JPH08269009A - Quaternary salt compound, methine compound and production of methine compound - Google Patents

Abstract

PURPOSE: To obtain a new compound capable of giving a new sufoalkyl- containing methine compound useful as a coloring agent, a light absorbing agent, a medicine, etc. CONSTITUTION: A quaternary salt compound of formula I (Z1 is a group of atoms necessary for forming a nitrogen-containing 5- or 6-membered heterocyclic ring; n1 is 0,1; R is formula II, formula III, etc.). The compound is obtained by reacting a compound of formula IV such as 5-phenyl-2-methylbenzooxazole with a compound of formula V (Ra is H and Rb is ethyl, Ra is H and Rb is phenyl, etc.) such as 1-ethyl-1,3-propane sultone preferably at 100-200 deg.C. The ratio of the compound of formula V/the compound of formula IV is preferably 1-4.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a colorant, a light absorber, a dye for optical disks, a spectral sensitizing dye for silver halide photography and electrophotography, and further a methine compound useful as a medicine and a quaternary raw material thereof. It relates to a salt compound.

[0002]

2. Description of the Related Art A compound that absorbs light in the visible region exhibits various colors depending on the wavelength of the absorbed light.
These compounds are called dyes or dyes, and are used for coloring various materials, and more advanced applications include dyes for optical disk materials, which are high-density information recording materials, and silver halide photographs and electronic materials, which are image information recording materials. It is used as a spectral sensitizing dye in photographs and as a filter dye. Also,
In recent years, it has been drawing attention as a medicine such as phototherapy.

The dyes used for these purposes are often processed into a solution and then processed to form a desired state, and are required to have excellent solubility. Further, when it is used as a dye for optical discs or a spectral sensitizing dye, it is in a solid state or an adsorbed state, and therefore, unlike a solution state, the property as a molecular assembly greatly influences the performance. It is not uncommon that a slight structural change of the molecule significantly affects the solubility and the formation of the molecular assembly.

It is well known that methine compounds have a heterocycle having a sulfoalkyl group as a partial structure. As the sulfoalkyl group, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3
The sulfobutyl group is well known. The slight difference in the structure of these sulfoalkyl groups affects the solubility of the dye and the formation of the molecular assembly described above. Therefore, further development of new sulfoalkyl groups is expected to be possible because it can impart diversity to the properties of methine compounds.

[0005]

An object of the present invention is to provide a methine compound having a novel sulfoalkyl group, and at the same time to provide a quaternary salt compound as a raw material of the methine compound.

[0006]

Means for Solving the Problems As a result of intensive studies by the present inventor, a methine compound represented by the following general formula (II) using a quaternary salt compound represented by the following general formula (I) as a raw material It was found that the above object of the present invention can be achieved by obtaining the above.

General formula (I)

[Chemical 10] General formula (II)

[Chemical 11] In the formula, Z ₁ and Z ₂ represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle, and n ₁ and n ₂ represent 0 or 1. Q ₁ represents a compound necessary for forming a methine compound. M ₁ represents a charge-neutralizing counterion, and m ₁ is a number of 0 or more and 4 or less necessary for neutralizing the charge.
R represents the substituent shown below.

[0008]

[Chemical 12] The general formulas (I) and (II) will be described in more detail.

In the general formula (II), when a cyanine dye is formed by Q ₁ , it can be expressed by the following resonance formula.

[0010]

[Chemical 13] Examples of the 5- or 6-membered nitrogen-containing heterocycle formed by Z ₁ include the following. However, for the sake of convenience, it is shown here by the name when it is not a quaternary salt.

Examples thereof include a thiazole nucleus, a benzothiazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a benzoselenazole nucleus, a 3,3-dialkylindolenine nucleus, a benzimidazole nucleus and a quinoline nucleus.

Z ₁ is preferably a benzoxazole nucleus, a benzothiazole nucleus, a benzimidazole nucleus or a quinoline nucleus, more preferably a benzoxazole nucleus or a benzothiazole nucleus. Particularly preferred is a benzoxazole nucleus.

