JPS62138474A - Production of 5-hydrazinopyrazole-4-carboxylate compound - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as an intermediate for magenta coupler from a corresponding compound in high yield by easy treatment of waste liquor without using a reagent having strong toxicity, by using a hydroxylamine compound. CONSTITUTION:A hydroxylamine compound is reacted with a compound (e.g., compound wherein R1 and R2 are methyl; =C(R3)R4 is group shown by formula II) shown by formula I (R1-R4 are H, alkyl, alkenyl, cycloalkyl, aryl or heterocyclic ring; A is protonic acid; n is 0 or positive integer) preferably at 40-80 deg.C to give a 5-hydrazinopyrazole-4-carboxylate compound shown by formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a method for producing 5-hydrazinopyrazole-4-carboxylate compounds, and more specifically, to a method for producing 5-hydrazinopyrazole-4-carboxylate compounds by reaction with a hydroxylamine compound. The present invention relates to a method for producing a carboxylate compound.

[Prior Art] A 5-hydrazinopyrazole-4-carboxylate compound is a compound useful as an intermediate for a photographic coupler, especially a magenta coupler. For example, British patents 1 and 2
No. 52,418, in Hata-sho, IH-pyrazolo[-3,2 -cl-1,2,4-triazole-
The method for producing 7-carboxylate compounds is
It is shown.

Further, the above-mentioned British patent specification describes a method other than the above-mentioned method, for example, in which the 5-hydrazinopyrazole-4-carboxylate compound is ring-closed in the presence of bromine and sodium acetate in acetic acid. A method for preparing pyrazolo[3,2-c-1,2,4-trizolezole-7-carboxylate-based compounds is disclosed.

Regarding the synthesis of 5-hydrazinopyrazole-4-carboxylate compounds, Hans Bayer (Han.
Ber, et al.

It was reported in Vol. 89, p. 255z (1956), and a similar report was made by Joseph Bayley.
Bailey) et al. in the Journal of the Chemical Society, Parkin, %l (J, C!h
em, Soc, .

Perkin Trans, ) ■, 2047~2
052 (1977). According to these documents, concentrated hydrochloric acid is added to thiocarbohydrazide dispersed and suspended in refluxing ethanol, and then ethyl-
Add 2-chloroacetoacetate and heat the mixture to diethyl-5-hydrazino-3-methylpyrazole-4
-carboxylate is produced.

However, according to the method of this document, the target 5-hydrazinopyrazole-4-carboxylate compound can be obtained from the starting material thiocarbohydrazide in a low yield of only about 20%.

Attempts have been made to obtain 5-hydrazinopyrazole-4-carboxylate compounds in high yields by improving synthetic methods. That is, in Tokusho No. 1 No. 59-140246 (Examination 13'lJ), it is disclosed that a thiocarbohydrazide and an α-halogen of a ketoester can be reacted in a substantially anhydrous state under a water chloride accumulation catalyst. Disclosed.

In addition, as another improved method, Japanese Patent Application No. 140267/1989 (Example) describes a method in which thiocarbohydrazide and benzaldehyde are reacted, and then reacted with a halogenated ketoester, and then reacted with hydrazine hittride. is proposed.

Furthermore, in Japanese Patent Application No. 6Q-94752 (Example),
A method has been disclosed in which a thiocarbohydrazide is reacted with benzaldehyde, etc., and then reacted with an α-halogen of a ketoester under an acid catalyst, and then reacted with hydrazine hittride.

Said Tokusho No. 59-140247, No. 6o-9475
Although the yield was improved by the method described in No. 2, it had the following drawbacks due to the use of hydrazine hydride.

That is, the strong odor and toxicity worsen the working environment, and the corrosive nature increases the load on equipment, leading to increased costs. Furthermore, since the reactivity of hydrazine hydride is low, it is necessary to use a large-scale stripping method, which causes a large amount of waste in terms of waste liquid treatment.

[Object of the invention].

