JPS5863777A - Metal ion complexation method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention is intended to reduce the complexing property of metal ions.

It pertains to a method for lead metal ion tubes using specific hydrazone compounds and/or azo compounds.

It is widely known that heteroatoms such as #/ice atoms and Kuboki atoms coordinate with metal ions.For example, cyclic polyethers called crown ethers and polyethers such as polyethylene glycol It is well known that metal salts coordinate with metal ions, and active research is being conducted on the extraction and separation of metal ions and their use as catalysts for reactions involving metal salts, making use of this property.

The present inventors have discovered that when a specific hydrazone compound and /f or azo compound is brought into contact with a metal salt in an organic solvent in the presence of a base, metal ions are easily complexed.
It was discovered that the state of color development and precipitation differs depending on the metal ion, which is advantageous for the analysis of metal ions, and the present invention was completed.That is, the gist of the present invention is to prepare a metal salt in an organic solvent. In the presence of a base, the general formula (1) (wherein Kl represents a lower alkyl group or an alkoxyalkyl group, R1 represents a halogen atom, a lower alkyl group,
Indicates a nitro group or an alkoxy group.

Ra is a hydrogen atom, a halogen glue, or a lower alkyl group.

11, n represents an integer of O-a), and/or a hydrazone compound represented by the general formula (Otori) W'' (wherein R1, R1, R1 and n are the above-mentioned and Okayoshi) A method for complexing metal ions to form an f% image consists in complexing the metal ions of the metal salt by bringing them into contact with an azo compound.

To explain the present invention as follows, in the present invention, the hydrazone compound and the azo compound which are converted into metal ions are represented by the above-mentioned general formula (summer) and the above-mentioned general formula (1), respectively. In these formulas, R' represents a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, or an alkoxyalkyl group such as a methoxyethyl group or an ethoxyethyl group; Atomic halogen atoms; methyl group, ethyl group.

Lower alkyl group of butyl group; nitro group, methoxy group, or ethoxy group alkoxy group 1-. R1 hydrogen atom; fluorine atom, chlorine atom, JI atom halogen atom; methyl group, ethyl group, butyl 1 fathom lower alkyl group; nitro group; methoxy group, ethoxy 1 group alkoxy group, or α-olefin System Compatible Material 1 For example, ethylene.

Polymers such as pyrene, vinyl polymers, such as vinyl chloride, vinyl acetate, methyl vinyl ether, styrene, etc., acrylic polymers, such as acrylic 11
．． Methacrylic acid, acrylic acid ester, a combination of methacrylic acid esters, celluloses, such as cellulose ester, cellulose ether, etc.
Phenoxy resin, epoxy resin, silicone - one of the Ik types
It represents a group of the polymer molecule excluding the combined substituent or connecting appropriate m'& substituents, and n represents an integer from θ to θ.

The hydrazone compound and azo compound of the present invention, lo-6 to /θ-1 mole relative to the solvent, preferably /θ″'
~io-'' moles are used.

The hydrazone compound used in the present invention can be easily synthesized according to, for example, a linear formula.

(m) (fatty) 1 (1) (wherein R1, R1, Ra and n have the same meanings as above), that is, ben'quinone represented by general formula (1) and phenyl represented by general formula (IV) Hydrazine can be mixed with alcohols such as methanol, ethanol, and impropanol, ethers such as tetrahydrofuran, and acetic acid.
In an organic solvent such as sulfuric acid, acetic acid, acetic acid, etc., in the presence of an acid or base such as sulfuric acid, acetic acid, etc.
It can be synthesized by reacting at /lA for OJ to Koda time.

Further, the azo compound used in the present invention can be easily synthesized according to the following formula, for example.

ff) (1) (In the formula, R1, R'', R'' and n have the same meanings as above) That is, the phenol represented by the general formula ff) and the general formula (
The diazonium salt represented by 1) is dissolved in water, alcohol, or an Ia solvent such as dimethylformamide, dimethylsulfoxide, or N-methylpyrrolidone in the presence of a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, or potassium carbonate. Lower K can usually be synthesized by carrying out a coupling reaction at room temperature or below for several hours.

The hydrazone compound represented by the general formula (1) and the azo compound represented by the general formula (Otori) are tautomers and often exist as a mixture of both isomers in the 9% bath solution, but triethylamine misaki When a base is present together, it becomes only an azo compound.

In the present invention, a gold IIf4 salt is brought into contact with a hydrazone compound represented by the above-mentioned general formula (1) and/or an azo compound represented by the general formula (Otori) in an organic solvent in the presence of a base to form a metal ion. As a metal salt that complexes 9@eha, LisMa-KsRb, 1
0s,, Mg, Oa, 8r, Ba, Ou, Mug
1Zn, 1OeL, Pb, Ni, co, Pd,
Pt', IJ, Mn.

