JPH07206406A - Production of polyoxo anion compound - Google Patents

Abstract

PURPOSE:To produce a polyoxo anion compd. useful as a catalyst for a reaction in org. synthesis, an electric conductor, a coloring material, an anti-cancer medicine, etc., by simple operation in a high yield. CONSTITUTION:A polyoxo anion compd. is subjected to reduction treatment to obtain a coordination unsatd. polyoxo anion compd. of reduced form, a metallic salt having a desired polyatom at the cation part is added to the unsatd. polyoxo anion compd. and this compd. is subjected to reoxidation treatment to selectively introduce the metallic cation as a polyatom of the polyoxo anion compd. in a desired compsn.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel method for producing a polyoxoanion compound. More specifically, the present invention uses a desired polyoxoanion compound useful as a reaction catalyst, an electric conductor, a dye, a carcinostatic agent, etc. in organic synthesis, using a readily available polyoxoanion compound as a raw material. In addition, the present invention relates to a method for producing a product with a high yield by a simple operation, which does not require a complicated process such as an operation of separating other ions mixed during the production.

[0002]

2. Description of the Related Art Polyoxoanion compounds are known to be useful compounds as reaction catalysts, conductors, dyes, carcinostatic agents and the like in organic synthesis. Then, as a method for producing the same, as represented by a heteropolyacid, a salt such as sodium phosphate, which is generally a hetero atom, and a metal oxide salt, which is a raw material of the poly atom, are mixed, and hydrochloric acid or the like is mixed. The method of manufacturing by lowering the pH is used. However, in such a manufacturing method,
The raw material for the poly atom must be in the form of an oxide anion, and when using a raw material that can be a poly atom or a hetero atom, it is difficult to control it, and the resulting polyoxoanion compound is Since it contains a salt that is always mixed during its production, there are problems that a complicated purification process is indispensable, or the yield is low.

So far, the polyoxoanion compounds
A lot of manufacturing research has been done, but the above problems are still sufficient.
Is not solved yet. For example, Polyoki
As a method for producing a soanion compound, (1) Na₂WO
_FourAnd H₃PO_FourAnd hydrochloric acid from Na₉PW₉O₃₄Got
M to this₃O (CH₃COO)₈(H₂O)₃(M is a transition
Transfer metal or Zn) and potassium chloride
R, K₇PW₉M₃O₃₇After that, with ammonium salt
And then fire it to H₇PW₉M₃O₃₇How to manufacture (US
Patent No. 4,898,989), (2) H₃PMo₁₂O₄₀
Li₂CO₃Weakly basic with n-Bu_FourNB
By processing with r, (n-Bu_FourN)_FourH₃PM
o₁₁O₃₉And to this MSO_Four(N-Bu_Four
N)_FourHPMo₁₁MO₃₉A method of manufacturing
Nick Chemistry (Inorg. Chem.) ", Volume 30, Vol.
4016 page (1991)], (3) Dawson
Type heteropolyacid K_TenP₂W₁₇O₆₁To M (NO₃)
_xBy adding P ₂W₁₇O₆₁(MOH₂)
Manufacturing method ["Journal of the American
Chemical Society (J. Am. Chem. Soc.) ”No. 11
3 Volume, page 7209 (1991)] etc.
ing.

However, the above method (1) is extremely complicated in process and the yield is as low as 70% or less, and in the method (2), calcination is required to obtain an acid type heteropolyacid. In addition, the yield is very low, 63% or less, and when Fe is used as M, there is a drawback that the desired compound cannot be obtained because the reduction of the heteropolyacid simply proceeds. . On the other hand, the method (3) has a high yield of 70 to 90%, but has a drawback that it cannot be applied to other heteropolyacids such as Keggin type.

