JP2008178865A - Heteropolyoxo methalate compound catalyst for acid-base reaction, oxide decomposition reaction and oxidation reaction - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heteropolyoxo methalate compound catalyst which can be used for an acid-base reaction, an oxide decomposition reaction and an oxidation reaction. <P>SOLUTION: The heteropolyoxo methalate compound catalyst is a catalyst for a specific reaction which is used for at least one reaction selected from a group comprising the acid-base reaction, the oxide decomposition reaction and the oxidation reaction and consists essentially of a heteropolyoxo methalate compound. The heteropolyoxo methalate compound used for the catalyst has a heteropolyoxo methalate structure that at least one kind of an element (B) selected from group XI-XV elements is introduced into a defective structure site of a two defective structure site-containing heteropolyoxo methalate anion (A) wherein a hetero atom is silicon, phosphorus or germanium and a poly atom is at least one or more kinds of elements selected from a group comprising molybdenum, tungsten and vanadium. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a catalyst for a specific reaction comprising a heteropolyoxometalate compound as an essential component. More specifically, a heteropolyoxometalate into which at least one element selected from Group 11 to 15 is introduced for use in at least one reaction selected from the group consisting of an acid-base reaction, an oxide decomposition reaction, and an oxidation reaction. The present invention relates to a catalyst for a specific reaction having a compound as an essential component.

It is widely known that a heteropolyoxometalate compound having a structure in which a polyatom is coordinated via oxygen to a heteroatom centered on a heteroatom can be used as a catalyst for an organic reaction such as an oxidation reaction. In particular, it has a defect structure in which two atoms that should be in the structure of Keggin type heteropolyoxometalate are missing, and contains one or more kinds of metal elements at that site, that is, one or more kinds of polyatoms Disubstituted heteropolyoxometalates that are disubstituted with other metal elements show unique oxidation catalytic activity compared to monosubstituted heteropolyoxometalates and trisubstituted heteropolyoxometalates It is known (see Non-Patent Document 1). However, the catalyst is applied only to the epoxidation reaction, and there has been room for improvement in developing a catalyst that can be used for oxidation reactions other than acid-base reaction, oxide decomposition reaction, and epoxidation reaction.

A method of synthesizing a dimer of disubstituted heteropolyoxometalate in which copper is introduced into a two-deficient structure site has been disclosed, and the structure has been clarified by X-ray crystal structure analysis (Non-patent Document 2). reference). However, the heteropolyoxometalate monomer compound and the method of using it as a catalyst are not disclosed, and there is room for contrivance to use a heteropolyoxometalate compound substituted with a late element as a catalyst.

A compound comprising a polyoxometalate substituted with a divalent transition metal cation, wherein a catalyst for producing an oxygen-containing organic compound by contacting an olefin, alcohol or aldehyde with a molecular oxygen-containing gas is provided. It is disclosed (for example, see Patent Document 1). However, the catalyst is applied only to the oxidation reaction, and there is room for improvement in developing a catalyst that can be used for acid-base reaction and oxide decomposition reaction.

Heteropolyoxometalate anion having two- and / or three-defect structural sites, vanadium, tantalum, niobium, antimony, bismuth, chromium, molybdenum, selenium, tellurium, rhenium, cobalt, nickel, ruthenium, rhodium, palladium, osmium Platinum, iridium, silver, gold, zinc, aluminum, gallium, indium, scandium, yttrium, titanium, zirconium, hafnium, germanium, tin and a catalyst containing at least one element selected from the group consisting of lanthanoids, It is disclosed that a target epoxy compound is obtained by oxidizing a heavy bond with an oxidizing agent (see, for example, Patent Document 2). However, the catalyst is applied only to the epoxidation reaction, and there has been room for improvement in developing a catalyst that can be used for oxidation reactions other than acid-base reaction, oxide decomposition reaction, and epoxidation reaction.

An element selected from the group consisting of nickel, palladium, iridium and platinum of rare earth, group 4, group 5, group 6, group 7, group 9, and group 10 is introduced into the defect site in the two-deficient polyoxometalate. It is disclosed that the target epoxy compound is obtained by oxidizing an ethylenic double bond with oxygen using a catalyst (see, for example, Patent Document 3). However, the catalyst is applied only to the epoxidation reaction, and there has been room for improvement in developing a catalyst that can be used for oxidation reactions other than acid-base reaction, oxide decomposition reaction, and epoxidation reaction.

It has been disclosed that a Keggin type heteropolyoxometalate compound functions as an acid catalyst (for example, Non-Patent Document 3). However, the catalyst utilizes a proton or the like present at the cation site of the heteropolyoxometalate compound, and develops a highly active catalyst utilizing a metal introduced into the deficient structure site of the heteropolyoxometalate as a catalyst active site. There was room for ingenuity.
It is disclosed that copper sulfate functions as a catalyst for 1,3-dipolar cycloaddition reaction (for example, Non-Patent Document 4). However, the reaction time is long and the number of catalyst turnovers is never high, and there has been room for improvement in developing a highly active catalyst for the reaction that can be industrially tolerated.

Y. Nishiyama, Y. et al. Nakagawa, N .; Mizuno, “Ange. Chem. Int. Ed.” (Germany), 2001, vol. 40, p. 3639.

P. Mialane, A.M. Dolbecq, J. et al. Marrot, E .; Riviere, F.M. Seceresse, “Chemistry European Journal (Chem. Eur. J.)” (Wiley), 2005, Vol. 11, p. 1771.

T.A. Okuhara, “Chem. Rev.” (USA), 2002, 102, p. 3641.

V. V. Rostovtsev, L.M. G. Green, V.M. V. Fokin, K. et al. B. Sharpless, Angewante Chemie International Edition (Angew. Chem. Int. Ed.) "(Germany), 2002, vol. 41, p. 2596.

