JPH0714940B2 - Process for producing pyrazolo [1,5-b [1,2,4 triazole-based photographic coupler - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to pyrazolo [1,5-b].
The present invention relates to a method for producing a novel photographic coupler composed of a [1, 2, 4] triazole derivative.

[0002]

2. Description of the Related Art There is a nitrogen atom at the bridgehead position and it is possible to interact with 10 π electrons including a lone pair of this nitrogen atom and another nitrogen atom. , A general formula with at least 2 and at most 6 nitrogen atoms in total

[Chemical 5] The 5-5 condensed polycyclic compound represented by is usually called "azapentalene". This compound has been mainly studied so far due to its interest in structural chemistry, as a physiologically active substance, and as a magenta coupler in photographic chemistry (J. Elgureo, R. Jacquier, S. Mignonac-Mondo.
n, J. Hetero- cyclic. Chem. , 10 , 411 (1973),
H. Koga, M. Hirobe, T. Okamoto, Chem. Pharm. Bull.
, 22 ,, 482 (1974), J. Bailey, JCS Perkin I 2047
(1977), Japanese Examined Patent Publication No. 47-27411, Japanese Patent Laid-Open No. 50-129586, etc.).

[0003]

The inventors of the present invention have conducted various studies on the synthetic method of such an azapentalene compound, and as a result, cyclized and condensed a certain N-aminotriazolium salt and an acid anhydride. As a result, it was possible to obtain an azapentalene compound having a novel skeleton, and it was found that the compound exhibited extremely excellent properties as a magenta coupler for color photography, and the present invention was completed based on this finding.

That is, the present invention has the general formula

[0005]

[Chemical 6] (In the formula, R ₁ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, R ₂ represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and X represents an acid radical. .) And an N-aminotriazolium salt represented by the general formula

[0006]

[Chemical 7] (In the formula, R ₃ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group.)

Cyclocondensation with an acid anhydride represented by the general formula

[0008]

[Chemical 8] (In the formula, R ₁ , R ₂ and R ₃ have the same meanings as described above.)

7-acylated pyrazolo [1,5 represented by
-B] [1,2,4] triazole is obtained, and the 7-acylated pyrazolo [1,5-b] [1,2,4] triazole is deacylated and then the 1-position is reduced, A group represented by the general formula by introducing a group Y which is released by a coupling reaction with an oxidation product of an aromatic primary amine developing agent (hereinafter simply referred to as a coupling-off group).

[0009]

[Chemical 9] (In the formula, R ₁ and R ₃ have the same meanings as described above, and Y represents a coupling-off group.)

The pyrazolo [1,5-b] [1,2, represented by
4] Pyrazolo characterized by obtaining a triazole compound
The present invention provides a method for producing a [1,5-b] [1,2,4] triazole-based photographic coupler.

In the compounds represented by the above general formulas (II), (III), (IV) and (V), the alkyl groups of R ₁ and R ₃ are lower alkyl groups such as methyl, ethyl, propyl and butyl groups. A higher alkyl group having up to 22 carbon atoms, for example, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, an undecyl group, a tridecyl group, an octadecyl group and the like, which may be linear or branched.
A methyl group is particularly preferred as R ₁ . Also R ₁ and R ₃
Examples of aryl groups include phenyl group and naphthyl group, substituted alkyl groups include benzyl group and phenethyl group, and substituted aryl groups include halogenophenyl group, nitrophenyl group, cyanophenyl group, alkoxyphenyl group, etc. Can be given. Further, R ₁ and R ₃ may have a group inactive to the reaction, for example, an alkoxyl group, a nitro group, a cyano group, a halogen atom and the like as a substituent.

Next, as the alkyl group of R _{2 in} the compounds represented by the above general formulas (II) and (IV), a lower alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, a pentyl group and a hexyl group. , Higher decyl groups such as dodecyl group are included, aryl groups include phenyl group, naphthyl group, etc., substituted alkyl groups include benzyl group, phenethyl group, p-methoxyphenylmethyl group, m-nitrophenylmethyl group, etc. Included, these are R ₁ , R
_It may have a group inert to the same reaction as ₃ as a substituent. In particular, when R ₂ is an optionally substituted benzyl group, the substituent can be easily removed reductively in a subsequent step, which is advantageous when the 1H-form is produced. In the general formula (II), the acid radical of X acid radical, such as chlorine, bromine, halogen anions such as iodine, NO ₃ ^-, SO
₄ ^2- ,

[0013]

[Chemical 10] Are included.

The pyrazolo obtained by the method of the present invention
A [1,5-b] [1,2,4] triazole derivative, wherein R
_The compound further having a substituent as described above on the group of ₁ , R ₂ or R ₃ can be directly obtained according to the following reaction scheme, and in this step, first, the basic skeleton of the present invention, pyrazolo- [1 After forming a 5,5-b] [1,2,4] triazole ring, it may be derivatized to a desired substituent by a subsequent reaction. If necessary, the compound may be derivatized with a compound having an acyl group at the 7-position and R ₂ having a protecting group such as a benzyl group. For example, as shown in Example 6 below, the amino group of compound 11 of the present invention can be derivatized to acid anilide 13 or the like by a known method. The reaction steps of the method of the present invention are as follows in the case where X in the general formula (II) is an iodine ion.

[0015]

[Chemical 11]

An embodiment of the method of the present invention will be described below according to the above reaction process formula. In the present invention, the triazole compound (IV) can be easily obtained by the reaction of the oxadiazole (VII) and the organic primary amine (VIII). The reaction temperature is usually started in the range of 50 to 150 ° C., and the reaction is completed under the condition that the water produced by the dehydration reaction is gently refluxed. Reaction time is normal
It is in the range of 0.1 to 6 hours, but is not limited thereto. Oxadiazole can be synthesized by the method described in Ber., 32, p. 797 (1899). Next, synthesis of N-aminotriazolium salt (II) by amination of triazole compound (V) is carried out by using hydroxylamine-O-sulfonic acid, O- (2,4-dinitrophenyl) as an aminating agent.
It can be carried out using hydroxylamine, O-diphenylphosphorylhydroxylamine. Other aminating agents that may be used in the present invention are described by Y. Tamura et, al, Synt.
hesis, 1977, 1-17 and the references cited therein. This amination reaction is usually performed at a reaction temperature of 0 ° C to 100 ° C.
For 0.1 to 5 hours. The molar ratio of the triazole compound to the aminating agent is generally 1: 1 but the cheaper one of the two may be used in excess.

