JP2011116898A - Manufacturing method for azomethine dye or indoaniline dye - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of making azomethine dye or indoaniline dye stably at a high yield and with high purity even during large quantity-production. <P>SOLUTION: A manufacturing method for azomethine dye or indoaniline dye includes carrying out oxidization condensation of a compound expressed by any of formula (1)-(3) and a p-phenylene diamine derivative under the coexistence of a compound expressed by formula (4) or (5), wherein Q represents a hydrogen atom or leaving group; A represents an oxygen atom or -C(R12) (R13)-; n is an integer of 2-6; a plurality of As may be the same or different; X represents a nitrogen atom, or is N→O, provided that when X is a nitrogen atom, at least one of R9-R11 is an OH group; Y represents -N (R14)- or -N[(R15)→O], provided that at least one of As is an oxygen atom, or an OH group as at least one of R12-14 or an OH group is present; or Y represents -N[(R15)→O]-; and R1-15 and X each independently represent a predetermined atom or predetermined group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing an azomethine dye or an indoaniline dye. The dye produced in the present invention is important as a thermal transfer recording material, an optical recording material, a color toner, an ink jet recording material, a color filter, a photographic photosensitive material, particularly a thermal transfer recording material and an optical recording material. .

  One of the methods for obtaining a hard copy from a temporary image such as a television, a video, or a still video camera is a sublimation type thermal transfer recording system. The sublimation type thermal transfer recording method is one of thermal transfer printing methods in which a transfer sheet in which a sublimable dye is coated on a base film is heated with a thermal head, and the dye in the transfer sheet is transferred to a recording paper. This method is particularly effective for pictorial color recording because the sublimation transfer amount of the dye can be controlled by changing the heating energy, and an image with good gradation can be obtained. In the sublimation type thermal transfer recording system, azomethine dyes, indoaniline dyes and the like have been widely used so far, and in recent years, these metal chelate dyes have been reported to have excellent performance (Patent Document 1). ~ 2).

On the other hand, there is an information recording system in which information is recorded and reproduced by irradiating an optical recording medium with laser light without directly heating. As an optical information recording medium capable of recording information only once by laser light, an optical disk called a recordable CD (CD-R) or a recordable DVD (DVD-R) is known. DVD-R has a recording layer made of a dye on a disc-shaped substrate, then usually a light reflecting layer on the recording layer, and further two discs having a protective layer, if necessary, or the same as the disc. It has a structure in which a disk-shaped protective substrate having a shape is bonded with an adhesive with the recording layer inside. Information recording / reproduction on a DVD-R is performed by irradiating visible laser light, and recording at a higher density than CD-R is possible.
Recently, with the widespread use of digital high-definition televisions, there is an increasing demand for large-capacity optical recording media capable of recording image information inexpensively and easily. Therefore, development of an optical disk having a higher recording capacity and a larger recording capacity than that of the DVD-R has been rapidly advanced.
It has been reported that indoaniline metal chelate dyes have excellent performance as dyes used in the optical recording system (see Patent Documents 3 to 4).

In the production of azomethine dyes and indoaniline dyes used in these sublimation type thermal transfer recording methods and optical recording methods, a compound having an active methylene group or an active methine group (hereinafter referred to as a coupler) and a p-phenylenediamine derivative are obtained. A method of oxidative condensation in the presence of an oxidizing agent such as red blood salt or alkali persulfate and a base is most widely used (see Non-Patent Document 1). Conventionally, various inorganic bases have been selected as the base used for producing the dye, but the yield and purity may be lowered depending on the type of coupler. In addition, since the base is usually prepared in an aqueous solution and used, the reaction volume increases, and is not suitable for industrial mass production. On the other hand, general organic amine bases such as pyridine, quinoline, and triethylamine are also used for dye production (see Patent Document 5). In this case, the reaction volume can be carried out on a relatively small scale, but on the other hand, a large amount of tar-like components and by-products are produced during the reaction, resulting in a problem that the yield and purity are significantly reduced. In the case of using an organic amine base, the reaction is usually carried out while dropping an oxidizing agent. However, since it involves heat generation, it is necessary to cool and control the internal temperature. This is due to the deterioration of the generated pigment.
For these reasons, it has been desired to establish a production method capable of stably obtaining a high yield and high purity azomethine dye or indoaniline dye even in mass production.

Japanese Patent Laid-Open No. 2-98492 JP-A-9-143382 Japanese Patent Laid-Open No. 2002-52825 JP-A-2004-90564 JP-A-9-1000041

Journal of American Chemical Society (J. Am. Chem. Soc.), 1957, 79, 583

  An object of the present invention is to provide a method for producing a high-purity and high-yield azomethine dye or indoaniline dye that overcomes the above-mentioned drawbacks and can be mass-produced on an industrial scale.

As a result of intensive studies to achieve the above object, the present inventors have found that at least one compound represented by the general formula (4) or (5) is obtained when the coupler and the p-phenylenediamine derivative are subjected to oxidative condensation. As a result, the target dye can be obtained in high yield and high purity, and the reaction volume can be reduced compared to the case of using conventional general inorganic bases and organic bases. We have completed a manufacturing method that enables mass production without being restricted by production facilities.
In order to solve the above-mentioned problems, the present inventors have studied in detail using organic amine compounds and N-oxide compounds substituted with various functional groups. As a result, only the compounds having a specific substituent are used. It was found that the yield and purity were remarkably improved. In particular, in the present invention, even in production on a large scale in which a p-phenylenediamine derivative or an oxidizing agent is added dropwise for a long time, compared with the case where a conventional base is used, deterioration of raw materials and dyes produced, and The production of tar components and by-products associated therewith can be suppressed to a high degree, and it is possible to obtain a high-yield dye having a satisfactory quality even at the stage of crude crystallization.
As primary organic bases used for the oxidative condensation reaction of azomethine dyes and indoaniline dyes, general primary to tertiary amine bases are disclosed, but azomethine dyes or indoaniline dyes can be obtained using the compounds of the present invention. The production method has not been reported so far, and its usefulness has been found for the first time by the present inventors.
That is, the present invention is achieved by the following method.

<1>
In the method for producing an azomethine dye or indoaniline dye, which comprises oxidizing and condensing a compound represented by any one of the following general formulas (1) to (3) and a p-phenylenediamine derivative in the presence of an oxidizing agent, the following general formula (4 Or azomethine dye or indoaniline dye, which reacts in the presence of the compound represented by (5) or (5).

Where
R1 represents an alkyl group, an aryl group, or a heterocyclic residue. R2 represents a carbamoyl group or a cyano group. R3 is an alkyl group, aryl group, carbamoyl group, sulfamoyl group, amino group, alkylcarbonylamino group, arylcarbonylamino group, heterocyclic carbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group Or a heterocyclic residue. R4 represents an alkyl group, an aryl group, or a heterocyclic residue.
R5 to R8 are each independently a hydrogen atom, alkyl group, aryl group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, heterocyclic carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group Sulfamoyl group, amino group, alkylcarbonylamino group, arylcarbonylamino group, heterocyclic carbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group Represents a heterocyclic sulfonylamino group, a heterocyclic residue, or a halogen atom. R5 and R6, and R7 and R8 may combine to form a ring having 5 to 8 carbon atoms.
Q represents a hydrogen atom or a leaving group.

Where
R9 to R11 each independently represent a hydrogen atom, an alkyl group, an arylalkyl group, a hydroxyalkyl group, an aminoalkyl group, or an alkenyl group. X represents a nitrogen atom or N → O. However, when X is a nitrogen atom, at least one of R9 to R11 is a hydroxyalkyl group.
A represents an oxygen atom or -C (R12) (R13)-. n represents an integer of 2 to 6, and a plurality of A may be the same or different. Y represents —N (R14) — or —N [(R15) → O] —. R12 to R14 each independently represents a hydrogen atom, an alkyl group, an arylalkyl group, an aminoalkyl group, a cyanoalkyl group, a hydroxyalkyl group, an alkenyl group, an aryl group, a hydroxy group, an oxo group, or a heterocyclic residue. . R15 represents an alkyl group, an arylalkyl group, an aminoalkyl group, a cyanoalkyl group, a hydroxyalkyl group, an alkenyl group, an aryl group, or a heterocyclic residue.
However, in General formula (5), at least one of A is an oxygen atom, or it has a hydroxyalkyl group or a hydroxy group as at least one of R12-R14, or Y is -N [(R15). → O] −.

<2>
The azomethine dye or indoaniline according to <1>, wherein the compound of the general formula (4) or the general formula (5) is an alkanolamine compound, a morpholine compound, a trialkylamine N-oxide compound, or a morpholine N-oxide compound. A method for producing a pigment.
<3>
The method for producing an indoaniline dye according to <1> or <2>, wherein the compound represented by the general formula (3) and a p-phenylenediamine derivative are oxidatively condensed.
<4>
The oxidative condensation is performed in the presence of at least one organic solvent selected from alcohol solvents, glycol solvents or derivatives thereof, or ketone solvents, or a mixed solvent of these organic solvents and water <1>. The manufacturing method of the azomethine dye or indoaniline dye in any one of-<3>.

  The present invention provides a method for producing an azomethine dye or an indoaniline dye having high purity, high yield, and industrial mass production.

The present invention will be described in more detail below.
The present invention relates to a method for producing an azomethine dye or an indoaniline dye, which comprises oxidizing and condensing a compound represented by general formulas (1) to (3) and a p-phenylenediamine derivative in the presence of an oxidizing agent. It reacts in the coexistence of at least 1 type selected from the compound represented by 4) or (5).

Where
R1 represents an alkyl group, an aryl group, or a heterocyclic residue.
R2 represents a carbamoyl group or a cyano group.
R3 is an alkyl group, aryl group, carbamoyl group, sulfamoyl group, amino group, alkylcarbonylamino group, arylcarbonylamino group, heterocyclic carbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group Or a heterocyclic residue.
R4 represents an alkyl group, an aryl group, or a heterocyclic residue.
R5 to R8 are each independently a hydrogen atom, alkyl group, aryl group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, heterocyclic carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group Sulfamoyl group, amino group, alkylcarbonylamino group, arylcarbonylamino group, heterocyclic carbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group Represents a heterocyclic sulfonylamino group, a heterocyclic residue, or a halogen atom. R5 and R6, and R7 and R8 may combine to form a ring having 5 to 8 carbon atoms.
Q represents a hydrogen atom or a leaving group.

The couplers represented by the general formulas (1) to (3) usually undergo rapid oxidative condensation with an oxidized form of a p-phenylenediamine derivative under basic conditions to form an azomethine dye or an indoaniline dye. In addition, the proton tautomers of the compounds of the general formulas (1) to (3) are also included in the category of the present invention.
Of the couplers represented by the general formulas (1) to (3), a coupler represented by the general formula (2) or the general formula (3) is preferable, and a coupler represented by the general formula (3) is more preferable. is there.

In general formulas (1) to (3), the alkyl group represented by R1, R3 to R8 may be linear, branched or cyclic. For example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl , Nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, etc. (preferably having 1 carbon atom) To 15), preferably a linear or branched alkyl group (preferably having 1 to 10 carbon atoms).
Examples of the aryl group represented by R1, R3 to R8 include monocyclic or bicyclic aryl groups (preferably 5 to 10 membered rings) such as phenyl and naphthyl.
Examples of the alkoxy group represented by R5 to R8 include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, Examples thereof include alkoxy groups (preferably having 1 to 20 carbon atoms) such as pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy, icosyloxy and the like.

Examples of the alkylcarbonyl group represented by R5 to R8 include acetyl, ethylcarbonyl, propylcarbonyl, butylcarbonyl, pentylcarbonyl, hexylcarbonyl, heptylcarbonyl, octylcarbonyl, nonylcarbonyl, decylcarbonyl, undecylcarbonyl, dodecylcarbonyl, tridecyl. Linear, branched or cyclic alkyl groups such as carbonyl, tetradecylcarbonyl, pentadecylcarbonyl, cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, cycloheptylcarbonyl, cyclooctylcarbonyl, cyclononylcarbonyl, cyclodecylcarbonyl, etc. Examples thereof include a carbonyl group substituted with (preferably having 1 to 15 carbon atoms).
Examples of the arylcarbonyl group represented by R5 to R8 include a carbonyl group substituted with a monocyclic or bicyclic aryl group (preferably a 5- to 10-membered ring) such as benzoyl or naphthoyl.
Examples of the heterocyclic carbonyl group represented by R5 to R8 include imidazolylcarbonyl, oxazolylcarbonyl, triazolylcarbonyl, thiazolylcarbonyl, 1,3,4-thiadiazolylcarbonyl, pyridylcarbonyl, pyrimidylcarbonyl, Heterocyclic residues containing at least one nitrogen atom, oxygen atom or sulfur atom such as pyrazylcarbonyl, furylcarbonyl, thienylcarbonyl, benzothiazolylcarbonyl, benzoxazolylcarbonyl, etc. (preferably a 5- to 7-membered ring) A carbonyl group substituted by.