Japanese Patent Publication No. 2001-240561 International Publication No. 02/072257 Specification In this way, at least one element selected from Groups 11 to 15 is introduced into a deficient structure site of a heteropolyoxometalate anion containing two deficient structure sites. An example in which an oxometalate compound is used as a catalyst for acid-base reaction and / or oxide decomposition reaction has not yet been disclosed, and has been an unexplored field.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a heteropolyoxometalate compound catalyst that can be used in acid-base reactions, oxide decomposition reactions, and oxidation reactions.

As a result of intensive investigations focusing on heteropolyoxometalate compounds useful as industrial catalysts, the present inventors have found that at least one selected from the groups 11 to 15 at the deficient site of the two-deficient heteropolyoxometalate anion. The inventors have found that a heteropolyoxometalate compound into which an element has been introduced serves as a catalyst for acid-base reaction and / or oxide decomposition reaction, and has conceived that the above problems can be solved brilliantly. The present inventors have also found that such a heteropolyoxometalate compound can be suitably used as a catalyst for an oxidation reaction, especially an oxidative coupling reaction, and have reached the present invention.

That is, the present invention is a catalyst for a specific reaction that is used in at least one reaction selected from the group consisting of an acid-base reaction, an oxide decomposition reaction, and an oxidation reaction, and includes a heteropolyoxometalate compound as an essential component. The heteropolyoxometalate compound used as is to contain a two-deficient structure site wherein the heteroatom is silicon, phosphorus or germanium and the polyatom is at least one element selected from the group consisting of molybdenum, tungsten and vanadium A heteropolyoxometalate compound having a heteropolyoxometalate structure in which at least one element (B) selected from Groups 11 to 15 is introduced into a deficient structure site of a telopolyoxometalate anion (A) It is a catalyst for specific reaction.

The present invention is also a catalyst for specific reaction in which the heteropolyoxometalate anion (A) is a γ-type Keggin-type heteropolyoxometalate anion and the elements (B) are cross-linked with each other. Is preferred.

The catalyst for a specific reaction (hereinafter also simply referred to as a catalyst for a specific reaction) using the heteropolyoxometalate compound of the present invention has the above-described configuration, and the element (B) is substituted with the above-described two-deficient structure-site-containing heteropolyoxometalate. The heteropolyoxometalate compound obtained by introduction into the rate anion (A) has (1) redox property (2) electronegativity (3) magnetism (4) dipole moment (5) acid basicity (6 ) Due to the excellent properties such as structure, in the acid-base reaction and / or oxide decomposition reaction, catalytic activity that could not be achieved conventionally is expressed, and in the oxidation reaction, excellent catalytic activity is also expressed.

The catalyst for specific reaction of the present invention contains a heteropolyoxometalate compound as an essential component. The catalyst for the specific reaction may be one that uses the heteropolyoxometalate compound itself as a catalyst, or may be used together with other components. When used together with other components, the main component of the catalyst for specific reaction is preferably a heteropolyoxometalate compound, and the ratio of the heteropolyoxometalate compound to 100% by mass of the catalyst for specific reaction is 10% by mass or more. preferable. More preferably, it is 20 mass% or more. More preferably, it is 50 mass% or more.
The specific reaction catalyst means that the catalyst of the present invention is a catalyst for use in an acid-base reaction, oxide decomposition reaction and oxidation reaction in which the heteropolyoxometalate compound exhibits a function as a catalyst. To do.

The catalyst for specific reaction using the heteropolyoxometalate compound of the present invention is at least one element selected from the group consisting of molybdenum, tungsten, and vanadium, and the heteroatom is silicon, phosphorus, or germanium. It is characterized in that at least one element (B) selected from Group 11 to 15 is introduced into the deficient structure part of the heteropolyoxometalate anion (A) containing the two deficient structure parts.

The form of the element (B) and the heteropolyoxometalate anion (A) in the catalyst for specific reaction using the heteropolyoxometalate compound of the present invention is as follows. The element (B) is a heteropolyoxometalate anion (A). It will be introduced into the defect site. The term “introduced into the two deficient sites” may be a form in which the element (B) is incorporated into the deficient site, that is, a form in which a desired poly atom is replaced by the element (B), and in particular, the element (B). When the ionic radius of is large, the element (B) may be coordinated without being incorporated into the two-deficient site. Preferably, the element (B) is incorporated into two deficient sites. In this case, it is preferable that the elements (B) are adjacent to each other. The isomers in which the element (B) is adjacent to each other include α, β, γ, δ, ε isomers, etc., but the α, β isomers are isomers sharing a corner, and the γ, δ, ε isomers are It is an isomer with shared ridges. More preferred is a form in which the element (B) is incorporated into the skeleton of a β-form and / or a γ-form two-deficient Keggin-type polyoxometalate anion. It is a form incorporated into an oxometalate anion. The heteropolyoxometalate compound may be a monomer or a multimer. A monomer means that one heteropolyoxometalate anion site is contained in the unit structure, and a multimer means that a plurality of heteropolyoxometalate anion sites are contained in the unit structure. More preferably, it is a monomer containing one heteropolyoxometalate anion moiety. The structure of such a heteropolyoxometalate compound is determined or estimated from X-ray crystal structure analysis, elemental analysis, UV or FT-IR spectroscopy, and the like.
The heteropolyoxometalate anion (A) is a heteropolyoxometalate anion having a two-deficient structure site lacking two poly atoms that should be present in the crystal structure, wherein the hetero atom is silicon, phosphorus, or germanium. And at least one poly atom selected from the group consisting of molybdenum, tungsten, and vanadium. Such a heteropolyoxometalate anion (A) has a crystal structure called a Keggin type in which 10 polyatoms are coordinated to heteroatoms via oxygen.

The heteropolyoxometalate anion (A) in the present invention is preferably a Keggin type heteropolyoxometalate anion represented by the following general formula (1).
General formula (1):
[QM ₁₀ O _j ] ^k- (1)
Here, in the general formula (1), Q represents a silicon, phosphorus, or germanium atom, and M represents a poly atom. j and k are positive numbers, and k is determined by the valences of Q and M. More preferably, it is a Keggin type heteropolyoxometalate anion in which Q is silicon and M is tungsten. More preferably, [β-SiW ₁₀ O ₃₆ ] ⁸⁻ and / or [γ-SiW ₁₀ O ₃₆ ] ⁸⁻ whose isomer structure is β-form and / or γ-form. Most preferred is [γ-SiW ₁₀ O ₃₆ ] ^8- .

