JP2003012953A - Preparation method for azomethine colorant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method capable of efficiently preparing an azomethine colorant without the necessity for heat. SOLUTION: This method for preparing an azomethine colorant comprises exposing an azomethine colorant precursor represented by general formula 1 (wherein Ar is an optionally substituted aromatic or heterocyclic ring; X is a divalent group; and Cp is a coupler residue optionally being cyclic), e.g. one represented by formula 10, to light.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for forming an azomethine dye using a heat-stable azomethine dye precursor.

[0002]

2. Description of the Related Art Azomethine dyes have excellent hue, heat resistance, and
It has light fastness and a high molecular extinction coefficient, and is extremely widely used as a dye for image formation in conventional silver salt color photography, and also occupies an important position in the field of dyes and pigments. As a method of forming this azomethine dye, as in a silver salt color photograph, a reducing paraphenylenediamine derivative called a coloring reagent or a paraaminophenol derivative is oxidized to form a phenol derivative, a naphthol derivative, a 5-pyrazolone derivative, or acetanilide. There is known a method of synthesizing by reacting with a proton-dissociative compound such as a derivative and benzenes having an electron-donating group such as N, N-dialkylaniline derivative (these are generally called couplers). Also known is a method of forming an azomethine dye by reacting a coupler with a color-forming reagent precursor which is stable against oxygen in the air (Japanese Patent Laid-Open No. 2000-2000).
-273337).

On the other hand, a method for forming an azomethine dye using an azomethine dye precursor which does not rely on a coupling reaction with a coupler is also known. For example, WO / 00978 describes an azomethine dye precursor that forms an azomethine dye by heating. Also, WO94 / 220
52 describes an azomethine dye precursor which is oxidized by an oxidizing agent such as a silver salt to form an azomethine dye. Further, JP-A-2000-281925 describes an azomethine dye precursor which forms an azomethine dye by the action of an electrophile. However, the above methods require heat alone, or heat and an oxidant, an electrophile, and a reaction accelerator such as a base, and there is a problem that a colorant (stain) other than the azomethine dye is easily generated. there were.

[0004]

Therefore, the present invention has been made in view of the above problems, and provides a method for forming an azomethine dye capable of efficiently forming an azomethine dye without requiring heat. It is an object of the present invention to achieve the object.

[0005]

Means for solving the problems Means for solving the above problems are as follows. <1> A method for forming an azomethine dye, which comprises irradiating an azomethine dye precursor with light to form an azomethine dye. <2> The azomethine dye forming method according to <1>, wherein the azomethine dye precursor is represented by the following general formula (1).

[0006]

[Chemical 5]

In the general formula (1), Ar represents an aromatic ring or a heterocycle which may have a substituent, and X represents a divalent group connecting a carbon atom and a nitrogen atom. Cp represents a coupler residue, which may or may not form a ring. <3> in general formula (1) wherein -X- ^{is, -Q 1 - (Q 2)} l
- (Q ³⁾ _m - is a is azomethine dye forming method according to ^{<2> - (Q 4)} n -Q 5. Q ¹ is a group bonded to a carbon atom, Q ⁵ is a group bonded to a nitrogen atom, and Q ¹ , Q ² ,
Q ³ , Q ⁴ , and Q ⁵ each represent a divalent group, and are 1, m, and n.
Represents 0 or 1, respectively.

<4> -Q ¹ -is -S- <3>
The method for forming an azomethine dye described in 1. <5> -Q ⁴ - is -NH -, - Q ⁵ - is -C (= O) -
The method for forming an azomethine dye according to <3> or <4>. <6> The azomethine dye forming method according to <1>, wherein the azomethine dye precursor is represented by the following general formula (2).

[0009]

[Chemical 6]

In the general formula (2), Ar represents an optionally substituted aromatic ring or heterocycle, Cp represents a coupler residue, and L represents a protecting group. <7> The azomethine dye forming method according to <1>, wherein the azomethine dye precursor is represented by the following general formula (3).

[0011]

[Chemical 7]

In the general formula (3), Ar represents an optionally substituted aromatic ring or heterocyclic ring, and Cp represents a coupler residue. L ¹ represents a protecting group, L ² represents a leaving group, or a protecting group L ¹ is deprotected after being deprotected desorbing after the L ¹ is deprotected. <8> L in the general formula (2) or L ¹ in the general formula (3) is represented by the following structural formula (a) <
6> or <7>, the azomethine dye forming method.

[0013]

[Chemical 8]

In the structural formula (a), R ^a represents a hydrogen atom or a substituent, which may be the same or different.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION First, an azomethine dye precursor used in the azomethine dye forming method of the present invention will be described. Examples of the azomethine dye precursor used in the azomethine dye forming method of the present invention include azomethine dye precursors represented by the following general formulas (1) to (3).

[0016]

[Chemical 9]

In the general formula (1), Ar represents an aromatic ring or a heterocycle which may have a substituent, and X represents a divalent group connecting a carbon atom and a nitrogen atom. Cp represents a coupler residue, which may or may not form a ring.

[0018]

[Chemical 10]

In the general formula (2), Ar represents an aromatic ring or a heterocyclic ring which may have a substituent, Cp represents a coupler residue, and L represents a protecting group.

[0020]

[Chemical 11]

In the general formula (3), Ar represents an optionally substituted aromatic ring or heterocyclic ring, and Cp represents a coupler residue. L ¹ represents a protecting group, L ² represents a leaving group, or a protecting group L ¹ is deprotected after being deprotected desorbing after the L ¹ is deprotected.

