JP2006316102A - Method for producing oxonol compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an oxonol pigment having multiple chromophores in the molecule, wherein these chromophores are bound together via no conjugated bonds. <P>SOLUTION: The method for producing the oxonol pigment as an oxonol compound comprises carrying out a reaction between a compound of the general formula (2) and a compound of the general formula (3) in the presence of a solvent with 15 or more donors followed by reaction with a bipyridinium compound of the general formula (4) to obtain the objective oxonol compound of the general formula (1) [wherein, Ma<SP>1</SP>to Ma<SP>3</SP>are each a methine group; Za<SP>1</SP>to Za<SP>3</SP>are each an acidic nucleus-forming atom group; n is an integer of 0-3; Y is a bivalent linkage group forming no π-conjugated system together with two bonds; R<SP>11</SP>to R<SP>18</SP>are each H or a substituent; R is a (substituted) (hetero)aryl or alkyl; R<SP>1</SP>is a substituent; p is an integer of 0-5; R<SP>2</SP>is H or a substituent; L<SP>1</SP>is H or an eliminable group; X is an anion; and y is a number necessary for neutralizing electric charges]. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing an oxonol compound used for a heat mode type information recording medium capable of writing (recording) and reading (reproducing) information using a laser beam having a high energy density.

  Conventionally, an information recording medium (optical disk) capable of recording information only once by a laser beam is known. The information recording medium is also referred to as a write-once CD (so-called CD-R). A typical structure of a CD-R type information recording medium is such that a recording layer made of an organic dye, a reflective layer made of a metal such as gold, and a protective layer made of resin are laminated in this order on a transparent disk-shaped substrate. It is. Information is recorded on the optical disk by irradiating a near-infrared laser beam (usually a laser beam having a wavelength of around 780 nm) to locally generate heat and deform the recording layer. On the other hand, reading (reproduction) of information is usually performed by irradiating a laser beam having the same wavelength as the recording laser beam, and reflecting the portion of the recording layer where heat is deformed (recorded portion) and the portion where the recording layer is not deformed (unrecorded portion). This is done by detecting the difference in rate. In addition, an optical disc called a recordable digital video disc (so-called DVD-R) has been proposed. DVD-R is recorded and reproduced by irradiating visible laser light (usually laser light having a wavelength in the range of 600 nm to 700 nm), and higher-density recording is possible than a CD-R type optical disk.

  Patent Document 1 discloses a CD-R type information recording medium in which a recording layer made of an oxonol dye is provided on a substrate. By using this dye compound, it is said that stable recording / reproducing characteristics can be maintained over a long period of time. Here, an oxonol dye compound in which ammonium is introduced in the form of a salt in the molecule is described. Patent Document 2 describes an oxonol dye compound that exhibits high light resistance and durability as a dye for DVD-R and provides an optical information recording medium with good recording characteristics.

Patent Document 3, Patent Document 4 and Patent Document 5 disclose various methods for producing oxonol dye compounds. However, there is no known method for producing an oxonol dye which has a plurality of chromophores in the molecule and these chromophores are bonded via a conjugated bond.
Japanese Patent Laid-Open No. 63-209995 JP 2000-52658 A JP-A-10-297103 JP 2000-52658 A JP 2002-249664 A

  An object of the present invention is to provide a method for producing an oxonol dye, wherein the production of the oxonol dye is carried out in one step without changing the solvent for each step.

The inventors of the present invention have attempted to synthesize a specific oxonol dye, which will be described later, by changing the solvent step by step for the convenience of the synthesis. However, industrially, it is required to carry out in one step without changing the solvent. Therefore, the present inventors have found that the above-mentioned problems can be solved by the following means, and have completed the present invention.
[1] [1] The compound represented by the general formula (2) and the compound represented by the general formula (3) are reacted in the presence of a solvent having a donor number of 15 or more,
[2] Subsequently, an oxonol compound represented by the general formula (1) is obtained by reacting with the bipyridinium compound represented by the general formula (4).
A method for producing an oxonol compound, characterized in that the above steps are performed consistently.

In the general formula (1), Ma ¹ , Ma ² and Ma ³ each independently represents a substituted or unsubstituted methine group. Za ¹ , Za ² and Za ³ each independently represent an atomic group forming an acidic nucleus, and n represents an integer of 0 to 3. Y represents a divalent linking group that does not form a π-conjugated system with two bonds. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or a substituent. R represents a (hetero) aryl group or an alkyl group which may have a substituent.