The cyclocondensation reaction between the N-aminotriazolium salt (II) and the acid anhydride (III) is carried out in the presence of a base. As the base, amines, sodium acetate, sodium propionate and the like can be used. In this reaction, it is desirable to use at least 3 equivalents of acid anhydride and at least 5 equivalents of base with respect to the N-aminotriazolium salt. If the amounts of the acid anhydride and the base are less than this lower limit, the reaction yield will decrease. This is considered to be because when the acid anhydride is less than the lower limit, a side reaction that does not give the desired product from the reaction intermediate proceeds. Reaction temperature is generally 100 ℃ ~ 18
Although 0 ° C. can be used, it is preferably 120 ° C. or higher, and the reaction time varies depending on the kind and amount of the acid anhydride and is not particularly limited, but is generally in the range of 0.5 to 20 hours. The reaction solvent may be any inert solvent, for example, dimethylformamide (DMF), dimethylacetamide, N-methylpyrrolidone and the like are usually used, but when a lower acid anhydride is used as a reaction component, This may be used as a solvent in an excess amount. Specific examples of the acid anhydride (III), formic anhydride, acetic anhydride, propionic anhydride, lauric anhydride, benzoic anhydride, methoxycarbonylpropionic anhydride, ethoxycarbonylpropionic anhydride, anhydrous
4- (p-nitrophenyl) butyric acid and the like can be mentioned. The acid anhydride of the general formula (III) also includes mixed acid anhydrides, and as a specific example in this case, a mixed acid anhydride with trimethylacetic acid is preferable. The product of this cyclized condensation reaction is 7-acylated pyrazolo
[1,5-b] [1,2,4] Triazole (IV) is deacylated and reduced to give compounds (IX) and (X).

The deacylation can be accomplished by heating under reflux in an aqueous solution containing a solvent such as ethanol which boils at room temperature to 200 ° C. under acidic conditions with a mineral acid according to a general method. After returning this to neutrality, the desired product is isolated by extraction and the like, and purified if necessary. When the 7-position is first nitrosated to introduce a leaving group having an N atom bonded to the 7-position, the deacylation reaction may be carried out simultaneously with the nitrosation. Next, by reducing the compound (IX), the substituent R ₂ bonded to the 1-position nitrogen atom is removed, and the 1H-pyrazolo [1,5-b] [1,2,4] triazole compound (X) is obtained. can get. It is desirable to select the substituent R ₂ that can be suitably removed by this reduction treatment. For such protecting groups, see for example Mcomie Pro.
tective Groups in Organic Chemistry (1973, Plen
(Published by um) or Protective Groups by TW Green
in Organic Synthesis (1981, Wiley-Interscience
Published in the company). Among these, preferable R ₂ for use in the present invention is —CH ₂ C ₆ H ₅ , —CH (C ₆ H ₅ ) ₂ , —CH ₂ C ₆ H ₃ − 3, 4- (OCH ₃ ) _{2, -CH 2 C 6 H 4} -o-NO 2, -CH 2 C 6 H 4 -p-OCH 3, -CH (C 6 H 4 -p-OCH 3) 2, -CH 2 - 2- pyridyl -N-oxide and the like. Reaction conditions for removing these substituents R ₂ include catalytic reduction and reduction with an alkali metal. Examples of this are palladium black / hydrogen, palladium-carbon / hydrogen, palladium-alumina /
Examples include hydrogen, sodium / liquid ammonia, lithium / liquid ammonia, and the like. Among them, sodium metal / liquid ammonium gives a high yield.

In each step of the above reaction steps, the desired compound obtained may be subjected to the subsequent reaction without isolation, but it is usually isolated and purified by a suitable isolation means. Examples of such means include solvent extraction method, recrystallization method, filtration method, column chromatography, thin layer chromatography and the like. In the method of the present invention, the 1H-pyrazolo [1,5-b] [1,2,4] triazole compound represented by the general formula (X) is further treated to introduce a coupling leaving group known per se at the 7-position. However, it may be used as a photographic coupler of a pyrazolo [1,5-b] [1,2,4] triazole compound represented by the general formula (V). This is appropriately performed for the compound used as the coupler in the photographic system for adjusting the coupling reaction rate with the oxidation product of the aromatic primary amine oxidized by silver halide and reducing the amount of silver used. Method, which is known per se. The general method for introducing the coupling-off group will be described below.

(1) Method for linking oxygen atoms The 4-equivalent mother nucleus coupler, pyrazolo [1,5-b] triazole type coupler of the present invention is reacted with an oxidation product of an aromatic primary amine to form a dye. And hydrolyze it into a ketone body in the presence of an acid catalyst.
7-Hydroxy-pyrazolo [1,5-b] triazole can be synthesized by hydrogenation using carbonic acid as a catalyst, reduction with Zn-acetic acid or reduction with sodium borohydride. This can be reacted with various halides to synthesize a coupler having a desired oxygen atom linked thereto. (See U.S. Pat. No. 3,926,631, JP-A-57-70817)

(2) Method for connecting nitrogen atoms There are roughly three methods for connecting nitrogen atoms. The first method is to nitrosate the coupling active site with a suitable nitrosating agent as described in U.S. Pat. No. 3,419,391, and reduce it by a suitable method (for example, P
hydrogenation method using d-carbon as a catalyst, chemical reduction method using stannous chloride, etc., and 7-amino-pyrazolo [1,5
The amide compound can be mainly synthesized by reacting various halides with -b] triazole. The second method is the method described in U.S. Pat.No. 3,725,067, that is, the 7-position is adjusted by a suitable halogenating agent such as sulfuryl chloride, chlorine gas, bromine, N-chlorosuccinimide, N-bromosuccinimide and the like. Halogenated, and then Japanese Patent Publication Sho 56
-By substituting the nitrogen heterocycle in the presence of a suitable base catalyst, triethylamine, sodium hydroxide, azabicyclo [2,2,2] octane, anhydrous potassium carbonate, etc. by the method described in No. 45135, and a nitrogen atom at the 7-position. Coupled couplers can be synthesized. Of the compounds linked by oxygen atoms,
A compound having a phenoxy group at the 7-position can also be synthesized by this method. The third method is an effective method for introducing a 6π or 10π electron-based aromatic nitrogen heterocycle into the 7-position, and as described in JP-B-57-36577,
Add 2 times or more moles of 6π or 10π electronic aromatic nitrogen heterocycle to the 7-halogen compound synthesized by method 2.
Aromatic nitrogen linked to the 7-position by a nitrogen atom by heating without solvent at 50 to 150 ° C or in an aprotic polar solvent such as dimethyformaldehyde, sulfolane or hexamethylphosphotriamide at 30 to 150 ° C. Heterocyclic groups can be introduced.

