JPH01299291A - Production of thiotropolonate-based metallic complex and novel bis(4-alkyldithiotropolonate) metallic complex - Google Patents

Abstract

PURPOSE:To readily obtain the subject compound useful as an infrared ray absorber, etc., in a simple step using an inexpensive raw material, by reacting a tropolone-based compound with phosphorus pentasulfide and then reacting the resultant reaction product with polyvalent metallic ions. CONSTITUTION:A tropolone-based compound (preferably tropolone, etc.) is initially reacted with phosphorus pentasulfide so as to provide preferably 1:1-1:1.25 molar ratio of the former:latter. The resultant reaction product is then reacted with polyvalent metallic ions to afford the objective compound. The tropolone-based compound is preferably reacted with the phosphorus pentasulfide in dioxane in a refluxing state for 2-4hr and then a polyvalent metallic ion compound in an amount of 0.5-0.7mol based on 1mol tropolone- based compound is added to the reaction system and reacted in a refluxing state for 1-2.5hr. Furthermore, a compound expressed by the formula (R is alkyl; M is polyvalent metal) in the objective compound is a novel substance.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention provides an improved method for producing a dithiotropolonate-based metal complex, which is expected to be useful as an infrared absorber or a stabilizer for various organic materials, and a new method. bis(4-alkyldithiotropolonate) metal complex.

[Prior art]

In recent years, with the development of recording media using semiconductor laser light, there has been a demand for near-infrared absorbers that have specific absorption in the near-infrared region. In addition to recording media, we also offer filters for infrared sensitive materials, infrared light selective absorption materials, heat ray blocking materials,
There is a need for new complexes that can be used as oxidizing agents, antioxidants, and bactericidal agents for various organic chemicals and plastics.

The present inventors have discovered a dithiotropolonate-based metal complex as a complex having such near-infrared absorption characteristics or as a complex as a stabilizer for various organic materials. Tazo,
Conventional methods for producing dithiotropolonate metal complexes, particularly bis(dithiotropolonate) metal complexes, have been described in C.
J, Am, Chem, Soc, 92.2297 by E, Forbes & R, H, Hoflm.
(+970), in which tropolone is chlorinated with thionyl chloride to give 2-glolotropolone, and then treated with triethyloxonium boron tetrafluoride salt to produce 1,2-diethoxytropolone. Penylium boron tetrafluoride salt is made, and further reacted with sodium hydrogen sulfide in a nitrogen gas atmosphere to obtain dithiotropolone sodium salt, and further reacted with metal ions to obtain a bis(dithiotropolonate) metal complex. . That is, since this metal complex is obtained through a complicated several-step synthetic reaction, it is expensive and its use is naturally limited.

Further, as for dithiotropolonate-based metal complexes, only bis(dithiotropolonate) metal complexes are known, and thiotropolone-based metal complexes having substituents are not known.

〔the purpose〕

The purpose of the present invention is to use a dithiotropolonate-based metal complex, which is expected to be useful as an infrared absorber or a stabilizer for various organic materials, by using an inexpensive chemical as a raw material.
The object of the present invention is to provide a method for easily and inexpensively producing a novel bis(4-alkyldithiotropolonate) gold R complex through a stepwise reaction.

〔composition〕

According to the present invention, there is provided a method for producing a dithiotropolonate-based metal complex, which comprises reacting a troborone-based compound with phosphorus pentasulfide, and then reacting the reaction product with a polyvalent metal ion, Further, a novel bis(4-alkyldithiotropolonate) metal complex represented by the following general formula is provided.

(In the formula, R represents an alkyl group, and B represents a polyvalent metal.) That is, in the production method of the present invention, a tropolone compound is first reacted with phosphorus pentasulfide to form a mixture of dithiol tropolones and phosphorus sulfide. A complex is produced and the produced complex is further reacted with a polyvalent metal ion, and a dithiotropolonate metal complex can be obtained easily and inexpensively by this method.

In the method of the present invention, trobolone-based compounds, ie, tropolone and its derivatives, are used as starting materials, and specific examples thereof include tropolone and 4-alkyltropolone represented by the following general formula (1).

(In the formula, R' represents a hydrogen atom or an alkyl group.) Furthermore, among the compounds represented by the above general formula (1), tropolone [(■) in the formula R' =
H) and hinokitiol [R' = C in the formula (■)
H(CH3)2) is particularly preferably used.

In the method of the present invention, both the first stage reaction for producing a dithioltropolone/phosphorus sulfide complex and the second stage reaction for producing a dithiotropolonate metal complex are usually carried out in an organic solvent. . That is.

