JPS62195367A - 5-hydrazino-1h-pyrazole compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (R1 is alkyl, cycloalkyl, aryl or hetero ring; X is H, halogen, cyano, alkoxycarbonyl, aryloxycarbonyl or carboxyl; A is protonic acid; n is 0 or positive integer). EXAMPLE:Methyl-5-hydrazino-3-methylthio-4-pyrazolecarboxylate. USE:An intermediate for synthesizing photography coupler of 1H-pyrazole[3,2-c]-S- triazole type shown by formula II (R2 is alkyl or aryl), especially a magenta coupler useful as a sensitized material for color photography. PREPARATION:A compound shown by formula IV is diazotized with a diazotizing agent such as NaNO2, etc., in a solvent such as water, etc., in the presence of an acid such as hydrochloric acid, etc., to form an intermediate shown by formula V and this compound is reduced with a reducing agent such as stannous chloride, etc., to give a compound shown by formula I when n is 0.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to novel 5-hydrazino-IH- and lazole compounds. More specifically, the present invention relates to 5-hydrazino-IH-pyrazole compounds useful as intermediates for photographic caprasies.

[Conventional technology]

IH-pyrazolo(3,2-C)-3-) lyazole compounds are compounds useful as photographic couplers, especially magenta couplers, and are disclosed in British Patent No. 1.252.418, for example.
No. 3,725,067, “Journal of the Chemical Society,” Perkin I (“J
internal of the chemical
5ociety”.

Parkin I) 2047-2052 (1977
) describes its importance.

Regarding the manufacturing method of this compound, please refer to the above patents and literature, as well as Research Disclosure (Research Disclosure).
closure) Vol 124, No 1244
3 (1977). Their manufacturing method can be represented by the reaction scheme shown below.

Shijigo Noyo (British Patent No. 1,252.418, U.S. Patent No. 3.725)
．． No. 067, “Journal of the Chemical Society” Perkin I″Journal of the
Chemical Society”, Parkin
I 2047-2052 (1977)) (Research Disclosure)
osure) Vol 124, No 12443 (
1977)) As evident in reaction schemes A and B,
IH-pyrazolo (3,2-C) known so far
For the synthesis of -8-triazole, 5-hydrazino-1H-
Pyrazole-4-carboxylate (1) or 3-
Mercapto-4-amino-48-1°2.4-) lyazole derivative (1) is used as a key intermediate. However, the 6-position substituent, that is, R, in IH-pyrazolo[3゜2-C)-3-) lyazole obtained using these intermediates (1) and (1) is extremely limited due to constraints on starting materials. When R is a group other than an alkyl group, an aryl group, or a heterocycle, the yield of IH-pyrazolo(3,2-C)-3-)riazole is very low or not obtained at all.

On the other hand, IH-pyrazolo (3,
A method for synthesizing 2-C)-3-) lyazoles is disclosed and described in US Pat. No. 3,725.067.

The reaction formula is shown in Scheme C.

Scheme C (US Pat. No. 3,725.067)■ As is clear from Scheme C, using this method, a methylthio group is certainly introduced at the 6-position of IH-pyrazolo(3,2-C)-3-triazole. Furthermore, by changing the structure of the starting material 0-ethyl-8-methyldithiomalonate (main), it is possible to introduce a sulfide bond other than a methylthio group.

However, since this method uses S-methylisothiocarbohydrazide, it necessarily requires IH-pyrazolo(3,2
-C)-3-) A methylthio group is also introduced at the 3-position of lyazole. Therefore, it can be said that the synthesis method is limited. IH with a sulfide bond at position 6 and no sulfide bond at position 3
In order to synthesize -pyrazolo(3,2-C)-3-)riazole, it was necessary to develop a new synthetic intermediate.

[Purpose of the invention]

The object of the present invention is to create a novel 5-hydrazino-IH- or
5-hydrazino-IH- useful as an intermediate for IH-pyrazolo(3,2-C)-s-triazole photographic couplers having a sulfide bond at the 6-position as shown in formula (1) An object of the present invention is to provide pyrazole compounds.

[Structure of the invention]

The novel 5-hydrazino-IH-pyrazole compound according to the present invention is represented by the following general formula (1).

General formula CI) In the formula, R 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 carboxy group. . A represents protonic acid, and n represents O or a positive integer. This compound is useful as a synthetic intermediate for IH-pyrazolo(3,2-C)-3-)riazole photographic couplers. Hereinafter, the compounds of the present invention will be explained in more detail.