The substituent of Z ₁ has, for example, 1 carbon atom.
To 18, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, substituted or unsubstituted alkyl group (eg, methyl, ethyl, propyl, butyl, hydroxyethyl, trifluoromethyl, benzyl, carboxyethyl, Ethoxycarbonylmethyl, acetylaminomethyl), substituted or unsubstituted C 6 to 20, preferably C 6 to 15 and more preferably C 6 to C 10 substituted or unsubstituted aryl group (eg, phenyl, naphthyl) , P-carboxyphenyl, p-nitrophenyl, 3,5-dichlorophenyl, p-cyanophenyl, m-fluorophenyl, p-tolyl), carbon number 1
To 20, preferably 2 to 10 carbon atoms, more preferably 4 to 6 carbon atoms, optionally substituted heterocyclic group (eg, pyridyl, 5-methylpyridyl, thienyl), halogen atom (eg, chlorine, bromine, Iodine, fluorine), mercapto group, cyano group, carboxyl group, sulfo group, hydroxy group, carbamoyl group having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 5 carbon atoms (eg, methylcarbamoyl). , Ethylcarbamoyl), having 0 to 10 carbon atoms, preferably 2 to 8 carbon atoms,
More preferably, a sulfamoyl group having 2 to 5 carbon atoms (eg, methylsulfamoyl, ethylsulfamoyl), an amino group, a nitro group, a carbon number of 1 to 20, preferably a carbon number of 1 to 10, and more preferably a carbon number. 1 to 8 optionally substituted alkoxy group (eg, methoxy, ethoxy, 2-methoxyethoxy, 2-phenylethoxy), 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, and more preferably 6 carbon atoms. To 10 aryloxy groups (eg, phenoxy, p-methylphenoxy, p-chlorophenoxy, naphthoxy, etc.), 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbon sialic groups. (For example, acetyl,
Benzoyl, trichloroacetyl, etc.), an acylamino group having 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (eg acetylamino), 1 to 20 carbon atoms, preferably 1 carbon atom From 1
0, more preferably a sulfonyl group having 1 to 8 carbon atoms (eg, methanesulfonyl, ethanesulfonyl, benzenesulfonyl, etc.), 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms. Sulfonylamino group (eg, methanesulfonylamino, ethanesulfonylamino, benzenesulfonylamino), having 1 to 20 carbon atoms, preferably 1 to 1 carbon atoms
2, more preferably a substituted amino group having 1 to 8 carbon atoms (eg, methylamino, dimethylamino, benzylamino), 1 to 20 carbon atoms, preferably 1 to 1 carbon atoms
2, more preferably an alkyl or arylthio group having 1 to 8 carbon atoms (for example, methylthio, ethylthio, carboxyethylthio, sulfobutylthio, phenylthio), 2 to 20 carbon atoms, preferably 2 to 1 carbon atoms.
2, more preferably an alkoxycarbonyl group having 2 to 8 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl) and the like. Further, it may have a structure in which a benzene ring or a naphthalene ring is condensed.

Preferred as substituents on Z ₁ are the above-mentioned alkyl groups (eg methyl, ethyl, propyl),
Alkoxy groups (eg methoxy, ethoxy), aryl groups (eg phenyl, p-bromophenyl), halogen atoms (eg chlorine, bromine, iodine) and acyl groups (eg acetyl), more preferably methyl. Group, methoxy group, phenyl group, chlorine atom, bromine atom, iodine atom.

The 5- or 6-membered nitrogen-containing heterocycle formed by Z _{2 is obtained} by moving the double bond of the heterocycle shown for Z ₁ so as to conform to the general formula (II). Is mentioned.

Z ₂ is preferably a benzoxazole nucleus, a benzothiazole nucleus, a benzimidazole nucleus or a quinoline nucleus, more preferably a benzoxazole nucleus or a benzothiazole nucleus. Particularly preferred is a benzoxazole nucleus.

As the substituent of Z _{2, the same as} the substituent of Z ₁ can be mentioned. More preferred are alkyl groups (eg methyl, ethyl, propyl), alkoxy groups (eg methoxy, ethoxy), aryl groups (eg phenyl, p-bromophenyl), halogen atoms (eg chlorine, bromine, iodine). , And an acyl group (eg, acetyl), and more preferably a methyl group, a methoxy group, a phenyl group, a chlorine atom, a bromine atom, or an iodine atom.

M ₁ represents a charge balancing counterion. M ₁ may be a cation or an anion, and examples of the cation include alkali metal ions such as sodium ion, potassium ion and lithium ion, hydrogen ion, tetraalkylammonium ion, and pyridinium ion. The anion may be either an inorganic anion or an organic anion, and a halogen anion (eg, fluorine ion, chlorine ion,
Iodine ion), substituted aryl sulfonate ion (for example, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion), aryl disulfonate ion (for example, 1,3-benzene sulfonate ion, 1,5-naphthalenedisulfonate ion) , 2,6-naphthalenedisulfonate ion) and alkylsulfate ion (for example, methylsulfate ion). m ₁ represents a number of 0 or more and 4 or less required to balance the charge, and is 0 when a salt is formed in the molecule.