In general formula (2), Ma ¹ , Ma ² and Ma ³ , n, and Za ¹ have the same meanings as in general formula (1). R ¹ represents a substituent, and p represents an integer of 0 to 5. R ² represents a hydrogen atom or a substituent.

In the general formula (3), Za ^2, Za ³ and Y have the same meaning as in the general formula (1). L ¹ represents a hydrogen atom or a leaving group.

In the general formula (4), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ , R are as defined in the general formula (1). X represents an anion, and y represents a number necessary for charge neutralization.
[2] The method for producing an oxonol compound according to [1], wherein the solvent having a donor number of 15 or more is an aprotic polar solvent, an ether solvent or an ester solvent having a donor number of 15 or more.

  According to the present invention, a process for producing an oxonol dye having a plurality of chromophores in a molecule and binding these chromophores without a conjugated bond in one step without changing the solvent industrially. Can be provided.

  The present invention is described in detail below. In the present specification, when a specific part is referred to as a “group”, it may be substituted with one or more (up to the maximum possible number) substituents unless otherwise specified. means. For example, “alkyl group” means a substituted or unsubstituted alkyl group. In the present specification, when “may be substituted” or “may have a substituent”, the number and type of substituents are not particularly limited, and a plurality of substituents are present. They may be the same or different. Examples of the substituent (represented as “Rs”) include halogen atoms, alkyl groups, haloalkyl groups (halogen atom-substituted alkyl groups), alkoxy groups, haloalkoxy groups (halogen atom-substituted alkoxy groups), aryl groups, and aryl groups. Oxy group, arylalkyl group, alkenyl group, alkynyl group, heterocyclic group, cyano group, hydroxyl group, carboxyl group, sulfo group, dialkylamino group, alkylcarbonylamino group, arylcarbonylamino group, alkylcarbonyloxy group, arylcarbonyloxy Group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, nitro group, formyl group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, alkylenediol And the like can be mentioned sheet group, is not limited thereto. Further, these substituents may further have one or two or more substituents. In such a case, the substituents exemplified above can be suitably used as the substituent. For example, the substituent having an aryl group such as an arylcarbonyl group may have about 1 to 5, preferably 1 to 2, such as an alkyl group, a halogen atom and an alkoxy group on the aryl ring. In the present invention, when a specific moiety is referred to as a “ring”, or when the “group” includes a “ring”, it may be a monocyclic ring or a condensed ring unless otherwise specified. It does not have to be.

In the present specification, the term “halogen atom” may be any of fluorine, chlorine, bromine, or iodine. When a substituent containing a halogen atom (for example, a haloalkyl group) has two or more halogen atoms, They may be the same or different. In the present specification, the term “alkyl group” refers to, for example, a linear, branched, or cyclic group having 1 to 22 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, or It means an alkyl group composed of a combination thereof, preferably a linear or branched alkyl group. In addition, in this specification, when a substituent containing an alkyl moiety (for example, an alkoxy group, a haloalkyl group, an arylalkyl group, an alkylcarbonyl group, an alkylsulfonyl group, etc.) is mentioned, the alkyl moiety in these substituents is as defined above. It is preferably composed of an alkyl group.
In the specification and claims, “low numerical value” to “high numerical value” mean “low numerical value” or more and “high numerical value” or less.

  First, the compound represented by the general formula (1) will be described.

In the general formula (1), Ma ¹ , Ma ² and Ma ³ each independently represents a substituted or unsubstituted methine group. When Ma ¹ , Ma ² and Ma ³ represent a substituted methine group, examples of the substituent include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a halogen atom, a carboxyl group, an alkoxycarbonyl group, a cyano group, Examples include acyl groups, carbamoyl groups, amino groups, substituted amino groups, sulfo groups, hydroxyl groups, nitro groups, sulfonamido groups, ureido groups, alkylsulfonyl groups, arylsulfonyl groups, sulfinyl groups, and sulfamoyl groups. Preferred substituents are an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom. Is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a heterocyclic group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a halogen atom, and more preferably 1 carbon atom. An alkyl group having 5 to 5 carbon atoms, a heterocyclic group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a halogen atom. Preferred Ma ¹ , Ma ² and Ma ³ are substituted with an unsubstituted methine group or an alkyl group having 1 to 5 carbon atoms, a heterocyclic group having 2 to 6 carbon atoms, a halogen atom, or an aryl group having 6 to 12 carbon atoms. Methine group.