In the method of the present invention, first, a trobolone compound is heated and reacted with phosphorus pentasulfide in an organic solvent, or in a nitrogen gas atmosphere as the case may be, to obtain a dithioltropolone/phosphorus sulfide composite, and then the reaction system is By adding a polyvalent metal ion compound or an aqueous solution thereof and causing a heating reaction between the resulting composite and the metal ion, the desired dithiotropolonate-based metal complex can be obtained. In this case, the intermediate dithioltropolone/phosphorus sulfide composite can be directly subjected to the second stage metal complex formation reaction without separating the organic solvent; It is also possible to take it out from the organic solvent and heat it to react with a polyvalent metal ion in the organic solvent again.

As the organic solvent used in the method of the present invention, both polar and non-polar solvents can be used, but polar solvents are preferable from the viewpoint of dissolution of the reaction system and solubility of the reactants, and alcohols, ketones, ethers, etc. , -esters, amides, etc. are suitable. These solvents have the advantage that the formed metal complex precipitates as crystals in the solvent at the same time as one reaction6.
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. A particularly suitable solvent is dioxane.

When carrying out the method of the present invention, the molar ratio of tropolones to phosphorus pentasulfide is preferably in the range of 1:1.0 to 1:2.0, particularly 1:1.1 to 1:1.25. A range is preferred. The amount of 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 of the tropolone. The reaction is preferably carried out under reflux, and the reaction time is 0.5 to 8.0 hours, preferably 2.0 to 4.0 hours. By maintaining the reaction system in dioxane for the above period of time, 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 as is or dissolved in a small amount of water in the above state. In this case, the amount of polyvalent metal ion compound added is 0.5 to 1 mole of raw material tropolone.
-1.0 mol, preferably 0.5-0.7 mol.

When a polyvalent metal ion compound is added, the reaction system generally turns black, but in the case of a reaction in which the reaction is carried out by heating and preferably under reflux (may be in a hot water bath), this state is reduced 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.

Through the above reaction, a dithiotropolonate-based metal complex is obtained, but when tropolone represented by the above general formula (1) and its derivatives are used as raw materials, a metal complex represented by the following general formula (II) is obtained. is obtained.

(In the formula, R' represents a hydrogen atom or an alkyl group, and A represents a polyvalent metal.) As a specific example of the polyvalent metal A in the above general formula (n), C
u, Zn, Cd, Pb, V, Mo, Mn, Fe, Co,
Examples include polyvalent metals such as Ni, Pd, Pt, As, and Si.

Among the dithiotropolonate metal complexes obtained by the method of the present invention, bis(
4-alkyldithiotropolonate) metal complexes are new substances.

(In the formula, R represents an alkyl group and also represents a polyvalent metal.) Specific examples of the polyvalent metal X in the above general formula (III) are the same as those described for the above general formula (II). Cu.

Zn, Cd, Pb, V, Mo, Mn, Fe, Co, Ni
, Pd, Pt, As, Si, and other polyvalent metals.

Further, as the alkyl group R, a lower alkyl group having 1 to 5 carbon atoms is preferable, and an isopropyl group is particularly important from the viewpoint of easy availability of raw materials.

Typical specific examples of the compound represented by the general formula (III) of the present invention include those shown in Table 1, but the present invention is not limited thereto.

Table 1 [Effects] As mentioned above, the method of the present invention uses inexpensive tropolone and its derivatives as raw materials, and moreover, it can easily and inexpensively obtain dithiotropolonate-based metal complexes through a two-step reaction. This can be said to be an industrially extremely advantageous manufacturing method. In addition, the bis(4-alkyldithiotropolonate) gold m-complex of the present invention is a new substance and has excellent near-infrared absorption properties, and can be used as a near-infrared absorber or to stabilize various organic materials. It is expected to be useful as a drug.

〔Example〕

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

Example 1 Synthesis of copper bis(dithiotropolonate) complex Tropolone 4.88 parts (0.04 mol) and phosphorus pentasulfide 10 parts (0.04 mol)
045 mol) was suspended in 45 parts of dioxane, heated under reflux, stirred, and reacted for 2.5 hours. During this time, the reaction color changed from orange to deep reddish-orange. After the reaction is completed, the reaction system is once cooled and copper acetate ((CH,Coo)2Cu.H
3.99 parts (0.02 mol) of 2O) was dissolved in 15 parts of water, added to the reaction system, heated under reflux in a hot water bath, and stirred for 2 hours. After the reaction, the reaction system was cooled and the precipitate was filtered off to obtain 5.36 parts of black-green crystals.

When this crystal was recrystallized from toluene, green-black crystals were obtained, the melting point of which was 268°C (decomposition), and the C,
The melting point was consistent with that of V., Forbes et al.

Example 2 Synthesis of bis(dithiotropolonate)nickel complex 5.00 parts (0,0409 mol) of tropolone and 10.91 parts (0,0491 mol) of phosphorous pentasulfide were mixed with 50 parts of dioxane.
Suspended in a portion.

According to Example 1, the reaction was carried out for 3 hours. After the reaction, the mixture was allowed to cool and the precipitate was filtered off to obtain 10.06 parts of a reddish-brown substance.