The azomethine dye precursors represented by the general formulas (1) to (3) will be described in detail below. As Ar in the general formulas (1) to (3), the following structural formula (1)
And a group represented by.

[Chemical 12]

In the above structural formula (1), R ¹¹ is hydrogen atom, alkyl group, aryl group, halogen atom, cyano group, nitro group, SO ₃ H, heterocyclic group, NR ¹³ R ¹⁴ , OR ¹⁵ , CO ₂
H, SR ¹⁵ , COR ¹⁶ , CO ₂ R ¹⁶ , SO ₂ R ¹⁶ , SOR
¹⁶ , CONR ¹⁷ R ¹⁸ and SO ₂ NR ¹⁷ R ¹⁸ are represented. R ¹¹ is preferably NR ¹³ R ¹⁴ . R ¹³ and R ¹⁴ represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group,
R ¹⁵ is a hydrogen atom, COR ¹⁶ , CO ₂ R ¹⁶ , SO ₂ R ¹⁶ , C
ONR ¹⁷ R ¹⁸ represents an alkyl group or an aryl group, R ¹⁶ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ¹⁷ or R ¹⁸ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Represents a group.

R ¹³ and R ¹⁴ are preferably a hydrogen atom, an alkyl having 1 to 30 carbon atoms or an aryl having 6 to 20 carbon atoms, specifically, for example, hydrogen, methyl, ethyl, propyl, butyl, octyl, octadecyl. , Hydroxyethyl, methanesulfonylaminoethyl, phenoxyethyl, cyanoethyl, benzoyloxyethyl, cyclohexyl, phenyl, tolyl, methoxyphenyl, benzyl and the like. NR ¹³ R ¹⁴ is R ¹³ and R ¹⁴ ,
It may form a ring which may contain a hetero atom such as O, S and N, or may form a ring together with the phenyl ring substituted with NR ¹³ R ¹⁴ . R ¹⁵ is a hydrogen atom, or COR ¹⁶ having 1 to 40 carbon atoms, CO ₂ R ¹⁶ ,
SO ₂ R ¹⁶ , CONR ¹⁷ R ¹⁸ , alkyl and aryl are preferable, and specific examples thereof include a hydrogen atom, methyl, ethyl, octyl, benzyl, phenyl, acetyl, benzoyl, ethoxycarbonyl, phenylsulfonyl and dibutylaminocarbonyl. To be The above S
O ₃ H, CO ₂ H, and OH may be salified.

In the structural formula (1), R ¹² represents the same group as R ¹¹ . R ¹¹ and R ¹² may be linked to form a ring. When R ¹¹ and R ¹² have dissociative protons such as OH, CO ₂ H, and SO ₃ H, various inorganic cations,
A salt may be formed with an organic cation such as a tetraalkylammonium cation.

Examples of Ar in the above general formulas (1) to (3) include heterocyclic groups. The heterocyclic group may have a substituent, pyridine, pyrimidine, triazine, pyridazine, pyrazine, furan, thiophene, pyrrole, pyrazole, triazole, isoxazole,
Examples include isothiazole, imidazole, oxazole, thiazole and tetrazole. As the substituent, R
^The groups represented by ¹¹ and R ¹² can be mentioned.

The alkyl group, aryl group and heterocyclic group mentioned for R ^{11 to} R ¹⁸ may further have a substituent, and the substituent may be an alkyl group, an aryl group, a hydroxy group or a nitro group. , Cyano group, halogen group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group,
Amino group, alkylamino group, dialkylamino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, heterocyclic group, arylamino group, diarylamino group, arylalkyl Examples thereof include amino group, alkoxy group and aryloxy group.

In the above general formulas (1) to (3), Ar may be condensed with an aromatic ring or a heterocycle. The alkyl group contained in Ar may be saturated, unsaturated, or cyclic.

Cp in the above general formulas (1) to (3) represents a coupler residue. As these couplers, all known couplers used in the field of silver salt photography, diazo heat-sensitive recording materials and the like can be used. As an example of the coupler, Research Disclosure No. 17643, VII
-CG, and the same No. 307105, VII-C-
As described in G, a non-diffusible substance having a hydrophobic group called a ballast group, a substance having no hydrophobic group, or a polymerized substance is preferable. Examples of couplers preferably used in the present invention include cyan couplers such as naphthol type couplers and phenol type couplers. US Pat. No. 2,369,929,
2,772,162, 2,801,171, 2,895,826, 3,446,622, 3,758,308, 3,772,002, 4 , 052,212, 4,126,396, 4,146,396, 4,228,233, 4,254,212, 4,296,199, 4,296. , 200, 4,327,173, 4,333,999, 4,334,011, 4,343,011, 4,427,767, 4,451,559. No. 4,690,889, No. 4,775,616, West German Patent Publication No. 3,329,72.
No. 9, European Patents 121,365A and 249,453A
And the couplers described in JP-A-61-42,658 and the like. Examples of magenta couplers include imidazole [1,2 described in U.S. Pat. No. 4,500,630 and the like.
-B] pyrazoles and pyrazolo [1,5-b] [1,2,4] triazoles described in U.S. Pat. No. 4,540,654 and the like.