Examples of the alkoxycarbonyl group represented by R5 to R8 include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, undecyl Oxycarbonyl, dodecyloxycarbonyl, tridecyloxycarbonyl, tetradecyloxycarbonyl, pentadecyloxycarbonyl, cyclopropyloxycarbonyl, cyclobutyloxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cycloheptyloxycarbonyl, cyclooctyloxycarbonyl, Cyclononyloxycarbonyl, cyclodecyloxy Such as carbonyl, straight chain, branched or cyclic alkyl group (preferably having 1 to 15 carbon atoms) are exemplified oxycarbonyl group is substituted.
Examples of the aryloxycarbonyl group represented by R5 to R8 include an oxycarbonyl group substituted with a monocyclic or bicyclic aryl group (preferably a 5- to 10-membered ring) such as phenoxycarbonyl or naphthyloxycarbonyl.
Examples of the heterocyclic oxycarbonyl group represented by R5 to R8 include imidazolyloxycarbonyl, oxazolyloxycarbonyl, triazolyloxycarbonyl, thiazolyloxycarbonyl, 1,3,4-thiadiazolyloxycarbonyl, pyridyloxy. Contains at least one nitrogen atom, oxygen atom or sulfur atom such as carbonyl, pyrimidyloxycarbonyl, pyrazyloxycarbonyl, furyloxycarbonyl, thienyloxycarbonyl, benzothiazolyloxycarbonyl, benzoxazolyloxycarbonyl An oxycarbonyl group substituted with a heterocyclic residue (preferably a 5- to 7-membered ring) is exemplified.

  Examples of the carbamoyl group represented by R2, R3, R5 to R8 include an unsubstituted carbamoyl group; N-methylcarbamoyl, N-ethylcarbamoyl, N- (tert-butyl) carbamoyl, N-hexylcarbamoyl, N-octylcarbamoyl, N -Linear, branched or cyclic alkyl groups such as dodecylcarbamoyl, N-octadecylcarbamoyl, N-phenylcarbamoyl, N-naphthylcarbamoyl, pyridylcarbamoyl, furylcarbamoyl, thienylcarbamoyl, benzothiazolylcarbamoyl, benzoxazolylcarbamoyl (preferably Is a monocyclic or bicyclic aryl group (preferably 5 to 10 members), or a heterocyclic residue containing at least one nitrogen atom, oxygen atom or sulfur atom (preferably 5 ~ Carbamoyl group monosubstituted by a member ring; N, N-dimethylcarbamoyl, N, N-diethylcarbamoyl, N, N-dihexylcarbamoyl, N, N-didodecylcarbamoyl, N-methyl-N-ethylcarbamoyl, N -Methyl-N-phenylcarbamoyl, N, N-diphenylcarbamoyl, N, N-dipyrimidylcarbamoyl, N-methyl-N-furylcarbamoyl, N-phenyl-N-pyridylcarbamoyl, N-propyl-N-thienylcarbamoyl A linear, branched or cyclic alkyl group (preferably having a carbon number of 1 to 15), a monocyclic or bicyclic aryl group (preferably a 5 to 10 membered ring), a nitrogen atom, an oxygen atom or a sulfur atom Two groups selected from heterocyclic residues (preferably 5 to 7 membered rings) containing at least one Disubstituted carbamoyl group.

  Examples of the sulfamoyl group represented by R3, R5 to R8 include an unsubstituted sulfamoyl group; N-methylsulfamoyl, N-ethylsulfamoyl, N- (iso-propyl) sulfamoyl, N-butylsulfamoyl, N- Hexylsulfamoyl, N-octylsulfamoyl, N-decylsulfamoyl, N-dodecylsulfamoyl, N-tetradecylsulfamoyl, N-cyclohexylsulfamoyl, N-phenylsulfamoyl, N- Naphtylsulfamoyl, N-imidazolylsulfamoyl, N-oxazolylsulfamoyl, N-thiazolylsulfamoyl, N-pyridylsulfamoyl, N-thienylsulfamoyl, N-benzoxazolylsulfamoyl Linear, branched or cyclic alkyl groups (preferably carbon 1 to 15), a monocyclic or bicyclic aryl group (preferably a 5- to 10-membered ring), or a heterocyclic residue containing at least one nitrogen atom, oxygen atom or sulfur atom (preferably a 5- to 5-membered ring) 7-membered ring) monosubstituted sulfamoyl groups; N, N-dimethylsulfamoyl, N, N-diethylsulfamoyl, N, N-diphenylsulfamoyl, N, N-dipyridylsulfamoyl, N, N-dipyrazylsulfamoyl, N-ethyl-N-methylsulfamoyl, N-methyl-N-phenylsulfamoyl, N-ethyl-N-pyridylsulfamoyl, N-phenyl-N-furylsulfa Moyl, etc., linear, branched or cyclic alkyl groups (preferably having 1 to 15 carbon atoms), monocyclic or bicyclic aryl groups (preferably 5 to 10 membered rings), or nitrogen Child, at least one or more containing heterocyclic residue with oxygen atom or sulfur atom (preferably a 5- to 7-membered ring) disubstituted sulfamoyl group with two groups selected from.

  Examples of the amino group represented by R3 and R5 to R8 include an unsubstituted amino group; N-methylamino, N-ethylamino, N-propylamino, N-butylamino, N-hexylamino, N-decylamino, and N-tetra. Linear, such as decylamino, N-octadecylamino, N-cyclopropylamino, N-cyclohexylamino, N-phenylamino, N-naphthylamino, N-thiazolylamino, N-pyrimidylamino, N-furylamino, N-thienylamino A branched or cyclic alkyl group (preferably having a carbon number of 1 to 15), a monocyclic or bicyclic aryl group (preferably a 5 to 10 membered ring), or at least one nitrogen atom, oxygen atom or sulfur atom An amino group mono-substituted by a heterocyclic residue (preferably a 5- to 7-membered ring) containing N; N-dimethylamino N, N-diethylamino, N, N-dibutylamino, N, N-dihexylamino, N, N-dioctylamino, N, N-didodecylamino, N, N-dioctadecylamino, N, N-diphenylamino N, N-difurylamino, N, N-dipyridylamino, N-ethyl-N-methylamino, N-ethyl-N-butylamino, N-methyl-N-phenylamino, N-ethyl-N-pyridylamino, etc. A linear, branched or cyclic alkyl group (preferably having a carbon number of 1 to 15), a monocyclic or bicyclic aryl group (preferably a 5 to 10 membered ring), or a nitrogen atom, oxygen atom or sulfur atom. Examples thereof include an amino group disubstituted with two groups selected from one or more heterocyclic residues (preferably a 5- to 7-membered ring).

Examples of the alkylcarbonylamino group represented by R3, R5 to R8 include acetylamino, ethylcarbonylamino, propylcarbonylamino, butylcarbonylamino, pentylcarbonylamino, hexylcarbonylamino, heptylcarbonylamino, octylcarbonylamino, nonylcarbonylamino, Decylcarbonylamino, undecylcarbonylamino, dodecylcarbonylamino, tridecylcarbonylamino, tetradecylcarbonylamino, pentadecylcarbonylamino, cyclopropylcarbonylamino, cyclobutylcarbonylamino, cyclopentylcarbonylamino, cyclohexylcarbonylamino, cycloheptylcarbonylamino , Cyclooctylcarbonylamino, cyclononylcarbonylamino Such as cyclo decyl carbonylamino, linear, branched or cyclic alkyl group (preferably having from 1 to 15 carbon atoms) are exemplified carbonylamino groups substituted.
Examples of the arylcarbonylamino group represented by R3 and R5 to R8 include a carbonylamino group substituted with a monocyclic or bicyclic aryl group (preferably a 5- to 10-membered ring) such as benzoylamino or naphthoylamino. It is done.
Examples of the heterocyclic carbonylamino group represented by R3, R5 to R8 include imidazolylcarbonylamino, oxazolylcarbonylamino, triazolylcarbonylamino, thiazolylcarbonylamino, 1,3,4-thiadiazolylcarbonylamino, At least one nitrogen atom, oxygen atom or sulfur atom such as pyridylcarbonylamino, pyrimidylcarbonylamino, pyrazylcarbonylamino, furylcarbonylamino, thienylcarbonylamino, benzothiazolylcarbonylamino, benzoxazolylcarbonylamino, etc. Examples thereof include a carbonylamino group substituted with a heterocyclic residue (preferably a 5- to 7-membered ring) contained above.

Examples of the alkoxycarbonylamino group represented by R3, R5 to R8 include methoxycarbonylamino, ethoxycarbonylamino, propoxycarbonylamino, butoxycarbonylamino, pentyloxycarbonylamino, hexyloxycarbonylamino, heptyloxycarbonylamino, octyloxycarbonylamino. An oxycarbonylamino group substituted with a linear, branched or cyclic alkyl group (preferably having a carbon number of 1 to 15), such as nonyloxycarbonylamino, decyloxycarbonylamino, undecyloxycarbonylamino, dodecyloxycarbonylamino, etc. Can be mentioned.
The aryloxycarbonylamino group represented by R3, R5 to R8 is, for example, an oxycarbonylamino substituted with a monocyclic or bicyclic aryl group (preferably a 5- to 10-membered ring) such as phenoxycarbonylamino or naphthyloxycarbonylamino. Groups.
Examples of the heterocyclic oxycarbonylamino group represented by R3, R5 to R8 include imidazolyloxycarbonylamino, oxazolyloxycarbonylamino, triazolyloxycarbonylamino, thiazolyloxycarbonylamino, 1,3,4-thia Diazolyloxycarbonylamino, pyridyloxycarbonylamino, pyrimidyloxycarbonylamino, pyrazyloxycarbonylamino, furyloxycarbonylamino, thienyloxycarbonylamino, benzothiazolyloxycarbonylamino, benzoxazolyloxycarbonylamino, etc. And an oxycarbonylamino group substituted with a heterocyclic residue (preferably a 5- to 7-membered ring) containing at least one nitrogen atom, oxygen atom or sulfur atom.

Examples of the alkylsulfonylamino group represented by R5 to R8 include methylsulfonylamino, ethylsulfonylamino, propylsulfonylamino, butylsulfonylamino, pentylsulfonylamino, hexylsulfonylamino, heptylsulfonylamino, octylsulfonylamino, nonylsulfonylamino, decyl. Sulfonylamino, undecylsulfonylamino, dodecylsulfonylamino, tridecylsulfonylamino, tetradecylsulfonylamino, pentadecylsulfonylamino, cyclopropylsulfonylamino, cyclobutylsulfonylamino, cyclopentylsulfonylamino, cyclohexylsulfonylamino, cycloheptylsulfonylamino, Cyclooctylsulfonylamino, cyclononylsulfonylamino , Such as cyclo-decyl sulfonylamino, linear, branched or cyclic alkyl group (preferably having from 1 to 15 carbon atoms), and a sulfonylamino group substituted by an.
Examples of the arylsulfonylamino group represented by R5 to R8 include a sulfonylamino group substituted with a monocyclic or bicyclic aryl group (preferably a 5- to 10-membered ring) such as phenylsulfonylamino or naphthylsulfonylamino.
Examples of the heterocyclic sulfonylamino group represented by R5 to R8 include imidazolylsulfonylamino, oxazolylsulfonylamino, triazolylsulfonylamino, thiazolylsulfonylamino, 1,3,4-thiadiazolylsulfonylamino, pyridylsulfonyl. Contains at least one nitrogen atom, oxygen atom or sulfur atom such as amino, pyrimidylsulfonylamino, pyrazylsulfonylamino, furylsulfonylamino, thienylsulfonylamino, benzothiazolylsulfonylamino, benzoxazolylsulfonylamino Examples thereof include a sulfonylamino group substituted with a heterocyclic residue (preferably a 5- to 7-membered ring).

