JPH072718B2 - N- (4-chloropyrazolyl) amido oxime compound and process for producing the same - Google Patents

Description

The present invention relates to a 1H-pyrazolo [1,5, b ] -1,2,4-triazole-based magenta coupler used in a silver halide color photographic light-sensitive material. Which is important as a synthetic intermediate of N- (4
-Chloropyrazolyl) amido oxime compound and a method for producing the same.

(Prior Art) 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. 171956
U.S. Pat. No. 4,540,654, and as a production method thereof, JP-A-60-197688 discloses a synthetic method of ring-closing reaction from aminopyrazole via an amidoxime (the following formula 1).

(In the formula, R ₁₁ and R ₁₂ represent a hydrogen atom or a substituent, and Y represents a leaving group.) In this method, introduction of the leaving group Y is proposed after formation of the pyrazolotriazole skeleton by a known method. However, subsequent studies by the present inventors have revealed that the introduction of a leaving group (Y) at the 4-position at the amide oxime stage significantly improves the synthetic yield in the ring closure reaction of the pyrazoloazole from the amide oxime. Was found. Therefore, when Y is a halogen atom, N- (4-halogenopyrazolyl) amidooxime becomes a key intermediate, and it is required to develop an effective synthetic method thereof.

By the way, Japanese Patent Application Laid-Open No. 61-145163 describes a method for producing an N-pyrazolylamide oxime compound. A specific description of the N- (4-chloropyrazolyl) amide oxime compound of the present invention and a method for producing the same. Is not disclosed.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to use 1H-pyrazolo [1,5, b ] -1 ,, used in a silver halide color photographic light-sensitive material.
An object of the present invention is to provide an N- (4-chloropyrazolyl) amide oxime compound which is important as a synthetic intermediate for a 2,4-triazole magenta coupler and a method for producing the same.

(Means for Solving Problems) The inventors of the present invention have conducted extensive studies to overcome such problems in the synthesis of conventional pyrazolotriazole compounds, and as a result, have derived aminopyrazole compounds into amidoxime compounds. Then, it was found that the desired N- (4-chloropyrazolyl) amide oxime compound can be obtained in good yield by subjecting it to a chlorination reaction, and based on this finding, the present invention was accomplished.

That is, the present invention is represented by the following general formula (In the formula, R ₁ is a hydrogen atom, an alkyl group (including a substituent), an aryl group (including a substituent), an alkoxy group (including a substituent), an aryloxy group ( R ₂ represents a hydrogen atom, an alkyl group (including a substituent), an aryl group (including a substituent) or a heterocyclic group. N- (4-chloropyrazolyl) amido oxime compound and general formula (In the formula, R ₁ and R ₂ have the same meanings as described above.) An N-pyrazolylamide oxime compound represented by the formula (I) is chlorinated, and N- (4- represented by the general formula (I) is characterized. The present invention provides a method for producing a chloropyrazolyl) amidooxime compound.

In the present invention, R ₁ and R _{2 in the} compounds represented by the general formulas (I) and (II) will be described in detail. R ₁ is a hydrogen atom,
Methyl group, ethyl group, isopropyl group, t-butyl group,
Alkyl group such as decyl group, benzyl group, methoxyethyl group, phenoxyethyl group, 3- (p-acetylamidophenyl) propyl group, phenyl group, p-methoxyphenyl group, o-methoxyphenyl group, m-benzenesulfonamide Aryl group such as phenyl group and naphthyl group, methoxy group, ethoxy group, methoxyethoxy group, phenoxyethoxy group, 2- (p-sulfonamidophenoxy) ethoxy group, 2-benzenesulfonamidoethoxy group, isopropoxy group, dodecyloxy And an aryloxy group such as a phenoxy group, a p-methoxyphenoxy group, an o-methoxyphenoxy group, a 2,4-methoxyphenoxy group and a 2,6-methoxyphenoxy group.

R ₂ is 5 such as the alkyl group, aryl group and 2-furyl group, 2-thienyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrimidyl group, 2-benzothiazolyl group described in R _1.
~ Represents a 7-membered heterocyclic group.

The N-pyrazolylamide oxime compound represented by the general formula (II) used in the method of the present invention is obtained by reacting an aminopyrazole with an orthoester or ketene acetal compound as described in JP-A-60-197688. It can be manufactured.

Next, typical specific examples of the N- (4-chloropyrazolyl) amide oxime compound which can be produced by the present invention are shown below, but the present invention is not limited thereto.

The physical properties of the above exemplified compounds are as follows.