Za ¹ , Za ² and Za ³ each independently represent an atomic group forming an acidic nucleus. Specific examples of Za ¹ , Za ² and Za ³ are defined by James, The Theory of the Photographic Process, 4th edition, Macmillan, 1977, 198 pages. Specifically, pyrazolone, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2- or 4-thiohydantoin, 2-iminooxazolidine-4-one, 2-oxazoline-5-one, isorhodanine, rhodanine , Indan-13-dione, terahydrothiophen-3-one, terahydrothiophen-3-one-1,1-dioxide, indoline-2-one, indoline-3-one, 5,7-dioxo-6,7 -Dihydrothiazolo [3,2-a] pyrimidine, 3,4-dihydroisoquinolin-4-one, 1,3-dioxolane-4,6-dione, barbituric acid, 2-thiobarbituric acid, coumarin-2 , 4-dione, indazolin-2-one, pyrido [1,2-a] pyrimidine-1,3-dione, pyrazolo [1 5-b] quinazolone nucleus such pyrazolopyridone. These acidic nuclei may be substituted. Pyrazolone, barbituric acid, 2-thiobarbituric acid, or 1,3-dioxolane-4,6-dione is preferable, and 1,3-dioxolane-4,6-dione is more preferable.

n represents an integer of 0 to 3. More preferably, it is 2 or 3. When n is 2 or more, a plurality of Ma ¹ , Ma ² and Ma ³ may be the same or different.

Y represents a divalent linking group that does not form a π-conjugated system with two bonds. The type of Y is not particularly limited as long as it does not form a π-conjugated system between chromophores to which they are bonded, but preferably an alkylene group having 1 to 20 carbon atoms (methylene, ethylene, propylene, butylene, pentylene, etc.), carbon arylene of 6 to 26 (phenylene, naphthylene), an alkenylene group having 2 to 20 carbon atoms (propenylene, etc.), alkynylene group having 2 to 20 carbon atoms (propynylene, etc.), - CO-N (R 21) -, _{-CO-O -, - SO 2} -N (R 22) -, - SO 2 -O -, - N (R 23) -CO-N (R 24) -, - SO 2 -, - SO -, - S-, -O-, -CO-, a heterylene group having 1 to 26 carbon atoms (6-chloro-1,3,5-triazine-2,4-diyl, pyrimidine-2,4-diyl, etc.), or these Charcoal composed of multiple combinations A linking group having 1 to 20. R ²¹ , R ²² , R ²³ and R ²⁴ each independently represents a hydrogen atom, an alkyl group or an aryl group. In addition, one or more linking groups represented by Y may be present between two chromophores to which they are linked, and a plurality (preferably two) may be bonded to form a ring. . Y is more preferably a group in which two alkylene groups are bonded to each other, and among them, a case where a 5- or 6-membered ring is formed is even more preferable. Most preferably, a cyclohexyl ring is formed.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ each independently represents a hydrogen atom or a substituent. Substituents include halogen atoms, alkyl groups, haloalkyl groups, alkoxy groups, haloalkoxy groups, aryl groups, aryloxy groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano groups, hydroxyl groups, carboxyl groups, sulfo groups, dialkylamino Groups, alkylthio groups, arylthio groups, alkylsulfonyl groups, arylsulfonyl groups, nitro groups, formyl groups, alkylcarbonyl groups, arylcarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, sulfamoyl groups, alkylenedioxy groups, and the like. However, it is not limited to these. In the present invention, it is more preferable that R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are all hydrogen atoms.