R is preferably a substituent shown below.

[0020]

Embedded image More preferably, R _a .

The methine compound formed by Q is one that forms an amidinium ion system (for example, cyanine dye), one that forms a bipolar amide system (for example, merocyanine dye), and a complex system thereof (for example, rhodacyanine). (Dye) and the like. Particularly preferred are methine compounds represented by the following general formula (III).

General formula (III)

[Chemical 15] In formula (III), Z ₃ and Z ₄ represent a sulfur atom or an oxygen atom. V ₁ , V ₂ , V ₃ , V ₄ , V ₅ , V ₆ , V ₇ ,
And V ₈ represents a hydrogen atom, methyl, methoxy, chlorine atom, bromine atom, iodine atom, or phenyl. R ₁
And R ₂ represents a substituted or unsubstituted alkyl group. However, at least one is R represented by the general formula (II).
M ₂ represents a charge-neutralizing counterion, and m ₂ is a number of 0 or more and 4 or less necessary for neutralizing the charge.

The general formula (III) will be described in more detail.

The substituted or unsubstituted alkyl group represented by R ₁ and R ₂ includes, for example, 1 to 18 carbon atoms,
Alkyl groups having 1 to 7 carbon atoms, particularly preferably 1 to 4 carbon atoms (eg, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), also substituted alkyl groups {eg, , An aralkyl group (eg, benzyl, 2-
Phenylethyl), hydroxyalkyl groups (eg 2
-Hydroxyethyl, 3-hydroxypropyl), carboxyalkyl group (eg, 2-carboxyethyl, 3
-Carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl groups (e.g. 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), sulfoalkyl groups (e.g. 2-sulfoethyl,
3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfatoalkyl group (for example, 3-
Sulfatopropyl, 4-sulfatobutyl), heterocyclic-substituted alkyl group (for example, 2- (pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl), 2-
Acetoxyethyl, carpomethoxymethyl, 2-methanesulfonylcarbamoylmethyl, allyl group and the like}.

As the substituted alkyl group for R ₁ and R ₂ ,
The carboxyalkyl group and the sulfoalkyl group described above are preferable, and the sulfoalkyl group is more preferable.

However, at least one of R ₁ and R ₂ is R represented by the general formula (II). Preferred are R _a , R _b , R _c and R _d described above, and more preferred is R _a .

M ₂ and m ₂ have the same meanings as M ₁ and m ₁ , respectively.

At least one of Z ₃ and Z ₄ is preferably an oxygen atom. Particularly preferably, both Z ₃ and Z ₄ are oxygen atoms.

V ₁ , V ₂ , V ₃ , V ₄ , V ₅ , V ₆ , V
More preferably, ₇ and V ₈ are hydrogen atoms,
This is the case where it represents a methyl atom, a bromine atom, an iodine atom, or phenyl.

Specific examples of the compounds represented by formulas (I), (II) and (III) of the present invention are shown below, but the present invention is not limited thereto. The general formula (II
Since I) is a subordinate concept of general formula (II), general formula (II)
Included in the specific examples of the compound represented by

Specific examples of the compound represented by formula (I)

Embedded image

[Chemical 17]

Embedded image

[Chemical 19]

Embedded image Specific examples of the compound represented by the general formula (II)

[Chemical 21]

[Chemical formula 22]

[Chemical formula 23]

[Chemical formula 24]

[Chemical 25]

[Chemical formula 26] The quaternary salt compound represented by the general formula (I) of the present invention can be synthesized according to the following scheme 1.

Scheme 1;

[Chemical 27] The reaction conditions for synthesizing the quaternary salt compound represented by formula (I) of the present invention will be described in detail. The reaction temperature can be selected from the range of 0 ° C to 270 ° C. 80
℃ to 230 ℃ range is preferred, 100 ℃ to 2
The range of 00 ° C is more preferable. N, N as a reaction solvent
-From polar solvents such as dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) sulfolane to non-polar solvents such as anisole and xylene, those that undergo alkylation with sultone (2) and sultone (2)
Any solvent may be used except for those that decompose. Also, no solvent may be used. Raw material charge ratio ((2) /
(1)) can be selected from the range of 0.5 to 20. The range of 0.75 to 7 is preferable, and the range of 1 to 4 is more preferable. An acid or a base may or may not be used as a catalyst in the reaction.

