JPH0278591A - New-type dithiotropolonate unsymmetrical metal complex and production thereof - Google Patents

Abstract

PURPOSE:To obtain a material having an absorptivity in a near infrared region by using a dithiotropolonate unsymmetrical metal complex having a specific composition. CONSTITUTION:A metal complex shown by a formula I, where R represents hydrogen or alkyl; H represents a multivalent metal; and A is a pair cation, is obtained by causing a dithiotropolonate metal complex shown by a formula II, where R represents hydrogen or alkyl; and M represents a multivalent metal, to react with a bis metal complex onium salt shown by a formula III. The metal complex shown by the formula II is obtained by a method in which a tropolone compound is caused to thermally react with a phosphorus pentasulfide in an organic solvent to obtain a dithiol tropolone-series/phosphorus sulfide complex; and a multivalent metal ion compound or an aqueous solution thereof is added to said complex to cause said formed complex to thermally react with a metal ion. The bis metal complex onium salt shown by the formula III is obtained by a method in which a sodium-cis-1,2- dicyano-1,2-ethylene dithiolate is synthesized to react with a polyvalent metal compound; and a quaternary ammonium or a phosphonium is added to this reaction liquid. The new-type metal complex of the formula I obtained in this manner is available for an optical recording medium because it has an absorptivity in a near infrared region.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel dithiotropolonate-based asymmetric metal complex having absorption in the near-infrared region and useful for optical recording media, etc., and a method for producing the same.

[Conventional technology]

In recent years, an organic dye thin film has been used instead of a metal thin film as the recording layer of an optical recording medium, and recording is performed by generating thermal deformation with laser beam irradiation, and reproduction is performed using the difference in reflected light from the undeformed part. Reading has been put into practical use. This organic dye thin film has an adjustable melting point and decomposition point, low thermal conductivity, and can form a recording thin film layer by coating, so this method is expected to improve productivity and reduce costs.

[Problem to be solved by the invention]

However, organic dye thin films have the disadvantage that the organic dye fades when exposed to natural light or a reproduction laser beam, and long-term stability is not sufficient.Also, the solvents used when forming thin films by coating methods are limited to halogenated hydrocarbons, etc. However, there are various practical problems related to the resin material used as the substrate. Accordingly, active research is currently being carried out on dyes with improved storage stability against light in the red to near-infrared region and resistance to reproduction deterioration, high-performance light stabilizers, and the like.

An object of the present invention is to provide a novel dithiotropolonate-based asymmetric metal complex that has absorption in the near-infrared region and is useful for optical recording media and the like, and a method for producing the same.

[Means for Solving the Problems] According to the present invention, the general formula [I] (wherein R represents a hydrogen atom or an alkyl group, traditionally represents a polyvalent metal, and A represents a counter cation, respectively). A novel dithiotropolonate-based asymmetric metal complex is provided, and is represented by the following general formula (n) (wherein R represents a hydrogen atom or alkyl J1 (and R represents a polyvalent metal, respectively). .

) and the bis(cxs -L2-dicyano-1,2-ethylene dithiolate) metal complex onium salt is reacted with the following general formula (11 (wherein, R is a hydrogen atom or an alkyl group, is a polyvalent metal, and A is a polyvalent metal). A method is provided for producing a novel dithiotropolonate-based asymmetric metal complex represented by:

The novel dithiotropolonate-based asymmetric metal complex of the present invention represented by the above-mentioned general formula CI) has absorption ability in the near-infrared region, so it is particularly suitable for use in optical recording media.
Useful as a heavyt oxygen quencher. In addition to optical recording media, the metal complexes can also be used as filters for infrared sensitive materials, heat ray blocking materials, various organic chemicals, plastics, and agricultural chemicals.

It is a useful compound that can also be used as a stabilizer for rubber, antioxidant, bactericide, etc.

Specific examples of the metal complex represented by the general formula (1) according to the present invention include, but are not limited to, combinations of lead anions and lead cations shown below.

(i) Specific examples of complex anions (in the formula, N is Cu, Zn, Cd, Pb, V, Mo, Mn
+Fe, Co, Nu, Pd.

Represents a polyvalent metal such as pt. ) (In the formula, the former represents a polyvalent metal similar to the upper part.) (n)
Specific example of complex cation (counter cation A) N'' (C, H,
), : tetraethylammonium cation, N”
(n-C4H9)4: Tetra n-butylammonium cation.

@-I7. H,,: N-laurylpyridinium cation.

