JPH0637476B2 - 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.

[Conventional technology]

1H-prazolo [3,2-C] -S-triazole compounds are compounds useful as photographic couplers, particularly magenta couplers, and are described in, for example, British Patent 1,252,418, U.S. Patent 3,725,067, "Journal of the Chemicals".・
Society ”Perkin I (“ Journal of the Chemical
Its importance is described in Society ”. Parkin I) 2047-2052 (1977).

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

Reaction Scheme A (UK Patent 1,252,418, US Patent 3,725,067, "Journal of the Chemical Society" Perkin I
“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, 5-hydrazino-1H-pyrazole-4 was used for the synthesis of 1H-pyrazolo [3,2-C] -S-triazole known so far.
-Carboxylate (1) or 3-mercapto-4
The -amino-4H-1,2,4-triazole derivative (2) is used as an important intermediate. However, the 6-position substituent of 1H-pyrazolo [3,2-C] -S-triazole obtained by using these intermediates (1) and (2), that is, R is extremely limited due to restrictions of starting materials, and R Is a group other than an alkyl group, an aryl group and a heterocycle, 1H-
The yield of pyrazolo [3,2-C] -S-triazole is very low or not obtained at all.

On the other hand, a 5-hydrazino-1H-pyrazole-based compound in which R has a nitrogen-containing substituent at the 3-position as shown in general formula [I] is difficult by the method of scheme A- (a), and general formula [ It is difficult to obtain 1H-pyrazolo [3,2-C] -S-triazole having a nitrogen-containing substituent at the 6-position as shown in I] by the methods of Scheme A and Scheme B. In order to synthesize 1H-pyrazolo [3,2-C] -S-triazole having a nitrogen-containing substituent at the 6-position as represented by the general formula [I], it is necessary to develop a new synthetic intermediate. there were.

[Object of the Invention]

An object of the present invention is to provide a novel 5-hydrazino-1H-pyrazole compound, more specifically, a compound having a nitrogen-containing substituent at the 6-position as shown by the general formula [I].
H-Pyrazolo [3,2-C] -S-triazole 5-hydrazino-1H-useful as an intermediate for photographic couplers
It is to provide a pyrazole-based compound.

[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, Ar represents an aryl group or a heteroaromatic ring having a 5- or 6-membered ring, R ₁ is a hydrogen atom, an alkyl group, an aryl group,
It represents a heteroaromatic ring having a 5- or 6-membered ring, 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. Provided that the aryl group that is Ar, the heteroaromatic ring having a 5- or 6-membered ring, and the alkyl group that is R ₁ described above.
Each group of the aryl group and the heteroaromatic ring having a 5- or 6-membered ring includes those having a substituent. This compound is 1H
-Pyrazolo [3,2-C] -S-triazole type photographic coupler useful as a synthetic intermediate. Hereinafter, the compound of the present invention will be described in more detail.

Examples of the aryl group represented by Ar in the general formula [I] include a phenyl group and a naphthyl group.
This aryl group may have a substituent (for example, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a nitro group, etc.). Examples of the 5- or 6-membered heteroaromatic ring represented by Ar include a thienyl group, a furyl group, a pyridyl group, a pyrimidyl group, and the like, and the heteroaromatic ring has a substituent (for example, a halogen atom, an alkyl group,
Alkoxy group, hydroxyl group, nitro group, cyano group, etc.).

Examples of the alkyl group represented by R ₁ in the general formula [I] include an alkyl group having 1 to 30 carbon atoms,
For example, methyl group, ethyl group, propyl group, heptyl group,
Examples thereof include a benzyl group, and these alkyl groups may have a substituent (for example, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, etc.).

Examples of the aryl group represented by R ₁ and the heteroaromatic ring having a 5- or 6-membered ring include the same as those described as Ar in the general formula [I].

Examples of the halogen atom represented by X in the general formula [I] include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkoxycarbonyl group represented by X include a methoxycarbonyl group, an ethoxycarbonyl group and a benzyloxycarbonyl group. Examples of the aryloxycarbonyl group 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. Typical examples thereof include hydrochloric acid, hydrobromic acid, sulfuric acid, acetic acid, methanesulfonic acid, toluenesulfonic acid and the like.

Next, a method for synthesizing the 5-hydrazino-1H-pyrazole compound according to the present invention will be described.

Scheme C Ar, R ₁ and X are the same as those described in the general formula [I].

In 3rd place 5-amino-1H-pyrazole derivatives having a group are known as Chemische Berichte 95 2861-287.
0 (1962), 2871 to 2880, the method can be referred to for synthesis. This 5-amino-1H-pyrazole derivative can be diazotized and then reduced to give a 5-hydrazino-1H-pyrazole derivative. For example, Organic Synthesis Collective
Volume (Organic Synthesis Coll.Vol.) I P.442 ~ 44
5, Annales de Kimika (An.Quim.) 66 911-918 (197
0), 70 959-961 (1974) and the like.

Sodium sulfite is generally used as the diazotizing agent. As the reducing agent, sodium sulfite, sodium hydrosulfite, stannous chloride and the like are used. Water is preferably used as the solvent used in the reaction, but it is also possible to use an organic solvent such as alcohols (methal, ethanol, etc.), tetrahydroclan,
A solvent compatible with water such as dioxane, N, N-dimethylformamide and acetic acid may be used.

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

The 5-hydrazino-1H-pyrazole compound obtained here is acylated according to the following scheme, and then chlorinating agent such as phosphorus oxychloride or thionyl chloride is used, followed by ring closure using a base. A 1H-pyrazolo- [3,2-C] -S-triazole compound having a nitrogen-containing substituent at the 6-position, which is useful as a magenta coupler for photography, can be synthesized.

Scheme D Ar, R ₁ and X are the same as those described in the general formula [I].

Next, specific examples of the 5-hydrazino-1H-pyrazole compound represented by the general formula [I] of the present invention are shown below, but the present invention is not limited thereto.

1) 2) 3) 4) 5) 6) 7) 8) 9) Ten) 11) 12) 13) 14) 15) 16) 17) 18) [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 the Exemplified Compound (1)] The above-mentioned Chemische Berichte 95 2
861-2870 (1962) 2,2-bismethyl mercapto-1-cyano-acrylic acid methyl ester obtained by the method described in Hemische Berichte (Chemische Berichte)
2-anilino-2 by the method described in 95 2871 to 2880 (1962).
-Methyl mercapto-1-cyanoacrylic acid methyl ester was obtained. 2-anilino-2-methylmercapto-1-cyanoacrylic acid methyl ester obtained here 24.8
g was refluxed with 125 ml alcohol and 6.0 ml hydrazine hydrate for 3 hours. After removing half of the solvent under reduced pressure, the mixture was cooled and the crystals were filtered and recrystallized from methanol.

8.5 g of the obtained 3-anilino-5-amino-4-methoxycarbonylpyrazole was taken, dissolved in 160 ml of 6N hydrochloric acid by heating and then cooled to 0 to -3 ° C, and 3.1 g of sodium nitrite was added to 5 ml of water. The solution dissolved in was added dropwise to diazotize. After cooling and stirring for 1 hour, add to this solution,
A solution of 17.0 g of stannous chloride (dihydrate) dissolved in 50 ml of concentrated hydrochloric acid was added dropwise. After stirring for 2 hours, 500 ml of water was added to saturate hydrogen sulfide. The generated tin sulfide was removed by filtration, and the filtrate was concentrated under reduced pressure. The crystals were dissolved in 100 ml of water, neutralized with an aqueous solution of sodium carbonate, filtered, dried and then recrystallized from alcohol to obtain 4.8 g of crystals. Recrystallization was repeated to obtain pure crystals.

This product decomposed without melting at 182 ° C.

From the results of elemental analysis, NMR and mass spectrum, it was confirmed that this was 3-anilino-5-hydrazino-4-methoxycarbonylpyrazole.

Elemental analysis As C ₁₁ H ₁₃ N ₅ O ₂ : calculated value% C: 53.43 H: 5.30 N: 28.33 measured value% C: 53.49 H: 5.43 N: 28.12 mass spectrum: FD-MS M ⁺ 247 (parent peak) synthesis Application Example Using Example 1 Synthesis of a 1H-pyrazolo [3,2-C] -S-triazole compound using the exemplified compound (1) obtained in the above Synthesis Example 1 will be described.

2.0 g of the 3-anilino-5-hydrazino-4-methoxycarbonylpyrazole obtained above was stirred in 70 ml of ethyl acetate and 1.1 g of triethylamine was added.
2.1 g of palmitoyl chloride was added dropwise. 30 minutes 80
After heating to ℃, the crystals were filtered and the filtrate was concentrated under reduced pressure. The residue was recrystallized from acetonitrile to give 3-anilino-4-methoxycarbonyl-palmitoylhydrazinopyrazole. 2.5 g of 3-obtained above
Anilino-4-methoxycarbonyl-5-palmitoylhydrazinopyrazole was refluxed with 25 ml toluene, 1.0 ml phosphorus oxychloride for 3 hours. After the reaction, the solution was washed with water and dried, and then the solvent was removed under reduced pressure. 1.5 ml to this
Of pyridine and 30 ml of acetonitrile were added and the mixture was refluxed for 2.5 hours. The crystals precipitated after cooling were filtered and recrystallized from methanol to obtain 0.9 g of crystals.

Recrystallization was repeated to obtain pure crystals. From the results of NMR, mass spectrum and elemental analysis, it was confirmed that this was a compound represented by the following formula.

Elemental analysis As C ₂₇ H ₄₁ N ₅ O ₂ : Calculated value% C: 69.34 H: 8.84 N: 14.98 Measured value% C: 69.34 H: 8.91 N: 14.82 When a silver halide photographic light-sensitive material was prepared using the obtained compound as a magenta coupler, a silver halide color photographic light-sensitive material having good light resistance and formalin resistance and high color development was obtained.

As described above, the 5-amino-1H-pyrazole compound of the present invention is useful as an intermediate for a photographic coupler.

Synthesis Example 2 [Synthesis of Exemplified Compound (5)] Chemische Berichte 95 2861-2
According to the method described in 870 (1962), using cyanic acid ethyl ester in place of cyanic acid methyl ester gives 2,2.
-Bismethylmercapto-1-cyano-acrylic acid ethyl ester was obtained. 10.8 g of this was mixed with 6.5 g of o-chloroaniline, and 1 ml was added together with 1.0 ml of triethylamine.
The mixture was heated with stirring at 20 to 130 ° C. for 5 hours. 2 in the reaction mixture after the reaction
0 ml of methanol was added, the mixture was allowed to stand, and the precipitated crystals were collected by filtration. 2-o-chloroanilino-2-methylmercapto-1-cyanoacrylic acid ethyl ester obtained here
Take 6.8g and 50ml with 1.4ml hydrazine hydrate
Reflux for 3 hours in ethanol. After the reaction, the mixture was cooled and the crystals were filtered. 5.1 g of the obtained 3-o-chloroanilino-5-amino-4-ethoxycarbonylpyrazole, 140 ml of 6N dilute hydrochloric acid, 1.6 g of sodium nitrite, and then 8.5 g of stannous chloride (dihydrate) in 20 ml of concentrated solution. Using the solution dissolved in hydrochloric acid, diazotization, reduction reaction, and treatment were carried out in the same manner as in Synthesis Example 1. The obtained crystals were dissolved in water, neutralized with an aqueous solution of sodium carbonate, and the crystals were recrystallized from a small amount of alcohol. This gave 2.6 g of crystals. Recrystallization was repeated to obtain a pure crystal.

This product decomposed at 198 ° C. without melting.

From the results of elemental analysis, NMR and mass spectrum, it was confirmed that the obtained compound was 3-o-anilino-5-hydrazino-4-ethoxycarbonylpyrazole.

Elemental analysis as C ₁₂ H ₁₄ ClN ₅ O ₂ : calculated% C: 48.73 H: 4.77 N: 23.68 Cl: 1
1.99 Measured value% C: 48.85 H: 4.70 N: 23.49 Cl: 1
1.71 Mass spectrum: FD-MS M ⁺ 295 (parent peak) Synthetic Examples 3 to 19 [Synthesis of Exemplified Compounds 2 to 4 and 6 to 18] Exemplified Compounds 2 to 4 using the same method as in the above Synthetic Example.
6-18 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.

Claims (1)

[Claims] 1. A 5-hydrazino-1H-pyrazole compound represented by the following general formula [I]. General formula [I] In the formula, Ar represents an aryl group or a heteroaromatic ring having a 5- or 6-membered ring, R ₁ is a hydrogen atom, an alkyl group, an aryl group,
It represents a heteroaromatic ring having a 5- or 6-membered ring, 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 aryl group which is Ar, the heteroaromatic ring having a 5- or 6-membered ring, and the alkyl group, the aryl group, which is R, or the heteroaromatic ring having a 5- or 6-membered ring each have a substituent Including those that have.