The compound represented by the general formula (II) is synthesized by using the compound represented by the general formula (I) as a starting material and combining it with other starting materials according to the structure of the target compound to carry out a reaction. You can Regarding selection of raw materials to be used in combination, FM Harm (FM Harm) is generally used.
er) “Heterocyclic Compounds-Cyanine and Relative Compound (He
terocyclicCompounds-Cyani
ne Dyes and RelatedCompou
nds) ", John Willie & Sons (Jo
hn Wiley & Sons) -New York,
London, 1964, D.M. Sturmer, "Heterocyclic.
Compounds-Special Topics in Heterocyclic Chemistry (Heterocycle)
c Compounds-Special topic
sin heterocyclic chemistr
y) ”, Chapter 18, Section 14, Paragraphs 482-515,
John Willie and Sons (John Wile
y & Sons) -New York, London, 19
Published in 1977, "Rods Chemistry of Carbon
Compounds (Rodd's Chemistry o
f Carbon Compounds) "2nd. E
d. vol. IV, part B, 1977, 15th
Chapter, 369-422, Elsevier Science
Public Company, Inc. (Elsevier
Science Publishing Compan
y Inc. ) The method described in the company publication, New York, etc. can be referred to.

Next, the reaction conditions for synthesizing the methine compound represented by the general formula (II) will be described in detail. The reaction temperature can be selected from the range of -20 ° C to 200 ° C. A range of 0 ° C to 180 ° C is preferred,
The range of 15 ° C to 160 ° C is more preferable. The reaction solvent is water and N, N-dimethylformamide (DM
It can be selected from a range from polar solvents such as F) and dimethyl sulfoxide (DMSO) to non-polar solvents such as benzene and hexane. Polar solvents such as DMF and DMSO, alcohols such as methanol and ethanol, nitriles such as acetonitrile and benzonitrile, esters such as ethyl acetate, tetrahydrofuran and 1,2
Ethers such as -dimethoxyethane are preferable, and polar solvents, alcohols, and nitriles are more preferable, and a mixed solution thereof can be used. An acid or a base can be used in the reaction. In some cases, it may be preferable to use a mixture of both acid and base. The acid can be selected from inorganic acids and organic acids, with organic acids being preferred. Particularly, carboxylic acids such as acetic acid propionic acid, phenols such as phenol and m-cresol are preferable. The base can be selected from an inorganic base and an organic base, and an organic base is preferable. Particularly preferred are tertiary amines such as triethylamine and aromatic heterocyclic amines such as pyridine.

The compound represented by the general formula (II) can be preferably used as a colorant, a light absorber, a dye for optical disks, a spectral sensitizing dye for silver halide photography or electrophotography, or a medicine.

[0036]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto.

Example 1 Synthesis of compound (I-1) 4-phenyl-2-methylbenzoxazole 4 g
(0.019 mol) and 1-ethyl-1,3-propanesultone (3.4 g, 0.023 mol) were heated and stirred on a 150 ° C. oil bath for 2 hours. While stirring the reaction solution, 50 ml of ethyl acetate was added, and after the reaction solution reached room temperature,
The obtained crystals were filtered by suction filtration and dried. A colorless powder of compound (I-1) was obtained. Yield 6.75 g, yield 99%, melting point 265-270 ° C.

Supplement: The Salton nomenclature follows.

[0039]

[Chemical 28] Reference Example 1; Synthesis of 1-ethyl-1,3-propanesultone Ethylene glycol 68 g (1.09 mol), propylsulfonyl chloride 343.2 g (2.406 mo)
1) and 650 ml of dichloromethane are cooled with dry ice / acetone under stirring, and triethylamine 335.
4 ml (2.406 mol) was added dropwise over 25 minutes. The internal temperature was maintained at -10 ° C or lower. Furthermore, at room temperature 4
After stirring for an hour, the reaction solution was added to water 11 and the dichloromethane layer was extracted and then dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 287 g of compound (10) as a colorless liquid. Yield 96%. 200 g of compound (10) (0.729 mo
1) and 2 l of tetrahydrofuran were cooled to -78 ° C with stirring, and n-butyllithium (1.65 mol / l) was added.
A solution of 464 ml (0.765 mol) was added dropwise over 30 minutes. Further, after stirring at -15 ° C for 1 hour, the reaction solution was added to ethyl acetate 3l / water 1.5l and the ethyl acetate layer was extracted. Further, it was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and then distilled under reduced pressure to obtain 53 g of 1-ethyl-1,3-propanesultone as a colorless liquid. Boiling point 1
15-122 ° C / 2 mmHg, yield 48%. The reaction formula of the above synthesis is shown below.