  R represents a (hetero) aryl group or an alkyl group which may have a substituent. Here, the (hetero) aryl group means a cyclic residue having aromaticity (aromatic heterocyclic group), and an aryl group composed of only carbon atoms, heteroatoms such as N, O, S, and Se. Although it may be any of the heteroaryl groups contained, it is preferably an aryl group composed of only carbon atoms. These include those having a substituent. When R is an aryl group composed of only carbon atoms, the aryl group is preferably a phenyl group, a 1-naphthyl group, or a 2-naphthyl group. These may have a substituent, and examples of the substituent that can be present include a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an aryl group, an aryloxy group, an arylalkyl group, and an alkenyl group. , Alkynyl group, cyano group, hydroxyl group, carboxyl group, sulfo group, dialkylamino group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, nitro group, formyl group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group Carbamoyl group, sulfamoyl group, alkylenedioxy group and the like. Among these, alkyl groups, aryl groups, aryloxy groups, arylalkyl groups, hydroxyl groups, carboxyl groups, sulfo groups, alkylsulfonyl groups, arylsulfonyl groups, nitro groups, alkylcarbonyl groups, arylcarbonyl groups, alkoxycarbonyl groups, carbamoyl groups Are preferred, alkyl groups, aryl groups, hydroxyl groups, carboxyl groups, or sulfo groups are more preferred, and alkyl groups, aryl groups, or hydroxyl groups are even more preferred. When R is a heteroaryl group containing a heteroatom such as N, O, S, or Se, the heteroaryl group preferably has 1 to 20 carbon atoms, more preferably 3 to 10 carbon atoms constituting the ring, Examples thereof include a thiazole ring, a benzothiazole ring, an imidazole ring, a benzimidazole ring, and a pyridine ring. When R is an alkyl group, the alkyl group is, for example, a linear, branched or cyclic group having 1 to 22 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, or a combination thereof. An alkyl group consisting of: a linear, branched or cyclic alkyl group is preferred. More specifically, an isopropyl group, a t-butyl group, a cyclohexyl group, a benzyl group, an adamantyl group, and the like can be given.

  Next, the compound represented by the general formula (2) will be described.

In general formula (2), Ma ¹ , Ma ² and Ma ³ , n, and Za ¹ have the same meanings as in general formula (1), and preferred specific examples and ranges are also the same.
R ¹ represents a substituent. Although the thing of the range demonstrated previously is mentioned as a substituent, As a preferable substituent which may exist, a halogen atom, a C1-C8 alkyl group, a C1-C8 alkoxy group, carbon number Examples include 1 to 10 alkoxycarbonyl groups, trifluoromethyl groups, and nitro groups. p represents an integer of 0 to 5.
When p is 2 or more, a plurality of R ¹ may be the same or different, but p is preferably 0 or 1.

R ² represents a hydrogen atom or a substituent. Examples of the substituent include Rs described above, and preferred R ² is a hydrogen atom.

  Next, the compound represented by formula (3) will be described.

In the general formula (3), Za ^2, Za ³ and Y have the same meaning as in the general formula (1), and preferred ranges are also the same. L ¹ represents a hydrogen atom or a leaving group. Specific examples of the leaving group include an arylthio group having 6 to 20 carbon atoms, an alkylsulfamoyl group having 1 to 12 carbon atoms, and an arylsulfamoyl group having 6 to 20 carbon atoms. Preferred L ¹ is a hydrogen atom.

  Finally, the bipyridinium compound represented by the general formula (4) will be described.

In the general formula (4), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ , R are as defined in the general formula (1), and the preferred ranges are also the same. . X represents an anion. Examples of the anions include halide ions represented by chloride ions and bromide ions, sulfate ions, hydrogen sulfate ions, nitrate ions, acetate ions, propionate ions, benzoate ions and other carboxylate ions, methanesulfonate ions, Examples thereof include organic sulfonate ions such as p-toluenesulfonate ions, tetrafluoroborate ions, hexafluorophosphate ions, and the like. Preferred X is a halide ion such as chloride ion or bromide ion. y represents a number necessary for charge neutralization. For example, when X is a chloride ion, y represents 2.

  The compound of the present invention represented by the general formula (1), the general formula (2), the general formula (3), or the general formula (4) has one or more asymmetric carbons depending on the type of the substituent. Any optical isomers or diastereoisomers based on these asymmetric carbons are included within the scope of the present invention, and in addition to the pure forms of isomers, any of those Mixtures, racemates and the like are also encompassed within the scope of the present invention. The compounds of the present invention represented by the general formulas (1) and (2) contain a plurality of double bonds, but any geometric isomer based on these double bonds is also included in the present invention. It is included in the range. Further, the compound of the present invention represented by the general formula (1) may exist as a hydrate or a solvate, and these are also included in the scope of the present invention. Although the kind of solvent which forms a solvate is not specifically limited, For example, solvents, such as methanol, ethanol, acetone, isopropyl alcohol, N-methylpyrrolidone, dimethyl sulfoxide, can be illustrated.

