JPH0713061B2 - 3-aryloxy-5-aminopyrazole compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention is a 6-aryloxy-1H-pyrazolo [1,5- b ] -1,2,4-triazole derivative useful as a silver salt color photographic coupler. Alternatively, it relates to a 3-aryloxy-5-aminopyrazole compound which is important as a synthetic intermediate for a 6-aryloxy-1H-pyrazolo [5,1- c ] -1,2,4-triazole derivative.

(Prior Art and Problems) 1H-pyrazolo [1,5- b ] -1,2,4-triazoles are useful as magenta couplers which give excellent hue in silver halide photographic light-sensitive materials. JP Sho 59
-171956, U.S. Pat.No. 4,540,654, and the production method thereof is described in, for example, JP-A-60-197688 and 60-1976.
There are methods described in 19779 and 60-215687. Also,
Related to this magenta coupler is, for example, JP-A-61-145163 for a method for synthesizing an intermediate. Also
A similar description is also provided for 1H-pyrazolo [5,1- c ] -1,2,4-triazoles in US Pat. No. 3,725,067,
As a manufacturing method thereof, there is, for example, JP-A-61-249987.

However, 6-aryloxy-1H-pyrazolo [1,5- b ]
-1,2,4-triazole derivative and its intermediate, or 6
-Aryloxy-1H-pyrazolo [5,1- c ] -1,2,4-
There is no specific description in any of these regarding a method for producing a triazole derivative and an intermediate thereof.

However, 6-aryloxy-1H-pyrazolo- [1,5-
b ] -1,2,4-triazole, 6-aryloxy-1H
It is clear from these contents that -pyrazolo- [5,1- c ] -1,2,4-triazole can be synthesized by using 3-aryloxy-5-aminopyrazole as an intermediate. , The development of the effective synthetic method was desired.

On the other hand, Japanese Examined Patent Publication (Kokoku) No. 48-2541 discloses a method for synthesizing 3-phenoxy-5-aminopyrazole, but this method is limited to an unsubstituted phenoxy group, the reaction time is long, and the product has a high purity Since it is low, it is not necessarily a method suitable for actual production because it requires purification by column chromatography.

Therefore, the object of the present invention is to provide a 6-aryloxy-1H-pyrazolo [1,5- b ] -1,2,4-triazole type magenta coupler or 6-aryloxy-1H- which is useful in a silver halide color photographic light-sensitive material. Pyrazolo [5,1-
The present invention provides a 3-aryloxy-5-aminopyrazole compound having various substituents, which is important as a synthetic intermediate for a c ] -1,2,4-triazole type magenta coupler, and particularly a method for producing the same. That is.

(Means for Solving Problems) The present inventors have various substituents at the aryl group site.
As a result of intensive studies to develop a synthetic method of an aryloxy-5-aminopyrazole compound, a novel cyano ketene acetal, which is important as a synthetic intermediate for a magenta coupler, can be obtained by reacting a certain cyanoketene acetal with hydrazine. It was found that the aryloxy-5-aminopyrazole compound can be obtained in good yield, and the present invention has been completed based on this finding.

That is, the present invention provides the following general formula (I) (In the formula, R ¹ is an alkoxy group at the o-position, a hydroxy group,
A phenyl group substituted with an alkyl group or a dialkylamino group is shown, n is 0 or a positive number, and X is an organic or inorganic acid radical. The present invention provides a 3-aryloxy-5-aminopyrazole compound represented by

The 3-aryloxy-5-aminopyrazole compound of the present invention represented by the above general formula (I) has the following general formula (I
I) (R ¹⁰ ) ₂ C═CHCN (wherein R ¹ has the same meaning as described above) and is produced by reacting a hydrazine with a cyanoketene acetal.