[0040]

[Chemical 29] Example 2; Synthesis of compound (I-2) 2.5 g of 5-phenyl-2-methylbenzoxazole
(0.012 mol) and 1-phenyl-1,3-propanesultone 2.6 g (0.013 mol) at 150 ° C.
The mixture was heated and stirred on the oil bath for 4 hours. 50 ml of ethyl acetate was added to the reaction solution while stirring, and after the reaction solution reached room temperature, the obtained crystals were filtered by suction filtration and dried. A colorless powder of compound (I-2) was obtained. Yield 4.84
g, yield 100%, melting point 300 ° C. or higher.

Reference Example 2; Synthesis of 1-phenyl-1,3-propanesultone Synthesis was carried out in the same manner as in Reference Example 1, except that benzylsulfonyl chloride was used instead of propylsulfonyl chloride. .

Example 3; Synthesis of compound (I-3) 3.5 g of 5-phenyl-2-methylbenzoxazole
(0.017 mol) and 1-benzyl-1,3-propanesultone 4.3 g (0.02 mol) were heated and stirred for 2 hours on an oil bath at 150 ° C. While stirring the reaction solution, 50 ml of ethyl acetate was added, and after the reaction solution reached room temperature,
The obtained crystals were filtered by suction filtration and dried. A colorless powder of compound (I-3) was obtained. Yield 7.03 g, 100% yield, melting point 268-272 ° C.

Reference Example 3; Synthesis of 1-benzyl-1,3-propane sultone and 1,1'-dibenzyl-1,3-propane sultone 20 g (0.164 mol) of 1,3-propane sultone
And tetrahydrofuran 400 ml under stirring at -78 ° C.
Cooled to normal butyl lithium (1.71 mol /
l) 105 ml (0.18 mol) of the solution was added dropwise over 5 minutes. Furthermore, 35 g of benzyl bromide (0.20
5 mol) was added dropwise over 5 minutes, and further 1-78 ° C.
After stirring for 30 minutes, the reaction solution was mixed with ethyl acetate (1/1).
The mixture was added to 0.5 l of water, and the ethyl acetate layer was extracted. Further, it was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography (developing solvent; ethyl acetate / hexane-1 / 2).
1'-dibenzyl-1,3-propanesultone 1.51
g (yield 3%, colorless powder), 15 g of 1-benzyl-1,3-propanesartone as the second eluent (yield 43%,
A colorless liquid) was obtained.

Example 4; Synthesis of compound (I-4) 4.1 g of 5-phenyl-2-methylbenzoxazole
(0.0195 mol) and 1-allyl-1,3-propanesultone 3.8 g (0.0234 mol) were added to 150
The mixture was heated and stirred for 3 hours and 30 minutes on an oil bath at ℃. 50 ml of ethyl acetate was added while stirring the reaction solution, and after the reaction solution reached room temperature, the obtained crystals were filtered off by suction filtration,
Dried. A colorless powder of compound (I-4) was obtained. Yield 7.11 g, yield 98%, melting point 235-240 ° C.

Reference Example 4; Synthesis of 1-allyl-1,3-propanesultone Synthesis was performed in the same manner as in Reference Example 3 except that allyl bromide was used instead of benzyl bromide. .

Example 5: Synthesis of compound (I-5) 5-phenyl-2-methylbenzoxazole 1 g
(0.0048 mol) and 1,1′-dibenzyl-1,
1.5 g (0.005 mol) of 3-propanesultone was heated and stirred on an oil bath at 150 ° C. for 4 hours. 50 ml of ethyl acetate was added while stirring the reaction solution, and after the reaction solution reached room temperature, the obtained crystals were filtered off by suction filtration,
Dried. A colorless powder of compound (I-4) was obtained. Yield 2.07 g, yield 85%, melting point 223-226 ° C.

Example 6; Synthesis of compound (I-6) 5 g of 5-bromo-2-methylbenzoxazole (0.
(0189 mol) and 1-ethyl-1,3-propanesartone (3.45 g, 0.0226 mol) were heated and stirred on a 150 ° C. oil bath for 3 hours. While stirring the reaction solution, 50 ml of ethyl acetate was added, and after the reaction solution reached room temperature,
The obtained crystals were filtered by suction filtration and dried. A colorless powder of compound (I-6) was obtained. Yield 6.33 g, yield 93%, decomposition at a melting point of 120 ° C or higher.