[0005]

Under the above circumstances, the present invention is directed to a reaction catalyst, an electric conductor, and a catalyst for reaction in organic synthesis.
A desired polyoxoanion compound useful as a dye or a carcinostatic agent is used as a raw material from a readily available polyoxoanion compound, and a complicated process such as a separation operation of other ions mixed during the production is performed. The object of the present invention is to provide a method that does not require and can be produced with a simple operation and a high yield.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to develop a method for producing a desired polyoxoanion compound by a simple operation and at a high yield. Is reduced to lead to a reduced coordinated unsaturated polyoxoanion compound, and a metal salt having a desired poly atom in the cation part is added to the compound for reoxidation to introduce a metal cation as a poly atom. It was found that the obtained polyoxoanion compound can be easily obtained in a high yield and can achieve the above object. The present invention has been completed based on such findings. That is, in the present invention, a polyoxoanion compound is subjected to a reduction treatment to obtain a reduced-type coordinated unsaturated polyoxoanion compound, and then a metal salt having a desired poly atom in the cation part is added thereto, and then reoxidized. The present invention provides a method for producing a polyoxoanion compound, which comprises selectively introducing a metal cation in a desired composition as a polyatom of the polyoxoanion compound by treatment.

In the method of the present invention, the polyoxoanion compound used as a raw material is not particularly limited and can be arbitrarily selected from those belonging to the polyoxoanion compound. The polyoxoanion constituting this polyoxoanion compound has one or more heteroatoms such as Si, P, As and Ge, and one or more polyatoms such as W, Mo, V, Co, Ni and Fe. The heteropolyoxoanion may have any structure. P and Si are particularly preferred as the heteroatom in the heteropolyoxoanion.

Preferred specific examples of the polyoxoanion
As for [PMo₁₂O₄₀]^3-, [PVMo
₁₁O₄₀]^Four-, [PV₂Mo_TenO₄₀]^Five-, [PV₃Mo₈
O₄₀]^6-, [PV_FourMo₈O₄₀]^7-, [PV_FiveMo₇O
₄₀]^8-, [PV₆Mo₆O₄₀]^9-, [PMo₆W
₈O₄₀]^3-, [SiMo₁₂O₄₀]^Four-, [SiVMo₁₁O
₄₀]^6-, [SiW₁₂O₄₀]^Four-, [SiMo₆W₆O₄₀]
^Four-, [P₂VMo₂W₁₅O₆₂]^7-, [P ₂VMo_FiveW₁₂
O₆₂]^7-, [V₃Mo₃O₁₉]^Five-, [V₂Mo₆O₂₆]
^6-, [V _FourMo₈O₃₆]^Four-, [V₆Mo₆O₃₆]^6-，
[V₈Mo_FourO₃₆]^8-, [V₂Mo ₃W₇O₃₆]^2-Such
Can be mentioned.

In the method of the present invention, the polyoxoanion compound used as a raw material is a compound comprising the above polyoxoanion and one or more cation components, and contains water of crystallization. Good
It may not be contained. Examples of the cation component include H ⁺ , NH ₄ ⁺ , Li ⁺ , Na ⁺ , K ⁺ , R
Examples thereof include b ⁺ , Cs ⁺ , Pd ²⁺ , and of these, H ⁺ is particularly preferable. In the method of the present invention,
Usually, reduction treatment and reoxidation treatment are performed in a solvent. As the solvent, any solvent can be used as long as it can dissolve the polyoxoanion compound and the metal salt having a poly atom in the cation portion and does not hinder synthesis. Preferred examples of this solvent include water, an organic solvent compatible with water, and a mixture of water and an organic solvent compatible with water.
When a mixture of water and an organic solvent compatible with water is used, the mixing ratio is not particularly limited. Preferred solvents include, for example, water, oxygen-containing organic solvents such as alcohols, glycols, aliphatic ethers, ketones, esters and carboxylic acids, nitrogen-containing organic solvents such as amines and amides, sulfoxides, Examples thereof include sulfur-containing organic solvents such as sulfides, and these solvents may be used alone or in combination of two or more kinds. In the present invention, the amount of the solvent used is not particularly limited, but is usually in the range of about 0.1 to 10000 liters, preferably 1 to 1,000 liters, per 1 mol of the polyoxoanion compound. Is.

