JPH0637477B2 - 5-hydrazino-1H-pyrazole compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel 5-hydrazino-1H-pyrazole compound. More specifically, it relates to 5-hydrazino-1H-pyrazole compounds useful as intermediates for photographic couplers.

[Prior art]

1H-pyrazolo [3,2-C] -S-triazole compounds are compounds useful as photographic couplers, particularly magenta couplers, and are described in, for example, British Patent No. 1,252,418, U.S. Patent No. 3,725,067, "Journal of. The Chemical Society, Perkin I (“Journal of the Che
Its importance is described in mical Society “Parkin I), 2047-2052 (1977).

Regarding the production method of this compound, the above-mentioned patents and literatures, Research Disclosure V
ol 124, No. 12443 (1977). The production method thereof can be represented by the reaction scheme shown below.

Reaction Scheme A (British Patent No. 1,252,418, US Patent No. 3,725,067 "Journal of the Chemical Society" Parkin I 2047
~ 2052 (1977)) Reaction Scheme B (Research Disclosure V
ol.124, No.12443 (1977)) As is clear from reaction schemes A and B, the synthesis of the previously known 1H-pyrazolo [3,2-C] -S-triazoles is achieved by using 5-hydrazino-1H-pyrazole-
4-carboxylate (1) or 3-mercapto-4
The -amino-4H-1,2,4-triazole derivative (2) is used as an important intermediate. But these intermediates
1H-pyrazolo [3,2-obtained using (1) and (2)
The 6-position substituent of C] -S-triazole, that is, R is extremely limited due to restrictions of starting materials, and when R is a group other than an alkyl group, an aryl group, or a heterocycle, 1H pyrazolo [3,2-C ] The yield of -S-triazole is very low or not obtained at all.

Therefore, in order to obtain a compound having an ether group bonded to the 6-position of 1H-pyrazolo [3,2-C] -S-triazole, it was necessary to develop a new synthetic intermediate.

[Object of the Invention]

An object of the present invention is to provide a novel 5-hydrazino-1H-pyrazole compound, more specifically 1H- having an ether bond as shown in the general formula [I] at the 6-position.
It is an object of the present invention to provide a 5-hydrazino-1H-pyrazole compound useful as an intermediate for a pyrazolo [3,2-C] -S-triazole photographic coupler.

[Structure of Invention]

The novel 5-hydrazino-1H-pyrazole compound according to the present invention is represented by the following general formula [I].

General formula [I] In the formula, R ₁ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and X represents a hydrogen atom, a halogen atom, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group or a carboxyl group. A represents a protonic acid, and n represents 0 or a positive integer. However,
The alkyl group, cycloalkyl group, aryl group, heterocyclic group which is R ₁ and each of the cyano group, alkoxycarbonyl group, aryloxycarbonyl group and carboxyl group which are X have a substituent group. Including. This compound is 1H-pyrazolo [3,2-C] -S-
It is useful as a synthetic intermediate for a triazole-based photographic coupler. Hereinafter, the compound of the present invention will be described in more detail.

The alkyl group represented by R ₁ in the general formula [I] is an alkyl group having 1 to 30 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group. , Pentyl group, hexyl group, heptyl group, benzyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and the like.

The cycloalkyl group represented by R ₁ is a 3- to 6-membered cycloalkyl group.

The aryl group represented by R ₁ is a phenyl group or a naphthyl group.

The heterocyclic group represented by R ₁ is a 5- or 6-membered heterocyclic group, for example, a thienyl group, a furyl group, a pyrrolyl group, a thiazolyl group, a pyridyl group, an imidazolyl group, a pyrrolysyl group, a piperidyl group, a morpholyl group, Etc.

The alkyl group, cycloalkyl group, aryl group and heterocyclic group represented by R ₁ may further have a substituent.