  Although the preferable specific example of the compound of this invention represented by General formula (1), General formula (2), General formula (3), General formula (4) below is shown, this invention is not limited to these. Absent. Although these compounds have tautomers, it should be understood that the chemical structural formulas described in this specification are for convenience only one of these tautomers. Needless to say, any tautomer is included in the scope of the present invention.

  Next, the manufacturing method of this invention is demonstrated. In the production method of the present invention, the first step of reacting the compound represented by the general formula (2) with the compound represented by the general formula (3), and then reacting the bipyridinium compound represented by the general formula (4) It consists of a second step for obtaining the oxonol compound represented by (1), characterized in that these two steps are performed consistently. First, in the first step of the production method of the present invention in which the compound represented by the general formula (2) and the compound represented by the general formula (3) are reacted, the mole of the compound represented by the general formula (2) used in the reaction. The ratio is in the range of 1.8 to 4.0 moles relative to the compound represented by the general formula (3). Even if it is used excessively beyond this range, the production rate / production speed of the target product is not significantly affected. On the other hand, if the compound represented by the general formula (2) is used excessively, the subsequent removal operation becomes complicated, resulting in an increase in the amount of waste and an increase in cost. In the present invention, the preferred amount of the compound represented by the general formula (2) with respect to the compound represented by the general formula (3) is 1.8 to 3.0 times mol, more preferably 1.9 to 2.4 times mol. It is.

  As a reaction solvent that can be used in the reaction of the compound represented by the general formula (2) and the compound represented by the general formula (3), it does not cause problems in process operation, does not disturb the progress of the reaction, and It is necessary to decompose under the reaction conditions of the present invention without adversely affecting the reaction. The object of the present invention was achieved by using a solvent having a donor number of 15 or more as such a solvent. For the number of donors, see V. Defined by Gutman, Hitoshi Otsuki, Isao Okada, "Molecular Interactions between Donors and Acceptors: Solvent Reaction", 1983, 21 pages, or "Dictionary of Chemistry" Tokyo Chemical Dojin, 1989, 1584 pages . As the solvent having a donor number of 15 or more, a solvent having a donor number of 15 or more is an aprotic polar solvent, an ether-based solvent or an ester solvent having a donor number of 15 or more. Specific examples of the solvent include aprotic polar solvents such as N-methylpyrrolidone, dimethyl sulfoxide, N, N-dimethylimidazolidinone, N, N-dimethylformamide, N, N-dimethylacetamide, and ether solvents such as tetrahydrofuran. Examples of the ester solvent such as methyl acetate and ethyl acetate include those having a donor number of 15 or more. Among these, N-methylpyrrolidone, N, N'-dimethylimidazolidinone, N, N-dimethylformamide, and N, N-dimethylacetamide are more preferable. The most preferred solvent is N-methylpyrrolidone, N, N'-dimethylimidazolidinone, N, N-dimethylacetamide, or a combination system of a plurality of solvents selected from these. In the reaction, the reaction may be carried out only with a solvent having a donor number of 15 or more, or another solvent may be added, but only the solvent having a donor number of 15 or more is preferred.

  In the reaction of the compound represented by the general formula (2) and the compound represented by the general formula (3), it is preferable to use a base. As the base, a tertiary organic base (triethylamine, tri-n-propylamine, tri-n-butylamine, N, N-diisopropylethylamine, N-methylpiperidine, N-methylmorpholine, 1,8-diazabicyclo [5.4. 0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,4-diazabicyclo [2.2.2] octane, etc.), pyridines (pyridine, 2-methylpyridine, 2,6-lutidine, etc.), alkali metal alkoxides (sodium methoxide, sodium ethoxide, sodium t-butoxide, etc.), alkali metal hydroxides (sodium hydroxide, potassium hydroxide, etc.), alkaline earth metal hydroxides (Magnesium hydroxide, etc.), sodium acetate, potassium carbonate, sodium carbonate and the like. Preferred bases are tertiary amines, more preferably triethylamine, tri n-butylamine, N, N-diisopropylethylamine, and even more preferably triethylamine. The amount of the base used is preferably 3.5 to 10.0 equivalents, more preferably 4.0 to 8.0 equivalents, relative to the compound represented by the general formula (3).