The present invention has been made in view of the above-mentioned circumstances, and its purpose is to produce 5-hydrazinopyrazole-4-carboxylate compounds in high yields while using a small number of reagents that are less burdensome on equipment. Our goal is to provide a method for manufacturing.

[Summary of the Invention] The above object of the present invention is to produce 5-hydrazinopyrazole-4 represented by the following general formula [TI] by reacting a hydroxylamine compound with a compound represented by the following general formula [I]. - Achieved by a method for producing carboxylate compounds.

General formula [■ General formula [■ In the formula, RIt R2+ R3 and R1 are each a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, 7
1J- represents a group or a heterocyclic group. A represents protonic acid, and n represents 0 or a positive number.

[Structure of the Invention] In the present invention, the compound represented by the general formula [I] to be reacted with the hydroxylamine compound is the compound represented by the above-mentioned Japanese Patent Application Nos. 59-14026, 59-44027, and 60.
It can be made into synthetic leather by the method described in No.-94752.

Specifically, RI + R2 + R2 and R4 in the general formula [I] include hydrogen ions, alkyl groups (e.g. methyl, ethyl, isopropyl, butyl, 7-butyl, octyl,
pentadecyl, eicosyl, etc.), Ryorukenyl iC
Example f is each group such as vinyl, propenyl, butenyl, hexenyl, pentadecenyl, octadecenyl, etc.
Mention may be made of lz/l' groups (eg, cyclopentyl, cyclohexyl), aryl groups (eg, phenyl, naphthyl), and heterocyclic groups (eg, pyridyl, furyl, chenyl, etc.).

These alkyl groups, alkenyl groups, aryl groups, and reconstituted ring groups can have substituents, and substituents include halogen atoms, hydroxyl groups, nitro groups, alkyl groups,
Examples include a sulfuroxy group, a sulfuryloxy group, an alkylsulfonyl group, and an acylamiz group.

As R8 and R2, an alkyl group or an alkyl group is preferable, and an alkyl group is particularly preferable. R3 and R
When R1 is a hydrogen atom, R1 is preferably a single group or a heterocyclic ring group, and when R1 is an alkyl group, R4 is preferably an alkyl group or an aryl group. In addition, when R1 and R4 are both alkyl groups, they are bonded to 5
A ~7-membered hydrocarbon ring may be formed. When R1 or R1 is a aryl group, the substituent is preferably an alkyl group (for example, a methyl group, an ethyl group, a hydroxyl group, a nitro group, or a rogene atom).

As the protonic acid represented by A, the organic acid or inorganic acid of Otsutsu A is used. Typical examples include hydrochloric acid, hydrobromic acid,
Examples include sulfuric acid, acetic acid, methanesulfonic acid, p-toluenesulfonic acid, and the like.

Next, typical examples of the compound represented by the general formula [I] are shown below, but the present invention is not limited thereto.

The hydroxylamine compound of the present invention has the following general formula [m
].

General formula [TrI] NH2OR5·n(A) In the formula, R5 represents a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group, etc.) or a sulfonic acid group.

A represents a protonic acid, and n represents 0 or a positive number, each having the same meaning as A and n in the general formula [I].

Next, representative examples of the compound represented by the general formula [ffI] are shown below, but the present invention is not limited thereto.

m −l NH2OH・l/2H2So4rll
-2NH,OH-HCf.

m -3NH2OH (50% aqueous solution) m -4NH,0OH5-Hc ill -5NH2O5O, H m -6NH,OH-HBr m -7NH2O02H5 Compound represented by general formula [I] and hydroxylamine represented by general formula [m] The reaction of the system compounds is carried out in a solvent. Examples of solvents that can be used include compounds that do not have carbonyl groups such as ketones and aldehydes, or ester bonds such as ethyl acetate, alcohols, benzenes, ethers, halogenated hydrocarbons, and ester bonds. This can be cited as a representative example. Among these, preferred are alcohols, ethers and hydramides, and particularly preferred are alcohols.