In the method of the present invention, first, the raw material polyoxoanion compound is subjected to a reduction treatment in the above-mentioned commonly used solvent to obtain a reduced coordinated unsaturated polyoxoanion compound. As the reducing agent used in this reduction treatment, any agent can be used as long as it can reduce the polyoxoanion compound as a raw material to produce a reduced coordinated unsaturated polyoxoanion compound. In consideration of isolation after the synthesis operation, a reducing agent that decomposes into a substance such as gas that can be easily removed from the reaction system after the operation is preferable. Examples of such a reducing agent include an inorganic reducing agent, an organic reducing agent, and a reducing gas. The inorganic reducing agent may be any agent as long as it can reduce the polyoxoanion compound, and various ones can be used. But there is
From the viewpoint of purification after the synthetic operation, hydrazines are particularly preferable. Further, the organic reducing agent may be any one as long as it can reduce the polyoxoanion compound, and there are various ones. For example, an organic phosphine compound and ascorbic acid are preferable. Further, as the reducing gas, any gas can be used as long as it can reduce the polyoxoanion compound, and there are various gases, and for example, hydrogen gas, carbon monoxide gas, nitrous oxide gas and the like can be preferably mentioned. . These reducing agents may be used alone or in combination of two or more. Further, the amount used is not particularly limited, but is usually an amount such that an amount equal to or more than the number of moles of the polyatom source metal newly introduced is reduced with respect to 1 mole of the raw material polyoxoanion compound. .

The reaction system in this reduction treatment is not particularly limited, and any system such as a batch system of the reaction mixed solution or a distribution system of the reducing agent into the reaction solution can be used. When a distribution method is adopted, the flow rate of the reducing agent is not particularly limited, but is usually about 1 to 200 mol / hour with respect to 1 mol of the polyoxoanion compound as a raw material. The reaction temperature cannot be unconditionally determined because it depends on the reducing agent used and the type of the raw material polyoxoanion compound, but it is usually 0 to 500.
C., preferably in the range of 50 to 200.degree. Further, the reaction pressure is not particularly limited, and it can be carried out in a wide range from normal pressure to high pressure, but economically it is from normal pressure to 1.
About 00 kg / cm ² is preferable.

Next, a metal salt having a desired poly atom in the cation portion is added to the reduced unsaturated polyoxoanion compound obtained by such a reduction treatment to obtain a reduced hetero atom-introduced polyoxoanion compound. After obtaining, it is reoxidized. The metal salt used in this case has a desired poly atom to be introduced into the polyoxoanion compound in the cation portion, and if it is soluble in a solvent, it may be, for example, an inorganic metal salt, an organic metal salt, an inorganic metal complex. ， Organic metal complexes etc.
It may be in any form. In addition, when there are a plurality of metals (polyatoms) to be newly introduced, a plurality of salts containing one kind of metal may be used, or one or more salts containing two or more kinds of metals may be used. . The amount of the metal salt used is not particularly limited, but it is usually used in an amount of about 1 to 2 times the molar amount of polyatoms to be newly introduced with respect to 1 mol of the raw material polyoxoanion compound. However, when all of the polyatoms are replaced with new ones, it is usually used in an amount of about equimolar to 20 times the number of polyatoms to be introduced, though it depends on the solubility of the metal salt in the solvent.

As the oxidizing agent used in this reoxidation treatment, any agent can be used as long as it can reoxidize the obtained reduced heteroatom-introduced polyoxoanion compound to the oxidized form. Preferable examples of such an oxidizing agent include oxygen gas, a mixed gas of oxygen gas such as air and a diluent gas, and peroxide. When a mixed gas of oxygen gas and diluent gas is used, its oxygen content is selected to be outside the range of explosion with the reaction solvent vapor. Further, as the peroxide,
As long as the reduced type heteroatom-introduced polyoxoanion compound can be reoxidized to the oxidized type, it can be selected from organic peroxides and inorganic peroxides as long as there is no danger due to its explosive property. Those selected can be used.
Examples of the organic peroxide include t-butyl hydroperoxide and m-chloroperoxybenzoic acid.
Examples of the inorganic peroxide include hydrogen peroxide. These oxidizing agents may be used alone or in combination of two or more.

The amount of the oxidant used is not particularly limited, but when a mixed gas of oxygen gas such as oxygen gas or air and a diluting gas is used, it can be converted into an oxidized form in terms of oxygen. It is advisable to appropriately add a necessary molar amount to about 200 times the molar amount until the oxidation finishes. On the other hand, when a peroxide is used, depending on its safety, the molar amount required to oxidize the reduced heteroatom-introduced polyoxoanion compound to the oxidized form is about 20 to 20 times. Good to use.