In the present invention, the substituent on the o-position in the o-substituted phenyl group represented by R ¹ in the compounds represented by the general formulas (I) and (II) is a hydroxy group, an alkyl group, an alkoxy group or a dialkylamino group. And preferably an alkyl group, an alkoxy group or a dialkylamino group, and when there are two or more substituents, they may be the same or different. More specifically, the above general formulas (I) and (II)
In the compound represented by, the substituent on the o-position of the o-substituted phenyl group is a hydroxy group or an alkyl group (having 1 to 3 carbon atoms).
2, preferably 1 to 20 straight chain, branched chain alkyl group, aralkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, which are linked by oxygen atom, nitrogen atom, sulfur atom, carbonyl group It may be substituted with a substituent, an amino group, a nitro group or a halogen atom, and examples thereof include a methyl group, a propyl group, a t-butyl group, a tridecyl group, a 2-methanesulfonylethyl group and a 3- (3-
Pentadecylphenoxy) propyl group, 2-methyl-2
-Nitropropyl group, 2-ethoxytridecyl group, trifluoromethyl group, cyclopentyl group, 3- (2,4-di-t-amylphenoxy) propyl group, etc.), alkoxy group (having 1 to 32 carbon atoms, preferably 1-20 alkoxy groups,
For example, methoxy group, ethoxy group, t-butoxy group, 2
-Methoxyethoxy group, 2-dodecylethoxy group, 2-
Methanesulfonylethoxy group, cyclohexyloxy group, etc.), dialkylamino group (eg dimethylamino group,
Dibutylamino group, didodecylamino group, methylbutylamino group, etc.).

In the cyanoketene acetal compound represented by the general formula (II) used as a starting material in the method for producing a compound of the present invention, two R ^{1 s} may be the same or different from each other. No. 22328, β, β-dichloroacrylonitrile or chlorocyanoacetylene can be synthesized by reacting a metal salt of a substituted phenol or a substituted or unsubstituted naphthol.

Next, typical specific examples of the 3-aryloxy-5-aminopyrazole compound of the present invention are shown below, but the present invention is not limited thereto.

Of the following compound examples, the compounds of 4), 5), 6) and 10) are not included in the general formula (I), but are shown for reference.

Next, a method for producing the compound of the present invention will be described.

This method is carried out by mixing based on the above formula (1) so that the molar ratio of hydrazine to ketene acetal is 1-20. Although the reaction temperature varies depending on the raw materials used, it is usually preferably in the range of room temperature to about 120 ° C,
More preferably, it is about 100 ° C. The reaction time is preferably in the range of 30 minutes to 3 hours, more preferably about 1 hour. However, the conditions are not limited to these.
The 3-aryloxy-5-aminopyrazole obtained by this method can be isolated as a salt of an organic or inorganic acid. This can be accomplished by adding the acids to the reaction mixture in some solvent. As the solvent, ester solvents such as ethyl acetate, ether solvents such as diethyl ether and tetrahydrofuran, dioxane, benzene,
It is an aromatic hydrocarbon solvent such as toluene or xylene, and more preferably ethyl acetate.

The acids are widely organic and inorganic acids, more preferably hydrochloric acid. By this operation, the desired acid salt of 3-aryloxy-5-aminopyrazole can be obtained in good yield. Alternatively, when it is not isolated as the hydrochloride, it may be purified by a method such as recrystallization, distillation, or column chromatography, alone or in combination, or may be used as it is as a starting material for the next reaction.

(Effect of the invention) The 3-aryloxy-5-aminopyrazole compound represented by the general formula (I) of the present invention is a desired 6-aryloxy-1H-pyrazolo [1,5- b ] -1,2 It is useful as a synthetic intermediate for a 4,4-triazole derivative or a 6-aryloxy-1H-pyrazolo [5,1- c ] -1,2,4-triazole derivative (see Reference Example 5 described later). Therefore, according to the present invention, 1H-pyrazolo [1,5- b ] -1,2,4-triazole compound, or 1H-pyrazolo [5,1- c ]
The utility value of the -1,2,4-triazole compound as a magenta coupler can be increased.

(Example) Next, the present invention will be described in more detail based on examples. The compound numbers correspond to the numbers in the exemplified compounds.