Ketones and aldehydes are not preferred because their carbonyl group reacts with the amine 7 group of the hydroxylamine compound. Ethyl acetate is also not preferred because the carbonyl group bonds with the amino group of the hydroxylamine compound to form an amide and the alcohol is eliminated, making it impossible to obtain the desired compound.

Examples of alcohols used in the present invention include methanol, ethanol, n-propanol, ethylene glycol, and ethylene glycol monomethyl ether.

Examples of the organic compounds include benzene, nitrobenzene, toluene, xylene, and the like. Furthermore, examples of the ethers include diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and dioxane. Examples of the halogenated hydrocarbons include carbon tetrachloride, chloroform, bromoform, etc., and examples of the compounds include formamide, N,N-dimethylformamide, and the like.

Among these solvents, alcohols, ethers, and hydramides that are miscible with water may be mixed with water. The solvent is used in an amount of 05 to 50 parts by weight, preferably 1 to IQ parts by weight, per 1 part by weight of the compound of general formula [I].

The hydroxylamine compound (general & [m]) is used in a ratio of 1.0 to 10 mol, preferably 1.0 to 5 mol, per 1 mol of the compound of general formula [I].

When the compound of general formula [I] and/or the hydroxylamine compound of general formula [■] forms a salt, it is preferable to neutralize it with a base. The base used is water! Examples include inorganic bases such as sodium chloride, potassium hydroxide, sodium carbonate, and potassium carbonate, and organic salts such as sodium methoxide, sodium ethoxide, and triethylamine. Among them, preferred are sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. Fun + → ÷ 10 bases are used in the general formula [
0.5 to 2 mol per mol of the salt of the compound of general formula [I] or/and general formula [m], and the pH of the reaction solution is 5 to 2 mol.
12 is preferred, and 6 to 10 are particularly preferred.

If the pH is too high, the product will decompose, which is undesirable.

The reaction temperature is preferably 0 to 150°C, especially 10 to 80°C.
°C is preferred. Reaction) If the reaction temperature is too high, the product will decompose, which is undesirable. The time required for the reaction is not particularly limited, but is preferably 5 minutes to 10 hours, more preferably 5 minutes to 5 hours.

-ff Either the compound of formula [I] or the hydroxylamine compound of general formula [ITI] may be added first.

According to the method of the present invention, a compound represented by the following general formula [fT] can be obtained.

General formula [[[] In the formula, RI + R2+ A and n are the general formula [I
It has the same meaning as R, , R2, A and n explained in 3.

Next, typical examples of the compound represented by the general formula [TI] are shown below, but the present invention is not limited thereto.

From now on,・'Bottom margin＼ ・－・・ノ＼り2゜＋I-I Tl
-2If -5H-6 H-7■-8 +1-11 n -1
2゜■ -13 IT -14 H21 ■ -22 The 5-hydrazinopyrazole-4-carboxylate compound represented by the general formula [I] obtained by the method of the present invention is useful as an intermediate for photographic couplers. It is a compound described in British Patent No. 1252418 and the Journal of Chemical Society, Parkin mI (cited in J, 1977).

This compound was used for photographic jy on pages 2047-2052.
An example of manufacturing 7'5- is described. Furthermore, Japanese Patent Application No. 59-243008, No. 59-243Q09,
No. 59-243010, No. 59-243011, No. 59-243012, No. 59-243QlZ, No. 5
No. 9-243015, No. 60-21308, No. 60-
It is also described in No. 70197, No. 60-70198, etc.

[Examples] Specific examples of the present invention will be described below, but the present invention is not limited thereto.

