JPH01131277A - Cyanine compound - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [X is-NR2R3(R2 and R3 are each H, lower alkyl or hydroxy lower alkyl); Y is H,-NR4R5 (R4 and R5 are the same as R2 and R3 respectively), lower alkyl or lower alkoxy; R1 is (substituted) lower alkyl; Z is acidic residue; where, in case Y is H, X is not lower alkoxy]. USE:Near-infrared-absorptive organic coloring matters for optical disc recording media for semiconductor laser. Having high reflectance comparable to that tellurium-based inorganic materials. PREPARATION:A condensation reaction is carried out between an indolenium salt of formula II and beta-anilino-acrolein-anil hydrochloride.

Description

[Detailed description of the invention] Industrial applications The present invention relates to a novel cyanine compound.

BACKGROUND TECHNOLOGY AND PROBLEMS 1 Conventionally, most inorganic recording media for semiconductor lasers have recording layers made of tellurium-based materials. However, tellurium-based materials have problems such as being toxic, having poor corrosion resistance, being expensive, and not being able to achieve high density.Therefore, there is a need to develop organic pigments to replace these tellurium-based inorganic materials. is being carried out.

The important properties required of organic dyes as recording media are:
It is as follows.

(1) It must strongly absorb near-infrared light in the vicinity of 700 to 900 nm, and undergo shape changes such as melting, sublimation, and decomposition due to its thermal energy.

(2) For signal detection during reproduction, it is desirable that the dye film strongly reflect light.

(3) Since the recording layer is formed by a wet coating method, it should have good solubility in solvents.

(4) It should have excellent shape stability and storage stability after recording, be free from deterioration due to reproduction light, and practically be able to withstand storage for 10 years or more.

Compared to the above inorganic materials, organic dyes have the advantages of low toxicity, excellent corrosion resistance, low cost, and the ability to achieve high density, but among the above characteristics (1) to (4), An organic dye satisfying the property (2) above has not yet been found.

Means for Solving the Problems One object of the present invention is to provide a cyanine compound that can be suitably used as an organic near-infrared absorbing dye in an optical disk recording medium for a semiconductor laser.

Another object of the present invention is to provide the above-mentioned (
An object of the present invention is to provide a cyanine compound having the properties 1) to (4).

Another object of the present invention is to provide a cyanine-based compound having a reflectance as high as that of tellurium-based inorganic materials.

Another object of the present invention is to provide a cyanine compound having extremely good solvent solubility.

The cyanine compound of the present invention is a novel compound that has not been described in any literature, and is represented by the following general formula (1).

[In the formula, X represents a -NR2R3 group (where R2 and R3 are the same or different and are a hydrogen atom, a lower alkyl group or a hydroxy lower alkyl group) or a lower alkoxy group. Y represents a hydrogen atom, a -NR, R5 group (where R4 and R5 are the same or different and are a hydrogen atom, a lower alkyl group or a hydroxy lower alkyl group), a lower alkyl group or a lower alkoxy group. R1 represents a lower alkyl group that may have a substituent. Z represents an acidic residue. However, when Y is a hydrogen atom, X must not be a lower alkoxy group. ]] JP-A-59-85791 discloses a compound represented by the following chemical formula (hereinafter referred to as "compound A") as a compound similar to the compound of the present invention.

However, compound A does not have good solvent solubility.
Furthermore, a dye film using Compound A has a low light reflectance, and therefore Compound A cannot be suitably used as an organic near-infrared absorbing dye in an optical disk recording medium for a semiconductor laser.

In the above general formula (1), X, YSR,, R2, R3
, R4, R5 and Z are as follows.

Examples of lower alkyl groups include methyl, ethyl, n-
Propyl, isopropyl, n-butyl, isobutyl, t
Examples include alkyl groups having 1 to 4 carbon atoms such as ert-butyl group.

Examples of hydroxy lower alkyl groups include hydroxymethyl, 1-hydroxyethyl, 2-hydroxydiethyl, 3-
Hydroxypropyl, 4-hydroxybutyl, 2-hydroxy-2,2-dimethylethyl, 2-hydroxy-1
Examples include lower alkyl groups having 1 to 4 carbon atoms substituted with one hydroxy group such as -methylethyl and 3-hydroxy-1-methylpropyl groups.

Lower alkoxy groups include methoxy, ethoxy, n-
propoxy, isopropoxy, n-butoxy, tert
Examples include alkoxy groups having 1 to 4 carbon atoms such as -butoxy group.