The reaction system in this reoxidation treatment is not particularly limited, and any system such as a batch system of the reaction mixed solution or a system of flowing an oxidant into the reaction solution can be used. When a flow system is adopted, the flow rate of the oxidizing agent is not particularly limited, but is usually 1 to 5 with respect to 1 mol of the reduced heteroatom-introduced polyoxoanion compound.
It is about 00 mol / hour. The reaction temperature cannot be unconditionally determined because it varies depending on the type of the oxidizing agent used and the reduced heteroatom-introduced polyoxoanion compound, but it is usually 0 to 500 ° C, preferably 50 to 200 ° C.
It is selected in the range of. Further, the reaction pressure is not particularly limited, and it can be carried out in a wide range from normal pressure to high pressure, but economically it is preferably about normal pressure to 100 kg / cm ² .
When a mixed gas of oxygen gas such as oxygen gas or air and a diluent gas is used as the oxidant, it is desirable to select the reaction pressure so as to be out of the range of explosion with the reaction solvent vapor. In this way, a polyoxoanion compound in which a metal cation is selectively introduced as a polyatom in a desired composition can be obtained in good yield.

[0016]

The present invention will be further described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Example 1 A 200 ml pear-shaped flask whose volume was replaced with nitrogen was charged with 50 ml of water, and 20.68 g of H ₆ PV ₃ Mo ₉ O ₄₀ which is a mixed coordination heteropolyacid (water content 18.1 wt%, 10 (Mmol) and added by magnetic stirring to dissolve for 5 minutes at room temperature. Then, to this was added 0.38 g of hydrazine monohydrate (7.
A solution prepared by dissolving 5 mmol) in 10 g of water was added dropwise, and the mixture was heated at 90 ° C. in an oil bath and stirred for 1 hour to carry out a reduction reaction. After cooling to room temperature, 2.68 g of iron citrate (water content 8.7 wt%, 10 mmol), which is a polyatomic source metal salt, was added, and the mixture was stirred at room temperature for 30 minutes in a nitrogen atmosphere. Then, this mixed solution was put into an autoclave, purged with nitrogen, heated to 80 ° C., and further pressurized with nitrogen at a pressure of 6 kg / cm ² G,
In addition, pressurize with oxygen at a pressure of 3 kg / cm ² to bring the total pressure to 9
The reoxidation reaction was carried out for 1 hour at a pressure of kg / cm ² G (holding pressure by oxygen supply). After cooling to room temperature and filtration, the solvent was removed by vacuum distillation under the conditions of 30 ° C. and 2 mmHg. As a result of IR analysis and elemental analysis of the obtained solid, mixed coordination heteropolyacid H ₇ PV ₃ Mo ₈ FeO ₃₉ 1
It was identified as 8.20 g (water content 13.6 wt%). The yield was 96%.

Example 2 In Example 1, the addition amount of hydrazine monohydrate was 0.1.
The reaction was carried out in the same manner as in Example 1 except that the amount was 3 g (2.5 mmol). The results are shown in Table 1.

Example 3 In Example 1, mixed coordination heteropolyacid H ₆ PV ₃ M
o ₉ O ₄₀ 20.68 g (water content 18.1 wt%, 10 mmol) was added to H ₃ PMo ₁₂ O ₄₀ 22.20 g (water content 17.8 wt.
%, 10 mmol), and the reaction was performed in the same manner as in Example 1. The results are shown in Table 1.

Example 4 In Example 1, 0.38 g of hydrazine monohydrate (7.5
The reaction was performed in the same manner as in Example 1 except that triphenylphosphine was changed to 3.93 g (15 mmol). The results are shown in Table 1.

Example 5 In Example 1, 0.38 g of hydrazine monohydrate (7.5
2.64 g (1 mmol) of L-(+)-ascorbic acid
The reaction was performed in the same manner as in Example 1 except that the amount was 5 mmol. The results are shown in Table 1.

Example 6 In Example 1, 2.68 g of iron citrate (water content 8.7 w)
t%, 10 mmol) was replaced by 2.19 g of cobalt citrate (water content 16.2 wt%, 3.3 mmol) to carry out the reaction in the same manner as in Example 1. The results are shown in Table 1.

Example 7 In Example 1, iron citrate 2.68 g (water content 8.7 w)
t%, 10 mmol) 4.55 g of iron perchlorate (water content 2
The reaction was performed in the same manner as in Example 1 except that the amount was 2.4 wt%, 10 mmol). The results are shown in Table 1.

