JPH07113018B2 - Process for producing pyrazolones and pyrazolone derivative - Google Patents

Description

TECHNICAL FIELD The present invention relates to pyrazolones having a benzyl group having at least one sulfonic acid group at the 1-position and a method for producing the same.

[Conventional technology]

In the photographic industry, pyrazolones are important compounds as the mother nucleus of light absorbing dyes. In particular, oxonol dyes having pyrazolones having a sulfonic acid group as a mother nucleus have the property of being decolorized in a developer containing sulfite, and are useful for dyeing light-sensitive materials with little adverse effect on photographic emulsions. Has been used.

Dyes having a pyrazolone group having at least one benzyl group having at least one sulfonic acid group at the 1-position as a nucleus are superior to those dyes having a pyrazolone group having a sulfophenyl group at the 1-position as a nucleus as a decolorizing agent. ing.

A method for synthesizing 3-amino-1-benzylpyrazolones is described in JP-A-49-62463, and a method for synthesizing pyrazolones having a ureido group at the 3-position is described in JP-A-61-194075. There is no description on a method for synthesizing pyrazolones having a benzyl group having a sulfonic acid group at the 1-position.

Further, JP-A Nos. 50-145125 and 50-147712 describe an oxonol dye having a pyrazolone having a sulfoaralkyl group at the 1-position as a nucleus, but a method for synthesizing a pyrazolone nucleus itself. There is no description.

[Problems to be solved by the invention]

The first object of the present invention is to provide a pyrazolone having a benzyl group having at least one sulfonic acid group at the 1-position, which is a mother nucleus of a pyrazolone oxonol dye having excellent decolorizing property, and a process for producing the same. ..

[Means for solving problems]

The present invention is a method for producing a pyrazolone represented by the general formula [V] by reacting a hydrazine represented by the general formula [I] with a compound represented by the general formula [II].

[Wherein X represents -OR (where R represents an alkyl group), Y represents -COOR, -CONR'R" or an alkyl group (R has the same meaning as described above, R', R "Represents a hydrogen atom or an alkyl group (which may be substituted)." ]

[V] [Wherein Ar is as defined above and Z ₁ is
COOR, -CONR'R" or an alkyl group (where R,
R′ and R″ are as defined above.)] According to the present invention, there are also provided pyrazolones of the general formula [VI].

(VI)

[Wherein Ar is as defined above, Z ₂ is —COOR, —CONR′R″, an alkyl or carboxylic acid group (wherein R is an alkyl group, and R′ and R″ are respectively Represents a hydrogen atom or an alkyl (which may be substituted) group. The general formulas [I], [II], [V] and [VI] will be described in detail below.

The alkyl group represented by Y, R, R′, R″, Z ₁ and Z ₂ is an alkyl group having 1 to 8 carbon atoms (eg, methyl,
Ethyl, isopropyl, n-butyl, sec-butyl, n
-Hexyl, n-octyl) is preferable, and a substituent [for example, a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a cyano group,
A halogen atom (for example, fluorine, chlorine, bromine), an alkoxy group having 1 to 4 carbon atoms (for example, methoxy, ethoxy), an ester group (for example, methoxycarbonyl, ethoxycarbonyl), an amino group (for example, dimethyl, diethylamino), Sulfonyl group (for example, methanesulfonyl), carbamoyl group (for example, methylcarbamoyl,
Ethylcarbamoyl), a sulfamoyl group (eg methylsulfamoyl), an amide group (eg acetylamino, methanesulfonylamino)].

For the reaction of the hydrazines represented by the general formula [I] with the compounds represented by the general formula [II], water, an organic solvent [for example, alcohols (for example, methanol, ethanol, isopropanol, butanol), ethers (for example, tetra Fudofuran, dioxane), amides (eg dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N,N′-dimethylimidazolidinone, hexamethylphosphoric triamide), sulfoxides (eg dimethylsulfoxide), nitrites (eg acetonitrile) ), acids (eg acetic acid), tertiary bases (eg pyridine, picoline)] or a mixed solvent of water and an organic solvent (eg water-ethanol, water-methanol, water-acetic acid, water-isopropanol, water-acetonitrile). Is used.

As the basic condensing agent, an inorganic (eg, alkali metal hydroxide such as sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium methoxide, sodium ethoxide) or organic (eg, triethylamine, pyridine) base can be used. Inorganic (for example, hydrogen halide, sulfuric acid) or organic (for example, acetic acid, p-toluenesulfonic acid) acid can also be used as the acidic condensing agent.

The reaction temperature is between 5° C. and 200° C. (preferably between 15 and 150° C.), and the reaction time is determined by the “compatibility” with the reaction temperature, but about 15 minutes to 3 days can be a standard.
The reaction is carried out under normal pressure, but at higher pressures in closed vessels.