Example 7: Synthesis of compound (I-7) 3.45 g of 5-iodo-2-methylbenzoxazole
(0.0133 mol) and 1-ethyl-1,3-propanesultone 2.4 g (0.016 mol) at 150 ° C.
The mixture was heated and stirred on the oil bath for 3 hours. 50 ml of ethyl acetate was added to the reaction solution while stirring, and after the reaction solution reached room temperature, the obtained crystals were filtered by suction filtration and dried. A colorless powder of compound (I-7) was obtained. Yield 5.45
g, 93% yield, melting point 115-120 ° C.

Example 8: Synthesis of compound (I-8) 3.5 g of 5-iodo-2-methylbenzoxazole
(0.0135 mol) and 1-phenyl-1,3-propanesultone 2.7 g (0.0135 mol)
The mixture was heated and stirred for 2 hours on an oil bath at 0 ° C. 50 ml of ethyl acetate was added to the reaction solution while stirring, and after the reaction solution reached room temperature, the obtained crystals were filtered by suction filtration and dried. A colorless powder of compound (I-8) was obtained. Yield 5.47
g, yield 89%, melting point 245-248 ° C.

Example 9: Synthesis of compound (I-9) 5,6-benzo-2-methylbenzooxide 5 g
(0.0273 mol) and 4.1-g (0.0273 mol) of 1-ethyl-1,3-propane sultone 150
The mixture was heated and stirred on an oil bath at ℃ for 3 hours. 50 ml of ethyl acetate was added to the reaction solution while stirring, and after the reaction solution reached room temperature, the obtained crystals were filtered by suction filtration and dried. A colorless powder of compound (I-9) was obtained. Yield 8.92
g, yield 98%, melting point 265-270 ° C.

Example 10: Synthesis of compound (I-10) 5,6-benzo-2-methylbenzoxazole 1.8
5 g (0.01 mol) and 1-phenyl-1,3-propanesartone 2 g (0.01 mol) were heated and stirred for 2 hours and 30 minutes on an oil bath at 150 ° C. 50 ml of ethyl acetate was added to the reaction solution while stirring, and after the reaction solution reached room temperature, the obtained crystals were filtered by suction filtration and dried. A colorless powder of compound (I-10) was obtained. Yield 3.5
8 g, yield 93%, melting point 300-305 ° C.