In addition, a pyrazolotriazole coupler having a branched alkyl group directly bonded to the 2-, 3- or 6-position of a pyrazolotriazole ring as described in JP-A-61-65,245, JP-A-61. -65,246, a pyrazoloazole coupler containing a sulfonamide group in the molecule, JP-A-61-147,254.
Pyrazoloazole couplers having an alkoxyphenyl sulfonamide ballast group as described in JP-A No. 296,861 and an alkoxy group or an aryloxy group at the 6-position as described in European Patent (Publication) Nos. 226,849 and 294,785. And other pyrazolotriazole couplers, and US Pat. Nos. 3,061,432 and 3,725,067
Issue 4,310,619, Issue 4,351,897
No. 4,556,630, European Patent 73,636.
JP-A-55-118,034 and 60-35,7.
30, No. 60-43, 659, No. 60-185, 9
51, 61-72,238, International Publication W088 /
04795 and Research Disclosure N
o. 24220, No. 24220. Examples thereof include couplers described in 24230. As a yellow coupler, for example,
U.S. Pat. Nos. 3,933,501 and 3,973,96
No. 8, No. 4,022,620, No. 4,248,961
Issue No. 4,314,023 Issue No. 4,326,024
Issue No. 4,401,752, No. 4,511,649
No., European Patent 249,473A, Japanese Patent Publication No. 58-10,
739, British Patents 1,425,020, 1,47
Examples thereof include couplers described in No. 6,760.

Typical examples of polymerized dye-forming couplers include US Pat. Nos. 3,451,820 and 4,0.
80, 211, 4,367,282, 4,40
9,320, 4,576,910, European Patent 34
No. 1,188A, British Patent No. 2,102,137 and the like. In addition, those described in Japanese Patent Application No. 9-260336, Japanese Patent Application No. 9-271395 and the like can be mentioned.

The linking group of X in the above general formula (1) will be described. -X- ^{is, -Q 1 - (Q 2)} l - (Q 3) m -
(Q ⁴⁾ _n -Q ⁵ - is preferably represented by. In the above formula, Q ¹ , Q ² , Q ³ , Q ⁴ , and Q ⁵ are linking groups that form X, and l, m, and n are each an integer of 0 or 1.
The following groups can be mentioned as Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ . Note that Q ¹ is a group that bonds to a carbon atom, and Q ⁵ is a group that bonds to a nitrogen atom.

[0033]

[Chemical 13]

In the above formula, R¹⁹, R²⁰, R^{twenty one}Represents a substituent
And R¹¹Substituents mentioned in 1. are mentioned. R¹⁹, R²⁰, R
^{twenty one}May form a ring with another atom in X. Up
R in the ceremony^{twenty two}Represents a substituent, R¹¹The substituents listed in
You can Also R^{twenty two}Forms a ring with another atom in X
You may stay. In the above formula, R^{twenty three}, R^{twenty four}Represents a substituent, R
¹¹Substituents mentioned in 1. are mentioned. Also R^{twenty three}, R^{twenty four}Is in X
It may form a ring with another atom of. In the above formula, R^{twenty five}
Represents a substituent, R¹¹Substituents mentioned in 1. are mentioned. Well
R ^{twenty five}May form a ring with another atom in X.

In the above formula, Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ are
Each of them may independently form an aryl group or a heterocyclic group (so-called arylene group, divalent heterocyclic group). Examples of the aryl group include a phenyl group, a chlorophenyl group, a methoxyphenyl group and a naphthyl group. As the heterocyclic group, pyrazole, imidazole, triazole,
Tetrazole, pyridine, pyrimidine, triazine, pyridazine, pyrazine, furan, thiophene, pyrrole,
Examples thereof include isoxazole, isothiazole, oxazole, thiazole and the like. The aryl group and the divalent heterocyclic group may have a bond at any position. These aryl group and heterocyclic group may have a substituent, and examples of such a substituent include an alkyl group, an aryl group, a hydroxy group, a nitro group, a cyano group, a halogen group, an alkylsulfonyl group, an arylsulfonyl group and an alkoxy group. Carbonyl group, aryloxycarbonyl group, acyl group,
Examples thereof include amino group, alkylamino group, dialkylamino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, heterocyclic group, alkoxy group and aryloxy group. Also,
The aryl group may be condensed with a heterocycle, and the heterocyclic group may be condensed with an aromatic ring. The aryl group and the heterocyclic group may be bonded at any position on the ring. In the above formula, the heterocyclic group for Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ may form a sulfonium salt, an oxonium salt or a quaternary salt.

[0036]

[Chemical 14]

In the above formula, R ^{26 to} R ³¹ represent an alkyl group or an aryl group, and examples thereof include the alkyl groups and aryl groups mentioned for R ¹³ and R ¹⁴ . Z ⁻ represents an anion. The anion may be either an inorganic anion or an organic anion. Examples of the inorganic anion include hexafluorophosphate ion, borofluoride ion, chloride ion, bromide ion, hydrogen sulfate ion and the like. Examples of the organic anion include polyfluoroalkyl sulfonate ion, polyfluoroalkyl carboxylate ion, tetraphenyl borate ion, aromatic carboxylate ion, aromatic sulfonate ion and the like.

In the general formula (1), the ring formed by X, N and C is preferably a 5- to 7-membered ring, more preferably a 6-membered ring or a 7-membered ring. Ar in the general formulas (1) to (3) more preferably has the following structure.

[0039]

[Chemical 15]

Cp in the general formulas (1) to (3) is acylacetoalinides, pyrazolotriazoles, pyrazolones, pyridones, barbituric acids, pyrrolotriazoles, naphthols, phenols, or imidazole. Classes are more preferred. At X in general formula (1)
Q ¹ -is preferably -S-. Further, -Q ⁴ - is -NH -, - Q ⁵ - is - (C = O) - is preferably. A combination of these is particularly preferable. The azomethine dye precursor having these structures can easily form an azomethine dye by light irradiation.