 Compound No. Melting point 1 165 ° C (decomposition) 2 195 to 196 ° C 3 152 to 155 ° C 4 230 ° C (decomposition) 5 211 ° C (decomposition) 6 180 to 186 ° C 7 210 to 215 ° C 8 to 198 ° C (decomposition) 9 142-143 ° C 10 130-132 ° C 11-145 ° C (decomposition) 12-163 ° C (decomposition) 13-155 ° C (decomposition) 14 125-127 ° C 15-183 ° C (decomposition) 16-142 ° C (decomposition) 17 160 to 162 ° C. 18 to 135 ° C. (decomposition) 19 Oily substance 20 to 144 ° C. (decomposition) 21 Oily substance 22 Oily substance 23 Oily substance Next, an embodiment of the production method of the present invention will be described.

In the present invention, the chlorination of the N-pyrazolylamide oxime compound represented by the general formula (II) is carried out under neutral conditions (neutral in the sense that no acid is added, but since N-pyrazolylamide oxime itself is weakly basic, the reaction conditions The reaction proceeds even if it is neutral to basic), but it is preferable to carry out the reaction in the presence of an acid in terms of yield.

Chlorinating agents used include sulfuryl chloride, chlorine,
Examples thereof include N-chlorosuccinimide. The amount of the chlorinating agent used is 1.0 to 1.5 equivalents, preferably 1.0 to 1.2 equivalents.

When performed under neutral conditions (as defined above), the solvent used is an amide-based solvent such as dimethylformamide and dimethylacetamide, a polar-based solvent such as sulfolane, a halogen-based solvent such as dichloromethane and chloroform, and a nitrile-based solvent such as acetonitrile. Solvents, ester solvents such as ethyl acetate, aromatic hydrocarbon solvents such as toluenebenzene, and ether solvents such as tetrahydrofuran. N
When chlorosuccinimide is the chlorinating agent, an alcohol solvent such as methanol can be used. When chlorine is used, tert-butanol can be used.

When performing in the presence of acid, there are the following two methods.

The first method is a method of reacting in a carboxylic acid that can be a solvent such as acetic acid and propionic acid, and the second method is to dissolve N-pyrazolylamide oxime in a soluble solvent and then to add acetic acid, In this method, an organic acid such as methanesulfonic acid or an inorganic acid such as hydrohalic acid or sulfuric acid is added and then chlorinated. In this case, the optimum amount of the acid varies depending on the N-pyrazolylamide oxime, but in the case of an organic acid, it is 0.5 to 20 equivalents, preferably 1 to 5 equivalents. In the case of an inorganic acid, it is 0.1 to 10 equivalents, preferably 0.2.
~ 2 equivalents. Which method is used depends on the type of N-pyrazolylamide oxime, but the first method is generally preferred because it is simple. The solvent used when carrying out the second method is the same as the solvent used when carrying out under neutral conditions, and the higher the solubility, the more preferable.

The reaction temperature is -20 to 40 ° C, preferably 5 to 25 ° C.

The N-4-chloropyrazolyl) amido oxime compound thus obtained can be isolated by a conventional method, but it is generally N
Since the-(4-chloropyrazolyl) amido oxime compound has good crystallinity, it can often be isolated as crystals only by pouring the reaction solution into water, but when it does not crystallize, extraction operation is preferable.

(Effect of the Invention) According to the present invention, an N- (4-chloropyrazolyl) amide oxime compound represented by the general formula (I) can be simply and
It is possible to obtain a high yield, and particularly in the presence of an acid, a high yield can be obtained.

As a result, if this N- (4-chloropyrazolyl) amide oxime compound is used, chlorine atom elimination type pyrazolo [1,5-
b ] -1,2,4-Triazole magenta couplers are easy to synthesize and the synthetic yield is dramatically improved, so that it is highly useful as an industrial method.

(Example) Next, the present invention will be described in more detail based on examples. In the examples, N- (4-chloropyrazolyl) amido oxime compounds are indicated by the numbers of the exemplified compounds.

Example 1 N-pyrazolylamide oxime (A) 100g (0.31mol)
Was dissolved in 750 ml of acetic acid, cooled until acetic acid did not solidify, and stirred vigorously. 27 ml of sulfuryl chloride (0.
34 mol) was slowly added dropwise, and after the mixture was gradually warmed to room temperature, the mixture was stirred for about 1 hour, poured into 2 liters of ice water, neutralized with heavy soda water, and the precipitated crystals were separated by filtration, and 1 part of acetonitrile and water were added.
After washing with a mixed solvent of 1: 1 and drying, 108 g of pure N-
(4-chloropyrazolyl) amido oxime (5) was obtained. Yield 97% Melting point 211 ° C. (decomposition) Next, this N- (4-chloropyrazolyl) amide oxime (5) was reacted according to the following formula: 1H-pyrazolo [1,5- b ]
-1,2,4-triazole compound (C) was obtained.