The molar ratio of the compound of the general formula [II] to the hydrazine of the general formula [I] can be 0.5 to 10 times, preferably 0.8 to 2 times.

When the pyrazolones of the general formula [V] are produced by reacting the hydrazines of the general formula [I] with the compounds of the general formula [II], not only the pyrazolones of the general formula [V] are directly obtained but The amidrazone may be separated as a product or generated in the reaction system, and then cyclized thermally or in the presence of a basic condensation catalyst.

The method for producing the pyrazolones represented by the general formula [VI] is the same as the production method for the pyrazolones represented by the general formula [V] described above, and Z ₂ is a carboxylic acid group in the general formula [VI]. When Z ₂ is —COOR (R has the same meaning as described above), pyrazolones can be produced by hydrolysis according to a conventional method under acidic or alkaline conditions, and Z ₂ is —CONR′R. When "(R', R" has the same meanings as described above), Z ₂ is -COOR (R has the same meanings as described above), the aminolysis of pyrazolones is carried out by a conventional method. Can be manufactured by

In the general formulas [I], [II], [V] and [VI], the sulfonic acid group is a free acid or a salt (for example, an alkali metal salt such as Na or K, an organic base salt such as triethylamine or pyridine, or an ammonium salt). ) May be formed.

Specific examples of the hydrazines represented by the general formula [I] are shown below.

The hydrazines represented by the general formula [I] can be obtained by reducing the hydrazone compound obtained by the reaction of the benzaldehyde derivative in charge with hydrazine.

Next, specific examples of the compound represented by the general formula [II] are shown below.

_{II-1 CH 3 COCH 2 COOC} 2 H 5 II-2 CH 3 COCH 2 COOCH 3 II-4 C 2 H 5 COCH 2 COOC 2 H 5 II-5 t-C 4 H 9 COCH 2 COOC 2 H 5 II- 6 C ₂ H ₅ OOCC(ONa)=CHCOOC ₂ H ₅ II-7 C ₂ H ₅ OOCCOCH ₂ COOC ₂ H _{5 The} compound represented by the general formula [III] is known from the literature or known from the literature. It can be manufactured by referring to the method. The following can be cited as the literature. British Patent Nos. 1,129,333, 1,129,334, Cope
"Journal of American Chemical Society" (J.Am.Chem.Soc.) 67 , 1047 (1945).

Specific examples of the pyrazolones represented by the general formula [V] are shown below.

Specific examples of the pyrazolones represented by the general formula [VI] include the specific examples of the pyrazolones represented by the general formula [V], and the following specific examples can be given.

[Examples] Next, synthetic examples of the compounds according to the present invention will be described in detail with reference to the following examples.

[Example 1 Synthesis of V-1] (Synthesis of I-2) A solution of 104 g of sodium 2-formylbenzenesulfonate dissolved in 500 ml of methanol was added to 30 g of hydrazine hydrate.
While cooling, the solution was added dropwise with stirring. The reaction temperature rose from 25°C to 35°C, and after the temperature stopped rising, the mixture was left at room temperature overnight. When 500 ml of isopropanol was added to the reaction mixture, white crystals were precipitated. The crystals were collected by filtration, washed with 100 ml of isopropanol and then dried to obtain 63 g of 2-sulfobenzaldehyde hydrazone sodium salt (yield 76%). Melting point above 300°C.

46 g of 2-sulfobenzaldehyde hydrazone sodium salt obtained above was dissolved in 120 ml of ethanol and 60 ml of water, and placed in an autoclave having an internal volume of 500 ml. Palladium-carbon catalyst (1 g) was added, and the mixture was reacted at 30° C. for 2 hours under hydrogen pressure of 40 kg/cm ² . After cooling to room temperature, the catalyst was filtered off and the solvent was removed under reduced pressure. When 200 ml of ethanol is added to the concentrated residue,
36 g of I-2 was obtained as white crystals. Melting point above 300°C.

(Synthesis of V-1) 33.6 g of I-2 obtained above was added to a mixed solution of 100 ml of acetic acid and 52.3 ml of triethylamine, and then ethyl acetoacetate (II
21.5 g of -1) was added, and the mixture was stirred at 18°C to 20°C for 15 hours.
The reaction mixture was concentrated under reduced pressure, 20 ml of concentrated hydrochloric acid (36%) was added, 500 ml of isopropanol was further added, and the mixture was left overnight at room temperature. The white crystals formed were collected by filtration and isopropanol
After washing with 50 ml and drying, 29.1 g of V-1 was obtained (yield 72%). Melting point 285-289°C.