L in the general formula (2) and L ¹ in the general formula (3) will be described. As L in the general formula (2) and L ¹ in the general formula (3), an ester group and a carbamoyl group are preferable, and ones represented by the following structural formulas (a) to (f) are particularly preferable. Among them, those represented by the structural formula (a) are more preferable.

[0042]

[Chemical 16]

In the structural formula (a), R ^a is a hydrogen atom,
Alternatively, they represent substituents, which may be the same or different. Examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group and the like, and each group may have a substituent.

The alkyl group represented by ^Ra is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. The halogen atom represented by R ^a is preferably fluorine, chlorine, bromine or the like. R ^a
The aryl group represented by is preferably a phenyl group, naphthyl or the like. The alkoxy group represented by ^Ra is preferably an alkoxy group having 1 to 12 carbon atoms, and more preferably an alkoxy group having 1 to 6 carbon atoms.

Specific examples of the structural formula (a) are shown below.

[0046]

[Chemical 17]

[0047]

[Chemical 18]

[0048]

[Chemical 19]

In the above structural formula (b), X is O, S, SO ₂
Or a single bond, R ³² and R ^{3 3} represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or EWG. EWG is an electron-withdrawing group, and more specifically, a substituent having a positive Hammett σ value, such as a halogen atom, a sulfamoyl group, a sulfonamide group,
An alkoxy group, a carbonyl group, a sulfonyl group and the like (the same applies hereinafter).

[0050]

[Chemical 20]

In the above structural formula (c), R ³⁴ and R ³⁵ represent a hydrogen atom, an alkyl group or an aryl group. R ³⁵ and E
WG and WG may form a ring together, and as an example of the structural formula (c) in the ring-formed state,

[0052]

[Chemical 21]

And the like.

[0054]

[Chemical formula 22]

In the above structural formula (d),

[0056]

[Chemical formula 23]

Represents an aryl group in which a heterocycle is condensed.
As an example of structural formula (d),

[0058]

[Chemical formula 24]

And the like.

[0060]

[Chemical 25]

In the above structural formula (e), R ³⁶ and R ³⁷ are
It represents the same group as R ³² and R ³³ above.

[0062]

[Chemical formula 26]

In the above structural formula (f), R ³⁸ and R ³⁹ are
It represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
The alkyl group, aryl group and heterocyclic group may be further substituted. As the substituent, an alkyl group, an aryl group, a hydroxy group, a nitro group, a cyano group, a halogen group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Examples thereof include an acyl group, an amino group, an alkylamino group, an acylamino group, a carbamoyl group, a sulfamoyl group, an alkylthio group, an arylthio group, a heterocyclic group, an alkoxy group, an aryloxy group and an acyloxy group. Also, R ³⁸
And R ³⁹ may combine to form a saturated or unsaturated ring.

L ² in the general formula (3) will be described.
When Cp in the general formula (3) is a 2-equivalent coupler residue, the general formula (3) is represented by the following general formula (3-1).

[0065]

[Chemical 27]

An example of L ²¹ will be given below.

[0067]

[Chemical 28]

In the above formula, R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are each independently a hydrogen atom, an alkyl group, an aryl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group or an aryloxycarbonyl group. It represents a group or an amide group, and R ⁴¹ and R ⁴² may be bonded to each other to form a ring structure (in this case, saturated or unsaturated). In addition, R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ ,
R ⁴⁹ , R ⁵⁰ , R ⁵¹ , R ⁵² and R ⁵³ each independently represent a hydrogen atom, an alkyl group or an aryl group. R ⁵² and R ⁵³ may combine with each other to form a saturated or unsaturated ring.

When Cp in the general formula (3) is a coupler residue having 4 equivalents, the general formula (3) is represented by the following general formula (3-2).

[0070]

[Chemical 29]

In the above formula, L ²² represents a protecting group which is deprotected after L ¹ is deprotected, and Cp represents a 4-equivalent coupler residue.

Specific examples of L ²² include protecting groups for nitrogen atom and oxygen atom, such as acyl, alkylsulfonyl, arylsulfonyl, formyl, and alkyloxycarbonyl.

Specific examples (1) to (102) of the azotimene dye precursors represented by the general formulas (1) to (3) are shown below, but the invention is not limited thereto.

[0074]

[Chemical 30]

[0075]

[Chemical 31]

[0076]

[Chemical 32]

[0077]

[Chemical 33]

[0078]

[Chemical 34]

[0079]

[Chemical 35]

[0080]

[Chemical 36]

[0081]

[Chemical 37]

[0082]

[Chemical 38]

[0083]

[Chemical Formula 39]

[0084]

[Chemical 40]

[0085]

[Chemical 41]

[0086]

[Chemical 42]

[0087]

[Chemical 43]

[0088]

[Chemical 44]

[0089]

[Chemical formula 45]

[0090]

[Chemical formula 46]

[0091]

[Chemical 47]

[0092]

[Chemical 48]

[0093]

[Chemical 49]

[0094]

[Chemical 50]

[0095]

[Chemical 51]

[0096]

[Chemical 52]

[0097]

[Chemical 53]

[0098]

[Chemical 54]

[0099]

[Chemical 55] Next, for example, a method for producing the azomethine dye precursor represented by the general formula (1) will be described. The azomethine dye precursor represented by the general formula (1) can be produced by three methods.

