JPH0714941B2 - 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] [1,2,4] triazole derivative. The present invention relates to a method for producing a novel photographic coupler.

[0002]

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

[0003]

[Chemical 4]

The 5-5 fused polycyclic compound represented by
Example Called "azapentalene". This compound is
Interest in structural chemistry, interest as a physiologically active substance, and
Mainly from interest as a magenta coupler in true chemistry
Research has been done (J. Elgureo, R. Jacquier, S. Mi
gnonac-Mondon,J. Heterocyclic. Chem.,Ten, 411 (19
73), H. Koga, M. Hirobe, T. Okamoto,Chem. Pharm.
Bull.,twenty two, 482 (1974), J. Bailey,JCS Perkin
I, 2047 (1977), JP-B-47-27411, JP-A-50-1295.
See No. 86). However, conventional azapentalene
The compound is a photographic magenta coupler that
Not yet satisfactory in terms of thermal robustness
It was

[0005]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies to develop a novel photographic coupler compound which overcomes the above-mentioned drawbacks of conventional azapentalene compounds, and as a result, amido oxime containing a pyrazolyl group has been obtained. It was found that a novel azapentalene compound having a skeleton was synthesized by a dehydration ring closure reaction of the compound, and a photographic coupler comprising the compound could satisfy the above object. The present invention has been accomplished based on this finding. That is, the present invention is
General formula

[0006]

[Chemical 5]

(Wherein R ₁ and R ₂ represent a hydrogen atom or a substituted or unsubstituted alkyl or aryl group) by dehydration cyclocondensation to give a compound of the general formula

[0008]

[Chemical 6]

(In the formula, R ₁ and R ₂ have the same meanings as described above.) Pyrazolo [1,5-b] [1,2,
4] A triazole derivative is produced, and a group (hereinafter, abbreviated as a coupling-off group) which is released by a coupling reaction with an oxidation product of an aromatic primary amine developing agent is introduced at the 7-position of the compound. General formula to be synthesized

[0010]

[Chemical 7]

(In the formula, R ₁ and R ₂ have the same meanings as described above, and X represents a coupling-off group.) A pyrazolo [1,5-b] [1,2,4] triazole derivative The present invention provides a photographic coupler characterized by comprising: In the method of the present invention, the compound of the general formula (II) is preferably a compound of the general formula

[0012]

[Chemical 8]

(Wherein R ₂ has the same meaning as described above) and an aminopyrazole represented by the general formula R ₁ C (OR ₃ ) ₃ ... (V) (wherein R ₁ is as defined above). have the same meaning, R ₃ is ortho ester represented by an alkyl group.), or _{R 1a CH = C (oR 3} ) in ₂ ··· (V ') (wherein, R _1a is a substituted or unsubstituted And a group having a relationship of R ₁ = R _1a CH ₂ — with R ₁ which is an alkyl group of
R ₃ has the same meaning as described above. ) And a ketene acetal represented by the general formula

[0014]

[Chemical 9]

(Wherein R ₁ , R ₂ , and R ₃ have the same meanings as described above), an imide ester of pyrazole is produced, and a compound represented by the general formula (VI) and hydroxylamine are added. It is manufactured by reacting.

In the present invention, the above general formulas (II) and (II
I), (IV), (V), (V ^' ), (VI) and (VII)
In the compound represented by, the alkyl groups of R ₁ , R ₂ and R ₃ are a lower alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group to a higher alkyl group having 22 carbon atoms,
For example, it means 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.

Examples of the aryl group of R ₁ and R ₂ include a phenyl group and a naphthyl group, and examples of the substituted alkyl group include a halogen-substituted alkyl group such as a 2-chloroethyl group and a trifluoromethyl group, and 2-ethoxytril group. Alkoxy-substituted alkyl groups such as decyl group, acyl-amide-substituted alkyl groups such as 2-acetamidoethyl group, sulfonamide-substituted alkyl groups such as 2-methanesulfonamidoethyl group, 3 (2,4-di-t-amylphenoxy) propyl group, 3- {4- {2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamide} phenyl}
Examples of the alkyl group substituted with a substituted or unsubstituted aryl group such as a propyl group, a benzyl group, and a phenethyl group, and examples of the substituted aryl group include a halogenophenyl group, a nitrophenyl group, a cyanophenyl group, and an alkoxyphenyl group. Further, R ₁ and R ₂ may have a group inert to the reaction, such as an alkoxyl group, a nitro group, a halogen atom, etc., as a substituent.

