JP3086341B2 - Novel iron complex and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is useful as an oxidizing agent, particularly as an oxidizing agent used in the field of silver halide photographic light-sensitive materials, for example, as a bleaching agent used in the bleaching process of silver halide color photographic light-sensitive materials. It relates to a useful new iron complex.

[0002]

2. Description of the Related Art Conventionally, iron complexes have been used in medical and cosmetic preparations,
It is widely used for photographic, information recording materials (magnetic recording materials, laser recording materials, etc.), copying materials (heat-sensitive materials, pressure-sensitive materials, etc.), but especially oxidation used in the field of silver halide photographic photosensitive materials. It is widely used as a bleaching agent, for example, a bleaching agent used in the bleaching process of silver halide color photographic light-sensitive materials. An iron complex that has been frequently used as a bleaching agent is a ferric ethylenediaminetetraacetate complex salt, which is hardly biodegraded in the environment, and is expected to develop an iron complex that is easily biodegradable from the viewpoint of environmental conservation. Was rare. Further, as another problem, the organic acid ferric complex salt as in the present invention,
The organic acid and the ferric salt are dissolved in water to be present in an aqueous solution, but are difficult to obtain as a solid, and there are limitations on their use.

[0003]

SUMMARY OF THE INVENTION The present invention provides an iron complex which is easily biodegradable.

[0004]

The above object has been achieved by an iron complex represented by the following general formula (I). General formula (I)

[0005]

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(Wherein L ₁ and L ₂ each represent an alkylene group or an arylene group; R represents a substituent; u represents an integer of 0 to 4; and M represents a cation or an anion. M ₁ , M ₂ and M ₃ each represent a carboxylate group, a carboxy group or a salt thereof, X represents an aquo ion or an anion, a represents an integer of 0 to 6, b represents an integer of 0 to 3, c represents an integer of 1 to 4.)

Hereinafter, the iron complex of the present invention will be described in detail. In the general formula (I), examples of the substituent represented by R include an alkyl group (for example, a methyl group and an ethyl group), an aralkyl group (for example, a phenylmethyl group), an alkenyl group (for example, an allyl group), an alkynyl group, and an alkoxy group. (Eg, methoxy group, ethoxy group), aryl group (eg, phenyl group, p-methylphenyl group), amino group (eg, dimethylamino group), acylamino group (eg, acetylamino group), sulfonylamino group (eg, methanesulfonylamino group) ), Ureido group, urethane group,
Aryloxy group (eg phenyloxy group), sulfamoyl group (eg methylsulfamoyl group), carbamoyl group (eg carbamoyl group, methylcarbamoyl group), alkylthio group (methylthio group), arylthio group (eg phenylthio group), sulfonyl group (Eg, methanesulfonyl group), sulfinyl group (eg, methanesulfinyl group), hydroxy group, halogen atom (eg, chlorine atom, bromine atom, fluorine atom), cyano group, sulfo group, carboxy group, phosphono group, aryloxycarbonyl group ( Phenyloxycarbonyl group), acyl group (eg, acetyl group, benzoyl group), alkoxycarbonyl group (eg, methoxycarbonyl group), acyloxy group (eg, acetoxy group), carbonamido group, sulfonamido group, Toromoto, such as a hydroxamic acid, and the like.

When the substituent has a carbon atom, it preferably has 1 to 4 carbon atoms, and R represents an alkyl group, an alkoxy group, an acylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group. , A hydroxy group, a halogen atom, a sulfo group, a carboxy group, a phosphono group, an alkoxycarbonyl group, an acyloxy group, a carbonamide group, and a sulfonamide group are preferable, and an alkyl group, an alkoxy group, a sulfonylamino group, a sulfamoyl group, an alkylthio group, and a hydroxy group. Groups, halogen atoms, sulfo groups, carboxy groups, phosphono groups, carbonamide groups, and sulfonamide groups are more preferred.

When u is 2 or more, Rs may be the same or different, and Rs may be connected to each other to form a ring. Examples of the ring in which Rs are connected to each other include a benzene ring. The alkylene group represented by L ₁ and L ₂ may be linear or branched, and preferably has 1 carbon atom.
~ 6. The arylene group represented by L ₁ and L ₂ preferably has 6 to 10 carbon atoms, among which a phenylene group is preferred, and an O-phenylene group is particularly preferred. L ₁ and L ₂ may be different from each other and may have a substituent. Examples of the substituent include the substituents described for R. L ₁ and L ₂ are preferably a methylene group or an ethylene group.