The first method is a method for producing by oxidatively coupling the compound A in which the coupler moiety and N-Ar are linked by X (reaction formula (1) below).

[0101]

[Chemical 56]

The second method is such that when the linking group X is decomposed into Y and Z, a coupler moiety having Y and N-having Z
In this method, Ar is preliminarily oxidatively coupled to form compound B, and then Y and Z are linked (converted to X) (reaction formula (2) below).

[0103]

[Chemical 57]

The third method is a coupler moiety having a substituent L which is easily eliminated as an anion and NA having X.
In this method, r is preliminarily oxidatively coupled to form compound C, and then X is introduced into the coupler moiety (the following reaction formula (3)).

[0105]

[Chemical 58]

The oxidative coupling reaction in the reactions represented by the above reaction formulas (1), (2) and (3) will be described. This oxidative coupling reaction may be carried out under any of acidic, neutral and basic conditions, but it is particularly preferred to carry out under basic conditions. Examples of the oxidizing agent include manganese dioxide, potassium permanganate, manganese (III) acetate, potassium hexacyanoferrate (III), chromium oxide (VI) -pyridine complex, mercury (II) acetate,
Examples thereof include lead tetraacetate and silver (II) oxide. Among these, manganese dioxide and potassium hexacyanoferrate (III) are preferable. The oxidizing agent is used in an amount of 1 to 10 equivalents, preferably 1 to 5 equivalents, relative to 1 equivalent of the substrate.

Examples of the base include organic bases such as triethylamine, pyridine and DBU; alkali metal hydrides such as sodium hydride and potassium hydride; metal alcoholates such as sodium methylate, sodium ethylate and potassium butyrate; and sodium hydroxide. , Alkali metal hydroxides such as potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, alkali metal carbonates such as sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate and potassium carbonate, formic acid Examples thereof include alkali metal salts of lower carboxylic acids such as sodium and sodium acetate. Among these, organic bases such as triethylamine and pyridine, and alkali metal carbonates are preferable. The amount of the base used is preferably 1 to 10 equivalents relative to 1 equivalent of the substrate.

Examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene, chain or cyclic aliphatic hydrocarbons such as pentane, hexane, heptane and cyclohexane, diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane. Ethers such as ethylene glycol dimethyl ether, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, nitriles such as acetonitrile, acetic acid esters such as methyl acetate and ethyl acetate, N, N-dimethylformamide, N, N -Various solvents such as dimethylacetamide, dimethylsulfoxide, acetic acid, or a mixture thereof can be used. Further, in the case of a non-water-soluble solvent, the reaction may be carried out in a two-phase system with the above-mentioned aqueous solution of base. The amount of these solvents used is not particularly limited.

The reaction temperature is usually selected from the range of room temperature to the boiling point of the solvent, but is preferably 20 to 70 ° C.
The reaction time is usually about 0.5 to 24 hours, though it depends on the reaction temperature. After completion of the reaction, the target product can be taken out by a usual post-treatment operation such as extraction, and if necessary, it can be further purified by a purification means such as silica gel column chromatography or recrystallization.

Hereinafter, specific synthesis examples of the azomethine dye precursor represented by the above general formula (1) will be shown. (Synthesis of Compound (28) by Reaction Formula (1))

[0111]

[Chemical 59]

In the above reaction formula, 4.44 g of the compound [1]
90 ml of ethyl acetate and 46 ml of 10% sodium carbonate aqueous solution were added to (4.64 mmol), and 3.21 g (9.75 mm) of potassium hexacyanoferrate (III) was added under stirring.
ol) was added. Then, it stirred at room temperature for 30 minutes. Then, the organic layer was separated, washed with water, dried and concentrated under reduced pressure. The oily substance obtained was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 3/1) to give compound (28). Obtained. (Light yellow solid 3.83 g, yield 86%). The physical properties of the obtained compound (28) are as follows.

[M. p. : 102 to 103 ° C, ¹ H-N
MR (CDCl ₃ ): 8.07 to 8.18 (m, 1
H), 7.25 to 7.46 (m, 1H), 7.11
7.25 (m, 2H), 6.96 to 7.11 (m, 1
H), 6.71 to 6.89 (m, 1H), 6.55
6.65 (m, 2H), 6.43 to 6.51 (m, 1
H), 6.30 to 6.43 (m, 1H), 6.02 to
6.23 (m, 1H), 5.80-5.87 (m, 1
H), 5.56 to 5.72 (m, 1H), 4.56
(T, 1H), 3.56 to 3.67 (m, 1H), 3.
42 to 3.56 (m, 1H), 3.40 (t, 2H),
3.32 (q, 2H), 3.21 (t, 2H), 2.9
5 to 3.03 (m, 1H), 2.91 (s, 3H),
2.33 (s, 3H), 2.05 to 2.18 (s, 3
H), 1.82 to 1.98 (m, 5H), 1.58
(Q, 2H), 1.05 to 1.40 (m, 25H),
0.85 (t, 3H), 0.56 to 0.68 (m, 6
H)]

The compound [1] in the above reaction formula can be synthesized as shown in the following reaction formula.

[0115]

[Chemical 60]

In the above reaction formula, 60 g of compound [2]
(0.105 mol), O-aminobenzenethiol 1
DMAc (500 ml) was added to 71 g (0.137 mol) to give 10.6 g (0.105 mol) of triethylamine.
Was added and stirred at 100 ° C. for 3 hours (a gas washing bottle containing antiformin was connected to the reaction vessel). afterwards,
The reaction solution was poured into ice water, and the precipitated pale yellow solid was collected by filtration and washed with water. After drying, recrystallization from ethyl acetate / hexane gave compound [3] as a white solid (1st 79 g). Further, the filtrate was concentrated and recrystallized from ethyl acetate / hexane to obtain compound [3] as a white solid (2nd 28.5 g) (total 107.5 g, yield 78%). less than,
The physical properties of the obtained compound [3] are as follows.