Example 8 In Example 1, the reoxidation reaction was carried out in a pear-shaped flask in an amount of 1.70 g of hydrogen peroxide solution (H ₂ O ₂ content of 30 wt.
%, H ₂ O ₂ 15 mmol) was added, and the reaction was performed in a nitrogen atmosphere at 80
The reaction was carried out in the same manner as in Example 1 except that heating and stirring were carried out at 0 ° C for 1 hour. The results are shown in Table 1.

Comparative Example 1 Sodium molybdate 26.
6 g (110 mmol) and 1.0 g (10 mmol) phosphoric acid were added and dissolved by stirring at room temperature for 25 minutes, and then 1
2N hydrochloric acid was added until the pH reached 7.1, and the formed precipitate was filtered off. This precipitate is added to potassium acetate / acetic acid buffer (p
H6) Dissolved in 200 ml of water, and then added thereto, 1.74 g (10 mmol) of iron acetate in 200 ml of water.
Was added and the mixture was heated and stirred at 50 ° C. for 1 hour. After cooling to room temperature, 5.2 g (70 mmol) of potassium chloride was added to obtain a heteropolyacid potassium salt K ₄ PMo ₁₁ FeO ₃₉ . This was added to 200 ml of an aqueous solution of 64.5 g (200 mmol) of tetrabutylammonium bromide, stirred at 50 ° C for 15 minutes, and then allowed to stand at 4 ° C for 12 hours. Resulting heteropolyacid ammonium salt _{[(n-C 4 H 9)} 4 N ] ₄ PM ₁₁
After FeO ₃₉ was filtered off, it was calcined at 500 ° C. for 1 hour. The results are shown in Table 1.

Comparative Example 2 The reaction was carried out in the same manner as in Example 1 except that the hydrazine monohydrate aqueous solution was added and the heating and stirring at 90 ° C. for 1 hour was not carried out. The results are shown in Table 1.

Comparative Example 3 A reaction was carried out in the same manner as in Example 1 except that the reoxidation reaction in the autoclave was not carried out. The results are shown in Table 1.

[0027]

[Table 1]

[0028]

[Table 2]

As is apparent from Table 1, in Examples 1 to 8 which are the methods of the present invention, the polyoxoanion compound having the newly introduced poly atom was obtained in a high yield of 85% or more. . On the other hand, in Comparative Example 1 of the conventional method, the operation is complicated and the yield is low at about 50%, and Comparative Example 2 in which the reduction treatment was not performed and Comparative Example 3 in which the reoxidation treatment was not performed. Has an extremely low yield.

[0030]

EFFECTS OF THE INVENTION According to the present invention, a polyoxoanion compound useful as a reaction catalyst, an electric conductor, a dye, a carcinostatic agent, etc. in organic synthesis is complicated to separate other ions mixed during its production. It can be produced in a high yield by a simple operation without requiring various steps.

Claims (6)

[Claims] 1. A polyoxoanion compound is subjected to a reduction treatment to obtain a reduced coordinatively unsaturated polyoxoanion compound, and then a metal salt having a desired poly atom in the cation portion is added thereto, followed by a reoxidation treatment. By so doing, a metal cation is selectively introduced as a polyatom of the polyoxoanion compound in a desired composition, which is a method for producing a polyoxoanion compound. 2. A polyoxoanion compound as a raw material is S
A heteropolyoxoanion compound having at least one heteroatom selected from i, P, As and Ge and at least one polyatom selected from W, Mo, V, Co, Ni and Fe. A method for producing the polyoxoanion compound according to claim 1. 3. The polyoxoanion compound as a raw material has H ⁺ , NH ⁺ , Li ⁺ , N as its cation component.
3. At least one selected from a ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ and Pd ²⁺ is contained.
A method for producing the described polyoxoanion compound. 4. The method for producing a polyoxoanion compound according to claim 1, wherein a hydrazine, an organic phosphine compound, ascorbic acid, hydrogen gas, carbon monoxide gas or nitrous oxide gas is used as a reducing agent in the reduction treatment. 5. The method for producing a polyoxoanion compound according to claim 1, wherein oxygen gas, a mixed gas of oxygen gas and a diluent gas, or a peroxide is used as the oxidant in the reoxidation treatment. 6. The poly according to claim 1, wherein the reduction treatment and the reoxidation treatment are carried out in the presence of at least one solvent selected from water and an organic solvent compatible with water. Process for producing oxoanion compound.