JP2004331652A - Metal complex and use of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method capable of more industrially advantageously producing epoxides and a carbonyl compound than ever, by using easily available reagents, without using a solvent which has problems in an environmental aspect and an aspect of occupational safety and health. <P>SOLUTION: A metal complex is formed by contacting (A) at least one kind selected from a group comprising a tungsten compound composed of tungsten and a group IIIb, group IVb, group Vb or group VIb element, a molybdenum compound composed of molybdenum and a group IIIb, group IVb, group Vb or group VIb element, tungsten metal and molybdenum metal, (B) at least one kind selected from a group comprising tertiary amines, tertiary amine oxides, a nitrogen-containing aromatic compound and an N-oxide of a nitrogen-containing aromatic compound, (C) hydrogen peroxide and (D) phosphates with each other. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a novel metal complex and use of the metal complex.

  Epoxides are important compounds as various chemical products such as resins and synthetic intermediates thereof. For example, epoxides are prepared by converting olefins to peracids such as m-chloroperbenzoic acid and peracetic acid. A method of oxidizing using an organic peroxide such as tert-butyl hydroperoxide is known (for example, see Non-Patent Document 1). However, because it uses relatively expensive peracids and organic peroxides that require careful handling, and post-reaction post-treatment is cumbersome, the development of a production method that does not use peracids or organic peroxides Was desired.

  In addition, carbonyl compounds are also important compounds as various chemical products and synthetic intermediates thereof. Examples of the production method include primary alcohols and secondary alcohols, such as potassium permanganate and potassium dichromate. Is known (for example, see Non-Patent Document 2). However, since a highly toxic metal oxide is used, there are problems in handling and disposal of waste, and the like, which has not always been industrially satisfactory.

  On the other hand, hydrogen peroxide has attracted attention in recent years as a clean and excellent oxidizing agent that is inexpensive, easy to handle, and becomes harmless water after the reaction, and is used in the production of epoxides and carbonyl compounds. Various examples using hydrogen have been reported.

  As a method for producing epoxides by reacting olefins with hydrogen peroxide, for example, there is known an example of producing cyclooctene oxide from cyclooctene using a tungsten peroxo complex catalyst having dimethyloctadecylamine oxide as a ligand. (For example, see Patent Document 1). However, since chloroform, which has environmental and occupational safety and health problems, is used as a reaction solvent, a method for producing epoxides from olefins without using solvents having environmental and occupational health and safety problems. The development of was desired.

  As a method for producing a carbonyl compound by reacting a primary alcohol or a secondary alcohol with hydrogen peroxide, for example, a method using sodium tungstate / quaternary ammonium hydrogen sulfate as a catalyst (for example, see Patent Reference 2), a method using methyltrioctylammonium tetrakis (oxodiperoxotungsto) phosphoric acid as a catalyst (for example, see Non-Patent Document 3) and the like have been reported. However, all of these methods require the use of a phase transfer catalyst, and the development of a production method using easily available reagents has been desired.

Japanese Patent Publication No. 11-512335 JP-A-11-158107 Comprehensive Organic Synthesis, 7,357 (1991) Comprehensive Organic Synthesis, 7,252 (1991) J. Org. Chem., 56, 5924 (1991)

  Under such circumstances, the present inventors have found that epoxides and carbonyl compounds can be more industrially advantageously used without using solvents having environmental and occupational safety and health problems, and using readily available reagents. As a result of diligent studies on a method for producing a compound, a novel metal complex was found, and the present invention was reached.

That is, the present invention
(A) Tungsten compound comprising tungsten and a Group IIIb, IVb, Vb or VIb element, molybdenum compound comprising molybdenum and a Group IIIb, IVb, Vb or VIb element And at least one selected from the group consisting of tungsten metal and molybdenum metal;
(B) hydrogen peroxide;
(C) at least one selected from the group consisting of tertiary amines, tertiary amine oxides, nitrogen-containing aromatic compounds, and nitrogen-containing aromatic compound N-oxides;
(D) a metal complex obtained by contacting phosphoric acids;
And its uses.

  By using the novel metal complex of the present invention as a catalyst, epoxides can be obtained from olefins and hydrogen peroxide without using, as a reaction solvent, a solvent such as chloroform which is problematic in terms of environment and occupational safety and health. Therefore, it is industrially advantageous. Further, by selecting the reaction conditions, a carbonyl compound such as an aldehyde in which the carbon-carbon double bond of the olefin is oxidatively cleaved or a β-hydroxyhydroperoxide compound can be obtained. Useful for Further, the metal complex is industrially useful in that it exhibits good activity as a catalyst for producing a carbonyl compound by reacting a primary or secondary alcohol with hydrogen peroxide.

  Hereinafter, the present invention will be described in detail.

  First, (A) a tungsten compound composed of tungsten and a group IIIb, IVb, Vb or VIb element, or molybdenum composed of a group IIIb, IVb, Vb or VIb element At least one selected from the group consisting of molybdenum compounds, tungsten metals and molybdenum metals; (B) hydrogen peroxide; (C) tertiary amines, tertiary amine oxides, nitrogen-containing aromatic compounds and nitrogen-containing aromatics A metal complex (hereinafter, referred to as a metal complex) obtained by contacting at least one selected from the group consisting of compound N-oxides and (D) phosphoric acid will be described.

  The component (A) is composed of a tungsten compound composed of tungsten and a group IIIb, group IVb, group Vb or group VIb element, or molybdenum and a group IIIb, group IVb, group Vb or group VIb element. At least one selected from the group consisting of a molybdenum compound, tungsten metal, and molybdenum metal (hereinafter abbreviated as a metal or a compound). Examples of the tungsten compound comprising tungsten and a Group IIIb element include tungsten boride. However, as a tungsten compound composed of tungsten and a Group IVb element, for example, tungsten carbide, tungsten silicide, etc., as a tungsten compound composed of tungsten and a Group Vb element, for example, tungsten nitride, tungsten phosphide, etc. As a tungsten compound comprising tungsten and a Group VIb element, For example tungsten oxide, tungstic acid, disodium tungstate, include tungsten sulfide and the like.

  As a molybdenum compound composed of molybdenum and a Group IIIb element, for example, molybdenum boride and the like, and as a molybdenum compound composed of molybdenum and a Group IVb element, for example, molybdenum carbide, molybdenum silicide, and the like, molybdenum and Group Vb Examples of the molybdenum compound composed of an element include molybdenum nitride and molybdenum phosphide, and examples of the molybdenum compound composed of molybdenum and a Group VIb element include molybdenum oxide, molybdic acid, and molybdenum sulfide.

  Among these metals or compounds, tungsten metal, tungsten boride, disodium tungstate, and molybdenum metal are particularly preferred. These metals or compounds may be used alone or in combination of two or more. Further, it is preferable to use a metal or a compound having a small particle diameter in terms of facilitating preparation of a metal complex.

  The component (B) is hydrogen peroxide. Usually, an aqueous solution of hydrogen peroxide is used, but an organic solvent solution may be used. It is preferable to use aqueous hydrogen peroxide in that handling is easier. The concentration of hydrogen peroxide in the aqueous hydrogen peroxide solution or the organic solvent solution is not particularly limited, but is practically about 1 to 60% by weight in consideration of volumetric efficiency, safety and the like. Hydrogen peroxide solution is usually used as it is or after adjusting the concentration by diluting, concentrating, etc. as needed or as needed.An organic solvent solution of hydrogen peroxide is, for example, an organic solvent solution of hydrogen peroxide solution. Those prepared by means such as extraction with a solvent or distillation in the presence of an organic solvent are used.

  The amount of hydrogen peroxide to be used is usually at least 3 mol times, preferably at least 5 mol times with respect to the metal or compound, and there is no particular upper limit, but it can be determined as appropriate depending on economy, safety and the like.

  The component (C) is at least one selected from the group consisting of tertiary amines, tertiary amine oxides, nitrogen-containing aromatic compounds, and nitrogen-containing aromatic compound N-oxides (hereinafter abbreviated as amines). The tertiary amines include, for example, trimethylamine, triethylamine, tri (n-propyl) amine, triisopropylamine, tri (n-butyl) amine, triisobutylamine, tri (n-pentyl) amine, tri (n- Hexyl) amine, tri (n-heptyl) amine, tri (n-octyl) amine, tri (n-nonyl) amine, tri (n-decyl) amine, tri (n-dodecyl) amine, tri (n-tetradecyl) Amine, tri (n-hexadecyl) amine, tri (n-octadecyl) amine, dimethylethylamine, dimethyl (n- Ropyl) amine, dimethylisopropylamine, dimethyl (n-butyl) amine, dimethylisobutylamine, dimethyl (n-pentyl) amine, dimethyl (n-hexyl) amine, dimethyl (n-heptyl) amine, dimethyl (n-octyl) Amine, dimethyl (n-nonyl) amine, dimethyl (n-decyl) amine, dimethyl (n-undecyl) amine, dimethyl (n-dodecyl) amine, dimethyl (n-tetradecyl) amine, dimethyl (n-hexadecyl) amine, Dimethyl (n-octadecyl) amine,

Methyl diethylamine, di (n-propyl) methylamine, diisopropylmethylamine, di (n-butyl) methylamine, diisobutylmethylamine, di (n-pentyl) methylamine, di (n-hexyl) methylamine, di (n -Heptyl) methylamine, di (n-octyl) methylamine, di (n-nonyl) methylamine, di (n-decyl) methylamine, di (n-dodecyl) methylamine, di (n-tetradecyl) methylamine Di (n-hexadecyl) methylamine, di (n-octadecyl) methylamine, dimethylbenzylamine, di (n-butyl) benzylamine, di (n-hexyl) benzylamine, di (n-octyl) benzylamine, Di (n-decyl) benzylamine, di (n-dodecyl) benzylamine, di (n-o Tadecyl) benzylamine, N, N-dimethylaniline, N, N-di (n-butyl) aniline, N, N-di (n-hexyl) aniline, N, N-di (n-octyl) aniline, N-di (n-decyl) aniline, N, N-di (n-dodecyl) aniline, N- (n-hexadecyl) aniline, N- (n-octadecyl) aniline,

N-methylmorpholine, N- (n-butyl) morpholine, N- (n-hexyl) morpholine, N- (n-octyl) morpholine, N- (n-decyl) morpholine, N- (n-dodecyl) morpholine, N- (n-hexadecyl) morpholine, N- (n-octadecyl) morpholine, N-methylpyrrolidine, N- (n-butyl) pyrrolidine, N- (n-hexyl) pyrrolidine, N- (n-octyl) pyrrolidine, N- (n-decyl) pyrrolidine, N- (n-dodecyl) pyrrolidine, N- (n-hexadecyl) pyrrolidine, N- (n-octadecyl) pyrrolidine, N-methylpiperidine, N- (n-butyl) piperidine, N- (n-hexyl) piperidine, N- (n-octyl) piperidine, N- (n-decyl) piperidine, N- (n-dodecyl) Perijin, N-(n- hexadecyl) piperidine, N-(n- octadecyl) piperidine, 4-dimethylaminopyridine, 4- [di (n- hexyl) amino] pyridine.

  Examples of the tertiary amine oxides include, for example, trimethylamine N-oxide, triethylamine N-oxide, N-methylmorpholine N-oxide and the like in which the nitrogen atom constituting the amino group of the tertiary amine is oxidized. As such tertiary amine oxides, those prepared in a system by reacting a mixed solution of the above-mentioned components (A) and (B) with the corresponding tertiary amines may be used. Following formation of the secondary amine oxides, the desired complex can be obtained. In this case, the amount of hydrogen peroxide used may be appropriately adjusted according to the amount of tertiary amines used.

  Examples of the nitrogen-containing aromatic compound include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine and 4-methylpyridine in which at least one of carbon atoms constituting an aromatic ring is replaced by a nitrogen atom. Ethyl pyridine, 4- (n-butyl) pyridine, 4- (1-hexyl) pyridine, 4- (1-hexyl) pyridine, 4- (1-octyl) pyridine, 4- (1-nonyl) pyridine, 4- Pyridines such as (5-nonyl) pyridine, 4- (1-decyl) pyridine, picolinic acid, pyridine-2,6-dicarboxylic acid and the like can be mentioned. Examples of the nitrogen-containing aromatic compound N-oxide include the above-described nitrogen-containing aromatic compounds. Nitrogen atoms constituting an aromatic ring of an aromatic compound are oxidized, for example, pyridine N-oxides such as pyridine N-oxide and 2-methylpyridine N-oxide; And the like.

  The amount of the amines to be used is generally 0.8 to 3 moles, preferably 0.9 to 1.2 moles, relative to the metal or the compound.

  The component (D) is a phosphoric acid, such as phosphoric acid; for example, trisodium phosphate, tripotassium phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and the like. And alkaline earth metal phosphates such as calcium pyrophosphate and magnesium phosphate. Among such phosphoric acids, when a hydrate is present, a hydrate may be used. The amount of the phosphoric acid used is usually 0.2 mol times or more based on the metal or the compound, and there is no particular upper limit. However, too large an amount tends to be disadvantageous economically. It is 1 mole or less.

  The novel metal complex of the present invention is prepared by contacting and mixing the four components (A) to (D). The mixing order is not particularly limited, but it is preferable that after mixing the components (A) and (B), the component (D) and then the component (C) are added to the mixture.

  The preparation of the metal complex may be performed without a solvent or may be performed in the presence of a solvent. Examples of the solvent include ether solvents such as diethyl ether, methyl tert-butyl ether, and tetrahydrofuran; ester solvents such as ethyl acetate; tertiary alcohol solvents such as tert-butanol; nitrile solvents such as acetonitrile and propionitrile; Examples thereof include an organic solvent such as a halogenated hydrocarbon solvent such as dichloromethane; and a mixed solvent of the organic solvent and water.

  The preparation temperature for preparing the metal complex is usually in the range of about -10 to 100 ° C.

  By contacting and mixing the four components, a preparation solution containing the metal complex is obtained.For example, by adjusting the pH of the preparation solution as it is or the pH of the preparation solution to neutral to acidic, and then performing a concentration treatment, The metal complex can be taken out. In addition, water and / or an organic solvent insoluble in water are added to the prepared solution or the prepared solution after adjusting the pH, if necessary, the mixture is extracted, and the resulting organic layer is concentrated to obtain a metal complex. You can also. Depending on the conditions, a metal complex may be precipitated in the preparation liquid. In such a case, the metal complex may be taken out by filtering the preparation liquid. Examples of the organic solvent insoluble in water include aromatic hydrocarbon solvents such as toluene and xylene; ether solvents such as tert-butyl ether; halogenated hydrocarbon solvents such as dichloromethane; and the like.

  Subsequently, applications of the metal complex thus obtained will be described. Such metal complexes have oxidation catalytic activity, for example, the production of epoxides, β-hydroxyhydroperoxide compounds or carbonyl compounds by the reaction of olefins with hydrogen peroxide and primary or secondary alcohols Can be used as a catalyst for the production of a carbonyl compound by the reaction of hydrogen with hydrogen peroxide.

  First, a method for producing epoxides by reacting olefins with hydrogen peroxide using a metal complex as a catalyst will be described.

  The amount of the metal complex used is usually about 0.001 to 0.95 mole times, preferably about 0.005 to 0.1 mole times, as the metal, relative to the olefins.

  The olefins may be compounds having at least one olefinic carbon-carbon double bond in the molecule, and the two carbon atoms forming the double bond are, for example, an alkyl group in addition to a hydrogen atom. , An aryl group, an aralkyl group, a silyl group, a substituent such as a halogen atom.

  Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, and n-hexyl. Examples include a linear, branched or cyclic alkyl group such as an octyl group, an isooctyl group, an n-nonyl group, an n-decyl group, a cyclopentyl group and a cyclohexyl group. Such an alkyl group may have a substituent. Examples of the substituent include an alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group and an n-butoxy group; and a silyl group such as a trimethylsilyl group. Groups; for example, halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom; and the like. Examples of the alkyl group substituted with such a substituent include a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, a trimethylsilylmethyl group, a fluoromethyl group, a chloromethyl group, a bromomethyl group, and a trifluoromethyl group.

  Examples of the aryl group include a phenyl group and a naphthyl group. The aryl group may have a substituent. Examples of the substituent include the alkyl group; the alkoxy group; the silyl group; For example, the aforementioned halogen atom; for example, an acyl group such as an acetyl group and a propionyl group; Examples of the aryl group substituted with such a substituent include a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2-chlorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, and a 2-bromophenyl Group, 2-methylphenyl group, 4-methylphenyl group, 4-methoxyphenyl group, 4-acetylphenyl group and the like.

  Examples of the aralkyl group which may be substituted include those composed of the alkyl group which may be substituted and the aryl group which may be substituted, for example, a benzyl group, a phenylethyl group, and a 4-phenyl group. Examples thereof include a fluorobenzyl group, a 4-methoxybenzyl group, and a 2-chlorobenzyl group.

  Examples of the silyl group include a trialkylsilyl group such as a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, and a methyldiphenylsilyl group.Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Can be

  Further, substituents of carbon atoms constituting the olefinic carbon-carbon double bond may be combined to form a part of a ring structure. Examples of the ring structure include a cyclobutane ring, a cyclopentane ring, Examples include a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cyclododecane ring, and the like. Of course, such a ring structure may be substituted with the alkyl group, the alkoxy group, the silyl group, the halogen atom, or the like.

  Examples of such olefins include ethylene, propylene, 1-butene, 1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, -Undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-octadecene, 3,3-dimethyl-1-butene, vinylcyclopentane, vinylcyclohexane, allylcyclohexane, styrene, Monosubstituted olefins such as-(tert-butyl) styrene, allylbenzene, 4-methoxystyrene, safrole, eugenol, 3,4-dimethoxy-1-allylbenzene;

For example, disubstitution such as isobutylene, 2-methyl-1-butene, 2-methyl-1-hexene, 2-methyl-1-heptene, 2-methyl-1-undecene, methylenecyclohexane, α-methylstyrene, β-pinene, etc. Terminal olefins; for example, 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 3-octene, 4-octene, 2-nonene, 3-nonene, Disubstituted internal olefins such as -nonene, 5-decene, cyclopentene, cyclohexene, 4-methylcyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, β-methylstyrene, stilbene, isosafrole, isoeugenol, norbornene;

For example, 2-methyl-2-butene, 2-methyl-2-pentene, 2-methyl-2-hexene, 2-methyl-2-nonene, 2,5-dimethyl-2,4-hexadiene, 2-methyl-2 Tri-substituted olefins such as -heptene, 1-methylcyclopentene, 1-methylcyclohexene, 1- (tert-butyl) -cyclohexene, 1-isopropylcyclohexene, 2-carene, 3-carene and α-pinene; Tetra-substituted olefins such as -dimethyl-2-butene and 2,3,4-trimethyl-2-pentene;

  Among such olefins, there are those in which geometric isomers and optical isomers exist.In the present invention, a single geometric isomer or optical isomer may be used, or a mixture of geometric isomers or A mixture of optical isomers may be used.

  Hydrogen peroxide is usually used as an aqueous solution, but an organic solvent solution may be used. It is preferable to use an aqueous solution of hydrogen peroxide because handling is easier. The concentration of hydrogen peroxide in the aqueous hydrogen peroxide solution or organic solvent solution is not particularly limited, but is practically about 1 to 60% by weight in consideration of volumetric efficiency, safety and the like. The aqueous hydrogen peroxide solution is usually used as it is or after adjusting the concentration by diluting or concentrating as needed, and an organic solvent solution of hydrogen peroxide is, for example, an organic solvent solution of hydrogen peroxide. Those prepared by means such as extraction with a solvent or distillation in the presence of an organic solvent are used.

  The amount of hydrogen peroxide to be used is usually 0.8 mol times or more, preferably 1 mol times or more with respect to the olefins, and there is no particular upper limit, but too much tends to be economically disadvantageous. Therefore, practically, it is 5 mol times or less with respect to the olefins.

  The reaction between the olefins and hydrogen peroxide may be performed without a solvent, or may be performed in an aqueous solvent or an organic solvent. Examples of the organic solvent include ether solvents such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran, and diglyme; ester solvents such as ethyl acetate; tertiary alcohol solvents such as tert-butanol; and solvents such as acetonitrile and propionitrile. A nitrile solvent; for example, an aromatic hydrocarbon solvent such as toluene, benzene, or xylene; a saturated aliphatic hydrocarbon solvent such as pentane, hexane, cyclohexane, pentane, or petroleum ether; The amount of the solvent used is not particularly limited.

  This reaction is carried out by bringing a metal complex, an olefin, and hydrogen peroxide into contact with each other at a pH of 2 or more and 4 or less. Therefore, if necessary, the reaction may be performed by adjusting the pH of the reaction solution to the above range using an acid or an alkali.

  The reaction temperature is usually about −10 to 130 ° C. and is usually carried out under normal pressure, but may be carried out under reduced pressure or increased pressure.

  Epoxides are generated with the progress of the reaction, and the progress of the reaction can be confirmed by ordinary analytical means such as gas chromatography, high performance liquid chromatography, thin layer chromatography, NMR and IR.

  After the completion of the reaction, the reaction solution is left as it is or, if necessary, the remaining hydrogen peroxide is decomposed with a reducing agent such as sodium sulfite, and then subjected to a concentration treatment, a crystallization treatment, and the like to take out the target epoxide. be able to. Further, epoxides can also be taken out by adding water and / or an organic solvent insoluble in water to the reaction solution, if necessary, performing an extraction treatment, and concentrating the obtained organic layer. The removed epoxides may be further purified by a usual purification method such as distillation, column chromatography, recrystallization and the like.

  Epoxides thus obtained include, for example, ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxypentane, 4,4-dimethyl-1,2-epoxypentane, 1,2-epoxyhexane, 2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxidedodecane, 1,2-epoxytridecane, 1, 2-epoxytetradecane, 1,2-epoxypentadecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, 3,3-dimethyl-1,2-epoxybutane, cyclopentylethylene oxide, cyclohexylethylene oxide, 3-cyclohexyl-1 , 2-epoxypropane, styrene Sid, 4- (tert-butyl) styrene oxide, 3-phenyl-1,2-epoxypropane, 4-methoxystyrene oxide, safrole oxide, 3- (4-hydroxy-3-methoxyphenyl) -1,2-epoxy Propane, 3- (3,4-dimethoxyphenyl) -1,2-epoxypropane, 2,3-epoxybutane, 2-methyl-1,2-epoxypropane, 2-methyl-1,2-epoxybutane, 2 2,3-epoxypentane, 2,3-epoxyhexane, 2-methyl-1,2-epoxyhexane, 3,4-epoxyhexane, 2,3-epoxyheptane, 3,4-epoxyheptane, 2,3-epoxy Octane, 3,4-epoxyoctane, 4,5-epoxyoctane, 2,3-epoxynonane,

2-methyl-1,2-epoxynonane, 3,4-epoxynonane, 4,5-epoxynonane, 5,6-epoxydecane, 2-methyl-1,2-epoxyundecane, cyclopentene oxide, cyclohexene oxide, -Methylcyclohexene oxide, cycloheptene oxide, cyclooctene oxide, cyclodecene oxide, cyclododecene oxide, β-methylstyrene oxide, stilbene oxide, isosafurol oxide, 1- (4-hydroxy-3-methoxyphenyl) -1 , 2-epoxypropane, β-pinene oxide, norbornene oxide, 2-methyl-2,3-epoxybutane, 2-methyl-2,3-epoxypentane, 2-methyl-2,3-epoxyhexane, 2,5 -Dimethyl-2,3-epoxyhex-4- Ene, 2-methyl-2,3-epoxyheptane, 1-methyl-1,2-epoxycyclopentane, 1-methyl-1,2-epoxycyclohexane, 1- (tert-butyl) -1,2-epoxycyclohexane , 1-isopropyl-1,2-epoxycyclohexane, 2-calene oxide, 3-calene oxide, α-pinene oxide, 2,3-dimethyl-2,3-epoxybutane, 2,3,4-trimethyl-2, 3-epoxypentane and the like.

  Next, a method for producing a β-hydroxyhydroperoxide compound or a carbonyl compound by reacting an olefin with hydrogen peroxide using a metal complex as a catalyst will be described.

  Examples of the olefins include the same ones as described above. When a monosubstituted olefin is used as the olefin, a β-hydroxyhydroperoxide compound, an aldehyde, a carboxylic acid, formaldehyde, and formic acid are obtained. When, for example, 1-hexene is used as the monosubstituted olefin, 2-hydroperoxy-1-hydroxyhexane and / or 1-hydroperoxy-2-hydroxyhexane, pentanal, and pentanoic acid are obtained.

  When disubstituted terminal olefins are used as olefins, β-hydroxyhydroperoxide compounds, ketones, formaldehyde, and formic acid are obtained. As the disubstituted terminal olefins, for example, when α-methylstyrene is used, 2-hydroperoxy-2-phenyl-1-propanol, acetophenone, formaldehyde, formic acid can be obtained.For example, when methylenecyclohexane is used, 1-Hydroperoxy-1- (hydroxymethyl) cyclohexane, cyclohexanone, formaldehyde and formic acid are obtained.

  When disubstituted internal olefins are used as the olefins, β-hydroxyhydroperoxide compounds, aldehydes, and carboxylic acids are obtained. When, for example, cyclopentene is used as the disubstituted internal olefin, 1-hydroperoxy-2-hydroxycyclopentane, glutaraldehyde, glutaric acid can be obtained. For example, when 2-hexene is used, 2-hydrocene is used. Peroxy-3-hydroxyhexane and / or 3-hydroperoxy-2-hydroxyhexane, butanal, butanoic acid, acetaldehyde, acetic acid are obtained.

  When trisubstituted olefins are used as olefins, β-hydroxy hydroperoxide compounds, ketones, aldehydes, and carboxylic acids are obtained. When 2-methyl-2-pentene is used as the trisubstituted olefin, for example, 2-methyl-2-hydroperoxy-3-hydroxypentane and / or 2-methyl-2-hydroxy-3-hydroperoxypentane , Acetone, propionaldehyde and propionic acid are obtained. When tetrasubstituted olefins are used as olefins, β-hydroxyhydroperoxide compounds and ketones are obtained. When, for example, 2,3-dimethyl-2-butene is used as the tetra-substituted olefin, 2,3-dimethyl-2-hydroperoxy-3-hydroxybutane and acetone are obtained.

  As with the above, an aqueous solution is usually used for hydrogen peroxide as well, but an organic solvent solution may be used. The amount of hydrogen peroxide used may be appropriately set depending on the target compound. The amount of hydrogen peroxide used for the purpose of ketones, β-hydroxyhydroperoxide compounds and aldehydes is usually at least 1 mole times the amount of olefins, and the amount used for the purpose of carboxylic acids. Is usually 2 mole times or more. Although there is no particular upper limit on the amount of the olefin, it is practically not more than 10 moles with respect to the olefin in consideration of economical aspects.

  The amount of the metal complex used is usually about 0.001 to 0.95 mole times, preferably about 0.005 to 0.1 mole times, as the metal, relative to the olefins.

  The reaction may be performed without a solvent, or may be performed in an aqueous solvent or an organic solvent. Examples of the organic solvent include the same ones as those exemplified as the solvent used in the production of epoxides.

  This reaction is carried out by bringing a metal complex, an olefin, and hydrogen peroxide into contact with each other in a pH range of pH 0 or more and less than 2. Therefore, if necessary, the reaction may be carried out by adjusting the pH of the reaction solution to the above range using an acid or an alkali.

  By performing the reaction in the above pH range, β-hydroxyhydroperoxide compounds, aldehydes, ketones, carbonyl compounds such as carboxylic acids can be obtained, and depending on the structure of the olefins and the reaction conditions, the type of product obtained is And the production ratio are different, so that the reaction conditions may be appropriately selected according to the target product.

  For example, when a β-hydroxyhydroperoxide compound is intended, the reaction is preferably performed in an organic solvent, and the reaction is also preferably performed under anhydrous conditions. Examples of a method for carrying out the reaction under anhydrous conditions include a method in which a dehydrating agent coexists in the reaction system. The dehydrating agent is not particularly limited as long as it is generally used for the purpose of removing water in the presence of an organic solvent. For example, anhydrous magnesium sulfate, anhydrous sodium sulfate, boric anhydride, polyphosphoric acid, phosphorus pentoxide And the like, and the amount of use is sufficient as long as the amount is such that water existing in the reaction system can be removed.

  If the reaction temperature is too low, the reaction hardly proceeds, and if the reaction temperature is too high, a side reaction such as polymerization of the raw material olefins may proceed. Therefore, a practical reaction temperature is 0 to 200 ° C. Range. When the reaction temperature is low, β-hydroxyhydroperoxide compounds and aldehydes are easily generated, and as the reaction temperature is increased, carboxylic acids and ketones are easily generated. Therefore, when the purpose is a β-hydroxyhydroperoxide compound or an aldehyde, the reaction temperature is preferably lower than 65 ° C., and when the purpose is a ketone or a carboxylic acid, the reaction temperature is 65 ° C. or higher. It is preferable that

  A carbonyl compound is generated with the progress of the reaction, and the progress of the reaction can be confirmed by ordinary analysis means such as gas chromatography in the same manner as described above.

  After completion of the reaction, the carbonyl compound can be taken out by leaving the reaction solution as it is or, if necessary, decomposing the remaining hydrogen peroxide with a reducing agent such as sodium sulfite, and then performing a concentration treatment, a crystallization treatment, and the like. . In addition, a carbonyl compound can also be obtained by adding water and / or an organic solvent insoluble in water to the reaction solution, if necessary, performing an extraction treatment, and concentrating the obtained organic layer. The removed carbonyl compound may be further purified by a usual purification method such as distillation, column chromatography, recrystallization and the like.

  Examples of the β-hydroxyhydroperoxide compound thus obtained include, for example, 1-hydroxy-2-hydroperoxyhexane, 2-hydroxy-1-hydroperoxyhexane, 1-hydroxy-2-hydroperoxyheptane, 2-hydroxy-1-hydroxy Peroxyheptane, 1-hydroxy-2-hydroperoxyoctane, 2-hydroxy-1-hydroperoxyoctane, 1-hydroxy-2-hydroperoxidedecane, 2-hydroxy-1-hydroperoxidedecane, 1-hydroxy-2-phenyl -2-hydroperoxyethane, 1-hydroxy-2- (4-methylphenyl) -2-hydroperoxyethane, 1-hydroxy-2-hydroperoxy-3-phenylpropane, 2-hydroxy-1-hydroperoxy- - phenyl propane, 1-hydroxy-2-hydroperoxy-3- (4-methoxyphenyl) propane, 2-hydroxy-1-hydroperoxy-3- (4-methoxyphenyl) propane.

  Examples of the carbonyl compound thus obtained include, for example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, pentylaldehyde, hexylaldehyde, heptylaldehyde, decylaldehyde, undecanylaldehyde, benzaldehyde, 5-oxohexylaldehyde, 2-methyl-5- Oxohexylaldehyde, 4-methyl-5-oxohexylaldehyde, 3-methyl-5-oxohexylaldehyde, 2,4-dimethyl-5-oxohexylaldehyde, 3,4-dimethyl-5-oxohexylaldehyde, 2, 3-dimethyl-5-oxohexylaldehyde, 2,3,4-trimethyl-5-oxohexylaldehyde, 6-oxoheptylaldehyde, 2-methyl-6-oxoheptylaldehyde , 4-methyl-6-oxoheptylaldehyde, 2,4-dimethyl-6-oxoheptylaldehyde, 2,3-dimethyl-6-oxoheptylaldehyde, 3,4-dimethyl-6-oxoheptylaldehyde, 2,3 , 4-Trimethyl-6-oxoheptylaldehyde, glutaraldehyde, adipaldehyde, heptanedialdehyde, octanedialdehyde, 2-chloroglutaraldehyde, 2-methylglutaraldehyde, 3-methylglutaraldehyde, 2,3-dimethylglutar Aldehydes such as aldehydes;

For example, acetone, methyl ethyl ketone, diethyl ketone, 2-pentanone, 4,4-dimethylpentan-2-one, diethyl ketone, methyl propyl ketone, acetophenone, cyclobutanone, cyclopentanone, cyclohexanone, benzophenone, nopinone, 1,3,3- Trimethylindolinone, 2,6-heptanedione, 2,7-octanedione, 1,6-cyclodecanedione, 4-acetoxyacetophenone, 2-methoxy-6- (propan-2-one) acetophenone, 2-ethoxycarbonyl Ketones such as -3-methylcyclopentanone and benzophenone;

For example, formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, benzoic acid, 4-methylbenzoic acid, phenylacetic acid, (4-methoxyphenyl) acetic acid, chloroacetic acid, ethoxyacetic acid, benzyloxyacetic acid, 3,3-dimethyl-2-methoxycarbonylcyclopropanecarboxylic acid, 3,3-dimethyl-2-ethoxycarbonylcyclopropanecarboxylic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, 2-methylglutaric acid, 3- Methylglutaric acid, 3-chloroglutaric acid, 2,3-dimethylglutaric acid, 2,4-dimethylglutaric acid, 2-methyladipic acid, 3-methyladipic acid, 2,3-dimethyladipic acid, 2,4- Dimethyl adipic acid, 3,4-dimethyl adipic acid, 2,3,4-trimethyl glutaric acid, Pentane-1,3-dicarboxylic acid, biphenyl-2,2′-dicarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, 1- (carboxymethyl) cyclopentane-2,3,4-tricarboxylic acid And carboxylic acids such as homophthalic acid and cyclopentane-1,2,3,4-tetracarboxylic acid.

  Next, a method for producing a carbonyl compound by reacting a primary or secondary alcohol with hydrogen peroxide using a metal complex as a catalyst will be described.

  The primary or secondary alcohol may be any compound having at least one hydroxyl group that is oxidized in its molecule. Here, the hydroxyl group to be oxidized refers to a group in which the bonding carbon atom is bonded to at least one hydrogen atom. Examples of the substituent other than the hydrogen atom bonded to the bonding carbon atom of the hydroxyl group include an alkyl group, an aryl group, an aralkyl group, and a silyl group.

  Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, and n-hexyl. Examples include a linear, branched or cyclic alkyl group such as an octyl group, an isooctyl group, an n-nonyl group, an n-decyl group, a cyclopentyl group and a cyclohexyl group. Such an alkyl group may have a substituent. Examples of the substituent include an alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group and an n-butoxy group; and a silyl group such as a trimethylsilyl group. Groups; for example, halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom; and the like. Examples of the alkyl group substituted with such a substituent include a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, a trimethylsilylmethyl group, a fluoromethyl group, a chloromethyl group, a bromomethyl group, and a trifluoromethyl group.

  Examples of the aryl group include a phenyl group and a naphthyl group. The aryl group may have a substituent. Examples of the substituent include the alkyl group; the alkoxy group; the silyl group; For example, the aforementioned halogen atom; for example, an acyl group such as an acetyl group and a propionyl group; Examples of the aryl group substituted with such a substituent include a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2-chlorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, and a 2-bromophenyl Group, 2-methylphenyl group, 4-methylphenyl group, 4-methoxyphenyl group, 4-acetylphenyl group and the like.

  Examples of the aralkyl group which may be substituted include those composed of the alkyl group which may be substituted and the aryl group which may be substituted, for example, a benzyl group, a phenylethyl group, and a 4-phenyl group. Examples thereof include a fluorobenzyl group, a 4-methoxybenzyl group, and a 2-chlorobenzyl group.

  Examples of the silyl group include a trialkylsilyl group such as a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, and a methyldiphenylsilyl group.

  Examples of such primary alcohols include ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, and 2-methyl-1. -Hexanol, 4-methyl-1-hexanol, 2,2-dimethyl-1-propanol, 1,6-hexanediol, benzyl alcohol, 2-fluorobenzyl alcohol, 3-fluorobenzyl alcohol, 4-fluorobenzyl alcohol, -Chlorobenzyl alcohol, 3-chlorobenzyl alcohol, 4-chlorobenzyl alcohol, 2-bromobenzyl alcohol, 3-bromobenzyl alcohol, 4-bromobenzyl alcohol, 2-methylbenzyl alcohol, 3-methylbenzyl alcohol 4-methylbenzyl alcohol, 4-methoxybenzyl alcohol, 2-phenylethanol, 2- (2-fluorophenyl) ethanol, 2- (3-fluorophenyl) ethanol, 2- (4-fluorophenyl) ethanol, 2- ( 2-chlorophenyl) ethanol, 2- (2-bromophenyl) ethanol, 2- (4-methoxyphenyl) ethanol, 2- (4-acetylphenyl) ethanol, and the like,

Examples of the secondary alcohols include 2-propanol, 2-butanol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 2-heptanol, 3-heptanol, 4-heptanol, and 2-octanol. , 3-octanol, 4-octanol, 2-nonanol, 3-nonanol, 4-nonanol, 5-nonanol, 2-decanol, 3-decanol, 4-decanol, 5-decanol, cyclobutanol, cyclopentanol, cyclohexanol , Cycloheptanol, cyclooctanol, cyclododecanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, 2-tert-butylcyclohexanol, 3-tert-butylcyclohexanol, tert-butylcyclohexanol, 1-phenylethanol, 1- (2-fluorophenyl) ethanol, 1- (3-fluorophenyl) ethanol, 1- (4-fluorophenyl) ethanol, 1- (2-chlorophenyl) ethanol, Examples thereof include 1- (2-bromophenyl) ethanol, 1- (4-methoxyphenyl) ethanol, 1- (4-acetylphenyl) ethanol, α-trimethylsilylbenzyl alcohol and the like.

  When primary alcohols are used, aldehydes and / or carboxylic acids are obtained as products. For example, when 1-butanol is used as a primary alcohol, butyraldehyde and / or butanoic acid are obtained.

  When secondary alcohols are used, ketones are obtained as products. For example, when 1-phenylethanol is used as the secondary alcohol, acetophenone is obtained.

  Hydrogen peroxide is also usually used in the same manner as described above, but an aqueous solution may be used, and the amount of the organic solvent used may vary depending on the primary or secondary alcohols and the carbonyl compound to be used. It should just be set as follows.

  When primary alcohols are used for aldehydes, the amount of hydrogen peroxide is usually 0.9 to 1.5 moles per mole of the primary alcohols used. When primary alcohols are used and carboxylic acids are intended, hydrogen peroxide is usually at least 1.5 mole times the primary alcohols used, and the upper limit of the amount used is particularly high. However, considering the economical aspect, practically, it is about 10 mole times or less of primary alcohols.

  When secondary alcohols are used and ketones are intended, hydrogen peroxide is usually 0.9 mole times or more of the secondary alcohols used, and the upper limit of the amount used is Although there is no particular limitation, considering the economical aspect, practically, it is about 10 mol times or less of the secondary alcohols.

  The amount of the metal complex used is usually about 0.001 to 0.95 mole times, and preferably about 0.005 to 0.1 mole times, relative to the primary or secondary alcohols as a metal.

  The reaction may be performed without a solvent, or may be performed in an aqueous solvent or an organic solvent. Examples of the organic solvent include the same ones as those exemplified as the solvent used in the production of epoxides.

  This reaction is carried out by bringing a metal complex, a primary or secondary alcohol into contact with hydrogen peroxide, and the mixing order is not particularly limited.

  If the reaction temperature is too low, the reaction hardly proceeds, and if the reaction temperature is too high, there is a possibility that side reactions such as dehydration of the primary or secondary alcohols as raw materials may proceed, so that the reaction is practical. The reaction temperature is in the range of about 0 to 200 ° C.

  A carbonyl compound is generated with the progress of the reaction, and the progress of the reaction can be confirmed by ordinary analysis means such as gas chromatography in the same manner as described above.

  After completion of the reaction, the carbonyl compound can be taken out by leaving the reaction solution as it is or, if necessary, decomposing the remaining hydrogen peroxide with a reducing agent such as sodium sulfite, and then performing a concentration treatment, a crystallization treatment, and the like. . In addition, a carbonyl compound can also be obtained by adding water and / or an organic solvent insoluble in water to the reaction solution, if necessary, performing an extraction treatment, and concentrating the obtained organic layer. The removed carbonyl compound may be further purified by a usual purification method such as distillation, column chromatography, recrystallization and the like.

  Examples of the carbonyl compound thus obtained include, for example, acetaldehyde, propionaldehyde, butyraldehyde, pentylaldehyde, hexylaldehyde, heptylaldehyde, octylaldehyde, nonylaldehyde, decylaldehyde, 2-methyl-1-hexylaldehyde, 4-methyl-1- Hexylaldehyde, 2,2-dimethyl-1-propionaldehyde, adipaldehyde, benzaldehyde, 2-fluorobenzaldehyde, 3-fluorobenzaldehyde, 4-fluorobenzaldehyde, 2-chlorobenzaldehyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde, 2-bromobenzaldehyde, 3-bromobenzaldehyde, 4-bromobenzaldehyde, 2-methylbenzaldehyde, Rubenzaldehyde, 4-methylbenzaldehyde, 4-methoxybenzaldehyde, 2-phenylacetaldehyde, 2- (2-fluorophenyl) acetaldehyde, 2- (3-fluorophenyl) acetaldehyde, 2- (4-fluorophenyl) acetaldehyde, 2- Aldehydes such as (2-chlorophenyl) acetaldehyde, 2- (2-bromophenyl) acetaldehyde, 2- (4-methoxyphenyl) acetaldehyde, and 2- (4-acetylphenyl) acetaldehyde;

For example, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, 2-methyl-1-hexanoic acid, 4-methyl-1-hexanoic acid, 2,2-dimethyl -1-propionic acid, adipic acid, benzoic acid, 2-fluorobenzoic acid, 3-fluorobenzoic acid, 4-fluorobenzoic acid, 2-chlorobenzoic acid, 3-chlorobenzoic acid, 4-chlorobenzoic acid, 2- Bromobenzoic acid, 3-bromobenzoic acid, 4-bromobenzoic acid, 2-methylbenzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, 4-methoxybenzoic acid, phenylacetic acid, (2-fluorophenyl) acetic acid , (3-fluorophenyl) acetic acid, (4-fluorophenyl) acetic acid, (2-chlorophenyl) acetic acid, (2-bromophenyl) acetic acid, (4-methoxyphenyl) acetic acid ) Acetic acid, (4-acetylphenyl) carboxylic acids such as acetic acid;

For example, acetone, 2-butanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 4-octanone, 2-nonanone , 3-nonanone, 4-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-decanone, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclododecanone, 2 -Methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 2-tert-butylcyclohexanone, 3-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, acetophenone, o-fluoroacetophenone, m-fluoroacetone Phenone, p- fluoro acetophenone, o- chloroacetophenone, o- bromoacetophenone, o- methoxyacetophenone, p- methoxyacetophenone, p- acetyl acetophenone, ketones such as benzoyl trimethylsilane; and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, gas chromatography was used for the analysis.

Example 1
At room temperature, 0.92 g of tungsten metal powder and 3.96 g of a 30% by weight aqueous hydrogen peroxide solution were charged into a 50 mL eggplant-shaped flask equipped with a reflux condenser, stirred and maintained for 15 minutes to obtain a colorless and transparent homogeneous solution. 0.49 g of phosphoric acid was added to the solution, and the mixture was stirred and maintained at room temperature for 2 hours. Then, 2.92 g of tri (n-dodecyl) amine and 8 mL of dichloromethane were added, and the mixture was stirred and maintained at room temperature for 4 hours. Thereafter, a liquid separation treatment was performed, and the obtained organic layer was concentrated to obtain 4.02 g of a tungsten complex as a yellow waxy solid. Yield 97% (based on tungsten metal).

¹ H-NMR (solvent: CDCl ₃ , TMS standard, unit: ppm)
δ 0.88 (t, 9H, J = 7.0 Hz), 1.25-1.30 (m, 54H),
1.73 (br, 6H), 3.59 (br, 6H)
¹³ C-NMR (solvent: CDCl ₃ , TMS standard, unit: ppm)
δ 14.1, 2.7, 22.9, 26.1, 99.4, 29.7, 31.9, 63.6
IR (neat, unit: cm ^-1 )
2956, 2921, 281, 2753, 1546, 1466, 1403, 1378, 1315, 1262, 1072, 1035, 941, 888, 848, 767, 751, 721, 678, 644
Elemental analysis: C: 54.4, H: 9.8, N: 1.6, P: 0.95

Example 2
At room temperature, 0.88 g of tungsten metal powder, 4 g of water, and 3.96 g of 30% by weight hydrogen peroxide solution were charged into a 50 mL eggplant-shaped flask equipped with a reflux condenser, stirred and maintained for 15 minutes, and a colorless transparent homogeneous solution was obtained. Obtained. 0.56 g of phosphoric acid was added to the solution, stirred and maintained at room temperature for 2 hours, 2.88 g of tri (n-dodecyl) amine N-oxide and 10 mL of dichloromethane were added, and the mixture was stirred and maintained at room temperature for 4 hours. Thereafter, a liquid separation treatment was performed, and the obtained organic layer was concentrated to obtain 4.00 g of a tungsten complex as a yellow waxy solid. Yield 100% (based on tungsten metal).

¹ H-NMR (solvent: CDCl3, based on TMS, unit: ppm)
δ 0.88 (t, 9H, J = 7.0 Hz), 1.25-1.30 (m, 54H),
1.73 (br, 6H), 3.59 (br, 6H)
¹³ C-NMR (solvent: CDCl ₃ , TMS standard, unit: ppm)
δ 14.1, 2.7, 22.9, 26.1, 99.4, 29.7, 31.9, 63.6
IR (neat, unit: cm ^-1 )
2956,2921,2871,2853,1466,1378,1078,1036,944,888,848,772,721,678
Elemental analysis: C: 54.4, H: 9.7, N: 1.7, P: 1.41

Example 3
At room temperature, 0.92 g of tungsten metal powder, 4 g of water and 3.96 g of 30% by weight hydrogen peroxide solution were charged into a 50 mL eggplant-shaped flask equipped with a reflux condenser, stirred and held for 15 minutes, and a colorless and transparent homogeneous solution was obtained. Obtained. 0.58 g of phosphoric acid was added to the solution, stirred and maintained at room temperature for 2 hours, and 1.77 g of tri (n-octyl) amine and 10 mL of diethyl ether were added, and the mixture was stirred and maintained at room temperature for 4 hours. Thereafter, a liquid separation treatment was performed, and the obtained organic layer was concentrated to obtain 3.20 g of a tungsten complex as a yellow waxy solid. Yield 99% (based on tungsten metal).

¹ H-NMR (solvent: CDCl ₃ , TMS standard, unit: ppm)
δ 0.89 (t, 9H, J = 7.0 Hz), 1.2-1.5 (m, 30H),
1.72 (br, 6H), 3.10 (br, 2H), 3.57 (br, 4H),
6.0 (br, 2H)
¹³ C-NMR (solvent: CDCl ₃ , TMS standard, unit: ppm)
δ 14.0, 22.6, 23.2, 26.0, 26.6, 28.9, 29.1, 29.2, 31.7, 52.8, 63.9
IR (neat, unit: cm ^-1 )
2956, 2926, 2856, 1458, 1376, 1086, 1034, 949,
891,845,723,677,647
Elemental analysis: C: 42.3, H: 7.9, N: 2.0, P: 1.82

Example 4
At room temperature, 0.66 g of the tungsten complex obtained in Example 1, 9.6 g of a 30% by weight hydrogen peroxide solution, 0.1 g of a 20% by weight aqueous sodium hydroxide solution were placed in a 100 mL Schlenk tube equipped with a reflux condenser at room temperature. A toluene solution (using 4 mL of toluene) containing 2.2 g of 1-octene was charged, and stirred and reacted at an internal temperature of 90 ° C. for 6 hours. The pH during the reaction was about 3.5. After completion of the reaction, the mixture was cooled to room temperature and subjected to liquid separation treatment to obtain an organic layer containing 1,2-epoxyoctane. The yield of 1,2-epoxyoctane was 84% (based on 1-octene).

Example 5
At room temperature, a toluene solution containing 0.66 g of the tungsten complex obtained in Example 1, 9.6 g of a 30% by weight aqueous hydrogen peroxide solution, and 2.2 g of 1-octene was placed in a 100 mL Schlenk tube equipped with a reflux condenser. (4 mL of toluene was used), and the mixture was stirred and reacted at an internal temperature of 90 ° C. for 6 hours. The pH during the reaction was about 1.7. After completion of the reaction, the mixture was cooled to room temperature and subjected to liquid separation treatment to obtain an organic layer containing heptanoic acid. The yield of heptanoic acid was 84% (based on 1-octene).

Example 6
A 50 mL flask equipped with a reflux condenser was charged with 66 mg of the tungsten complex obtained in Example 2, 5.7 g of a 30% by weight aqueous hydrogen peroxide solution, and 980 mg of 1-heptene at room temperature for 6 hours at an internal temperature of 90 ° C. The mixture was stirred and reacted. After completion of the reaction, the mixture was cooled to room temperature, 10 ml of diethyl ether was added, and the mixture was subjected to liquid separation treatment to obtain an organic layer containing hexanoic acid. The yield of hexanoic acid was 60% (based on 1-heptene). 1-Heptene was recovered by 35%.

Example 7
A 50 mL flask equipped with a reflux condenser was charged at room temperature with 66 mg of the tungsten complex obtained in Example 2 above, 3.4 g of 30% by weight aqueous hydrogen peroxide, and 1.08 g of benzyl alcohol. The mixture was stirred and reacted for an hour. After completion of the reaction, the mixture was cooled to room temperature, 10 ml of toluene was added, and the mixture was subjected to liquid separation treatment to obtain an organic layer containing benzoic acid. The yield of benzoic acid was 94% (based on benzyl alcohol).

Example 8
A 50 mL flask equipped with a reflux condenser was charged with 70 mg of the tungsten complex obtained in Example 2, 1.37 g of a 30% by weight aqueous hydrogen peroxide solution, and 1.31 g of benzyl alcohol at room temperature. The mixture was stirred and reacted for an hour. After the completion of the reaction, the mixture was cooled to room temperature, 10 ml of toluene was added, and the mixture was subjected to liquid separation treatment to obtain an organic layer containing benzaldehyde. The yield of benzaldehyde was 89% (based on benzyl alcohol). Benzoic acid was by-produced by 10%.

Example 9
A 50 mL flask equipped with a reflux condenser was charged at room temperature with 60 mg of the tungsten complex obtained in Example 3 above, 3.4 g of a 30% by weight aqueous hydrogen peroxide solution, and 1.02 g of 1-hexanol. The mixture was stirred and reacted for 6 hours. After completion of the reaction, the mixture was cooled to room temperature, 10 ml of diethyl ether was added, and the mixture was subjected to liquid separation treatment to obtain an organic layer containing hexanoic acid. The yield of hexanoic acid was 89% (based on 1-hexanol).

Example 10
A 50 mL flask equipped with a reflux condenser was charged at room temperature with 60 mg of the tungsten complex obtained in Example 3 above, 3.4 g of a 30% by weight aqueous hydrogen peroxide solution and 1.22 g of 1-phenethyl alcohol, and an internal temperature of 90 ° C. And reacted for 6 hours. After completion of the reaction, the mixture was cooled to room temperature, 10 ml of toluene was added, and the mixture was subjected to liquid separation treatment to obtain an organic layer containing acetophenone. The yield of acetophenone was 99% (based on 1-phenethyl alcohol).

Example 11
In a 50 mL eggplant-shaped flask equipped with a reflux condenser, 1.58 g of disodium tungstate dihydrate, 4 g of water and 3.96 g of 30% by weight aqueous hydrogen peroxide were charged at room temperature, and stirred and held for 15 minutes. Thus, a pale yellow transparent homogeneous solution was obtained. To this solution, 1.66 g of phosphoric acid was added, and the mixture was stirred and maintained at room temperature for 2 hours. Then, 1.77 g of tri (n-octyl) amine and 10 mL of diethyl ether were added, and the mixture was stirred and maintained at room temperature for 4 hours. Thereafter, a liquid separation treatment was performed, and the obtained organic layer was concentrated, thereby obtaining 2.8 g of a tungsten complex as a yellow waxy solid. Yield 88% (based on tungsten).

¹ H-NMR (solvent: CDCl ₃ , TMS standard, unit: ppm)
δ 0.89 (t, 9H, J = 7.0 Hz), 1.2-1.5 (m, 30H),
1.73 (br, 6H), 3.10 (br, 2H), 3.55 (br, 4H),
6.0 (br, 2H)
¹³ C-NMR (solvent: CDCl ₃ , TMS standard, unit: ppm)
δ 14.0, 22.6, 23.2, 26.0, 26.6, 28.9, 29.1, 29.2, 31.7, 52.6, 63.8
Elemental analysis values: C: 45.6, H: 8.1, N: 2.2, P: 1.73

Example 12
A 50 mL flask equipped with a reflux condenser was charged at room temperature with 60 mg of the tungsten complex obtained in Example 11 above, 3.4 g of a 30% by weight aqueous hydrogen peroxide solution, and 1.08 g of benzyl alcohol. The mixture was stirred and reacted for an hour. After completion of the reaction, the mixture was cooled to room temperature, 10 ml of toluene was added, and the mixture was subjected to liquid separation treatment to obtain an organic layer containing benzoic acid. The yield of benzoic acid was 94% (based on benzyl alcohol).

Comparative Example 1
The same procedures as in Example 1 were carried out except that 0.49 g of phosphoric acid was not used, to obtain 4.13 g of a waxy pale yellow solid tungsten complex.
IR (neat, unit: cm ^-1 )
2956, 2922, 2853, 1550, 1466, 1378, 1045, 977,
958,876,815,782,720

Claims (12)

(A) Tungsten compound comprising tungsten and a Group IIIb, IVb, Vb or VIb element, molybdenum compound comprising molybdenum and a Group IIIb, IVb, Vb or VIb element And at least one selected from the group consisting of tungsten metal and molybdenum metal;
(B) at least one selected from the group consisting of tertiary amines, tertiary amine oxides, nitrogen-containing aromatic compounds, and nitrogen-containing aromatic compound N-oxides;
(C) hydrogen peroxide;
(D) A metal complex obtained by contacting phosphoric acids. 2. The metal complex according to claim 1, wherein the component (A) is at least one selected from the group consisting of tungsten and tungsten metal comprising tungsten and a group IIIb, IVb, Vb or VIb element and tungsten metal. 3. . The metal complex according to claim 1, wherein the Group IIIb element is boron. The metal complex according to claim 1, wherein the Group IVb element is carbon. The metal complex according to claim 1, wherein the group Vb element is phosphorus. The metal complex according to claim 1, wherein the Group VIb element is oxygen or sulfur. An epoxide production method comprising reacting an olefin with hydrogen peroxide in the presence of the metal complex according to claim 1 at a pH of 2 to 4. The catalyst comprising the metal complex according to claim 1, which is used for producing an epoxide by reacting an olefin with hydrogen peroxide. A method for producing a β-hydroxyhydroperoxide compound or a carbonyl compound, comprising reacting an olefin with hydrogen peroxide in the presence of the metal complex according to claim 1 in a range of pH 0 to less than 2. The catalyst comprising the metal complex according to claim 1, which is used for reacting an olefin with hydrogen peroxide to produce a β-hydroxyhydroperoxide compound or a carbonyl compound. A method for producing a carbonyl compound, comprising reacting a primary or secondary alcohol with hydrogen peroxide in the presence of the metal complex according to claim 1. The catalyst comprising the metal complex according to claim 1, which is used for producing a carbonyl compound by reacting a primary or secondary alcohol with hydrogen peroxide.