[M. p. : 185 to 187 ° C, ¹ H-N
_{MR (CDCl 3): 7.13~7.20 (} m, 2
H), 6.98 to 7.04 (m, 1H), 6.80 (d
d, 1H), 6.71 (dd, 1H), 6.56-6.
66 (m, 2H), 6.36 (d, 1H), 4.55
(T, 1H), 4.31 (brs, 2H), 3.42 ~
3.70 (m, 2H), 3.08 to 3.22 (m, 1
H), 2.43 (s, 3H), 1.77 to 1.90.
(M, 5H), 1.55 (q, 2H), 1.12 to 1.
36 (m, 22H), 0.87 (t, 3H), 0.58
~ 0.67 (m, 6H)]

Furthermore, 3.95 g of the obtained compound [3]
(5.98 mmol), 3.04 g of compound [4] (7.
Acetonitrile (60 ml) was added to (77 mmol), triethylamine (0.664 g, 6.57 mmol) was added, and the mixture was stirred under reflux for 4 hours. Then, 6 ml of 1N base was added, and the mixture was extracted with ethyl acetate. Then, the organic layer was washed with water, dried, and then concentrated under reduced pressure to give an oily substance,
Hexane was added and the precipitated solid was collected by filtration to obtain a compound [1] (4.24 g of white solid, yield 74%). The physical properties of the obtained compound [3] are as follows.

[M. p. : 175-176 ° C, ¹ H-N
_{MR (CDCl 3): 7.49 (} d, 1H), 7.14
Up to 7.25 (m, 2H), 7.02 to 7.14 (m, 3)
H), 6.91-7.02 (m, 2H), 6.51-
6.65 (m, 3H), 6.38 to 6.51 (m, 2
H), 4.80 (brs, 1H), 4.42 to 4.51
(M, 1H), 3.71 to 3.82 (m, 1H), 3.
50 to 3.58 (m, 1H), 3.47 (t, 2H),
3.38 (q, 2H), 3.39 (t, 2H), 3.0
1-3.13 (m, 1H) 2.91 (s, 3H), 2.
34 (s, 3H), 2.26 (s, 3H), 1.81
1.89 (m, 5H), 1.56 (q, 2H), 1.0
6 to 1.39 (m, 25H), 0.85 (t, 3H),
0.56-0.68 (m, 6H)]

The compound [2] in the above reaction formula can be synthesized by the method described in JP-A-64-6274. In addition, compound [4] can be synthesized as shown below.

4-amino-3-methyl-N-ethyl-N
-(Methanesulfonamidoethyl) alinine 1.5 sulfate-hydrate 4.365 g (10 mmol) in 10 m of water
1, 30 ml of ethyl acetate were added, and under stirring at room temperature, 2.94 g of sodium hydrogencarbonate (35 mmol) was added (addition is slow because foaming occurs. Addition time is about 10
Minutes). Then, under cooling, 1.64 g of phenyl chloroformate
(10.5 mmol) was added dropwise (dripping time 30 minutes, internal temperature 7-8 ° C). Then, the temperature was returned to room temperature, and the mixture was further stirred for 2 hours. Then, liquid separation, the organic layer was washed with water, dried, and concentrated under reduced pressure. Ethyl acetate / hexane was added to the obtained oily substance, and the precipitated solid was collected by filtration to obtain a compound [4] (white solid 3 0.6 g, yield 92%). The physical properties of the obtained compound [4] are as follows.

[M. p. : 89-90 ° C, ¹ H-NMR
_{(CDCl 3): 7.46 (brs} , 1H), 7.30
~ 7.40 (m, 2H), 7.15 ~ 7.24 (m, 3
H), 6.53 to 6.64 (m, 3H), 4.74 (b
rs, 1H), 3.41 (t, 2H), 3.34 (q,
2H), 3.26 (t, 2H), 2.89 (s, 3)
H), 2.31 (s, 3H), 1.12 (t, 3H)]

(Synthesis of Compound (28) by Reaction Formula (2))

[0124]

[Chemical formula 61]

In the above reaction formula, ammonium chloride 0.2
1 g of water and 50 ml of isopropanol were added to g (3.74 mmol), and 1.9 g (34 g of reduced iron was added at room temperature with stirring.
mmol) was added. Then, the mixture was vigorously stirred under reflux for 20 minutes, to which 5.33 g (4.94 mm) of compound [5] was added.
ol) was added portionwise over about 10 minutes. 1 more under reflux
After stirring for an hour, the mixture was cooled and the reaction solution was filtered through Celite.
Water was added to the filtrate, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried, and concentrated under reduced pressure, and the obtained oily substance was subjected to silica gel column chromatography (dissolved solution: ethyl acetate /
The compound (28) was obtained by purification with hexane = 3/1) (pale yellow solid 3.21 g, yield 68%).

In the above reaction formula, the compound [5] can be synthesized by oxidative coupling of the compound [6] and the compound [4] as shown in the following reaction formula.