Example 1 Synthesis of Exemplified Compound (1) To 90 g of 3,3-bis- (2-methoxyphenoxy) -acrylonitrile was added 90 ml of an 80% aqueous solution of hydrazine hydrate,
The mixture was heated and stirred at an internal temperature of 100 ° C for 1 hour. After cooling to room temperature, sodium chloride was added, the mixture was extracted with 540 ml of ethyl acetate, and the obtained ethyl acetate layer was washed 3 times with 180 ml of saturated saline. After drying over anhydrous sodium sulfate, 22 g of hydrochloric acid gas was blown into the mixture while keeping the internal temperature at 15 ° C. or lower under ice cooling, and the obtained crystals were suction-filtered to obtain 50 g of crystals of the desired exemplary compound (1) (yield 69g) Got it. Melting point
221.0 ° C NMR (DMSO d ₆ ): δ = 9.50 (brs, 4H), 6.8-7.9 (m, 4
H), 4.80 (s, 1H), 3.83 (s, 3H) Example 2 Synthesis of Exemplified Compound (2) 54 g of 3,3-bis- (2-methoxyphenoxy) acrylonitrile and 54 ml of 80% aqueous solution of hydrazine hydrate were added. In addition, the mixture was heated and stirred at an internal temperature of 100 ° C for 1 hour. After cooling to room temperature, sodium chloride was added and the mixture was extracted with 350 ml of ethyl acetate, and the obtained ethyl acetate layer was washed 3 times with 100 ml of saturated saline. The ethyl acetate layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the obtained residue was purified by column chromatography to obtain 23 g (yield 61%) of an oily target compound (2).

NMR (CDCl ₃ ): δ = 6.6−7.1 (m, 4H), 6.1 (brs, 3H),
4.73 (s, 1H), 3.66 (s, 3H) Example 3 Synthesis of Exemplified Compound (3) 23.5 g of 3,3-bis- (2,6-dimethoxyphenoxy) acrylonitrile in 24 ml of 80% hydrazine hydrate. The aqueous solution was added, and the mixture was heated with stirring at an internal temperature of 100 ° C. for 3 hours. After cooling to room temperature, 150 ml of ethyl acetate and sodium chloride were added thereto for extraction. The obtained ethyl acetate layer was washed 3 times with 50 ml of saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. 40 ml of acetonitrile was added to the resulting residue, followed by 10 ml of chloroform.
ml was added and stirred, and the obtained crystals were collected by filtration to obtain 8.9 g (yield 38%) of the target Exemplified compound (3). Melting point 122.0-12
_{4.0 ℃ NMR (CDCl 3):} δ = 6.5-7.1 (m, 3H), 5.9 (brs, 3H),
4.68 (s, 1H), 3.63 (s, 6H) Reference Example 1 Synthesis of Exemplified Compound (4) To 30 g of 3,3-bis- (4-methoxyphenoxy) acrylonitrile was added 30 ml of an 80% aqueous solution of hydrazine hydrate. ,
The mixture was heated and stirred at an internal temperature of 100 ° C for 30 minutes. After cooling to room temperature, sodium chloride was added thereto and the mixture was extracted with 200 ml of ethyl acetate. The obtained ethyl acetate layer was washed 3 times with 60 ml of saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to column chromatography to obtain 10.7 g (yield 52%) of the target Exemplified Compound (4) as an oil.

NMR (CDCl ₃ ): δ = 6.4−7.1 (m, 4H), 5.9 (brs, 3H),
4.70 (s, 1H), 3.53 (s, 3H) Reference Example 2 Synthesis of Exemplified Compound (5) To 8.0 g of 3,3-bis- (4-methylphenoxy) acrylonitrile was added 8 ml of an 80% aqueous solution of hydrazine hydrate. The mixture was heated and stirred at an internal temperature of 100 ° C for 30 minutes. After cooling to room temperature,
Salt was added, extraction was performed with 100 ml of ethyl acetate, and the obtained ethyl acetate layer was washed 3 times with 30 ml of saturated saline. The ethyl acetate layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to give a residue, which was subjected to column chromatography to obtain 4.4 g of the desired exemplary compound (5) as an oil (yield 78
%).