The cation represented by M is an alkali
Metals (eg, Li⁺, Na⁺, K ⁺, Cs⁺), Al
Potassium earth metals (eg, Ca²⁺, Mg²⁺), Ammoniu
(E.g., ammonium, tetramethylammonium
System, tetraethylammonium, 1,2-diethylene
Monium), pyridinium, phosphonium (eg,
Tetrabutylphosphonium, tetraphenylphosphonium
)). An anion represented by M
As nitrate ion, sulfate ion, halogen ion
(Eg, chloride ion, bromine ion, iodine ion),
Rate ions (eg, tetraphenylborate)
No. When the complex ion is an anion, M is
When the complex ion is a cation, M is
Is an anion.

A represents an integer of 0 to 6, and when a is plural, plural Ms may be the same or different. M ₁ , M ₂ and M ₃ each independently represent a carboxylate group, a carboxy group or a salt thereof. That is,
In the iron complex of the present invention, M ₁ , M ₂ and M ₃ are CO 2
O ^- not only that all are dissociated as, CO
Dissociative hydrogen or a salt thereof such as OH may be present.

X represents an aquo ion or an anion. X
Is an anion having a coordinating force with respect to the Fe ³⁺ ion, such as a hydroxo ion, a halogen ion (eg, Cl ⁻ , Br ⁻ , I ⁻ ), a nitrate ion, and an alkoxy ion (eg, methoxy ion). , Aryloxy ion (for example, phenoxy ion), thiocyanate ion, isothiocyanate ion,
Acetylacetonates, anions of organic acids (for example,
Acetate ion, glyoxynate ion, salicylate ion, oxalate ion, malonate ion,
Succinate ion, tartrate ion, glycinate ion, maleate ion, O-phthalate ion,
Picolinate ion) and the like. X is preferably an aquo ion, a hydroxo ion, a chloro ion,
These are oxalate ion, maleate ion, salicinate ion and picolinate ion, and in the present invention, aquo ion is most preferable.

B represents an integer of 0 to 3. When b is plural, a plurality of Xs may be the same or different. b is preferably 1 to 3, and when b is 3, X is preferably an aquo ion. In the present invention, b is 2 when X is a monodentate ligand.
Is preferred, and when X is a bidentate ligand, 1 is preferred.
C represents an integer of 1 to 4, preferably 1 or 2, and particularly preferably 1. a, b and c are integers determined so that the iron complex represented by the general formula (I) becomes neutral. The iron complex of the present invention may, of course, form a hydrate. Specific examples of the iron complex represented by the general formula (I) are shown below in the form of hydrates, but the present invention is not limited to these.

[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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Next, a method for synthesizing the iron complex of the present invention will be described. The iron complex of the present invention can be synthesized by reacting a compound represented by the following general formula (II) with an iron salt.

[0023]

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(Where L ₁ , L ₂ , R, u, M, M ₁ ,
M ₂ , M ₃ , a, b and c have the same meanings as in the general formula (I). M _{1 ′} , M _{2 ′} and M _{3 ′} each represent a carboxy group or a salt thereof. ) The compound represented by the general formula (II) which is a ligand in the iron complex of the present invention is commercially available, for example, "Journal of Di
American Society "(Journal of the American
Chemical Society), 80, 800 (1958) and the like. That is, it can be obtained by reacting an anthranilic acid derivative with a halogen-substituted carboxylic acid derivative. Specific examples of the compound represented by the general formula (II) are shown below, but the present invention is not limited thereto.

[0025]

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[0026]

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[0027]

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[0028]

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The iron salt to be reacted with the compound represented by the general formula (II) includes, for example, ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate. Iron salts, ferric oxide and the like. The solvent used here is not limited as long as it does not participate in the reaction. Examples include water, alcohols (methanol, ethanol, isopropanol, butanol, pentanol, etc.), dioxane, dimethylformamide and the like. Preferred are water and alcohol-based solvents, with water being particularly preferred.