The pyrazolo [1,5-b] [1,2,4] triazole derivative obtained by the method of the present invention, wherein R ₁ or R ₂ further has a substituent as described above, It can be obtained directly according to the reaction scheme described below, but in this scheme, the basic skeleton pyrazolo [1,5
-B] [1,2,4] triazole ring is formed,
Subsequent reaction may lead to the desired substituent. For example, as shown in Example 4 below, compound 2 of the present invention
The amino group of 0 can be derived to the acid anilide 22 or the like by a known method. The method of the present invention can be represented by the following reaction scheme. In the reaction process formula, the method of the present invention is (II) → (III
(III) obtained by the dehydration cyclocondensation step of
) → (VII) is a step of introducing a coupling-off group.

[0019]

[Chemical 10]

An embodiment of the present invention will be described according to the above reaction process formula. The reaction of aminopyrazole (IV) with orthoester (V) or ketene acetal (V ') is preferably in the presence of a solvent, in a temperature range of 40 to 150 ° C, preferably 100 to 120 ° C, and a reaction time of 10 minutes. ~ 2
Perform in the range of 0 hours. When the reaction temperature is less than the above lower limit,
The reaction does not proceed sufficiently and requires a long reaction time,
If it exceeds the upper limit, the reaction yield may be reduced. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as chloroform, dichloroethane and trichloroethane, and ether solvents such as tetrahydrofuran and dioxane. When the reaction with the ketene acetal is carried out, an acid catalyst is preferably used when the reaction with the orthoester is slow. Examples of the acid catalyst include methanesulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid and the like. The molar ratio of aminopyrazole (IV) and orthoester (V) is preferably in the range of 2: 1 to 1: 2.

Specific examples of aminopyrazole (IV) include 3-aminopyrazole, 5-amino-3-methylpyrazole, 5-amino-3-phenylpyrazole, 5-
Amino-3- [3 '-(p-nitrophenyl) propyl]
Examples include pyrazole. Specific examples of orthoesters include triethyl orthoformate, triethyl orthoacetate, triethyl orthopropionate, triethyl orthobutyrate, trimethyl orthoisocaproate, trimethyl ortho-4- (p-nitrophenyl) butyrate, and ketene acetal. Examples include methyl ketene diethyl acetal, phenyl ketene dimethyl acetal, p-nitrophenyl dimethyl acetal and the like.

Aminopyrazole (IV) may be commercially available, but if necessary, it was obtained by reacting an acid halide (VIII) with an enolate (IX) of sodium cyanoacetate as shown in the above formula. It can be synthesized by reacting the oxopropiononitrile derivative (X) with hydrazine. When R ₂ is a methyl group, the reaction of 3-aminocrotononitrile, which can be easily synthesized from acetonitrile and sodium, with hydrazine produces (IV) (R ₂ =
--CH ₃ ) can be synthesized (J. Heterocycl. Chem., Vol. 11, 423.
P., 1974). Next, by reacting the imide ester compound of general formula (VI) with hydroxylamine, general formula (II)
The amide oxime compound is synthesized at 0 to 80 ° C. for a reaction time of 0.5 to 12 hours. If the reaction temperature is lower than the lower limit of the above range, the reaction progress is insufficient, and if it exceeds the upper limit, decomposition of hydroxylamine occurs, or side reactions occur when excess hydroxylamine is used. As the reaction solvent, alcohols such as methanol and ethanol are used. In this reaction, the molar ratio of hydroxylamine to imide ester is preferably 1 to 20.

The amidoxime compound of the general formula (II) obtained by this reaction is subjected to the cyclodehydration condensation reaction of the general formula (III
The synthesis of the pyrazolotriazole compound (1) is carried out using a suitable dehydrating agent in the presence of a base. This reaction is preferably carried out in an inert solvent such as tetrahydrofuran or dioxane in such an amount that the reaction proceeds sufficiently (usually 1 equivalent).
It is desirable to use the dehydrating agent described above and the reaction temperature is 4
The range of 0 to 100 ° C. and the reaction time of 2 to 10 hours is preferable. As the dehydrating agent, in addition to p-toluenesulfonic acid chloride, methanesulfonyl chloride, trifluoromethanesulfonyl chloride, phosphorus oxychloride, thionyl chloride and the like can be used. As the base, in addition to triethylamine, a tertiary amine such as diisopropylethylamine, pyridine, 4-dimethylaminopyridine and the like can be used. The amount of this base is 0.5 to 2 equivalents, preferably 1 equivalent. In the above reaction step, 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 pyrazolo [1,5-b] [1,2,4] triazole compound represented by the general formula (III) is further treated to give a photographic coupler at the 7-position of the compound. As known per se, a group capable of leaving by a coupling reaction with an oxidation product of an aromatic primary amine developing agent (coupling leaving group) can be introduced. This is appropriately carried out in the production of photographic couplers in order to adjust the coupling reaction rate with the oxidation product of an aromatic primary amine oxidized by silver halide and to reduce the amount of silver used. It is a method and is known per se.