(3) Method for Linking Sulfur Atoms A coupler having an aromatic mercapto or heterocyclic mercapto group substituted at the 7-position is a method described in US Pat. No. 3,227,554, that is, an aryl mercaptan, a heterocyclic mercaptan and a corresponding disulfide thereof. Dissolved in a halogenated hydrocarbon solvent, converted to sulphenyl chloride with chlorine or sulfuryl chloride, and dissolved in an aprotic solvent 4
It can be synthesized by adding an equivalent amount of pyrazolo [1,5-b] triazole coupler. Alkyl mercapto group 7
The method described in U.S. Pat. No. 4,264,723 is a method described in U.S. Pat. No. 4,264,723, that is, a method in which a mercapto group is introduced at the coupling active position of the coupler and a halide is allowed to act on the mercapto group, and A method of synthesizing in one step with bromine chloride) is effective. Further, in the method of the present invention, the compound represented by the general formula (X)
And pyrazolo [1,5-b] [1,2,4] represented by (V)
The substituents R ₁ and R ₃ at the 2- and 6-positions of the triazole compound are appropriately treated according to a method known per se, for example, the above-mentioned method for introducing a coupling-off group to obtain a desired group which is photochemically acceptable. May be converted to Thus, the pyrazolo [1,5-b] [1,2,4] derived using the method of the present invention
A photographic coupler comprising a triazole derivative can be represented by the following general formula.

[0023]

[Chemical 12]

However, in the formula, R ₄ and R ₅ represent a hydrogen atom or a substituent, and Y ₁ represents a hydrogen atom or a coupling-off group. Preferably, R ₄ and R ₅ are hydrogen atoms, halogen atoms, aliphatic groups, aryl groups, heterocyclic groups, cyano groups, alkoxy groups, aryloxy groups, acylamino groups, anilino groups, ureido groups, sulfamoylamino groups. , An alkylthio group, an arylthio group, an alkoxycarbonylamino group, a sulfonamide group, a carbamoyl group,
Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, Represents an acyl group, Y ₁ represents a hydrogen atom, a halogen atom, a carboxy group or an oxygen atom, a nitrogen atom, a carbon atom, or a group capable of coupling off with a group bonded to the carbon at the coupling position via a sulfur atom. , R ₄ , R ₅ or Y ₁ may be a divalent group to form a bis form, and when the moiety represented by the general formula (XI) is contained in the vinyl monomer, R ₄ or R ₅ Represents a mere bond or a linking group, through which the moiety represented by the general formula (XI) is bonded to the vinyl group. It

More specifically, R ₄ and R ₅ are each a hydrogen atom or a halogen atom (eg, chlorine atom, bromine atom, etc.).
Alkyl group (C1-C32 straight chain, branched chain alkyl group,
Aralkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, which are oxygen atom, nitrogen atom, sulfur atom, substituent linked by carbonyl group, hydroxy group, amino group, nitro group, carboxy group, It may be substituted with a cyano group or a halogen atom, and examples thereof include a methyl group, a propyl group, a t-butyl group, a trifluoromethyl group, a tridecyl group, a 2-methanesulfonylethyl group, and a 3- (3-pentadecylphenoxy group. ) Propyl group, 3- {4- {2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecaneamino} phenyl} propyl group, 2-ethoxytridecyl group, trifluoromethyl group, cyclopentyl group, 3- ( 2,4-di-t-amylphenoxy) propyl group, etc.) aryl group (eg, phenyl group, 4-t Butylphenyl group,
2,4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, etc.), heterocyclic group (for example, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.) , Cyano group, alkoxy group (eg, methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecylethoxy group, 2-methanesulfonylethoxy group, etc.), aryloxy group (eg, phenoxy group, 2-methylphenoxy group) , 4-t-butylphenoxy group, etc.), acylamino group (for example, acetamide group, benzamide group, tetradecanamide group, α- (
2,4-di-t-amylphenoxy) butyramide group,
γ- (3-t-butyl-4-hydroxyphenoxy) butyramide

A group, α- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide group, etc.), anilino group (for example, phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecaneaminoanilino group,
2-chloro-5-dodecyloxycarbonylanilino group, N-acetylanilino group, 2-chloro-5- {α-
(3-t-butyl-4-hydroxyphenoxy) dodecanamide} anilino group, etc.), ureido group, for example, phenylureido group, methylureido group, N, N dibutylureido group, etc.), sulfamoylamino group (For example, N, N-dipropylsulfamoylamino group, N-
Methyl-N-decylsulfamoylamino group, etc., alkylthio group (for example, methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3- (4-t -Butylphenoxy) propylthio group, etc.), an arylthio group (for example, phenylthio group, 2-butoxy-5-t-
Octylphenylthio group, 3-pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group, etc.), alkoxycarbonylamino group (for example, methoxycarbonylamino group, tetradecyloxycarbonylamino group, Etc.), a sulfonamide group (for example, a methanesulfonamide group, a hexadecanesulfonamide group, a benzenesulfonamide group, p-
Toluenesulfonamide group, octadecanesulfonamide group, 2-methyloxy-5-t-butylbenzenesulfonamide group, etc.), carbamoyl group (for example, N-ethylcarbamoyl group, N, N-dibutylcarbamoyl group, N- ( 2-dodecyloxyethyl) carbamoyl group, N-methyl-N-dodecylcarbamoyl group, N-
{3- (2,4-di-tert-amylphenoxy) propyl} carbamoyl group, etc.), sulfamoyl group (for example, N-ethylsulfamoyl group, N, N-dipropylsulfamoyl group, N- (2 -Dodecyloxyethyl) sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N, N-diethylsulfamoyl group,
Etc.), sulfonyl group (eg, methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxy)