Example 11: Synthesis of compound (II-1) 6.79 g (0.019 mol) of compound (I-1), 17 ml of orthopropionic acid ethyl ester (0.084)
5 mol), 11 ml of acetic acid, and 11 ml of pyridine were heated and stirred on an oil bath at 140 ° C., 7 ml (0.05 mol) of triethylamine was further added, and the mixture was heated and stirred for 2 hours. 100 ml of ethyl acetate was added to the reaction solution while stirring, and the mixture was heated with stirring for 2 hours. 100 ml of ethyl acetate was added to the reaction solution while stirring, and after the reaction solution reached room temperature, the obtained crystals were filtered off by suction filtration. The crystals obtained were dissolved in 50 ml of methanol, and potassium acetate was added to 0.9
A g / methanol (20 ml) solution was added, and the obtained crystals were filtered off by suction filtration. Further, 50 ml of methanol was added to the crystals to dissolve them by heating under reflux, followed by gravity filtration, distilling off about 20 ml of the solvent in the filtrate under normal pressure, and allowing to cool to room temperature. The precipitated crystal was filtered by suction filtration and dried to obtain the compound (II-1). (Red powder,
Yield 0.85 g, yield 11.4%, λmax = 502n
m, ε = 143000 (methanol), melting point: decomposed at 220 ° C. or higher) Example 12; Synthesis of compound (II-2) Compound (I-2) instead of compound (I-1) and potassium acetate Compound (II-2) was obtained in the same manner as in Example 11 except that sodium acetate was used as the solvent. (Red powder, yield 7%, λmax = 505 nm,
ε = 146000 (methanol), melting point 195-200
C.) Example 13: Synthesis of compound (II-3) Compound (I-3) 6.7 g (0.016 mol), orthopropionic acid ethyl ester 14.5 ml (0.07).
2 mol), acetic acid 9 ml, and pyridine 9 ml 14
The mixture was heated and stirred on an oil bath at 5 ° C. Further, 6 ml (0.043 mol) of triethylamine was added, and the mixture was heated and stirred for 2 hours. While stirring the reaction solution, add 20 ml of ethyl acetate,
After the reaction solution reached room temperature, the obtained crystals were separated by suction filtration. The obtained crystals were dissolved in 40 ml of methanol by heating under reflux, and after natural filtration, 30 ml of isopropanol and 60 ml of ethyl acetate were added to the filtrate, and the precipitated crystals were suction filtered. This operation was repeated once more and the compound (II-3) was obtained after drying. (Red powder, yield 0.
65 g, yield 8.3%, λmax = 504 nm, ε = 1
50000 (methanol), melting point 245-250 ° C.) Example 14; Synthesis of compound (II-4) Same as Example 11 except that compound (I-4) was used instead of compound (I-1). Method by compound (II-4)
I got (Red powder, yield 29%, λmax = 504n
m, ε = 148000 (methanol), melting point 215-2
20 ° C.) Example 15: Synthesis of compound (II-35) Example 11 except that compound (I-5) was used instead of compound (I-1) and sodium acetate was used instead of potassium acetate. Compound (II-35) was obtained by the same method. (Red powder, yield 14%, λmax = 504 nm,
ε = 140,000 (methanol), melting point 220-222
C.) Example 16: Synthesis of compound (II-6) 6.33 g (0.0175 mol) of compound (I-6),
Orthopropionic acid ethyl ester 12.4 g (0.0
7 mol), 8 ml of acetic acid, and 14 ml of pyridine
The mixture was heated and stirred on an oil bath at 0 ° C., 4.9 ml (0.035 mol) of triethylamine was further added, and the mixture was heated and stirred for 1 hour. 100 ml of ethyl acetate was added to the reaction solution while stirring, and after the reaction solution reached room temperature, the supernatant was removed by decantation, and 10 m of methanol was added to the remaining oily substance.
1 and then 1.44 g of potassium acetate / methanol (20 ml) solution were added, and 100 ml of acetone was added, and the mixture was left in the refrigerator for 1 day. The supernatant was removed by decantation, and the remaining oily substance was separated by Sephadex LH-
20 columns (developing solvent; methanol)
The methanol solvent was distilled off under reduced pressure to 10 ml, 30 ml of isopropanol was further added, and the precipitated crystals were filtered by suction filtration and dried to obtain the compound (II-6). (Red powder, yield 0.2 g, yield 2.9%, λma
x = 498 nm, ε = 137,000 (methanol), melting point 240-245 ° C.) Example 17; Synthesis of compound (II-8) Other than using compound (I-7) instead of compound (I-6) Was obtained in the same manner as in Example 16 to obtain (II-8). (Red powder, yield 4%, λmax = 500 nm, ε
= 132000 (methanol), melting point 233-240
C.) Example 18: Synthesis of compound (II-9) 5.37 g (0.0117 mol) of compound (I-8),
10.6 ml of ethyl orthopropionate (0.
053 mol), acetic acid 11 ml, and pyridine 11 ml
Was heated and stirred on a 140 ° C. oil bath for 1 hour. After the reaction solution reached room temperature, the precipitated crystals were separated by suction filtration. Methanol (20 ml) was added to the crystals, potassium acetate 0.8 g / methanol (20 ml) solution was added, and isopropanol (100 ml) was added, and the obtained crystals were separated by suction filtration. The crystals were purified by a SENUFUdex LH-20 column (developing solvent; methanol), evaporated under reduced pressure until the methanol solvent became 10 ml, 30 ml of isopropanol was further added, and the precipitated crystals were separated by suction filtration and dried. , Compound (II-
9) was obtained. (Red powder, yield 1.1 g, yield 19.0
%, Λmax = 502 nm, ε = 132000 (methanol), melting point 250-256 ° C.) Example 19; Synthesis of compound (II-16) Other than using compound (I-9) instead of compound (I-8). In the same manner as in Example 18
6) was obtained. (Red powder, yield 10%, λmax = 51
4 nm, ε = 18000 (methanol), melting point 290
-295 ° C) Example 20: Synthesis of compound (II-17) Compound (II-1) was prepared in the same manner as in Example 18 except that compound (I-10) was used instead of compound (I-8).
7) was obtained. (Red powder, yield 8%, λmax = 516
nm, ε = 166000 (methanol), melting point 300 ° C.
Above) Example 21: Synthesis of Compound (II-20) 31.79 g (0.0884mo) of Compound (I-1)
l), 31.2 g of ethyl orthopropionate
(0.177 mol), m-cresol 32 ml 11
The mixture was heated and stirred for 2 hours on an oil bath at 0 ° C. After the reaction solution reached room temperature, 300 ml of ethyl acetate was added, and the precipitated crystals were separated by suction filtration and dried, and then 1-ethyl-3-
16 g of [2- (2-ethoxy-1-butenyl) -3-benzoxazolio] propanesulfonate (yield 41
%) Was obtained. 3 g (0.0068 mol) of this crystal, 4
1.32 g (0.0423)-(5,6-dimethyl-2-methyl-3-benzothiazolio) butanesulfonate
mol) and 13 ml of benzyl alcohol at 70 ° C.
The mixture was heated and stirred on the oil bath for 30 minutes. After the reaction solution reached room temperature, 100 ml of ethyl acetate was added, and the precipitated crystals were filtered off by suction filtration. 24m of this crystal
0.6 g of potassium acetate in the filtrate
/ Methanol (20 ml) solution was added, and ethanol 12
After adding ml, the obtained crystals were filtered off by suction filtration. The crystals were heated to 20 ml of methanol under reflux to be completely dissolved, allowed to stand at room temperature, and the precipitated crystals were separated by suction filtration. This operation was repeated once more, and the obtained crystals were dried to obtain the compound (II-20). (Red powder, yield 1.48 g, yield 47.0%, λmax = 528 nm,
ε = 107,000 (methanol), melting point 240-244
Application Example-Application to Optical Recording Material A 2% methanol solution of the compound (II-2) was spin-coated on a glass substrate. The rotation speed was 300 rpm during coating and 1500 rpm during drying. The thickness of the obtained dye thin film was 100 nm. Semiconductor laser excitation Y
AGSHG device (AmocoLaser
r Co. )), Light intensity 1 mw, beam diameter 10
Light having a wavelength of 532 nm and a wavelength of 0 μm was irradiated at intervals of 10 mm for 10 seconds. After irradiation, when observed with an optical microscope, destruction of the dye film was observed at the irradiated site. From the above,
It can be seen that this dye film functions as an optical disc.

