JPS62228066A - 5-hydrazino-1h-pyrazole based compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R1 is cycloalkyl, alkyl, aryl or heterocyclic group; X is H, halogen, cyano, alkoxycarbonyl, aryloxycarbonyl or carboxyl; A is protonic acid; n is 0 or a positive integer). EXAMPLE:3-Ethoxy-4-ethoxycarbonyl-5-hydrazinopyrazole. USE:An intermediate for photographic couplers. PREPARATION:A 5-amino-1H-pyrazole derivative expressed by formula II is diazotized with a diazotizing agent, e.g. sodium nitrite, in the presence of hydrochloric acid, etc., and the resultant product is then reduced with sodium hydrosulfite, etc., to afford the aimed substance.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel 5-hydrazino-I H-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)-3-triazole compounds are useful compounds as photographic couplers, especially magenta couplers, and are described, for example, in British Patent No. L252,41.
No. 8, U.S. Patent No. 3,725,067, “Journal of the Chemical Society” Perkin I (“J
internal of the chemical 5o
Parkin I), 2047-205
2 (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 Di
sclosure) Vol 124.11h12443
(1977). Their manufacturing method can be represented by the reaction scheme shown below.

Reaction Scheme A (UK Patent No. L252,418, U.S. Patent No. 3,72
No. 5,067 "Journal of the Chemical Society" Perkin I Journal of the
Chemical 5ociety"Parkin I
2047-2052 (1977)) Reaction Scheme B (Research Disclosure)
closure) Vol, 124. Na12443
(1977)) As is clear from reaction schemes A and B, the previously known 1H-pyrazolo (3,2-C
)-S-triazole, 5-hydrazino-1
H-pyrazole-4-carboxylate or 3-
Mercapto-4-amino-4H-R2,4-triazol derivatives are used as key intermediates. but,
The 6-position substituent of 1H-pyrazolo(3,2-C)-3-triazole obtained using these intermediates,
That is, R is extremely limited due to constraints on starting materials, and when R is a group other than an alkyl group, a ring group, or a heterocycle, the yield of 1H pyrazolo(3,2-C)-3-triazole is very low or not obtained at all.

Therefore, in order to obtain a compound in which an ether group is bonded to the 6-position of 1H-pyrazolo(3,2-C)-3-)lyazole, it was necessary to develop a new synthetic intermediate.

[Purpose of the invention]

An object of the present invention is to provide a novel 5-hydrazino-1H-pyrazole compound, and more specifically, a 1H-pyrazole compound having an ether bond as shown in the general formula (1) at the 6-position.
5-hydrazino-1H- useful as an intermediate for pyrazolo(3,2-C)-3-triazole photographic couplers
An object of the present invention is to provide pyrazole compounds.

[Structure of the invention]

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

General formula (1) 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, or an alkoxycarbonyl group.

Represents an oxycarbonyl group or a carboxyl group.

A represents protonic acid, and n represents O or a positive integer.

This compound is L H-pyrazolo[3,2-C)-3-
It is useful as a synthetic intermediate for 1-lyazole photographic couplers. Hereinafter, the compounds of the present invention will be explained in more detail.

The alkyl group represented by R1 in 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, etc. group, hexyl group, heptyl group, hensyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group,
etc. can be mentioned.

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

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

The heterocyclic group represented by Ro is a 5- to 6-membered heterocyclic group, such as chenyl group, furyl group, pyrrolyl group, thiazolyl group, pyridyl group, imidazolyl group, pyrrolidyl group, piperidyl group, morpholyl group, etc.

The alkyl group, cycloalkyl group, aryl group, and heterocyclic group represented by R1 may further have a substituent.

In general formula [I], the halogen atom represented by X includes a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom, with a chlorine atom and a bromine atom being preferred, and a chlorine atom being more preferred. 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 phe-carbonyl group.

General formula CI) also includes salts formed with protic acids, although this is not an essential component of the invention. Various organic acids and inorganic acids are used. A typical example is
Hydrochloric acid, hydrobromic acid, sulfuric acid, acetic acid, methanesulfonic acid,
Examples include toluenesulfonic acid.