Carbonyl group, etc.), heterocyclic oxy group (eg, 1-phenyltetrazole-5-oxy group,
2-tetrahydropyranyloxy group, etc.), acyloxy group (eg, acetoxy group, etc.), carbamoyloxy group (eg, N-methylcarbamoyloxy group, N-
Phenylcarbamoyloxy group, etc.), silyloxy group (eg, trimethylsilyloxy group, dibutylmethylsilyloxy group, etc.), aryloxycarbonylamino group (eg, phenoxycarbonylamino group, etc.),
Imido group (for example, N-succinimido group, N-phthalimido group, 3-octadecenylsulcinimido group,
Etc.), heterocyclic thio group (for example, 2-benzothiazolylthio group, 2,4-di-phenoxy-1,3,5-triazole-6-thio group, 2-pyridylthio group, etc.), sulfinyl group ( For example, dodecanesulfinyl group, 3-pentadecylphenylsulfinyl group, 3-phenoxypropylsulfinyl group, etc.), phosphonyl group (for example,
Phenoxyphosphonyl group, octyloxyphosphonyl group, phenylphosphonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), acyl group (eg, acetyl group, 3-phenylpropanoyl group, benzoyl group) , 4-dodecyloxybenzoyl group, etc., and Y ₁ is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, iodine atom, etc.), a carboxy group, or a group linked by an oxygen atom (eg, acetoxy group). , Propanoyloxy group, benzoyloxy group, 2,
4-dichlorobenzoyloxy group, ethoxyoxaloyloxy group, pyruvinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenoxyl group, 4-methanesulfonamidophenoxy group, 4-methanesulfonylphenoxy group, α- Naphthoxy group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group,
2-phenethyloxy group, 2-phenoxyethoxy group,
5-phenyltetrazolyloxy group, 2-benzothiazolyloxy group, etc.), a group linked by a nitrogen atom (for example,
Benzenesulfonamide group, N-ethyltoluenesulfonamide group, heptafluorobutanamide group, 2, 3,
4, 5, 6-pentafluorobenzamide group, octanesulfonamide group, p-cyanophenylureido group,
N, N-diethylsulfamonoylamino group

1-piperidyl group, 5,5-dimethyl-
2,4-dioxo-3-oxazolidinyl group, 1-benzyl-ethoxy-3-hytantoinyl group, 2N-1,1
-Dioxo-3 (2H) -oxo-1,2-benzisothiazolyl group, 2-oxo-1,2-dihydro-1-pyridinyl group, imidazolyl group, pyrazolyl group, 3,5-
Diethyl-1,2,4-triazol-1-yl, 5 or 6-bromobenzotriazol-1-yl, 5-methyl-1,2,3,4-triazol-1-yl group, benzimidazolyl group, 4 -Methoxyphenylazo group, 4-
Pivaloylaminophenylazo group, 2-hydroxy-4
-Propanoylphenylazo group, etc.), a group linked by a sulfur atom (for example, phenylthio group, 2-carboxyphenylthio group, 2-methoxy-5-t-octylphenylthio group, 4-methanesulfonylphenylthio group, 4-
Octanesulfonamide phenylthio group, benzylthio group, 2-cyanoethylthio group, 1-ethoxycarbonyltridecylthio group, 5-phenyl-2,3,4,5-tetrazolylthio group, 2-benzothiazolyl group, thiocyano group, N, N-diethylthiocarbonylthio group, dodecyloxythiocarbonylthio group, etc.), groups linked by carbon atoms (for example, triphenylmethyl group, hydroxymethyl group, N-morpholinomethyl group,

[0029]

[Chemical 13]

However, R ₆ and R ₇ are hydrogen atoms, alkyl groups,
Represents an aryl group, a heterocyclic group, R ₄ and R ₅ have the same meanings as defined above, etc.). R ₄ ,
R ₅ or Y ₁ becomes a divalent group to form a bis form 2
To describe the valent group in more detail, R ₄ and R ₅ are substituted or unsubstituted alkylene groups, for example, methylene group, ethylene group, 1,10-decylene group, —CH ₂ CH ₂ —O—CH ₂
CH ₂ -, etc.), a substituted or unsubstituted phenylene group (e.g., 1, 4-phenylene group, 1,3-phenylene group,

[0031]

[Chemical 14] -NHCO-R ₈ -CONH- group (R ₈ represents a substituted or unsubstituted alkylene group or a phenylene group, e.g.

[0032]

[Chemical 15] Indicates. ).

Next, the above general formulas (IV), (IX) and (X)
Or pyrazolo [1,5-b] [1,2,4] represented by (XI)
Specific examples of the triazole derivative are shown below, but it goes without saying that the present invention is not limited thereto.

[0034]

[Chemical 16]

[0035]

[Chemical 17]

[0036]

[Chemical 18]

[0037]

[Chemical 19]

[0038]

[Chemical 20]

[0039]

According to the present invention, pyrazolo [1,5-b] [1,
A photographic coupler comprising a 2,4] triazole derivative can be produced. The photographic coupler obtained according to the present invention couples with an oxidation product of an aromatic primary amine to form a magenta dye which has an extremely good hue and is superior in light and heat fastness to conventional pyrazolone dyes. .

[0040]

The present invention will be described in more detail based on the following examples. Reference Example 1 (Synthesis of Exemplified Compounds 1 , 2 and 3 ) (A) Synthesis of 1-amino-4-benzyl-3,5-dimethyltriazolium iodide (II)

[0041]

[Chemical 21]

In the following Examples, as (II), this 1-amino-4-benzyl-3,5 was used unless otherwise specified.
-Dimethyltriazolium iodide was used. (I) 2,5-Dimethyl-1,3,4-oxadiazole (VII) obtained by thermal decomposition of tetraacetylhydrazine
19g (0.19mol) and benzylamine 31g (0.29mol)
Was reacted at 110 ° C. for 4 hours to obtain 26 g of 4-benzyl-3,5-dimethyl-1,2,4-triazole (VI). Yield 73
%, Melting point 125-127 ° C. Hydroxylamine-O-sulfonic acid 66 g (0.58 mol)
80 g of an aqueous solution of potassium hydroxylamine-O-sulfonate prepared from 40 g (85%, 0.61 mol) of potassium hydroxide and 75 g (0.4 mol) of the above triazole (VI).
After reacting at 90 ° C. for 6 hours and returning to room temperature, the pH was adjusted to 8 to 9 with a 50% potassium carbonate aqueous solution. The potassium sulfate produced was filtered off, and the filtrate was extracted three times with chloroform. From this chloroform extract, 44 g (59%) of the starting material, triazole, was recovered. When the aqueous layer was adjusted to pH 3 with a 57% aqueous solution of hydroiodic acid under ice cooling, crystals were precipitated. The crystals were separated by filtration and recrystallized from ethanol at −20 ° C. to obtain 39 g (31%) of (II) as pale yellow crystals. (Ii) O- (2,4-dinitrophenyl) hydroxylamine as an aminating agent (J. Org. Chem. 38 1239 (1973)
) Was used to synthesize (II) as follows.