A general method for introducing a coupling-off group will be described below. (1) Method of linking oxygen atoms By reacting a 4-equivalent core coupler, a pyrazolo [1,5-b] triazole type coupler, synthesized by the method of the present invention, with an oxidation product of an aromatic primary amine. Forming a dye, hydrolyzing it in the presence of an acid catalyst to give a ketone, and hydrogenating the ketone with Pd-carbon as a catalyst;
After reduction with Zn-acetic acid or reduction with sodium borohydride, 7-hydroxy-pyrazolo [1,5-
b] Triazole can be synthesized. This can be reacted with various halides to synthesize a coupler having a desired oxygen atom linked thereto. (U.S. Patent 3,926,631
(See No. 57-70817) (2) Method of connecting nitrogen atoms There are roughly three methods of connecting nitrogen atoms. The first method is to nitrosate the coupling active site with a suitable nitrosating agent as described in U.S. Pat.
hydrogenation method using d-carbon or the like, chemical reduction method using stannous chloride or the like) to obtain 7-amino-pyrazolo [1,
5-b] triazole is reacted with various halides,
Mainly amide compounds can be synthesized.

The second method is the method described in US Pat. No. 3,725,067, that is, by a suitable halogenating agent such as sulfuryl chloride, chlorine gas, bromine, N-chlorosuccinimide, N-bromosuccinimide and the like. The -position is halogenated, and then the nitrogen heterocycle is treated with a suitable base catalyst, triethylamine, by the method described in JP-B-56-45135.
Substituting in the presence of sodium hydroxide, diazabicyclo [2,2,2] octane, anhydrous potassium carbonate and the like, a coupler having a nitrogen atom linked to the 7-position can be synthesized. Of the compounds linked by an oxygen atom, 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 type aromatic nitrogen heterocycle into the 7-position and is synthesized by the second method as described in JP-B-57-36577. 2 times the molar amount of 6π with respect to the
Alternatively, by adding a 10π electron type aromatic nitrogen heterocycle,
Aromatic nitrogen hetero linked to the 7-position by a nitrogen atom by heating without solvent at 150 ° C or in an aprotic polar solvent such as dimethylformaldehyde, sulfolane or hexamethylphosphotriamide at 30 to 150 ° C. A ring group can be introduced.

(3) Method for Linking Sulfur Atoms A coupler in which an aromatic mercapto or heterocyclic mercapto group is substituted at the 7-position is a method described in US Pat. No. 3,227,554, that is, aryl mercaptan, heterocyclic mercaptan and its corresponding disulfide. Can be synthesized by dissolving it in a halogenated hydrocarbon solvent and adding it to a 4-equivalent pyrazolo [1,5-b] triazole coupler dissolved in an aprotic solvent as sulfenyl chloride with chlorine or sulfuryl chloride. 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.

In the method of the present invention, the general formula (II
I)) pyrazolo [1,5-b] [1,2,
4] Substituent R at 2-position and 6-position of triazole compound
₁ and R ₂ may be appropriately treated according to a method known per se, for example, the method for introducing a coupling-off group described above, to convert it into a desired group which is photochemically acceptable. Thus, the pyrazolo [1,5-b] derived using the method of the present invention
The [1,2,4] triazole derivative can be represented by the following general formula.

[0029]

[Chemical 11]

However, in the formula, R ₄ and R ₅ represent a hydrogen atom or a substituent, and X represents a coupling-off group. Preferably, R ₄ and R ₅ are hydrogen atom, halogen atom, aliphatic group, aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, acylamino group, anilino group,
Ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group,
Sulfonamide group, 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 A group, an aryloxycarbonyl group, an acyl group,
X represents 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, and R ₄ , R ₅ or X is It may be a divalent group to form a bis form. Further, when the portion represented by the general formula (XI) is contained in the vinyl monomer, either R ₄ or R ₅ represents a simple bond or a linking group and is represented by the general formula (XI). The moieties are attached to vinyl groups.