Example 2 Synthesis of V-3 Hydrazine derivative I-2 obtained by the method described in Example 1
Was added to 150 ml of acetic acid, and then 36 g of oxalacetic acid sodium diethyl ester (II-6) was added, and the mixture was heated to 90° C. for 3 hours while stirring. After cooling to room temperature, 50 ml of ethanol-hydrochloric acid (hydrogen chloride gas was blown into ethanol to adjust to 36 wt%) was added, and the precipitated salt was removed by filtration. Add 500 ml of acetone to the filtrate and V-3
Was obtained (42.3 g, yield 78%). Melting point 257-262°C.

Example 3 Synthesis of V-4 (Synthesis of I-3) Instead of sodium 2-formylbenzenesulfonate used in the synthesis of I-2 in Example 1, 2-formyl-
The same operation was performed using 1,5-disulfonic acid disodium salt to obtain 2,4-disulfobenzaldehyde hydrazone disodium salt (melting point: 300° C. or higher). Furthermore, in Example 1, the 2-sulfobenzaldehyde hydrazone sodium salt was replaced with 2,4-disulfobenzaldehyde hydrazone disodium salt to carry out catalytic reduction (I-
3) was obtained (melting point: 300° C. or higher.) (Synthesis of V-4) I-3 (90 g) obtained above and 56 g of oxal acetic acid diethyl ester (II-7) were dissolved in 300 ml of methanol and heated under reflux for 1 hour. .. When methanol was concentrated to 150 ml and cooled (ice cooling for 2 hours), 99 g of V-4 (yield 80%) was obtained. Melting point above 300°C.

Example 5 Synthesis of VI-3 V-3 was added to a solution of 7.8 g of sodium hydroxide dissolved in 20 ml of water.
17.9 g was added and the mixture was heated with stirring at an internal temperature of 70° C. for 5 hours. After cooling to room temperature, 16 ml of concentrated hydrochloric acid (36%) was added, the mixture was concentrated under reduced pressure until white crystals began to appear from the reaction mixture, and cooled with ice water to precipitate white crystals. The crystals were collected by filtration, washed with acetone, and dried to give VI-3 (14.2 g, yield 87%). Melting point 223-226°C.

[Example 6 Synthesis of VI-4] VI-4 was obtained in a yield of 85% by the same procedure as in Example 5, except that V-4 was used instead of V-3. Melting point 300
℃ or more.

Example 7 Synthesis of VI-6 V-3 (70 g) was suspended in 70 ml of water, and n-butylamine 160 was added.
ml was added dropwise under water cooling. After heating under reflux for 10 hours, 150 ml of concentrated hydrochloric acid (36%) was added dropwise while cooling with ice. The generated crystals were collected by filtration and recrystallized from methanol to give VI-6.
62 g (yield 83%) was obtained. Melting point 281-284°C (decomposition).

Example 8 Synthesis of VI-7 In the same manner as in Example 7, except that 70% ethylamine aqueous solution was used instead of n-butylamine, VI-7 was changed to 40%.
Obtained in a yield of %. Melting point above 300°C.

[Example 9 Synthesis of VI-8] VI-8 was obtained in a yield of 64% by the same procedure as in Example 7 except that n-butylamine was used instead of n-butylamine. Melting point 291-292°C (decomposition).

[Synthesis of Example 10 VI-12] V-3 (14.5 g) and ethanolamine (15.3 g) were mixed, the pressure inside the reaction vessel was reduced (30 mmHg), and the reaction was carried out at an external temperature of 120°C for 2 hours. After cooling to room temperature, 30 ml of methanol was added to dissolve it, and 300 ml of isopropanol was further added to precipitate crystals. The crystals were collected by filtration, washed with isopropanol and then dried to obtain 13 g of VI-12 (yield 86.5%). Melting point 215-21
9 ℃ (decomposition).

Claims (2)

[Claims] 1. A hydrazine represented by the general formula [I]:
A method for producing a pyrazolone represented by the general formula [V], which comprises reacting with a compound represented by the general formula [II]. [I] ArCH ₂ NHNH ₂ (In the formula, Ar represents a phenyl group directly substituted with a sulfonic acid group.) [II] XCOCH ₂ COY [In the formula, X represents —OR (where R represents an alkyl group). )
And Y represents -COOR, -CONR'R" or an alkyl group (R has the same meaning as described above, and R'and R" each represent a hydrogen atom or an alkyl group (which may be substituted). ) Is represented. ] [V] [In the formula, Ar represents the same meaning as described above, Z ₁ represents -COOR,-
CONR'R" or an alkyl group (wherein R, R', R" have the same meanings as described above). ] 2. A general formula [VI]: [In the formula, Ar represents a phenyl group directly substituted with a sulfonic acid group, Z ₂ is —COOR, —CONR′R″, an alkyl or carboxylic acid group (wherein R is an alkyl group, R′ and R″ are Each represents a hydrogen atom or an alkyl (which may be substituted) group. ] The pyrazolone derivative represented by these.