NMR (CDCl ₃ ): δ = 6.8-7.3 (m, 4H), 5.8 (brs, 3H),
4.81 (s, 1H), 2.23 (s, 3H) Reference Example 3 Synthesis of Exemplified Compound (6) To 61 g of 3,3-bis- (2-chlorophenoxy) acrylonitrile was added 60 ml of an 80% aqueous solution of hydrazine hydrate to give 100 ℃
The mixture was heated and stirred for 1 hour. After cooling to room temperature, sodium chloride was added, the mixture was extracted with 500 ml of ethyl acetate, and the obtained ethyl acetate layer was washed 3 times with 170 ml of saturated saline. After drying the ethyl acetate layer with anhydrous sodium sulfate, 15 g of hydrochloric acid gas was blown into the reaction mixture under ice cooling while keeping the internal temperature at 15 ° C or lower, and the obtained crystals were collected by filtration to obtain 42 g of the desired exemplified compound (6) Rate 86%). Melting point 151.4 ° C NMR (CMSO): δ = 9.65 (brs, 4H), 7.2-7.7 (m, 4H),
5.08 (s, 1H) Example 4 Synthesis of Exemplified Compound (7) To 59 g of 3,3-bis- (2-ethylphenoxy) acrylonitrile was added 60 ml of an 80% aqueous solution of hydrazine hydrate at an internal temperature of 100 ° C. The mixture was heated and stirred for 1 hour. After cooling to room temperature, sodium chloride was added, extraction was performed with 360 ml of ethyl acetate, and the obtained ethyl acetate layer was washed 3 times with 120 ml of saturated saline. After drying this ethyl acetate layer with anhydrous sodium sulfate, the internal temperature was kept under ice cooling.
While keeping the temperature below 15 ° C, 15 g of hydrochloric acid gas was blown in, and the obtained crystals were collected by filtration to obtain 36 g of the desired exemplified compound (7) (yield 75
%) Was obtained. Mp _{151.7 ℃ NMR (CDCl 3):} δ = 9.82 (brs, 4H), 7.1-7.5 (m, 4H),
4.91 (s, 1H), 2.62 (q, J = 7.5Hz, 2H), 1.17 (t, J = 7.5H
z, 3H) Example 5 Synthesis of Exemplified Compound (8) To 36 g of 3,3-bis- (2,4-dimethoxyphenoxy) acrylonitrile was added 36 ml of an 80% aqueous solution of hydrazine hydrate, and the mixture was heated with stirring at an internal temperature of 100 ° C. for 1 hour. did. After cooling to room temperature, sodium chloride was added and the mixture was extracted with 210 ml of ethyl acetate. The obtained ethyl acetate layer was washed 3 times with 70 ml of saturated saline and dried over anhydrous sodium sulfate. 7.1 g of hydrochloric acid gas was blown into the ethyl acetate layer while keeping the internal temperature under ice-cooling at 15 ° C. or lower, and the obtained crystals were collected by filtration to obtain 20 g (yield 75%) of the target compound (8). . Melting point 1
84.4 ° C NMR (CDCl ₃ ): δ = 7.17 (d, J = 9Hz1H), 6.73 (d, J = 3H)
z, 1H), 6.53 (dd, J = 3Hz, 9Hz, 1H), 6.6 (brs, 4H), 4.73
(S, 1H), 3.83 (s, 6H) Example 6 Synthesis of Exemplified Compound (9) To 32 g of 3,3-bis- (2-dimethylaminophenoxy) acrylonitrile was added 32 ml of an 80% aqueous solution of hydrazine hydrate. The mixture was heated and stirred at a temperature of 100 ° C. for 1 hour. After cooling to room temperature, sodium chloride was added and the mixture was extracted with 200 ml of ethyl acetate, and the obtained ethyl acetate layer was washed 3 times with 50 ml of saturated saline. The ethyl acetate layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residue was purified by column chromatography to obtain 12 g (yield 53%) of the target Exemplified Compound (9) crystals. Melting point 1
_{54.7 ℃ NMR (CDCl 3):} δ = 6.7-7.1 (m, 4H), 4.73 (s, 1H), 4.
5 (brs, 3H), 2.78 (s, 6H) Reference Example 4 Synthesis of Exemplified Compound (10) 3,3-Bis- (2-naphthoxy) -acrylonitrile 13.
13.5 ml of 80% aqueous solution of hydrazine hydrate was added to 5 g, and the internal temperature was adjusted to 10
The mixture was heated and stirred at 0 ° C for 1 hour. After cooling to room temperature, sodium chloride was added and the mixture was extracted with 90 ml of ethyl acetate, and the obtained ethyl acetate layer was washed 3 times with 30 ml of saturated saline. The residue obtained by drying over anhydrous sodium sulfate and concentrating under reduced pressure was purified by column chromatography to obtain 5.4 g (yield 60%) of the desired exemplary compound (10) as an oil.
%)Obtained.