More specifically, R ₄ and R ₅ are each a hydrogen atom or a halogen atom (eg, chlorine atom, bromine atom, etc.).
Alkyl group (straight chain, branched chain alkyl group having 1 to 32 carbon atoms, aralkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, which are oxygen atom, nitrogen atom, sulfur atom, carbonyl group, It may be substituted with a connecting substituent, a hydroxy group, an amino group, a nitro group, a carboxy group, a cyano group, or a halogen atom, and examples thereof include a methyl group, a propyl group, a t-butyl group, a tridecyl group, and 2-methane. Sulfonylethyl group, 3- (3
-Pentadecylphenoxy) 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 (for example, phenyl group, 4-t-butylphenyl group, 2,4-di-t-amylphenyl group, 4-tetradecanamidophenyl group,
Etc.), a heterocyclic group (for example, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group,
Etc.), cyano group, alkoxy group (for example, methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecylethoxy group, 2-methanesulfonylethoxy group, etc.), aryloxy group (for example, phenoxy group, 2-methyl). Phenoxy group, 4-t-butylphenoxy group, etc.), acylamino group (for example, acetamide group, benzamide group,
Tetradecanamide group, α- (2,4-di-t-amylphenoxy) butylamide group, γ- (3-t-butyl-
4-hydroxyphenoxy) butyramide group, α- {4
-(4-Hydroxyphenylsulfonyl) phenoxy}
Decanoamide 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 (eg, phenylureido group, methylureido group, N, N-dibutylureido group, etc.), sulfamoylamino group (eg, N, N-dipropylsulfamoylamino group, N-methyl- N-decylsulfamoylamino group, etc.), alkylthio group (eg, methylthio group, octylthio group, tetradecylthio group, 2
-Phenoxyethylthio group, 3-phenoxypropylthio group, 3- (4-t-butylphenoxy) propylthio group, etc.), arylthio group (for example, phenylthio group,
2-butoxy-5-t-octylphenylthio group, 3-
Pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group,
Etc.), alkoxycarbonylamino group (eg, methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), sulfonamide group (eg, methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfone) Amide 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-t-amylphenoxy) propyl} carbamoyl Group, etc.), sulfamoyl group (eg, N-ethylsulfamoyl group, N, N-dipropylsulfamoyl group, N- (2-
Dodecyloxyethyl) sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N, N-diethylsulfamoyl group, etc., sulfonyl group (for example, methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluene) Sulfonyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl 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.), a heterocyclic thio group (eg, 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.).

More specifically, X is 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). Base,
2,4-dichlorobenzoyloxy group, ethoxyoxaloyloxy group, pyrvinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenoxyl group, 4
-Methanesulfonamidephenoxy group, 4-methanesulfonylphenoxy group, α-naphthoxy group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group, 2-phenethyloxy group , A 2-phenoxyethoxy group, a 5-phenyltetrazolyloxy group, a 2-benzothiazolyloxy group, and the like), a group linked by a nitrogen atom (for example, a benzenesulfonamide group, an 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.), sulfur atom Linking group (for example, phenylthio group, 2-carboxyphenylthio group, 2-methoxy-5-t-octylphenylthio group,
4-methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio 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 (eg, triphenylmethyl group, hydroxymethyl group, N
-Morpholinomethyl group,

[0033]

[Chemical 12]

(In the formula, R ₄ and R ₅ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₄ and R ₅
Has the same meaning as previously defined), etc.).

[0035] R _4, R ₅ or Stated X further detail a divalent group forming a bis-become a divalent group, R _4,
R ₅ is a substituted or unsubstituted alkylene group (eg, methylene group, ethylene group, 1,10-decylene group, —CH ₂ C
_{H 2 -O-CH 2 CH 2} -, etc.), a substituted or unsubstituted phenylene group (e.g., 1,4-phenylene group, 1,3
Phenylene group,

[0036]

[Chemical 13]

, Etc.), --NHCO--R ₈ --CONH-- group (R ₈ represents a substituted or unsubstituted alkylene group or phenylene group, for example,

[0038]

[Chemical 14]

Is shown. ). Next, the above general formula (X
Pyrazolo [1,5-b] [1,2, represented by I)
4] Specific examples of the triazole derivative are shown below.
Of course, the present invention is not limited to this.
Is. In the following specific examples, it was obtained by the method of the present invention.
Photographic couplers are compoundsTwo，10，12~1
6，21，23~27，35，38Is indicated by
It

[0040]

[Chemical 15]

[0041]

[Chemical 16]

[0042]

[Chemical 17]

[0043]

[Chemical 18]

[0044]

[Chemical 19]

[0045]

[Chemical 20]

[0046]

[Chemical 21]

[0047]

[Chemical formula 22]

[0048]

[Chemical formula 23]

The melting points are summarized in Table 1 below as a representative of the physical data of the above exemplified compounds.

[0050]

[Table 1]

[0051]

INDUSTRIAL APPLICABILITY According to the present invention, a pyrazolo pigment which is coupled with an oxidation product of an aromatic primary amine and has an extremely good hue and which is more excellent in light and heat fastness than conventional pyrazolone dyes. A photographic coupler comprising a 1,5-b] [1,2,4] triazole derivative can be obtained. This compound is a novel azapentalene compound useful as a magenta coupler for color photography, as a dye development agent for color diffusion transfer photography, as a synthetic intermediate for a dye releasing agent, and as an intermediate for the production of sensitizing dyes for photography. is there. In addition, this compound has the potential to be used as a physiologically active substance,
Furthermore, it can be an intermediate in the manufacture of pharmaceuticals.