[0053]

INDUSTRIAL APPLICABILITY By using the novel methine compound having a sulfoalkyl group provided by the present invention, various optical functional materials can be produced.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C07D 263/60 C07D 277/22 277/22 277/64 277/64 293/12 293/12 403 / 06 209 403/06 209 417/06 209 417/06 209 215 215 263 263 C09B 23/00 L C09B 23/00 G03C 1/12 G03C 1/12 1/18 1/18 1/22 1/22 7416-2H B41M 5/26 Y

Claims (4)

[Claims] 1. A quaternary salt compound represented by the following general formula (I): General formula (I) In formula (I), Z ₁ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle, and n ₁ represents 0 or 1. R represents the substituent shown below. Embedded image 2. A methine compound represented by the following general formula (II). General formula (II): In the formula (II), Z ₂ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle, and Q ₁ represents a compound necessary for forming a methine compound. M ₁ represents a charge-neutralizing counterion, and m ₁ is 0 or more and 4 necessary for neutralizing the charge.
The following numbers. n ₂ represents 0 or 1. R represents the substituent shown below. [Chemical 4] 3. The methine compound according to claim 2, which is represented by the following general formula (III). General formula (III): In formula (III), Z ₃ and Z ₄ represent a sulfur atom or an oxygen atom. V ₁ , V ₂ , V ₃ , V ₄ , V ₅ , V ₆ , V ₇ and V ₈ represent a hydrogen atom, a methyl group, a methoxy group, a chlorine atom, a bromine atom, an iodine atom or a phenyl group. R
₁ and R ₂ represent a substituted or unsubstituted alkyl group.
However, at least one is R shown below. M ₂ represents a charge-neutralizing counterion, and m ₂ is a number of 0 or more and 4 or less necessary for neutralizing the charge. [Chemical 6] 4. A method for producing a methine compound represented by the following general formula (II) using a quaternary salt compound represented by the following general formula (I) as a raw material. General formula (I) In formula (I), Z ₁ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle, and n ₁ represents 0 or 1. R represents the substituent shown below. Embedded image General formula (II): In the formula (II), Z ₂ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle, and Q ₁ represents a compound necessary for forming a methine compound. M ₁ represents a charge-neutralizing counterion, and m ₁ is 0 or more and 4 necessary for neutralizing the charge.
The following numbers. n ₂ represents 0 or 1. R represents the substituent shown above.