Examples of the heterocyclic residue represented by R1, R3 to R8 include nitrogen such as imidazolyl, oxazolyl, triazolyl, thiazolyl, 1,3,4-thiadiazolyl, pyridyl, pyrimidyl, pyrazyl, furyl, thienyl, benzothiazolyl, benzoxazolyl, etc. Examples thereof include heterocyclic residues (preferably 5 to 7 membered rings) containing at least one atom, oxygen atom or sulfur atom.
Examples of the halogen atom represented by R5 to R8 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Each substituent in R1 to R8 may further have a substituent. Specifically, alkyl group, aryl group, hydroxy group, alkoxy group, aryloxy group, carbonyl group substituted with alkyl or aryl group, carbonyl group substituted with alkoxy or aryloxy group, alkyl and / or aryl group Mono- or di-substituted carbamoyl group, sulfonyl group substituted with alkyl or aryl group, amino group mono- or di-substituted with alkyl and / or aryl group, carbonylamino group substituted with alkyl or aryl group, cyano Group, a halogen atom, and a heterocyclic residue are mentioned, These are the substituents of 15 or less carbon atoms comprised individually or in combination of these. Specific examples of these groups are the same as those in R1 to R8.
The ring having 5 to 8 carbon atoms formed by combining R5 and R6 and R7 and R8 may be a partially saturated ring, an aromatic ring, or a heterocyclic ring.
Examples of the partially saturated ring formed by combining R5 and R6 and R7 and R8 include a cyclopentene ring, a cyclohexene ring, a cyclopentadiene ring, and a cyclohexadiene ring.
Examples of the aromatic ring formed by combining R5 and R6 and R7 and R8 include a benzene ring and a naphthalene ring.
Examples of the heterocycle formed by combining R5 and R6 and R7 and R8 include a pyrrole ring, an imidazole ring, a pyridine ring, a pyrimidine ring, and a pyrazine ring.
These formed partially saturated rings, aromatic rings, and heterocycles may further have a substituent. Specific examples of the further substituent include an alkyl group, an aryl group, a hydroxy group, an alkoxy group, a cyano group, and a halogen atom. Specific examples of these groups are the same as those in R1 to R8.

Q is a hydrogen atom or a leaving group. The leaving group represented by Q may be any substituent as long as it is eliminated during the oxidative condensation reaction. Preferably, a group bonded to the active site (site to which Q is bonded) via a nitrogen atom, an oxygen atom, a sulfur atom, or the like, or a halogen atom. Specifically, alkoxy groups such as methoxy, propoxy and methoxyethoxy; aryloxy groups such as phenoxy, phenylsulfonylphenoxy and naphthyloxy; carbonyloxy groups such as acetyloxy, benzoyloxy and carbamoyloxy; methylsulfonyloxy, n- Sulfonyloxy groups such as propylsulfonyloxy and trifluoromethylsulfonyloxy; alkylsulfonyl groups such as methylsulfonyl and ethylsulfonyl; arylsulfonyl groups such as phenylsulfonyl and naphthylsulfonyl; N-ethylsulfamoyl and N-butylsulfamoyl N-nonylsulfamoyl, phenylsulfamoyl, naphthylsulfamoyl, etc., sulfamoyl groups substituted with alkyl groups or aryl groups; phenylazo, naphthyla Arylthio groups such as methylthio and octylthio; arylthio groups such as phenylthio and nitrophenylthio; heterocyclic thio groups such as tetrazolylthio, benzothiazolylthio and benzoxazolylthio; imidazolidinyl, oxazolidinyl, triazolyl and benzotriazolyl And heterocyclic residues such as ruthenium; cyclic imide groups such as succinimide, phthalimide and hydantoinyl; and halogen atoms such as iodine, bromine and chlorine.
Q is preferably a hydrogen atom, an aryloxy group, a heterocyclic residue, a cyclic imide group, or a halogen atom in the case of the compound represented by the general formula (1), and the compound represented by the general formula (2) A hydrogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and a halogen atom. In the case of the compound represented by the general formula (3), a hydrogen atom, an alkoxy group, an aryloxy group, and a halogen atom. .

R1 is preferably a linear or branched alkyl group (preferably having a carbon number of 1 to 10), a phenyl group substituted with an alkyl group or an alkoxy group, or a heterocyclic residue. More preferably, it is a phenyl group substituted with a linear or branched alkyl group (preferably having 1 to 4 carbon atoms), an alkyl group or an alkoxy group.
R2 is preferably an aryl group or a carbamoyl group substituted with a heterocyclic residue, or a cyano group.
R3 is preferably a linear or branched alkyl group (preferably having a carbon number of 1 to 10), an aryl group, an alkylamino group, an arylamino group, an alkylcarbonylamino group, or an arylcarbonylamino group. More preferably, they are a linear or branched alkyl group (preferably having 1 to 4 carbon atoms), an aryl group, an alkylamino group (preferably having 1 to 4 carbon atoms), and an arylamino group.
R4 is preferably a linear or branched alkyl group (preferably having 1 to 10 carbon atoms), an aryl group, or a heterocyclic residue. More preferably, they are a linear or branched alkyl group (preferably having 1 to 4 carbon atoms) and an aryl group.

R5 is preferably a hydrogen atom, an alkyl group, an arylamino group, an alkylcarbonylamino group, an arylcarbonylamino group, a heterocyclic carbonylamino group, a heterocyclic residue, or a halogen atom. More preferably, they are a hydrogen atom, a linear or branched alkyl group (preferably having 1 to 4 carbon atoms), and a halogen atom.
R6 is preferably a hydrogen atom, a linear or branched alkyl group (preferably having 1 to 4 carbon atoms). More preferably, they are a hydrogen atom or a methyl group.
R7 is preferably an alkylcarbamoyl group, arylcarbamoyl group, heterocyclic carbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, heterocyclic sulfamoyl group, alkylcarbonylamino group, arylcarbonylamino group, heterocyclic carbonylamino group An alkylsulfonylamino group, an arylsulfonylamino group, and a heterocyclic sulfonylamino group. More preferably, an alkylcarbamoyl group (preferably having a carbon number of 2 to 5), an arylcarbamoyl group, a heterocyclic carbamoyl group, an alkylcarbonylamino group (preferably having a carbon number of 2 to 5), an arylcarbonylamino group, or a heterocyclic carbonylamino group It is.
R8 is preferably a hydrogen atom.
A ring formed by combining R5 and R6 and R7 and R8 is preferably a benzene ring or a naphthalene ring.

  Next, the p-phenylenediamine derivative used in the present invention will be described in detail. The p-phenylenediamine derivative in the present invention is a compound represented by the following general formula (6).

  In the formula, R16 to R19 are hydrogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfonyl. Represents a group, an arylsulfonyl group, an alkylsulfamoyl group, an arylsulfamoyl group, a cyano group, an alkylcarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, or a halogen atom. R20 represents a hydrogen atom, an alkyl group or an aryl group. R21 represents an alkyl group or an aryl group. R20 and R21 may combine to form a heterocyclic ring (preferably a 5- to 7-membered ring) containing at least one nitrogen atom. R17 and R20 and / or R19 and R21 may combine to form a heterocycle (preferably a 5- to 7-membered ring) containing at least one nitrogen atom.

The alkyl group represented by R16 to R21 may be linear, branched, or cyclic, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, Examples include pentadecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like, linear, branched or cyclic alkyl groups (preferably having 1 to 15 carbon atoms).
Examples of the aryl group represented by R16 to R21 include monocyclic or bicyclic aryl groups such as phenyl and naphthyl (preferably 5 to 10 membered rings).
Examples of the alkoxy group represented by R16 to R19 include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, Examples thereof include alkoxy groups (preferably having 1 to 20 carbon atoms) such as pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy, icosyloxy and the like.
Examples of the aryloxy group represented by R16 to R19 include monocyclic or bicyclic aryloxy groups (preferably 5 to 10 membered rings) such as phenoxy and naphthyloxy.

Examples of the alkylcarbonyl group represented by R16 to R19 include acetyl, ethylcarbonyl, propylcarbonyl, butylcarbonyl, pentylcarbonyl, hexylcarbonyl, heptylcarbonyl, octylcarbonyl, nonylcarbonyl, decylcarbonyl, undecylcarbonyl, dodecylcarbonyl, tridecyl. Linear, branched or cyclic alkyl groups such as carbonyl, tetradecylcarbonyl, pentadecylcarbonyl, cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, cycloheptylcarbonyl, cyclooctylcarbonyl, cyclononylcarbonyl, cyclodecylcarbonyl, etc. (Preferably having 1 to 15 carbon atoms) includes a carbonyl group.
Examples of the arylcarbonyl group represented by R16 to R19 include a carbonyl group substituted with a monocyclic or bicyclic aryl group (preferably a 5- to 10-membered ring) such as benzoyl or naphthoyl.

Examples of the alkoxycarbonyl group represented by R16 to R19 include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, undecyl Oxycarbonyl, dodecyloxycarbonyl, tridecyloxycarbonyl, tetradecyloxycarbonyl, pentadecyloxycarbonyl, cyclopropyloxycarbonyl, cyclobutyloxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cycloheptyloxycarbonyl, cyclooctyloxycarbonyl, Cyclononyloxycarbonyl, cyclodecyl Such as alkoxycarbonyl, linear, branched or cyclic alkyl group (preferably having 1 to 15 carbon atoms) are exemplified oxycarbonyl group is substituted.
Examples of the aryloxycarbonyl group represented by R16 to R19 include an oxycarbonyl group substituted with a monocyclic or bicyclic aryl group (preferably a 5- to 10-membered ring) such as phenoxycarbonyl or naphthyloxycarbonyl.

Examples of the alkylcarbamoyl group represented by R16 to R19 include N-methylcarbamoyl, N-ethylcarbamoyl, N-propylcarbamoyl, N-butylcarbamoyl, N-hexylcarbamoyl, N-octylcarbamoyl, N-decylcarbamoyl and N-dodecyl. Carbamoyl, N-tetradecylcarbamoyl, N-cyclopropylcarbamoyl, N-cyclohexylcarbamoyl, N, N-dimethylcarbamoyl, N, N-diethylcarbamoyl, N, N-dibutylcarbamoyl, N, N-dihexylcarbamoyl, N-ethyl -N-methylcarbamoyl, N-methyl-N-propylcarbamoyl, N, N-dicyclohexylcarbamoyl, etc., linear, branched or cyclic alkyl groups (preferably having 1 to 15 carbon atoms) are mono- or disubstituted Carbamoyl group.
Examples of the arylcarbamoyl group represented by R16 to R19 include monocyclic groups such as N-phenylcarbamoyl, N-naphthylcarbamoyl, N, N-diphenylcarbamoyl, N, N-dinaphthylcarbamoyl, N-phenyl-N-naphthylcarbamoyl and the like. Alternatively, a carbamoyl group in which a bicyclic aryl group (preferably a 5- to 10-membered ring) is mono-substituted or di-substituted can be mentioned.

Examples of the alkylsulfonyl group represented by R16 to R19 include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, pentylsulfonyl, hexylsulfonyl, heptylsulfonyl, octylsulfonyl, nonylsulfonyl, decylsulfonyl, undecylsulfonyl, dodecylsulfonyl, tri Linear, branched or cyclic alkyl such as decylsulfonyl, tetradecylsulfonyl, pentadecylsulfonyl, cyclopropylsulfonyl, cyclobutylsulfonyl, cyclopentylsulfonyl, cyclohexylsulfonyl, cycloheptylsulfonyl, cyclooctylsulfonyl, cyclononylsulfonyl, cyclodecylsulfonyl, etc. Examples thereof include a sulfonyl group substituted with a group (preferably having 1 to 15 carbon atoms).
Examples of the arylsulfonyl group represented by R16 to R19 include a sulfonyl group substituted with a monocyclic or bicyclic aryl group (preferably a 5- to 10-membered ring) such as phenylsulfonyl or naphthylsulfonyl.
Examples of the alkylsulfamoyl group represented by R16 to R19 include N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-butylsulfamoyl, N-hexylsulfamoyl, N -Octylsulfamoyl, N-decylsulfamoyl, N-dodecylsulfamoyl, N-tetradecylsulfamoyl, N-cyclopropylsulfamoyl, N-cyclohexylsulfamoyl, N, N-dimethylsulfa Moyl, N, N-diethylsulfamoyl, N, N-dibutylsulfamoyl, N, N-dihexylsulfamoyl, N-methyl-N-ethylsulfamoyl, N-methyl-N-propylsulfamoyl , N, N-dicycloheptylsulfamoyl and the like, linear, branched or cyclic alkyl groups (preferably It includes sulfamoyl groups having 1 to 15 carbon atoms) is monosubstituted or disubstituted.
Examples of the arylsulfamoyl group represented by R16 to R19 include N-phenylsulfamoyl, N-naphthylsulfamoyl, N, N-diphenylsulfamoyl, N, N-dinaphthylsulfamoyl and N-phenyl. Examples thereof include a sulfamoyl group in which a monocyclic or bicyclic aryl group (preferably a 5- to 10-membered ring) such as -N-naphthylsulfamoyl is mono-substituted or di-substituted.