When X in the iron complex of the present invention is other than an aquo ion, an acid or salt corresponding to X may be used when reacting the compound represented by the above general formula (II) with an iron salt. . Such acids or salts include, for example, hydrochloric acid,
Nitric acid, alcohol (eg, methanol, phenol), thiocyanic acid, isothiocyanic acid, acetylacetone, organic acid (eg, acetic acid, glyoxyic acid, salicylic acid, oxalic acid, malonic acid, succinic acid, tartaric acid, glycine, maleic acid, O-phthalic acid) , Picolinic acid). When b is 1 and X is a divalent anion, these acids or salts are 1.0 to 3.0 moles, preferably 1 mole, to the compound represented by the general formula (II). 0.0 to 2.0
Times mole, particularly preferably 1.0 to 1.5 times mole,
When b is 2 and one of X is an aquo ion and the other is a monovalent anion, the compound represented by the general formula (II) has a molar amount of 1.0 to 4.0 times, Preferably 1.0 to 2.5 times mol, particularly preferably 1.0 to 1.5 times.
When b is 2 and X is a monovalent anion, it is used in a molar amount of 1.0 to 4.0 times, preferably 1 to 1 times the amount of the compound represented by the general formula (II). 0.5-3.5
It is used in a molar amount of 2.0 times, particularly preferably 2.0 to 3.0 times.

In the case where X is an anion in the compound represented by the general formula (I), a compound in which X is an acoion is isolated, and then an anion is coordinated by a ligand exchange reaction. Can also be synthesized.

In the reaction of the present invention, in order to dissolve the compound represented by the general formula (II), which is a ligand, and the obtained iron complex, it is possible to add a base and adjust the pH to 3 to 12. The pH is preferably adjusted to 4 to 8, and more preferably to 4 to 6. Examples of the base used herein include amines (eg, aqueous ammonia, trimethylamine, triethylamine, ethylenediamine, pyridine), hydroxides (eg, LiOH, N
aOH, KOH) and the like. The reaction can be carried out usually at a temperature of 0 to 100 ° C, preferably 10 to 8 ° C.
0 ° C.

Although the isolation of the iron complex of the present invention can be carried out by a usual method, the adjustment of pH is particularly important. p
If H is too low, a stable iron complex cannot be formed, and if H is too high, iron hydroxide will be generated, making it difficult to isolate the desired iron complex. From such a viewpoint, in the synthesis of the iron complex of the present invention, it is possible to carry out the reaction at pH 0.5 to 10, but preferably at pH 1 to 5,
1.5 to 4.0 is more preferable. For pH adjustment at this time, an acid (for example, nitric acid, sulfuric acid, hydrochloric acid) or a base (for example, amines (for example, aqueous ammonia, trimethylamine, triethylamine, ethylenediamine, pyridine), a hydroxide (for example, LiOH, NaOH, KO
H)) may be used.

As described above, when the complex ion is an anion, M is a cation, and when the complex ion is a cation, M is an anion. When M is a cation, the cation of the base used for pH adjustment (for example, when an amine is used, its conjugate acid; when a hydroxide is used, its metal ion (for example, Na ⁺ , K ^{+) +} )) May be used, or after the reaction, another cation may be newly added for cation exchange. When M is an anion,
An anion of the acid used for pH adjustment (for example, nitrate ion when nitric acid is used, sulfate ion when sulfuric acid is used, and hydrochloric acid ion when hydrochloric acid is used) may be used. Thereafter, another anion may be newly added to perform anion exchange. Further, as the above-mentioned ion exchange method, an acid or salt can be added during the reaction as described above to synthesize a desired complex. A compound in which an anion is coordinated by a child exchange reaction can also be synthesized.

Next, the synthesis of the iron complex of the present invention will be described with reference to typical synthesis examples. Synthesis Example 1 Synthesis of Compound K-1 1- (1) Synthesis of Compound (1) 20.0 g (0.146 mol) of anthranilic acid, 20 ml of water
Into a three-necked flask, stirring well in an ice bath,
29.2 ml of 5N aqueous sodium hydroxide solution (0.146mo
l) was added. After dissolution of the anthranilic acid, the temperature was returned to room temperature, and 52.3 g (0.449 mol) of chloroacetic acid and 2.1 g (0.0146 mol) of sodium iodide were added. 60 in oil bath
The mixture was heated and stirred at ℃, and 85 ml of 5N aqueous sodium hydroxide solution was added dropwise. (However, the aqueous sodium hydroxide solution was added dropwise so that the reaction solution maintained pH 7 to 9.) After heating and stirring for 20 hours, the temperature was returned to room temperature, and 45.6 g of concentrated hydrochloric acid (0.450 g) was added.
mol) was added. The precipitated crystals were separated by filtration and washed with water.
The crystals were transferred to a beaker, 300 ml of water was added, and the pH was adjusted to 1.6 to 1.7 with concentrated hydrochloric acid. After stirring for 1 hour, the solid was collected by filtration and washed well with water. By recrystallizing from water,
32.5 g of 1/3 hydrate of compound (1) as a white solid
(0.125 mol). 86% yield