_{NMR (CDCl 3): δ =} 7.0-8.0 (m, 7H), 6.4 (brs, 3H),
4.88 (s, 1H) Example 7 Synthesis of Exemplified Compound (11) 3,3- (o-Phenylenedioxy) -acrylonitrile 1
To 5.9 g, add 16 ml of an 80% aqueous solution of hydrazine hydrate and set the internal temperature to 10
The mixture was heated and stirred at 0 ° C for 1 hour. After cooling to room temperature, sodium chloride was added, the mixture was extracted with 100 ml of ethyl acetate, and the obtained ethyl acetate layer was washed 3 times with 30 ml of saturated saline. The residue obtained by drying over anhydrous sodium sulfate and concentrating under reduced pressure was purified by column chromatography to obtain 11.6 g of the desired exemplary compound (11) as an oil.
(Yield 61%) was obtained.

NMR (CDCl ₃ : MeOH (d-4) = 4: 1): δ = 6.1-7.1 (m,
4H), 5.7 (brs, 4H), 4.80 (s, 1H) Now, the 3-aryloxy-5 obtained by the present invention
-Aminopyrazole compounds as various synthetic intermediates
-Aryloxy-1H-pyrazolo [1,5- b ] -1,2,4-
Triazoles or 6-aryloxy-1H-pyrazolo [5,1- c ] -1,2,4-triazoles could be obtained. As an example, 6-aryloxy-1H-pyrazolo [1,5- b ] -1,2,4 using the following exemplified compound (1)
-Shows the synthesis of triazole compounds.

