JPS62158259A - 5-amino-1h-pyrazole compound - Google Patents

Abstract

NEW MATERIAL:The 5-amino-1H-pyrazole compound of formula I (Ar is aryl or 5-6-membered heteroaromatic group; R1 is H, alkyl, aryl or 5-6-membered heteroaromatic group; X is H, halogen, cyano, alkoxycarbonyl, aryloxycarbonyl or carboxyl). EXAMPLE:3-Anilino-5-amino-4-methoxycarbonylpyrazole. USE:An intermediate for photographic coupler having substituted amino group at 6-site. PREPARATION:A compound of formula I wherein X is Y can be produced by reacting a compound of formula II (Y is cyano or alkoxycarbonyl) with CS2 in an alcohol in the presence of Na, alkylating the product, reacting the resultant compound of formula III (Alk is alkyl) with the compound of formula Ar-N(R1)H to obtain a compound of formula 3 and cyclizing the compound together with NH2-NH2.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention relates to a novel 5-amino-1H-pyrazole compound. More specifically, it relates to 5-amino-1H-pyrazole compounds useful as intermediates for photographic couplers.

[Prior art]

1H-pyrazolo(3,2-C) -s triazole compounds are compounds useful as photographic couplers, especially magenta couplers, and are described in British Patent No. 1°252.41, for example.
No. 8, U.S. Patent No. 3,725.067, “Journal.
Of the Chemical Society” Ba-Kin 1 (J
internal of the chemical 5o
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 Di
sclosure Vol 124, No 1244
3 (1977). Their manufacturing method can be represented by the reaction scheme shown below.

Reaction Scheme A British Patent No. 1,252,418, US Patent No. 3,725,
067 No. 1 Journal of the Chemical Society 4' Parkin I
Chemical 5ociety”Parkin I
)204732052 (1977)) Reaction Scheme A Reaction Scheme B (Research Disclosure CRe5earchD
isclosure) Vol, 124, No 12
443 (1977)) As shown in reaction schemes A and B, the previously known LH-pyrazolo-(
5-hydrazino-1H-pyrazole-4-carboxylate (1
) or 3-mercapto-4-amino-4H-1,2
, 4-) lyazole derivatives (1) are used as key intermediates. However, the 6-position substituent, that is, R, of 1H-pyrazolo(3,2-C)-s-triazole obtained using these intermediates (1) and (2) is extremely limited due to constraints on starting materials. When R is a group other than an alkyl group, an alkyl group, or a heterocyclic group, LH-pyrazolo (3,2-C
) -s -) Reesol yields are very low or not obtained at all.

On the other hand, 1H-pyrazolo[1,5-b), which is an isomer of 1H-pyrazoO(3,2-C)-s-trisol,
, -1,2,4-) lyazole compounds are also similarly useful as magenta couplers for photography, as described in, for example, JP-A-59-171956.

The synthesis method is described in JP-A-59-171956 and JP-A-60-1-2911i2, and can be represented by the reaction scheme shown below.

Reaction scheme C C-■ (R represents alkyl, substituted alkyl, phenyl, substituted phenyl, R' represents an alkyl group.) C-■ N (R0R' represents an alkyl group, substituted alkyl group, phenyl group, substituted phenyl group, 1Iall represents a halogen atom.) (R, R', R', R'' have the same meaning as ■.)
As is clear from the schemes C-■ to ■, 1H-pyrazolo (1,5-b) obtained using these synthetic methods
-The substituent at the 6-position of the 1,2,4-triazole compound, that is, R, is limited, and in the above schemes C-■ to ■, R is limited to an alkyl group, a substituted alkyl group, and a substituted aryl group. .

1H-pyrazolo (3,2-C) -s -) lyazole compounds and 1H-pyrazolo (1,5-b) -1
, the light resistance and absorption wavelength of magenta dye produced by the reaction between a 2,4-triazole compound and a color developing agent,
The rate of dye formation and the like are strongly influenced by the substituent R at the 6-position. Therefore, it was necessary to variously change the substituent at the 6-position in order to obtain a magenta coupler having the optimum target performance.

Therefore, 1H-pyrazolo(3,2-C)-s triazole compounds having a substituted amino group as shown in the general formula CI) at the 6-position and 1H-pyrazolo[1°5-b)-
In order to obtain 1,2,4-) lyazole compounds, it was necessary to develop new synthetic intermediates.