4-benzyl-1,2,4-triazole (V
I) 35 g (0.19 mol) was added to 300 ml of dichloroethane, and the mixture was vigorously stirred while heating to 70 ° C., and O- (2,4
-Dinitrophenyl) hydroxylamine 25 g (0.13
mol) was added in portions (over about 35 minutes) and further stirred at this temperature for 2 hours. The dichloroethane was distilled off under reduced pressure, the residue was dissolved in 100 ml of water, and the pH was adjusted to 3 with a 57% aqueous hydroiodic acid solution. Although 2,4-dinitrophenol started to precipitate, it was removed by extraction with ethyl acetate (three times). The aqueous layer was concentrated and the residue was recrystallized from ethanol to obtain (II) in a yield of 70%. As an aminating agent, O
-Diphenylphosphinylhydroxylamine (Synthe
sis, 592 (1982), Tetrahedron Lett., 23 , 3835 (198
When 2)) is used, the procedure is almost the same, but in this case, after treatment with hydriodic acid, diphenylphosphinic acid could be recovered (90% or more) by filtration without extraction. (B) Synthesis of 7-acetyl-1-benzyl-2,6-dimethylpyrazolo [1,5-b] [1,2,4] triazole ( 1 )

[0044]

[Chemical formula 22]

N-aminotriazolium iodide (II)
8 g (0.025 mol) of DMF (dimethylformamide)
It was dissolved in 50 ml, 40 ml of acetic anhydride was added, and the mixture was heated to 120 ° C. Then add 12.5 g of sodium acetate, 120-130
The mixture was stirred at ℃ for 4 hours. After distilling off DMF, acetic anhydride, etc. under reduced pressure, the mixture was made basic with a saturated aqueous sodium carbonate solution, extracted with chloroform, the extract was dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a brown oily substance. It was This was purified by a silica gel column in a solvent system of n-hexane-ethyl acetate to give 7-acetyl-1-benzyl-2,6-dimethylpyrazolo [1,5-b] [1,2,4] triazole ( 1 ) 3.2 g (47%) was obtained. Melting point 105-107
℃ Nuclear magnetic resonance spectrum (CDCl ₃ ) δ (ppm): 2.36 (3H, s) 2.43 (3H, s) 2.60 (3H, s)
5.80 (2H, s) 7.0 ~ 7.2 (2H) 7.2 ~ 7.36 (3H) (C) 1-benzyl-2,6-dimethylpyrazolo [1,5-
b] [1,2,4] Synthesis of triazole ( 2 )

[0046]

[Chemical formula 23]

1, 2 g (7.5 mmol) is dissolved in 20 ml of ethanol, 20 ml of concentrated hydrochloric acid is added thereto, and the mixture is heated under reflux. After about 6 hours, ethanol was distilled off under reduced pressure, basified with a saturated aqueous solution of sodium bicarbonate, and then extracted with ethyl acetate to obtain almost pure deacetylated 1-benzyl-2,6-dimethylpyrazolo [1,5- b] [1, 2, 4] triazole
( 2 ) 1.6 g (95%) was obtained. Melting point 87-88 ° C Nuclear magnetic resonance spectrum (CDCl ₃ ) δ (ppm): 2.32 (3H, s) 2.44 (3H, s) 5.02 (2H, s)
5.22 (1H, s) 7.10 to 7.40 (5H) (D) 1H-2,6-dimethylpyrazolo [1,5-b] [
Synthesis of 1,2,4] triazole ( 3 )

[0048]

[Chemical formula 24] 1-benzyl-2,6-dimethylpyrazolo [1,5-b] [1,
1.6 g (7.1 mmol) of 2,4] triazole ( 2 ) was reduced with about 0.8 g of metallic sodium in liquid ammonia to obtain the target 1H-2,6-dimethylpyrazolo [1,5-b] [1, 2,4]
0.67 g (70%) of triazole ( 3 ) was obtained as colorless crystals. Melting point 274-275 [deg.] C. (decomposition) Mass spectrometry 136 (M ⁺ , 100%) Elemental analysis value C (%) H (%) N (%) Theoretical value 52.93 5.92 41.15 Measured value 52.856 .02 41.01 nuclear magnetic resonance spectrum (CDCl ₃ : pyridine-d ₅ = 1:
1) δ (ppm): 2.35 (3H, s) 2.43 (3H, s) 5.50 (1H, s)

Reference Example 2 (Synthesis of Exemplified Compound 5)

[0050]

[Chemical 25]

5 g (16 mmol) of N-aminotriazolium iodide (II) shown in Reference Example 1, 30 g (79 mmol) of 5 equivalents of lauric anhydride and 11 g (77 mm of tripropylamine)
ol) was heated in 140 ml of DMF at 140-150 ° C. for about 10 hours. DMF was removed with an evaporator, ethyl acetate was added, the unreacted lauric anhydride that had precipitated was removed by filtration, the filtrate was transferred to a separatory funnel, 2N aqueous sodium hydroxide solution was added, and the mixture was shaken well and separated. The aqueous layer was extracted twice more with ethyl acetate, the ethyl acetate layer was washed with saturated brine and dried over magnesium sulfate, and the resulting residue was concentrated with 30 ml of concentrated hydrochloric acid.
And 50 ml of ethanol were added and the mixture was heated under reflux for about 4 hours, ethanol was removed, and the mixture was extracted with ethyl acetate. Perform the usual post-treatment and purify with a silica gel column to remove 1-benzyl form.
0.8 g (14%) was obtained. Nuclear magnetic resonance spectrum (CDCl ₃ ) δ (ppm): 0.88 (3H, brt, J = 〜7) 1.30 (20 H, brs)
2.40 (3H, s) 2.60 (2H, t, J = 7.5) 5.03 (2H, s) 5.25 (1H,
s) 7.10 to 7.45 (5H) Exemplified compound 5 which is poorly soluble in an organic solvent other than alcohol by reducing the 1-benzyl derivative with sodium in liquid ammonia.
Was obtained in a yield of about 90%. Melting point 154-155 ° C. Reference Example 3 (Synthesis of Exemplified Compound 6 )