-NR2R3 group and -NR4R5 group include amino,
N, N-dimethylamino, N, N-diethylamino, N
-ethyl-N-(2-hydroxyethyl)amino, N,
N-bis(hydroxymethyl)amino, N,N-bis(
Examples include hydroxyethyl)amino, N-methyl-N-ethylamino, N-methyl-Nn-propylamino, and N-methyl-Nn-butylamino groups.

Examples of lower alkyl groups that may have a substituent include methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-hydroxyethyl, 2-ethoxyethyl, 2-(n -butoxy)ethyl, n-butoxymethyl, -1(CH2) n SO
3Na (n is an integer from 1 to 4), -(CH2)
COONa (n is an integer of 1 to 4), C as a substituent of methylaminomethyl, dimethylaminomethyl, acetoxymethyl, methoxycarbonylmethyl group, etc.
1-4 alkoxy group, hydroxyl group, sulfonic acid group, carboxy group' (C1-4 alkyl) amino group, acetoxy group and (C1-4 alkoxy) carbonyl group having at least one group. Examples include certain alkyl groups having 1 to 4 carbon atoms.

Examples of Z include a halogen atom, an alkyl sulfate residue, an aryl sulfonate residue, a barchlorate residue, a tetrafluoroborate residue, an aryl carboxylic acid residue, and the like. When Z is a halogen atom, specific examples of Z″″ include CQ-1Br-1I-1F- and the like.

When Z is an alkyl sulfate residue, specific examples of Z- include CHa S 0a-1C2H5SO4-1n-C,
3R7SO4", n-C4H95O4-, etc. Z is an arylsulfonate residue and CH30S O3-
etc. can be exemplified. When Z is a barchlorate residue,
As a specific example of Z''', CC04- etc. can be given.Z
When is a tetrafluoroborate residue, specific examples of 2'' include BF4- and the like. When Z is an arylcarboxylic acid residue, specific examples of Z''' include (Σcoo-).

Among the compounds of the present invention, in particular, X is a lower alkoxy group,
Compounds in which Y is a lower alkoxy group, R1 is a lower alkyl group or a lower alkoxy-lower alkyl group, and Z is a halogen atom or a barchlorate residue are preferred. Further, Y is preferably a compound substituted at the 6-position or 7-position, particularly at the 6-position, of the indolenine ring.

The compound of the present invention represented by the above-killing (1) is a species,
Although it can be produced by various methods, it can be easily produced according to the preferred method, for example, shown below.

That is, the compound of the present invention has the following formula: [wherein X, YSR, and Z are the same as above. It is produced by subjecting an indolenium salt represented by the formula % to a condensation reaction with a known β-anilino-acrolein-anil hydrochloride represented by the formula % (3).

The above condensation reaction is carried out in a dehydrated organic acid in the presence of a fatty acid salt. Examples of fatty acid salts include sodium acetate, potassium acetate, calcium acetate, sodium propionate, potassium propionate, etc., which are usually used in an amount of 0.0000 per mole of the compound of general formula (2).
It is used in an amount of about 5 to 3 moles, preferably about 1 to 2 moles. Examples of dehydrating organic acids include acetic anhydride, propionic anhydride, butyric anhydride, and γ-butyrolactone. Such a dehydrating organic acid is compound 1 of general formula (2)
Per mole, usually about 10 to 100 moles, preferably 20
About 50 moles are used. The ratio of the compound of general formula (2) and the compound of general formula (3) to be used is usually about 0.2 to 1.5 times the former by mole, preferably 0.4 to 1.5 times the latter by mole.
It is preferable to set it to about 0.7 times the mole. The above reaction usually involves 5
The reaction proceeds suitably at about 0 to 150°C, preferably 100 to 140°C, and is generally completed in about 10 to 60 minutes.

Indolenium salt of the above general formula (2) (general formula (2a)
and the compound of general formula (2b)) include novel compounds that have not been described in literature, and the salts thereof are produced, for example, according to the method shown below.

R1 (2a) R1 R1 (2b) [In the formula, 21 represents an acidic residue other than a verchlorate residue or a tetrafluoroborate residue, and Z2 represents a verchlorate residue or a tetrafluoroborate residue. X, Y and R
1 is the same as above. ] The reaction between the known aniline derivative represented by the general formula (4) and the known 3-bromo-3-methyl-2-butanone represented by the formula (5) is carried out in the presence of a deoxidizing agent. Examples of deoxidizers include pyridine,
Tertiary amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, sodium carbonate,
Examples include alkali metal carbonates such as potassium carbonate and calcium carbonate, alkali metal salts of acetate such as sodium acetate, potassium acetate, and calcium acetate, and these have the general formula (
It is usually used in an amount of about 0.3 to 5 times the mole, preferably about 0.5 to 1.5 times the mole of the compound (4). Compound(
The ratio of 4) and compound (5) to be used is usually about 0.3 to 5 times the molar amount of the latter to the former, preferably 0.3 to 5 times the molar amount of the latter.
The amount is preferably about 5 to 1.5 times the molar amount. The reaction is
It is usually carried out at room temperature to about 200°C, preferably about 50 to 150°C, and is completed in about several hours to about 25 hours, preferably about 5 to 15 hours.