[Purpose of the invention]

An object of the present invention is to provide novel 5-amino-1H-pyrazole compounds, and more specifically, 1H-pyrazolo(3,2-C)-s) lyazole compounds and 1H-pyrazolo(1, 5-b) = 1.2.4-1-
5-Amino-1H- useful as an intermediate for photographic couplers having a general amino group at the 6-position of lyazole compounds
An object of the present invention is to provide pyrazole compounds.

[Configuration of the present invention]

The novel 5-amino-I H-pyrazole compound according to the present invention is represented by the following general formula CI).

In the formula, Ar represents an aryl group, a heteroaromatic ring having 5 to 6 members, and R1 represents a hydrogen atom, an alkyl group, an aryl group, 5
represents a heteroaromatic ring having ~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.

[1,5-b) -1,2,4-) It is useful as a synthetic intermediate for lyazole photographic couplers.

The compounds of the present invention will be explained in more detail below.

Examples of the aryl group represented by Ar in RQ formula (1) 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- to 6-membered heteroaromatic ring represented by Ar include a chenyl group, a furyl group, a pyridyl group, and a pyrimidyl group. , hydroxyl group, cyano group, nitro group, etc.).

Examples of the alkyl group represented by R2 in general formula (1) include alkyl groups having 1 to 30 carbon atoms, such as a methyl group and an ethyl group.

Examples include propyl group, heptyl group, benzyl group, etc.
These alkyl groups include a FfA group (for example, an aryl group represented by Heloge R1, and examples of the heteroaromatic ring having 5 to 6 members include those mentioned as Ar in general formula [I]). .

In general formula (1), the halogen atom represented by X is a fluorine atom, a chlorine atom, or a bromine atom.

An example is an iodine atom. The alkoxycarbonyl group represented by X is a methoxycarbonyl group.

Examples of the group include a phenynoxycarbonyl group.

General formula (1) may form a salt with a protonic acid (
However, this is not an essential component of the present invention). Typical protonic acids include hydrochloric acid, hydrobromic acid, sulfuric acid, acetic acid, and methanesulfonic acid.

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

The following is a blank scheme D. Y represents a cyano group, an alkoxycarbonyl group, or an aryloxycarbonyl group, - represents an alkyl W at A1, and Ar and R' are the same as those described in general formula (1).

Scheme E In the above scheme, R' represents an alkyl group or an aryl group,
Hal represents a halogen atom, Ar, R, is -4 formula [I]
Represents the same thing as described in .

The compound described in this patent is Hemisch Berichte (C
952861
2870 (1962) and 2871 to 2880, a ring-closing reaction is carried out in a solvent together with hydrazine hittride to produce 5-amino-3-substituted amino-alkoxycarbonylpyrazole or 5-amino- It is possible to synthesize 3-substituted amino-4-oxyluponylpyrazoles or 5-amino-3-substituted amino-4-cyanopyrazoles.

Furthermore, 5-amino-3-substituted amino-4-alkoxycarbonylpyrazole and 5-amino-3-substituted amino-
4-Arylcarbonylpyrazole is easily hydrolyzed by heating with an inorganic acid such as dilute sulfuric acid or an inorganic base such as sodium base oxide to obtain a 4-carboxypyrazole derivative.

This 4-carboxypyrazole derivative easily undergoes a decarboxylation reaction when heated without a solvent or in a solvent.
-Amino-3-substituted amino-pyrazole derivative.

When this is reacted with a halogenating agent such as sulfuryl chloride or N-halogensuccinimide without a solvent or in a solvent, 5
-Amino-4-halogeno-pyrazole is obtained.

As shown in the following scheme, the 5-amino-1H-pyrazole compound thus obtained is a 1H pyrazolo[3,2-C)-s-)lyazole compound useful as a photographic coupler and a 1H -pyrazolo (1,5-b)
-1,2,4-) lyazole compounds.

Scheme F: A 5-amino-pyrazole compound is diazotized by a commonly used method, and then reduced using a reducing agent such as stannous chloride or sodium sulfite to form a 5-hydrazino-1H-pyrazole compound. After further acylation, if the ring is closed using a chlorinating agent such as phosphorus oxychloride or thionyl chloride and in the presence of a base,
1H-pyrazolo-(3,2-c)- having a nitrogen-mediated substituent at the 6-position, useful as a magenta coupler for photography
It is possible to synthesize s-triazole compounds.