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 is thought to be a complex or ester of dithioltropolone and phosphorus sulfide, but its structure has not yet been elucidated. 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. The mixture began to heat in a hot water bath and turned purple-black at about 50° C., and was stirred under reflux for 2 hours 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 (decomposition), and the melting point was 328°C (decomposition).
The melting point was consistent with that of .

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

Elemental analysis values: Example 3 Synthesis of bis(4-isopropyldithiotropolonate) nickel complex 4-isopropyltropolone (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 nickel chloride hexahydrate 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 reaction 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 recrystallized from acetone, the melting point was 206.
Green-black crystals of ~207°C were obtained.

The elemental analysis values of the purified nickel complex obtained are as follows, and its infrared absorption spectrum (KBr tablet method) was
As shown in the figure.

Elemental analysis values: Example 4 Synthesis of bis(4-isopropyldithiotropolonate) palladium complex 16.41 parts (0.1 mol) of hinoashi thiol and 26.67 parts (0.12 mol) of phosphorus pentasulfide were added to dioxane. Suspend in 350 parts.

Heat and stir the reaction under reflux in a nitrogen gas atmosphere for 5 minutes.
I did it for an hour. After the reaction, the mixture was allowed to cool, the precipitate was filtered off, and dried under reduced pressure to obtain 24.74 parts of reddish brown crystals. This result shows that it is poorly soluble in toluene and 1,1-dichloroethane, and its melting point is sintered at 203°C, 204-205°C.
It showed the property of decomposing at ℃. The crystals are thought to be a composite or ester of 4-isopropyldithioltropolone and phosphorus sulfide, but the structure has not yet been elucidated. However, the reaction took place.

2.79 parts of the above composite were suspended in 20 parts of dioxane, and 1.33 parts (0,0075 mol) of palladium chloride was suspended in 10 parts of water and added thereto. The reaction was stirred in a water bath under reflux for 2 hours. After the reaction, the reaction system was allowed to cool, and the precipitate was filtered and washed with methanol to obtain dark purple crystals.
．． Obtained 66 copies. The melting point of the obtained crystals is 203-205
℃ was shown. When this crystal was recrystallized from acetone, dark purple crystals with a melting point of 204-205°C were obtained.

The elemental analysis values of the purified palladium complex obtained are as follows, and its infrared absorption spectrum (KBr tablet method) is shown in FIG.

Elemental analysis values: Example 5 Synthesis of bis(4-isopropyldithiotropolonate) iron complex Hypothetical structure 5 believed to be the 4-isopropyldithiotropolone/phosphorus sulfide complex or ester obtained as an intermediate in Example 4 .59 parts suspended in 50 parts of dioxane,
Furthermore, 4.05 parts (0,015 mol) of iron chloride salt was added to 1 part of water.
The solution was dissolved in 5 parts and added, and 3.91 parts of dark brown crystals were obtained in the same manner as in Example 4. The melting point of the obtained crystals was 252-257°C (decomposed). This crystal is 1,
1-dichloroethane/acetone mixed solvent (mixing ratio l/1
), the melting point was 254-255℃ (decomposition).
Dark brown crystals were obtained.

The elemental analysis values of the obtained purified iron complex are as follows, and its infrared absorption spectrum (KBr tablet method) is shown in FIG.

Elemental analysis values: Example 6 Synthesis of bis(4-isopropyldithiotropolonate) cobalt complex According to Example 4, 5.59 parts of a hypothetical structure believed to be a 4-isopropyldithiotropolone/phosphorus sulfide complex or ester , 50 parts of dioxane and 1 part of anhydrous cobalt chloride
．． A reaction was carried out using 95 parts (0,015 mol) to obtain 3.86 parts of purple-black crystals. The melting point of the crystals obtained is 26
It showed a temperature of 4 to 267°C. When this crystal was recrystallized from acetone, black crystals with a melting point of 265 to 266°C were obtained.

The elemental analysis values of the obtained purified cobalt complex are as follows, and its infrared absorption spectrum (KBr tablet method) is
As shown in the figure.

Table 2 shows the visible to near-infrared absorption characteristics and physical properties of the metal complexes obtained by the method of the present invention, including the novel metal complex of the present invention.

Table-2

[Brief explanation of the drawing]

Figures 1 to 4 are Embodiment 3 of the present invention and Embodiment 4 of the present invention. The infrared absorption spectra of the metal complexes obtained in Examples 5 and 6 are shown.

Claims (2)

[Claims] (1) After reacting a tropolone compound with phosphorus pentasulfide,
A method for producing a dithiotropolonate metal complex, which comprises reacting the reaction product with a polyvalent metal ion. (2) A novel bis(4-alkyldithiotropolonate) metal complex represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R represents an alkyl group, and M represents a polyvalent metal.)