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

Scheme D R,,X is the same as general formula CI). R, O- in 3rd place
5-amino-1H-pyrazole derivatives substituted with groups (4
) is W, J, Middleton, ν, A, Enge.
lhard, Journal of American Chemical Society 4J, Am, Chem, Soc, Dan 0.2
788 (195B), W.J., Middleton.
V. A. Engelhard, Journal of American Chemistry Society 4. J, 8m, che
Reference may be made to the method of Scheme E described in ``M, soc+ 80°2829 (195B).

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

A conventional method can be used for diazotization and reduction of the 5-amino-1H-pyrazole derivative.

For example, Organic Synthesis Collective Volume (Organic 5ynthesis Co1
1. Vol.) l.

P, 442-445, Anares de Quimica (An,
Mouth uim.

) Plate 911-918 (1970), “Jfl 95
9-961 (1974) etc. can be referred to.

As the dianation reagent, sodium sulfite, isoamyl sulfite, etc. are generally used. As the reducing agent, sodium sulfite, sodium hydrosulfite, stannous chloride, etc. are used.

Although water is preferred as the solvent used in the reaction, it is also possible to use organic solvents, such as alcohols (
(metal, ethanol, etc.), tetrahydrocran, dioxane, N,N-dimethylformamide, acetic acid, and other solvents that are compatible with water.

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

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

Next, 5-hydrazino- represented by the general formula [I] of the present invention
Specific examples of 1H-pyrazole compounds are shown below in 1-1 to ■-2.
3, but the present invention is not limited thereto.

Compound example ■-4 N CI! .

Go□Go11 ■ - 1 0 ■ -1 2 ■ -1 3 ■ -1 4 ■ -1 5 ■-16 ■ -17 ■ -18 ■-19 C7! ■ -20 ■ -21 ■ -22 ■-23 Using the 5-hydrazino-114-pyrazole compound of the present invention, 1H-pyrazolo(3,2-c)-s-1-lyazole, which is a magenta coupler for photography, The route for synthesizing these compounds is shown below.

In the above route, R,, X, A and n are represented by the general formula (1)
It is synonymous with the explanation of R2 represents an alkyl group or an aryl group.

1H-pyrazolo[3,2-C] thus obtained
-3-1-Riazole compounds are found in 5-pyrazolone couplers, which have traditionally been used in large amounts as magenta couplers used in color photographic light-sensitive materials.
There is no secondary absorption near nm.

Alternatively, it is a coupler that has attracted attention in recent years because of its sharp cut in the long wavelength region.

The 1H-pyrazolo(3,2-c)-s-triazole coupler having an ether 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 yields are very low or cannot be obtained at all, making industrialization impossible.

Next, 11■-pyrazolo[3°2-C] derived from the 5-hydrazino-L H-pyrazole compound of the present invention
Typical examples of -3-triazole compounds are listed below.
1 to ■-10.

(I I[-3 CP CI! ■ I11 I-6 CI! ic:+l17 ■-10 C7! [Examples] Examples of the present invention will be described below. It should be noted that the present invention Not limited only to the following examples: 5-hydrazino-1 encompassed by the present invention
Examples will be explained by showing specific synthesis examples of H-pyrazole compounds.

8 Example 1 [Synthesis of the above exemplified compound (■-3)] (ii
5-Amino-4-cyano-3-ethoxypyrazole 15.2 g (Journal of American Chemical Society, J. Am. Chem. Soc.
llQ.

2829 (195B)) is dissolved in 100 mm1 of ethanol and 2Qmj2 of concentrated hydrochloric acid is added. Heating reflux 8
After a period of time, the mixture was neutralized with sodium hydroxide and cooled to obtain 13.0 g of 5-amino-3-ethoxy-4-ethoxycarbonylpyrazole in the form of white crystals.

(ii) 10.0 g of 5-amino-3-ethoxy-4-ethoxycarbonylpyrazole was dissolved in 150 m of 6N hydrochloric acid.
! ! , and then cooled to 0°C. A solution of 3.8 g of sodium nitrite dissolved in 10 mm 2 of water is added dropwise to this. After stirring at 0° C. for 30 minutes, a solution of 24 g of stannous chloride in 70 ml of concentrated hydrochloric acid is added dropwise.

After stirring at 0°C for 1 hour, the mixture was further left at room temperature for 1 hour. Next is 500m7 of water! was added to remove the tin salt precipitated by hydrogen sulfide gas 'f-'4. After concentrating the filtrate, the obtained white crystals are washed with ethanol. The crystals were dissolved in water and neutralized with sodium hydrogen carbonate to produce white crystals, the target product 3-
3.8 g of ethoxy-4-ethoxycarbonyl-5-hydrazinopyrazole are obtained. Decomposed at 185°C or higher.