  The preferable reaction temperature in the step of reacting the compound represented by the general formula (2) and the compound represented by the general formula (3) is −30 to 20 ° C., more preferably −15 to 10 ° C. Preferably it is -10-10 degreeC. The reaction time varies depending on the structure of the substrate, the amount charged, and the reaction temperature, but is usually 0.5 to 8 hours, and more preferably 1 to 6 hours. In the reaction step, an inert atmosphere is not particularly required, but the reaction may be performed under an argon or nitrogen stream. In the reaction, the compound represented by the general formula (2) and the general formula (3) and the base are added in the order of −30 to 30 while the compound represented by the general formula (2) and the base are dissolved in the reaction solvent. A method of adding a compound represented by the general formula (3) at 20 ° C., a compound represented by the general formula (3) and a base dissolved in a reaction solvent at −30 to 20 ° C. at a general formula (2) A method of adding a compound represented by formula (2) and a method of adding a base at −30 to 20 ° C. while dissolving the compound represented by general formula (2) and general formula (3) in a reaction solvent, Preferably, the compound represented by the general formula (2) is added at −30 to 20 ° C. while dissolving the compound represented by the general formula (3) and the base in the reaction solvent. The addition method is preferably divided addition. If the compound is a crystalline substance, it may be added as it is, or may be added after dissolving in the reaction solvent.

  According to the method described above, a skeleton of an oxonol dye is formed which has a plurality of chromophores in a molecule and these chromophores are bonded via a conjugate bond. For example, when triethylamine is used as the base, the product is a bistriethylamine salt of an oxonol dye. This can be used consistently in the second step without isolation, and is an industrially advantageous advantage from the viewpoint of efficiency, cost, and safety.

  Next, the 2nd process of the manufacturing method of this invention which reacts with the bipyridinium compound represented by General formula (4) and obtains the oxonol compound represented by General formula (1) is demonstrated. The molar ratio of the bipyridinium compound represented by the general formula (4) used in the reaction is generated by the reaction of the compound represented by the general formula (2) and the compound represented by the general formula (3) in the first step. The range is 0.8 to 1.5 times mol, preferably 0.85 to 1.1 times mol, more preferably 0.85 to 1.00 times mol with respect to the theoretical amount of oxonol dye molecule. is there. Even if the bipyridinium compound represented by the general formula (4) is used excessively, the yield of the target oxonol compound represented by the general formula (1) is not improved, and the bipyridinium compound represented by the general formula (4) is not improved. This is not preferable because it remains and leads to a decrease in the quality of the target product. Conversely, when the amount of the bipyridinium compound free form represented by the general formula (4) is less than the above range, the yield of the oxonol compound represented by the general formula (1) is lowered.

As a method of reacting the bipyridinium compound represented by the general formula (4) in the second step of the production method of the present invention, the compound represented by the general formula (2) and the compound represented by the general formula (3) are used. A method in which the bipyridinium compound represented by (4) is added to the reacted reaction mixture, and a bipyridinium compound represented by the general formula (4) is suspended or dissolved in a solvent and represented by the general formula (2). Although the method of adding the reaction mixture which made the compound and the compound represented by General formula (3) react is mentioned, In the manufacturing method of this invention, any method can be used.
When the bipyridinium compound represented by the general formula (4) is added to the reaction mixture obtained by reacting the compound represented by the general formula (2) and the compound represented by the general formula (3), split addition is preferable. The bipyridinium compound, which is a crystalline substance, may be added in portions as it is, or those suspended or dissolved in a solvent may be added in portions. A method in which a suspension or solution dissolved in a bipyridinium compound solvent represented by the general formula (4) is preferably added in portions. A reaction mixture obtained by reacting a compound represented by general formula (2) and a compound represented by general formula (3) in a mixture in which a bipyridinium compound represented by general formula (4) is suspended or dissolved in a solvent. Also in the case of adding, split addition is preferred.

  Examples of the solvent for suspending or dissolving the bipyridinium compound represented by the general formula (4) include alcohol solvents such as water, methanol, ethanol, and 2-propanol, N-methylpyrrolidone, sulfolane, dimethyl sulfoxide, and N, N. -Aprotic polar solvents such as dimethylimidazolidinone, N, N-dimethylformamide, N, N-dimethylacetamide, ester solvents such as ethyl acetate and n-butyl acetate, 1,2-dimethoxyethane, tetrahydrofuran, etc. Examples include ether solvents. Among these, use of water, an alcohol solvent, and an aprotic polar solvent is more preferable, and use of water or an alcohol solvent is still more preferable. The most preferred solvent is water, methanol, ethanol, 2-propanol, or a combination system of 2 to 3 solvents selected from these.

