JP3294303B2 - Aminopolycarboxylic acid derivative and chelating agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal ion shielding agent, particularly an intermediate of a metal ion shielding agent and an oxidizing agent (for example, a bleaching agent for a photosensitive material), a detergent composition, and a cleaning agent in the field of silver halide photographic light-sensitive materials. The present invention relates to novel aminopolycarboxylic acid derivatives and chelating agents which are useful as compositions, medical and cosmetic preparation compositions, and coating compositions for metal materials.

[0002]

2. Description of the Related Art Aminopolycarboxylic acids represented by ethylenediaminetetraacetic acid and the like are often used as chelating agents, but these have a large complex stability constant with metal ions, but are not suitable for disposal. Both the compound itself and the metal chelate compound are difficult to biodegrade, which is problematic, and there is a demand for providing a new chelating agent.

[0003]

The present invention relates to a metal ion shielding agent, particularly a metal ion shielding agent and an oxidizing agent in the field of silver halide photographic light-sensitive materials (for example, a bleaching agent for light-sensitive materials).
Intermediates, detergent compositions, cleaning compositions, medical,
An object of the present invention is to provide a novel aminopolycarboxylic acid derivative and a chelating agent which are useful as a cosmetic preparation composition and a coating material composition for a metal material and are easily biodegradable.

[0004]

The aminopolycarboxylic acid derivative and the chelating agent of the present invention have the following general formula (1):

[0005]

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(Wherein R ¹ and R ² represent a hydrogen atom, an alkyl group or an aryl group. L ₁ , L ₂ , L ₃ and L ₄
Each represents an alkylene group. W represents an alkylene group or an arylene group. n represents 0 or 1. M ₁ ,
M ₂ , M ₃ and M ₄ each represent a hydrogen atom or a cation. ).

In the formula, the alkyl group represented by R ¹ and R ² may be linear, branched or cyclic, and is preferably an alkyl group having 1 to 4 carbon atoms. Also, R ¹ and R
² may be linked to form a ring.

The aryl group represented by R ¹ and R ² is a monocyclic or bicyclic aryl group, for example, a phenyl group,
A naphthyl group is mentioned, and a phenyl group is more preferred.

The alkylene groups represented by L ₁ , L ₂ , L ₃ and L ₄ may be linear, branched or cyclic;
It is preferably an alkylene group having 1 to 5 carbon atoms, for example, a methylene group, an ethylene group, a trimethylene group, a propylene group and the like, and particularly preferably a methylene group. L ₁ , L ₂ , L
₃ and L ₄ may be the same or different from each other.

The alkylene group represented by W may be linear, branched or cyclic, and preferably has 1 to 6 carbon atoms.
Alkylene group, for example, a methylene group, an ethylene group, a propylene group, a cyclohexylene group and the like, and particularly preferably a methylene group. The arylene group represented by W is a phenylene group or a naphthylene group, and is preferably a phenylene group.

R ¹ , R ² , L ₁ , L ₂ , L ₃ , L ₄ and W may have a substituent. Examples of the substituent include an alkyl group, an aralkyl group, an alkenyl group and an alkynyl group. Group, alkoxy group, aryl group, amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen Atom, cyano group, sulfo group, carboxy group, phosphono group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, nitro group, hydroxamic acid group, heterocyclic group, etc. Can be When the substituent has a carbon atom, it preferably has 1 to 10 carbon atoms, and more preferably has 1 to 4 carbon atoms. n represents 0 or 1, and is preferably 0.

Cations represented by M ₁ , M ₂ , M ₃ and M ₄ include alkali metals (Li, Na, K, etc.), alkaline earth metals (Mg, Ca, etc.), ammonium (ammonium, triethylammonium) And the like. M ₁ , M ₂ , M ₃ and M ₄ may be the same or different from each other.

Specific examples of the compound represented by the general formula (1) of the present invention include the following compounds 1 to 11,
It is not limited to these.

[0014]

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[0015]

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The compound represented by the general formula (1) can be synthesized, for example, by reacting a hydrazine derivative with a diketone derivative as shown below.

[0017]

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Where R ¹ , R ² , L ₁ , L ₂ , L ₃ ,
L ₄ , W, n, M ₁ , M ₂ , M ₃ and M ₄ have the same meanings as those in formula (1). The hydrazine derivative as a raw material can be synthesized by reacting a carboxylic acid derivative or an α, β-unsaturated carboxylic acid derivative with a halogen-substituted hydrazine. In this case, a solvent may be used, and the solvent is not limited as long as it does not participate in the reaction, and examples thereof include water, alcohol (eg, methanol, ethanol, isopropanol, etc.), acetonitrile, dimethylformamide and the like.

The synthesis from a halogen-substituted carboxylic acid derivative is preferably carried out in the presence of a base. The base may be an alkali (such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate) or a tertiary base. Amines (such as triethylamine); This reaction is usually performed at 0 to 100 ° C., preferably 10 to 80 ° C.
° C.

The reaction between the hydrazine derivative and the diketone derivative is usually carried out at 0 to 100 ° C., preferably at 10 to 100 ° C.
0 ° C. In this reaction, a solvent may be used, and the solvent is not limited as long as it does not participate in the reaction. Examples of the solvent include water, alcohol (eg, methanol, ethanol, isopropanol, etc.), acetonitrile, dimethylformamide and the like.

[0021]

The compound of the present invention can be used as a metal ion shielding agent such as a photographic processing solution, a silver halide photographic light-sensitive material, a detergent composition, a cleaning composition, a medical composition,
It is suitable for use as a cosmetic preparation composition or a composition for a coating material of a metal material. Next, examples will be given to specifically describe the present invention.

[0022]

EXAMPLES The method for synthesizing Compound 1 is described below.

[0023]

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Synthesis of Compound 1a 506 g (3.89 mol) of hydrazine sulfate were dissolved in 1 liter of water, and 934 g of sodium chloroacetate was added at room temperature.
(8.02 mol) was added. A small amount of phenolphthalene was added, and 622 g (15.6 g) of sodium hydroxide was added with stirring.
Mol) was slowly added dropwise so that the solution remained pale red.

After completion of the dropwise addition, the mixture was further reacted at room temperature for 3 hours, and about 670 ml (7.81 mol) of concentrated hydrochloric acid was added.
After standing overnight, the precipitated crystals were collected by filtration, washed with 4 liters of water, and dried under reduced pressure to obtain 41a of white crystals.
5 g (2.80 mol) were obtained. Yield 72%.

Synthesis of Compound 1 29.6 g (0.20 mol) of Compound 1a synthesized above
And 14.5 g (0.10 mol) of a 40% aqueous glyoxal solution were suspended in 60 ml of water, reacted under a nitrogen atmosphere at room temperature for 6 hours, and then the solid was collected by filtration. After washing with water,
By drying under reduced pressure, 29.0 g of pale yellow crystal 1 was obtained.
(0.0911 mol). Yield 91%, melting point 176-
177 ° C (decomposition).

Elemental analysis value C ₁₀ H ₁₄ N ₄ O ₈ = 318.25 HCN calculated value (%) 4.43 37.74 17.60 measured value (%) 4.32 37.62 17.56 ¹ HNMR (D ₂ O + NaOD) δ ppm δ 3.91 (s 8H) δ 6.86 (s 2H) Stability constant Stability constant with Fe ³⁺ 8.8

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) CA (STN) REGISTRY (STN) CAOLD (STN)

Claims (2)

(57) [Claims] 1. An aminopolycarboxylic acid derivative represented by the following general formula (1). Embedded image (In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group or an aryl group. L ₁ , L ₂ , L ₃ and L ₄ each represent an alkylene group. W represents an alkylene group or an arylene group. n represents 0 or 1. M ₁ , M ₂ , M ₃ and M ₄ each represent a hydrogen atom or a cation. 2. An aminopolycarboxylic acid derivative chelating agent represented by the following general formula (1). Embedded image (In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group or an aryl group. L ₁ , L ₂ , L ₃ and L ₄ each represent an alkylene group. W represents an alkylene group or an arylene group. n represents 0 or 1. M ₁ , M ₂ , M ₃ and M ₄ each represent a hydrogen atom or a cation.