N”(CH3)3(czcHii): trimethyl-
〇-Hexadecane ammonium cation, P@(n-CJg)4: Tetra n-butylphosphonium cation, F'(C2H,)((IJ1□),: Ethyltri n-hexylphosphonium cation, F"((4H1?) 4: Tetra n-octylphosphonium cation.

The metal complex of general formula (1) provided by the present invention is:
For example, a dithiotropolonate metal complex represented by the general formula [■] (wherein R represents a hydrogen atom or an alkyl group, and H represents a polyvalent metal, respectively) and the following general formula (m) (formula (wherein, A represents a polyvalent metal, and A represents a counter cation.)
Ethylene dithiolate) can be easily obtained by reacting with a metal complex onium salt.

That is, in order to easily and conveniently obtain the metal complex represented by the general formula (1) of the present invention, the dithiotropolonate metal complex represented by the general formula [II] and the bis( It is preferable to utilize a ligand exchange reaction with a cis-1,2-dicyano-1,2-ethylenedithiolate) metal complex onium salt.

The production method of the present invention is usually carried out in an organic solvent.

Preferably it is carried out under reflux conditions. In this case, the organic solvent is acetone or acetonitrile that dissolves the metal complexes represented by the general formulas [1) and CIII).

1,2-dichloroethane, dimethyl sulfoxide and the like are preferably used.

In carrying out the present invention, the molar ratio of the metal complex of general formula [■] and the metal complex of general formula (m) is 1:1 to 1:0.
．． One reaction proceeds by dissolving these two types of metal complexes, preferably No. 8, in the organic solvent and heating the system to the reflux temperature of the solvent or 80 to 90°C. Reaction time is 0.5
-6 hours, preferably 1-2 hours. The reaction is completed by maintaining the reaction system for the above period of time.

Note that the dithiotropolonate metal complex represented by the general formula (11), which is one of the raw materials in the production method of the present invention, can be easily obtained by the following method. That is, first, a tropolone compound such as a 4-alkyltropolone is heated and reacted with phosphorus pentasulfide in an organic solvent, or in some cases in a nitrogen gas atmosphere, to obtain a dithioltropolone/phosphorus sulfide composite. A dithiotropolonate-based metal complex is obtained by adding a polyvalent metal ion compound or an aqueous solution thereof to the reaction system and causing a heating reaction between the resulting composite and the metal ion.

In this case, the intermediate dithioltropolones,
The phosphorus sulfide composite can be directly subjected to the second-stage metal complex formation reaction without separating the organic solvent, but the composite can also be taken out of the organic solvent and then subjected to multiple reactions in the organic solvent. It can also be heated to react with valent metal ions.

As the organic solvent in this case, both polar and non-polar solvents can be used, but polar solvents are preferred from the viewpoint of solubility of one reaction system and one reactant, and alcohols, ketones, ethers, esters, etc. and amides are suitable. These solvents have the advantage that the formed metal complex precipitates as crystals in the solvent simultaneously with the reaction. When non-polar hydrocarbon or halogenated hydrocarbon solvents are used, the resulting metal complex often dissolves in the solvent, which increases the number of post-reaction processing steps, but otherwise there are no particular problems. There isn't. A particularly suitable solvent includes dioxane.

In carrying out this method, the molar ratio of tropolones to phosphorus pentasulfide is 1:1. O to l: preferably in the range of 2.0,
Particularly preferred is a ratio of 1:L, 1 to 1:1.25. The amount of the solvent to be used is not particularly restricted, but in the case of dioxane, it is usually preferably in the range of 2 to 20 times the weight of the tropolones, particularly preferably about 8 to 10 times the weight. The first stage reaction is preferably carried out under reflux under heating, and the reaction time is 0.5 to 8.0 hours, preferably 2.0 to 4.0 hours. By maintaining the above time in dioxane,
The color of the reaction system changes from pale yellow to deep reddish brown, and a reddish brown precipitate appears.

Subsequently, when subjecting to the second stage reaction, the polyvalent metal ion compound is added in the above state either as it is or after being dissolved in a small amount of water. In this case, the amount of polyvalent metal ion compound added is 0.5 to 1 mole of raw material troborone.
-1.0 mol, preferably 0.5-0.7 mol.

When a polyvalent metal ion compound is added, the reaction system generally turns black, but the reaction is carried out by heating with S and preferably under reflux (may be in a hot water bath). The reaction changes this state to 0.5
The process is maintained for ~4.0 hours, preferably 1-2.5 hours until almost complete.

In the case of many polyvalent metals, black crystals are precipitated by cooling after the reaction is completed. The desired dithiotropolonate metal complex can be obtained by filtering the crystals. The obtained metal complex is.