In the production method of the present invention, the reaction temperature in the second step is in the range of 10 to 100 ° C., preferably 40 to 85 ° C., more preferably 50 to 80 ° C. for improving the reaction efficiency.
Although reaction time changes with preparation amounts and reaction temperature, it is 0.5 to 6 hours normally, and the range of 1 to 5 hours is more preferable. The process does not require an inert atmosphere, but the reaction may be performed under an argon or nitrogen stream.

  The oxonol compound represented by the general formula (1) produced by the production method of the present invention described above has good crystallinity, and usually precipitates as crystals by cooling the reaction mixture or adding a poor solvent. This can be easily isolated by carrying out separation. The oxonol compound represented by the general formula (1) obtained as described above has such a high purity that it is not necessary to perform further purification.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Synthesis of Compound (1) -1 Compound (1) -1 was synthesized by the following method. The synthesis route is shown.

(1) Synthesis of Intermediate 1 Concentrated sulfuric acid (2 mL) was added to a mixture of acetic anhydride (68.7 g) and malonic acid (50 g), and then 2-pentanone (41.4 g) was added dropwise at an internal temperature of 10 ° C. or lower. . The reaction mixture was stirred at 20 ° C. for 2 hours, and toluene (200 mL) and 10% brine (70 mL) were added. The organic layer was separated and concentrated, and the residue was crystallized from 2-propanol / water (volume ratio 1/3, crystallization temperature 5 ° C.) and mixed with 2-propanol / water (volume ratio 1/3). Filtration, washing, and drying yielded 57.9 g of intermediate 1 (2-methyl-2-propyl-1,3-dioxolane-4,6-dione) as colorless crystals (yield 70%).
Melting point: 38-39 ° C

Synthesis of Compound (2) -1 A mixture of 1-phenylamino-5-phenylimino-1,3-pentadiene hydrochloride (60 g), methanol (400 mL) and triethylamine (47 g) was added to Intermediate 1 (40. 0 g) in methanol (50 mL) was added dropwise at 25 ° C. After the reaction mixture was stirred at 25 ° C. for 3 hours, water was added dropwise to precipitate crystals. The reaction mixture was stirred as it was for 1 hour, and the precipitated crystals were filtered, washed with methanol, and dried to obtain 45 g of compound (2) -1 as a dark red crystalline powder (yield 65%).
Melting point: 190 ° C (decomposition)

(3) Synthesis of Compound (3) -1 Concentrated sulfuric acid (1 mL) was added to a mixture of acetic anhydride (55 g) and malonic acid (60 g), followed by cyclohexane-1,4-dione (20 g) at an internal temperature of 30 ° C. Add in portions. The reaction mixture was stirred at 55 ° C. for 10 hours, poured into a mixed medium consisting of 2-propanol (40 mL) and water (80 mL) at 20 ° C., and neutralized to pH 4 with an aqueous sodium hydroxide solution. After stirring the reaction mixture at 15 ° C. for 1 hour, the precipitated crystals were filtered, washed with a mixed solution of 2-propanol / water (volume ratio 1/2), and dried to give 31 g of compound (3) -1 as a light brown color. Obtained as crystals. Yield 61.1%.
¹ H-NMR (TMS, DMSO-d ₆ ) δ (ppm): 2.20 (s, 8H), 4.07 (s, 4H)

(4) Synthesis of Compound (1) -1 Compound (2) -1 (24.6 g) was converted into Compound (3) -1 (10.0 g), N-methylpyrrolidone (NMP, 150 mL), triethylamine (21. 3 g) was added in portions at an internal temperature of 0 ° C. or lower and the reaction mixture was stirred at −10 to 10 ° C. for 4 hours. On the other hand, Compound (4) -4 (19.5 g) was suspended in methanol (400 mL) and refluxed, and a reaction mixture obtained by reacting Compound (2) -1 and Compound (3) -1 was added dropwise thereto. The reaction mixture was stirred at 68 ° C. for 3 hours and then cooled to room temperature. The precipitated crystals were filtered, washed with methanol, and dried to obtain 35.1 g of Compound (1) -1 as a glossy deep green crystalline powder. (Yield 80%).