The compound represented by general formula 1 (2a) is represented by general formula (6)
It is produced by treating the indolenine derivative represented by the formula with an alkylating agent. As an alkylating agent,
For example, alkyltoluenesulfonates such as methyl toluenesulfonate, ethyl toluenesulfonate, n-propyl toluenesulfonate, isopropyl toluenesulfonate, n-butyl toluenesulfonate, ethyl bromide, n-propyl bromide, n-butyl bromide. , ethyl iodide, koka n
- Alkyl halides such as propyl, n-propyl chloride, n-butyl chloride, dialkyl sulfates such as dimethyl sulfate and diethyl sulfate, mixtures of acids and epoxy compounds (e.g. inorganic acids such as hydrochloric acid and sulfuric acid, acetic acid, propionic acid, etc.) (mixtures of organic acids, etc. with ethylene oxide, propylene oxide, etc.). The amount of alkylating agent used per 1 mole of compound (6) is usually about 0.3 to 5 times the molar amount, preferably about 0.5 to 2 times the molar amount.
. The reaction is carried out without a solvent or with alkylbenzenes such as toluene and xylene, aliphatic hydrocarbons such as n-octane, n-decane, cyclohexane, and decalin, aromatic hydrocarbons such as benzene, naphthalene, and tetralin, trichloroethane, It is carried out in a solvent such as halogenated hydrocarbons such as tetrachloroethane, chlorobenzene, dichlorobenzene, etc. The reaction is usually carried out at room temperature to about 200°C, preferably about 50 to 150°C, and is generally completed in about 2 to 30 hours, preferably about 3 to 15 hours.

The compound represented by general formula (7) is produced by treating compound (2a) with an alkali in a suitable solvent, such as water. As the alkali to be used, any conventionally known alkali can be used, such as sodium hydroxide, potassium hydroxide, and the like. The amount of alkali to be used is usually about 1 to 20 times the molar amount per mole of compound (2a); 4. Preferably, the amount is about 1 to 5 times the molar amount. In addition, as the usage amount 7 of the solvent, compound (2a)
The amount per mole is usually about 2 to 100 times the molar amount, preferably about 2 to 20 times the molar amount. The above reaction is usually carried out at about 0 to 150°C, preferably about 0 to 100°C, and generally for about several tens of minutes to 10 hours, preferably about 1 to 100°C.
It will be completed in about 5 hours.

The compound represented by the general formula (2b) is prepared by adding a compound represented by the general formula (8) to the compound (7) in methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert.
- In an appropriate solvent such as alcohols such as butyl alcohol, hydrocarbons such as benzene, toluene, xylene, n-octane, n-decane, cyclohexane, decalin, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, etc. It is produced by reacting with The usage ratio of compound (7) and compound (8) is usually about 0.3 to 10 times the molar amount of the latter to the former.
Preferably, the amount is about 0.5 to 3 times the molar amount. The reaction is carried out at a temperature of about 0 to 70°C, and generally takes 10 minutes to 30 minutes.
It will be completed in about an hour.

The compound of the present invention thus obtained can be easily isolated and purified from the reaction mixture by conventional isolation and purification means, such as recrystallization and column separation.

Effects of the Invention The compound of the present invention represented by the above general formula (1) exhibits good solubility in organic solvents such as alcohols such as methanol, ethanol, diacetone alcohol, and fatty acid halogenated hydrocarbons such as dichloromethane and dichloroethane. ,6
70-750nm! , : Has a maximum absorption wavelength and has a high molar extinction coefficient. In addition, when used as an optical disk recording medium for semiconductor laser, reproduction laser light (780n
m) has an extremely high light reflectance and is of particularly high utility value.

EXAMPLES Below, a production example of compound (2) is listed as a reference example, and then a production example of the compound of the present invention is listed.

Reference Example 2. A mixture of 15.36 g of 4-dimethoxyaniline, 16.06 g of 3-bromo-3-methyl-2-butanone, and 8.0 g of pyridine was reacted at 50 to 55°C for 5 hours, and further reacted under reflux for 7 hours. I let it happen.