[0127]

[Chemical formula 62]

(Synthesis of Compound (28) by Reaction Formula (3))

[0129]

[Chemical formula 63]

In the above reaction formula, 3.1 g of compound [7]
0.43 g (3 mmo) of potassium carbonate in (3 mmol)
1) and 20 ml of methanol were added, and the mixture was stirred under reflux for 3 hours. After cooling, water was added to the reaction solution and neutralized with 1N base,
It was extracted with ethyl acetate. The organic layer was washed with water, dried, and concentrated under reduced pressure, and the resulting oil was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 3/1) to give compound (28) (light Yellow solid 1.75
g, 61% yield).

In the above reaction scheme, compound [7] can be synthesized by oxidative coupling of the compound [2] with the following compound [8].

[0132]

[Chemical 64]

The azomethine dye precursor represented by the above general formula (1) can be used in various recording materials. For example, it can be used for a heat-sensitive recording material widely used in the fields of facsimiles, printers and the like.
The azomethine dye precursor represented by the above general formula (1) can also be used in a silver halide light-sensitive material. Further, it can also be used as a coloring material for general silver salt photography, an inkjet, and a coloring material for a transfer material.

The azomethine dye precursor obtained as described above forms an azomethine dye by irradiation with light. The wavelength of the irradiation light is preferably 200 to 1100 nm, more preferably 200 to 600 nm, and further preferably 200 to 400 nm. In addition, the illuminance of the irradiation light is 500 to 50.
10,000 lux (lx), preferably 10,000 to 500,000 lux, more preferably 50,000 to 200,000 lux.
Is more preferable. The irradiation time is preferably 0.1 to 10 hours, and more preferably 0.1 to 2 hours in the above illuminance. By irradiating with light under the above irradiation conditions, an azomethine dye can be easily formed from the above-mentioned azomethine dye precursor, and the formed azomethine dye exhibits a good hue.

Various fluorescent lamps, xenon lamps, mercury lamps and the like can be used as the light source used for photo-coloring.
During light irradiation, the azomethine dye precursor may be dissolved in a solvent, or may be in a solid state or an emulsion state. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene, chain or cyclic aliphatic hydrocarbons such as pentane, hexane, heptane and cyclohexane, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane and ethylene glycol dimethyl ether. And the like, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, nitriles such as acetonitrile, acetic acid esters such as methyl acetate and ethyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide , Dimethyl sulfoxide, acetic acid and the like.

[0136]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. <Example 1> 5 × 10 ⁻⁵ mo of the compound (10) of the present invention
A 1 / l butyl acetate solution (sample solution) was prepared. 4 ml of this sample solution was put in a 1 cm cell and irradiated with light for 60 minutes with a merry-go-round 500 w xenon lamp (manufactured by USHIO INC.) With a thermal edge cut filter HA50 while confirming that the solution temperature did not rise above 60 ° C. (170000 lux) The amount of dye formed was measured by HPLC (high performance liquid chromatography) to determine the pigmentation ratio, which is the ratio of pigmentation to the azomethine dye precursor.

Example 2 Example 1 was repeated except that the compound (10) of the present invention was replaced with the compound (14) of the present invention. <Example 3> The procedure of Example 1 was repeated except that the compound (10) of the present invention was replaced with the compound (23) of the present invention. <Example 4> The procedure of Example 1 was repeated, except that the compound (10) of the present invention was replaced with the compound (26) of the present invention.

Example 5 The same procedure as in Example 1 was carried out except that the compound (10) of the present invention was replaced with the compound (28) of the present invention. <Example 6> The procedure of Example 1 was repeated except that the compound (10) of the present invention was replaced with the compound (40) of the present invention. <Example 7> The procedure of Example 1 was repeated, except that the compound (10) of the present invention was replaced with the compound (41) of the present invention.

Example 8 The same procedure as in Example 1 was carried out except that the compound (10) of the present invention was replaced with the compound (76) of the present invention. <Example 9> The procedure of Example 1 was repeated except that the compound (10) of the present invention was replaced with the compound (84) of the present invention. <Example 10> The procedure of Example 1 was repeated except that the compound (10) of the present invention was replaced with the compound (89) of the present invention.

Example 11 The procedure of Example 1 was repeated, except that the compound (10) of the present invention was replaced with the compound (90) of the present invention. <Example 12> The procedure of Example 1 was repeated, except that the compound (10) of the present invention was replaced with the compound (94) of the present invention.

Example 13 The same procedure as in Example 1 was carried out except that the compound (10) of the present invention was replaced with the compound (101) of the present invention. <Example 14> The procedure of Example 1 was repeated except that the compound (10) of the present invention was replaced with the compound (102) of the present invention.

The above results are shown in Table 1 below.

[0143]

[Table 1]

As is clear from Table 1, Examples 1 to 14
In Example 1, the azomethine dye precursor was efficiently produced by irradiating the azomethine dye precursor with light.

<Comparative Example 1> The sample solution (Compound (10) of the present invention) prepared in Example 1 was allowed to stand for 7 days at 60 ° C., and the amount of dye produced was measured by HPLC to determine the pigmentation rate. I asked.

<Control Example 2> The sample solution (Compound (14) of the present invention) prepared in Example 2 was allowed to stand at 60 ° C. for 7 days, and the amount of dye produced was measured by HPLC to determine the pigmentation rate. I asked. <Control Example 3> The sample liquid (Compound (23) of the present invention) prepared in Example 3 was allowed to stand for 7 days under the condition of 60 ° C., and the amount of dye formed was measured by HPLC to obtain the pigmentation rate. <Control Example 4> The sample liquid (Compound (26) of the present invention) prepared in Example 4 was allowed to stand for 7 days under the condition of 60 ° C., and the dye formation amount was measured by HPLC to obtain the dye formation rate.