[0036] As the melting point 214 to 216 ° C. (decomposition) Elemental analysis _{C 11 H 11 N 1 O 6} · 1/3 H 2 O

1- (2) Synthesis of compound K-1 46.4 g (0.17) of compound (1) synthesized in 1- (1)
9 mol) was suspended in 46 ml of water, and 29% aqueous ammonia 1 was added.
0.5 g (0.179 mol) was added and dissolved. The pH at this time was 4.6. To this was added 72 ml of an aqueous solution in which 72.3 g (0.179 mol) of iron (III) nitrate 9 hydrate was dissolved, and then a 1N aqueous HNO ₃ solution was added to adjust the pH to 2.9. The precipitated crystals were collected by filtration, washed with water and acetone, and dried to give Compound K- as a yellow solid.
65.8 g (0.166 mol) of 1 were obtained. 93% yield

Melting point ≧ 130 ° C. (decomposition) IR spectrum (KBr) ν _{c = 0} 1610 cm ⁻¹ Elemental analysis value C ₁₁ H ₈ N ₁ O ₆ .Fe.5H ₂ O (molecular weight 396.11)

Synthesis Example 2 Synthesis of Compound K-4 2- (1) Synthesis of Compound (4) 72.4 g (0.400 mol) of 2-aminoterephthalic acid,
200 ml of water was placed in a three-necked flask, and an aqueous solution in which 32.0 g (0.800 mol) of sodium hydroxide was dissolved in 50 ml of water was added while stirring at room temperature. The mixture was heated and stirred at 90 ° C. in an oil bath, and an aqueous solution of 64.0 (1.60 mol) of sodium hydroxide dissolved in 100 ml of water and sodium chloroacetate 1
200 ml of an 85 g (1.60 mol) aqueous solution was added dropwise. (During this period, the reaction solution was added dropwise so as to keep the pH at 8 to 10.) After heating and stirring for 4 hours, the temperature was returned to room temperature, and concentrated hydrochloric acid was added to pH 1.5.
Was adjusted. The precipitated solid was collected by filtration and recrystallized from water / methanol to obtain 80.2 g (0.262 mol) of a compound (4) 1/2 hydrate as a pale yellow solid. 66% yield

Melting point> 208 ° C. (gradual decomposition) Elemental analysis value C ₁₂ H ₁₁ N ₁ O ₈ · 1 / 2H ₂ O

2- (2) Synthesis of Compound K-4 30.6 g (0.10 g) of compound (4) synthesized in 2- (1)
0 mol) was converted to 27.0 g (0.10 g) of iron (III) chloride hexahydrate.
mol) was dissolved in 50 ml of water, and the pH was adjusted to 5 by adding 29% aqueous ammonia. After filtering the solution, 1N HC
1 was added and the pH was adjusted to 4. Leave at room temperature for 2 hours,
Upon concentration, a yellow solid precipitated. The crystals were collected by filtration, recrystallized from water / methanol, and dried to obtain 14.1 g (0.0%) of compound K-4 as a yellow solid.
32 mol). 32% yield

Melting point ≧ 145 ° C. (decomposition) IR spectrum (KBr) ν _{c = 0} 1615 cm ⁻¹ Elemental analysis value C ₁₂ H ₁₁ N ₂ O ₈ .Fe.4H ₂ O (molecular weight 439.14)

Synthesis Example 3 Synthesis of Compound K-6 3- (1) Synthesis of Compound (6) 74.9 g of 3-amino-2-naphthoic acid (0.400 mol)
l) and water (300 ml) were placed in a three-necked flask, and 32.0 g of sodium hydroxide (0.800 mol) was stirred at room temperature.
An aqueous solution of l) dissolved in 50 ml of water was added. 90 ° C in oil bath
With stirring and sodium hydroxide 64.0 (1.60 mol
l) in 100 ml of water and 200 ml of an aqueous solution of 185 g (1.60 mol) of sodium chloroacetate were added dropwise.
(During this period, the reaction solution was added dropwise so as to maintain the pH at 8 to 10.) After heating and stirring for 6 hours, the mixture was returned to room temperature and adjusted to pH 1.5 with concentrated hydrochloric acid. The precipitated solid was collected by filtration and recrystallized from water / methanol to obtain 96.0 g (0.317 mol) of compound (6) as a pale yellow solid. Yield 7
9%