After the reaction is complete, pour into 70ml of water and add 30ml of dichloromethane.
After extraction and removal of the solvent, 2.3.3 is extracted by vacuum distillation.
-) dimethyl-5,7-simethoxyindolenine 12.
Obtained 0g.

Boiling point 125-130°C/2-3 mmHg 10.96 g of 2,3.3-)dimethyl-5°7-simethoxyindolenine obtained above, ethyl p-toluenesulfonate 11. A mixture of 60 g of OOg and toluene was refluxed to 8
Allowed time to react.

After the reaction was completed, 1-ethyl-2,3,3-trimethyl-5,7-simethoxyindolenium toluenesulfonate was extracted with 50 g of water.

20g of 20% NaOH was added to this extract, and after reacting at 70°C for 3 hours, the mixture was extracted with 30w2 of toluene. After distilling off toluene, 1-ethyl-2-methylene-3,3-dimethyl-5,7-simethoxyindoline 6 was obtained by vacuum distillation.
．． 00g was obtained.

Boiling point 122-129℃/3-4mmHg 1-ethyl-2-methylene-3゜3-dimethyl-5,7 obtained above
- 70% HCQO into a mixture of 4.95 g of cymethoxyindoline and 60 mQ of isopropanol at below 20°C.
a 2.87g was added. After stirring at room temperature for 1 hour, the mixture was cooled to below 5°C. The precipitated crystals are separated in a furnace, washed and dried,
6.54 g of 1-ethyl-2,3,3-)dimethyl-5,7-simethoxyindolenium verchlorate was obtained.

Melting point 225.5-226.5°C Production example 1.

Compound of general formula (2) (X=N, N-dimethylamino group, Y=hydrogen atom, R,=methyl group, Z″′=CQ04″
') 4.75 g, β-anilino-acrolein-anil hydrochloride 1.94 g and potassium acetate 2.5 g were added to acetic anhydride 60III2, and after refluxing for 10 minutes, water 350 g
I put it into m12. The precipitated crystals were separated in a furnace, washed with water, and then recrystallized with methanol to form the compound of -Sakuhatsu (1) [X=N,
3.44 g of N-dimethylamino group, Y=hydrogen atom, R,=methyl group, 2-=CΩ04''') was obtained.The melting point, maximum absorption wavelength (λmax), and molar extinction coefficient (ε) of this compound were It is as follows.

Melting point: 219-221°C λmax: 732nm (Diacetone alcohol)
ε: 2.30X105cl' Production Example 2 Compound of general formula (2) [X=N, N-dimethylamino group, Y=hydrogen atom, R3=ethyl group, Z-=C・QO4
'-34,96g, the compound of general formula (1) [X=N, N-dimethylamino group, Y-
Hydrogen atom, R,=ethyl group, Z-=CQOa-]3.8
Obtained 0g.

Melting point: 195-200°C λmax: 728nm (methanol) ε: 2
．． 34 x 105 cm" Production Example 3 Compound of general formula (2) (X = methoxy group, Y = methoxy group (7th position of indolenine ring, same hereinafter), R, = ethyl group, Z-teCQOa -]5. Production example 1 using 22g
Similarly, the compound of general formula (1) (X=methoxy group,
Y=methoxy group (7th position), R,=ethyl group, Z-=CQ
4.21 g of Oa-] was obtained.

Melting point: 250-252℃ λm body: 693nm (Diacetone alcohol) ε:
1.84 The compound of general formula (1) (X = ethoxy group, Y = ethoxy (7th position), RI = ethyl group, Z
-=Ca04-3 was obtained.

λmax: 698 nm (dichloromethane) ε:
1.72×10 5 cm −1 Compounds of Production Examples 5 to 22 were obtained in the same manner as in Production Example 1 above using an appropriate compound of general formula (2).