Examples of the halogen atom represented by X in the general formula [I] include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom, but a chlorine atom and a bromine atom are preferable, and a chlorine atom is more preferable. Examples of the alkoxycarbonyl group represented by X include a methoxycarbonyl group, an ethoxycarbonyl group, a propyloxycarbonyl group and a benzyloxycarbonyl group. Examples of the aryloxycarbonyl group represented by X include a phenoxycarbonyl group.

The general formula [I] also includes salts formed with a protic acid, but this is not an essential component of the present invention. Various organic acids and inorganic acids are used. As a typical one
Hydrochloric acid, hydrobromic acid, sulfuric acid, acetic acid, methanesulfonic acid,
Examples thereof include toluene sulfonic acid.

Next, Reaction Scheme D describes a method for synthesizing the 5-hydrazino-1H-pyrazole compound according to the present invention.

Scheme D R ₁ and X are the same as those in the general formula [I]. The 5-amino-1H-pyrazole derivative (4) in which the R ₁ O- group is substituted at the 3-position is
WJMiddleton, VA Engelhard, Journal of American Chemical Society, J. Am. Chem. Soc, 80 , 2
788 (1958), WJ Middleton, VA Engelhard, Journal ·
Of American Chemical Society, J.Am.Che
The method of Scheme E described in m.Soc, 80 , 2829 (1958) can be referred to.

Scheme E Conversion of the CN group to other substituents can be accomplished by commonly known methods.

A usual method can be used for the diazotization and reduction of the 5-amino-1H-pyrazole derivative. For example, Organic Synthesis Collective Volume (Organ
ic Synthesis Coll.Vol.) I, P.442〜445,
De Kimika 66 911-918 (1970), 70 959-9
61 (1974) etc. can be referred to.

As the diazotizing agent, sodium sulfite, isoamyl sulfite and the like are generally used. As the reducing agent, sodium sulfite, sodium hydrosulfite, stannous chloride and the like are used. Water is preferable as the solvent used in the reaction, but it is also possible to use an organic solvent, for example, alcohols (methal, ethanol, etc.), tetrahydrofuran, dioxane, N, N-dimethylformamide, acetic acid and the like are compatible with water. The solvent can be mentioned.

The amount of solvent used depends on the starting material, aminopyrazole 1
1 to 1000 parts by weight, preferably 5 to 10 parts by weight
The ratio is 0 part by weight.

The acid used for diazotization is preferably hydrochloric acid, sulfuric acid or the like.

Next, 5-hydrazino-represented by the general formula [I] of the present invention
Specific examples of the 1H-pyrazole compound are shown below as I-1 to I-2.
However, the present invention is not limited to these.

Compound Example I-1 I-2 I-3 I-4 I-5 I-6 I-7 I-8 I-9 I-10 I-11 I-12 I-13 I-14 I-15 I-16 I-17 I-18 I-19 I-20 I-21 I-22 I-23 A route for synthesizing a 1H-prazolo [3,2-C] -S-triazole-based compound, which is a magenta coupler for photography, using the 5-pydrazino-1H-pyrazole-based compound of the present invention is shown below.

In the above route, R ₁ , X, A and n are each represented by the general formula [I]
Is synonymous with the explanation of. R ₂ represents an alkyl group or an aryl group.

1H-pyrazolo [3,2-C] -obtained in this way
The S-triazole-based compound does not have the secondary absorption around 430 nm, which is seen in the 5-pyrazolone-based coupler which has been most often used as a magenta coupler used in a color photographic light-sensitive material. Alternatively, it is a coupler that has recently been attracting attention because of its sharp cut in the long wavelength portion.

The 1H-pyrazolo [3,2-C] -S-triazole couplers having an ether bond at the 6-position derived from the compound of the present invention are useful photographic couplers for forming magenta dyes having particularly excellent light resistance. is there. Attempts to synthesize these couplers by conventional production methods have either very low yields or none at all and cannot be industrialized.

Next, 1H-pyrazolo [3,2-C] -S-derived from the 5-hydrazino-1H-pyrazole compound of the present invention.
Typical examples of triazole compounds are shown below as II-1 to II.
-10.

II-1 II-2 II-3 II-4 II-5 II-6 II-7 II-8 II-9 II-10 [Examples] Examples of the present invention will be described below. Of course, the present invention is not limited to the following examples. 5-hydrazino-1 included in the present invention
The examples are described by showing specific synthetic examples of examples of H-pyrazole compounds.

Synthesis Example 1 [Synthesis of Exemplified Compound (1-3)] (i) 5-Amino-4-cyano-3-ethoxypyrazole 15.2 g (Journal of American Chemical
Society, J. Am. Chem. Soc., 80 , 2829 (1958)) 100
Dissolve in ml of ethanol and add 20 ml of concentrated hydrochloric acid.
After heating and refluxing for 8 hours, the mixture was neutralized with sodium hydroxide and then cooled to obtain 13.0 g of white crystals of 5-amino-3-ethoxy-4-ethoxycarbonylpyrazole.

(Ii) After dissolving 10.0 g of 5-amino-3-ethoxy-4-ethoxycarbonylpyrazole in 150 ml of 6N hydrochloric acid,
Cool to 0 ° C. To this, add 3.8 g of sodium nitrite to 10 parts of water.
The solution dissolved in ml is added dropwise. After stirring at 0 ° C. for 30 minutes, a solution of 24 g of stannous chloride dissolved in 70 ml of concentrated hydrochloric acid is added dropwise. After stirring at 0 ° C. for 1 hour, the mixture is left at room temperature for 1 hour. Next, 500 ml of water is added, and hydrogen sulfide gas is passed through to remove the precipitated tin salt. After concentrating the filtrate, the obtained white crystals are washed with ethanol. The crystals are dissolved in water and neutralized with sodium hydrogen carbonate to obtain 3.8 g of the desired product, 3-ethoxy-4-ethoxycarbonyl-5-hydrazinopyrazole, as white crystals. Decomposed above 185 ° C.

Elemental analysis, as C ₈ H ₁₄ N ₄ O ₃ , The FD mass spectrum showed a parent peak at M ⁺ 214, supporting that this compound has the desired I-3 structure.

[Application Example Using Synthesis Example 1] 7-Chloro-6, which belongs to 1H-pyrazolo [3,2-C] -S-triazole compound, using the exemplified compound I-3 obtained in Synthesis Example 1 above A synthesis example of -ethoxy-3-pentadecyl-1H-pyrazolo [3,2-C] -S-triazole will be described.

(I) 3.5 g of 3-ethoxy-4-ethoxycarbonyl-5-hydrazinopyrazole obtained in Synthesis Example 1 and 4.5 g of palmitic acid chloride are added to 120 ml of ethyl acetate and stirred. 1.7 g of triethylamine was added dropwise to this,
Stir at room temperature for 1 hour 30 minutes. The precipitated crystals are filtered off,
Further, it is washed with water to obtain white crystals. Recrystallized from acetonitrile to give 3-ethoxy-4-ethoxycarbonyl-5-
5.8 g of (2-palmitoylhydrazino) pyrazole were obtained.

(Ii) 3-ethoxy-4-ethoxycarbonyl-5-
5.0 g of (2-palmitoylhydrazino) pyrazole is dissolved in 150 ml of toluene, and 1.7 g of phosphorus oxychloride is added. After heating under reflux for 1 hour, the solvent is distilled off under reduced pressure. Acetonitrile (150 ml) and pyridine (2.6 g) are added to the residue, and the mixture is heated under reflux for 1 hour. The pyridine hydrochloride is removed by filtration while hot and cooled. The precipitated crystals were further recrystallized from acetonitrile to give 6-ethoxy-7-ethoxycarbonyl-3-pentadecyl-1H-pyrazolo [3,2-
3.6 g of C] -S-triazole are obtained.

(Iii) 6-ethoxy-7-ethoxycarbonyl-3-
3.5 g of pentadecyl-1H-pyrazolo [3,2-C] -S-triazole was added to 100 ml of acetic acid, and sulfuric acid 25
Add 5 ml of water and 5 ml of water and heat to reflux for 1 hour. The reaction mixture is neutralized with 6N aqueous sodium hydroxide solution while cooling below 10 ° C. Extract with ethyl acetate and evaporate the solvent under reduced pressure. 50 ml of water is added to the tar residue, and the precipitated crystals are filtered off. Further reconstitution with acetonitrile gives 2.4 g of 6-ethoxy-3-pentadecyl-1H-pyrazolo [3,2-C] -S-triazole.

(Iv) 2.3 g of 6-ethoxy-3-pentadecyl-1H-pyrazolo [3,2-C] -S-triazole was added to 80 ml of chloroform, and N-chlorosuccinimide was added with stirring.
Add 0.85g in small portions. After stirring at room temperature for 30 minutes, the solvent is distilled off under reduced pressure, ethyl acetate and water are added, and the ethyl acetate layer is separated. Further, the solvent is distilled off under reduced pressure, and the residue is recrystallized from acetonitrile to obtain 1.8 g of a white target compound. The structure of the target product was confirmed by NMR, mass spectrum and elemental analysis.

Elemental analysis, as C ₂₁ H ₃₇ N ₄ OCl, Synthesis Example 2 [Synthesis of Exemplified Compound I-11] (i) 12.8 g of tetracyanoethylene and 2.0 g of urea are added to 100 ml of 2-methoxyethanol and heated to 90 to 100 ° C. When the purple color that first appeared disappeared and the solution turned yellow, cool and pour into water. Extract the organic layer with ethyl acetate and purify by silica gel column chromatography. The target substance was distilled off with a mixed solvent of ethyl acetate and hexane (1: 1) to obtain 13.0 g of a pale yellow viscous liquid dicyanoketene di-2-methoxyethyl acetal.

(Ii) 11.3 g of dicyanoketene di-2-methoxyethyl acetal and 2.5 g of hydrazine hydrate are added to 50 ml of water and stirred. Crystals gradually begin to precipitate as the stirring is continued at room temperature. After cooling, the crystals are separated by filtration and recrystallized from water to give 6.3 g of 5-amino-4-cyano-3- (2-methoxyethoxy) pyrazole.

(Iii) Dissolve 6.0 g of 5-amino-4-cyano-3- (2-methoxyethoxy) pyrazole in 50 ml of ethanol, and add 10 ml of concentrated hydrochloric acid. After heating under reflux for 7 hours, the solution was neutralized with an aqueous sodium hydroxide solution and then cooled to obtain 3.8 g of white crystals of 5-amino-4-ethoxycarbonyl-3- (2-methoxyethoxy) -pyrazole.

(Iv) 5-amino-4-ethoxycarbonyl-3- (2
-Methoxyethoxy) pyrazole 3.8g was added to 6N hydrochloric acid 50m.
After dissolving in 1 liter, it is cooled to 0 ° C. To this, an aqueous solution of 1.2 g of sodium nitrite dissolved in 5 ml of water is added dropwise. After stirring at 0 ° C for 30 minutes, a solution of 7.7 g of stannous chloride in 20 ml of concentrated hydrochloric acid is added dropwise. After stirring at 0 ° C. for 1 hour, the mixture is left at room temperature for 1 hour. Next, 200 ml of water is added and hydrogen sulfide gas is passed to remove the precipitated tin salt. The filtrate was concentrated, the obtained white crystals were washed with ethanol, and the target compound, 4-ethoxycarbonyl-3- (2-methoxyethoxy) -5-hydrazinopyrazole hydrochloride, 2.1 g
To get Decomposed above 212 ° C.

Elemental analysis, as C ₉ H ₁₇ N ₄ O ₄ Cl, FD-mass spectrum showed a parent peak at M ⁺ 280, supporting that this compound is the desired structure of I-11.

Synthesis Example-3 [Synthesis of Exemplified Compound I-12] (i) Tetracyanoethylene 12.8 g, urea 3.0 g and p
-Add 12.4 g of methoxyphenol to 100 ml of toluene,
Heat to reflux. When the purple color that first appeared disappeared and the solution turned yellow, the solution was cooled and the precipitated crystals were filtered off to give 16 g of 1,1-dicyano-2,2-di- (p-methoxyphenoxy) ethylene.
To get

(Ii) 1,1-Dicyano-2,2-di- (p-methoxyphenoxy) ethylene (16 g) and heptahydrazine hydrate (2.5 g) are added to 100 ml of ethanol and heated under reflux for 1 hour. After cooling, the precipitated crystals are separated by filtration and recrystallized from ethanol to obtain 8.4 g of 5-amino-4-cyano-3- (p-methoxyphenoxy) pyrazole.

(Iii) 8.4 g of 5-amino-4-cyano-3- (p-methoxyphenoxy) pyrazole is added to a mixed solution of 10 ml of concentrated sulfuric acid and 50 ml of water, and the mixture is heated under reflux for 12 hours. After cooling, the solution is neutralized with an aqueous sodium hydroxide solution, and the precipitated crystals are separated by filtration.
6.1 g of 5-amino-3- (p-methoxyphenoxy) pyrazole-4-carboxylic acid are obtained.

(Iv) 6.0 g of 5-amino-3- (p-methoxyphenoxy) pyrazole-4-carboxylic acid is heated to 110 ° C to 120 ° C. It foams violently. After cooling, the product is recrystallized from ethanol to obtain 4.2 g of 5-amino-3- (p-methoxyphenoxy) pyrazole.

(V) 4.1 g of 5-amino-3- (p-methoxyphenoxy) pyrazole was dissolved in 100 ml of chloroform to give 2.7 g of N 2.
-Add chlorosuccinimide. After stirring for 30 minutes at room temperature,
Ethyl acetate and water are added, and the organic layer is separated. Concentrate under reduced pressure, recrystallize from a mixed solvent of ethanol and hexane, 2.
9 g of 5-amino-4-chloro-3- (p-methoxyphenoxy) pyrazole are obtained.

(Vi) 2.4 g of 5-amino-4-chloro-3- (p-methoxyphenoxy) pyrazole, 5 ml of concentrated hydrochloric acid and 10 ml of water are mixed and cooled to 0 ° C. To this, 0.7 g of sodium nitrite
Is added dropwise to a solution of 10 ml in water. After stirring at 0 ° C. for 30 minutes, 4.0 g of sodium sulfite was added to a solution of 20 ml of water. After heating the diazonium solution to 80 to 90 ° C., 10 ml of concentrated hydrochloric acid is added dropwise. After stirring for 30 minutes as it is, it is neutralized with sodium hydrogen carbonate. The precipitated solid was filtered off and recrystallized from acetonitrile to give the desired compound 4-chloro-5-hydrazino-3- (p-methoxyphenoxy) pyrazole 1.
Get 6g. Decomposed above 198 ° C.

Elemental analysis, as C ₁₀ H ₁₁ N ₄ O ₂ Cl, The FD-mass spectrum showed a parent peak at M ⁺ 254, supporting this compound to be the desired structure of I-12.

Next, 1H-pyrazolo [3.2-C] -S derived from the 5-hydrazino-1H-pyrazole compound of the present invention
-Indicates triazole compounds.

Synthetic Example-4 [Synthesis of Exemplified Compound II-2] (i) 3.5 g of 3-ethoxy-4-ethoxycarbonyl-5-hydrazinopyrazole and 4.5 g of palmitic acid chloride
Is added to 120 ml of ethyl acetate and stirred. 1.7 g of triethylamine was added dropwise to this, and the mixture was stirred at room temperature for 1 hour and 30 minutes. The precipitated crystals are separated by filtration and washed with water to obtain white crystals. Recrystallized from acetonitrile to 3-ethoxy-4
5.8 g of -ethoxycarbonyl-5- (2-palmitoylhydrazino) pyrazole are obtained.

(Ii) 3-ethoxy-4-ethoxycarbonyl-5-
5.0 g of (2-palmitoylhydrazino) pyrazole is dissolved in 150 ml of toluene, and 1.7 g of phosphorus oxychloride is added. After heating under reflux for 1 hour, the solvent is distilled off under reduced pressure. To the residue are added 150 ml of acetonitrile and 2.6 g of pyridine, and the mixture is further heated under reflux for 1 hour. The pyridine hydrochloride is removed by filtration while hot and cooled. The precipitated crystals were recrystallized from acetonitrile to give 6-ethoxy-7-ethoxycarbonyl-3-pentadecyl-1H-pyrazolo [3,2-C] -S.
-Obtain 3.6 g of triazole.

(Iii) 6-ethoxy-7-ethoxycarbonyl-3-
3.5 g of pentadecyl-1H-pyrazolo [3,2-C] -S-triazole is added to 100 ml of acetic acid, 25 ml of sulfuric acid and 5 ml of water are added, and the mixture is heated under reflux for 1 hour. Reaction mixture 10
Neutralize with a 6N aqueous sodium hydroxide solution while cooling to below ℃. Extract with ethyl acetate and evaporate the solvent under reduced pressure. 50 ml of water is added to the tar residue, and the precipitated crystals are filtered off. Further reconstituted from acetonitrile to give 6-ethoxy-3-pentadecyl-1H-pyrazolo [3,2-C] -S
-2.4 g of triazole are obtained.

(Iv) 6-ethoxy-3-pentadecyl-1H-pyrazolo [3,2-C] -S-triazole (2.3 g) in chloroform 8
In addition to 0 ml, with stirring, N-chlorosuccinimide 0.85 g
Is added little by little. After stirring at room temperature for 30 minutes, the solvent was evaporated under reduced pressure, ethyl acetate and water were added, and the ethyl acetate layer was separated. Further, the solvent is distilled off under reduced pressure, and the residue is recrystallized from acetonitrile to obtain 1.8 g of a white target compound. The structure of the target substance was confirmed by NMR, mass spectrum, and elemental analysis.

Elemental analysis, as C ₂₁ H ₃₇ N ₄ OCl, Synthesis Examples 3 to 22 [The above-exemplified compounds I-1, I-2, I-
4-Synthesis of I-10 and I-13 to I-23] Exemplified Compound I-1,
I-2, I-4 to I-10, and I-13 to I-23 were synthesized.

The obtained product was confirmed to be each exemplified compound by analysis. The results of elemental analysis are summarized in Table 1.

EFFECTS OF THE INVENTION As described above, according to the present invention, novel 5-hydrazino-1 is used.
An H-pyrazole compound can be provided, which is useful as an intermediate for a 1H-pyrazolo [3,2-C] -S-triazole photographic coupler.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location // C07D 487/04 139 7019-4C G03C 7/38

Claims (1)

[Claims] 1. A 5-hydrazino-1H-pyrazole compound represented by the following general formula [I]. General formula [I] In the formula, R ₁ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and X represents a hydrogen atom, a halogen atom, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group or a carboxyl group. A represents a protonic acid, and n represents 0 or a positive integer. However, the above R ₁ is an alkyl group, a cycloalkyl group,
An aryl group, a heterocyclic group, and the cyano group represented by X above,
Each of the alkoxycarbonyl group, the aryloxycarbonyl group, and the carboxyl group includes those having a substituent.