[0052]

[Chemical formula 26]

7.2 g (55 mmol) of n-heptanoic acid was dissolved in 15 ml of dimethylformamide (DMF), 7.9 g (55 mmol) of tri-n-propylamine was added thereto, and then trimethylacetyl chloride was dissolved in 10 ml of DMF.
1 g (51 mmol) was added dropwise. After stirring at room temperature for 10 minutes, 5 g of N-aminotriazolium iodide (II) (1
5.8 mmol) and tri-n-propylamine 11.3 g (79 mmo
l) was added and the mixture was gradually heated to 150 ° C. and stirred at that temperature for about 5 hours. DMF and amine were distilled off under reduced pressure, 100 ml of 2N aqueous sodium hydroxide solution was added, and the mixture was extracted 3 times with ethyl acetate. The extract was washed with water and saturated saline and dried over magnesium sulfate. After filtration and concentration under reduced pressure, the residue was purified by silica gel chromatography, and (IV) (R ₁ ═CH ₃ ,
R ₂ = benzyl, R ₃ = -C ₆ H ₁₃ ) 2.9 g (45%)
Obtained. This was deacylated and debenzylated by the method shown in (C) and (D) of Example 1 to give 6 g (68 g).
%) I was able to get it. Mp devices 105 through 110 ° C. Nuclear magnetic resonance spectrum _{(DMSO-d 6) δ (} ppm): 0.85 (3H, brt, J = ~7) 1.32 (8H, brs)
2.45 (3H, s) 2.58 (2H, t, J = 7.5) 5.60 (1H, s) Reference Example 4 (Synthesis of Exemplified Compound 7 )

[0054]

[Chemical 27]

(II) 1.0 g (3.16 mmol) of anhydrous DMF
Dissolve it in 8 ml and add 3.6 g (1
5.8mmol) and tri-n-propylamine 2.3g (15.8mmo
l) was added and the mixture was heated with stirring at 130 ° C. for 24 hours. DMF and tri-n-propylamine were distilled off under reduced pressure and then ethanol 30m
1, 10 ml of concentrated hydrochloric acid were added, and the mixture was heated under reflux for 5 days. Ethanol and concentrated hydrochloric acid were distilled off under reduced pressure, followed by extraction with ethyl acetate and drying,
After concentrating and purifying by silica gel chromatography, 1
-0.2 g (22%) of benzyl form was obtained. Nuclear magnetic resonance spectrum (CDCl ₃ ) δ (ppm): 2.35 (3H, s) 4.95 (2H, s) 5.65 (1H, s)
7.05-7.50 (8H) 7.8022 (2H, dd, J = 9.0,1.5) 0.2 g (0.69 mmol) of 1-benzyl compound in liquid ammonia
Reduced with 0.05g sodium, 0.12g of target 7
(87%) obtained. Melting point ~ 190 ° C (decomposition)

Reference Example 5 (Synthesis of Exemplified Compounds 8 and 9 )

[0057]

[Chemical 28]

1.00 g (32 mmol) of (II) was added to 15 ml of N-
Methylpyrrolidone was added, and the mixture was stirred at room temperature, 2.93 g of methoxycarbonylpropionic anhydride and 4.8 ml of tripropylamine were sequentially added, and the mixture was heated on an oil bath at 130 ° C. for 3 hours. After cooling, it was diluted with ethyl acetate and washed with water (100
ml x 2). The ethyl acetate layer was dried over anhydrous magnesium sulfate and then concentrated, to which 30 ml of methanol and 20 ml of concentrated hydrochloric acid were added, and the mixture was heated under reflux for 7 hours. After cooling, ethanol was removed by concentration under reduced pressure, and the residue was poured into 100 ml of ice water to neutralize the pH.
After setting to 7, it was extracted with ethyl acetate (50 ml × 3).
The ethyl acetate layer was dried over anhydrous magnesium sulfate, concentrated, and purified with a silica gel column (20 g) to give 8 0.16 g.
(17%) was obtained as an oil. Nuclear magnetic resonance spectrum (CDCl ₃ ) δ (ppm): 2.42 (3H, s) 2.60 to 3.15 (4H, m) 3.63 (3
H, s) 5.02 (2H, s) 5.26 (1H, s) 7.12-7.50 (5H, m) Elemental analysis value C (%) H (%) N (%) Theoretical value 64.41 6.08 18.78 Measured value 64.22 6.30 18.55 This N-benzyl compound was reduced with sodium in the same manner as above to obtain Exemplified Compound 9 in a yield of about 80%. Melting point
120 to 122 ° C

Example 1 (Synthesis of Exemplified Compounds 11 , 12 , 13 , 14 )

[0060]

[Chemical 29]

9.5 g (30 mmol) of (II) and 65 g (150 mm
ol) anhydrous 4- (p-nitrophenyl) butyric acid and 57 ml
(300 mmol) tripropylamine was dissolved in 150 ml DMF. The mixture was heated under stirring on a 130 ° C. oil bath for 4 hours, then on a 140 ° C. oil bath for 2 hours and then on a 160 ° C. oil bath for 6 hours. DMF was distilled off under reduced pressure, and the residue was dissolved in ethyl acetate.
It was washed with an aqueous OH solution (twice). The ethyl acetate layer was dried over anhydrous magnesium sulfate, concentrated, and subjected to silica gel column chromatography (silica gel 600 g, eluent hexane: ethyl acetate = 2: 1 to 1: 1) to give 7.6 g (45
%) Of (IV) (R ₁ = -CH ₃ , R ₂ = benzyl, R ₃
= Give the _{(CH 2) 3 C 6 H} 4 -NO 2). Nuclear magnetic resonance spectrum (CDCl ₃ ) δ (ppm): 2.40 (3H, s) 1.8 to 3.3 (12H, m) 5.80
(2H, s) 7.0 ~ 7.4 (9H, m) 8.1 (4H, m)