Examples include Oe, Pr, and 8m metal salts. Among them,
Separation of e @, bi, 'gb c& which can be suitably applied to alkali metal salts and alkali metal salts.

Suitable for analysis.

Examples of organic solvents include alcohols such as methanol, ethanol, and propatool, ketones a such as acetone and methyl ethyl ketone, aromatic swollen hydrogens such as benzene, toluene, and ethylbenzene, and ethers such as diethyl ether and tetrahydrofuran. , methyl acetate, ethyl acetate ester, dichloromethane, taloloform,
/, J-dichloroethane, trichlorethylene, coolbenzene, etc. halogenated water volume 1lII% acetonitrile, dimethylformamide.

Examples include aprotic solvents such as N-methylpyrrolidone and dimethylsulfoxide.

Examples of bases include alkylamines such as triethylamine, diethylamine, and tributylamine, aromatic amines such as aniline, toluidine, and N-methylaniline, pyridine, α-picoline, co-, ≦-lutidine, quinoline, and 4-noxaline. , imidazole, diazabicyclooctane and the like.

The choice of organic solvent and base depends on the amount of metal salt used.
It is selected in consideration of the balance between the polarity and the basic strength.

Such a base is usually 0.0/~/ with respect to the metal salt.
Used in a suite of θO times the mole, preferably #i, 0.1 to 10 times the mole Metal salt and the hydrazone compound represented by the general formula (1) and/or the azo compound h represented by the general formula (Otori) The contact with Fi may be carried out at a temperature range from room temperature to the boiling point of the solvent, usually for several minutes to several hours at room temperature.

As mentioned above, according to the present invention, when a specific hydrazone compound and/or a specific azo compound is used, the selectivity for metal ions is high, and due to the integral formation, a specific absorption occurs, so that the separation of metal salts, Useful for analysis. In particular, lead metal ions can be easily identified and quantified by analyzing their absorption spectra, which is an extremely simple separation and analysis method. Examples are given below. Further, the present invention will be explained in detail.

Production example / 14t-dinitrophenylhydrazine 4t/, -ki(
Ethanol containing several drops of pseudosulfur (0, 4 mmol)
In addition to the roux, dissolve 91llli [KJ,! -bis(methoxymethyl)-p-benzoquinone 7.4ta19 (
0.2 co/11 m+01) was added, and the mixture was stirred at room temperature for 7 minutes. Separate the resulting precipitate and wash with ethanol to obtain crude crystals of 7/,/5y (9J, 7%). Obtained. Its physical properties were as follows.

Melting point /-3, θ~ /-ta, j℃ λwax (9 g #/O) lols) 4'
00 nla (4', j7)0
'HM side candy j 31X4t, iz%/1.7 da% calculated value (C!,,H,,N40.) j/,06%da,ko2%/@Ijishima of the obtained crystals The interference spectrum obtained by the nuclear method is shown in Figure -/, and the 'H-NMR spectrum of the obtained crystal (/00 MHz,
0 DOI, ) is −j constant [, where the azo form is j 1,1
It was observed that the % saving drashin form exists at a ratio of &/,, 2 lights. The results are shown in Table 7.

One drop of triethylamine was added to this #*.

The hydrazone type peak in the ll1-spectrum disappeared and 1
, only the azo form became K. The results are shown in Table λ.

Table - MMR spectrum data of hydrazone after addition of triethylamine Example/Dissolve the crystals obtained in Production Example 1 in acetonitrile I1,
When triethylamine is added, the protons of the hydroxyl group dissociate and 1. The solution became blue. Add the alkali metal salts shown in Table 3 to this solution in a crystal tube.

I looked at #1F to see how the hair color looked. The results are shown in Table 3.

Table 3 clearly shows that among Fi and alkali metals, only lithium selectively undergoes a significant change in complex form *L, kt & q+ color under the conditions of % acetonitrile-triethylamine in a manner similar to fk.

Table J Practical side In place of acetonitrile in Example 1, chloroform was used, and in the same manner as in Example 1, crystals of alkali metal salts or alkaline earth metal salts shown in Table 4tK were added.
As is clear from the results shown in the table, only calcium ions showed a significant change in absorption when exposed to alkali metals, lithium, and alkaline earth metals.

Figure 1 shows an infrared spectrum of the needle-like crystals obtained in Example/.

Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase - #1/name

Claims (1)

[Scope of Claims] (11 Metal salts of the general formula (1
) (In the formula, R1 represents an alkoxyalkyl group spanning a lower alkyl group, y #i halogen atom, lower alkyl group,
Indicates a nitro group or an alkoxy group, 1m is a hydrogen atom,
I. rogen atom, lower alkyl group, nitro group, 7 represents a koxy group or a group of one unitary molecule s "Fi'~4t
) and/or an azo compound represented by the general formula (1) (wherein H+, Hz, Bs and n are the same as defined above), the metal of the metal salt is Complexing property of metal ions, which is characterized by complexing ions.