Furthermore, by applying the method of Scheme C-■ and Scheme C-■, 1H-pyrazolo(1,5-b) 1.2.4-triazole-based photographic material having a substituent via nitrogen at the 6-position can be obtained. It can lead to an acenter coupler (R represents Ar2N-R3).

In scheme F, A r and R+ + X represent the same as those described in general formula (1).

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

Margin below.

: Bow [Example] Examples of the present invention will be described below. It should be noted that, as a matter of course, the present invention is not limited only to the following examples.

Examples will be explained by showing specific synthesis examples of examples of 5-amino-1H-pyrazole compounds included in the present invention.

Synthesis Example 1 [The above-mentioned exemplified compound (1)]
8erichte) 952861~2B70 (196
Using 2,2-bismethylmercapto-1-cyanoacrylic acid methyl ester obtained by the method described in 2),
Chemische Beri
2-anilino-2-methylmercapto-1-cyanoacrylic acid methyl ester was obtained by the method described in 952871-2880 (1962).

24.8 g of the above 2-anilino-2-methylmercapto-1-cyanoacrylic acid methyl ester was added to 6, Omj
The mixture was refluxed for 3 hours in 125mj+ alcohol with 2 hydrazine hydroxide. After half of the solvent was removed under reduced pressure, the mixture was cooled and the crystals were filtered. The crystals were recrystallized from methanol to obtain 19.5 g of crystals.

A pure product was obtained by repeated recrystallization. From the results of elemental analysis, NMR, and mass spectra, 3-anilino-5-amino-
It was confirmed that it was 4-methoxycarbonylpyrazole.

Elemental analysis C+ + H+ z N a O□: Calculated value % C: 56.88 H: 5.21 N
: 24.12 Actual value% C: 56.91 H:
5.25 N: 24.08 Mass vector: FD-MS M 232 (parent peak) Application example using Synthesis Example 1 1H-pyrazolo (3 , 2-c) The synthesis of -s-triazole compounds will be described.

8.5 g of the 3-anilino-5-amino-4-methoxycarbonylpyrazole obtained above, 160 ml of 6
Once heated and dissolved in N-hydrochloric acid, the mixture was cooled to 0 to -5°C, and an aqueous solution of sodium nitrite (3.1) was added dropwise to diazotize the mixture according to a conventional method. 17.0 g of the obtained diazonium salt solution
A solution of stannous chloride in hydrochloric acid was added dropwise under cooling. After stirring for 2 hours, the mixture was diluted with water, hydrogen sulfide gas was passed through to remove the tin salt as sulfide, and the solution was concentrated under reduced pressure. The obtained 3-anilino-5-hydrazino-4-methoxycarbonylpyrazole hydrochloride was dissolved in water and neutralized with an aqueous sodium carbonate solution. The crystals were filtered and dried under reduced pressure. 2.0 g of this hydrazinopyrazole compound was stirred in 10 ml of ethyl acetate, 1.1 g of triethylamine was added, and then 2.1 g of palmitoylochloride was added dropwise with ml of toluene and 1.0 mj of phosphorus oxychloride. Refluxed for an hour. After the reaction? After washing the 8 liquids with water and drying them, the solvent was removed under reduced pressure. Add to this 1.5 mA of pyridine and 30 mA of pyridine.
g of acetonitrile was added and the mixture was refluxed for 2.5 hours. The crystals precipitated by cooling were filtered and recrystallized from methanol to obtain 0.9 g of crystals.

A pure product was obtained by repeated recrystallization. From the results of NMR, mass vector, and elemental analysis, we can confirm that this is a compound represented by the following formula! Approved.

Elemental analysis As C'zdL+N5Oz: Calculated value %
C: 69.34 H: 8.84 N: 14
．． 98 Actual 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 with good light fastness and formalin resistance and high color development was obtained. Ta.

As described above, the 5-amino-1H-pyrazole compound of the present invention is obtained by using 23.2 g of 3-anilino-5-amino-4-tomexycarbonylpyrazole obtained in Synthesis Example 1 as an intermediate for a photographic coupler. The mixture was stirred and refluxed for 2 hours with 200 mff of 2N hydroxide aqueous solution. The homogeneous solution was cooled and made acidic by adding acetic acid. The crystals were filtered, washed with cold water, then alcohol, and dried.