7.6 g (13 mmol) of (IV) was added to EtOH 150
It was dissolved in a mixed solvent of 50 ml of concentrated hydrochloric acid and heated under reflux for 10 hours. After adding 100 ml of water, ethanol was removed by concentration under reduced pressure. After neutralizing with aqueous ammonia, the mixture was extracted with ethyl acetate, and the ethyl acetate layer was dried over anhydrous magnesium sulfate. After concentration, silica gel column chromatography (silica gel 140 g, eluent hexane: ethyl acetate = 1: 1)
1) (IX) (R ₁ = CH ₃ , R ₂ = benzyl, R
_{3 = (CH 2) 3 C} 6 H 4 NO 2) was obtained 3.8g (76%). Nuclear magnetic resonance spectrum (CDCl ₃ ) δ (ppm): 2.03 (2H, m) 2.44 (3H, s) 2.58 to 2.85 (4
H, m) 5.02 (2H, s) 5.20 (1H, s) 7.04 ~ 7.40 (7H, m) 8.
04 (2H, d, J = 8.0) Reduced iron 18g (0.32mol
), Ammonium chloride (1.3 g, 25 mmol) and water (8 ml) were added, and the mixture was heated to reflux with vigorous stirring. To this, 0.2 ml of concentrated hydrochloric acid was added, and the mixture was heated under reflux for 30 minutes. To this, 18.0 g (47.9 mmol) of the nitro compound was added little by little over 20 minutes, and the mixture was heated under reflux for 1 hour. After filtering through Celite, the Celite was thoroughly washed with ethanol. The filtrate was concentrated, dissolved in ethyl acetate, washed with water, and dried over anhydrous magnesium sulfate. Concentration to give the crude product aniline ((IX) R ₃ = (CH ₂ ) ₃ C ₆ H
₄ NH ₂ ) (15.8 g, 95%) was obtained. Nuclear magnetic resonance spectrum (CDCl ₃ ) δ (ppm): 1.95 (2H, m) 2.38 (3H, s) 2.40 to 2.76 (4
H, m) 3.36 (2H, br) 4.97 (2H, s) 5.20 (1H, s) 6.53 (2
H, m) 6.91 (2H, m) 7.00 ~ 7.38 (5H, m)

15.8 g (45.7 mmol) of this aniline body was added to 200 ml of liquid ammonia in a reflux state and stirred. To this, 2.6 g (0.11 mol) of sodium metal was added little by little.
Ammonium chloride was added little by little to this, and the mixture was left overnight to remove ammonia. The residue was dissolved in 2N aqueous HCl solution and washed with ethyl acetate. The aqueous layer was neutralized with aqueous ammonia, and the deposited precipitate was collected by filtration. The precipitate was washed with water, followed by acetonitrile, and then dried to obtain almost pure 11 7.9 g (68%). Melting point 199-203 ° C Nuclear magnetic resonance spectrum (CDCl ₃ + DMSO-d ₆ ) δ (ppm): 1.88 (2H, br, quintet, J = 〜7) 2.41 (3
H, s) 2.3 to 2.8 (4H) 5.42 (1H, s) 6.56 (2H, d, J = 8.5)
6.90 (2H, d, J = 8.5) mass spectrum ^{255 (M +, 20%)} 136 (100), 119 (90) 106 (50) Infrared absorption spectrum (KBr) 3340, 1605, 1507 , 1380, 1270cm - ¹

11 3.00 g (11.7 mmol) of acetonitrile 5
In addition to 0 ml, N, N-dimethylacetamide 25
ml was added and the mixture was heated with stirring until it reached a reflux state. To this acid chloride _{(C 6 H 5 -CH 2 O} -C 6 H 5 -SO 2
_{-C 6 H 5 -OCH (n-} C 10 H 21) COCl) 7.19g
A solution of (12.9 mmol) in acetonitrile (20 ml) was added dropwise over 20 minutes, and the mixture was refluxed for 20 minutes. Furthermore, a solution of the above acid chloride 0.72 g (0.13 mmol) in acetonitrile (10 ml)
Was added dropwise over 10 minutes, and then reflux was continued for 30 minutes. After cooling, the mixture was poured into 500 ml of water and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate, concentrated, and subjected to silica gel column chromatography (silica gel 300 g, eluent chloroform: methanol = 60: 1) to give 7.25 g.
(80%) of 12 (solid) was obtained. Elemental analysis value C (%) H (%) N (%) S (%) Theoretical value 69.65 6.88 9.02 4.13 Measurement value 68.99 6.90 8.90 4.07 Mass spectrometry (FD) 776 (M ⁺ , bp) Nuclear magnetic resonance spectrum ( CDCl ₃ ) δ (ppm): 0.86 (3H, brt, J = 7) 1.0 to 2.2 (20H, m)
2.38 (3H, s) 2.5 ~ 2.8 (4H, m) 4.68 (1H, brt, J = 6)
5.05 (2H, s) 5.45 (1H, s) 6.9 ~ 7.4 (13H, m) 7.7 ~ 7.9
(4H, m) 8.17 (1H, s) 11.6 (1H, br)

3.3 g (4.3 mmol) of benzyl derivative 12 was added to TH
It was dissolved in 60 ml of F and 0.66 g of 10% Pd / C was added. This was stirred at 60 ° C. for 3 hours under a hydrogen atmosphere of 60 atm. After cooling, the catalyst was filtered off and the filtrate was concentrated. Subjected to silica gel column chromatography (silica gel 90 g, eluent chloroform: methanol = 1: 0 to 30: 1), 2.7 g
(92%) of 13 was obtained as a solid. Mass spectrometry ^{(FD) 687 (M + +} 2,50%) 686 (M + + 1, 100) 685 (M +, 30) and 13 and THF50ml of 4.25 g (6.20 mmol) in dichloromethane 100 ml, at room temperature Stir to dissolve. to this
795 mg (5.95 mmol) of N-chlorosuccinimide was added and stirred for 15 minutes at room temperature. Wash with water (150ml x 2)
After that, it was dried over anhydrous magnesium sulfate. After concentration, silica gel column chromatography (silica gel 100
g, eluate chloroform: methanol = 50: 1 to 30: 1) to obtain 14 4.04 g (90%) as a solid. Mass spectrometry (FD) 722, 721, 720 (9: 7: 9) 220 (bp)