If necessary, it can be recrystallized from a mixed solvent such as acetone/ethanol.

In addition, the raw material in the production method of the present invention is
The bis(cis-1,2-dicyano-1,2-ethylenedithiolate) metal onium salt represented by the R formula (III) can be obtained, for example, by the following method. That is, first, Inorganic 5ynthesj
Sodium-cis-1,2-dicyano-1,2 according to the method described in J.S. 10,8 (1967)
- By synthesizing ethylene dithiolate, then reacting the compound with a polyvalent metal compound such as nickel chloride, and further adding, for example, quaternary ammonium or phosphonium to the reaction solution, bis(cis-1, 2-dicyano-1,2-ethylene dithiolate) metal complex onium salt is obtained.

〔Effect of the invention〕

The novel gold Ma1 represented by the general formula (1) of the present invention has absorption ability in the near-infrared region and is therefore useful for optical recording media, especially as a heavyt oxygen quencher. be. In addition to optical recording media, the metal complex can also be used for
Filters for infrared sensitive materials, heat ray blocking materials or stabilizers for various organic chemicals, plastics, agricultural chemicals, rubber, etc.
It can also be used as an antioxidant, bactericide, etc.

Furthermore, the production method of the present invention may utilize a ligand exchange reaction between the metal complex represented by the above general formula (II) and the metal complex onium salt represented by the above general formula [■], so that it is industrially possible. This can be said to be an extremely advantageous manufacturing method.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples. Note that all percentages and parts shown below are based on weight.

Reference Example 1 Synthesis of bis(dithiotropolonate)nickel complex
The mixture was suspended in a portion of water, heated under reflux, and stirred to carry out a reaction for 3 hours.

After the reaction, the precipitate was filtered off after being allowed to cool, and a reddish-brown substance 10.06
I got the department. This product was hardly soluble in acetone, 1,1-dichloroethane, etc., and no melting or decomposition was observed even when heated to 300°C. The product appears to be a complex or ester of dithioltropolone and phosphorous sulfide;
It took some time to elucidate its structure. but.

I did it.

4.99 parts of the above composite were suspended in 50 parts of dioxane.

Furthermore, 3.57 parts (0,015 mol) of nickel chloride hexahydrate
was dissolved in 15 parts of water and added. In a hot water bath, the mixture began to be heated to a purple-black color at about 50° C., and was stirred for 2 hours under reflux to carry out the reaction. After the reaction, the reaction system was cooled and the precipitate was filtered off to obtain 1.18 parts of black crystals. When this crystal was recrystallized from pyridine, the melting point of the purified crystal obtained was 328°C (decomposed). (Consistent with the literature value.) The elemental analysis values of the obtained purified nickel complex were as follows.

Elemental analysis values: Reference example 2 Synthesis of bis(4-isopropyldithiotropolonate) nickel complex 4-isopropyltroborone (hinokitiol) 2.4
6 parts (0,015 mol) and 3.99 parts (0,015 mol) of phosphorus pentasulfide
018 mol) was suspended in 50 parts of dioxane, heated under reflux, stirred, and reacted for 3.5 hours. Initially, the red color changed to deep reddish brown, and dark reddish brown precipitates were observed. After the reaction is completed, the reaction system is cooled once, and 1
．． Dissolve 83 parts (0,0075 mol) in 10 parts of water to give 1
The mixture was added to the reaction system and stirred in a water bath under reflux for 2 hours to carry out the reaction. After the reaction, the system was allowed to cool, and the precipitate was filtered off to obtain 2.52 parts of green-black crystals. The melting point of the obtained crystals was 205-207°C.

The yield was 74.4% based on hinokitiol.

When this crystal was crystallized from acetone (■i), the melting point was 2
Green-black crystals with a temperature of 0.06-207°C were obtained.

The elemental analysis values of the obtained purified nickel complex were as follows.

Elemental analysis values: Reference Example 3 Synthesis of bis(1,2-dicyano-1,2-ethylenedithiolate)nickel tetra-n-butylammonium salt Inorganic 5synthesis 10,8(
Sodium-c synthesized as described in (1967)
5.6 parts of is-1,2-dicyano-1,2-ethylene dithiolate was dissolved in 60 parts of water/methanol (1:l V/V), and 3.6 parts of nickel chloride hexahydrate was dissolved in 20 parts of water.
When you add the dissolved liquid to the part.