[0052]

The present invention will be described in more detail based on the following examples. Reference Example 1 (Synthesis of Exemplified Compound 1 )

[0053]

[Chemical formula 24]

2.4 g (25 mmol) of 5-amino-3-methylpyrazole (IV) obtained by reaction of 3-aminocrotononitrile with hydrazine hydrate and 6.0 g (37 mmol) of triethyl orthoacetate in 20 ml of toluene. The mixture is heated under reflux for about 10 hours, then toluene is distilled off (V
The crude product of I) was obtained as an oil. Nuclear magnetic resonance spectrum (CDCl ₃ ) δ (ppm): 1.28 (3
H, t, J = 7.5) 1.96 (3H, s) 2.22 (3H, s) 4.19 (2H, q, J
= 7.5) 5.50 (1H, s) 2.6 g (37 mmol) of hydroxylamine hydrochloride was dissolved in 20 ml of methanol, and 7.4 ml of 28% sodium methoxide methanol solution was added at 0 ° C. While removing the precipitated salt by filtration, add it to the methanol solution of (VI) at 0 ° C.
Added in. After the addition was completed, the temperature was returned to room temperature, the mixture was stirred for about 1 hour, methanol was distilled off, and the formed crystals were washed with chloroform to obtain 3.2 g (83%) of (II). Melting point 180
~ 185 ° C (decomposition) Nuclear magnetic resonance spectrum (DMSO-d ₆ ) δ (p
pm): 1.87 (3H, s) 2.12 (3H, s) 5.65 (1H, s) Elemental analysis value C (%) H (%) N (%) Theoretical value 46.74 6.54 36.34 Measured value 46 1.56 g (9.7 mmol) of .66 6.63 36.10 (II) was dissolved in 150 ml of tetrahydrofuran (THF), and triethylamine 1.
2 g was added, then p-toluenesulfonic acid chloride 2.
Add 2 g in small portions at room temperature. After stirring for 30 minutes, 150 ml of THF is added and the mixture is heated under reflux for 7 hours. The amine salt produced as a precipitate was filtered off, the filtrate was concentrated, the resulting residue was purified by chromatography 1, 0.9 g
(68%) was obtained. Melting point 274 to 275 ° 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) Also, a small amount of 2 (melting point 250-255 ° C (decomposition)) was obtained as a by-product. Reference Example 2 (Synthesis of Exemplified Compound 17 )

[0055]

[Chemical 25]

Trimethyl ortho-isocaproate is about 50% from isocapronitrile via imide ester hydrochloride.
Could be synthesized in a yield of Boiling point 75-77 ° C / 28 mmHg.
This orthoester (19.8 g, 0.11 mol) and (I
10.9 g (0.11 mol) of V) was heated under reflux in 200 ml of toluene for about 24 hours, and then toluene was distilled off under reduced pressure to obtain a crude product of (VI) as an oil. To this, a methanol solution of hydroxylamine prepared from 11.7 g (0.17 mol) of hydroxylamine hydrochloride and 34 ml of 28% sodium methoxide was added at 0 ° C.
After stirring for an hour, methanol was distilled off under reduced pressure. Chloroform was added to the residue to precipitate (II) powder crystals, 12 g (5
2%) was collected by filtration, the crystals were dissolved in tetrahydrofuran (3 liters), and 6.9 g (68 mmol) of triethylamine and 13.1 g (68 mmol) of p-toluenesulfonic acid chloride were added, and the same as in <Example 1>. it by 17 for the operation, it was possible to obtain 7.1g (65%). Melting point 140-142 ° C Mass spectrometry 192 (M ⁺ ) 136 (bp) Nuclear magnetic resonance spectrum (CDCl ₃ ) δ (ppm): 0.90 (6
H, d, J = 6) 1.55 to 1.90 (3H) 2.45 (3H, s) 2.90 (2H, br
t, J = 7) 5.60 (1H, s) 13.3 (1H) Reference Example 3 (Synthesis of Exemplified Compound 19 )

[0057]

[Chemical formula 26]