Melting point: 214 to 215 ° C. (decomposition) Elemental analysis: C ₁₅ H ₁₃ N ₁ O ₆

3- (2) Synthesis of compound K-6 30.3 g (0.10 g) of compound (6) synthesized in 3- (1)
0 mol) was converted to 27.0 g (0.10 g) of iron (III) chloride hexahydrate.
mol) was dissolved in 50 ml of water, and the pH was adjusted to 5 by adding 29% aqueous ammonia. After filtering the solution, 1N HC
1 was added and the pH was adjusted to 2. After leaving for 2 days at room temperature, the precipitated crystals were collected by filtration and recrystallized from water / methanol.
By drying, compound K-6 was obtained as a yellow solid in 3 parts.
3.0 g (0.074 mol) were obtained. 74% yield

Melting point ≧ 162 ° C. (decomposition) IR spectrum (KBr) ν _{c = 0} 1608 cm ⁻¹ Elemental analysis value C ₁₅ H ₁₀ N ₁ O ₆ .Fe.5H ₂ O (molecular weight 446.18)

Synthesis Example 3 Synthesis of Compound K-24 3.96 g of Compound (K-1) synthesized in Synthesis Example 1 (1.
00 × 10 ^-2 mol), 1.14 g of malonic acid (1.10 × 1 mol)
0 ^-2 mol) was suspended in 10 ml of water, adjusted to pH 5.0 with 0.1 N NaOH, and dissolved. After heating and stirring at 60 ° C. for 1 hour, the mixture was concentrated and purified by gel filtration chromatography using Sephadex G-25 (manufactured by Aldrich, eluent H ₂ O). The obtained yellow eluate was concentrated and then recrystallized from a small amount of water and acetone to obtain 1.57 g (3.20 × 10 ⁻³ mol) of compound K-24 as a yellow solid. 32% yield

IR spectrum (KBr) ν _{c = 0} 161
2 cm ^-1, 1630 cm ^-1 elemental analysis _{C 14 H 10 NO 10 · Na} 2 · Fe · 2H 2 O
(Molecular weight 490.10) Other compounds can be synthesized in the same manner.

(Biodegradability test) When a biodegradability test was carried out based on the modified SCAS method specified in the OECD guidelines, ferric ammonium ethylenediaminetetraacetate did not decompose. Iron complex K-
1, K-2, K-3, K-7, K-20, K-22, K
-24 decomposed, and it was found to be excellent in biodegradability.

(Measurement of Redox Potential) The redox potential of the iron complex of the present invention was measured by a conventional method. The results are shown in Table 1 below.

[0051]

[Table 1]

* Supporting electrolyte [KNO ₃ ] = 1.0 M 0.4 M CH ₃ COOH / CH ₃ COONH ₄ Buffer Reference electrode; SSCE working electrode; Glassy carbon reference electrode; Platinum electrode

[0053]

Industrial Applicability The iron complex of the present invention is suitable for use in medical and cosmetic preparations, photographs, information recording materials, copying materials, etc., and contributes to environmental conservation from the viewpoint of biodegradability. .

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C07F 15/02 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. An iron complex represented by the following general formula (I). General formula (I) (Wherein L ₁ and L ₂ each represent an alkylene group or an arylene group. R represents an alkyl group, an aralkyl group,
Alkenyl group, alkynyl group, alkoxy group, aryl
Group, amino group, acylamino group, sulfonylamino group,
Ureido group, urethane group, aryloxy group, sulfa
Moyl group, carbamoyl group, alkylthio group, aryl
Thio 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, carbo
Amide group, sulfonamide group, nitro group or hydroxy
Represents a succinic acid group . u represents an integer of 0 to 4. M represents a cation or an anion. M ₁ , M ₂ and M ₃ each represent a carboxylate ion, a carboxy group or a salt thereof. X represents an aquo ion or an anion. a
Represents an integer of 0 to 6, b represents an integer of 1 to 3,
c represents an integer of 1 to 4. ) 2. The method for producing an iron complex represented by the general formula (I) according to claim 1, wherein a compound represented by the following general formula (II) is reacted with an iron salt. pH1
5. A method for producing an iron complex, comprising isolating the iron complex in the range of 5. General formula (II) (In the formula, L ₁ , L ₂ , R and u have the same meanings as in the general formula (I). M _{1 ′} , M _{2 ′} and M _{3 ′} represent a carboxy group or a salt thereof.) 3. The iron complex according to claim 1, wherein at least one of X is an anion.