Production Example 5 Compound of general formula (1) [X=N, N-dimethylamino group, Y=methyl group (7th position), RI=methyl group, Z-=CQ
O4-) λmax: 737 nm (Diacetone alcohol)
ε: 2.20XIO5cm" Production Example 6 Compound of general formula (1) (X=N, N-dimethylamino group, Y=methoxy group (7th position), R+=ethyl group, Z-=C
Q'''] λwax: 747nm (Diacetone alcohol)
E: 2.28X 105cm-' Production Example 7 Compound of general formula (1) (X=N, N-diethylamino group, Y-hydrogen atom, R,=ethyl group, Z-=C2Hs 8
04-) λmax: 735nm (Diacetone alcohol)
ε: 2. IOXIO5cm" Production Example 8 Compound of general formula (1) [X=N-ethyl-N-(2-hydroxyethyl)amino group, Y=hydrogen atom, R,=ethyl group, 2-=λmax: 735 nm (diacetone Alcohol) ε: 2. 10XIO5c"1 Production Example 9 Compound of general formula (1) (X = methoxy group, Y = methoxy group (6th position), R1 = methoxymethyl group, λmax:
702nm (Diacetone alcohol) ε: 1.60
X105cm-1 Production Example 1〇Compound of general formula (1) (X=methoxy group, Y=methyl group (7th position), Rr=2-hydroxyethyl group, Z″″=C
QO4-) λmax: 679nm (Diacetone alcohol)
ε: 1.84 x 105 cm-' Production Example 11 Compound of general formula (1) (X = methoxy group, Y = methyl group (7th position), R+ = 2-methoxyethyl group 1.z-=
cQo4-] λmax: 679 nm (Diacetone alcohol) ε: 1.85X105 cm-1 Production Example 12 Compound of general formula (1) (X = methoxy group, Y = methyl group (6th position), R+ = n-propyl group, Z-=I-3 λwax: 683nm (Diacetone alcohol)
ε: 1. 74 x 105 cm" Production Example 13 Compound of general formula (1) (X = ethoxy group, Y = methyl group (7th position), RI = ethyl group, 2- = BF4-) λmax: 681 nm (dichloroethane) ε
: 1. 75X105cm” Production Example 14 Compound of general formula (1) CX = n-propoxy group, Y = methyl group (7th position), R1 = ethyl group, Z- = CJO4-) λmax: 683 nm (Diacetone alcohol)
ε: 1.63X105cm" Production Example 15 Compound of general formula (1) [X = methoxy group, Y = ethyl group (7th position), RI = ethyl group, 2-=CQO4-] λmax: 681 nm (Diacetone alcohol)
ε: 1.82X105cm" Production Example 16 Compound of general formula (1) [X = methoxy group, Y = isopropyl group (7th position), RI = methyl group, Z- = I-) λmax: 681 nm (diacetone alcohol) ε: 1.62X105Cm" Production Example 17 Compound of general formula (1) (X = methoxy group, Y = methoxy group (6th position), R1 = n-butyl group, Z- = 1-) λmax: 703 nm (Diacetone Alcohol) ε: 1.62X105cm-1 Production Example 18 Compound of general formula (1) (X = Niamino, Y = Hydrogen atom,
R1=1-F-ru group, Z-=CQOalλmax:
730nm (Diacetone Alcohol) E: 2.
30X 105cm-' Production Example 19 Compound of general formula (1) [X=N, N-bis(hydroxymethyl)amino group, Y=hydrogen atom, R,=ethyl group, Z
'''2CQO4-]λmax: 734nm (Diacetone alcohol) ε: 2. 13x 1 O5
Cm" Production Example 20 Compound of general formula (1) [X = methoxy group, Y = methoxy group (6th position), R, = n-butyl group, Z"' = CI20
4-:] λmix: 699 nm (dichloromethane) ε:
1.61X105cm-' Production Example 21 Compound of general formula (1) (X = methoxy group, Y = methoxy group (7th position), R, = acetoxyethyl group, Z"' = C
QO4-) λmax: 693nm (Diacetone alcohol)
ε: 1.75X105 cm-' Production Example 22 Compound of general formula (1) (X = methoxy group, Y = methoxy group (7th position), RI = methoxyethyl group, Z- = 1-) λmax: 695 nm (Diacetone Alcohol) ε: 1.80 x 105 cm” Reflectance measurement test Various cyanine dyes shown in Table 1 below were dissolved in dichloromethane at a concentration of 20 g/Q, and coated on an acrylic plate at 1500 rpm using a spin coater. Thickness is 6
It was coated to give a coating of 0.00 to 700 people and dried. 780
The reflectance of the acrylic plate from the substrate surface side at a wavelength of nm was measured.

The results are shown in Table 1 below.

Table 1 Solvent Solubility Test Various cyanine dyes shown in Table 2 below were dissolved in methanol and their solubility at room temperature was measured.

The results are shown in Table 2 below.

Table 2 (that's all)

Claims (1)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X is -NR_2R_3 group (here R_2 and R_
3 is the same or different and represents a hydrogen atom, a lower alkyl group, a hydroxy lower alkyl group) or a lower alkoxy group. Y is a hydrogen atom, -NR_4R_5 group (here R_4
and R_5 are the same or different and represent a hydrogen atom, a lower alkyl group or a hydroxy lower alkyl group), a lower alkyl group, or a lower alkoxy group. R_1 represents a lower alkyl group that may have a substituent. Z represents an acidic residue. However, when Y is a hydrogen atom, X must not be a lower alkoxy group. ] A cyanine compound represented by