Synthesis of Compound (1) -8 Compound (1) -8 was synthesized by the following method. The synthesis route is shown.

Synthesis of Intermediate 2 Concentrated sulfuric acid (1 mL) was added to a mixture of acetic anhydride (44 g) and malonic acid (50 g), followed by dropwise addition of cyclohexanone (40 g) at an internal temperature of 30 ° C. The reaction mixture was stirred at 40 ° C. for 5 hours, poured into a mixed medium consisting of 2-propanol (80 mL) and water (170 mL) at 20 ° C., and neutralized to pH 3 with an aqueous sodium hydroxide solution. After stirring the reaction mixture at 20 ° C. for 1 hour, the precipitated crystals are filtered, washed with a mixed solution of 2-propanol / water (volume ratio 1/2), and dried to give 40.5 g of Intermediate 2 as off-white crystals. Obtained. Yield 54%.
MS: M + 184
Derivation to Compound (1) -8 The following is performed according to the method of Example 1, using Intermediate 2 in place of Intermediate 1 and almost following the method described in Synthesis Example 1, and the target compound (1 ) -8 was obtained as a glossy dark green crystalline powder.

Synthesis of Compound (1) -4 Compound (1) -4 was synthesized by the following method. The synthesis route is shown.

(1) Synthesis of Intermediate 3 Concentrated sulfuric acid (1 mL) was added to a mixture of acetic anhydride (25.6 g) and malonic acid (18.7 g), and then ethyl levulinate (28.9 g) was added at an internal temperature of 30 ° C. or lower. It was dripped. After stirring the reaction mixture at 35 ° C. for 2 hours, ethyl acetate (150 mL) and 10% brine (100 mL) were added, and the organic layer was separated. After washing twice with 10% brine (100 mL), drying over magnesium sulfate and concentration, the residue was crystallized from ethanol / water (volume ratio 1/3, crystallization temperature 5 ° C.), filtered, washed and dried. 27.7 g of 2-methyl-2- (2′-ethoxycarbonylethyl) -1,3-dioxolane-4,6-dione was obtained as colorless crystals (yield 63%).
Melting point: 63-64 ° C
Induction to Compound (1) -4 The following is carried out according to the method of Example 1, using Intermediate 3 in place of Intermediate 1, almost according to the method described in Synthesis Example 1, and the target compound (1 ) -4 was obtained as a glossy deep green crystalline powder.

Synthesis of Compound (1) -6 In (2) of Example 1, instead of 1-phenylamino-5-phenylimino-1,3-pentadiene hydrochloride, 1-phenylamino-5-phenylimino-3-methyl Synthesis was carried out almost in accordance with the method described in Synthesis Example 1 except that -1,3-pentadiene hydrochloride was used, and Compound (1) -6 was obtained as dark red crystals.

Claims (2)

[1] The compound represented by the general formula (2) and the compound represented by the general formula (3) are reacted in the presence of a solvent having a donor number of 15 or more,
[2] Subsequently, an oxonol compound represented by the general formula (1) is obtained by reacting with the bipyridinium compound represented by the general formula (4).
A method for producing an oxonol compound, characterized in that the above steps are performed consistently.

In the general formula (1), Ma ¹ , Ma ² and Ma ³ each independently represent a substituted or unsubstituted methine group. Za ¹ , Za ² and Za ³ each independently represent an atomic group forming an acidic nucleus, and n represents an integer of 0 to 3. Y represents a divalent linking group that does not form a π-conjugated system with two bonds. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or a substituent. R represents a (hetero) aryl group or an alkyl group which may have a substituent.

In general formula (2), Ma ¹ , Ma ² and Ma ³ , n, and Za ¹ have the same meanings as in general formula (1). R ¹ represents a substituent, and p represents an integer of 0 to 5. R ² represents a hydrogen atom or a substituent.

In the general formula (3), Za ^2, Za ³ and Y have the same meaning as in the general formula (1). L ¹ represents a hydrogen atom or a leaving group.

In the general formula (4), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ , R are as defined in the general formula (1). X represents an anion, and y represents a number necessary for charge neutralization.   The method for producing an oxonol compound according to claim 1, wherein the solvent having a donor number of 15 or more is an aprotic polar solvent, an ether solvent or an ester solvent having a donor number of 15 or more.