Synthesis Example of Raw Materials 10.6 p of thiocarbohydrazide was suspended in 180 ml of alcohol. While stirring under reflux, 10.6 g of benzaldehyde was added dropwise over 30 minutes. After the dropwise addition was completed, the mixture was refluxed for another 30 minutes, and then cooled. When the internal temperature reached 19°C, 3.7 g of hydrochloric acid gas (hydrogen chloride) was dissolved in the reaction solution. Then, the internal temperature was maintained at 50 to 60°C. , 21.2 g of ethyl-2-chloroisobutyryl acetate was added dropwise over 30 minutes. After stirring at the same temperature for 3 hours, it was heated to reflux. After 30 minutes, the reaction solution was filtered to remove insoluble matter. Ta Pg
The alcohol was then distilled off under reduced pressure. aom on the residue
After adding 1 liter of acetonitrile and heating, the mixture was allowed to cool. The precipitated crystals were washed with 25 ml of cetonitrile and dried.
25.9.9 (77%) of the hydrochloride of ethyl-5-β-benzylidenehydrazino-3-isopropylpyrazole-4-carboxylate (exemplified compound 1-7) was obtained. Melting point 195-1986 CFD mass spectrum shows 300, only 1 NIT! R also supported the above structure.

Elemental analysis value (C16H21N40201) calculated value)
C:5'? , 06 H:6.29 N:16.
63 Cl: 10.52 Actual value (support)) C: 5
7.22 H:6.51 N+16.46 C!
l: 10.21 Comparative Example-1 10.0 g of the finished salt of exemplified compound [-7 was added to 20 g of ethanol.
Hydrazine Hitlerde 3.3.9 (Exemplary Compound 1
2.2 of -7 (fj morno) was added dropwise. Then, a solution of 0.9 g of sodium hydroxide dissolved in 3 me of water was added, and the mixture was heated under reflux for 2 hours.
30 ml of water was added and cooled on ice. The precipitated crystals were filtered, washed with water, and dried to obtain 5.8 g of crude crystals.

The crude crystals were added to 20 ml of ethyl acetate, heated under reflux for 30 minutes, cooled, and the precipitated crystals were filtered, washed, and dried. However, when analyzed by high performance liquid chromatography, the desired ethyl-
In addition to 5-hydrazino-3-isopropylpyrazole-4-carboxylate (■-11), 23% of the raw material (1-
7) were mixed.

Comparative Example-2 The hydrazine hydrogen tride of Comparative Example-1 was added to 12. Comparative Example-1 except that C17 (8 times the mole of Exemplified Compound 1-7) was used.
It took exactly the same operation.

Target ethyl-5-hydrazino-3-isopropylpyrazole-4-carboxylate (exemplary compound ■-1
1) Obtained 4.6.9 (72.5%).

Melting point 160-1619 CFD mass spectrum showed 212, and R and NMR also supported the above structure.

Example-1 Hydrochloride 20.0.9 of Exemplified Compound I-7 was added to ethanol +
Add to a mixed solvent of oml and 20 ml of water, heat to 55°C, and prepare a 50% hydroxylamine aqueous solution < PH-50.
, manufactured by Nisshin Kogyo Co., Ltd.) 8.7 g (Example 1 compound 1-'
2.2 times the amount of y and 1.8 g of sodium hydroxide in 6 ml of water
ml of the solution was added and reacted at the same temperature for 1 hour. After the reaction, insoluble matter was removed by filtration, 60 ml of water was added, and the mixture was cooled with ice. Furthermore, add 2.4 g of sodium hydroxide to 8 m of water.
Add a solution dissolved in 100ml of water, filter the precipitated crystals, wash with water,
After drying, 11.7 g of crude crystals were obtained. 50 pieces of this coarse crystal
ml of ethyl acetate, heated under reflux for 30 minutes, cooled, and precipitated crystals were filtered, washed, and dried to give ethyl-5-
9.9 g (78
,0%) obtained. The melting point was 160-161° CFD mass spectrum showed 212, and the chemical R1 NMR was also completely consistent with the compound of Comparative Example-2.

Example-2 Hydroxylamine sulfate 11.7% was added to a mixed solvent of 40 ml of ethanol and 20 mg of water. j9 (2.2 times the mole of Exemplified Compound 1-3) was added, heated to 60°C, and 20.0 g of the hydrochloride of Exemplified Compound T-3 was added. Then add 7.5 g of IJum to 5 ml of water! A solution adjusted to mH was added to the mixture, and the mixture was reacted at the same temperature for 2 hours. After the reaction, insoluble matter was removed by filtration, 6 oml of water was added, and the mixture was cooled on ice.