First, 174 g (0.48 mol) of the compound (5) was dissolved in 160 ml of dimethylacetamide, 160 ml of acetonitrile was further added, and the mixture was stirred. In it p-toluenesulfonyl chloride 92
g (0.48 mol) and pyridine (39 ml, 0.38 mol) were added, and the mixture was stirred under water cooling. After about 1 hour 1.2 liters of methanol and 39 ml of pyridine
(0.38 mol) was added and the mixture was heated under reflux for about 2 hours. About 2 reactions
After concentrating to 00 ml, it was poured into 1.2 l of water and the precipitated crystals were collected by filtration. The crystals were heated in 240 ml of methanol, returned to room temperature and collected by filtration to obtain 175 g of compound (C) (yield 85%). mp213-126 ° C. At this time, almost no by-products were detected.

Example 2 100 g (0.31 mol) of N-pyrazolylamide oxime (A)
Was dissolved in 500 ml of dimethylformamide, 23 ml (0.32 mol) of methanesulfonic acid was added, and the mixture was cooled to about 5 ° C and stirred. Sulfuryl chloride (27 ml, 0.34 mol) was slowly added dropwise to it, and the mixture was stirred for about 1 hour while returning to room temperature and then poured into 2 liters of ice water and neutralized with heavy soda water. When washed with a 1: 1 mixed solvent and then dried
103 g of pure N- (4-chloropyrazolyl) amide oxime (5) was obtained. Yield 93% Example 3 100 g (0.31 mol) of N-pyrazolylamide oxime (A)
Was dissolved in 500 ml of dimethylformamide, cooled to about 5 ° C and stirred. 27 ml (0.34 mol) of sulfuryl chloride in it
Was slowly added dropwise. After the dropping, the remaining TLC
Since it was confirmed with, further sulfuryl chloride 5ml (0.06mol)
Was added dropwise, and then the mixture was stirred for about 1 hour while returning to room temperature, poured into ice water, neutralized with heavy soda water, and the precipitated crystals were separated by filtration.
It could be observed by TLC that the crystal contained several kinds of products in addition to the compound (5), so 200 ml of acetonitrile was added to the crystal, heated to about 80 ° C., returned to room temperature, and then separated. However, 61 g of pure compound (5) could be obtained. Yield 55% Example 4 N-pyrazolylamide oxime (B) 100g (0.24mol)
Was dissolved in 500 ml of methanol and cooled in an ice bath, and 20 ml (about 0.24 mol) of concentrated hydrochloric acid (about 12N) was added thereto. 35 g (0.26 mol) of N-chlorosuccinimide into it while stirring
Little by little, and after the addition was completed, the ice bath was removed and the mixture was stirred for about 30 minutes, then the reaction solution was poured into ice water, neutralized with heavy soda water, and the precipitated crystals were filtered off, and acetonitrile and water were mixed in a ratio of 1: 1. The crystals were washed with a mixed solvent and dried to obtain 103 g of pure N- (4-chloropyrazolyl) amide oxime (15). 95% yield
Melting point to 183 ° C. Example 5 100 g (0.24 mol) of N-pyrazolylamide oxime (B)
Was dissolved in 500 ml of methanol, cooled in an ice bath, and 35 g (0.26 mol) of N-chlorosuccinimide was added little by little thereto while stirring. 9g more until the material completely disappears by TLC
(0.07 mol) of N-chlorosuccinimide was added, then the reaction solution was poured into ice water, and the precipitated crystals were separated by filtration. Since this crystal contained a few by-products in addition to the target product (15), 200 ml of acetonitrile was added thereto, and the temperature was about 50 ° C.
After heating to room temperature, the mixture was returned to room temperature and then separated to obtain 64 g of pure (15). Yield 59%

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location // C07D 487/04 139 7019-4C G03C 7/38

Claims (2)

[Claims] 1. The following general formula (In the formula, R ₁ is a hydrogen atom, an alkyl group (including a substituent), an aryl group (including a substituent), an alkoxy group (including a substituent), an aryloxy group ( R ₂ represents a hydrogen atom, an alkyl group (including a substituent), an aryl group (including a substituent) or a heterocyclic group. N- (4-chloropyrazolyl) amido oxime compound. 2. General formula (In the formula, R ₁ is a hydrogen atom, an alkyl group (including a substituent), an aryl group (including a substituent), an alkoxy group (including a substituent), an aryloxy group ( R ₂ represents a hydrogen atom, an alkyl group (including a substituent), an aryl group (including a substituent) or a heterocyclic group. A general formula characterized by chlorinating an N-pyrazolylamide oxime compound (In the formula, R ₁ and R ₂ have the same meanings as described above.) A method for producing an N- (4-chloropyrazolyl) amido oxime compound represented by: