JPH0613478B2 - 5-hydrazino-1H-pyrazole compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel 5-hydrazino-1H-pyrazole compound, and more particularly to a 5-hydrazino-1H-pyrazole compound useful as an intermediate for a photographic coupler. Is.

[Prior Art] 1H-pyrazolo [3,2-C] -1,2,4-triazole compounds are compounds useful as photographic couplers, particularly magenta couplers, and are described in, for example, British Patent 1,252,4.
18, US Pat. No. 3,725,067, Journal
Of the Chemical Society, Perkin, Chapter I (Jo
urnal of the Chemical Society, Perkin Transactions
I), 1977, pp. 2047-2052, its importance is described.

For the production method of this compound, see the above-mentioned patents, literatures and Research Disclosur.
e), Volume 124, Item 12443 (1974), etc. The production method thereof can be represented by the reaction scheme shown below.

Reaction scheme A (UK patent, US patent, J. Chem, Soc.) Reaction Scheme B (Research Disclosure) As is clear from the reaction scheme, 5-hydrazino-1H
Although -pyrazole-4-carboxylate or 3-mercapto-4-amino-4H-1,2,4-triazole are used as important intermediates, these processes have major drawbacks. In summary, sulfur formation in steps (a) and (f).

Use of large amounts of sulfuric acid in steps (d ₁ ) and (d ₂ ) and the accompanying neutralization treatment and disposal of the sodium sulfate produced.

High temperature of 250 ° C in step (f).

Narrow coverage and low yield in step (a).

All of these impede industrialization, but the narrow application range and low yield are the most important factors that make the development of useful photographic couplers impossible.

[Object of the Invention] An object of the present invention is to provide a 5-hydrazino-1H-pyrazole compound, and more specifically to provide a 5-hydrazino-1H-pyrazole compound useful as an intermediate for a photographic coupler. Especially.

[Structure of the Invention] The 5-hydrazino-1H-pyrazole compound represented by the following general formula [I] is useful as an intermediate capable of producing excellent photographic couplers in a wide range and in high yield.

General formula [I] In the formula, R ₁ represents a primary alkyl group having 1 to 30 carbon atoms and optionally having a substituent, and X represents a chlorine atom. A represents a protonic acid and n represents 0 or a positive number.

Hereinafter, the present invention will be described more specifically.

₁ to 30 carbon atoms represented by R ₁ in the general formula [I]
The primary alkyl group of is specifically a methyl group, an ethyl group,
Examples thereof include propyl group, butyl group, hexyl group, octyl group, nonyl group, tetradecyl group, octadecyl group, eicosyl group and triacontyl group. Of these, an alkyl group having 1 to 20 carbon atoms is more preferable. These alkyl groups may have a substituent, and examples of the substituent include a halogen atom, a hydroxy group, an alkoxy group, an aryl group, and the like. Examples of the alkyl group having such a substituent include Examples thereof include 2-hydroxyethyl group, 3-chloropropyl group, benzyl group and phenethyl group.

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.

The general formula [I] includes a salt formed by a protic acid, but this is not an important component of the present invention, and a wide range of organic acids and inorganic acids are used. Typical examples thereof include hydrochloric acid, hydrobromic acid, sulfuric acid, acetic acid, methanesulfonic acid, pyromellitic acid and the like.

The 5-hydrazino-1H-pyrazole compound of the present invention can be obtained by diazotizing the corresponding 5-amino-1H-pyrazole compound by a conventional method and then reducing the compound. For example, Organic Synthesis / Collaboration (Organic
Syntheses Collective Volume), Volume I, p. 442, and Journal of the Chemical Society (Jo
urnal of the Chemical Society), 1971, 16
It can be synthesized by the method described on page 7.

The 3-alkyl-4-halogeno-5-hydrazino-1H-pyrazole compound of the present invention can be obtained in a higher yield than the 3-alkyl-5-hydrazino-1H-pyrazole compound in which the 4-position is not substituted.

Sodium sulfite is generally used as the diazotizing agent.

As the reducing agent, sodium sulfite, hydrosulfite, zinc, tin and the like are used. In addition, reduction using a palladium carbon catalyst can also be performed.

Water is preferably used as the solvent used in the reaction, but it is also possible to use an organic solvent, for example, alcohols (methanol, ethanol, etc.), tetrahydrofuran, dioxane, N, N-dimethylformamide, etc., which are compatible with water. Can be mentioned. The amount of the solvent used is 1 to 10 parts by weight per 1 part by weight of aminotriazole as a starting material.
The amount is 00 parts by weight, preferably 5 to 100 parts by weight.

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

Next, representative specific examples of the compound of the present invention are shown below, but the present invention is not limited thereto.

From the 5-hydrazino-1H-pyrazole compound of the present invention, a photographic magenta coupler 1H-pyrazolo [3,2-
The synthetic route leading to the C] -1,2,4-triazole compound is as follows.

In the above route, R ₁ , X, A and n have the same meanings as R ₁ , X, A and n described in the general formula [I], R ₂ represents an alkyl group, and Y represents a chlorine atom or a hydroxy group. Represent

1H-pyrazolo [3,2-C] thus obtained
The -1,2,4-triazole-based compound is found in the 5-pyrazolone-based coupler which has been most often used as a magenta coupler used in a color photographic light-sensitive material.
It is a coupler that has been attracting attention in recent years because it has no secondary absorption near 430 nm or has a sharp break in the long wavelength region.

A 1H-pyrazolo [3,3-C] -1,2,4-triazole coupler having a halogen atom at the 7-position derived from the compound of the present invention is a 2-equivalent coupler (2 Particularly preferred as an economical coupler which is sufficient for the development of mole silver halide). When it was attempted to synthesize it by the conventional production method, 1H was obtained by cyclization.
-There is nothing but the halogenation of pyrazolo [3,2-C] -1,2,4-triazole, but in this case, by-product of dihalogeno form (this product causes fog in emulsion and is harmful) is avoided. No, it is difficult to obtain a pure compound.

1H-pyrazolo [3,2-C] -1, derived from the following 5-hydrazino-1H-pyrazole compounds of the present invention
Representative specific examples of 2,4-triazole compounds are shown below.

M-1 M-2 M-3 M-5 M-6 M-7 M-8 M-9 M-10 M-11 Couplers such as M-5 and M-8 are
Hydrolysis with sulfuric acid and decarboxylation step (reaction scheme A
The substituent at the 3-position is destroyed at d ₁ , d ₂ ) in ( ₁ ), and the intended product cannot be obtained.

[Examples] Hereinafter, the synthesis of the compound of the present invention and the synthesis of a photographic coupler derived from the compound of the present invention will be described with reference to specific examples.

Synthesis Example-1 (Synthesis of Exemplified Compound I-1) 9,7 g of 5-amino-3-methyl-1H-pyrazole is dissolved in 100 ml of chloroform. 13.3 g N-
Add chlorosuccinimide at 0-5 ° C. and then react for 30 minutes. The reaction mixture is washed with 50 ml of 5% aqueous sodium hydrogen carbonate solution, then with water and dried over magnesium sulfate. Chloroform was distilled off under reduced pressure below 40 ° C and 100m
20 g of an aqueous solution containing 7 g of sodium nitrite was added dropwise at -5 to 0 ° C. After 30 minutes, a solution of 50 g of stannous chloride dihydrate in 35 ml of concentrated hydrochloric acid was added to -5.
Add dropwise at ~ 0 ° C. After stirring at -5 to 0 ° C for 30 minutes, the precipitated crystals are collected by filtration and washed with concentrated hydrochloric acid and then with acetonitrile.
8.4g (45.9%) of 4-chloro-
5-Hydrazino-3-methyl-1H-pyrazole.hydrochloride was obtained. Melting point 158 ° C (decomposition) Elemental analysis value as C ₄ H ₇ ClN ₄ · HCl Calculated value (%) C: 26.24 H: 4.41 Cl: 3
8.74 N: 30.61 Found (%) C: 26.28 H: 4.39 Cl: 3
8.72 N: 30.55 FD mass spectrum showed 146, supporting that this compound has the desired structure of I-1.

Table 1 shows the characteristic values of the exemplified compounds synthesized in the same manner as in the above Synthesis Example.

Synthesis example-2 8.0 g of Exemplified Compound I-1 was dispersed in 80 ml of acetonitrile, and 14 g of triethylamine was added while maintaining -5 ° C. Further, a solution prepared by dissolving 7.1 g of octanoyl chloride in 15 ml of acetonitrile is added dropwise at -5 ° C or lower.
The reaction solution was concentrated and then purified by column chromatography to obtain 7.6 g (64%) of the desired product in the form of caramel.

Elemental analysis value as C ₁₂ H ₂₁ N ₄ ClO Calculated value (%) C: 52.83 H: 7.76 N: 2
0.54 Cl: 13.00 Found (%) C: 52.78 H: 7.71 N: 2
0.60 Cl: 12.97 FD mass spectrum value showed 272.

Synthesis Example-3 (Synthesis of Exemplified Coupler M-1) 5.4 g of 4-chloro-3-methyl-5-octanoylhydrazino-1H-pyrazole (the compound obtained in Synthesis Example-2) was added to 60 ml of benzene. Reflux with 3.2 g of phosphorus oxychloride for 3 hours with stirring. The reaction solution was separated and purified by column chromatography to give caramelized 7-chloro-3.
-Hebutyl-6-methyl-1H-pyrazolo [3,2-
C] -1,2,4-triazole (3.6 g, 71%) was obtained.

Elemental analysis value as C ₁₂ H ₁₉ N ₄ Cl Calculated value (%) C: 56.57 H: 8.31 Cl: 1
3.92 N: 22.00 Found (%) C: 56.51 H: 8.27 Cl: 1
3.90 N: 21.95 FD mass spectrum showed 254.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasuhiko Kawashima 1 Sakura-cho, Hino-shi, Tokyo Konishi Roku Photo Industrial Co., Ltd. Examiner Naoko Tsukanaka (56) References Chemical Abstracts, Vol. 101: 221167 r

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 a primary alkyl group having 1 to 30 carbon atoms and optionally having a substituent, and X represents a chlorine atom. A
Represents a protonic acid and n represents 0 or a positive number. ]