The alkyl group represented by R1 in the general formula CI] is an alkyl group having 1 to 30 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, pentyl group, Examples include hexyl group, heptyl group, benzyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, and octadecyl group.

The cycloalkyl group represented by R1 is a 3- to 6-membered cycloalkyl group.

The aryl group represented by RI is a phenyl group or a naphthyl group.

The heterocyclic group represented by R1 is a 5- to 6-membered heterocyclic group, such as a chenyl group, a furyl group, a pyrrolyl group,
Examples include thiazolyl group, 4-pyridyl group, imidazolyl group, pyrrolidyl group, piperidyl group, and morpholyl group.

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

In general formula (I), examples of the halogen atom represented by
More preferred is a chlorine atom.

Examples of the alkoxycarbonyl group represented by X include methoxycarbonyl group, ethoxycarbonyl group, propyloxycarbonyl group, benzyloxycarbonyl group, and the like. The aryloxycarbonyl group represented by X includes a phenoxycarbonyl group.

General formula (1) also includes salts formed by protic acids, but these are not important components of the present invention, and a wide range of organic acids and inorganic acids can be used.Typical examples include:
Examples include hydrochloric acid, hydrobromic acid, sulfuric acid, acetic acid, methanesulfonic acid, and pyromellitic acid.

Next, a general method for synthesizing the 5-hydrazino-IH-pyrazole compound of the present invention will be described. (Scheme D) Scheme D However, R1 and X are the same as in general formula (r).

The weight of the 5-amino-IH-pyrazole derivative substituted with a RIS-group at the 3rd position is R, Gomper, W, T6
pfl.

Hemische Berichte (Cheap, Ber,) 9
5.2881 (1962) can be referred to. (Scheme E) Scheme E For the diazotization and reduction of the compound ↓, a conventional method can be used. For example, Organic Synthesis Collective
lective), Volun+e 1. p442
, J. de Mendoza.

J, M, Garcia-Marquina Rod
rigo, Anal,
Quim, ), 911 (1970), E.

Alcalde, J. M., Garcia-Mar.
QuLna, J. de Mendoza's Anal.

The method described in J. Quim, ) 959 (1974) can be referred to.

As the diazotizing agent, sodium nitrite, isoamyl nitrite, etc. are generally used.

As the reducing agent, sodium sulfite, sodium hydrosulfide, stannous chloride, etc. are used.

Water is preferred as the solvent used in the reaction, but it is also possible to use organic solvents. For example, alcohols (methanol, ethanol, etc.), tetrahydrofuran, dioxane, N,N-dimethylformamide, Examples include acetic acid and the like. The amount of solvent used is from 1 to 1 part by weight of aminopyrazole as the starting material.
The proportion is 1000 parts by weight, preferably 5 to 100 parts by weight.

As the acid used for diazotization, hydrochloric acid, sulfuric acid, etc. are preferable.

Next, typical examples of the 5-hydrazino-IH-pyrazole compound represented by the general formula (1) of the present invention are shown below, but the present invention is not limited thereto.

Compound Example ■-11 lF ■-23 Using the 5-hydrazino-IH-pyrazole compound of the present invention, IH-pyrazolo(,3,2-C)-3-triazole compound, which is a magenta coupler for photography, was prepared. The synthesis route is shown below.

In the above route, R1, X, A and n are represented by the general formula [1]
aRg, which has the same meaning as in the explanation above, represents an alkyl group or an aryl group.

IH-pyrazolo[3,2-C] thus obtained
-3-) The lyazole compound is 430n, which is found in the 5-mpyrazolone coupler, which has traditionally been used in large amounts as a magenta coupler used in color photographic light-sensitive materials.
It is a coupler that has been attracting attention in recent years because it has no secondary absorption near m or has a sharp cut in the long wavelength region.

The IH-pyrazolo(3,2-C)-3-triazole coupler having a sulfide bond at the 6-position derived from the compound of the present invention is a particularly useful photographic coupler that forms a magenta dye with excellent light resistance. be. Even if attempts are made to synthesize these couplers by conventional production methods, the yield is very low or cannot be obtained at all, making industrialization impossible.

Next, IH-pyrazolo[3°2-C) - derived from the 5-hydrazino-IH-pyrazole compound of the present invention.
3-) Typical specific examples of lyazole compounds are shown below.

11-2 CI Hl C.I.

H3 [Example] 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 explained by giving specific examples. Of course, the present invention is not limited to the following examples.

Synthesis Example-1 (Synthesis of the Exemplified Compound 1-1) (i) 100 g of methyl 2,2-bismethylmercapto-1-cyanoacrylate (R. Gomper. W.

T6pf1. Hemisier Berichte, Chew. Be
r. +95+2861 (1962)) and 25g
of 100% hydrazine hydrate is added to 600 m# of ethanol and heated to reflux for 1 hour. After the reaction was completed, the solvent was distilled off under reduced pressure, and the residue was recrystallized from methanol to yield 66.2 g.
methyl-5-amino-3-methylthio-4-virazolecarboxylate is obtained.

(ii) 9.4 g of methyl-5-amino-3-methylthio-4-
Virazole carboxylate in 150mj of 6N hydrochloric acid!
and cooled to 0°C. Add 3.8g of sodium nitrite to 10ml of water! Add the aqueous solution dissolved in the solution little by little. After stirring for 30 minutes, a solution of 24 g of stannous chloride dihydrate dissolved in 10 tons of concentrated hydrochloric acid was added dropwise at -5 to 0°C. Stir for 30 minutes at 0°C and further stir for 1 hour at room temperature. Next, 500ml of water! and pass hydrogen sulfide gas. The precipitated inorganic salts are filtered off, and the filtrate is concentrated under reduced pressure. Wash the precipitated crystals with ethanol. The crystals are dissolved in 50 ml of water and neutralized with sodium bicarbonate to obtain 5.3 g of methyl-5-hydrazino-3-methylthio-4-virazolecarboxylate. Decomposes above 207℃.

Elemental analysis value, C4H6゜N, O, S, C(X)
H(χ) N(χ) S(χ) Calculated value:
35.63 4.98 27.71 15.85
Actual value: 35.45 5.18 27.48
The 15.99 FD mass spectrum showed M''202 as a parent peak, supporting that this compound had the desired structure of I-1.

Synthesis Example 2 (Synthesis of Exemplified Compound 1-3) 7.7 g of 5-amino-4-cyano-3-methylmercaptopyrazole was added to a mixed solvent of 12 mA of hydrochloric acid and 60-12 of water, and the mixture was cooled to 0°C. do. To this, an aqueous solution of 3.8 g of sodium nitrite dissolved in 10 ml of water is added dropwise little by little. After stirring for 30 minutes, the reaction solution was poured into an aqueous solution of 23 g of sodium sulfite dissolved in 50 ml of water at 0-5°C. To this solution, 60 l of concentrated hydrochloric acid is added dropwise at 80-90°C. After reacting for 30 minutes, it was neutralized with sodium hydrogen carbonate, the precipitated solid was filtered, and further hot-washed with acetonitrile, resulting in 4.2 g of 4-cyano-5-hydrazino-
3-Methylmercaptopyrazole is obtained. Decomposes above 185℃.

Elemental analysis value, C, II? As NsS, Cα)H(χ”
) N(X) S(χ) Calculated value: 35.49
4.17 41.39 18.95 Actual value:
35,64 4.20 41.36 18.54
The FD mass spectrum showed M''169 as a parent peak, supporting that this compound had the desired structure of I-3.

Synthesis Example-3 (Above Exemplary Compound Il-7) (i) 32.5 g of methyl 2,2-bismethylmercapto-1-cyanoacrylate was added to 300 mj! of toluene and heated under reflux for 8 hours. The precipitated solid is filtered off, and the filtrate is concentrated.

500 taβ ethanol and 12.3 g of 100% hydrazine hydrate are added to the residue, and the mixture is heated under reflux for 2 hours.

After the reaction is completed, the solvent is distilled off under reduced pressure, and the residue is recrystallized from methanol to obtain 25 g of methyl-5-amino-3-phenylthio-4-virazolecarboxylate.

(ii) 24.0 g of methyl-5-amino-3-phenylthio-
4-virazole carboxylate in 4N sodium hydroxide 300sj! and heat under reflux for 2 hours. After cooling, adjust the pH to around 5 with hydrochloric acid.

18.2 g of 5-amino-3-phenylthio-4-pyrazolecarboxylic acid are obtained. Decomposes above 120℃.

(iii) Heat 18.0 g of 5-amino-3-phenylthio-4-virazolecarboxylic acid at 140-150'C for 20 minutes. After intense foaming has finished, cool and weigh 9.5g.
5-amino-phenylthiopyrazole is obtained.

(iv > Dissolve 9.3 g of 5-amino-3-phenylthiopyrazole in 100a+j! of chloroform and add 6.5 g of N-chlorosuccinimide. After stirring at room temperature for 30 minutes, evaporate the solvent under reduced pressure. Dissolve the residue in ethyl acetate, wash with water, dehydrate the organic layer, and evaporate the solvent under reduced pressure. Recrystallize from methanol to give 6.1 g of 5-amino-4
-chloro-3-phenylthiopyrazole is obtained.

(V) 5.6 g of 5-amino-4-chloro-3-phenylthiopyrazole and 1.9 g of sodium nitrite and 12 g
2.9 g of 5-hydrazino-4-chloro-3
- Obtain the hydrochloride of phenylthiopyrazole. Decomposes above 202℃.

Elemental analysis value, CJ+JnSCJ! As z, C(χ)■
(χ) N(χ) S(χ) Calculated value: 39.00
3.64 20.22 11.57 Actual value: 3
9.22 3.59 20.32 11.39F
D mass spectrum shows M'240 as the parent peak,
It was supported that this compound had the desired structure of l-7.

Next, IH-pyrazolo[3°2-C) - derived from the 5-hydrazino-IH-pyrazole compound of the present invention.
3-) An example of synthesis of a lyazole compound will be shown.

Synthesis Example-4 (Above Exemplified Compound ■-1) (i) 3.5 g of Exemplified Compound I-1 (synthesized in Synthesis Example 1) and 4.8 g of palmitic acid chloride in 180 m 1
In addition to the ethyl acetate in step 2, 1.8 g of triethylamine is added dropwise. After stirring at room temperature for 1.5 hours, the precipitated crystals were filtered off, washed with water, and further recrystallized from acetonitrile. 4.2 g of methyl-5-(2-valmitoylhydrazino)-3-methylmercapto-4-carboxilade are obtained.

(ii) 4.2 g of methyl-5-(2-valmitoylhydrazino)-3-methylmercapto-4-carboxilade and 1
．． Add 5g of toluene to 10011Il of toluene,
Heat to reflux for 1.5 hours. Next, the solvent was distilled off under reduced pressure.
Add 2.2 g of pyridine and 1001 Wll of acetonitrile, and heat under reflux for an additional 1.5 hours. After filtering while hot and cooling, 3.5 g of 6-methylmercabuto-7-methoxycarponyl-3-pentadecyl-IH-pyrazolo [
3,2-C)-3-triazole is obtained.

(iii) 3.4 g of 6-methylmercabuto 7-methoxy.

Dicarbonyl-3-pentadecyl-IH-pyrazolo(3
, 2-C)-S-) is added to a mixed solvent of 100 ml of acetic acid, 25 ml of sulfuric acid, and 511 Il of water, and heated under reflux for 1 hour. After adjusting the pH to 5 with an aqueous sodium hydroxide solution, extracting with ethyl acetate, concentrating, and adding water.
．． 8g of 6-methylmercapto-3-pentadecyl-I
H-pyrazolo(3,2-C)-S-)riazole is obtained.

(iv) 1.7 g of 6-methylmercapto-3-pentadecyl-
IH-pyrazolo(3,2-C)-3-triazole to 6
0a+j! of chloroform and add 0.62 g of N-chlorosuccinimide.

After stirring at room temperature for 30 minutes, the mixture is concentrated, ethyl acetate and water are added, and the organic layer is separated. Concentrate under reduced pressure and recrystallize from acetonitrile to obtain 1.3 g of the target compound.

Elemental analysis value, C2゜HkosN*scj! As, C(χ
) H(χ) N(χ') 5(X) Calculated value: 60.20 8.84 14.04 8.
03 actual measurement value: 59.80 8.96 13.82
The 8.28FD-mass spectrum showed M''39B as a parent peak, supporting that this compound had the desired U-t structure.

Synthesis Examples-5 to 24 (the above-mentioned exemplified compounds I-2, I-4 to I
-6, I-8 to ■-23) Exemplified compounds 1-2.
I-4~! -6, I-8 to ■-23 were synthesized.

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

〔Effect of the invention〕

As mentioned above, according to the present invention, the novel 5-hydrazino-I
H-pyrazole compounds can be provided which are useful as intermediates for IH-pyrazolo(3,2-C)-3-)lyazole photographic couplers.

Claims (1)

[Claims] 1. 5-hydrazino- represented by the following general formula [I]
1H-pyrazole compound. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 represents an alkyl group, cycloalkyl group, aryl group, or heterocycle, and X represents a hydrogen atom, a halogen atom,
Represents a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a carboxy group. A represents protonic acid, and n represents 0 or a positive integer.