JPH04305572A - Carboxyl group-containing cyclic amine compound - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as a metallic ion masking agent and an intermediate for a bleaching agent for photosensitive material. CONSTITUTION:A compound shown by the formula (R1 and R2 are H, halogen or alkyl; L is alkylene; La, Lb, Lc and Ld are >=2C alkylene; M is H or cation; l, m and n are 0, 1 or 2 with the proviso that l+m+n is >=1). The compound, for example, is obtained by subjecting a malonic ester derivative (dimethyl malonate derivative or diethyl molonate derivative) and a chained polyamine to ring formation reaction. The reaction is carried out usually in a solvent such as methanol or ethanol.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention provides a novel cyclic oxidizing agent useful as a metal ion shielding agent, and particularly useful as an oxidizing agent used in the field of silver halide photographic light-sensitive materials, such as a bleaching agent for light-sensitive materials. Regarding amine compounds.

0002

[Prior art] Conventionally, as a cyclic amine compound

000
3]

[Chemical 2]

[0004] However, these metal chelate compounds of cyclic amine compounds have problems such as low stability over time and low redox properties, and require strong oxidizing power and high stability. It is difficult to use it as an oxidizing agent (for example, a bleaching agent used in the field of silver halide photographic light-sensitive materials).

[0005]

OBJECTS OF THE INVENTION The present invention provides novel oxidizing agents useful as metal ion shielding agents, particularly as intermediates for oxidizing agents used in the field of silver halide photographic light-sensitive materials, such as processing bleaching agents. The objective of this invention is to provide a cyclic amine compound.

[0006]

[Means for Solving the Problems] The above object has been achieved by a cyclic amine compound having a carboxyl group represented by the following general formula (I).

[0007]

[C3]

(wherein R1 and R2 are hydrogen atoms,
Represents a halogen atom or an alkyl group. L represents an alkylene group. La, Lb, Lc and Ld each represent an alkylene group having 2 or more carbon atoms. M represents a hydrogen atom or a cation. l, m and n each represent 0, 1 or 2. However, l+m+n is 1 or more. )

The cyclic amine compound of the present invention will be explained in detail below. The halogen atoms represented by R1 and R2 include fluorine atom, chlorine atom, bromine atom,
Examples include an iodine atom, and the halogen atom is preferably a fluorine atom.

The alkyl groups represented by R1 and R2 may be linear, branched or cyclic. Also,
R1 and R2 may have a substituent, and examples of the substituent include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, an acylamino group, a sulfonylamino group, and a ureido group. 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, Examples include an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamide group, a sulfonamide group, and a nitro group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group or an ethyl group. Most preferably R1 and R2 are hydrogen atoms.

The alkylene group represented by L may be linear, branched or cyclic, and may have a substituent. Examples of the substituent include those exemplified as substituents for R1 and R2. It will be done. Furthermore, the alkylene groups represented by L in general formula (I) may be the same or different. Examples of L include methylene, ethylene, trimethylene, and propylene. Particularly preferred as L is a methylene group.

The alkylene group having 2 or more carbon atoms as La, Lb, Lc and Ld may be linear, branched or cyclic, and may have a substituent.
Examples of substituents for 1 and R2 include those exemplified. Preferred as La, Lb, Lc and Ld are ethylene group or trimethylene group.

[0013] l, m, and n are preferably 0 or 1;
Particularly preferred is l+m+n=2. Examples of the cation represented by M include alkali metals (Li, Na, K, etc.), alkaline earth metals (Mg, Ca, etc.), ammonium (ammonium, triethylammonium, etc.), and the like.

Specific examples of the compounds of the present invention are shown below.
The present invention is not limited to these.

[0015]

[C4]

[0016]

[C5]

The amine compound of the present invention can be synthesized, for example, by the method shown below.

The dioxocyclic amine compound used as the raw material is
For example, Journal of the American Chemical Society, Vol. 110, p. 3679 (1
988) (Journal of American
Chemical Society, 110, 36
79 (1988)).

That is, it is synthesized by a cyclization reaction between a malonic acid ester derivative (dimethyl malonate derivative, diethyl malonate derivative, etc.) and a chain polyamine. This reaction is usually carried out in a solvent. The solvent is not limited as long as it does not participate in the reaction, but the reaction proceeds particularly advantageously when lower alcohols such as methanol and ethanol are used. The reaction is usually carried out at 0°C to 100°C, preferably at 20°C.
Perform at ~80°C. Among the dioxocyclic amine compounds, 1,4,8,11-tetraazacyclotetradecane-5,7-dione is commercially available, and one manufactured by Aldrich was used in the synthesis.

The compound of the present invention can be synthesized from the above dioxocyclic amine compound and a carboxylic acid derivative having a carbonyl group by hydrogenation reaction. The above reaction in the present invention is usually carried out in a solvent. The solvent is not limited as long as it does not participate in the reaction, but in particular water, alcohol (
The process is advantageous when lower alcohols such as methanol are used. As the catalyst used for the hydrogenation reaction, in addition to palladium, platinum, and cobalt supported on activated carbon, Raney nickel and the like can be used.

It can also be synthesized by alkylating the amino group of a dioxocyclic amine compound. The alkylation is preferably carried out in the presence of a base, and examples of the base include alkali or tertiary amines (triethylamine, etc.), and are usually equivalent to 10 times the alkylating agent, preferably equimolar to 4 times the alkylating agent. Use twice the mole. The reaction is usually carried out in a solvent, and the solvent is not limited as long as it does not participate in the reaction, but the reaction proceeds advantageously when water, alcohol (lower alcohol such as methanol), etc. are used.

[0022] The reaction is usually carried out at a temperature of 0°C to 100°C, preferably 10°C to 60°C.

[0023]

[Operation and Effects of the Invention] The cyclic amine compound represented by the above general formula (I) of the present invention can be used, for example, as a metal ion shielding agent in photographic processing solutions, chelate titrations, medical analytical reagents, medicines, etc. It is also useful as an oxidizing agent, particularly as an intermediate for metal chelate compounds useful as oxidizing agents used in the field of silver halide photographic light-sensitive materials, such as bleaching agents for light-sensitive materials.

[0024] Next, examples will be given to specifically explain the present invention.

[0025]

[Example] Synthesis of compound 1 1,4,8,11-tetraazacyclotetradecane-5,7-dione 2.00 g (8
．． 76 x 10-3 mol), glyoxylic acid-hydrate 2.00 g (2.17 x 10-2 mol) and 10%
1 g of Pd-C was suspended in 100 ml of methanol, and hydrogen pressure was applied. After reacting at room temperature for 8 hours, the catalyst was filtered off through Celite, the filtrate was concentrated, and recrystallized with methanol/ethanol to obtain 5/2 of the target compound 1.
1.30 g (3.34 x 10-3 mol) of hydrate was obtained. Yield 38%

[0026] Melting point: 130-132°C
(Decomposition) Elemental analysis value C14H24N4O6
5/2 H2O
HC
N calculated value (%): 7.51
43.18 14.39 Actual value (%): 7.35 43.46
14.54'HNMR (D2O)
δppm

Claims (1)

[Claims] 1. A cyclic amine compound having a carboxyl group represented by the following general formula (I). [Formula 1] (In the formula, R1 and R2 represent a hydrogen atom, a halogen atom, or an alkyl group. L represents an alkylene group. L
a, Lb, Lc and Ld each represent an alkylene group having 2 or more carbon atoms. M represents a hydrogen atom or a cation. l
, m and n each represent 0, 1 or 2. However, l
+m+n is 1 or more. )