The crystals were dissolved in DMF while cold and diluted with alcohol. From the results of the spectrum, it was determined that this was 3-anilino-5-amino 4-
It was confirmed that it was carboxypyrazole.

Elemental analysis C+ o HIo N 40 as z: Calculated value % C: 55.04 H: 4.62 N
: 25.6B actual value% C: 54.88 H:
4.90 N: 25.51 Mass spectrum: FD-MS M 218 (It peak) Synthesis example 3 (
Synthesis of Exemplified Compound (3)] 10.9 g of 3-anilino-5-amino 4-carboxypyrazole obtained in Synthesis Example 2 was mixed with 10Qmn of alcohol,
Water 1000n+j! Stir and reflux together. 7. Foaming begins.
9 g of crystals were obtained. Mackerel size ≠ = Kishu elemental analysis.

It was confirmed from mass vector and NMR results that it was 5-anilino-3-aminopyrazole.

Elemental analysis As C9HI ON 4: Calculated value % C:
62.04 H: 5.79 N: 32.1
6 Actual value% C: 62.39 H: 5.79
N: 32.45 Mass spectrum: FD-MS M” 174 (parent peak)
- Chemische Berichte
) 952861-2870 (1962) and using ethyl cyanacetate in place of methyl cyanacetate, 2.2 bismethylmercapto-1-cyano-acrylic acid ethyl ester was obtained.

Mix 10.8 g of this and 6.5 g of 0-chloroaniline together with 1.0 ml of triethylamine to give 120 to 13
The mixture was stirred and heated to 0° C. for 5 hours. After the reaction, 20 ml of methanol was added and allowed to stand, and the precipitated crystals were filtered.

2-0-chloroanilino-2-methylmercapto-1-cyanoacrylic acid ethyl ester obtained here 6.8
g with 1.4 ml of hydrazine hydratate.
ml of ethanol and stirred and refluxed for 3 hours.

After the reaction, the mixture was cooled and the crystals were filtered. Recrystallization from alcohol yielded 5.6 g of crystals. From the results of elemental analysis, mass vector, and NMR, 5-o-chloroanilino-3
-Amino-4-ethoxycarbonylpyrazole was confirmed. Elemental analysis C1□Hl 3 CI N
a As O2: Calculated value % C: 51.34 H:
4.67 N 719.96 Actual value% C: 51
．． 27 H: 4.71 N: 19.88 Mass spectrum: FD-MS M 174 (parent peak) Synthesis Example 5 [Synthesis of Exemplary Compound (6)] 5-anilino-3-amino obtained in Synthesis Example 3 above 1.7 g of pyrazole was dissolved in 15n+1 acetic acid, and a solution of 1.3 g of surifuryl chloride dissolved in 5 ml of acetic acid was added dropwise while cooling. After stirring for 2 hours, add 2.5 g of sodium acetate and 20 mJ of water and reduce pressure. W Shrunk. The residue was extracted with ethyl acetate, and the extract was washed with water and dried. Concentration under reduced pressure gave a greenish candy-like substance. From the mass vector and NMR results, 3=anilino-5-amino-4
- It was confirmed that it was chloropyrazole.

Mass spectrum: FD-MS M” 208 (!1 peak) Synthesis example 6
~18-[Exemplary compound (5), (Synthesis of 71-α odor)]
Using the same method as the above synthesis example, exemplified compounds 5.7 to
Synthesize 18.

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

Table 1 16 1! (7) [Effects of the Invention] As mentioned above, according to the present invention, the novel 5-amino-1H-
Pyrazole compounds can be provided which are useful as intermediates for 1H-pyrazolo(3,2-C)-s-triazole photographic couplers.

Claims (1)

[Claims] 1. 5-amino-1H- represented by the following general formula [I]
Pyrazole compound. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Ar represents an aryl group, a heteroaromatic ring having a 5- to 6-membered ring, and R_1 represents a hydrogen atom, an alkyl group, an aryl group,
Represents a heteroaromatic ring having a 5- to 6-membered ring, X is a hydrogen atom,
Represents a halogen atom, cyano group, alkoxycarbonyl group, aryloxycarbonyl group, and carboxyl group.