Although the heteropolyoxometalate anion used in the present invention is a two-deficient type, it may include a one-deficient or three-deficient type as long as it has the effects of the present invention.

Examples of counter cations that form salts of heteropolyoxometalate anions include protons, alkali metal cations, alkaline earth cations, zinc ions, lanthanide ions, aluminum ions, indium ions, tin ions, lead ions, iron ions, copper Ions such as ions, titanium ions, zirconium ions, manganese ions, ruthenium ions, cobalt ions, quaternary ammonium salts (ammonium salts, tetramethylammonium salts, tetraethylammonium salts, tetrapropylammonium salts, tetrabutylammonium salts, tributyl) Methylammonium salt, trioctylmethylammonium salt, trilaurylmethylammonium salt, benzyltrimethylammonium salt, benzyltriethylammonium salt, benzyltrimethyl Organic cations such as tylammonium salt, cetylpyridinium salt), quaternary phosphonium salt (tetramethylphosphonium salt, tetraethylphosphonium salt, tetrabutylphosphonium salt, tetraphenylphosphonium salt, ethyltriphenylphosphonium salt, benzyltriphenylphosphonium salt) Is preferred. One kind or two or more kinds of cations can be used. In order to obtain the heteropolyoxometalate monomer compound catalyst, the selection of the cation is one of the important factors.

The element (B) is at least one element selected from Group 11 to Group 15, but can be appropriately selected depending on the intended use. The element (B) is preferably Cu, Ag, Au, Zn, B, Al, Ga, In, Sn, Pb, Sb, Bi, and more preferably Cu, Ag, Au, Zn, Al, In, Sn, Sb and Bi. More preferred are Cu, Zn, Al, and In, and particularly preferred is Cu or Al. When the element (B) is Cu or Al, the element arranged in the ridge sharing type exhibits (1) sufficient oxidation-reduction characteristics and exhibits a specific activity for the oxide decomposition reaction or oxidation reaction. (2) An empty coordination locus works to express high Lewis acidity.
In addition, when synthesizing a mixture of heteropolyoxometalate compounds into which element (B) is introduced or heteropolyoxometalate compounds into which heterogeneous elements are introduced, two or more elements selected from the above elements (B) are used. May be.

The form used when introducing the element (B) may be a salt form or an oxide form. The salt may be an inorganic salt or an organic salt. Among them, acetate salt, nitrate salt, halide salt, sodium salt, potassium salt, ammonium salt, proton salt, ammonium salt, tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt. Salts, tetrabutylammonium salts and the like are preferred. It is also possible to use a complex salt such as a polynuclear complex containing the element (B) to be introduced.

The molar amount of the salt containing the element (B) used for preparing the catalyst is preferably more than 1 mol per 1 mol of the heteropolyoxometalate anion (A). More preferably, it is 1.1 mol or more, More preferably, it is 1.5 mol or more. Moreover, it is preferable that it is 8 mol or less. More preferably, it is 3 mol or less, More preferably, it is 2.5 mol or less.
As the addition of the element (B) at the time of catalyst preparation, the salt or compound of the element (B) is added as a powder or as a solution to the solution or mixture containing the heteropolyoxometalate anion (A). However, it may be added at the same time as (A) or may be carried out in the state of being dissolved in a solvent first. The element (B) salt or compound may be added all at once or gradually. The production of the heteropolyoxometalate compound may be carried out in one step or in several steps. For example, a method may be used in which a product is once taken out while leaving a part of a predetermined amount of (B), the product is redissolved in a solvent, and then the remaining (B) is added.

The pH of the solution during catalyst preparation is preferably in the range of 0.1 to 7.5, preferably 1.0 to 7.3, more preferably 1.5 to 7.0, still more preferably. Is 1.8 to 7.0. The setting of the pH is one of the important factors that determine the structure of the heteropolyoxometalate compound, and may be appropriately selected within the above range depending on the type of the element (B). In the case where the pH changes with the addition of the element (B), an optimum value may be appropriately set with an acid or a base.

Although it does not specifically limit as a solvent used at the time of catalyst preparation of this invention, Water, a water-containing organic solvent, and an organic solvent can be used. The organic solvent may be either soluble or insoluble in water, but acetone, acetonitrile, methanol, ethanol, propanol, t-butanol, chloroform and the like are suitable. In order to obtain the heteropolyoxometalate compound monomer, the selection of the solvent is one of the important factors.

The volume of the solvent is preferably 0.5 mL or more per 1 mmol of the heteropolyoxometalate anion (A). More preferably, it is 1 mL or more, More preferably, it is 1.5 mL or more. Moreover, it is preferable that it is 300 mL or less. More preferably, it is 200 mL or less, More preferably, it is 180 mL or less.

The liquid temperature of the solvent is preferably 0 ° C. or higher and 120 ° C. or lower. More preferably, it is 5 degreeC or more and 75 degrees C or less, More preferably, it is 10 degreeC or more and 50 degrees C or less.

When the element (B) is incorporated into the two deficient sites, the element (B) is preferably adjacent to each other, and the elements (B) adjacent to each other are nitrogen, oxygen, phosphorus, sulfur, selenium. And at least one element selected from tellurium and / or bonded via the element-containing group, that is, crosslinked with the element and / or the element-containing group. More preferred are nitrogen, oxygen and sulfur, and still more preferred are nitrogen and oxygen. Specific examples include nitrogen-containing groups such as nitrogen atoms, amino groups, and azide groups, and oxygen-containing groups such as oxygen atoms, hydroxyl groups, alcohol groups, alkoxy groups, and water.

The heteropolyoxometalate compound of the present invention is preferably one in which the elements (B) are crosslinked with a nitrogen-containing group and / or an oxygen-containing group among the above-mentioned crosslinked structures. More preferably, the element (B) crosslinked with a nitrogen-containing group and / or an oxygen-containing group is copper and / or aluminum. More preferably, the element (B) is copper and the copper elements are cross-linked with a nitrogen-containing group, or the element (B) is aluminum and the aluminum elements are cross-linked with an oxygen-containing group. Is.

In order to introduce the nitrogen-containing group, a salt and / or compound containing nitrogen such as sodium azide or amine is added during the preparation of the catalyst, or the salt and / or the compound is isolated after the heteropolyoxometalate compound is isolated. Treatment with compounds. Similarly, in order to introduce an oxygen-containing group, special treatment may not be required. However, a salt and / or a compound or acid containing oxygen such as alcohol may be added during the preparation of the catalyst, The oxometalate compound can also be treated with the salt and / or the compound or acid after isolation. It is preferable that 1 or more and 4 or less of this element exists between elements (B). More preferably, it is 1 or more and 3 or less.

The total content of the element (B) in the catalyst of the present invention is preferably more than 0.1 with respect to one hetero atom in the unit structure. More preferably, it is 0.5 or more, and more preferably 1 or more. Moreover, it is preferable that it is 5 or less. More preferably, it is 3 or less, and more preferably 2.5 or less. When used as a catalyst in the reaction, the valence of the element (B) may vary.

When the catalyst for specific reaction of the present invention is used, it can be used in any reaction field such as a gas phase, a liquid phase, and a supercritical phase. As a usage form, when used in a gas phase reaction, a form in which the reaction is carried out with the catalyst itself as a solid or a form in which the reaction is carried by supporting the catalyst on a carrier is possible. As the catalyst carrier, carriers generally used for gas-solid reactions such as various ion exchange resins, silica, alumina, titania, sirconia, tin oxide and other oxides can be used.

When the catalyst itself is used as a solid, preferred counter cations are protons, potassium ions, sodium ions, cesium ions, magnesium ions, calcium ions, barium ions, zinc ions, aluminum ions, lanthanide ions, iron ions, copper ions, palladium. Ion, platinum ion, cobalt ion, nickel ion, titanium ion, zirconium ion, vanadium ion, niobium ion, chromium ion, manganese ion, ruthenium ion, rhodium ion, iridium ion, and indium ion.

When used in a liquid phase reaction, a form in which the catalyst is dissolved and reacted in a homogeneous system, and a form in which the reaction is carried out by suspending the catalyst in the liquid phase without dissolving it in a solvent can be mentioned. It is also possible to carry out the reaction using the catalyst as a solid phase. At this time, by changing the counter cation, the catalyst itself can be used as a solid, and the catalyst and the product after the reaction can be easily separated.

Further, the catalyst can be used as a solid phase by supporting the catalyst on a carrier. As the catalyst carrier, carriers generally used for heterogeneous reactions such as various ion exchange resins, silica, alumina, titania, zirconia, tin oxide and other oxides can be used. In carrying out the reaction in a homogeneous system and / or heterogeneous system, preferred counter cations are protons, potassium ions, sodium ions, cesium ions, magnesium ions, calcium ions, barium ions, zinc ions, aluminum ions, lanthanide ions, iron ions. , Copper ion, palladium ion, platinum ion, cobalt ion, nickel ion, titanium ion, zirconium ion, vanadium ion, niobium ion, chromium ion, manganese ion, ruthenium ion, rhodium ion, iridium ion, indium ion tetrabutylammonium salt, Tetraoctyl ammonium salt, trioctyl ammonium salt, cetyl trimethyl ammonium salt, methyl tricetyl ammonium salt, and cetyl pyridinium salt. When the catalyst becomes insoluble in the solution due to the selection of the counter cation, the catalyst itself can be used as a heterogeneous catalyst without being supported on the carrier.

The heteropolyoxometalate compound of the present invention can be suitably applied as a catalyst to various acid-base reactions and oxide decomposition reactions. Thus, it is one of the preferred embodiments of the present invention that the catalyst for a specific reaction using the heteropolyoxometalate compound of the present invention is used for the acid-base reaction and / or the oxide decomposition reaction.

Specific examples of the acid-base reaction of the present invention are not particularly limited. For example, (1) esterification reaction, (2) carbon skeleton isomerization reaction, (3) polymerization reaction, (4) addition reaction, (5) opening Ring reaction, (6) elimination reaction, (7) acetalization reaction, (8) ketalization reaction, (9) aromatic electrophilic substitution reaction, (10) aromatic nucleophilic substitution reaction, (11) aldol reaction, (12) Pinacol transfer reaction, (13) Beckmann transfer reaction, (14) Cannizzaro reaction, (15) Claisen condensation reaction, (16) Darzens condensation reaction, (17) Diels-Alder reaction, (18) Friedel-Crafts reaction, (19) Fries transfer reaction, (20) Gutterman-Koch reaction, (21) Mannich reaction, (22) Michael reaction, (23) Prince reaction, (24) Glycosylation reaction, (25) Solvent Solution reaction, (26) 1,3-dipolar cycloaddition reaction, (27) ene reaction or carbonyl - ene reaction, and (28) thereof (1) reaction of non - (27) below. By such an acid-base reaction, it is possible to produce an organic compound in which a functional group or a skeleton is newly constructed.

Specific examples of the oxide decomposition reaction of the present invention are not particularly limited, and examples thereof include decomposition reactions such as hydrogen peroxide and nitric oxide. By such an oxide decomposition reaction, for example, the catalyst can be applied to a bleach activator, a bleach composition, an environmental purification catalyst, or the like.

The catalyst for specific reaction of the present invention is particularly suitable for 1,3-dipolar cycloaddition reaction among the acid-base reaction and / or oxide decomposition reaction. The 1,3-dipolar cycloaddition reaction is represented, for example, by the following general formula (2). Hereinafter, the reaction substrate, reaction conditions, and the like in the case where the above catalyst is used as a preferred embodiment of the present invention and triazole is produced by 1,3-dipolar cycloaddition reaction will be described.
General formula (2)

R and R ′ in the general formula (2) may be the same or different, and may be a hydrogen atom,
It is preferable that they are a C1-C18 alkyl group, a C1-C18 cycloalkyl group, and an aromatic group. More preferably, they are a C1-C12 alkyl group, a C1-C12 cycloalkyl group, a phenyl group, a methylphenyl group, a methoxyphenyl group, a halogenated phenyl group, a benzyl group, and a methylbenzyl group. The azide compound may be an isolated compound or a compound generated in the system. When it is generated in the system, the method is not particularly limited. For example, a compound in which the N3 portion of R′-N3 is replaced with halogen and sodium azide can be used. When using azide compounds, special care must be taken not to cause an explosion.

The amount of the specific reaction catalyst used in the acid-base reaction and / or oxide decomposition reaction is preferably 0.0001 parts by mass or more with respect to 100 parts by mass of the reaction substrate, and 3000 It is preferable to set it as a mass part or less. More preferably, it is 0.01 parts by mass or more and 1500 parts by mass or less. Moreover, as a kind of catalyst, 1 type, or 2 or more types can be used.

As the reaction method of the acid-base reaction and / or oxide decomposition reaction, the catalyst of the present invention can be used in any reaction method of gas phase reaction or liquid phase reaction. It is more preferable in terms of reaction activity to carry out the reaction.

When the acid-base reaction and / or oxide decomposition reaction is performed in a liquid phase, the solvent to be used is water and / or an organic solvent, and the organic solvent can be used singly or in combination. Examples of such an organic solvent include primary, secondary, and tertiary monohydric alcohols having 1 to 6 carbon atoms such as methanol, ethanol, normal or isopropanol, and tertiary butanol, ethylene glycol, propylene glycol, and glycerin. Polyhydric alcohols, ethylene oxides such as diethylene glycol and triethylene glycol, oligomers with ring-opened propylene oxide, ethers such as ethyl ether, isopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and acetyl acetone , Nitrogen compounds such as dimethylformamide, nitromethane, acetonitrile and benzonitrile, phosphorus compounds such as phosphate esters such as triethyl phosphate and diethylhexyl phosphate, Chloroform, halogenated hydrocarbons such as dichloromethane and normal hexane, aliphatic hydrocarbons n-heptane, toluene, xylene and like aromatic hydrocarbons, cyclohexane, alicyclic hydrocarbons such as cyclopentane and the like.

Among the above solvents, it is preferable to use alcohols having 1 to 4 carbon atoms, dichloromethane, heptane, hexane, acetonitrile, benzonitrile, dimethyl sulfoxide, dimethylformamide, toluene, xylene, or a mixture thereof. When the substrate compound is liquid under the reaction conditions, it is possible to carry out the reaction neat without using the solvent.

As a reaction condition in the acid-base reaction and / or oxide decomposition reaction, for example, in the case of a liquid phase reaction, the reaction temperature is preferably 0 ° C. or higher, more preferably room temperature or higher. Moreover, 250 degrees C or less is preferable, More preferably, it is 180 degrees C or less. The reaction time is preferably several minutes or longer, and is preferably within 150 hours. More preferably, it is within 48 hours. The reaction pressure is preferably normal pressure or higher, and is preferably 150 atm or lower. More preferably, it is 50 atm or less. The reaction can also be performed under reduced pressure. In the case of a gas phase reaction, 100 ° C. or higher is preferable, and 150 ° C. or higher is more preferable. Moreover, 600 degrees C or less is preferable, More preferably, it is 500 degrees C or less. The reaction time is preferably several minutes or longer, and is preferably within 1000 hours. More preferably, it is within 800 hours. The reaction pressure is preferably normal pressure or higher, and is preferably 150 atm or lower. More preferably, it is 100 atm or less.

In the above acid-base reaction and / or oxide decomposition reaction, a triazole compound can be produced by using a specific reaction catalyst of the heteropolyoxometalate compound of the present invention, and an intermediate used in the production of various industrial products, The present invention can be suitably applied as a production method for supplying a compound that is a useful compound as a raw material.

The heteropolyoxometalate compound of the present invention can also be suitably applied as various oxidation reaction catalysts. Thus, it is also one of the preferred embodiments of the present invention that the catalyst for specific reaction using the heteropolyoxometalate compound of the present invention is used for the oxidation reaction.

Specific examples of the oxidation reaction of the present invention are not particularly limited. For example, (1) oxidation of unsaturated bond (oxidation of unsaturated double bond or unsaturated triple bond of alkene or alkyne), (2) oxidation of hydroxyl group (3) Oxidation of heteroatoms (oxidation of sulfur atoms, nitrogen atoms, etc.), (4) Oxidation of saturated hydrocarbon moieties, (5) Oxidation of aromatic rings, (6) Other than (1) to (5) An oxidation reaction such as an oxidative coupling reaction may be mentioned.

The catalyst for a specific reaction using the heteropolyoxometalate compound of the present invention is preferably used for an oxidative coupling reaction among the above oxidation reactions. The catalyst for specific reaction of the present invention can exhibit excellent catalytic activity when used in an oxidative coupling reaction. The oxidative coupling reaction is represented, for example, by the following general formula (3).

R ″ and R ′ ″ in the general formula (3) may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, An aromatic group is preferred. More preferably, they are a C1-C12 alkyl group, a C1-C12 cycloalkyl group, a phenyl group, a methylphenyl group, a methoxyphenyl group, a halogenated phenyl group, a benzyl group, and a methylbenzyl group. Moreover, these groups may contain functional groups such as ester groups, ketone groups, aldehyde groups, hydroxyl groups, carboxyl groups, ether groups, halogen groups, amine groups, and nitrile groups.

When molecular oxygen is used as the oxidizing agent, the oxygen pressure is preferably 0.0001 atm or more and 150 atm or less. More preferably, it is 0.01 atm or more and 50 atm or less. When hydrogen peroxide is used as an oxidizing agent, a practical use form of hydrogen peroxide is preferably an aqueous solution of 0.01 to 70% by mass or a solution of alcohols. Can also be used. The amount used is preferably such that the molar ratio of the reaction substrate to hydrogen peroxide (number of moles of reaction substrate / number of moles of hydrogen peroxide) is 1000/1 or less, more preferably 100/1 or less. is there. Moreover, it is preferable to set it as 1/1000 or more, More preferably, it is 1/500 or more.

When the specific reaction catalyst is used for the oxidation reaction, the amount used is preferably 0.0001 parts by mass or more and preferably 3000 parts by mass or less with respect to 100 parts by mass of the reaction substrate. More preferably, it is 0.01 parts by mass or more and 1500 parts by mass or less. Moreover, as a kind of catalyst, 1 type, or 2 or more types can be used.

As the reaction method of the oxidation reaction, the catalyst of the present invention can be used in any reaction method of a gas phase reaction or a liquid phase reaction. It is more preferable in terms of surface.

When the oxidation reaction is performed in a liquid phase, water and / or an organic solvent are used as the solvent, and one or more organic solvents can be used. Examples of such an organic solvent include primary, secondary, and tertiary monohydric alcohols having 1 to 6 carbon atoms such as methanol, ethanol, normal or isopropanol, and tertiary butanol, ethylene glycol, propylene glycol, and glycerin. Polyhydric alcohols, ethylene oxides such as diethylene glycol and triethylene glycol, oligomers with ring-opened propylene oxide, ethers such as ethyl ether, isopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and acetyl acetone , Nitrogen compounds such as dimethylformamide, nitromethane, acetonitrile and benzonitrile, phosphorus compounds such as phosphate esters such as triethyl phosphate and diethylhexyl phosphate, Chloroform, halogenated hydrocarbons such as dichloromethane, n-hexane, aliphatic hydrocarbons n-heptane, toluene, xylene and like aromatic hydrocarbons, cyclohexane, alicyclic hydrocarbons such as cyclopentane and the like.

Among the above solvents, it is preferable to use alcohols having 1 to 4 carbon atoms, dichloromethane, heptane, hexane, acetonitrile, benzonitrile, dimethyl sulfoxide, dimethylformamide, toluene, xylene, or a mixture thereof. When the substrate compound is liquid under the reaction conditions, it is possible to carry out the reaction neat without using the solvent.

As reaction conditions in the oxidation reaction, for example, in the case of a liquid phase reaction, the reaction temperature is preferably 0 ° C. or higher, more preferably room temperature or higher. Moreover, 250 degrees C or less is preferable, More preferably, it is 180 degrees C or less. The reaction time is preferably several minutes or longer, and is preferably within 150 hours. More preferably, it is within 48 hours. The reaction pressure is preferably normal pressure or higher, and is preferably 150 atm or lower. More preferably, it is 50 atm or less. The reaction can also be performed under reduced pressure. In the case of a gas phase reaction, 100 ° C. or higher is preferable, and 150 ° C. or higher is more preferable. Moreover, 600 degrees C or less is preferable, More preferably, it is 500 degrees C or less. The reaction time is preferably several minutes or longer, and is preferably within 1000 hours. More preferably, it is within 800 hours. The reaction pressure is preferably normal pressure or higher, and is preferably 150 atm or lower. More preferably, it is 100 atm or less.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, the scope of the present invention is not limited only to these Examples. For the X-ray crystal structure analysis, SHELXH-97 was used. Two-deficient Keggin-type polyoxometalate K ₈ [γ-SiW ₁₀ O ₃₆ ] · 12H ₂ O was synthesized according to the following literature. A. Tze, G.M. Herve, “Inorganic Synth.” (USA), 1990, 27, p.85. JASCO FT / IR-460 for IR measurement, JEOL JNM-EX-270 for NMR measurement, JEOL JMS-T100LC for CSI-MS measurement, RIGAKU AFC-10 Saturn 70 CCD detector for X-ray measurement It was used.

Example 1 Synthesis of C ₆₄ H ₁₆₄ N ₁₀ SiW ₁₀ O ₄₅ Cu ₂ (isolated as a non-hydrate)
1.0 g (0.34 mmol) of K ₈ [γ-SiW ₁₀ O ₃₆ ] · 12H ₂ O was added to 20 mL of water. A solution prepared by dissolving 0.090 g (0.68 mmol) of CuCl _{2 in} 20 mL of water was added thereto, followed by stirring at room temperature for 1 minute. Subsequently, a solution obtained by dissolving 0.11 g (0.68 mmol) of NaN _{3 in} 20 mL of water was added. The pH of the solution at this time was 6.3. A solution of 2.0 g (6.0 mmol) of tetrabutylammonium bromide dissolved in 20 mL of water was added, and the pH was set to 6.0 using 1 M aqueous nitric acid solution. The mixture was stirred for 20 minutes and suction filtered to collect the precipitate. The green precipitate was washed with water (10 mL) and diethyl ether (50 mL). Yield: 0.78g. FT-IR analysis results: (KBr) / cm ⁻¹ : 3433, 2961, 2934, 2872, 2078, 1485, 1463, 1421, 1381, 1365, 1347, 1268, 1152, 1100, 1064, 1026, 994, 977, Peaks were detected at positions 957, 914, 895, 873, 847, 809, 769, 734, 697, 552, 511, 477, 461, 387, 363, 352, 316, 305. 29Si-NMR analysis result (CD3CN): -122.8 ppm. 185W-NMR (CD3CN): -130.6, -136.3 ppm. CSI-MS analysis result (MeCN): m / z 3866 {[(C ₄ H ₉ ) ₄ N] ₅ H ₂ [SiW ₁₀ O ₃₆ Cu ₂ (N ₃ ) ₂ ]} ⁺ . The results of X-ray crystal structure analysis are shown in FIG.