Elemental analysis, as CeH+4N4.03, C(χ)11
(χ) N(χ) Calculated value 44.85 6.59 26.16 Actual value 44.62 6.65 25.86 The FD mass spectrum shows a parent peak at M” 214, and this compound shows the target I-3. I supported that it was a structure.

[Application example using Synthesis Example 1] Using Exemplified Compound 1-3 obtained in Synthesis Example 1 above, 7-chloro, which belongs to 1H-pyrazolo(3,2-c)-3-)azole compounds, was prepared. An example of the synthesis of -6-nitoxy3-pentadecyl-1H-pyrazolo[3°2-C)-3-)riazole will be described.

(i) 3-ethoxy-4- obtained in Synthesis Example 1 above
Ethoxycarbonyl-5-hydrazinopyrazole 3.5
g and 4.5 g of palmitic acid chloride, ethyl acetate 1
20m7! Add to and stir. 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 further washed with water to obtain white crystals.

Recrystallized from acetonitrile to give 3-ethoxy-4-ethoxycarbonyl-5-(2-valmitoylhydrazino)
5.8 g of pyrazole was obtained.

(ii) 3-ethoxy-4-ethoxycarbonyl-5-(2-valmitoylhydrazino)pyrazole5.
Dissolve 0g in 15Qmffi of toluene and add 1.7g of phosphorus oxychloride. After heating under reflux for 1 hour, the solvent was distilled off under reduced pressure. 150 ml of acetonitrile and 2.6 g of pyridine were added to the residue, and the mixture was further heated under reflux for 1 hour. Pyridine hydrochloride is removed by hot filtration and cooled. The precipitated crystals were further recrystallized from acetonitrile to give 6-nitoxy-7-ethoxycarbonyl-3-pentadecyl-1H.
-Pyrazole [3゜2-C] -3-) Riazole 3.6
get g.

(iii) 6-nitoxy7-ethoxycarbonyl-3-pentadecyl-1H-pyrazolo(3,2-C)
Add 3.5 g of -3-1 riazole to 10 QmJ of acetic acid, and then add 25 mJ of sulfuric acid! and 5 m II of water, and 1
Heat to reflux for an hour. The reaction mixture is cooled to below 10°C and neutralized with 6N aqueous sodium hydroxide solution. Extract with ethyl acetate and evaporate the solvent under reduced pressure. 50 mj of water on tar-like residue! is added, and the precipitated crystals are separated by filtration. Furthermore, by reconsolidation with acetonitrile, 6-nitoxy3-
Pentadecyl-1H-pyrazolo(3,2-C) -3-
2.4 g of triazole are obtained.

(iv) 6-nitoxy-3-pentadecyl-1H
-Pyrazolo(3,2-C)-3-1-riazole2.
3g to 80 mjl of chloroform! In addition to this, 0.85 g of N-chlorosuccinimide is added little by little while stirring.

After stirring at room temperature for 30 minutes, the solvent was distilled off under reduced pressure, ethyl acetate and water were added, and the ethyl acetate layer was separated.

Further, the solvent was distilled off under reduced pressure, and the residue was recrystallized from acetonitrile to obtain 1.8 g of a white target compound. The structure of the target product was confirmed by NMR, mass spectrometry, and elemental analysis.

Elemental analysis, C*+HzqNaOCA, C(χ)
H(χ) N(χ) Theoretical value 63.53
9.40 14.11 Actual value 63.26 9.
10 14.01 case Example 2 [1-Self Demonstrator ■-1
1] (ii Tetracyanoethylene 12.8g
and 2.0g of urea in 100mj+ of 2-methoxyethanol
and heat to 90-100°C. When the first purple color disappears and the solution turns yellow, cool and pour into water. Extract the organic layer with ethyl acetate and purify by column chromatography on silica gel. The target product was distilled out using a mixed solvent of ethyl acetate and hexane (1:1) to obtain 13.0 g of dicyanoketenedi-2-methoxyethyl acetal as a pale yellow viscous liquid.