Next, 10.3 parts of tetra-n-butylammonium bromide was mixed with water/methanol (1:l).
A solution dissolved in 20 parts of V/V) was added to the above product and stirred at room temperature for 1 hour.

The precipitated orange-red crystals were filtered and recrystallized from an acetone/butanol mixed solvent to obtain 11.2 parts of purified crystals. The melting point of the purified crystals obtained was 141-142°C (literature value: 143-144°C).

Reference Example 4 Synthesis of bis(1,2-dicyano-1,2-ethylenedithiolet 1)nickel tetra-n-butylphosphonium salt In Reference Example 3, tetra-n-butylammonium bromide was replaced with tetra-n-butylphosphonium salt. Purified crystals with a melting point of 168 to 169°C were prepared in the same manner as in Reference Example 3 except that -butylphosphonium bromide was used. )is.

Example 1 Synthesis of (dithiotropolonate) (1,2-dicyanoethylene thiolate) nickel tetra-n-butylammonium salt metal complex ~)
0.55 parts of nickel complex and the bis(
], ] 0.99 parts of 2-dicyano 1,2-ethylenedithiolate nickel tetra-n-butylammonium salt was heated and stirred under reflux for 2 hours with 40 parts of 2-dichloroethane. After the reaction, the solvent was distilled off and the crude product was recrystallized from a mixed solvent of 1,2-dichloroethane/vinegar and ethyl ester (1,:IV/V) to give a bright black color. 0.61 parts of crystals were obtained. Melting point: 161-162°C.

The elemental analysis values and near-infrared absorption spectrum of the obtained metal fjV body are as follows, and the infrared absorption spectrum (KBr tablet method) is shown in FIG.

Elemental analysis value: *: Example 2 (4-isopropyldithiotropolonate) (1,2-
dicyanoethylene thiolate) nickel tetra-n-
Synthesis of butylammonium salt metal complex 0.45 parts of the bis(4-isobrobyldithiotroborone-1~)nickel complex obtained in Reference Example 2 and the bis(1
,2-dicyano-1,2-ethylenedithioleyl-)nickel te1hecy n-butylammonium salt 0.83
The reaction mixture was stirred with acetonitrile under reflux for 2.5 hours. After the reaction was completed, the crude product obtained by distilling off the solvent was extracted with methanol to obtain crystals, and further using silica gel (trade name: Wakogel C-300), I'
? li 11 ethyl ester/chloroform (]:
IV/V) Using dA mixed solvent as a developing solvent, fractional purification was performed by column chromatography to obtain bright black crystals of 0.48
I got the department. Melting point 105-106°C.

The elemental analysis values and near-infrared absorption spectrum of the obtained metal complex are as follows.
KBr tablet method) is shown in FIG.

Elemental analysis value: Example 3 (4-isopropyldithi-1-roboronate) (1,Z
Synthesis of nickel (dicyanoethylene thiolate) nickel tetraroptylphosphonium salt metal complex 0.90 part of the bis(4-isopropyldithiotropolonate) nickel complex obtained in Reference Example 2 and the bis(4-isopropyldithiotropolonate) nickel complex obtained in Reference Example 4. (1
, 2-dicyano-1,2-ethylenedithiolate) nickel tetra-n-butylphosphonium salt was used together with 50 parts of 2-dichloroethane.
0.98 parts of black crystals were obtained by the same operation as fll 2. Melting point: 99-102°C.

The elemental analysis values and near-infrared t″11< absorption spectrum of the obtained metal complex are as follows, and its infrared absorption spectrum 1H (KI3r tablet method) is shown in FIG.

Elemental analysis value:

[Brief explanation of the drawing]

1 to 3 show infrared absorption spectra of the respective metal complexes obtained in Examples 1 to 3 of the present invention.

Claims (2)

[Claims] (1) General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, R represents a hydrogen atom or an alkyl group, M represents a polyvalent metal, and A represents a countercation, respectively. ) A novel dithiotroboronate-based asymmetric metal complex. (2) General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] (In the formula, R represents a hydrogen atom or an alkyl group, and M represents a polyvalent metal, respectively.) Dithio Troboronate metal complexes and the following general formula [III] ▲Mathematical formulas, chemical formulas, tables, etc. are available▼[III] (In the formula, M represents a polyvalent metal and A represents a counter cation, respectively.) bis(cis-1,2-dicyano-1,2-
Ethylene dithiolate) metal complex onium salt is reacted with the following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, R is a hydrogen atom or an alkyl group, and M is a polyvalent metal. and A represents a countercation, respectively.) A method for producing a novel dithiotroboronate-based asymmetric metal complex.