9. Trimethyl ortho-4- (p-nitrophenyl) butyrate [Synthesis of nitrile from 4- (p-nitrophenyl) butyric acid and Pinner method]
2 g (34 mmol) and 3-amino-5-methylpyrazole (IV) 5 g (51 mmol) in 100 ml of toluene, 2
After heating under reflux for 0 hour, toluene was distilled off under reduced pressure, and the obtained crude (VI) was dissolved in 100 ml of methanol. Into it, in the same manner as in <Example 1>, 3.5 g (50 mmol)
A methanol solution of hydroxylamine prepared from the hydroxylamine hydrochloride of was added at 0 ° C., and after the addition was completed, the mixture was stirred at room temperature for 1 hour. Water 1 while stirring the solution
Since a precipitate was generated when it was poured into liter, it was absorbed and filtered, and washed well with dichloromethane to obtain powder crystals of (II). Yield 6.7 g (65%) melting point 1
65-166 ° C. 2 g (6.6 mmol) of (II) was added to tetrahydrofuran (T
HF) was dissolved in 80 ml, 0.73 g (7.3 mmol) of triethylamine was added, and the mixture was stirred. Into it, THF50
p-toluenesulfonic acid chloride 1.4 dissolved in ml
g (7.3 mmol) was slowly added, and after the addition was completed,
After stirring for about 15 minutes, the triethylamine hydrochloride which had precipitated was filtered off and washed with 10 ml of THF. The filtrate was heated under reflux for about 7 hours under a nitrogen stream, then THF was distilled off under reduced pressure, the residue was dissolved in a small amount of methanol, and 100 ml of water was added.
When the mixture was poured into and stirred, a light brown precipitate was formed. It is suction filtered and recrystallized from a mixed solvent of acetonitrile and methanol 19 to give 1.2g (63%). Melting point 2
03-212 ° C. Mass spectrometry ^{285 (M +) 149 (bp} ) Nuclear magnetic resonance spectrum _{(DMSO-d 6) δ (} ppm): 2.
05 (2H, m) 2.45 (3H, s) 2.56 ~ 2.86 (4H, m) 5.60 (1H,
s) 7.25 (2H, d, J = 8.0) 8.05 (2H, d, J = 8.0) Example 1 (Synthesis of Exemplified Compounds 20 , 22 , 25 )

[0059]

[Chemical 27]

20 g (0.36 mol) of reduced iron and 1.4 g of ammonium chloride in 100 ml of isopropyl alcohol.
(2.8 mmol) and 10 ml of water were added, and the mixture was heated to reflux with vigorous stirring. Then concentrated hydrochloric acid 0.
3 ml was added and the mixture was heated under reflux for 30 minutes. 19 15.2
g (53.2 mmol) was added little by little over 20 minutes, and the mixture was heated under reflux for 1 hour. It was filtered through Celite and washed well with ethanol. After concentrating the filtrate, 2N H
It was dissolved in a Cl aqueous solution and washed with ethyl acetate. The aqueous layer was neutralized with aqueous ammonia and the deposited precipitate was collected by filtration. The precipitate with water, 20 nearly pure dried After washing with acetonitrile followed to give 10.9g (80%). Melting point
To 180 ° C. Nuclear magnetic resonance spectrum _{(DMSO-d 6) δ (} ppm): 1.
90 (2H, br, quintet, J = ~ 7) 2.46 (3H, s) 2.3 ~ 2.8 (4H)
5.60 (1H, s) 6.55 (2H, d, J = 8.5) 6.93 (2H, d, J = 8.5) 3.6g (14.0mmol) of 20 was mixed solvent of 30 ml of N, N-dimethylacetamide and 60 ml of acetonitrile. And heated to reflux. Acid chloride [(tC ₅ H ₁₁ )
An acetonitrile solution (20 ml) of 6.1 g (15.4 mmol) of ₂ C ₆ H ₃ OCH (nC ₆ H ₁₃ ) COCl] was added dropwise over 20 minutes, and the mixture was heated under reflux for 30 minutes. After cooling, water 300m
It was poured into 1 and extracted with ethyl acetate. After washing with saturated saline,
After drying over anhydrous magnesium sulfate, concentrating, separating and purifying by silica gel column chromatography, 22 7.0 g
(81%) was obtained. Nuclear magnetic resonance spectrum (CDCl ₃ ) δ (ppm): 0.50 ~
1.00 (7H, m) 1.00 ~ 2.15 (30H, m) 2.45 (3H, s) 2.46 ~
2.80 (4H, m) 4.68 (1H, t, J = 6.5) 5.60 (1H, s) 6.88 ~
7.33 (6H, m) 7.66 (1H, d, J = 9.0) 7.88 (1H, br, s) 3.1 g (5.00 mmol) of 22 was added to 25 ml of acetic acid and stirred at room temperature. This is isoamyl nitrite 586m
g (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. Dried under vacuum, 2.9 g (91%)
The 7-nitroso form of was obtained as a solid. A 7-nitroso compound having a melting point of about 90 ° C and 2.9 g (4.5 mmol) was dissolved in 50 ml of ethanol and heated to a reflux state under a nitrogen stream. To this, a concentrated hydrochloric acid solution (10 ml) of 4.27 g (22.5 mmol) of stannous chloride was added dropwise over 10 minutes. After heating under reflux for an additional 30 minutes, cool and mix with 150 ml of water.
And extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate and then concentrated to dryness to obtain a 7-amino compound-tin complex. This was used in the next reaction without converting it to the free amino form. To this 7-amino compound, 100 ml of toluene and 2,5-dimethyl-1,3,4-oxadiazole (0.49 g, 5.0 mmol) were added, and the mixture was heated under reflux for about 5 hours. This was poured into 250 ml of water and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate, concentrated, and separated and purified by silica gel column chromatography to obtain 25 , 2.2 g (70%) as a solid. Melting point to 120 ° C Nuclear magnetic resonance spectrum (CDCl ₃ ) δ (ppm): 0.48 to
1.00 (7H, m) 1.05 to 2.20 (30H, m) 2.43 (3H, s) 2.46 (6
H, s) 2.46 ~ 2.80 (4H, m) 4.67 (1H, t, J = 6.5) 6.60 (1
H, d, J = 8.5) 6.90 to 7.35 (6H, m) 7.85 (1H, s) Reference Example 4 (Synthesis of Exemplified Compound 30 )