Example 2 (Synthesis of Exemplified Compounds 15 and 16 )

[0067]

[Chemical 30]

11 , 1.79 g (7.00 mmol) and 15 ml of N, N-dimethylamide were added to 30 ml of acetonitrile, and the mixture was heated and stirred until it became a reflux state. Acid chloride [(t-
_{C 5 H 11) 2 C 6} H 3 OCH (n-C 4 H 9) COC
l] 2.83 g (7.70 mmol) of acetonitrile solution (10 m
1) was added dropwise over 15 minutes, and reflux was continued for another 30 minutes. After cooling, it was poured into 300 ml of water and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate, concentrated, and subjected to silica gel column chromatography (silica gel 100 g, eluent chloroform: methanol 70:
Fractionation in 1) gave 15 as 3.12 g (76%) solid. Elemental analysis value C (%) H (%) N (%) theoretical value 73.81 8.77 11.95 measured value 73.64 8.95 11.93 nuclear magnetic resonance spectrum (CDCl ₃ ) δ (ppm): 0.50 ~ 1.00 (7H, m) 1.00 ~ 2.16 (26H, m)
2.44 (3H, s) 2.46 ~ 2.80 (4H, m) 4.66 (1H, t, J = 6.0)
5.44 (1H, s) 6.90 ~ 7.34 (6H, m) 7.64 (1H, d, J = 9.0)
7.87 (1H, br, s)

3.10 g (5.29 mmol) of 15 and 50 ml of THF were added to 100 ml of dichloromethane and dissolved by stirring at room temperature. N-chlorosuccinimide 706mg (5.29mm
ol) was added and the mixture was further stirred for 10 minutes. Washing with water (150 ml x
After 2), it was dried over anhydrous magnesium sulfate. After concentration, acetonitrile was added to crystallize, and the mixture was heated under reflux once. After cooling, it was collected by filtration, washed with acetonitrile, and then dried to obtain 2.4 g (73%) of 16 as a solid. Elemental analysis value C (%) H (%) N (%) Cl (%) Theoretical value 69.71 8.12 11.29 5.72 Measured value 69.36 8.21 11.25 5.78 Nuclear magnetic resonance spectrum (CDCl ₃ ) δ (ppm): 0.48 to 1.00 (7H, m) 1.06 to 2.18 (26H,
m) 2.45 (3H, s) 2.48 ~ 2.82 (4H, m) 4.67 (1H, t, J = 6.
0) 6.65 (1H, d, J = 8.5) 6.91 ~ 7.34 (6H, m) 7.87 (1H,
s)

Example 3 (Synthesis of Exemplified Compounds 21 , 22 , 17 )

[0071]

[Chemical 31]

2.93 g (5.00 mmol) of 15 was added to 25 ml of acetic acid and stirred at room temperature. Isoamyl nitrite 586mg
(5.00 mmol) was added dropwise, and the mixture was further stirred for 1 hour. This was slowly added to 300 ml of water, and the deposited precipitate was collected by filtration and washed with water. Dry under reduced pressure to give 7-nitroso 21
2.95 g (96%) were obtained as a solid. Melting point: 95 ° C. 2.85 g (4.63 mmol) of 7-nitroso form 21 in ethanol 50
It was dissolved in ml and heated to reflux under a nitrogen atmosphere.
To this, a concentrated hydrochloric acid solution (10 ml) of 4.38 g (23.1 mmol) of stannous chloride was added dropwise over 10 minutes. Refluxing was continued for another 30 minutes and then cooled. This was poured into 150 ml of water and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate and then concentrated to dryness. Thus, a complex of 7-amino compound 22 and tin was obtained. Free 22 can be obtained by treating with base, but is easily aerated by air. Here, the complex was used for the next reaction as it was. This 7
-Amino compound 22 was dissolved in 25 ml of pyridine and stirred under a nitrogen stream while cooling with water. Acid chloride [H (CF
₂ ) ₈ COCl] 2.15 g (4.63 mmol) was added dropwise, and the mixture was further stirred for 1 hour. This was poured into 250 ml of water and extracted with ethyl acetate. The ethyl acetate layer was washed with 2N hydrochloric acid and then with water. The ethyl acetate layer was dried over anhydrous magnesium sulfate and then concentrated. Collect by silica gel column chromatography (silica gel 150 g, eluent chloroform: methanol = 100: 1) and concentrate the eluate to dryness. 17
3.43 g (72%) was obtained. Nuclear magnetic resonance spectrum (CDCl ₃ ) δ (ppm): 0.52 to 1.01 (7H, m) 1.02 to 2.15 (26H, m)
2.42 (3H, s) 2.46 ~ 2.78 (4H, m) 4.60 (1H, t, J = 6.0)
6.30 (1H, tt, J = 51.0, 5.0) 7.45 (1H, d, J = 8.5) 6.85
~ 7.36 (6H, m) 8.90 (1H, brs) 10.0 (1H, brs) 10.3 (1H,
brs)

Claims (1)

[Claims] 1. A general formula: (In the formula, R ₁ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, R ₂ represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and X represents an acid radical. .) And an N-aminotriazolium salt represented by the general formula: (In the formula, R ₃ is a hydrogen atom, an alkyl group, a substituted alkyl group,
An aryl group or a substituted aryl group is shown. ) An acid anhydride represented by the formula (In the formula, R ₁ , R ₂ and R ₃ have the same meanings as described above.) 7-acylated pyrazolo [1,5-b]
[1, 2, 4] triazole was obtained, which was deacylated at the acyl group at the 7-position, reduced at the 1-position, and then released at the 7-position by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. By introducing a group Y to (In the formula, R ₁ and R ₃ have the same meanings as described above, and Y represents the above-mentioned coupling-off group.) A pyrazolo [1,5-b] [1,2,4] triazole compound represented by A process for producing a pyrazolo [1,5-b] [1,2,4] triazole-based photographic coupler, which is obtained.