<Comparative Example 5> The sample solution (Compound (28) of the present invention) prepared in Example 5 was allowed to stand at 60 ° C. for 7 days, and the amount of dye formed was measured by HPLC to determine the pigmentation rate. I asked. <Control Example 6> The sample liquid (Compound (40) of the present invention) prepared in Example 6 was allowed to stand for 7 days under the condition of 60 ° C., and the amount of dye formed was measured by HPLC to obtain the dye conversion rate. <Comparative Example 7> The sample solution (Compound (41) of the present invention) prepared in Example 7 was allowed to stand for 7 days at 60 ° C, and the amount of dye formed was measured by HPLC to obtain the dye conversion rate.

<Comparative Example 8> The sample solution (Compound (76) of the present invention) prepared in Example 8 was allowed to stand at 60 ° C. for 7 days, and the amount of dye formed was measured by HPLC to determine the dye formation rate. I asked. <Control Example 9> The sample liquid (Compound (84) of the present invention) prepared in Example 9 was allowed to stand for 7 days under the condition of 60 ° C., and the amount of dye formed was measured by HPLC to obtain the dye conversion rate. <Control Example 10> The sample solution (Compound (89) of the present invention) prepared in Example 10 was allowed to stand for 7 days at 60 ° C., and the amount of dye formed was measured by HPLC to obtain the dye conversion rate.

<Comparative Example 11> The sample solution (Compound (90) of the present invention) prepared in Example 11 was allowed to stand for 7 days at 60 ° C., and the amount of dye formed was measured by HPLC.
The pigmentation rate was calculated. <Control Example 12> The sample liquid (Compound (94) of the present invention) prepared in Example 12 was allowed to stand for 7 days under the condition of 60 ° C., and the amount of dye formed was measured by HPLC to obtain the pigmentation rate.

<Comparative Example 13> The sample solution (Compound (101) of the present invention) prepared in Example 13 was allowed to stand at 60 ° C. for 7 days, and the amount of dye produced was measured by HPLC to determine the pigmentation rate. I asked. <Control Example 14> The sample liquid (Compound (102) of the present invention) prepared in Example 14 was allowed to stand for 7 days at 60 ° C., and the amount of dye formed was measured by HPLC to obtain the dye conversion rate.

The above results are shown in Table 2.

[0152]

[Table 2]

As is clear from Table 2, Examples 1 to 14
The compound used in 1. showed almost no formation of azomethine dye by heat, and showed high thermal stability. Therefore, Example 1
It can be seen that the formation of the azomethine dye in ~ 14 is almost due to photoreaction.

[0154]

According to the azomethine dye forming method of the present invention, it is possible to efficiently form an azomethine dye without requiring heat. In addition, the azomethine dye formed by the azomethine dye forming method exhibits a good hue.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07D 513/20 C07D 513/20 513/22 513/22 515/20 515/20 F term (reference) 4C050 AA01 BB06 CC04 EE03 FF02 FF03 FF05 GG02 GG03 GG04 GG06 HH01 HH04 4C072 AA04 AA06 BB02 BB03 BB06 CC04 CC05 CC16 EE19 FF02 FF04 GG08 HH02

Claims (8)

[Claims] 1. A method for forming an azomethine dye, which comprises irradiating an azomethine dye precursor with light to form an azomethine dye. 2. The azomethine dye forming method according to claim 1, wherein the azomethine dye precursor is represented by the following general formula (1). [Chemical 1] In general formula (1), Ar represents an aromatic ring or a heterocyclic ring which may have a substituent, and X represents a divalent group connecting a carbon atom and a nitrogen atom. Cp represents a coupler residue, which may or may not form a ring. Wherein in general formula (1) wherein -X- is, -Q ¹ -
_{^{(Q 2) l - (Q}} 3) m - (Q 4) n -Q 5 - a is claim 2
A method for forming an azomethine dye according to 1. Q ¹ is a group bonded to a carbon atom, Q ⁵ is a group bonded to a nitrogen atom, and Q ¹ , Q
² , Q ³ , Q ⁴ and Q ⁵ each represent a divalent group, and l, m,
n represents 0 or 1, respectively. 4. The method for forming an azomethine dye according to claim 3, wherein -Q ¹ -is -S-. 5. —Q ⁴ — is —NH—, and —Q ⁵ — is —C (=
The method for forming an azomethine dye according to claim 3 or 4, which is O)-. 6. The azomethine dye forming method according to claim 1, wherein the azomethine dye precursor is represented by the following general formula (2). [Chemical 2] In formula (2), Ar represents an aromatic ring or a heterocycle which may have a substituent, Cp represents a coupler residue, and L represents L.
Represents a protecting group. 7. The method for forming an azomethine dye according to claim 1, wherein the azomethine dye precursor is represented by the following general formula (3). [Chemical 3] In general formula (3), Ar represents an aromatic ring or a heterocycle which may have a substituent, and Cp represents a coupler residue. L
¹ represents a protecting group, L ² represents a leaving group, or a protecting group L ¹ is deprotected after being deprotected desorbing after the L ¹ is deprotected. 8. The azomethine dye formation according to claim 6 or 7, wherein L in the general formula (2) or L ¹ in the general formula (3) is represented by the following structural formula (a). Method. [Chemical 4] In structural formula (a), R ^a represents a hydrogen atom or a substituent, and may be the same or different.