Examples of the alkylcarbonylamino group represented by R16 to R19 include acetylamino, ethylcarbonylamino, propylcarbonylamino, butylcarbonylamino, pentylcarbonylamino, hexylcarbonylamino, heptylcarbonylamino, octylcarbonylamino, nonylcarbonylamino, decylcarbonyl. Amino, undecylcarbonylamino, dodecylcarbonylamino, tridecylcarbonylamino, tetradecylcarbonylamino, pentadecylcarbonylamino, cyclopropylcarbonylamino, cyclobutylcarbonylamino, cyclopentylcarbonylamino, cyclohexylcarbonylamino, cycloheptylcarbonylamino, cyclo Octylcarbonylamino, cyclononylcarbonylamino, Such as black decyl carbonylamino, linear, branched or cyclic alkyl group (preferably having from 1 to 15 carbon atoms) are exemplified carbonylamino groups substituted.
Examples of the alkoxycarbonylamino group represented by R16 to R19 include methoxycarbonylamino, ethoxycarbonylamino, propoxycarbonylamino, butoxycarbonylamino, pentyloxycarbonylamino, hexyloxycarbonylamino, heptyloxycarbonylamino, octyloxycarbonylamino, and nonyl. Oxycarbonylamino, decyloxycarbonylamino, undecyloxycarbonylamino, dodecyloxycarbonylamino, tridecyloxycarbonylamino, tetradecyloxycarbonylamino, pentadecyloxycarbonylamino, cyclopropyloxycarbonylamino, cyclobutyloxycarbonylamino, Cyclopentyloxycarbonylamino, cyclohexyloxycal Oxycarbonyl substituted with a linear, branched or cyclic alkyl group (preferably having 1 to 15 carbon atoms) such as nylamino, cycloheptyloxycarbonylamino, cyclooctyloxycarbonylamino, cyclononyloxycarbonylamino, cyclodecyloxycarbonylamino An amino group is mentioned.
The aryloxycarbonylamino group represented by R16 to R19 is, for example, an oxycarbonylamino group substituted by a monocyclic or bicyclic aryl group (preferably a 5- to 10-membered ring) such as phenoxycarbonylamino or naphthyloxycarbonylamino. Can be mentioned.

Examples of the halogen atom represented by R16 to R19 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the ring formed by combining R20 and R21 include a heterocyclic ring (preferably a 5- to 7-membered ring) containing at least one nitrogen atom such as pyrrolidine, imidazolidine, pyrazolidine, piperidine, piperazine, morpholine, indoline and the like. Can be mentioned.
The ring formed by combining R17 and R20 and / or R19 and R21 is, for example, a heterocyclic ring containing at least one nitrogen atom such as pyrrolidine, imidazolidine, pyrazolidine, piperidine, piperazine, morpholine, indoline ring (preferably 5-7 membered ring).
Each substituent in R16 to R19 may further have a substituent. Specifically, an alkyl group (preferably having 1 to 4 carbon atoms), an alkoxy group (preferably having 1 to 4 carbon atoms), and a halogen atom are exemplified.
Each substituent in R20 and R21 may further have a substituent. Specifically, an alkyl group (preferably 1 to 4 carbon atoms), a hydroxy group, an alkoxy group (preferably 1 to 4 carbon atoms), an alkoxycarbonyl group (preferably 2 to 5 carbon atoms), a carbamoyl group, a sulfamoyl group. , A cyano group, and a halogen atom.

R16 to R19 are preferably each independently a hydrogen atom, an alkyl group (preferably having 1 to 4 carbon atoms), an alkoxy group (preferably having 1 to 4 carbon atoms), or an alkylcarbonylamino group (preferably having 2 to 5 carbon atoms). ), An alkoxycarbonylamino group (preferably having 2 to 5 carbon atoms), an alkylsulfonyl group (preferably having 1 to 4 carbon atoms), an arylsulfonyl group, and a halogen atom. More preferably, they are a hydrogen atom, an alkyl group (preferably having 1 to 4 carbon atoms), and an alkoxy group (preferably having 1 to 4 carbon atoms).
R20 and R21 are preferably each independently an alkyl group (preferably having a carbon number of 1 to 6), or a hydroxy group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a cyano group, or a halogen atom. It is an alkyl group (preferably having 2 to 10 carbon atoms) as a substituent. More preferably, it is an alkyl group (preferably having 1 to 6 carbon atoms), or an alkyl group having a hydroxy group, alkoxy group, alkoxycarbonyl group, cyano group, or halogen atom as a substituent (preferably having 2 to 2 carbon atoms). 8).
In the ring formed by combining R20 and R21 with each other, pyrrolidine, piperidine and morpholine are preferred.
The ring formed by combining R17 and R20 and / or R19 and R21 is preferably pyrrolidine, piperidine, or morpholine.

The p-phenylenediamine derivative represented by the general formula (6) can be appropriately selected according to the structure of the target thermal transfer recording dye or optical recording dye. As the p-phenylenediamine derivative (6), a commercially available one can be used, for example, a compound synthesized by a general method using an N-acyl-p-phenylenediamine derivative as a raw material may be used. When synthesized and used, the p-phenylenediamine derivative may be used after isolation, or may be used as it is in an organic solvent solution without isolation. The p-phenylenediamine derivative can be used as an addition salt such as hydrochloride or sulfate.
The usage-amount of p-phenylenediamine derivative is 1-5 mol normally with respect to 1 mol of couplers, Preferably it is 1-2 mol.

  The azomethine dye or indoaniline dye in the present invention is preferably a compound having a structure represented by the following general formulas (1 ′) to (3 ′), specifically, (A-1) to ( Examples thereof include those having the structure represented by the specific example of C-68). In the formula, R1 to R8 and R16 to R21 are as defined above.

Next, the manufacturing method of the present invention will be described.
The present invention relates to a method for producing an azomethine dye or an indoaniline dye, which comprises oxidative condensation of one kind selected from compounds represented by general formulas (1) to (3) and a p-phenylenediamine derivative in the presence of an oxidizing agent. The production method in which at least one compound represented by the general formula (4) or (5) is allowed to coexist and react.
An example of the synthesis method of the present invention is shown below, but the present invention is not limited to this.

In the present invention, the target product can be synthesized by various methods depending on the situation. The synthesis example is shown below.
(A) Add at least one compound represented by the general formula (4) or (5), a coupler and a p-phenylenediamine derivative to a reaction solvent and dissolve or suspend it, and then add an aqueous oxidizing agent solution into the reaction system. A method of performing an oxidative condensation reaction at a predetermined temperature while dropping.
(B) In a reaction solvent, at least one compound represented by the general formula (4) or (5) and a coupler are dissolved or suspended, and an organic solvent solution of a p-phenylenediamine derivative and an oxidizing agent aqueous solution are added thereto. , A method in which an oxidative condensation reaction is carried out at a predetermined temperature while being dropped into each reaction system (preferably simultaneously).
(C) A p-phenylenediamine derivative and at least one compound represented by the general formula (4) or (5) are added to a reaction solvent and dissolved or suspended therein, and an organic solvent solution of the coupler and an oxidizing agent aqueous solution are added thereto. In each reaction system (preferably at the same time), and an oxidative condensation reaction is performed at a predetermined temperature.
(D) A coupler is added to a reaction solvent to dissolve or suspend, and a mixed organic solvent solution of a p-phenylenediamine derivative and a compound represented by the general formula (4) or (5) and an oxidizing agent aqueous solution are mixed therewith. A method in which an oxidative condensation reaction is carried out at a predetermined temperature while dropping (preferably simultaneously) into each reaction system.
(E) A p-phenylenediamine derivative is added to a reaction solvent and dissolved or suspended, and a coupler, an organic solvent solution of a compound represented by the general formula (4) or (5), and an oxidizing agent aqueous solution are reacted respectively. A method of performing an oxidative condensation reaction at a predetermined temperature while dropping (preferably simultaneously) into the system.
In any case, the compounds represented by the general formula (4) or (5) can be used alone or in combination of two or more. By reacting in the presence of these compounds, compared with the conventional method. This significantly improves the yield and purity of the target product.

Next, the base used in the present invention will be described.
The base used in the reaction of the present invention is a compound represented by the general formula (4) or (5).

式中、Ｒ９〜Ｒ１１は独立して、水素原子、アルキル基、アリールアルキル基、ヒドロキシアルキル基、アミノアルキル基、又はアルケニル基を表す。Ｘは窒素原子又はＮ→Ｏを表す。但し、Ｘが窒素原子である場合、Ｒ９〜Ｒ１１の少なくとも１つはヒドロキシアルキル基である。尚、「→」は配位結合を表す。
Ａは酸素原子又は−Ｃ（Ｒ１２）（Ｒ１３）−を表す。ｎは２〜６の整数を表し、複数のＡは同じでも異なってもよい。Ｙは−Ｎ（Ｒ１４）−、又は−Ｎ［（Ｒ１５）→Ｏ］−を表す。Ｒ１２〜Ｒ１４は独立して、水素原子、アルキル基、アリールアルキル基、アミノアルキル基、シアノアルキル基、ヒドロキシアルキル基、アルケニル基、アリール基、ヒドロキシ基、オキソ基、又はヘテロ環残基を表す。
Ｒ１５は、アルキル基、アリールアルキル基、アミノアルキル基、シアノアルキル基、ヒドロキシアルキル基、アルケニル基、アリール基、又はヘテロ環残基を表す。
但し、Ａの少なくとも１つが酸素原子であるか、Ｒ１２〜Ｒ１４の少なくとも１つがヒドロキシアルキル基、ヒドロキシ基であるか、又はＹがＮ（Ｒ１５）→Ｏである。

In the formula, R9 to R11 independently represent a hydrogen atom, an alkyl group, an arylalkyl group, a hydroxyalkyl group, an aminoalkyl group, or an alkenyl group. X represents a nitrogen atom or N → O. However, when X is a nitrogen atom, at least one of R9 to R11 is a hydroxyalkyl group. “→” represents a coordination bond.
A represents an oxygen atom or -C (R12) (R13)-. n represents an integer of 2 to 6, and a plurality of A may be the same or different. Y represents —N (R14) — or —N [(R15) → O] —. R12 to R14 independently represent a hydrogen atom, an alkyl group, an arylalkyl group, an aminoalkyl group, a cyanoalkyl group, a hydroxyalkyl group, an alkenyl group, an aryl group, a hydroxy group, an oxo group, or a heterocyclic residue.
R15 represents an alkyl group, an arylalkyl group, an aminoalkyl group, a cyanoalkyl group, a hydroxyalkyl group, an alkenyl group, an aryl group, or a heterocyclic residue.
However, at least one of A is an oxygen atom, at least one of R12 to R14 is a hydroxyalkyl group or a hydroxy group, or Y is N (R15) → O.

The alkyl group represented by R9 to R15 may be either linear or branched, for example, an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl (preferably having 1 to 1 carbon atoms). 10). Preferably, it is a C1-C4 linear or branched alkyl group.
Examples of the arylalkyl group represented by R9 to R15 include linear or branched alkyl substituted with a monocyclic or bicyclic aryl group (preferably 5 to 10 membered ring) such as benzyl, phenethyl, phenylpropyl, phenylbutyl, etc. Group (preferably having 1 to 10 carbon atoms). Preferably, they are a benzyl group and a phenethyl group.
Examples of the hydroxyalkyl group represented by R9 to R15 include a straight chain substituted with a hydroxy group such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, hydroxyoctyl, hydroxynonyl, hydroxydecyl and the like. Or the branched alkyl group (preferably C1-C10) is mentioned. Preferably, it is a linear or branched alkyl group (preferably having 1 to 4 carbon atoms) substituted with a hydroxy group.