[0061]

[Chemical 28]

8.3 g of commercially available 3-aminopyrazole
(0.1 mol) and triethyl orthoformate 22.2 g
Dissolve (0.15 mol) in 100 ml of toluene,
The mixture was heated under reflux for 0 hours. After toluene was distilled off under reduced pressure, the residue was dissolved in 50 ml of methanol, and a methanol solution of hydroxylamine prepared from 10.4 g (0.15 mol) of hydroxylamine hydrochloride in the same manner as in <Example 2> was added at 0 ° C. After the addition was completed, the mixture was stirred at room temperature for 1 hour. After that, methanol was distilled off under reduced pressure at a temperature as low as possible, and dichloromethane was added to the residue to give (II) (R ₁ = R
₂ = H) was precipitated as crystals. Yield 8.2g (65
%) 5 g (40 mmol) of this amidoxime was reacted with p-toluenesulfonic acid chloride and triethylamine in THF as shown in <Example 1>, heated to reflux, and purified by silica gel column chromatography.
2.6 g (60%) of 30 could be obtained. Melting point 20
0 to 205 ° C Nuclear magnetic resonance spectrum (DMSO-d ₆ ) δ (ppm): 5.
75 (1H, d, J = 2.5) 7.53 (1H, d, J = 2.5) 8.05 (1H, s) Reference Example 5 (Synthesis of Exemplified Compound 31 )

[0063]

[Chemical 29]

8.3 g of 3-aminopyrazole (0.1 m
ol) and 27.1 g (0.1 mol) of trimethyl ortho-4- (p-nitrophenyl) butyrate (II) (R ₂ = H, R ₁ ) in almost the same manner as in <Example 3>. =
- and _{(CH 2) 3 C 6 H} 4 NO 2) can be a 19 g (69%) is obtained. From 5 g (18 mmol) of this amidoxime, 3.1 g (68%) of 31 could be obtained. Melting point 1
65-170 ° C Nuclear magnetic resonance spectrum (DMSO-d ₆ ) δ (ppm): 2.
04 (2H, m) 2.55 to 2.86 (4H, m) 5.78 (1H, d, J = 2.5) 7.2
5 (2H, d, J = 8.0) 7.54 (1H, d, J = 2.5) 8.05 (2H, d, J =
8.0) Reference example 6

[0065]

[Chemical 30]

The p-nitrophenyl ketene dimethyl acetal was synthesized by the following method. First, 100 g (0.617 mol) of commercially available p-nitrobenzyl cyanide was added to 19.8 g (0.617 mol) of methanol and 7 of dioxane.
The mixture was vigorously stirred in 5 ml of the solution, dry hydrogen chloride gas was injected into the solution over about 1.5 hours, and when 22.5 g or more had been absorbed, the injection was stopped and the mixture was left in the refrigerator overnight. The precipitate was crushed, added to ether, collected by filtration, and thoroughly washed with ether. 138g (79%) dried in a vacuum desiccator
The imide ester hydrochloride of 211 ml of methanol was added to this imide ester hydrochloride and stirred for a while. When completely dissolved, add 400 ml of ether, about 15
After heating to reflux and returning to room temperature, 10% in the reaction solution
About 300 ml of Na ₂ CO ₃ was gradually added, and then 1 liter of ethyl acetate was added for extraction. 10% N ethyl acetate layer
It was washed with a ₂ CO ₃ , dried over anhydrous K ₂ CO ₃ , filtered, and the solvent was distilled off under reduced pressure to precipitate crystals. The crystals were thoroughly washed with ether to obtain 36 g (49 g) of almost pure p-nitrophenyl ketene dimethyl acetal.
%)Obtained. Aminopyrazole (IV) 12.0 g (0.12
4 mol) and 26.0 g (0.124 mol) of p-nitrophenyl ketene dimethyl acetal in 200 ml of toluene.
0.04 ml (0.5 mol%) of methanesulfonic acid in the solution
Was added and the mixture was heated under reflux for about 4 hours. After distilling off the toluene under reduced pressure,
The residue was dissolved in 200 ml of methanol, and while cooling in an ice bath, 51.8 g (0.74) of hydroxylamine hydrochloride was obtained.
4 mol) and 28% sodium methoxymethanol solution 1
The methanol solution of hydroxylamine prepared from 50 ml was added in two portions, and after the addition was completed, the temperature was returned to room temperature, the mixture was stirred for about 2 hours, and left overnight. Methanol was distilled off under reduced pressure to a volume of about ½ (temperature of 50 ° C. or lower), poured into 1 liter of water, and the precipitated crystals were collected by filtration and dried to give 22.9 g (67%) of (II ) Got. 32 was obtained in the same manner as in <Example 3> from 5.0 g (II) of 2.7 g (58%), melting point ~ 251 ° C (decomposition) Example 2