(ii) 11.3 g of dicyanoketendi-2-methoxyethyl acecure and 2.5 g of hydrazine hydrate at 50%
Add to m# of water and stir. If you continue stirring at room temperature,
Gradually crystals begin to precipitate. After cooling, the crystals were filtered and recrystallized from water to give 5-amino-4-cyano-3-(2-
6.3 g of methoxyethoxy)pyrazole are obtained.

(iii) 5-amino-4-cyano-3-(2-
methoxyethoxy) pyrazole 6.0g in 50m7! of ethanol and add 10 ml of concentrated hydrochloric acid. After heating under reflux for 7 hours, neutralization with aqueous sodium hydroxide solution and cooling yields 3.8 g of 5-amino-4-ethoxycarbonyl-3-(2-methoxyethoxy)-pyrazole as white crystals.
get.

(iv) 5-amino-4-ethoxycarbonyl-
3.8g of 3-(2-methoxyethoxy)pyrazole in 6
After dissolving in 50 ml of N-hydrochloric acid, cool to 0°C. Add 1.2 g of sodium nitrite to 5 mjl of water! Add dropwise an aqueous solution dissolved in . After stirring for 30 minutes at 0°C, tin chloride 7
．． A solution of 7 g dissolved in concentrated hydrochloric acid 2Q m j2 is added dropwise. After stirring at 0°C for 1 hour, the mixture was further left at room temperature for 1 hour. Next, add 200 mff of water, pass hydrogen sulfide gas,
Remove precipitated tin salt.

Concentrate the filtrate, wash the obtained white crystals with ethanol,
The target compound, 4-ethyl-1-oxycarbonyl-3-(2
2.1 g of hydrochloride of -methoxyethoxy)-5-hydrazinopyrazole are obtained. It was over 212 degrees Celsius.

Elemental analysis, C1III7N404Cl, C(χ)
11(χ) N(″”A)Cff(χ) Calculation Directly
3B, 51 6.11 19.96
12.63 Actual value 38.66 6.35 20
．． 26 12.51FD-mass spectrum is M”2
The parent peak is shown at 80, and this compound has the target l-1
1 structure was supported.

Synthesis Example-3 [Synthesis of the above-mentioned exemplified compound 1-12] (i)
12.8 g of tetracyanoethylene, 3.0 g of urea and 12.4 g of p-methoxyphenol are added to 100 ml of toluene and heated to reflux. When the initially appearing purple color disappears and the solution turns yellow, it is cooled and the precipitated crystals are filtered off to obtain 16 g of 1,1-dicyano-2,2-di(p-methoxyphenoxy)ethylene.

(ii) 16 g of 1,1-dicyano-2,2-di(p-methoxyphenoxy)ethylene and 2 hydrazine hydrates
Add 5 g to 100 m2 of ethanol and heat under reflux for 1 hour. After cooling, the precipitated crystals were filtered and further recrystallized from ethanol to give 5-amino-4-cyano-3-
8.4 g of (p-methoxyphenoxy)pyrazole are obtained.

(iii) 5-amino-4-cyano-3-(p-
8.4 g of methoxyethoxy) pyrazole was added to 10 g of concentrated sulfuric acid.
Add to a mixed solution of ml and 50 ml of water, and heat under reflux for 12 hours. After cooling, the mixture 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 was added to 110
Heat to 120"C. Vigorous foaming. After cooling,
Reconsolidation from ethanol yields 4.2 g of 5-amino-3-(p-methoxyphenoxy) pyrazole.

(V) Dissolve 4.1 g of 5-amino-3-(p-methoxyphenoxy)pyrazole in chloroform Loom R and add 2.78 g of N-chlorosuccinimide.

After stirring at room temperature for 30 minutes, ethyl acetate and water were added, and the organic layer was separated. Concentrate under reduced pressure and recrystallize from a mixed solvent of ethanol and hexane to obtain 2.9 g of 5-amino-4-chloro-3-(p-methoxyphenoxy) pyrazole.

(vi) 2.4 g of 5-amino-4-chloro-3-(p-methoxyphenoxy)pyrazole and 5 mj of concentrated hydrochloric acid
! .

Mix 10 mβ of water and cool to 0°C. A solution of 0.7 g of sodium nitrite dissolved in 10 mA of water is added dropwise to this. After stirring for 30 minutes at 0°C, sodium sulfite 4
．． Pour 0 g into a solution of 20 ml of water. After heating this diazonium solution to 80 to 90°C, 10 ml of concentrated hydrochloric acid
drip. After stirring for 30 minutes, neutralize with sodium hydrogen carbonate. The precipitated solid was filtered and recrystallized with acetonitrile to obtain the target compound 4-chloro-5-hydrazino-3-(p-methoxyphenoxy)pyrazole 1.6
get g. It was over 198 degrees Celsius.

