invention is longer than that of the comparative compound 1A, and is suitable for reproduction of recorded information using laser light.

[Effects of the Invention] The metal-containing indoaniline compound of the present invention has a long spectral absorption wavelength, has high solubility in organic solvents, can be coated by coating, has high reflectance, and provides high contrast. The effects of the compounds of the present invention are completely unexpected and surprising, as they can be read by an optical reading device and have significantly improved storage stability.

[Brief explanation of drawings]

Figure 1 shows the spectral absorption spectrum of the compound 3 of the present invention.
FIG. 2 is a diagram showing the spectral absorption spectrum of Comparative Compound 1A.

Claims (1)

[Scope of Claims] A metal-containing indoaniline compound represented by the following general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, M represents a metal ion that can be chelated, and R^
1 is an alkyl group or an aryl group, R^2 and R^3 are a halogen atom or a monovalent organic group, X is a ▲numerical formula, chemical formula, table, etc.▼ or a hydroxyl group, Z^- is an anion , R^4, R^5 and R^6 represent an alkyl group, m and n represent integers of 0 to 3, and when m and n are 2 or more, R^2 and R^3 are the same, respectively. It may be different or different. )