  Examples of the aminoalkyl group represented by R9 to R15 include an alkyl group having an unsubstituted amino group such as aminomethyl, aminoethyl, aminopropyl, and aminobutyl (preferably having 1 to 10 carbon atoms); N-methylaminomethyl, N A linear, branched or cyclic alkyl group (preferably carbon), such as -ethylaminomethyl, N-propylaminoethyl, N-butylaminoethyl, N-hexylaminopropyl, N-octylaminobutyl, N-cyclohexylaminoethyl An alkyl group having a monosubstituted amino group (preferably having a carbon number of 1 to 10); a monocyclic or bicyclic aryl group such as N-phenylaminomethyl, N-naphthylaminopropyl ( An alkyl group (preferably having a carbon number of 1 to 10) having an amino group monosubstituted by 5 to 10-membered rings N-furylaminoethyl, N-thienylaminobutyl and the like having an amino group monosubstituted by a heterocyclic residue (preferably a 5- to 7-membered ring) containing at least one nitrogen atom, oxygen atom or sulfur atom Alkyl group (preferably having 1 to 10 carbon atoms); N, N-dimethylaminoethyl, N, N-diethylaminopropyl, N, N-dibutylaminomethyl, N, N-dihexylaminobutyl, N, N-diphenylaminoethyl N, N-difurylaminobutyl, N, N-dipyridylaminopropyl, N-ethyl-N-methylaminoethyl, N-ethyl-N-butylaminobutyl, N-methyl-N-phenylaminomethyl, N- Linear, branched or cyclic alkyl groups (preferably having 1 to 15 carbon atoms) such as ethyl-N-pyridylaminopropyl, monocyclic or 2 selected from a cyclic aryl group (preferably a 5- to 10-membered ring) and / or a heterocyclic residue (preferably a 5- to 7-membered ring) containing at least one nitrogen atom, oxygen atom or sulfur atom. Examples thereof include an alkyl group (preferably having 1 to 10 carbon atoms) having an amino group disubstituted with one group. An unsubstituted aminoalkyl group and an N-alkylaminoalkyl group are preferable.

As the cyanoalkyl group represented by R12 to R15, an alkyl group substituted with a cyano group such as cyanomethyl, cyanoethyl, cyanopropyl, cyanobutyl, cyanopentyl, cyanohexyl, cyanoheptyl, cyanooctyl, cyanononyl, cyanodecyl (preferably having 1 carbon atom) To 10). Preferably, it is a linear or branched alkyl group (preferably having 1 to 4 carbon atoms) substituted with a cyano group.
Examples of the alkenyl group represented by R9 to R15 include vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, A linear, branched or cyclic alkenyl group such as hexadienyl, dodecatrienyl and the like is represented. A linear or branched alkenyl group (preferably having 2 to 6 carbon atoms) is preferable.
Examples of the aryl group represented by R12 to R15 include monocyclic or bicyclic aryl groups such as phenyl and naphthyl (preferably 5 to 10 membered rings).
Examples of the heterocyclic residue represented by R12 to R15 include pyrrolidyl, piperidyl, morpholyl, imidazolyl, oxazolyl, triazolyl, thiazolyl, 1,3,4-thiadiazolyl, pyridyl, pyrimidyl, pyrazyl, furyl, thienyl, benzothiazolyl, benzoxazolyl And a heterocyclic residue (preferably a 5- to 7-membered ring) containing at least one nitrogen atom, oxygen atom, or sulfur atom. Preferred are pyrrolidyl, piperidyl, morpholyl, pyridyl, furyl, and thienyl.
Each substituent in R9 to R15 may further have a substituent. Specific examples include an alkyl group, an alkenyl group, an arylalkyl group, a hydroxyalkyl group, an aminoalkyl group, an aryl group, an alkoxy group, a hydroxy group, and an amino group.

When the compound of the general formula (4) or (5) is a tertiary amine compound, the yield is improved because the effect of suppressing deterioration of the produced dye is remarkably exhibited and the dyeing reaction proceeds efficiently. Therefore, it is more preferable.
Likewise preferred are so-called N-oxide compounds in which X in the general formula (4) is N → O or Y in the general formula (5) is —N [(R15) → O] —. Furthermore, when X in the general formula (4) is N → O, R9 to R11 each preferably have 8 or less carbon atoms, and Y in the general formula (5) is —N [(R15) → O] —. N is preferably 4 or 5. In these cases, the dyeing reaction proceeds very efficiently.

Although the suitable specific example of the compound represented by General formula (4) or (5) used by this invention below is given, this invention is not limited to this.
For example, 2-aminoethanol, 2-methylaminoethanol, 2-ethylaminoethanol, 2-butylaminoethanol, 2- (hydroxymethylamino) ethanol, 2- (2-aminoethoxy) ethanol, 2-[(3- Aminopropyl) amino] ethanol, 1-phenyl-2-aminoethanol, 1-phenyl-2- (N-methylamino) ethanol, 1-phenyl-2- (N-ethylamino) ethanol, 1- (3-hydroxy Phenyl) -2-aminoethanol, 1- (4-hydroxyphenyl) -2-aminoethanol, 1- (3,4-dihydroxyphenyl) -2-aminoethanol, 1- (3-hydroxyphenyl) -2- ( N-methylamino) ethanol, 1- (4-hydroxyphenyl) -2- (N-methylamino) ) Ethanol, 1- (3,4-dihydroxyphenyl) -2- (N-methylamino) ethanol, N- (2-hydroxyethylamino) ethylenediamine, 2- (2-hydroxypropylamino) ethylamine, 2- (3 -Hydroxypropylamino) ethylamine, diethanolamine, 1-amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol, 3-amino-2-phenylpropanol, 1,3-diamino-2- Propanol, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, 2-amino-1-phenyl-1,3-propanediol, 2-amino-2- (hydroxymethyl)- 1,3-propanediol, 1-deoxy-1- (methylamino) -D-glucito , Diisopropanolamine, 4-aminobutanol, 4-methylaminobutanol, 2-dimethylaminoethanol, 2-diethylaminoethanol, 2-dibutylaminoethanol, N-methyl-diethanolamine, N-ethyl-diethanolamine, N-isobutyl- Diethanolamine, triethanolamine, 1-dimethylamino-2-propanol, 3-dimethylamino-1-propanol, 3-diethylamino-1-propanol, 3-dipropylamino-1-propanol, 3-dibutylamino-1-propanol 2-dimethylamino-2-methylpropanol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 3-dipropylamino-1,2-propanediol , Alkanolamine compounds such as triisopropanolamine, 3-dimethylamino-1-butanol, 4-dibutylamino-1-butanol, 5-diethylamino-2-pentanol;

2-piperidinemethanol, 3-piperidinemethanol, 4-piperidinemethanol, 2-piperidineethanol, 4-piperidineethanol, 1-pyrrolidino-2-propanol, 1-pyrrolidineethanol, 2- (1-methylpyrrolidine) ethanol, 2- (1-methylpiperidine) methanol, 3- (1-methylpiperidine) methanol, 4- (1-methylpiperidine) methanol, 4- (1-butylpiperidine) methanol, 2- (1-methylpiperidine) ethanol, 1- Piperidine ethanol, 1- (4-hydroxypiperidine) ethanol, 1-piperidinepropanol, 1- (2-methylpiperidine) ethanol, 3-piperidino-1,2-propanediol, 3-morpholino-1,2-propanediol, 1-piperazine Ethanol, alkanol cyclic amine compounds such as 1-piperazine propanol;

Morpholine, 2.6-dimethylmorpholine, 3-morpholinone, 5,6-dimethylmorpholine-2,3-dione, 4-methylmorpholine, 4-ethylmorpholine, 4-n-butylmorpholine, 4-i-butylmorpholine, 4-cyclohexylmorpholine, 4- (1-cyclopenten-1-yl) morpholine, 4- (1-cyclohexen-1-yl) morpholine, 4- (2-methyl-1-propenyl) morpholine, 4- (2-ethyl) -1-butenyl) morpholine, 4-benzylmorpholine, 4- (2-phenylethyl) morpholine, 4-morpholine acetonitrile, 4-morpholine butyronitrile, 2,6-dimethyl-4-morpholine propionitrile, 4-morpholine Valeronitrile, 4- [2- (dimethylamino) ethyl] morpholine, 4 (2-hydroxyethyl) morpholine, 4- (2-hydroxypropyl) morpholine, 4- (3-hydroxypropyl) morpholine, 2,6-dimethyl-4-morpholineethanol, 3- (4-morpholinyl) -1,2 -Propanediol, 4- (2-aminoethyl) morpholine, 3- (4-morpholinyl) -1-propylamine, 4- (2-isocyanoethyl) morpholine, 4-phenyl-3,5-morpholinedione, 4- Phenylmorpholine, 4- (4-piperidinyl) morpholine, 4,4′-methylenedimorpholine, 4- (3-pyridyl) morpholine, 4- (4-pyridyl) morpholine, 4- (2-pyridyl) methylmorpholine, 4 Morpholine compounds such as-(2-pyridyl) ethylmorpholine and 4- (2-thienylmethyl) morpholine ;

2-pyrrolidinol, 3-pyrrolidinol, 2-piperidinol, 3-piperidinol, 4-piperidinol, 1-ethyl-3-pyrrolidinol, 1-methyl-3-pyrrolidinol, 1-methyl-3-piperidinol, 1-methyl-4- Cyclic amine compounds having a hydroxy group such as piperidinol, 1,2,2.6.6-pentamethyl-4-piperidinol, 3- (3-hydroxyphenyl) -1-propylpiperidine, 1-methyl-L-prolinol; Arylalkyl groups such as (1-benzyl-4-piperidino) methanol, 2- (benzylmethylamino) ethanol, 2- (dibenzylamino) ethanol, 2- (benzylmethylamino) ethane-1,1-diol, and the like; An amine compound having a hydroxyalkyl group; 1-benzyl 3-pyrrolidinol, 1-benzyl-3-piperidinol, cyclic amine compound having an arylalkyl group and a hydroxy group such as 1-benzyl-4-piperidinol;

Trimethylamine N-oxide, triethylamine N-oxide, tri-n-propylamine N-oxide, tri-n-butylamine N-oxide, tri-n-octylamine N-oxide, tri- (2-ethylhexyl) amine N-oxide , Triallylamine N-oxide, ethyl (diisopropyl) amine N-oxide, diallyl (methyl) amine N-oxide, diethyl (methyl) amine N-oxide, butyl (dimethyl) amine N-oxide, ethyl (diisopropyl) amine N- Oxide, allyl (dimethyl) amine N-oxide, methyldi (n-octyl) amine N-oxide, (n-hexyl) dimethylamine N-oxide, (2-ethylhexyl) dimethylamine N-oxide, (2-ethylhexyl) diisopropyl A N-oxide, dibutyl (2-ethylhexyl) amine N-oxide, n-heptyl (dimethyl) amine N-oxide, dimethyl (octyl) amine N-oxide, dimethyl (nonyl) amine N-oxide, decyl (dimethyl) amine Trialkylamine N-oxide compounds such as N-oxide, dimethyl (undecyl) amine N-oxide, dodecyl (dimethyl) amine N-oxide, dimethyl (tridecyl) amine N-oxide, dimethyl (octadecyl) amine N-oxide;

2-dimethylaminoethanol N-oxide, 2-diethylaminoethanol N-oxide, 2-dibutylaminoethanol N-oxide, N-methyl-diethanolamine N-oxide, N-ethyl-diethanolamine N-oxide, N-isobutyl-diethanolamine N -Oxide, triethanolamine N-oxide, 1-dimethylamino-2-propanol N-oxide, 3-dimethylamino-1-propanol N-oxide, 3-diethylamino-1-propanol N-oxide, 3-dipropylamino -1-propanol N-oxide, 3-dibutylamino-1-propanol N-oxide, 2-dimethylamino-2-methyl-1-propanol N-oxide, 3-dimethylamino-1,2-propanediol N-oxide 3-diethylamino-1,2-propanediol N-oxide, 3-dipropylamino-1,2-propanediol N-oxide, triisopropanolamine N-oxide, 3-dimethylamino-1-butanol N-oxide, 4 -Alkanolamine N-oxide compounds such as dibutylamino-1-butanol N-oxide, 5-diethylamino-2-pentanol N-oxide;

1-methylpyrrolidine N-oxide, 1- (1-cyclopenten-1-yl) pyrrolidine N-oxide, 1- (3-butyl) pyrrolidine N-oxide, 1- (3-butenyl) pyrrolidine N-oxide, 1- (2-Ethyl-1-butenyl) pyrrolidine N-oxide, 1-pyrrolidineacetonitrile N-oxide, 1-pyrrolidinepropionitrile N-oxide, 1-pyrrolidinebutyronitrile N-oxide, 1-pyrrolidinevaleronitrile N-oxide 3- (2-oxo-1-pyrrolidinyl) propanenitrile N-oxide, 1-vinylpyrrolidine N-oxide, 1- (1-cyclohexenyl) pyrrolidine N-oxide, 4-pyrrolidinopyridine N-oxide, 1- Methylpiperidine N-oxide, 1-ethylpiperidine N-oxide, 1- Til-4-methylpiperidine N-oxide, 1-propyl-4-methylpiperidine N-oxide, 1-butyl-4-methylpiperidine N-oxide, 1- (2-methylpropenyl) piperidine N-oxide, 1-piperidine Acetonitrile N-oxide, 1-piperidinepropionitrile N-oxide, 1-piperidinebutyronitrile N-oxide, 1-piperidinevaleronitrile N-oxide, 1-piperidinepentanenitrile N-oxide, N-cyclohexylpiperidine N-oxide 1-methyl-4-piperidinone N-oxide, 1-ethyl-3-piperidinone N-oxide, 1-ethyl-4-piperidinone N-oxide, 1-propyl-4-piperidinone N-oxide, 1-isopropyl-4 -Piperidinone N-oxide, 1- Cyclic amine N- oxide compound such Sobuchiru piperidinone N- oxide;

1-pyrrolidinyl-2-propanol N-oxide, 2- (1-pyrrolidinyl) propanol N-oxide, (1-methylpyrrolidin-2-yl) ethanol N-oxide, (1-methylpiperidin-2-yl) methanol N -Oxide, (1-methylpiperidin-3-yl) methanol N-oxide, (1-methylpiperidin-4-yl) methanol N-oxide, (1-butylpiperidin-4-yl) methanol N-oxide, (1 -Methylpiperidin-2-yl) ethanol N-oxide, 1-piperidineethanol N-oxide, (4-hydroxypiperidin-1-yl) ethanol N-oxide, 1-piperidinepropanol N-oxide, (2-methylpiperidine- 1-yl) propanol N-oxide, 3-piperidyl-1, - propanediol N- oxide, 3-morpholinyl-1,2-propanediol N- oxide, 1 piperazineethanol N- oxides, alkanol cyclic amine N- oxide compound such as 1-piperazine propanol N- oxide;

4-methylmorpholine N-oxide, 4-ethylmorpholine N-oxide, 4-n-butylmorpholine N-oxide, 4-i-butylmorpholine N-oxide, 4-cyclohexylmorpholine N-oxide, 4- (1-cyclopentene) -1-yl) morpholine N-oxide, 4- (1-cyclohexen-1-yl) morpholine N-oxide, 4- (2-methyl-1-propenyl) morpholine N-oxide, 4- (2-ethyl-1) -Butenyl) morpholine N-oxide, 4-benzylmorpholine N-oxide, 4-phenylethylmorpholine N-oxide, 4-morpholine acetonitrile N-oxide, 4-morpholine butyronitrile N-oxide, 2,6-dimethyl-4 -Morpholine propionitrile N-oxide, 4-morpholine valeroni Ryl N-oxide, 4- [2- (dimethylamino) ethyl] morpholine N-oxide, 2- (morpholin-4-yl) ethanol N-oxide, 1- (morpholin-4-yl) -2-propanol N- Oxide, 3- (morpholin-4-yl) propanol N-oxide, 2,6-dimethyl-4-morpholine ethanol N-oxide, 3- (4-morpholinyl) -1,2-propanediol N-oxide, 4- (2-aminoethyl) morpholine N-oxide, 3- (4-morpholinyl) -1-propanamine N-oxide, 4- (2-isocyanoethyl) morpholine N-oxide, 4-phenyl-3,5-morpholinedione N-oxide, 4-phenylmorpholine N-oxide, 4- (4-piperidinyl) morpholine N-oxide, 4,4 -Methylenedimorpholine N-oxide, 4- (3-pyridyl) morpholine N-oxide, 4- (4-pyridyl) morpholine N-oxide, 4- (pyridin-2-ylmethyl) morpholine N-oxide, 4- (pyridine Morpholine N-oxide compounds such as 2-ylethyl) morpholine N-oxide, 4- (2-thienylmethyl) morpholine N-oxide;

Benzyl (dimethyl) amine N-oxide, benzyl (diethyl) amine N-oxide, tribenzylamine N-oxide, 3-methoxybenzyl (dimethyl) amine N-oxide, 2- (dimethylaminomethyl) phenol N-oxide, 4 -Arylalkylamine N-oxide compounds such as (dimethylaminomethyl) phenol N-oxide, dimethyl-1-phenylethylamine N-oxide;
Arylalkyl cyclic amines N such as 1-benzylpyrrolidine N-oxide, 1-benzylpyrrolidin-3-ol N-oxide, 4-benzyl-1-butylpiperidine N-oxide, 4-benzyl-1-hexylpiperidine N-oxide An oxide compound;
1-ethylpyrrolidin-3-ol N-oxide, 1-methylpyrrolidin-3-ol N-oxide, 1-methylpiperidin-3-ol N-oxide, 1-methylpiperidin-4-ol N-oxide, 1, Hydroxy such as 2,2.6.6-pentamethylpiperidin-4-ol N-oxide, 3- (3-hydroxyphenyl) -1-propylpiperidine N-oxide, 1-methyl-L-prolinol N-oxide A cyclic amine N-oxide compound having a group;

(1-benzylpiperidin-4-yl) methanol N-oxide, 2- (benzylmethylamino) ethanol N-oxide, N, N-dibenzylaminoethanol N-oxide, 2- (benzylmethylamino) ethane-1, Cyclic amine N-oxide compounds having an arylalkyl group and a hydroxyalkyl group, such as 1-diol N-oxide;
Cyclic amine N- having arylalkyl group and hydroxy group such as 1-benzylpyrrolidin-3-ol N-oxide, 1-benzylpiperidin-3-ol N-oxide, 1-benzylpiperidin-4-ol N-oxide An oxide compound is mentioned.

  Preferred are alkanolamine compounds, alkanol cyclic amine compounds, morpholine compounds, trialkylamine N-oxide compounds, arylalkylamine N-oxide compounds, cyclic amine N-oxide compounds, morpholine N-oxide compounds, more preferably An alkanolamine compound, a morpholine compound, a trialkylamine N-oxide compound, and a morpholine N-oxide compound.

More preferably,
2-aminoethanol, 2-methylaminoethanol, 2-ethylaminoethanol, 2-butylaminoethanol, 2- (hydroxymethylamino) ethanol, 1-phenyl-2-aminoethanol, 1-phenyl-2- (N- Methylamino) ethanol, 1-phenyl-2- (N-ethylamino) ethanol, diethanolamine, 1-amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol, 3-amino-2 -Phenylpropanol, 1,3-diamino-2-propanol, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, 2-amino-1-phenyl-1,3-propanediol , Diisopropanolamine, 4-aminobutanol, 4-methylaminobutano 2-dimethylaminoethanol, 2-diethylaminoethanol, 2-dibutylaminoethanol, N-methyl-diethanolamine, N-ethyl-diethanolamine, N-isobutyl-diethanolamine, triethanolamine, 1-dimethylamino-2-propanol, 3-dimethylamino-1-propanol, 3-diethylamino-1-propanol, 3-dipropylamino-1-propanol, 3-dibutylamino-1-propanol, 2-dimethylamino-2-methylpropanol, 3-dimethylamino -1,2-propanediol, 3-diethylamino-1,2-propanediol, 3-dipropylamino-1,2-propanediol,

Morpholine, 2,6-dimethylmorpholine, 4-methylmorpholine, 4-ethylmorpholine, 4-n-butylmorpholine, 4-i-butylmorpholine, 4-cyclohexylmorpholine, 4-benzylmorpholine, 4- (2-phenylethyl) ) Morpholine, 4- [2- (dimethylamino) ethyl] morpholine, 4- (2-hydroxyethyl) morpholine, 4- (2-hydroxypropyl) morpholine, 4- (3-hydroxypropyl) morpholine, 2,6- Dimethyl-4-morpholine ethanol, 3- (4-morpholinyl) -1,2-propanediol, 4- (2-aminoethyl) morpholine, 3- (4-morpholinyl) -1-propylamine, 4-phenylmorpholine, Trimethylamine N-oxide, triethylamine N-oxide, tri n-propylamine N-oxide, tri-n-butylamine N-oxide, tri-n-octylamine N-oxide, triallylamine N-oxide, methyldiethylamine N-oxide, ethyldiisopropylamine N-oxide, diallyl (methyl) Amine N-oxide, diethyl (methyl) amine N-oxide, n-butyl (dimethyl) amine N-oxide, ethyl (diisopropyl) amine N-oxide, allyl (dimethyl) amine N-oxide, 4-methylmorpholine N-oxide 4-ethylmorpholine N-oxide, 4-n-butylmorpholine N-oxide, 4-i-butylmorpholine N-oxide, 4-cyclohexylmorpholine N-oxide, 4-benzylmorpholine N-oxide, 4-phenylmorpholine N -Oxy Benzyl (dimethyl) amine N-oxide, benzyl (diethyl) amine N-oxide, tribenzylamine N-oxide, dimethyl-1-phenylethylamine N-oxide, 2- (benzylmethylamino) ethanol N-oxide, N, N-dibenzylaminoethanol N-oxide is mentioned.

  Particularly preferably, 2-aminoethanol, 2-methylaminoethanol, diethanolamine, 1,3-diamino-2-propanol, 2-dimethylaminoethanol, 2-diethylaminoethanol, N-methyl-diethanolamine, triethanolamine, morpholine, 4-methylmorpholine, 4-ethylmorpholine, trimethylamine N-oxide, triethylamine N-oxide, tri-n-butylamine N-oxide, ethyldiisopropylamine N-oxide, 4-methylmorpholine N-oxide, benzyl (dimethyl) amine N -Oxide, tribenzylamine N-oxide, 2- (benzylmethylamino) ethanol N-oxide, N, N-dibenzylaminoethanol N-oxide.

The particularly preferred compound groups listed above exhibit particularly excellent effects in improving the yield and purity of the dye. These compounds may be used as they are commercially available, or known methods (for example, alkanolamine compounds are US Pat. No. 2,194,294, Pharmaceutical Journal, 1971, 91 (1), 134, etc. N-oxide compounds can be easily synthesized by US Pat. No. 4,748,275, J. Soc. Cosmet. Chem. Jpn. 1994, 28 (1), 57, etc.). In addition, these compounds may be used after being isolated, and amine N-oxide compounds may be used as they are in the oxidative condensation reaction without being taken out after preparation.
Among these, alkanolamine compounds are generally widely used as raw materials for synthetic detergent neutralizers, foam stabilizers, agricultural chemicals, surfactants, and additives such as emulsifiers, cosmetics, lubricants, and inks for ink jet recording. It is preferable because inexpensive industrial raw materials are available.

The compound of the general formula (4) or (5) in the present invention is considered to act as a coupler activation or deoxidizer in the reaction system. The amount used varies depending on the coupler used, but is usually 3 to 20 moles per mole of coupler. When the p-phenylenediamine derivative is an addition salt such as sulfate or hydrochloride, the amount of the compound represented by general formula (4) or (5) must be determined in consideration of the neutralization of the addition salt. There is.
In addition, the compound of the general formula (4) or (5) in the present invention can be used in addition salts such as sulfates, hydrochlorides and phosphates in the presence of a neutralized base in advance. It is.

As the reaction solvent used in the present invention, water, an organic solvent, or a mixed solvent of water and an organic solvent can be used, and the compound of the general formula (4) or (5) is used as it is as a reaction solvent. Is also possible.
When using an organic solvent, it may be used alone or in a mixed solvent using a plurality of organic solvents. In addition, any water-soluble or water-insoluble general organic solvent can be used, and in the case of a mixed solvent, a single-layer system or a multilayer system may be used.

  Examples of the water-soluble organic solvent used in the present invention include alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol; acetone, ethyl methyl ketone, methyl isopropyl ketone, diisopropyl ketone, and methyl isobutyl ketone. , Ketone solvents such as diisobutyl ketone; ether solvents such as diethyl ether, diisopropyl ether, methyl-tert-butyl ether, tetrahydrofuran, dioxane; dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, tetramethylurea, 1, Amide solvents such as 3-dimethylimidazolinone; Sulfur-containing solvents such as dimethyl sulfoxide and sulfolane; Nitrile solvents such as acetonitrile; Ether ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-iso-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, ethylene glycol mono-iso-butyl ether acetate, ethylene glycol mono-tert-butyl ether Acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene Recall monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and a glycol-based solvents such as diethylene glycol mono -n- butyl ether acetate.

Examples of the water-insoluble organic solvent used in the present invention include halogen solvents such as methylene chloride, chloroform and chlorobenzene; ester solvents such as methyl acetate, ethyl acetate, isopropyl acetate and butyl acetate; toluene, xylene, mesitylene, tetrahydronaphthalene and the like. And an aromatic solvent such as ethylene glycol diacetate, ethylene glycol distearate, ethylene glycol diacrylate, diethylene glycol diacetate, and diethylene glycol diacrylate.
In the present invention, water or an alcohol solvent, a glycol solvent or a derivative thereof, a ketone solvent, an ether solvent, or a nitrile solvent is preferably used alone or in combination with several solvents, an alcohol solvent, a glycol solvent More preferred is at least one organic solvent selected from solvents or derivatives thereof, or ketone solvents, or a mixed solvent of these organic solvents and water.

When a mixed solvent of an organic solvent and water is used, the ratio can be arbitrarily set depending on the coupler to be used, but the water content in the total reaction solvent is preferably 30 (V / V)% or more, more preferably 50 The range is from (V / V)% to 90 (V / V)%. When the water content is within this range, the yield and purity are both good and preferable.
The amount of the reaction solvent used is not particularly limited, but is usually 2000 parts by weight or less with respect to 100 parts by weight of the coupler. Preferably it is 1-1500 weight part, More preferably, it is 2-1000 weight part, More preferably, it is 5-800 weight part. By using a smaller amount at 2000 parts by weight or less, productivity is improved, and an azomethine dye or indoaniline dye can be produced at low cost.

The oxidizing agent used in the present invention is not particularly limited as long as it oxidizes the p-phenylenediamine derivative. For example, double salt (OXONE) composed of potassium hydrogen persulfate, potassium hydrogen sulfate, potassium sulfate, etc .; persulfate such as potassium persulfate, sodium persulfate, ammonium persulfate; ferricia such as potassium ferricyanate, sodium ferricyanate Examples thereof include hypochlorites such as potassium hypochlorite and sodium hypochlorite; silver nitrate and the like. Of these, persulfates are preferred, with ammonium persulfate being particularly preferred. In general, the reaction proceeds efficiently when the oxidizing agent is prepared in an aqueous solution and dropped into the system. Moreover, it is preferable to perform the dripping speed | rate of oxidizing agent aqueous solution for a short time, suppressing the heat_generation | fever in a reaction system under cooling.
Although the usage-amount of the oxidizing agent in this invention changes with p-phenylenediamine derivatives to be used, it is normally 1-10 mol with respect to 1 mol of couplers, Preferably it is 1-4 mol.

The reaction temperature of the oxidative condensation reaction of the present invention is 60 ° C. or lower, preferably 0 to 40 ° C. The reaction time is preferably 5 minutes to 2 hours. The reaction can be performed under atmospheric pressure, for example, under a pressure of 0.5 to 2 atmospheres.
After completion of the reaction, the precipitated pigment is filtered off, or water or a poor solvent is added to the reaction solution, and the precipitated target product is filtered off. Moreover, you may introduce | transduce an extraction process, a concentration process, a crystallization process, etc. according to a condition.
In addition, the target product may be washed or recrystallized with water, alcohol, acetone, ethyl acetate, toluene, hexane, etc., if necessary, silica gel, alumina, zeolite, activated clay, montmorillonite clay mineral acidic clay, activated carbon, etc. It can be purified by adsorption purification using an adsorbent, vacuum distillation, sublimation or the like.
In the case of adsorption purification, the contact method (contact filtration method) in which the dye dissolved in the organic solvent and the adsorbent are mixed, stirred and brought into contact with each other and the adsorbent packed in the adsorption tower filled with the organic solvent For example, a percolation method (circulation filtration method) for adsorbing and purifying by passing a dye dissolved in the solution can be used. After contact, the dye solution and the adsorbent are separated by a filter, and a purified product is obtained by a conventional method such as crystallization or distillation. The adsorption process may be performed repeatedly, or may be performed alternately with various adsorbents. It is also possible to combine two or more purification methods.

An azomethine dye or an indoaniline dye can be synthesized by the above-described synthesis method of the present invention. Specific examples (dyes A-1 to A-10, B-1 to B-12, C-1 to C-68) of azomethine dyes or indoaniline dyes are shown below, but are not limited to the following examples. Absent.
In specific examples, Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group. The wavy line represents a bond, and for example, Compound C-65 has the following structure.

The method of the present invention will be described below with reference to examples, but the present invention is not limited thereto. The purity was evaluated by high performance liquid chromatography (abbreviated as HPLC).
The HPLC purity of the azomethine dyes (A) and (B) was evaluated under the following conditions.
Column: CAPCELL-PACK C8 DD,
Detection UV: 254 nm, flow rate 1.0 ml / min,
Eluent: methanol / water = 85/15 (V / V),
Buffering agents: triethylamine 0.1 (V / V)% and acetic acid 0.1 (V / V)%.
The HPLC purity of the indoaniline dye (C) was evaluated under the following conditions.
Column: YMC-PACK A-312,
Detection UV: 254 nm, flow rate 1.0 ml / min,
Eluent: methanol / water = 90/10 (V / V)
Buffer: Triethylamine 0.2 (V / V)% and acetic acid 0.2 (V / V)%.

Example 1 Synthesis of Dye A-1
In a mixed solvent of 20 ml of acetone and 40 ml of water, 13.8 g of (2E) -N- [5- (acetylamino) -2-chlorophenyl] -2-chloro-3-hydroxy-4,4-dimethylpent-2-enamide is used. (40.0 mmol) and 6.9 g (48.0 mmol) of N, N-diethylbenzene-1,4-diamine hydrochloride were added, and 14.6 g (160.0 mmol) of N-methyl-diethanolamine was added while cooling in an ice bath. It was dripped. After cooling, an aqueous solution prepared by dissolving 26.3 g (80.0 mmol) of potassium ferricyanate in 40 ml of water was added dropwise thereto over 3 hours. The mixture was stirred at an internal temperature of 20 to 25 ° C. for 1 hour, and crystals precipitated after completion of the reaction were separated by filtration. The obtained crystals were washed with water and isopropyl alcohol, and dried to obtain 18.4 g of the desired product (crude yield 97.5%). The HPLC purity of the crude crystals was 99.3%.

Examples 2-30
In Example 1, it carried out on the conditions similar to Example 1 except having changed N-methyl- diethanolamine into the compound shown in Table 1.

Comparative Examples 1-24
In Example 1, it carried out on the conditions similar to Example 1 except having changed N-methyl- diethanolamine into the compound shown in Table 1. The results of Examples 1 to 30 and Comparative Examples 1 to 24 are shown in Table 1.

Example 31 Synthesis of Dye A-3
19.8 g (40.0 mmol) of N, N-dibutyl-4-{[(2E) -2-chloro-3-hydroxy-3- (4-methoxyphenyl) prop-2-enoyl] amino} benzamide as a coupler, Using 13.0 g (48.0 mmol) of N, N-dibutyl-2-methylbenzene-1,4-diamine hydrochloride as the p-phenylenediamine derivative, the other raw materials used, the amount used, and the operation were the same as in Example 1. The target product was 27.1 g (crude yield 98.2%). The HPLC purity of the crude crystals was 99.3%.

Examples 32-59
The same procedure as in Example 31 was performed except that N-methyl-diethanolamine was changed to the compounds shown in Table 2 in Example 31.

Comparative Examples 25-48
The same procedure as in Example 31 was performed except that N-methyl-diethanolamine was changed to the inorganic base and amine compound shown in Table 2 in Example 31. Table 2 shows the results of Examples 31 to 59 and Comparative Examples 25 to 48.

Example 60 Synthesis of Dye A-6
7.4 g (40.0 mmol) of (2E) -2-chloro-3-hydroxy-3- (2-thienyl) acrylonitrile as a coupler, p-phenylenediamine derivative to 4-piperidin-1-yl-phenylamine hydrochloride 10 0.2 g (48.0 mmol) was used, and other raw materials used, the amount used and the operation were the same as in Example 1 to obtain 12.7 g of the desired product (crude yield 98.5%). The HPLC purity of the crude crystals was 99.2%.

Examples 61-88
In Example 60, it carried out on the conditions similar to Example 60 except having changed N-methyl- diethanolamine into the compound shown in Table 3.

Comparative Examples 49-72
In Example 60, it carried out on the conditions similar to Example 60 except having changed N-methyl- diethanolamine into the inorganic base and amine compound which are shown in Table 3. Table 3 shows the results of Examples 60 to 88 and Comparative Examples 49 to 72.

Example 89 Synthesis of dye B-3
To a mixed solvent of 10 ml of propylene glycol monomethyl ether and 50 ml of water, 17.1 g (160.0 mmol) of triethanolamine was added, and further ethyl 4-chloro-5-hydroxy-1-phenyl-1H-pyrazole-3-carboxylate 9 .3 g (40.0 mmol) was added. After cooling, a solution obtained by dissolving 10.1 g (56.8 mmol) of N, N-diethyl-2-methylbenzene-1,4-diamine in 60 ml of acetone and 21.6 g (80.0 mmol) of potassium persulfate were added thereto. An aqueous solution dissolved in 50 ml of water was added dropwise over 3 hours. The mixture was stirred at an internal temperature of 20 to 25 ° C. for 1 hour, and the precipitated crystals were separated by filtration. The obtained crystals were washed with water and methanol, respectively, and dried to obtain 14.5 g of the desired product (crude yield 97.6%). The HPLC purity of the crude crystals was 99.4%.

Examples 90-118
The test was performed under the same conditions as in Example 89, except that the triethanolamine in Example 89 was changed to the compounds shown in Table 4.

Comparative Examples 73-96
In Example 89, it carried out on the conditions similar to Example 89 except having changed triethanolamine into the inorganic base and amine compound which are shown in Table 4. Examples 89-118
Table 4 shows the results of Comparative Examples 73 to 96.

Example 119 Synthesis of Dye B-8
10.1 g (40.0 mmol) of 4-chloro-5-hydroxy-N-methyl-1-pyridin-2-yl-1H-pyrazole-3-carboxamide as a coupler, 2-[(4- Aminophenyl) methylamino] ethanol hydrochloride (9.7 g, 48.0 mmol) was used, and other starting materials, amounts and operations were the same as in Example 89, and 15.1 g of the desired product (crude yield 99.0%) ) The HPLC purity of the crude crystals was 99.0%.

Examples 120-148
The test was performed under the same conditions as in Example 119, except that the triethanolamine in Example 119 was changed to the compounds shown in Table 5.

Comparative Examples 97-120
In Example 119, it carried out on the conditions similar to Example 119 except having changed triethanolamine into the inorganic base and amine compound which are shown in Table 5. Table 5 shows the results of Examples 119 to 148 and Comparative Examples 97 to 120.

Example 149 Synthesis of Dye B-12
10.8 g (40.0 mmol) of N- (4-chloro-5-hydroxy-1-isopropyl-1H-pyrazol-3-yl) -2-furamide as a coupler, and 2,2 ′-[ Using 11.8 g (48.0 mmol) of (4-amino-3-methylphenyl) imino] diethanol hydrochloride, the other starting materials, amounts and operations were the same as in Example 89, and 17.4 g (crude crude) was obtained. Yield 98.4%). The HPLC purity of the crude crystals was 99.2%.

Examples 150-178
The test was conducted under the same conditions as in Example 149, except that the triethanolamine in Example 149 was changed to the compounds shown in Table 6.

Comparative Examples 121-144
In Example 149, it carried out on the conditions similar to Example 149 except having changed triethanolamine into the inorganic base and amine compound which are shown in Table 6. Table 6 shows the results of Examples 149 to 179 and Comparative Examples 121 to 144.