Was (Example _{2) C 52 H 127 N 5} O 43 SiW 10 Al 2 Synthesis _{K 8 [γ-SiW 10 O} 36] · 12H 2 O 1.0g of (0.34 mmol) was added to the water 10 mL. _Al a _{(NO 3) 3 · 9H 2} O 0.26g (0.69mmol) was added a solution prepared by dissolving in water 10mL here. Subsequently, the pH was adjusted to 3.4 to 3.6 with 1 M aqueous potassium carbonate solution, and the mixture was stirred at room temperature for 15 minutes. Tetramethylammonium chloride 0.48 g (4.4 mmol) was added, stirred for 30 minutes, and suction filtered to collect the precipitate. The white precipitate was washed with water (10 mL) and diethyl ether (50 mL). Yield: 0.57g. FT-IR analysis result: (KBr) / cm ⁻¹ : 3457, 3257, 3034, 2966, ¹
635, 1484, 1449, 1418, 1384, 1286, 997, 957, 901, 875, 795, 717, 628, 538, 510, 490, 474, 415, 399, 386, 368, 353, 337, 312 , Peaks were detected. The results of X-ray crystal structure analysis are shown in FIG. 2 and Tables 3-4.

Example 3 Synthesis of Triazole Compound Utilizing 1,3-Dipolar Cycloaddition Reaction Compound Catalyst C ₆₄ H ₁₆₄ N ₁₀ SiW ₁₀ O ₄₅ Cu ₂ Obtained in Example 1 2 mol%), benzyl azide (0.50 mmol), phenylacetylene (1.0 mmol) and acetonitrile (1.5 mL) were added, and the mixture was stirred at 60 ° C. for 5 hours under air to obtain 91% of the desired triazole compound. Obtained at a rate. The yield was determined by gas chromatography using naphthalene as an internal standard compound. After the reaction, the reaction solution was cooled to −30 ° C., and the resulting crystals were filtered to obtain an elementally pure triazole compound with a yield of 90%. When the filtrate containing the catalyst after obtaining the triazole compound was reused and used again in the same reaction as described above, the desired triazole compound was obtained in a yield of 93% in a reaction time of 3 hours.

(Comparative Example 1)
The reaction was performed in the same manner as in Example 3 except that the catalyst was changed from C ₆₄ H ₁₆₄ N ₁₀ SiW ₁₀ O ₄₅ Cu ₂ to Cu (ClO ₄ ) ₂ · 6H ₂ O. The yield of the triazole compound was 1%.

(Comparative Example 2)
The reaction was performed in the same manner as in Example 3 except that the catalyst was changed from C ₆₄ H ₁₆₄ N ₁₀ SiW ₁₀ O ₄₅ Cu ₂ to CuCl ₂ . The yield of the triazole compound was 1%.

(Comparative Example 3)
The reaction was performed in the same manner as in Example 3 except that the catalyst was changed from C ₆₄ H ₁₆₄ N ₁₀ SiW ₁₀ O ₄₅ Cu ₂ to CuSO ₄ .5H ₂ O. The yield of the triazole compound was less than 1%.

Example 4
The reaction was performed in the same manner as in Example 3 except that the substrate was changed from phenylacetylene to 3-methylphenylacetylene. The yield of the triazole compound was 98%.

(Example 5)
The reaction was performed in the same manner as in Example 3 except that the substrate was changed from benzyl azide to 4-methylbenzyl azide and the reaction time was changed to 6 hours. The yield of the triazole compound was 99%.

(Example 6)
The reaction was performed in the same manner as in Example 3 except that the substrate was changed from benzyl azide to adamantyl azide and the reaction time was 13 hours. The yield of the triazole compound was 95%.

(Example 7)
The reaction was carried out in the same manner as in Example 3 except that the substrate was changed from benzyl azide to octyl azide and the reaction time was 6 hours. The yield of the triazole compound was 97%.

(Example 8)
The compound catalyst C ₆₄ H ₁₆₄ N ₁₀ SiW ₁₀ O ₄₅ Cu ₂ (2 mol% based on chloride) obtained in Example 1 was taken in a test tube, and benzyl chloride (0.50 mmol), sodium azide (0. 52 mmol), acetonitrile / methanol (2 mL, v / v = 1/1) mixed solvent was added, and the mixture was stirred at 60 ° C. for 7 hours under air. To this was added phenylacetylene (1.0 mmol), and the mixture was further stirred for 24 hours under the same conditions. The desired triazole compound was obtained in 90% yield. The yield was determined by gas chromatography using naphthalene as an internal standard compound.

Example 9
The reaction was performed in the same manner as in Example 8 except that the substrate was changed from phenylacetylene to 4-methoxyphenylacetylene. The yield of the triazole compound was 99%.

(Example 10)
The reaction was performed in the same manner as in Example 8 except that the substrate was changed from benzyl chloride to 4-methylbenzyl chloride. The yield of the triazole compound was 94%.

(Example 11)
The reaction was performed in the same manner as in Example 8 except that the substrate was changed from benzyl chloride to octyl iodide. The yield of the triazole compound was 91%.

(Example 12)
The compound catalyst C ₆₄ H ₁₆₄ N ₁₀ SiW ₁₀ O ₄₅ Cu ₂ (0.1 mol% with respect to benzyl azide) obtained in Example 1 was taken in a flask, and benzyl azide (50 mmol), phenylacetylene (100 mmol), acetonitrile (150 mL) was added, and the mixture was stirred at 60 ° C. for 24 hours under air to obtain the desired triazole compound in 91% yield. The yield was determined by gas chromatography using naphthalene as an internal standard compound. The catalyst turnover frequency was 40 h ⁻¹ and the turnover number was 910. Compared with the system of Non-Patent Document 4, the turnover number is 9.1 times higher.

(Example 13)
The compound catalyst C ₆₄ H ₁₆₄ N ₁₀ SiW ₁₀ O ₄₅ Cu ₂ (5 mol% with respect to hydrogen peroxide) obtained in Example 1 was taken in a test tube, 35% hydrogen peroxide water (5.0 mmol), water (5 mL) was added and stirred at room temperature for 1 hour. After the reaction, the absence of hydrogen peroxide in the solution was confirmed by redox titration using an aqueous tetraammonium cerium sulfate solution.

The heteropolyoxometalate compound catalyst of the present invention has the above-described structure, and is a compound in which an element selected from Group 11 to 15 is introduced into a deficient site of a two-deficient heteropolyoxometalate anion. Alternatively, it can be suitably used as a catalyst for oxide decomposition reaction.

(Example 14)
The compound catalyst C ₆₄ H ₁₆₄ N ₁₀ SiW ₁₀ O ₄₅ Cu ₂ (4.4 mol% in terms of copper based on the substrate) obtained in Example 1 was taken in a flask, and phenylacetylene (1.0 mmol), benzonitrile ( 1.0 mL) was added, and the mixture was stirred at 100 ° C. for 3 hours under 1.0 atm of oxygen to obtain the desired homocoupling compound in 91% yield. The yield was determined by gas chromatography using naphthalene as an internal standard compound.

(Example 15)
The reaction was performed in the same manner as in Example 14 except that the substrate was changed from phenylacetylene to p-fluorophenylacetylene. The yield of the desired homocoupling compound was 96%.

(Example 16)
The reaction was performed in the same manner as in Example 14 except that the substrate was changed from phenylacetylene to p-methoxyphenylacetylene. The yield of the desired homocoupling compound was 97%.

(Example 17)
The reaction was performed in the same manner as in Example 14 except that the substrate was changed from phenylacetylene to 2-hydroxy-2-methyl-3-butyne and the reaction time was 2 hours. The yield of the desired homocoupling compound was 99%.

(Comparative Example 4)
The reaction was performed in the same manner as in Example 14 except that the catalyst was changed from C ₆₄ H ₁₆₄ N ₁₀ SiW ₁₀ O ₄₅ Cu ₂ to CuCl. The yield of the desired homocoupling compound was 2.0%.

(Example 18)
10 g (3.4 mmol) of K ₈ [γ-SiW ₁₀ O ₃₆ ] · 12H ₂ O was added to 100 mL of water. _Al a _{(NO 3) 3 · 9H 2} O 2.6g (6.9mmol) was added a solution prepared by dissolving in water 100mL here. Subsequently, the pH was adjusted to 3.8 with 1M aqueous potassium carbonate solution, and the mixture was stirred at room temperature for 15 minutes. 4.8 g (44 mmol) of tetramethylammonium chloride salt was added, stirred for 30 minutes, and suction filtered to collect the precipitate. The white precipitate was washed with water (100 mL) and diethyl ether (500 mL). Yield: 7.0 g. The obtained compound (6.0 g) was dissolved in 300 mL of water, insoluble matters were filtered, tetrabutylammonium bromide (20 g, 62 mmol) was added thereto, and then a 1M aqueous nitric acid solution was added to adjust the pH to 2. Adjusted to 6. The mixture was stirred at room temperature for 30 minutes, and [SiW ₁₀ O ₃₆ Al ₂ (OH) ₂ ] ^4- having tetrabutylammonium as a counter cation was obtained by filtration and drying. Yield: 6.1 g. The compound was added to acetonitrile (3.0 mL) as a catalyst (5.0 mol% in terms of aluminum with respect to the substrate), (+)-citronellal (1.0 mmol) was added, and 10 at 75 ° C. under argon of 1.0 atm. The mixture was stirred for a period of time to obtain (-)-isopulegol (yield: 81%), (+)-neo-isopulegol (yield: 9%), and (+)-neoiso-isopulegol (yield: 3%). The yield was determined by gas chromatography.

(Comparative Example 5)
[SiW ₁₀ O ₃₆ Al ₂ (OH) ₂ ] having tetrabutylammonium as a counter cation ^4-
The reaction was carried out in the same manner as in Example 18 except that the catalyst was changed from aluminum nitrate to aluminum nitrate. (-)-Isopulegol (yield: 15%), (+)-neo-isopulegol (yield: 13%), (+)-iso-isopulegol (yield: 0.3%), (+)-neoisogol -Isopulegol (yield: 1.7%) was obtained.

The catalyst for a specific reaction having a heteropolyoxometalate compound as an essential component for use in at least one reaction selected from the group consisting of acid-base reaction, oxide decomposition reaction and oxidation reaction of the present invention is a two-deficient heterogeneous compound. A new heteropolyoxometalate compound in which an element selected from the group 11 to 15 is introduced into the defect site of the polyoxometalate anion is essential, and it is used as a catalyst or bleach activator for producing intermediates for medical and agricultural chemicals. It is expected to be possible.

Polyoxometalate compound was replaced with Cu _C 64 is the molecular structure of the _{H 164 N 10 SiW 10 O 45} Cu 2. Anion structure site [γ-SiW ₁₀ O ₃₆ Cu ₂ in a heteropolyoxometalate compound catalyst in which two Cu atoms are introduced into a γ-Keggin type two-deficient structure site and Cu elements are cross-linked by two azide groups. N ₆ ]. Polyoxometalate compound was replaced with _{Al C 52 H 127 N 5 O} 43 is the molecular structure of _SiW 10 Al _2. Anion structure site [γ-SiW ₁₀ O ₃₆ Al _{2 of} heteropolyoxometalate compound catalyst in which two Al atoms are introduced into a γ-Keggin type two-deficient structure site and Al elements are bridged by two oxygen atoms (OH ₂ ) ₂ ].

Claims (3)

A catalyst for a specific reaction that is used in at least one reaction selected from the group consisting of an acid-base reaction, an oxide decomposition reaction, and an oxidation reaction, comprising a heteropolyoxometalate compound as an essential component;
The heteropolyoxometalate compound used as the catalyst has a two-deficient structure site in which the heteroatom is silicon, phosphorus or germanium and the polyatom is at least one element selected from the group consisting of molybdenum, tungsten and vanadium A heteropolyoxometalate having a heteropolyoxometalate structure in which at least one element (B) selected from Group 11 to 15 is introduced into a deficient structure site of the contained heteropolyoxometalate anion (A) Catalyst for specific reaction by rate compound. The heteropolyoxometalate compound according to claim 1, wherein the heteropolyoxometalate anion (A) is a γ-type Keggin-type heteropolyoxometalate anion. Specific reaction catalyst. The catalyst for a specific reaction using a heteropolyoxometalate compound according to claim 1 or 2, wherein the heteropolyoxometalate compound is cross-linked between elements (B).

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