Furthermore, a solution of 2.6 g of sodium hydroxide dissolved in 9 ml of water was added, and the precipitated crystals were filtered, washed with water, and dried.
0.3 g of crude crystals were obtained. Purification was carried out in the same manner as in Example-1, and ethyl-5-hydrazino-3-methylpyrazole-4-carboxylate (exemplified compound n-2) was purified to 9.0%
g (75.2%) was obtained. Melting point 176-178° CFD mass spectrum showed 184, and R and NMR also supported the above structure.

Example-3 Exemplified compound 1-5 hydrochloride 35.0.9 and 0-methylhydroxylamine hydrochloride 178.9 (exemplified compound 1-5
) Add 3x Morno to 250 ml of methanol,
While heating under reflux, a solution of 14.3 g of potassium hydroxide dissolved in 50 ml of methanol was added dropwise. After refluxing for 1 hour, insoluble materials were removed by filtration and the mixture was cooled.

The precipitated crystals were filtered, washed with methanol, washed with water, and then dried to obtain 21.5 g (82.5%) of methyl-5-hydrazino-3-pentadecylpyrazole-4-carboxylate (exemplified compound IT-16). .Z (points 160-162
°CFD mass spectrum shows 366, engineering R, NMR
also supported the above structure.

Elemental analysis value (02°HsmN40t) Calculated value (support))
C: 65.54 H: 10.45 N: 15.
29 actual measured value) C2 65.29 H: 10.61
N: 15.33 Implementation-4 Exemplified Compound 1-10.11.9 g and hydroxylamine hydrochloride 3.6 g (1.1 times the mole of Exemplified Compound I-'10) were mixed in a mixed solvent of 2 oml of ethanol and 10 ml of water. and heated to 50°C. Sodium hydroxide 1.9
A solution of g dissolved in 14 ml of water was added, and the mixture was reacted for 30 minutes at the same temperature. Insoluble matters were removed by filtration and the mixture was cooled. The precipitated crystals were filtered, washed with water, and dried to obtain 9.1 g of crude crystals. Purification was carried out in the same manner as in Example-1, and 7.7 g (77,
0%) obtained. The melting point: 160-161° CFD mass spectrum, EMR and NMR completely matched those of the compound of Example-1.

Example-5 10.0 g of hydrochloride of Exemplified Compound T-'7 was added to ethanol 4
0ml! and 10 ml of water at 45°C.
heated to. Hydroxylamine-〇-sulfonic acid7.
4.51 (2.2 times the amount of Exemplary Compound!-7) and a solution of 5.1 g of sodium carbonate dissolved in 20 ml of water were added and reacted at the same temperature for 3 hours. After the reaction, insoluble materials were removed by filtration and cooled. The precipitated crystals were filtered, washed with water, and dried to obtain 5.5 g of crude crystals. The crude crystals were recrystallized from 30 ml of ethanol to give ethyl-5-hydrazi-7-3-isopropylpyrazole-4-carboxylate. (Exemplary compound n-1,"x) 4.79 (74.0%) was obtained.

The melting point: 160-161'CF'D mass spectrum, EMR and NMR were completely consistent with the compound of Example-1.

As is clear from the comparative examples and examples, the manufacturing method using the hydroxylamine compound of the present invention is disclosed in Japanese Patent Application No. 1986.
Compared to the method using a hydrazine compound disclosed in No. 94752, the reaction proceeded even when the amount of reagent was 173 to 1/7, and the yield increased.

Furthermore, since the method of the present invention does not use highly toxic reagents, the load on equipment is small, and it is also very advantageous in treating waste liquid.

Claims (1)

[Claims] A 5-hydrazinopyrazole-4-carboxylate system represented by the following general formula [II], which is characterized by reacting a hydroxylamine compound with a compound represented by the following general formula [I]. Method of manufacturing the compound. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2, R_3 and R_4 are each,
Represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. A represents protonic acid, and n represents 0 or a positive number. ]