Elemental analysis, C1゜I! ,,N40□C4, C(χ
)11(χ) N(χ) C#(χ) Calculation Directly
47.16 4.35 22.00 13.
92 actual value 47.49 4.47 22.25 14
．． The 1.5FD-mass spectrum showed a parent peak at 254, supporting that this compound had the desired structure of ■-12.

Next, 1H-pyrazolo(3,2-C) derived from the 5-hydrazino-1H-pyrazole compound of the present invention
-3-Triazole compound is shown.

Case-4 [1-Synthesis of self-indicating compound n-2] (j)
3.5 g of 3-ethoxy-4-ethoxycarbonyl-5-hydrazinopyrazole and valmitic acid chloride 4.
Add 5 g to 120 ml of ethyl acetate and stir. To this, 1.7 g of triethylamine was added dropwise, and the mixture was stirred at room temperature for 1 hour and 30 minutes. The precipitated crystals are filtered and further washed with water to obtain white crystals. Recrystallize from acetonitrile to obtain 3-
5.8 g of 1-4-ethoxycarbonyl-5-(2-valmitoylhydrazino)pyrazole are obtained.

(ii) 3-ethoxy-4-ethoxycarbonyl-5-(2-valmitoylhydrazino)pyrazole5.
0g to toluene 150m 7! and add 1.7 g of phosphorus oxychloride. After heating under reflux for 1 hour, the solvent was distilled off under reduced pressure. 150 ml of ace-1-nitrile and 2.6 g of pyridine were added to the residue, and the mixture was further heated under reflux for 1 hour.

Pyridine hydrochloride is removed by hot filtration and cooled.

The precipitated crystals were further recrystallized from acetonitrile, and 6
3.6 g of -nitoxy7-ethoxycarbonyl-3-pentadecyl-1H-pyrazolo(3,2-C)-3-)riazole are obtained.

(iii) 3.5 g of 6-nitoxy-7-ethoxy-1-dicarbonyl-C)-S-triazole was added to 100 g of acetic acid.
ml, 25 mβ of sulfuric acid and 5 mj2 of water were added, and the mixture was heated under reflux for 1 hour. The reaction mixture is cooled to below 10°C and neutralized with a 6N aqueous solution of 1-lium hydroxide. Extract with ethyl acetate and remove the solvent under reduced pressure. 50 mj+ of water is added to the tar-like residue, and the precipitated crystals are separated by filtration. Further, by reconsolidation from acetonitrile, 6-nitoxy-3-pentadecyl-L H-pyrazolo[3,2-C]
2.4 g of -S-triazole are obtained.

(iv) 6-nitoxy-3-pentadecyl-L
H-pyrazolo(3,2-C)-S-triazole 2.3
g to 80mj2 of chloroform, and while stirring, N-
Add 0.85 g of chlorosuccinimide in portions.

After stirring at room temperature for 30 minutes, the solvent was distilled off under reduced pressure, ethyl acetate and water were added, and the ethyl acetate layer was separated. Further, the solvent was distilled off under reduced pressure, and the residue was recrystallized from acetonitrile to obtain 1.8 g of a white target compound. Confirmation of the structure of the target is N
It was conducted by MR, mass spectrum, and elemental analysis.

Elemental analysis, Cz+H*, NtOC A, C(χ)
II(χ) N(χ) Calculated value 63.53 9.40 14.11 Actual value 63.26 9.10 14.01 1
13-22 [The above-mentioned exemplified persons 1-1 and I-2, using the same method as the above synthesis example, exemplified compounds I-1 and I-2
, T-4 to I-10, and (1)-13 to I-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-1
H-pyrazole compounds can be provided which are useful as intermediates for I N-pyrazolo(3,2-C)-5-)lyazole photographic couplers.

Claims (1)

[Claims] 1. 5-hydrazino-1H represented by the following general formula [I]
-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 heterocyclic group, and X represents a hydrogen atom, a halogen atom,
Represents a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, and a carboxyl group. A represents protonic acid, and n represents 0 or a positive integer.