Example 179 Synthesis of dye C-6
To a mixed solvent of 35 ml of methanol and 35 ml of water, 14.3 g (160.0 mmol) of 2-dimethylaminoethanol was added dropwise, and further 9.4 g of N- (3,5-dichloro-2-hydroxy-4-methylphenyl) acetamide. (40.0 mmol) was added and dissolved. After cooling, 9.2 g (48.0 mmol) of N, N-dipropylbenzene-1,4-diamine was dissolved in 70 ml of methanol, and 18.3 g (80.0 mmol) of ammonium persulfate was dissolved in 70 ml of water. Each of the aqueous solutions was added dropwise over 3 hours. The mixture was stirred at an internal temperature of 20 to 25 ° C. for 30 minutes, and the precipitated crystals were separated by filtration. The obtained crystals were washed with water and methanol, respectively, and dried to obtain 14.5 g of the desired product (crude yield 93.4%). The HPLC purity of the crude crystals was 99.0%.

Examples 180-207
The same conditions as in Example 179 were used, except that 2-dimethylaminoethanol of Example 179 was changed to the compounds shown in Table 7.

Comparative Examples 145 to 167
The same procedure as in Example 179 was performed except that 2-dimethylaminoethanol was changed to the inorganic base and amine compound shown in Table 7 in Example 179. Table 7 shows the results of Examples 179 to 207 and Comparative Examples 145 to 167.

Example 208 Synthesis of Dye C-53
N- (3,5-dichloro-4-ethyl-2-hydroxyphenyl) benzamide 12.4 g (40.0 mmol) as a coupler, p-phenylenediamine derivative with N, N-dipropylbenzene-1,4-diamine 9 0.2 g (48.0 mmol) was used, and other materials used, amounts used, and operations were the same as in Example 179, to obtain 18.5 g of the desired product (crude yield 99.5%). The HPLC purity of the crude crystals was 99.2%.

Examples 209-237
The test was performed under the same conditions as in Example 208, except that 2-dimethylaminoethanol of Example 208 was changed to the compounds shown in Table 8.

Comparative Examples 168-191
In Example 208, it carried out on the conditions similar to Example 208 except having changed 2-dimethylaminoethanol into the inorganic base and amine compound which are shown in Table 8. Table 8 shows the results of Examples 208 to 237 and Comparative Examples 168 to 191.

Example 238 Synthesis of Dye C-65
9.4 g (40.0 mmol) of N- (4-chloro-1-hydroxy-2-naphthyl) acetamide as a coupler, 2-methoxy-N, N-dipropylbenzene-1,4-diamine as a p-phenylenediamine derivative 10.7 g (48.0 mmol) was used, and other raw materials used, the amount used, and the operation were the same as in Example 179, to obtain 15.1 g of the desired product (crude yield 93.6%). The HPLC purity of the crude crystals was 99.6%.

Examples 239-266
The test was performed under the same conditions as in Example 238, except that 2-dimethylaminoethanol of Example 238 was changed to the compounds shown in Table 9.

Comparative Examples 192 to 215
In Example 238, it carried out on the conditions similar to Example 238 except having changed 2-dimethylaminoethanol into the inorganic base and amine compound which are shown in Table 9. Table 9 shows the results of Examples 238 to 266 and Comparative Examples 192 to 215.

Example 267 Synthesis of Dye A-1
29.7 g (160.0 mmol) of tri (n-butyl) amine was added to 30 ml of isopropyl alcohol, and the temperature was raised to an internal temperature of 65 ° C. While maintaining the internal temperature, 21.8 g (224.0 mmol) of 35% aqueous hydrogen peroxide was added dropwise over 15 minutes, and stirred for 5 hours to prepare tri (n-butyl) amine N-oxide. The preparation was cooled, 30 ml of water, (2E) -N- [5- (acetylamino) -2-chlorophenyl] -2-chloro-3-hydroxy-4,4-dimethylpent-2-enamide 13.8 g (40.0 mmol), N, N-diethylbenzene-1,4-diamine hydrochloride 6.9 g (48.0 mmol) was added. While cooling, an aqueous solution in which 26.3 g (80.0 mmol) of potassium ferricyanate was dissolved in 40 ml of water was added dropwise over 3 hours. The mixture was stirred at an internal temperature of 20 to 25 ° C. for 1 hour, and crystals precipitated after completion of the reaction were separated by filtration. The obtained crystals were washed with water and isopropyl alcohol and dried to obtain 18.2 g of the desired product (crude yield 96.2%). The HPLC purity of the crude crystals was 99.0%.

Example 268 Synthesis of Dye B-3
20.7 g (160.0 mmol) of ethyl (diisopropyl) amine was added to 30 ml of ethanol, and the temperature was raised to an internal temperature of 65 ° C. While maintaining the internal temperature, 21.8 g (224.0 mmol) of 35% hydrogen peroxide solution was added dropwise over 15 minutes and stirred for 5 hours to prepare ethyl (diisopropyl) amine N-oxide. After cooling, 30 ml of water and 10.1 g (56.8 mmol) of N, N-diethyl-2-methylbenzene-1,4-diamine were added and cooled. there,
A solution obtained by dissolving 9.3 g (40.0 mmol) of ethyl 4-chloro-5-hydroxy-1-phenyl-1H-pyrazole-3-carboxylate in 60 ml of acetone and 21.6 g (80.0 mmol) of potassium persulfate were added. An aqueous solution dissolved in 50 ml of water was simultaneously added dropwise over 3 hours. The mixture was stirred at an internal temperature of 20 to 25 ° C. for 1 hour, and the precipitated crystals were separated by filtration. The obtained crystals were washed with water and methanol, respectively, and dried to obtain 14.2 g (crude yield 95.8%) of the desired product. The HPLC purity of the crude crystals was 98.9%.

Example 269 Synthesis of Dye C-6
Triethylamine (16.2 g, 160.0 mmol) was added to methanol (35 ml), and the internal temperature was raised to 65 ° C. While maintaining the internal temperature, 21.8 g (224.0 mmol) of 35% aqueous hydrogen peroxide was added dropwise over 15 minutes, and then stirred for 5 hours to prepare triethylamine N-oxide. The triethylamine N-oxide preparation was cooled, and 30 ml of water and 9.4 g (40.0 mmol) of N- (3,5-dichloro-2-hydroxy-4-methylphenyl) acetamide were added and stirred. Next, a solution obtained by dissolving 9.2 g (48.0 mmol) of N, N-dipropylbenzene-1,4-diamine in 70 ml of methanol and an aqueous solution obtained by dissolving 18.3 g (80.0 mmol) of ammonium persulfate in 70 ml of water were simultaneously used. Each was added dropwise over 3 hours. The mixture was stirred at an internal temperature of 20 to 25 ° C. for 30 minutes, and the precipitated crystals were separated by filtration. The obtained crystals were washed with water and methanol, respectively, and dried to obtain 14.2 g (crude yield 91.2%) of the desired product. The HPLC purity of the crude crystals was 98.7%.

Example 270 Synthesis of Dye A-8
29.7 g (160.0 mmol) of tri (n-butyl) amine was added to 30 ml of isopropyl alcohol, and the temperature was raised to an internal temperature of 65 ° C. While maintaining the internal temperature, 21.8 g (224.0 mmol) of 35% aqueous hydrogen peroxide was added dropwise over 15 minutes, and then stirred for 5 hours to prepare tri (n-butyl) amine N-oxide. The prepared solution was cooled, and 10.6 g (48.0 mmol) of N, N-diisobutylbenzene-1,4-diamine was added thereto to obtain a p-phenylenediamine derivative solution.
30 ml of water and 14.3 g (40.0 mmol) of (2E) -2-chloro-N- (2,4-dichlorophenyl) -3-hydroxy-3- (4-methylphenyl) acrylamide were added to 30 ml of isopropyl alcohol. While cooling, the previous p-phenylenediamine derivative solution and an aqueous solution prepared by dissolving 26.3 g (80.0 mmol) of potassium ferricyanate in 40 ml of water were simultaneously added dropwise over 3 hours. The mixture was stirred at an internal temperature of 20 to 25 ° C. for 1 hour, and crystals precipitated after completion of the reaction were separated by filtration. The obtained crystal was washed with water and isopropyl alcohol and dried to obtain 20.7 g of the desired product (crude yield 96.2%). The HPLC purity of the crude crystals was 99.0%.

Example 271 Synthesis of Dye B-4
20.7 g (160.0 mmol) of ethyl (diisopropyl) amine was added to 30 ml of ethanol, and the internal temperature was raised to 65 ° C. While maintaining the internal temperature, 21.8 g (224.0 mmol) of 35% aqueous hydrogen peroxide was added dropwise over 15 minutes, and then stirred for 5 hours to prepare ethyl (diisopropyl) amine N-oxide. The prepared solution was cooled, and 9.5 g (40.0 mmol) of 4-chloro-3- (dimethylamino) -1-phenyl-1H-pyrazol-5-ol was added thereto.
A solution prepared by dissolving 30 ml of ethanol, 30 ml of water, and 9.3 g (56.8 mmol) of N, N-diethylbenzene-1,4-diamine in 60 ml of acetone was added to another container and cooled. The solution prepared previously and an aqueous solution obtained by dissolving 21.6 g (80.0 mmol) of potassium persulfate in 50 ml of water were simultaneously added dropwise over 3 hours. The mixture was stirred at an internal temperature of 20 to 25 ° C. for 1 hour, and the precipitated crystals were separated by filtration. The obtained crystals were washed with water and methanol, respectively, and dried to obtain 13.9 g (crude yield: 95.8% by mass) of the desired product. The HPLC purity of the crude crystals was 98.9%.

  From the results of Examples 1 to 271 and Comparative Examples 1 to 215, the method using the compound of the present invention has a higher yield of the target azomethine dye or indoaniline dye than the conventional method using a general base during the reaction. And can be synthesized with high purity and is extremely useful as an industrial production method.

Claims (4)

In the method for producing an azomethine dye or indoaniline dye, which comprises oxidizing and condensing a compound represented by any one of the following general formulas (1) to (3) and a p-phenylenediamine derivative in the presence of an oxidizing agent, the following general formula (4 Or azomethine dye or indoaniline dye, which reacts in the presence of the compound represented by (5) or (5).

Where
R1 represents an alkyl group, an aryl group, or a heterocyclic residue.
R2 represents a carbamoyl group or a cyano group.
R3 is an alkyl group, aryl group, carbamoyl group, sulfamoyl group, amino group, alkylcarbonylamino group, arylcarbonylamino group, heterocyclic carbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group Or a heterocyclic residue.
R4 represents an alkyl group, an aryl group, or a heterocyclic residue.
R5 to R8 are each independently a hydrogen atom, alkyl group, aryl group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, heterocyclic carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group Sulfamoyl group, amino group, alkylcarbonylamino group, arylcarbonylamino group, heterocyclic carbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group Represents a heterocyclic sulfonylamino group, a heterocyclic residue, or a halogen atom. R5 and R6, and R7 and R8 may combine to form a ring having 5 to 8 carbon atoms.
Q represents a hydrogen atom or a leaving group.

Where
R9 to R11 each independently represent a hydrogen atom, an alkyl group, an arylalkyl group, a hydroxyalkyl group, an aminoalkyl group, or an alkenyl group.
X represents a nitrogen atom or N → O. However, when X is a nitrogen atom, at least one of R9 to R11 is a hydroxyalkyl group.
A represents an oxygen atom or -C (R12) (R13)-.
n represents an integer of 2 to 6, and a plurality of A may be the same or different.
Y represents —N (R14) — or —N [(R15) → O] —.
R12 to R14 each independently represents a hydrogen atom, an alkyl group, an arylalkyl group, an aminoalkyl group, a cyanoalkyl group, a hydroxyalkyl group, an alkenyl group, an aryl group, a hydroxy group, an oxo group, or a heterocyclic residue. . R15 represents an alkyl group, an arylalkyl group, an aminoalkyl group, a cyanoalkyl group, a hydroxyalkyl group, an alkenyl group, an aryl group, or a heterocyclic residue.
However, in General formula (5), at least one of A is an oxygen atom, or it has a hydroxyalkyl group or a hydroxy group as at least one of R12-R14, or Y is -N [(R15). → O] −.   The azomethine dye according to claim 1, wherein the compound represented by the general formula (4) or the general formula (5) is an alkanolamine compound, a morpholine compound, a trialkylamine N-oxide compound, or a morpholine N-oxide compound. Or the manufacturing method of an indoaniline pigment | dye.   The method for producing an indoaniline dye according to claim 1 or 2, wherein the compound represented by the general formula (3) and a p-phenylenediamine derivative are oxidatively condensed.   The oxidative condensation is performed in the presence of at least one organic solvent selected from alcohol solvents, glycol solvents or derivatives thereof, or ketone solvents, or a mixed solvent of these organic solvents and water. A process for producing an azomethine dye or indoaniline dye according to any one of.