[0067]

[Chemical 31]

To 20 ml of water, 17 g of reduced iron, 1.1 g of ammonium chloride and 1.2 ml of acetic acid were added, and the amount was reduced to about 2 under a nitrogen stream.
After heating under reflux for 0 minutes, 100 ml of isopropyl alcohol was added and the mixture was heated under reflux. Into it 32 , 11.0g
(42.8 mmol) was added dropwise over 15 minutes. After about 30 minutes, 32 disappeared on TLC, so 100 ml of DMF was added and stirred for 5 minutes. The reaction solution was filtered through Celite without cooling, DMF 50 ml, ethanol 200 m.
Wash with l. Crystals obtained by evaporating the filtrate under reduced pressure were suspended in acetonitrile, filtered, and washed with acetonitrile to give 9.8 g (101 g) of 33 containing some iron.
%)Obtained. Melting point 236 ° C. (decomposition) 33 , 3.5 g (15.4 mmol) of acetonitrile 50
ml and 25 ml of dimethylacetamide (DMAC) and heated to reflux. In it

[0069]

[Chemical 32]

6.09 g (15.4 mmol) was dissolved in 10 ml of acetonitrile, added dropwise over 10 minutes, and heated under reflux for 1 hour. The reaction solution was poured into 500 ml of ice water, neutralized and extracted with ethyl acetate. The extract was dried over magnesium sulfate, filtered, evaporated under reduced pressure, and the residue was recrystallized from acetonitrile to obtain 5.36 g (59%) of 34 .
Melting point 201 to 205 ° C. 34 , 5.32 g (9.08 mmol) was dissolved in 50 ml of THF and 100 ml of dichloromethane and stirred. 1.15 g (8.63 mmol) of N-chlorosuccinimide in it
Was added and stirred for 15 minutes. Transfer the reaction solution to a separating funnel,
Wash with water, dry the organic layer over magnesium sulfate, filter, and concentrate under reduced pressure to precipitate crystals. This was dissolved in ethanol, treated with activated carbon, and reconstituted from a mixed solvent of acetonitrile-ethyl acetate (4: 1) to give 2.9.
9 g (53%) of 35 was obtained. Melting point 206-209 ° C. 33 , 2.50 g (11.0 mmol) of acetonitrile 4
Dissolve it in 0 ml and 20 ml of DMAC and heat to reflux.

[0071]

[Chemical 33]

A solution of 6.74 g (12.1 mmol) in 25 ml of acetonitrile is added over 30 minutes. After the addition was completed, the mixture was heated under reflux for 1 hour, and the reaction solution was added with water
It is poured into 1 l, extracted with ethyl acetate, dried, concentrated under reduced pressure, and acetonitrile is added to crystallize 36 . 5.5
8 g (68%). Melting point 204-214 ° C 36 , 5.25 g (7.02 mmol) in 70 ml THF
0.5 g of 10% Pd / C was added, and the mixture was stirred in an autoclave under hydrogen atmosphere at 50 at 70 ° C. for 15 hours. After cooling, the catalyst was filtered off, THF was distilled off under reduced pressure, and then ethyl acetate-hexane (4: 1) mixed catalyst 100 was added.
After reconstitution from ml, 3.86 g (84%) of 37 was obtained. 2.44 g of 38 by chlorination of 36.35 g (5.55 mmol) of melting point 182-188 ° C. 37 with 726 mg (5.44 mmol) of N-chlorosuccinimide in the same manner as in the synthesis of 35.
(64%, reconstituted from ethyl acetate-n-hexane) was obtained.
Melting point 175-180 ° C

Claims (1)

[Claims] 1. A general formula: (In the formula, R ₁ and R ₂ represent a hydrogen atom or a substituted or unsubstituted alkyl or aryl group.) The compound represented by the general formula: (In the formula, R ₁ and R ₂ have the same meanings as described above.) A pyrazolo [1,5-b] [1,2,4] triazole derivative represented by A compound represented by the general formula: embedded image which is synthesized by introducing a group (hereinafter abbreviated as a coupling-off group) which is released by a coupling reaction with an oxidation product of a primary amine primary developing agent. (In the formula, X represents a coupling-off group, and R ₁ and R ₂ have the same meanings as described above.) Pyrazolo [1,5
-B] [1,2,4] triazole derivative. A method for producing a photographic coupler.