(Reference example 5) (Reference example 5) Synthesis of Compound (22) 32.4 g of Exemplified Compound (1) was added to 100 ml of methanol, and 18.6 ml of triethylamine was added dropwise while stirring at an internal temperature of 5 ° C or lower. Subsequently, 54 g of compound (21) was added, and the mixture was stirred at room temperature for 3 hours and 30 minutes. On the other hand, 14 g of hydroxylamine hydrochloride was dissolved in 140 ml of methanol, and 40 ml of a 28% methanol solution of sodium methoxide was added thereto to prepare a solution, which was added to the above reaction solution while filtering generated sodium chloride. Then, after stirring at room temperature for 4 hours and 30 minutes, 300 ml of water was added, and the obtained crystals were collected by filtration, washed with water and dried to obtain 48.2 g (yield 85%) of the target compound (22). Melting point 1
69.5 to 171.0 ° C NMR (DMSO-d ₆ ): δ = 11.60 (brs, 1H), 9.87 (brs, 1)
H), 8.03 (brs, 1H), 7.87 (s, 4H), 6.7-7.3 (m, 4H),
5.47 (brs, 1H), 3.80 (s, 3H), 3.21 (t, J = 6.0Hz, 2H),
2.69 (t, J = 6.0 Hz, 2H) Synthesis of Compound (23) To 60 ml of N, N-dimethylacetamide, 21.1 g of Compound (22) was added and dissolved. The internal temperature was adjusted to 10 ° C or lower, 9.5 g of p-toluenesulfonyl chloride was added thereto, and then pyridine 4.
0 ml was added dropwise. After stirring at room temperature for 1 hour, water was added to obtain an oily substance. After removing water by decantation, N,
10 ml of N-dimethylacetamide was added, followed by 200 ml of methanol and 4.0 ml of pyridine, and heated under reflux conditions to 1
Stir for hours. After distilling off methanol under reduced pressure, water was added to obtain an oily substance. Remove water by decantation,
Methanol was added and the mixture was stirred, and the obtained crystals were collected by filtration and dried to obtain 11.3 g (yield 56%) of the target compound (23). Mp _{192.0~193.0 ℃ NMR (DMSO-d 6} ): δ = 12,68 (brs, 1H), 7.87 (s, 4H),
6.8-7.2 (m, 4H), 5.24 (s, 1H), 3.96 (t, J = ~ 6Hz, 2
H), 3.77 (s, 3H), 3.07 (t, J = ~ 6Hz, 2H) Synthesis of compound (25) 8.0 g of compound (24) was added to 40 ml of 1,2-dichloroethane,
To this, 1.0 ml of sulfuryl chloride was added dropwise. After stirring for 10 minutes, 1,2-dichloroethane was distilled off under reduced pressure. On the other hand, 11.3 g of compound (23) was dissolved in 30 ml of DmF, and the compound prepared from the compound (24) and sulfuryl chloride was dissolved in 10 ml of DmF and added dropwise at room temperature over 10 minutes. After stirring for 30 minutes as it was, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The obtained ethyl acetate layer was washed with saturated brine and concentrated under reduced pressure to give an oil. 30 ml of acetonitrile was added here, and the obtained crystals were collected by filtration,
9.8 g (yield 91%) of the target compound (25) was obtained. Melting point 169.0
_{~169.5 ℃ NMR (CDCl 3):} δ = 10.93 (brs, 1H), 6.5-7.8 (m, 11
H), 3.8-4.1 (m, 4H), 3.70 (s, 3H), 3.03 (t, J = 6.0H
z, 2H), 0.7-1.9 (m, 15H), 0.60 (s, 9H) Synthesis of compound (27) 7.0g of compound (25) was added to 20 ml of isopropyl alcohol, and 0.75 ml of 80% hydrazine hydrate was added dropwise. Then, the mixture was stirred under heating and reflux conditions for 3 hours. After the solvent was distilled off under reduced pressure, 30 ml of N, N-dimethylacetamide was added, and 5.0 g of compound (26) was added dropwise at room temperature followed by 1.66 ml of triethylamine. After stirring as it is for 1 hour, water and ethyl acetate are added, the by-produced phthalhydrazide is filtered off, the filtrate is extracted, the obtained ethyl acetate layer is washed with saturated brine, dried over anhydrous sodium sulfate and concentrated. did.

3 ml of ethyl acetate was added to the residue to dissolve it, followed by n-
300 ml of hexane was added and stirred, and the obtained crystals were collected by filtration. 3 ml of ethyl acetate was added to the obtained crystals to dissolve them, and then 200 ml of n-hexane was added to carry out recrystallization to finally obtain 6.6 g of the target compound (27) (yield 69%). Melting point 10
0.0 to 101.0 ° C NMR (CDCl ₃ ): δ = 10.30 (brs, 1H), 6.5-7.9 (m, 10
H), 5.50 (t, J = 6.0Hz, 1H), 3.8-4.2 (m, 4H), 3.73
(S, 3H), 2,9-3.4 (m, 2H), 2.6-2.9 (m, 2H), 0.7-1.
9 (m, 38H), 0.70 (s, 9H), 0.60 (s, 9H)

Claims (1)

[Claims] 1. The following general formula (In the formula, R ¹ is an alkoxy group at the o-position, a hydroxy group,
A phenyl group substituted with an alkyl group or a dialkylamino group is shown, n is 0 or a positive number, and X is an organic or inorganic acid radical. ) A 3-aryloxy-5-aminopyrazole compound represented by: