JP2012092142A - Method for producing ketone and carboxylic acid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing ketones and carboxylic acids by oxidizing trisubstituted olefins with hydrogen peroxide.SOLUTION: The method for producing ketones and carboxylic acids is characterized by reaction of a trisubstituted olefin expressed by general formula (1) (in the formula, R, Rand Rare each an optionally substituted alkyl or the like; or Rand R, Rand Ror Rand Rmay together form a part of a cyclic structure) with hydrogen peroxide at 65-200°C in the presence of a metal oxide catalyst obtained by reacting at least one metal compound selected from the group consisting of compounds of a tungsten metal, a molybdenum metal, etc., with hydrogen peroxide.

Description

  The present invention relates to a method for producing ketones and carboxylic acids important as various chemical products and synthetic intermediates thereof.

  Hydrogen peroxide has attracted attention in recent years as a clean and excellent oxidant that is inexpensive, easy to handle and harmless after the reaction, and various oxidation methods using hydrogen peroxide have been reported. However, a method for producing β-hydroxyhydroperoxides by oxidizing trisubstituted olefins with hydrogen peroxide has not been reported.

In addition, various methods for producing ketones, aldehydes and carboxylic acids by the reaction of trisubstituted olefins with hydrogen peroxide have been reported, for example, as described below, but both methods are relatively expensive catalysts. However, the method is not always satisfactory industrially in that an organic acid solvent is necessary to improve the activity of the catalyst and the point that a reagent is used.
Production method of aldehydes and ketones: Method using methylrhenium trioxide as catalyst (Patent Document 1), etc. Production method of carboxylic acids: (i) Method using heteropolyacid and cetylpyridinium chloride as catalyst (J. Org. Chem) , 53 , 3587 (1988)) (ii) a method using tungstic acids and quaternary ammonium hydrogen sulfate as a catalyst (Patent Document 2), etc.

WO98 / 47847 JP 2000-86547 A

  Under such circumstances, the present inventors have intensively studied to develop a method for industrially advantageously producing β-hydroxyhydroperoxides by oxidizing trisubstituted olefins with hydrogen peroxide. Easily available tungsten metal such as tungsten metal and tungsten boride, and metal oxide obtained by reacting molybdenum compound such as molybdenum metal and molybdenum boride with hydrogen peroxide is high in oxidation reaction of trisubstituted olefins. Β-hydroxyhydroperoxides, ketones and carboxylic acids can be obtained by reacting trisubstituted olefins with hydrogen peroxide in the presence of the metal oxide catalyst in the presence of the metal oxide catalyst, Hydrolysis of hydroxyhydroperoxides proceeds by heat treatment, alkali treatment or treatment with specific compounds. By reduction treatment ketones and that aldehydes can be obtained and the β- hydroxy hydroperoxides, found that diol is obtained, leading to the present invention.

  That is, the present invention provides tungsten metal, molybdenum metal, tungsten and group IIIb, group IVb, group Vb, or a tungsten compound composed of group VIb excluding oxygen and molybdenum and group IIIb, group IVb, group IV. Trisubstituted olefins in the presence of a metal oxide catalyst obtained by reacting hydrogen peroxide with at least one metal compound selected from the group consisting of molybdenum compounds consisting of group Vb or group VIb elements excluding oxygen; A process for producing β-hydroxyhydroperoxides, ketones and carboxylic acids characterized by reacting with hydrogen peroxide and its catalyst, and further ketones and aldehydes or diols from β-hydroxyhydroperoxides. A method of manufacturing is provided.

  According to the method of the present invention, hydrogen peroxide is allowed to react with at least one metal compound selected from tungsten metal, molybdenum metal, tungsten compound such as tungsten boride, and molybdenum compound such as molybdenum boride, which are easily available. Β-hydroxyhydroperoxides, ketones and carboxylic acids can be easily obtained by reacting trisubstituted olefins with inexpensive hydrogen peroxide in the presence of a metal oxide catalyst. Diols, ketones and aldehydes can be easily obtained from hydroxy hydroperoxides, which is industrially advantageous.

  First, the catalyst used for reacting trisubstituted olefins with hydrogen peroxide will be described. Catalysts include tungsten metal, molybdenum metal, tungsten and group IIIb, group IVb, group Vb or tungsten compound consisting of group VIb excluding oxygen and molybdenum and group IIIb, group IVb, group Vb. Alternatively, a metal oxide obtained by reacting hydrogen peroxide with at least one metal compound selected from the group consisting of molybdenum compounds composed of Group VIb elements excluding oxygen is used.

  Examples of the tungsten compound composed of tungsten and a group IIIb element include tungsten boride, and examples of the tungsten compound composed of tungsten and a group IVb element include tungsten carbide, tungsten silicide, and the like. Examples of the tungsten compound composed of the element include tungsten nitride and tungsten phosphide, and examples of the tungsten compound composed of the group VIb element excluding tungsten and oxygen include tungsten sulfide.

  Examples of molybdenum compounds composed of molybdenum and Group IIIb elements include molybdenum boride, and examples of molybdenum compounds composed of molybdenum and Group IVb elements include molybdenum carbide and molybdenum silicide. Examples of molybdenum compounds composed of elements include molybdenum nitride and molybdenum phosphide, and examples of molybdenum compounds composed of molybdenum and Group VIb elements excluding oxygen include molybdenum sulfide.

  Among these metal compounds, tungsten metal, molybdenum metal, tungsten boride, molybdenum boride, tungsten sulfide, and molybdenum sulfide are preferable. These metal compounds may be used alone or in combination of two or more. In addition, it is preferable to use a metal compound having a small particle diameter in terms of facilitating preparation of a metal oxide as a catalyst.

  By reacting such a metal compound with hydrogen peroxide, a metal oxide serving as a catalyst for producing β-hydroxyhydroperoxides, ketones and carboxylic acids is prepared by oxidizing trisubstituted olefins. . The reaction between the metal compound and hydrogen peroxide is usually carried out in an aqueous solution. Of course, for example, ether solvents such as diethyl ether, methyl tert-butyl ether and tetrahydrofuran, ester solvents such as ethyl acetate, alcohol solvents such as methanol, ethanol and tert-butanol, nitrile solvents such as acetonitrile and propionitrile, etc. You may implement in the organic solvent of this, or the mixed solvent of this organic solvent and water.

  Hydrogen peroxide is usually used as an aqueous solution, but an organic solvent solution may be used. In view of easier handling, it is preferable to use an aqueous hydrogen peroxide solution. The concentration of hydrogen peroxide in the aqueous hydrogen peroxide solution or the organic solvent solution is not particularly limited, but is practically 1 to 60% by weight in consideration of volume efficiency, safety and the like. As the hydrogen peroxide aqueous solution, a commercially available solution may be used as it is or after adjustment of the concentration by dilution, concentration, etc., if necessary. It can be prepared by means such as extraction with a solvent or distillation in the presence of an organic solvent. The amount of hydrogen peroxide used in preparing the metal oxide is usually 3 mol times or more, preferably 5 mol times or more, relative to the metal compound, and there is no particular upper limit.

  The reaction between the metal compound and hydrogen peroxide is usually carried out by mixing the two, so that the metal compound is sufficiently dispersed in the metal oxide preparation solution in order to improve the contact efficiency between the metal compound and hydrogen peroxide. It is preferable to carry out the reaction while stirring. In addition, it is preferable to use a metal compound having a small particle diameter, such as a powdered metal compound, in order to increase the contact efficiency between the metal compound and hydrogen peroxide and to facilitate control during preparation of the metal oxide. The preparation temperature at the time of preparation of the metal oxide is usually −10 to 100 ° C.

  By reacting the metal compound with hydrogen peroxide in water or an organic solvent, all or part of the metal compound is dissolved, and a homogeneous solution or suspension containing the metal oxide can be prepared. The metal oxide may be taken out of the preparation liquid by, for example, concentration treatment and used as a catalyst, or the preparation liquid may be used as it is as a catalyst.

  Next, the reaction between trisubstituted olefins and hydrogen peroxide using the metal oxide as a catalyst will be described.

  Trisubstituted olefins (hereinafter abbreviated as olefins) have an olefinic carbon-carbon double bond, and three substituents are bonded to the two carbon atoms forming the double bond. If it is what. Further, among the substituents bonded to the carbon atom forming such a carbon-carbon double bond, any two substituents may be combined to form a part of the ring structure. Examples of the olefin when the substituents are combined to form a part of the ring structure include cyclic olefins containing the carbon-carbon double bond and olefins substituted with a cyclic substituent.

（式中、Ｒ¹、Ｒ²およびＲ³はそれぞれ同一または相異なって、置換されていてもよいアルキル基、置換されていてもよいアルコキシ基、置換されていてもよいアリール基、置換されていてもよいアリールオキシ基、置換されていてもよいアラルキル基、置換されていてもよいアラルキルオキシ基、置換されていてもよいアシル基、置換されていてもよいカルボアルコキシ基、置換されていてもよいカルボアリールオキシ基、置換されていてもよいカルボアラルキルオキシ基、カルボキシル基またはハロゲン原子を表わす。また、Ｒ¹とＲ²、Ｒ¹とＲ³またはＲ²とＲ³が一緒になって環構造の一部を形成してもよい。）
で示されるオレフィン類が挙げられる。 As such olefins, for example, the general formula (1)

(Wherein R ¹ , R ² and R ³ are the same or different and each may be an alkyl group which may be substituted, an alkoxy group which may be substituted, an aryl group which may be substituted, An optionally substituted aryloxy group, an optionally substituted aralkyl group, an optionally substituted aralkyloxy group, an optionally substituted acyl group, an optionally substituted carboalkoxy group, and optionally substituted Represents a good carboaryloxy group, an optionally substituted carboaralkyloxy group, a carboxyl group or a halogen atom, and R ¹ and R ² , R ¹ and R ^3, or R ² and R ³ together form a ring Part of the structure may be formed.)
And olefins represented by

  Examples of the alkyl group which may be substituted include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms such as decyl group, cyclopropyl group, 2,2-dimethylcyclopropyl group, cyclopentyl group, cyclohexyl group and menthyl group, and these alkyl groups May be substituted with an alkoxy group, an aryloxy group, an aralkyloxy group, a halogen atom, an acyl group, a carboalkoxy group, a carboaryloxy group, a carboaralkyloxy group, a carboxyl group, etc., which will be described later. Examples of the substituted alkyl group include a chloromethyl group, a fluoromethyl group, and a trifluoro group. Tyl group, methoxymethyl group, ethoxymethyl group, methoxyethyl group, carbomethoxymethyl group, 1-carbomethoxy-2,2-dimethyl-3-cyclopropyl group, 1-carboethoxy-2,2-dimethyl-3- A cyclopropyl group etc. are mentioned.

  Examples of the optionally substituted alkoxy group include those composed of the optionally substituted alkyl group and an oxygen atom. For example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n -Butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, n-decyloxy group, cyclopentyloxy group, cyclohexyloxy group, menthyloxy group, etc. A cyclic alkoxy group having 1 to 20 carbon atoms and a group in which these alkoxy groups are substituted with a substituent such as a halogen atom or an alkoxy group, such as a chloromethoxy group, a fluoromethoxy group, a trifluoromethoxy group, a methoxymethoxy group, An ethoxymethoxy group, a methoxyethoxy group, etc. are mentioned.

  Examples of the aryl group which may be substituted include, for example, a phenyl group, a naphthyl group and the like, and an aromatic ring constituting the phenyl group, naphthyl group and the like, an alkyl group, an aryl group, an alkoxy group, an aralkyl group and an aryloxy described later. A 2-methylphenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, a 4-methoxyphenyl group, a 3-phenoxyphenyl group, and the like substituted with a substituent such as a group, an aralkyloxy group, or a halogen atom. . Examples of the optionally substituted aryloxy group include those composed of the optionally substituted aryl group and an oxygen atom, such as a phenoxy group, 2-methylphenoxy group, 4-chlorophenoxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 3-phenoxyphenoxy group and the like can be mentioned.

  Examples of the aralkyl group which may be substituted include those composed of the aryl group which may be substituted and the alkyl group described above. For example, a benzyl group, a 4-chlorobenzyl group, a 4-methylbenzyl group. 4-methoxybenzyl group, 3-phenoxybenzyl group, 2,3,5,6-tetrafluorobenzyl group, 2,3,5,6-tetrafluoro-4-methylbenzyl group, 2,3,5,6 -Tetrafluoro-4-methoxybenzyl group, 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl group and the like. Examples of the optionally substituted aralkyloxy group include those composed of the optionally substituted aralkyl group and an oxygen atom, such as a benzyloxy group, 4-chlorobenzyloxy group, 4- Methylbenzyloxy group, 4-methoxybenzyloxy group, 3-phenoxybenzyloxy group, 2,3,5,6-tetrafluorobenzyloxy group, 2,3,5,6-tetrafluoro-4-methylbenzyloxy group 2,3,5,6-tetrafluoro-4-methoxybenzyloxy group, 2,3,5,6-tetrafluoro-4-methoxymethylbenzyloxy group and the like.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the optionally substituted acyl group include those composed of a carbonyl group and the optionally substituted alkyl group, an optionally substituted aryl group, and an optionally substituted aralkyl group. Examples thereof include carbomethyl group, carboethyl group, carbophenyl group, carbobenzyl group and the like.

  As the optionally substituted carboalkoxy group, the optionally substituted carboaryloxy group and the optionally substituted carboaralkyloxy group, a carbonyl group and the above optionally substituted alkoxy group, substituted Examples thereof include an aryloxy group which may be substituted and an aralkyloxy group which may be substituted, such as a carbomethoxy group, a carboethoxy group, a carbophenoxy group, a carbobenzyloxy group and the like.

  Examples of the ring structure when such substituents together form a part of the ring structure include a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a cyclohexene ring, and the like.

  Examples of such olefins include 2-methyl-2-pentene, 3-methyl-2-pentene, 3-ethyl-2-pentene, 2-methyl-2-hexene, 3-methyl-2-hexene, and 2-methyl. -1-phenylpropene, 2-phenyl-2-butene, 1-methylcyclopentene, 1,3-dimethylcyclopentene, 1,4-dimethylcyclopentene, 1,5-dimethylcyclopentene, 1,3,5-trimethylcyclopentene, 1 , 3,4-trimethylcyclopentene, 1,4,5-trimethylcyclopentene, 1,3,4,5-tetramethylcyclopentene, 1-methylcyclohexene, 1,3-dimethylcyclohexene, 1,4-dimethylcyclohexene, 1, 5-dimethylcyclohexene, 1,3,5-trimethylcyclohexene, 1 3,4-trimethylcyclohexene, 1,4,5-trimethylcyclohexene, 1,3,4,5-tetramethylcyclohexene, isophorone, 2-carene, 3-carene, α-pinene, 3,3-dimethyl-2- (Methyl (2-methyl-1-propenyl) -cyclopropanecarboxylate, ethyl 3,3-dimethyl-2- (2-methyl-1-propenyl) -cyclopropanecarboxylate, 3,3-dimethyl-2- (2 -Methyl-1-propenyl) -cyclopropanecarboxylate isopropyl, 3,3-dimethyl-2- (2-methyl-1-propenyl) -cyclopropanecarboxylate tert-butyl, 3,3-dimethyl-2- (2 -Methyl-1-propenyl) -cyclopropanecarboxylic acid cyclohexyl, 3,3-dimethyl-2- (2-methyl-1-propenyl) L) -Methylyl cyclopropanecarboxylate, benzyl 3,3-dimethyl-2- (2-methyl-1-propenyl) -cyclopropanecarboxylate,

3,3-dimethyl-2- (2-methyl-1-propenyl) -cyclopropanecarboxylic acid (4-chlorobenzyl), 3,3-dimethyl-2- (2-methyl-1-propenyl) -cyclopropanecarboxylic acid Acid (2,3,5,6-tetrafluorobenzyl), 3,3-dimethyl-2- (2-methyl-1-propenyl) -cyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4) -Methylbenzyl), 3,3-dimethyl-2- (2-methyl-1-propenyl) -cyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-methoxybenzyl), 3,3-dimethyl -2- (2-methyl-1-propenyl) -cyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-methoxymethylbenzyl), 3,3-dimethyl-2- (2-methyl) -1-propenyl) - cyclopropane carboxylic acid (3-phenoxybenzyl) and the like.

  Some olefins have an asymmetric carbon in the molecule and have optical isomers, but either optical isomers alone or a mixture thereof may be used.

  In this reaction, olefins and hydrogen peroxide are reacted in the presence of the metal oxide catalyst described above, and β-hydroxyhydroperoxides in which the carbon-carbon double bond sites of the olefins are oxidized. Then, ketones and carboxylic acids in which carbon-carbon double bonds of olefins are oxidatively cleaved are formed.

（式中、Ｒ¹、Ｒ²およびＲ³は上記と同一の意味を表わす。）
で示されるβ−ヒドロキシヒドロペルオキシド類、炭素−炭素二重結合が酸化開裂した一般式（４）

（式中、Ｒ¹およびＲ²は上記と同一の意味を表わす。）
で示されるケトン類および一般式（５）

（式中、Ｒ³は上記と同一の意味を表わす。）
で示されるカルボン酸類が生成する。なお、本反応においては、オレフィン類の別の酸化物であるジオール類やβ−ヒドロキシヒドロペルオキシド類が分解したアルデヒド類が、副生物として生成することがある。上記一般式（１）で示されるオレフィン類の場合には、一般式（３）

（式中、Ｒ¹、Ｒ²およびＲ³は上記と同一の意味を表わす。）
で示されるジオール類や一般式（６）

（式中、Ｒ³は上記と同一の意味を表わす。）
で示されるアルデヒド類が副生物として挙げられる。 When the olefin represented by the general formula (1) is used as the olefin, the general formula (2) in which the carbon-carbon double bond is oxidized.

(In the formula, R ¹ , R ² and R ³ have the same meaning as described above.)
Β-hydroxyhydroperoxides represented by the general formula (4) wherein a carbon-carbon double bond is oxidatively cleaved:

(In the formula, R ¹ and R ² represent the same meaning as described above.)
And the general formula (5)

(Wherein R ³ represents the same meaning as described above.)
Is produced. In this reaction, diols, which are other oxides of olefins, and aldehydes decomposed by β-hydroxyhydroperoxides may be produced as by-products. In the case of the olefins represented by the general formula (1), the general formula (3)

(In the formula, R ¹ , R ² and R ³ have the same meaning as described above.)
Diols represented by the general formula (6)

(Wherein R ³ represents the same meaning as described above.)
The aldehydes represented by can be mentioned as by-products.

  More specifically, taking specific olefins as examples, when 2-methyl-2-pentane is used as the raw material olefins, 2-methyl-2-hydroperoxy-3-hydroxypentane, acetone And propionic acid is produced. When 1-methylcyclopentene is used as the raw material olefins, 1-methyl-1-hydroperoxy-2-hydroxycyclopentane and 6-oxoheptanoic acid are obtained. When methyl 3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate is used as the starting olefin, 3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy) 2-methylpropyl) cyclopropanecarboxylic acid, acetone and 3,3-dimethyl-2-carbomethoxycyclopropanecarboxylic acid are obtained. When 3-carene is used as a raw material olefin, 3-hydroperoxy-4-hydroxycalene and [2,2-dimethyl-3- (2-oxopropyl) cyclopropyl] acetic acid are produced.

  The amount of metal oxide used as a catalyst for the reaction between olefins and hydrogen peroxide is usually 0.001 mol times or more with respect to olefins, and there is no upper limit, but considering the economical aspect. Then, it is 1 mol times or less practically with respect to olefins.

  Hydrogen peroxide is usually used as an aqueous solution. Of course, an organic solvent solution of hydrogen peroxide may be used. The hydrogen peroxide concentration in the hydrogen peroxide solution or the organic solvent solution is not particularly limited, but is practically 1 to 60% by weight in consideration of volume efficiency, safety and the like. As the hydrogen peroxide solution, a commercially available one is usually used as it is or after adjusting the concentration by dilution, concentration or the like, if necessary. The organic solvent solution of hydrogen peroxide can be prepared, for example, by means such as extraction treatment of hydrogen peroxide water with an organic solvent or distillation treatment in the presence of an organic solvent.

  The amount of hydrogen peroxide used is usually 1 mol times or more with respect to olefins, and there is no particular upper limit of the amount used, but considering economic aspects, practically, with respect to olefins, It is 10 mol times or less. In addition, when using a metal oxide preparation liquid obtained by reacting a metal compound and hydrogen peroxide as a catalyst, the amount of hydrogen peroxide used may be set including the amount of hydrogen peroxide in the preparation liquid. Good.

  This reaction is usually carried out in an aqueous solvent or an organic solvent. Examples of the organic solvent include ether solvents such as diethyl ether, methyl tert-butyl ether and tetrahydrofuran, ester solvents such as ethyl acetate, alcohol solvents such as methanol, ethanol and tert-butanol, and nitriles such as acetonitrile and propionitrile. System solvents and the like. The amount of water solvent or organic solvent used is not particularly limited, but considering volume efficiency and the like, it is practically 100 weight times or less with respect to olefins.

  In this reaction, since the product production ratio varies depending on the reaction conditions, the reaction conditions may be appropriately selected according to the target product. For example, when β-hydroxyhydroperoxides are intended, the reaction is preferably carried out in an organic solvent, and when ketones and carboxylic acids are intended, the reaction may be carried out in an aqueous solvent. preferable. In addition, when β-hydroxyhydroperoxides are intended, it is preferable to carry out the reaction under anhydrous conditions. Examples of the method for carrying out the reaction under anhydrous conditions include a method in which a dehydrating agent is allowed to coexist in the reaction system. Examples of the dehydrating agent include anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous boric acid, polyphosphoric acid, diphosphorus pentoxide and the like, and the amount used is more than the amount capable of dehydrating and removing water present in the reaction system. If there is enough.

  The reaction temperature is usually 0 to 200 ° C., but β-hydroxyhydroperoxides are more likely to be generated as the reaction temperature is lower, and ketones and carboxylic acids are more likely to be generated as the reaction temperature is higher. When hydroperoxides are aimed, the reaction temperature is preferably in the range of 0 to 65 ° C., and when ketones and carboxylic acids are aimed, 65 ° C. or higher is preferred.

  This reaction may be carried out under normal pressure conditions or under pressurized conditions. In addition, the progress of the reaction can be confirmed by ordinary analysis means such as gas chromatography, high performance liquid chromatography, thin layer chromatography, nuclear magnetic resonance spectrum analysis, infrared absorption spectrum analysis and the like.

  In addition, this reaction may be carried out in the presence of a boron compound such as boric anhydride. Examples of the boron compound include boric anhydride, metaboric acid, normal boric acid, alkali metal borate, and alkali metal borate. Examples include earth metal salts, alkali metal salts of normal borates, and alkaline earth metal salts of borates, and the amount used is not particularly limited. Is usually 1 mol times or less with respect to olefins.

  After completion of the reaction, β-hydroxyhydroperoxides, ketones and carboxylic acids can be separated and removed from the reaction solution, for example, by subjecting the reaction solution to concentration treatment, column chromatography treatment or the like. Moreover, these products can be separated and taken out by adding water and / or an organic solvent insoluble in water to the reaction solution as necessary, performing an extraction treatment, and concentrating the resulting organic layer. The extracted β-hydroxyhydroperoxides, ketones and carboxylic acids may be further purified by means such as distillation, column chromatography and the like.

  Examples of the organic solvent insoluble in water include aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as dichloromethane, chloroform, and chlorobenzene, and ethers such as diethyl ether, methyl tert-butyl ether, and tetrahydrofuran. Examples of the solvent include ester solvents such as ethyl acetate, and the amount used is not particularly limited.

  As described above, in this reaction, diols and aldehydes are produced as by-products, but diols and aldehydes by-produced from the reaction solution can be taken out by the same treatment as described above.

  Since the filtrate and aqueous layer after removing β-hydroxyhydroperoxides, ketones and carboxylic acids contain a metal oxide which is a catalyst for this reaction, the aqueous layer is used as it is or as necessary. After the concentration treatment and the like, the catalyst can be used again as a catalyst for the reaction between olefins and hydrogen peroxide.

  When an optically active substance is used as the olefin, an optically active product is obtained depending on the position of the asymmetric carbon.

  Examples of the β-hydroxyhydroperoxides thus obtained include 2-methyl-2-hydroperoxy-3-hydroxypentane, 3-methyl-3-hydroperoxy-2-hydroxyhexane, 1-methyl-1-hydroperoxy- 2-hydroxycyclopentane, 1,3-dimethyl-1-hydroperoxy-2-hydroxycyclohexane, 1,3,5-trimethyl-1-hydroperoxy-2-hydroxycyclohexane, 3-hydroperoxy-4-hydroxycarene, Methyl 3,3-dimethyl-2- (2-methyl-2-hydroperoxy-1-hydroxypropyl) cyclopropanecarboxylate, 3,3-dimethyl-2- (2-methyl-2-hydroperoxy-1-hydroxy) Propyl) ethyl cyclopropanecarboxylate, 3 3-dimethyl-2- (2-methyl-2-hydroperoxy-1-hydroxypropyl) cyclopropanecarboxylate, 3,3-dimethyl-2- (2-methyl-2-hydroperoxy-1-hydroxypropyl) Tert-butyl cyclopropanecarboxylate, 3,3-dimethyl-2- (2-methyl-2-hydroperoxy-1-hydroxypropyl) cyclopropanecarboxylic acid cyclohexyl, 3,3-dimethyl-2- (2-methyl-) 2-hydroperoxy-1-hydroxypropyl) menthosyl cyclopropanecarboxylate, benzyl 3,3-dimethyl-2- (2-methyl-2-hydroperoxy-1-hydroxypropyl) cyclopropanecarboxylate,

3,3-dimethyl-2- (2-methyl-2-hydroperoxy-1-hydroxypropyl) cyclopropanecarboxylic acid (4-chlorobenzyl), 3,3-dimethyl-2- (2-methyl-2-hydro) Peroxy-1-hydroxypropyl) cyclopropanecarboxylic acid (2,3,5,6-tetrafluorobenzyl), 3,3-dimethyl-2- (2-methyl-2-hydroperoxy-1-hydroxypropyl) cyclopropane Carboxylic acid (2,3,5,6-tetrafluoro-4-methylbenzyl), 3,3-dimethyl-2- (2-methyl-2-hydroperoxy-1-hydroxypropyl) cyclopropanecarboxylic acid (2, 3,5,6-tetrafluoro-4-methoxybenzyl), 3,3-dimethyl-2- (2-methyl-2-hydroperoxy-1) Hydroxypropyl) cyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-methoxymethylbenzyl), 3,3-dimethyl-2- (2-methyl-2-hydroperoxy-1-hydroxypropyl) cyclo Examples include propanecarboxylic acid (3-phenoxybenzyl).

  Examples of ketones include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, and acetophenone. Examples of carboxylic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, and 6-oxoheptanoic acid. 2-methyl-6-oxoheptanoic acid, 3-methyl-6-oxoheptanoic acid, 4-methyl-6-oxoheptanoic acid, 5-methyl-6-oxoheptanoic acid, 2,3-dimethyl-6-oxo Heptanoic acid, 2,4-dimethyl-6-oxoheptanoic acid, 3,4-dimethyl-6-oxoheptanoic acid, 2,3,4-trimethyl-6-oxoheptanoic acid, 5-oxohexanoic acid, 2-methyl -5-oxohexanoic acid, 3-methyl-5-oxohexanoic acid, 4-methyl-5-oxohexanoic acid, 2,3-di Til-5-oxohexanoic acid, 2,4-dimethyl-5-oxohexanoic acid, 3,4-dimethyl-5-oxohexanoic acid, 2,3,4-trimethyl-5-oxohexanoic acid, 3,3- Dimethyl-5-oxohexanoic acid,

3- (3-oxobutyl) -2,2-dimethylcyclopropanecarboxylic acid, 3- (2-oxopropyl) -2,2-dimethyl-1-carboxymethylcyclopropane, 3- (2-oxoethyl) -2, 2-dimethyl-1-carboxymethylcyclobutane, methyl 3,3-dimethyl-2-carboxycyclopropanecarboxylate, ethyl 3,3-dimethyl-2-carboxycyclopropanecarboxylate, 3,3-dimethyl-2-carboxycyclo Isopropyl propanecarboxylate, tert-butyl 3,3-dimethyl-2-carboxycyclopropanecarboxylate, cyclohexyl 3,3-dimethyl-2-carboxycyclopropanecarboxylate, 3,3-dimethyl-2-carboxycyclopropanecarboxylic acid Menthyl, 3,3-dimethyl-2-carbo Benzyl cyclocyclopropanecarboxylate, 3,3-dimethyl-2-carboxycyclopropanecarboxylic acid (4-chlorobenzyl), 3,3-dimethyl-2-carboxycyclopropanecarboxylic acid (2,3,5,6-tetra Fluorobenzyl), 3,3-dimethyl-2-carboxycyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-methylbenzyl), 3,3-dimethyl-2-carboxycyclopropanecarboxylic acid (2 , 3,5,6-tetrafluoro-4-methoxybenzyl), 3,3-dimethyl-2-carboxycyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-methoxymethylbenzyl), 3, 3-dimethyl-2-carboxycyclopropane carboxylic acid (3-phenoxybenzyl) and the like.

（式中、Ｒ³は上記と同一の意味を表わす。）
で示されるアルデヒド類が得られる。具体的な化合物を例にしてさらに詳しく説明すると、例えば２−メチル−２−ペンテンから得られる２−メチル−２−ヒドロペルオキシ−３−ヒドロキシペンタンからは、アセトンおよびプロピオンアルデヒドが生成し、１−メチルシクロペンテンから得られる１−メチル−１−ヒドロペルオキシ−２−ヒドロキシシクロペンタンからは、６−オキソヘプチルアルデヒドが得られる。 The produced β-hydroxy hydroperoxide can be decomposed by alkali treatment or heat treatment to obtain ketones and aldehydes. For example, from the β-hydroxyhydroperoxides represented by the general formula (2), the ketones represented by the general formula (4) and the general formula (6)

(Wherein R ³ represents the same meaning as described above.)
Is obtained. More specifically, taking a specific compound as an example, for example, 2-methyl-2-hydroperoxy-3-hydroxypentane obtained from 2-methyl-2-pentene produces acetone and propionaldehyde, and 1- From 1-methyl-1-hydroperoxy-2-hydroxycyclopentane obtained from methylcyclopentene, 6-oxoheptylaldehyde is obtained.

  Examples of the alkali in the alkali treatment include alkali metal alcoholates such as sodium methylate, and the amount used is usually 0.01 mol times or more with respect to β-hydroxyhydroperoxides, and the upper limit thereof. There is no particular. Moreover, the temperature to heat-process is 60-200 degreeC normally.

  In addition, β-hydroxyhydroperoxides, Group Va element compound, Group VIIa element compound, Group VIII element compound, Group Ib element compound, Group IIb element compound, Group IIIb element compound, Group IVb element By reacting at least one compound selected from the group consisting of a compound, a Group Vb element compound and a lanthanide compound, the β-hydroxyhydroperoxides are decomposed to obtain ketones and aldehydes.

Examples of the Group Va element compound include vanadium metal, vanadium oxide, ammonium vanadate, vanadium oxide obtained by reacting vanadium metal with hydrogen peroxide, vanadium compounds such as vanadium carbonyl complex, such as niobium metal, niobium oxide, and chloride. Examples thereof include niobium compounds such as niobium (V) (NbCl ₅ ) and niobium carbonyl complexes. Examples of Group VIIa element compounds include rhenium compounds such as rhenium metal and rhenium chloride. Examples of Group VIII element compounds include iron compounds such as iron metal, iron chloride, Fe (CO) ₅ and Fe (acac) ₃ , such as ruthenium metal, ruthenium chloride, Ru ₃ (CO) ₁₂ and Ru (acac) _3. Ruthenium compounds such as RuCl ₂ (PPh ₃ ) ₃ such as cobalt metal, cobalt acetate, cobalt compounds such as [Co ₂ (CO) ₈ ] ₂ such as rhodium metal, rhodium chloride, rhodium such as Rh ₄ (CO) ₁₂ Examples thereof include iridium compounds such as iridium metal and iridium chloride, nickel compounds such as nickel metal and Ni (CO) ₄ , and palladium compounds such as palladium metal, palladium acetate and palladium carbon.

Examples of the Group Ib element compound include copper metal such as copper compounds such as cuprous chloride, cupric chloride, cuprous bromide and cupric bromide. Examples of the group IIb element compound include zinc compounds such as zinc compounds such as zinc chloride. Examples of the group IIIb element compound include boron compounds such as boron trifluoride, and aluminum compounds such as aluminum metal and aluminum chloride. Examples of Group IVb element compounds include tin compounds such as tin metal and tin chloride. Examples of the Group Vb element compound include bismuth compounds such as bismuth metal and bismuth chloride (BiCl ₃ ), for example, antimony compounds such as antimony metal, antimony chloride (V) (SbCl ₅ ), and antimony chloride (III) (SbCl ₃ ). Etc. Examples of lanthanide compounds include samarium compounds such as samarium metal and samarium triflate (Sm (OTf) ₂ ), gadolinium compounds such as gadolinium metal, dysprosium compounds such as dysprosium metal and dysprosium triflate (Dy (OTf) ₃ ), and the like. And dysprosium compounds are preferred.

  Among these compounds, vanadium compounds, copper compounds, ruthenium compounds, palladium compounds, and mixtures thereof are preferable. Such compounds may be used alone or in combination.

  The amount of the compound used is usually 0.001 mol times or more with respect to β-hydroxyhydroperoxides, and there is no particular upper limit, but considering the economical aspect, it is practically 1 mol times or less. It is.

  To make a compound related to β-hydroxyhydroperoxides act, both of them may be mixed, and the mixing temperature is usually −20 to 100 ° C. Usually, it is carried out in the presence of a solvent in which β-hydroxyhydroperoxides are dissolved. Examples of such solvents include ether solvents such as diethyl ether, methyl tert-butyl ether, and tetrahydrofuran, ester solvents such as ethyl acetate, alcohol solvents such as methanol, ethanol, and tert-butanol, such as acetonitrile and propionitrile. The use amount of β-hydroxyhydroperoxides is not particularly limited as long as β-hydroxyhydroperoxides are dissolved. However, in consideration of volumetric efficiency, β-hydroxyhydroperoxide is practically used. 100 weight times or less with respect to a kind.

  When using a reaction solution containing β-hydroxyhydroperoxides obtained by oxidizing olefins with, for example, tungsten metal, tungsten boride or the like, the compound may be allowed to act on the reaction solution as it is. The β-hydroxyhydroperoxides may be extracted from the reaction solution by extraction or the like, and then reacted with the compound.

  Examples of the ketones thus obtained include those similar to those described above. Examples of the aldehydes include acetaldehyde, propionaldehyde, butyraldehyde, pentylaldehyde, benzaldehyde, 5-oxohexylaldehyde, 2-methyl-5- Oxohexyl aldehyde, 4-methyl-5-oxohexyl aldehyde, 3-methyl-5-oxohexyl aldehyde, 2,4-dimethyl-5-oxohexyl aldehyde, 3,4-dimethyl-5-oxohexyl aldehyde, 2, 3-dimethyl-5-oxohexylaldehyde, 2,3,4-trimethyl-5-oxohexylaldehyde, 6-oxoheptylaldehyde, 2-methyl-6-oxoheptylaldehyde, 4-methyl-6-oxoheptylaldehyde, 2, - dimethyl-6-oxo-heptyl aldehyde, 2,3-dimethyl-6-oxo-heptyl aldehyde, 3,4-dimethyl-6-oxo-heptyl aldehyde, 2,3,4-trimethyl-6-oxo-heptyl aldehyde,

2,2-dimethyl-3- (2-oxopropyl) cyclopropaneacetaldehyde, 2,2-dimethyl-3- (3-oxobutyl) cyclopropylaldehyde, 2,2-dimethyl-3- (2-oxoethyl) cyclobutaneacetaldehyde , Methyl 3,3-dimethyl-2-formylcyclopropanecarboxylate, ethyl 3,3-dimethyl-2-formylcyclopropanecarboxylate, isopropyl 3,3-dimethyl-2-formylcyclopropanecarboxylate, 3,3- Tert-butyl dimethyl-2-formylcyclopropanecarboxylate, cyclohexyl 3,3-dimethyl-2-formylcyclopropanecarboxylate, menthyl 3,3-dimethyl-2-formylcyclopropanecarboxylate, 3,3-dimethyl-2 -Formylcyclopropanecarboxyl Benzyl, (4-chlorobenzyl) -3,3-dimethyl-2-formylcyclopropanecarboxylate, (2,3,5,6-tetrafluorobenzyl) -3,3-dimethyl-2-formylcyclopropanecarboxylate , (2,3,5,6-tetrafluoro-4-methylbenzyl) -3,3-dimethyl-2-formylcyclopropanecarboxylate, (2,3,5,6-tetrafluoro-4-methoxybenzyl) −3,3-dimethyl-2-formylcyclopropanecarboxylate, (2,3,5,6-tetrafluoro-4-methoxymethylbenzyl) -3,3-dimethyl-2-formylcyclopropanecarboxylate, (3 -Phenoxybenzyl) -3,3-dimethyl-2-formylcyclopropanecarboxylate and the like That.

（式中、Ｒ¹、Ｒ²およびＲ³はそれぞれ上記と同一の意味を表わす。）
で示されるジオール類が生成する。還元処理は、通常β−ヒドロキシヒドロペルオキシドと還元剤を混合することにより実施され、還元剤としては、例えばチオ硫酸ナトリウム等の無機還元剤、例えばジメチルスルフィド、トリフェニルホスフィン等の有機還元剤等が挙げられる。かかる還元剤の使用量は、β−ヒドロキシヒドロペルオキシド類に対して、通常１モル倍以上であり、その上限は特にないが、実用性を考慮すると、β−ヒドロキシヒドロペルオキシド類に対して５モル倍以下である。 Also, diols can be obtained by reducing β-hydroxy hydroperoxides. When the β-hydroxyhydroperoxides represented by the general formula (2) are reduced, the general formula (3)

(Wherein R ¹ , R ² and R ³ each have the same meaning as described above.)
Is produced. The reduction treatment is usually carried out by mixing β-hydroxyhydroperoxide and a reducing agent. Examples of the reducing agent include inorganic reducing agents such as sodium thiosulfate, and organic reducing agents such as dimethyl sulfide and triphenylphosphine. Can be mentioned. The amount of the reducing agent to be used is usually 1 mol or more with respect to β-hydroxyhydroperoxides, and there is no particular upper limit, but considering practicality, 5 mol with respect to β-hydroxyhydroperoxides. Is less than double.

  The temperature of the reduction treatment is usually in the range of 10 to 100 ° C. This reduction treatment is also usually performed in the presence of a solvent in which β-hydroxyhydroperoxides are dissolved. When using a reaction solution containing β-hydroxyhydroperoxides obtained by oxidizing olefins with hydrogen peroxide in the presence of the above-described metal oxide catalyst, the reaction solution is directly mixed with a reducing agent. However, since there are many cases where an unreacted hydrogen peroxide or other oxidizing substance remains in the reaction solution, after removing β-hydroxyhydroperoxides from the reaction solution by, for example, extraction treatment Mixing with a reducing agent is preferable from an economical viewpoint.

  Examples of diols include 2-methyl-2,3-dihydroxypentane, 3-methyl-2,3-dihydroxyhexane, 1-methyl-1,2-dihydroxycyclopentane, 1-methyl-1,2-dihydroxycyclohexane. 1,3-dimethyl-1,2-dihydroxycyclohexane, 1,3,5-trimethyl-1,2-dihydroxycyclohexane, 3,4-calendiol, 3,3-dimethyl-2- (2-methyl-1) , 2-Dihydroxypropyl) methyl cyclopropanecarboxylate, ethyl 3,3-dimethyl-2- (2-methyl-1,2-dihydroxypropyl) cyclopropanecarboxylate, 3,3-dimethyl-2- (2-methyl) -1,2-dihydroxypropyl) cyclopropanecarboxylate isopropyl, 3,3-dimethyl-2- (2 Tert-butyl methyl-1,2-dihydroxypropyl) cyclopropanecarboxylate, cyclohexyl 3,3-dimethyl-2- (2-methyl-1,2-dihydroxypropyl) cyclopropanecarboxylate, 3,3-dimethyl-2 -(2-methyl-1,2-dihydroxypropyl) cyclopropanecarboxylate menthyl, benzyl 3,3-dimethyl-2- (2-methyl-1,2-dihydroxypropyl) cyclopropanecarboxylate,

3,3-dimethyl-2- (2-methyl-1,2-dihydroxypropyl) cyclopropanecarboxylic acid (4-chlorobenzyl), 3,3-dimethyl-2- (2-methyl-1,2-dihydroxypropyl) ) Cyclopropanecarboxylic acid (2,3,5,6-tetrafluorobenzyl), 3,3-dimethyl-2- (2-methyl-1,2-dihydroxypropyl) cyclopropanecarboxylic acid (2,3,5, 6-tetrafluoro-4-methylbenzyl), 3,3-dimethyl-2- (2-methyl-1,2-dihydroxypropyl) cyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-methoxy) Benzyl), 3,3-dimethyl-2- (2-methyl-1,2-dihydroxypropyl) cyclopropanecarboxylic acid (2,3,5,6-tetrafluoro- - methoxymethylbenzyl) 3,3-dimethyl-2- (2-methyl-1,2-dihydroxypropyl) cyclopropane carboxylic acid (3-phenoxybenzyl) and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples. The conditions for gas chromatography analysis (hereinafter abbreviated as GC analysis) and high performance liquid chromatography analysis (hereinafter abbreviated as LC analysis) are as follows.

<GC analysis conditions>
Column: DB-1 (φ0.25 μm × 30 m, film thickness 1.0 μm)
Carrier gas: helium (flow rate: 1 m / min)
Split ratio: 1/10, sample injection volume: 1 μL
Column temperature: 100 ° C. (0 min) → 180 ° C. (temperature rising rate: 2 ° C./min, holding time at 180 ° C .: 0 min) → 300 ° C. (temperature rising rate: 10 ° C./min, holding at 300 ° C.) (Time: 15 minutes)
Inlet temperature: 200 ° C, detector temperature: 250 ° C

<LC analysis conditions>
Column: SUMPAX ODS A-212 (5 μm, φ6 mm × 15 cm)
Mobile phase: Liquid A; 0.1 vol% trifluoroacetic acid aqueous solution
B liquid: 0.1 vol% trifluoroacetic acid / acetonitrile solution A liquid / B liquid = 90/10 (volume ratio) to 40 liquids, linear change from A liquid / B liquid = 10/90 (volume ratio) And held for 20 minutes at a composition ratio of liquid A / liquid B = 10/90 (volume ratio).
Flow rate: 1.0 mL / min, sample injection amount: 10 μL, detection wavelength: 220 nm

Example 1 <Preparation of oxide by reaction of tungsten metal and hydrogen peroxide>
4 g of tungsten metal powder was added to the beaker, and 50 g of a 15 wt% aqueous hydrogen peroxide solution was further added, and the mixture was stirred at room temperature. While the oxygen gas was generated, the tungsten metal powder was dissolved (internal temperature increased to 60 ° C.), and a uniform transparent liquid colored pale yellowish brown was obtained. After cooling this solution to room temperature and decomposing the remaining hydrogen peroxide using a platinum net, water was distilled off from the solution at room temperature using a rotary evaporator to obtain a pale yellow solid (tungsten oxide). Obtained. This solid was dried to a constant weight at room temperature and in an open air system to obtain 5.8 g of solid.

UV spectrum of homogeneous transparent liquid before concentration λ ^H2O _max : 204,238 nm
IR spectrum of uniform transparent liquid before concentration (aqueous solution; 4000 to 750 cm ⁻¹ )
ν _max : 3342, 1275, 1030, 967, 837 cm ⁻¹
IR spectrum (KBr) of the obtained solid
ν _max : 3531, 3452, 2945, 1653, 1619, 973, 906, 638, 551 cm ⁻¹
Elemental analysis value; W: 63.9, O: 31.2, H: 1.6

Example 2 <Preparation of oxide by reaction of tungsten boride and hydrogen peroxide>
To a 100 mL flask equipped with a magnetic rotor and a reflux condenser, 4.2 g of tungsten boride powder and 25 g of water were added, and 18 g of a 60 wt% hydrogen peroxide aqueous solution was stirred for 2 hours at an internal temperature of 40 ° C. It was dripped. The mixture was further kept warm at the same temperature for 2 hours to obtain a colorless solution in which white crystals slightly floated. After cooling this solution to room temperature and decomposing the remaining hydrogen peroxide using a platinum net, water was distilled off from the solution using a rotary evaporator at room temperature to obtain a white solid (oxide). This was dried to a constant weight at room temperature and in an open air system to obtain 5.8 g of a solid.

UV spectrum of colorless solution before concentration λ ^H2O _max : 200,235 (s) nm
IR spectrum of colorless solution before concentration (aqueous solution; 4000-750 cm ⁻¹ )
ν _max : 3350, 2836, 1275, 1158, 965, 836 cm ⁻¹
IR spectrum (KBr) of the obtained solid
ν _max : 3527, 3220, 2360, 2261, 1622, 1469, 1196, 973, 904.5, 884, 791, 640, 549 cm ⁻¹
Elemental analysis value; W: 51.2, O: 39.0, H: 2.2, B: 3.98

Example 3 <Preparation of oxide by reaction of tungsten sulfide and hydrogen peroxide>
In Example 2, it replaced with the tungsten boride powder, and it implemented similarly to Example 2 except having used 5.4 g of tungsten sulfide and having changed the quantity of water to 12 g, and obtained 10.1 g of pale yellow solid.
UV spectrum of solution before concentration λ ^H2O _max : 200,240 (s) nm
IR spectrum of colorless solution before concentration (aqueous solution; 4000-750 cm ⁻¹ )
ν _max : 3373, 1187, 1044, 974, 878, 837 cm ⁻¹
IR spectrum (KBr) of the obtained solid
ν _max : 3435, 3359, 1730, 1632, 1320, 1285, 1178, 1103, 1070, 1008, 981, 887, 839, 851, 660, 615, 578 cm ⁻¹
Elemental analysis value; W: 35.3, O: 47.7, H: 3.0, S: 12.4

Example 4 <Preparation of Oxide by Reaction of Molybdenum Metal with Hydrogen Peroxide>
In Example 2, instead of tungsten boride powder, 2.1 g of molybdenum metal was used, the amount of water was 12 g, and the amount of 60 wt% aqueous hydrogen peroxide was 12 g. Carried out 4.0 g of yellow solid.
UV spectrum of solution before concentration λ ^H2O _max : 207,300 nm
IR spectrum of colorless solution before concentration (aqueous solution; 4000-750 cm ⁻¹ )
ν _max : 3359, 2480, 1372, 974, 866 cm ⁻¹
IR spectrum (KBr) of the obtained solid
ν _max : 3530, 1621, 964, 927, 902, 840, 633, 557, 530, 522 cm ⁻¹
Elemental analysis value; Mo: 47.8, O: 46.2, H: 2.1

Example 5 <Preparation of oxide by reaction of molybdenum boride and hydrogen peroxide>
In Example 2, instead of tungsten boride powder, 2.3 g of molybdenum boride was used, the amount of water was 12 g, and the amount of 60 wt% aqueous hydrogen peroxide solution was 12 g. To obtain 5.2 g of a yellow solid.
UV spectrum of the solution before concentration λ ^H2O _max : 200,310 nm
IR spectrum (KBr) of the obtained solid
ν _max : 3221, 2520, 2361, 2262, 1620, 1463, 1439, 1195, 965, 927, 887, 840, 799, 674, 634, 547, 529 cm ⁻¹
Elemental analysis value; Mo: 35.5, O: 51.0, H: 2.9, B: 4.1

Comparative Example 1 <Preparation of Oxidized Compound by Reaction of Tungstic Acid and Hydrogen Peroxide>
To a beaker, 5.4 g of tungstic acid (H ₂ WO ₄ ) was added, and 50 g of a 15 wt% aqueous hydrogen peroxide solution was further added, and the mixture was stirred at room temperature. Since the crystals of tungstic acid were not completely dissolved, the internal temperature was raised to 55 ° C., and further stirred and held for 2 hours. After cooling, unreacted crystals were filtered off, and the resulting solution was decomposed with hydrogen peroxide using a platinum net, and then water was distilled off from the solution at room temperature using a rotary evaporator. A solid was obtained. This solid was dried to a constant weight at room temperature and in an open air system to obtain 3.0 g of a solid.

UV spectrum of the solution before concentration λ ^H2O _max : 210,250 (s) nm
IR spectrum of the solution before concentration (aqueous solution; 4000 to 750 cm ⁻¹ )
ν _max : 3400, 2833, 1355, 967, 836 cm ⁻¹
IR spectrum (KBr) of the obtained solid
ν _max : 3416, 1623, 1385, 975, 880, 839, 749, 700, 643, 625, 550 cm ⁻¹
Elemental analysis value; W: 63.9, O: 31.2, H: 1.6
These spectral data were compared with the oxide obtained by the reaction between the tungsten metal obtained in Example 1 and hydrogen peroxide, but they were different oxides.

Example 6
A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 2 g of 30 wt% hydrogen peroxide and 97 mg of tungsten metal, and stirred and held at an internal temperature of 60 ° C. for 0.5 hour. To this, 3.5 g of isophorone and 25.8 g of 30% by weight hydrogen peroxide were added dropwise over 20 minutes. After completion of the dropping, the reaction solution was heated and stirred for 6 hours in an oil bath having an internal temperature of 95 ° C. After completion of the reaction, the reaction mixture was cooled to an internal temperature of 25 ° C. and analyzed by GC. As a result, 3,3-dimethyl-5-oxohexanoic acid was produced (area percentage value: 55%).

Example 7
A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 2 g of 30 wt% aqueous hydrogen peroxide and 30 mg of tungsten metal, and stirred and held at an internal temperature of 60 ° C. for 0.5 hour. This was charged with 3.0 g of methyl 3,3-dimethyl-2- (2-methyl-1-propenyl) -cyclopropanecarboxylate and 7.3 g of 30 wt% aqueous hydrogen peroxide. Thereafter, the reaction solution was heated and stirred for 6 hours in an oil bath having an internal temperature of 95 ° C. After completion of the reaction, the reaction mixture was cooled to an internal temperature of 25 ° C. and analyzed by GC. As a result, 3,3-dimethyl-2-carbomethoxycyclopropanecarboxylic acid was produced (area percentage value: 43%). The production of acetone was also confirmed.

Example 8
A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 2 g of 30 wt% hydrogen peroxide water and 90 mg of tungsten metal, and stirred and held at an internal temperature of 60 ° C. for 0.5 hour. This was charged with 4.7 g of 1-methylcyclohexene and 25.6 g of 30% by weight hydrogen peroxide solution. Thereafter, the reaction solution was heated and stirred in an oil bath having an internal temperature of 95 ° C. for 10 hours. After completion of the reaction, the mixture was cooled to 25 ° C. and subjected to GC analysis (internal standard method). As a result, 6-oxohexanoic acid was produced (yield: 92%).

Example 9
A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 200 mg of 30 wt% hydrogen peroxide and 40 mg of tungsten boride and stirred and reacted at an internal temperature of 40 ° C. for 0.5 hour. After cooling the resulting solution to an internal temperature of 25 ° C., 1.5 g of tert-butanol, 30 wt% aqueous hydrogen peroxide and 530 mg of anhydrous magnesium sulfate were added and stirred and held for 1 hour. A liquid mixture consisting of 350 mg of 3-carene and 1.5 g of tert-butanol was dropped into the resulting slurry liquid over 10 minutes, and the mixture was stirred and held at an internal temperature of 25 ° C. for 24 hours. To the reaction solution, 10 g of toluene and 5 g of water were added and extracted to obtain 9.4 g of an organic layer. LC analysis of the organic layer revealed that 3-hydroperoxy-4-hydroxycarene and 3,4-calendiol were produced. In addition, 2,2-dimethyl-3- (2-oxopropyl) cyclopropaneacetaldehyde was not detected.

GC analysis of the organic layer revealed that 3-hydroperoxy-4-hydroxycalene was thermally decomposed at the inlet and detected as 2,2-dimethyl-3- (2-oxopropyl) cyclopropaneacetaldehyde. The yield of 2,2-dimethyl-3- (2-oxopropyl) cyclopropaneacetaldehyde was calculated from the results of GC analysis (internal standard method), and the yield was calculated according to 3-hydroperoxy-4-hydroxycarene. Yield.
Yield of 3-hydroperoxy-4-hydroxycarene: 70.4%
Yield of 3,4-calendiol: 21.7%

Physical property data of 3-hydroperoxy-4-hydroxycarene LC analysis retention time: 20.9 minutes, LC-MS: M ⁺ = 186

A 50 mL flask equipped with a magnetic rotator and a reflux condenser was charged with 200 mg of 30 wt% hydrogen peroxide and 20 mg of vanadium metal powder at room temperature and stirred, and reacted vigorously to obtain a reddish brown uniform solution. To the reddish brown uniform solution, 9 g of the organic layer was added, and the mixture was reacted by stirring at room temperature for 16 hours and further at an internal temperature of 60 ° C. for 3 hours. When the reaction solution was analyzed by LC, 3-hydroperoxy-4-hydroxycarene disappeared, and 2,2-dimethyl-3- (2-oxopropyl) cyclopropaneacetaldehyde and 3,4-calendiol were detected. When the yield of 2,2-dimethyl-3- (2-oxopropyl) cyclopropaneacetaldehyde was determined by GC analysis (internal standard method), the yield was 71.4% (based on 3-carene).

Example 10
A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 400 mg of 30 wt% aqueous hydrogen peroxide and 80 mg of tungsten metal powder, and stirred and reacted at an internal temperature of 40 ° C. for 30 minutes. The obtained solution was cooled to an internal temperature of 25 ° C., 2 g of tert-butanol and 800 mg of 30 wt% hydrogen peroxide solution were added, and the mixture was stirred for 1 hour. To this solution, a mixed solution composed of 600 mg of 3-carene and 2.0 g of tert-butanol was dropped over 10 minutes, and the mixture was stirred at an internal temperature of 25 ° C. for 24 hours to be reacted. 27 g of 5% by weight aqueous sodium thiosulfate solution was added to the resulting reaction solution (including 3-hydroperoxy-4-hydroxycarene and 3,4-calendiol), and reduction treatment was performed to obtain 3,4-calendiol. Obtained. The yield was determined by GC analysis (internal standard method) and found to be 70% (3-carene basis).

Example 11
A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 200 mg of 30 wt% hydrogen peroxide water, tert-butanol and 22 mg of tungsten boride, and stirred and reacted at an internal temperature of 60 ° C. for 1 hour. After cooling to an internal temperature of 25 ° C., 530 mg of anhydrous magnesium sulfate was added, and a mixed solution consisting of 270 mg of 1-methylcyclohexene, 1.0 g of tert-butanol and 500 mg of 30 wt% hydrogen peroxide was added dropwise over 20 minutes, When the mixture was stirred and reacted at an internal temperature of 25 ° C. for 20 hours, a reaction solution containing 1-methyl-1-hydroperoxy-2-hydroxycyclohexane was obtained. When the reaction solution was analyzed by GC, 1-methyl-1-hydroperoxy-2-hydroxycyclohexane was thermally decomposed at the GC inlet and detected as 6-oxoheptylaldehyde. The area percentage value of 6-oxoheptylaldehyde detected was 77.0%.

Example 12
A 500 mL flask equipped with an induction stirrer and a reflux condenser was charged with 1 g of tungsten metal powder and 7.5 g of water, and with stirring, 7.5 g of 60 wt% hydrogen peroxide water at an internal temperature of 60 ° C. over 1 hour. The solution was added dropwise, stirred and reacted at the same temperature for 1 hour to obtain a uniform solution. The homogeneous solution was cooled to room temperature, charged with 38 g of tert-butanol and 13.3 g of anhydrous magnesium sulfate, and further stirred at room temperature for 14 hours. To the obtained slurry solution, a mixed solution composed of 10 g of methyl trans-3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate and 12 g of tert-butanol was dropped over 20 minutes. The mixture was stirred and reacted at an internal temperature of 25 ° C. for 24 hours. Thereafter, 60 g of water was added, and the mixture was extracted twice with 50 g of toluene to obtain 167.4 g of a toluene solution. LC analysis of the toluene solution revealed that methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate, trans-3,3-dimethyl-2- Methyl (1,2-dihydroxy-2-methylpropyl) cyclopropanecarboxylate and methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate were formed.

Physical property data of trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate methyl LC analysis retention time: 18.7 minutes, LC-MS: M ⁺ = 232
¹ H-NMR spectrum: δ 8.82 ppm, bs (derived from —OOH)

  In GC analysis, methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate was thermally decomposed at the inlet, and trans-3,3-dimethyl was obtained. -2-formylcyclopropanecarboxylate is detected as methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate and trans-3, The yield of methyl 3-dimethyl-2-formylcyclopropanecarboxylate was calculated using both GC analysis and LC analysis. Yield of methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate: 52.6% trans-3,3-dimethyl-2-formylcyclo Yield of methyl propanecarboxylate: 5%

  A 500 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 500 mg of vanadium pentoxide and 100 g of toluene. At an internal temperature of 60 ° C., 167 g of the toluene solution was added dropwise over 2 hours, and the mixture was further stirred at the same temperature for 1 hour. Reacted. When the reaction solution was analyzed by LC, methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate disappeared, and trans-3,3- A peak of methyl dimethyl-2-formylcyclopropanecarboxylate was detected. According to GC analysis (internal standard method), the yield of methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 54.5%.

Example 13
A 100 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 400 mg of tungsten metal powder and 3 g of water, and 3 g of 60 wt% hydrogen peroxide water was added dropwise over 1 hour at an internal temperature of 40 ° C. Stir for hours and react to give a homogeneous solution. The homogeneous solution was cooled to room temperature, charged with 15 g of tert-butanol and 5.3 g of anhydrous magnesium sulfate, and further stirred at room temperature for 1 hour. To the obtained slurry solution, a mixed solution consisting of 4 g of methyl trans-3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate and 8 g of tert-butanol was dropped over 20 minutes. The mixture was stirred and reacted at an internal temperature of 25 ° C. for 24 hours. Thereafter, 50 g of a 5 wt% aqueous sodium thiosulfate solution was added, and the mixture was further stirred at room temperature for 24 hours. Thereafter, extraction was performed twice with 20 g of toluene to obtain 83.7 g of a toluene solution. GC analysis of the toluene solution revealed that the toluene solution contained methyl trans-3,3-dimethyl-2- (1,2-dihydroxy-2-methylpropyl) cyclopropanecarboxylate. The rate (according to the internal standard method) was 80%.

Example 14
A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 40 mg of tungsten metal powder and 600 mg of 30 wt% hydrogen peroxide solution, and stirred for 1 hour at an internal temperature of 40 ° C. for reaction. The mixture was cooled to room temperature, charged with 1.5 g of tert-butanol and 530 mg of anhydrous magnesium sulfate, and stirred at room temperature for 1 hour. To the resulting slurry solution was added a mixture of 400 mg methyl trans-3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate and 1.5 g tert-butanol, and the internal temperature was 60. After stirring and reacting at 4 ° C. for 4 hours, 5 g of water was added, and the mixture was extracted twice with 5 g of toluene to obtain a toluene solution. GC analysis and LC analysis of the toluene solution revealed that methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate and trans-3,3-dimethyl- Methyl 2-formylcyclopropanecarboxylate was contained, and the yields (according to the internal standard method) were 33% and 12%, respectively.

Example 15
A 100 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 450 mg of tungsten boride powder and 3 g of water. At an internal temperature of 40 ° C., 3 g of 60 wt% hydrogen peroxide was added dropwise over 1 hour. The mixture was stirred for 1 hour and reacted to obtain a homogeneous solution. The homogeneous solution was cooled to room temperature, charged with 15 g of tert-butanol and 5.3 g of anhydrous magnesium sulfate, and stirred at room temperature for 1 hour. To the resulting slurry solution, a mixed solution consisting of 4 g of methyl trans-3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate and 8 g of tert-butanol was added at an internal temperature of 15 ° C. The solution was added dropwise over a period of time, and the mixture was further stirred at the same temperature for 21 hours to be reacted. Thereafter, 50 g of water was added, and extraction processing was performed twice with 50 g of toluene to obtain a toluene solution. GC analysis and LC analysis of the toluene solution revealed that methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate and trans-3,3-dimethyl- Methyl 2-formylcyclopropanecarboxylate was contained, and the yields (according to the internal standard method) were 58% and 4%, respectively.

Example 16
A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 45 mg of tungsten boride powder and 200 mg of 30 wt% hydrogen peroxide water, and stirred and reacted at an internal temperature of 40 ° C. for 1 hour to obtain a uniform solution. The mixture was cooled to room temperature, charged with 1.5 g of tert-butanol, 400 mg of 30% by weight hydrogen peroxide and 530 mg of anhydrous magnesium sulfate, and further stirred at room temperature for 2 hours. To the resulting slurry solution, a mixed solution consisting of 400 mg of trans-3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate and 0.8 g of tert-butanol was added at an internal temperature of 25 ° C. Was added dropwise over 20 minutes, and the mixture was further stirred at the same temperature for 16 hours to be reacted. Thereafter, 5 g of water was added, and extracted twice with 5 g of toluene to obtain a toluene solution. GC analysis and LC analysis of the toluene solution revealed that methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate and trans-3,3-dimethyl were used. Methyl-2-formylcyclopropanecarboxylate was contained, and the yields (according to the internal standard method) were 60.8% and 6%, respectively.

Example 17
A 500 mL flask equipped with an induction stirrer and a reflux condenser was charged with 2 g of tungsten metal powder and 15 g of water, and 7.3 g of 60 wt% hydrogen peroxide water was added dropwise at an internal temperature of 40 ° C. over 1 hour. The mixture was stirred and reacted for 1 hour to obtain a uniform solution. The homogeneous solution was cooled to room temperature, charged with 78 g of tert-butanol, 12 g of 60 wt% hydrogen peroxide and 26.6 g of anhydrous magnesium sulfate, and stirred and maintained at room temperature for 2 hours. To the resulting slurry solution, a mixed solution composed of 20 g of methyl trans-3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate and 24 g of tert-butanol was added at an internal temperature of 20 ° C. The solution was added dropwise over a period of time, and the mixture was further stirred and reacted at the same temperature for 20 hours. Thereafter, 120 g of water was added, and the mixture was extracted twice with 50 g of toluene to obtain 251.7 g of a toluene solution. GC analysis and LC analysis of the toluene solution revealed that methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate and trans-3,3-dimethyl- Methyl 2-formylcyclopropanecarboxylate was contained, and the yields (according to the internal standard method) were 58% and 3%, respectively.

  To a 500 mL flask equipped with a magnetic rotor and a reflux condenser, 245 g of the above toluene solution was charged, and 10.6 g of 28 wt% sodium methylate solution was added at an internal temperature of 15 ° C., and reacted at the same temperature for 6 hours. The obtained reaction solution was neutralized with 100 g of 10 wt% aqueous hydrochloric acid, washed with 100 g of 5 wt% aqueous sodium thiosulfate solution and then with 100 g of water, and then subjected to LC analysis to obtain trans-3,3-dimethyl-2- (1- It was confirmed that methyl hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate disappeared and a peak of methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was detected. According to GC analysis (internal standard method), the yield of methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 26.8%.

Example 18
A 500 mL flask equipped with an induction stirrer and a reflux condenser is charged with 1 g of tungsten metal powder and 3 g of water, and 9 g of 60 wt% hydrogen peroxide water is added dropwise over 1 hour at an internal temperature of 40 ° C. The mixture was stirred and reacted to obtain a uniform solution. The homogeneous solution was cooled to room temperature, charged with 38 g of tert-butanol, and stirred at room temperature for 1 hour. To the obtained solution, a mixed solution consisting of 10 g of methyl trans-3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate and 12 g of tert-butanol was dropped over 20 minutes, The mixture was stirred and reacted at an internal temperature of 25 ° C. for 18 hours. Thereafter, 60 g of water was added, and the mixture was extracted twice with 50 g of toluene to obtain a toluene solution. GC analysis and LC analysis of the toluene solution revealed that methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate and trans-3,3-dimethyl- Methyl 2-formylcyclopropanecarboxylate was contained, and the yields (according to the internal standard method) were 50.5% and 5%, respectively.

Example 19
In the same manner as in Example 17, 250 g of a toluene solution containing methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate was obtained (content) : 4.28% by weight). After dehydrating this solution with 15 g of anhydrous magnesium sulfate, 0.75 g of cupric chloride was added, and the mixture was stirred and reacted at an internal temperature of 25 ° C. for 12 hours. The reaction solution was washed with 100 g of 5 wt% aqueous sodium thiosulfate solution and then with 100 g of water to obtain 187 g of a toluene solution. LC analysis of the toluene solution revealed that methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate disappeared and trans-3,3-dimethyl was removed. Methyl-2-formylcyclopropanecarboxylate was detected. The yield of methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was determined by GC analysis (internal standard method) and found to be 60.3% (trans-3,3-dimethyl-2- (Based on methyl 1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate).

Example 20
4.1 wt% methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate and trans-3,3-dimethyl-2-formylcyclopropanecarboxylic acid To 50 g of a toluene solution containing 0.61% by weight of methyl acid, 50 g of tert-butanol and 0.11 g of ruthenium chloride were added, and the mixture was stirred and reacted at room temperature for 5 hours. LC analysis of the reaction solution confirmed the disappearance of methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate. To the reaction solution from which insolubles were removed by filtration, 113 g of toluene was charged and concentrated under reduced pressure to distill off about 80 g of light boiling components such as tert-butanol. Further, it was washed with 23 g of a 5 wt% aqueous sodium thiosulfate solution to obtain 130 g of a toluene solution. As a result of GC analysis, the content of methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 1.1% by weight, and the yield was 79% (trans-3,3-dimethyl- 2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate methyl basis).

Example 21
3.73 wt% methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate and trans-3,3-dimethyl-2-formylcyclopropanecarboxylic acid To 40 g of a toluene solution containing 0.37 wt% of methyl acid, 0.16 g of palladium acetate was added, and the mixture was stirred and reacted at room temperature for 6 hours. Insoluble matter was filtered off from the reaction solution (washed with 5 g of toluene), washed twice with 9 g of 5 wt% aqueous sodium thiosulfate solution and then with 5 g of 5 wt% aqueous sodium hydrogen carbonate solution, to obtain 34.2 g of toluene solution. Obtained. As a result of GC analysis, the content of methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 2.25% by weight, and the yield was 61.9% (trans-3,3- Dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate methyl basis).

Examples 22-25
In Example 21, it replaced with palladium acetate and implemented similarly to Example 21 except having used the compound of the following table 1. The yield of methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate is shown in Table 1 below.

Example 26
3.73 wt% methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate and trans-3,3-dimethyl-2-formylcyclopropanecarboxylic acid 0.040 g of ammonium vanadate was added to 40 g of a toluene solution containing 0.37% by weight of methyl acid, stirred at room temperature for 5 hours, and then reacted at an internal temperature of 85 ° C. for another 5 hours. The reaction solution was cooled to room temperature and subjected to the same post treatment as in Example 21 to obtain 37.0 g of a toluene solution. As a result of GC analysis, the content of methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 1.5% by weight, and the yield was 40.2% (trans-3,3- Dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate methyl basis).

Example 27
In Example 26, 36 g of a toluene solution was obtained in the same manner as in Example 26 except that 0.18 g of cobalt (II) acetate tetrahydrate was used instead of ammonium vanadate. Content of methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate: 2.2% by weight, yield: 63.8% (trans-3,3-dimethyl-2- (1-hydroxy-2- Hydroperoxy-2-methylpropyl) methyl cyclopropanecarboxylate).

Example 28
4.1 wt% methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate and trans-3,3-dimethyl-2-formylcyclopropanecarboxylic acid To 40 g of a toluene solution containing 0.61% by weight of methyl acid, 0.1 g of niobium (V) chloride was added, stirred at room temperature for 15 hours, and then reacted at an internal temperature of 85 ° C. for another 5 hours. As a result of LC analysis, methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate was observed. 0.1 g of the product was added to the reaction solution, and further reacted at room temperature for 5 hours. The post-process similar to Example 19 was performed, and the toluene solution 36.0g was obtained. Content of methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate: 2.2% by weight, yield: 63.8% (trans-3,3-dimethyl-2- (1-hydroxy-2- Hydroperoxy-2-methylpropyl) methyl cyclopropanecarboxylate).
Table 2 shows the results (area percentage values) of LC analysis of the reaction solution (before addition of cupric chloride) obtained using the raw material toluene solution and niobium chloride (V). In Table 2 below, the hydroperoxide form is methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate, and the formyl form is trans- It means methyl 3,3-dimethyl-2-formylcyclopropanecarboxylate, and the same applies to the following examples.

Examples 29-31
In Example 28, it carried out similarly to Example 28 except having used the compound shown in the following table 3 instead of niobium chloride (V). The yield of methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate in each example is shown in Table 3 below. The LC analysis results (area percentage values) of the reaction solution before adding cupric chloride are shown in Table 4 below.

Example 32
3.78% by weight methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate and trans-3,3-dimethyl-2-formylcyclopropanecarboxylic acid 50 g of tert-butanol and 0.20 g of antimony (III) chloride were added to 50 g of a toluene solution containing 0.37% by weight of methyl acid, and the mixture was stirred and reacted at an internal temperature of 85 ° C. for 9 hours. After cooling to room temperature, 0.10 g of cupric chloride was added, and the mixture was further stirred and reacted for 5 hours. The reaction solution was charged with 113 g of toluene and concentrated under reduced pressure to distill off about 120 g of light boiling components such as tert-butanol. Further, it was washed with 23 g of a 5% by weight aqueous sodium thiosulfate solution to obtain 83.6 g of a toluene solution. Content of methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate: 1.2% by weight, yield: 66.7%.
Table 5 shows the results (area percentage values) of LC analysis of the reaction solution (before addition of cupric chloride) obtained using the raw material toluene solution and antimony (III) chloride.

Example 33
A 500 mL flask equipped with a stirrer and a reflux condenser was charged with 1 g of tungsten metal powder and 9 g of water, and 9 g of 60 wt% hydrogen peroxide water was added dropwise over 1 hour at an internal temperature of 50 ° C., and further at that temperature for 1 hour. The mixture was stirred and reacted to obtain a uniform solution. The homogeneous solution was cooled to room temperature, charged with 38 g of tert-butanol and 17 g of anhydrous magnesium sulfate, and stirred at an internal temperature of 10 ° C. for 1 hour. To the resulting slurry solution, a mixed solution consisting of 10 g of methyl trans-3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate and tert-butanol was added dropwise over 1 hour, The mixture was stirred and reacted at the same temperature for 20 hours to obtain 67.2 g of a reaction solution. To the 9.6 g of the reaction solution, 0.15 g of cuprous bromide was added, and the mixture was further stirred and reacted at an internal temperature of 10 ° C. for 2 days. Table 6 below shows the LC analysis results (area percentage values) of the reaction liquid before and after adding cuprous bromide.

Examples 34-35
In Example 33, it carried out like Example 33 except having replaced with the cuprous bromide and having used the compound shown in the following table 7. The LC analysis results (area percentage values) of the reaction liquid after addition of the compounds shown in Table 7 are shown in Table 7 below.

Example 36
A 100 mL flask was charged with 10 g of tert-butanol, 2 g of 30% by weight hydrogen peroxide solution and 215 mg of tungsten boride, and stirred and reacted at an internal temperature of 60 ° C. for 1 hour. After cooling to an internal temperature of 20 ° C., 5.3 g of anhydrous magnesium sulfate was added, and 4 g of methyl trans-3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate and 30% by weight peroxidation. A mixed solution consisting of 5 g of hydrogen water and 10 g of tert-butanol was added dropwise over 20 minutes. The mixture was stirred and reacted at an internal temperature of 25 ° C. for 36 hours, methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate and trans-3,3-dimethyl. A reaction solution containing methyl 2-formylcyclopropanecarboxylate was obtained. GC analysis and LC analysis of the reaction solution revealed that the yield of methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate was 48.3%. The yield of methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 5%.

Example 37
A 50 mL flask was charged with 3 g of tert-butanol, 200 mg of 30% by weight hydrogen peroxide, 16 mg of boric anhydride and 40 mg of tungsten metal powder, and stirred and reacted at an internal temperature of 60 ° C. for 1 hour. After cooling to an internal temperature of 25 ° C., 530 mg of anhydrous magnesium sulfate was charged, and further 400 mg of trans-3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate and 30% by weight hydrogen peroxide solution A mixture of 600 mg and 1.8 g of tert-butanol was added dropwise over 20 minutes, and the mixture was stirred and reacted at the same temperature for 16 hours to obtain trans-3,3-dimethyl-2- (1-hydroxy-2-hydro A reaction solution containing methyl peroxy-2-methylpropyl) cyclopropanecarboxylate and methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was obtained. The reaction solution was analyzed by GC and LC. The yield of methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate was 54.8%. The yield of methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 6%.

Example 38
A 100 mL flask was charged with 10 g of tert-butanol, 2.0 g of 30 wt% hydrogen peroxide solution and 215 mg of tungsten boride, and stirred and reacted at an internal temperature of 60 ° C. for 1 hour. After cooling to an internal temperature of 20 ° C., from 4 g of methyl trans-3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate, 4 g of 30 wt% aqueous hydrogen peroxide and 10 g of tert-butanol The resulting mixture was added dropwise over 20 minutes, stirred and reacted at the same temperature for 48 hours, and trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxyl. A reaction solution containing methyl acetate and methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was obtained. The reaction solution was analyzed by GC and LC. As a result, the yield of methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate was 36%. The yield of methyl 3,3-dimethyl-2-formylcyclopropanecarboxylate was 4%.

Example 39
A 50 mL flask was charged with 3 g of tert-butanol, 200 mg of 30% by weight hydrogen peroxide, and 40 mg of tungsten metal powder, and stirred and reacted at an internal temperature of 60 ° C. for 1 hour. After cooling to an internal temperature of 25 ° C., 400 mg of methyl trans-3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate, 400 mg of 30 wt% hydrogen peroxide and 1.8 g of tert-butanol A mixed solution consisting of and added dropwise over 20 minutes, stirred and reacted at the same temperature for 24 hours, trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclo A reaction solution containing methyl propanecarboxylate and methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was obtained. The reaction solution was analyzed by GC and LC. As a result, the yield of methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate was 45%. The yield of methyl 3,3-dimethyl-2-formylcyclopropanecarboxylate was 5%.

Example 40
A 50 mL flask was charged with 3 g of methyl tert-butyl ether, 1.2 g of 30 wt% hydrogen peroxide water and 40 mg of tungsten boride, and the mixture was stirred and reacted at an internal temperature of 50 ° C. for 1 hour. To this, 2.3 g of anhydrous magnesium sulfate was added, and a mixed solution consisting of 400 mg of trans-3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate methyl and 1.8 g of methyl tert-butyl ether. Is added dropwise over 20 minutes and stirred at the same temperature for 2 hours to react with methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate. A reaction solution containing methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was obtained. The reaction solution was analyzed by GC and LC. As a result, the yield of methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate was 37%. The yield of methyl 3,3-dimethyl-2-formylcyclopropanecarboxylate was 4%.

Example 41
A 50 mL flask was charged with 3 g of tert-butanol, 2.3 g of magnesium sulfate, 300 mg of boric anhydride and 40 mg of tungsten boride. It consists of 400 mg of trans-3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate, 600 mg of 30 wt% aqueous hydrogen peroxide and 1.8 g of tert-butanol at an internal temperature of 60 ° C. The mixture was added dropwise over 20 minutes, stirred and reacted at the same temperature for 2 hours, trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylic acid A reaction solution containing methyl and methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was obtained. GC analysis and LC analysis of the reaction solution revealed that the yield of methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate was 42.2%. The yield of methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 5%.

Example 42
A 50 mL flask was charged with 3 g of tert-butanol and 51 mg of tungsten sulfide, and at an internal temperature of 60 ° C., 400 mg of methyl trans-3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate and 30 wt% A mixture of 1.5 g of hydrogen peroxide and 1.8 g of tert-butanol was added dropwise over 20 minutes, and the mixture was stirred and reacted at the same temperature for 2 hours to obtain trans-3,3-dimethyl-2- (1 A reaction solution containing methyl -hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate was obtained. When the reaction solution was analyzed by GC, methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate was thermally decomposed at the GC inlet, Detected as methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate. The GC area percentage value of the detected methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 23.8%.

Examples 43-44
In Example 42, it carried out similarly to Example 42 except having used the metal compound shown in the following table 8 instead of tungsten sulfide. The GC area percentage values of the detected methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate are shown in Table 8 below.

Example 45
A 50 mL flask was charged with 20 mg of molybdenum metal powder, 200 mg of 30 wt% hydrogen peroxide water was added, 1.5 g of tert-butanol and 530 mg of anhydrous magnesium sulfate were charged, and trans-3,3-dimethyl-2- A liquid mixture consisting of 400 mg of methyl (2-methyl-1-propenyl) cyclopropanecarboxylate, 600 mg of 30% by weight hydrogen peroxide and 1.5 g of tert-butanol was added dropwise over 20 minutes. Stirring and reaction at an internal temperature of 25 ° C. for 40 hours, methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate and trans-3,3-dimethyl A reaction solution containing methyl 2-formylcyclopropanecarboxylate was obtained. GC analysis and LC analysis of the reaction solution revealed that the yield of methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate was 51.7%. The yield of methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 5%. Moreover, 18.2% (GC area percentage value) of the raw material trans-3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate remained.

Examples 46-48
In Example 45, it implemented similarly to Example 45 except having changed reaction conditions into the conditions shown in the following Table 9. Yield of methyl trans-3,3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate and methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate Table 9 shows the GC area percentage values of the starting material and methyl trans-3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate. In the table, MTBE means methyl tert-butyl ether.

Claims (6)

Metal oxide catalyst obtained by reacting hydrogen peroxide with at least one metal compound selected from the group consisting of tungsten metal, molybdenum metal, tungsten boride, molybdenum boride, tungsten sulfide, molybdenum sulfide, tungsten carbide, and molybdenum carbide In the presence of general formula (1)

(Wherein R ¹ , R ² and R ³ are the same or different and each may be an alkyl group which may be substituted, an alkoxy group which may be substituted, an aryl group which may be substituted, An optionally substituted aryloxy group, an optionally substituted aralkyl group, an optionally substituted aralkyloxy group, an optionally substituted acyl group, an optionally substituted carboalkoxy group, and optionally substituted Represents a good carboaryloxy group, an optionally substituted carboaralkyloxy group, a carboxyl group or a halogen atom, and R ¹ and R ² , R ¹ and R ^3, or R ² and R ³ together form a ring Part of the structure may be formed.)
A process for producing ketones and carboxylic acids, characterized in that the trisubstituted olefins represented by formula (II) and hydrogen peroxide are reacted in the range of 65 to 200 ° C.   The method for producing ketones and carboxylic acids according to claim 1, wherein hydrogen peroxide water is used.   A trisubstituted olefin obtained by reacting hydrogen peroxide with at least one metal compound selected from the group consisting of tungsten metal, molybdenum metal, tungsten boride, molybdenum boride, tungsten sulfide, molybdenum sulfide, tungsten carbide, and molybdenum carbide. A metal oxide catalyst for producing ketones and carboxylic acids by oxidizing benzene.   Tri-substitution, obtained by reacting hydrogen peroxide with at least one metal compound selected from the group consisting of tungsten metal, molybdenum metal, tungsten boride, molybdenum boride, tungsten sulfide, molybdenum sulfide, tungsten carbide and molybdenum carbide. An aqueous metal oxide catalyst solution for producing ketones and carboxylic acids by oxidizing olefins.   A metal oxide catalyst solution for producing ketones and carboxylic acids by oxidizing a trisubstituted olefin comprising the metal oxide catalyst aqueous solution according to claim 4 and an organic solvent.   The metal compound is sufficiently dispersed in at least one metal compound selected from the group consisting of tungsten metal, molybdenum metal, tungsten boride, molybdenum boride, tungsten sulfide, molybdenum sulfide, tungsten carbide, and molybdenum carbide and hydrogen peroxide water. A method for preparing a metal oxide catalyst aqueous solution for producing ketones and carboxylic acids by oxidizing a trisubstituted olefin, wherein the reaction is carried out with stirring.