JP2003238462A - Method for producing aldehyde and ketone - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an aldehyde and a ketone under mild conditions, comprising decomposing a β-hydroxyhydroperoxide derived from a trisubstituted olefin compound. <P>SOLUTION: This method for producing the aldehyde represented by general formula (2) and the ketone represented by general formula (3) (R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>are each identically or differently an alkyl which may be substituted, or the like) comprises treating a β-hydroxyhydroperoxide represented by general formula (1) (either one of X and Y is OH, and the other is hydroperoxy) with a group VIa element. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing ketones and aldehydes, which are important as various chemical products and their synthetic intermediates.

[0002]

2. Description of the Prior Art Regarding β-hydroxyhydroperoxides derived from disubstituted olefins such as cyclopentene and α-methylstyrene, aldehydes and ketones can be obtained by thermal decomposition at a high temperature of 150 ° C. or higher. Are known (for example, JP-A-58-12123).
No. 4, Chem. Ber. , 129 , 1453 (1
996) etc.) derived from trisubstituted olefins
No method has been known for decomposing hydroxyhydroperoxides to produce aldehydes and ketones.

[0003]

Under these circumstances, the present inventors decomposed β-hydroxyhydroperoxides derived from trisubstituted olefins under mild conditions to give aldehydes and ketones. As a result of extensive studies to develop a method for producing compounds, the β-hydroxyhydroperoxides are allowed to react with a Group VIa element compound such as a molybdenum compound so that the decomposition reaction easily proceeds to give ketones and aldehydes. The inventors have found that a class of compounds can be obtained and completed the present invention.

[0004]

That is, the present invention is based on the general formula (1) (In the formula, R ¹ , R ² and R ³ are the same or different and each is an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group or a substituted Represents an optionally substituted acyl group, an optionally substituted carboalkoxy group, an optionally substituted carboaryloxy group, an optionally substituted carboaralkyloxy group or a carboxyl group.
R ¹ and R ² , R ¹ and R ³ or R ² and R ³ may together form a part of a ring structure. One of X and Y represents a hydroxyl group and the other represents a hydroperoxy group. ) To β-hydroxyhydroperoxides, the VI
The present invention provides a method for producing ketones and aldehydes, which comprises reacting a group a element compound.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION First, the general formula (1) which is a raw material of the present invention is described. (In the formula, R ¹ , R ² and R ³ are the same or different and each is an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group or a substituted Represents an optionally substituted acyl group, an optionally substituted carboalkoxy group, an optionally substituted carboaryloxy group, an optionally substituted carboaralkyloxy group or a carboxyl group.
R ¹ and R ² , R ¹ and R ³ or R ² and R ³ may together form a part of a ring structure. One of X and Y represents a hydroxyl group and the other represents a hydroperoxy group. ) Β-hydroxy hydroperoxides (hereinafter,
It is abbreviated as β-hydroxyhydroperoxides (1). ) Will be described.

The alkyl group which may be substituted includes, 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. Group, an n-decyl group, a cyclopropyl group, a 2,2-dimethylcyclopropyl group, a cyclopentyl group, a cyclohexyl group, a menthyl group and the like, which has a linear, branched or cyclic carbon number of 1 to 2.
Alkyl groups of 0 and these alkyl groups are, for example, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, aralkyloxy groups such as benzyloxy group, and halogen atoms such as fluorine atom and chlorine atom. , An acyl group, a carboalkoxy group, a carboaryloxy group, a carboaralkyloxy group, a carboxyl group and the like may be substituted, and examples of the alkyl group substituted with such a substituent include a chloromethyl group, a fluoromethyl group, Trifluoromethyl group, methoxymethyl group, ethoxymethyl group, methoxyethyl group, carbomethoxymethyl group, 1-carboethoxy-2,2-
A dimethyl-3-cyclopropyl group etc. are mentioned.

The aryl group which may be substituted includes, for example, a phenyl group, a naphthyl group and the like, and an alkyl group, an aryl group, an alkoxy group and the aralkyl group which will be described later in which the aromatic ring constituting the phenyl group, the naphthyl group and the like are described above. Substituted with a substituent such as an aryloxy group, an aralkyloxy group, and a halogen atom, for example, 2-methylphenyl group, 4-chlorophenyl group, 4-methylphenyl group, 4-methoxyphenyl group, 3-phenoxyphenyl group, etc. Is mentioned. Examples of the optionally substituted aralkyl group include those which are composed of the optionally substituted aryl group and the alkyl group described above, and include, for example, a benzyl group, a 4-chlorobenzyl group, and 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 Groups and the like.

The acyl group which may be substituted includes
A carbonyl group and an optionally substituted alkyl group,
And those which are composed of an optionally substituted aryl group and an optionally substituted aralkyl group,
Examples thereof include a carbomethyl group, a carboethyl group, a carbophenyl group, a carbobenzyl group and the like.

The carboalkoxy group which may be substituted, the carboaryloxy group which may be substituted and the carboaralkyloxy group which may be substituted are respectively a carbonyl group and the aforementioned alkoxy group which may be substituted. , An optionally substituted aryloxy group and an optionally substituted aralkyloxy group, and examples thereof include a carbomethoxy group, a carboethoxy group, a carbophenoxy group, and a carbobenzyloxy group. To be

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

Examples of such β-hydroxyhydroperoxides (1) include 2-methyl-2-hydroperoxy-3-hydroxypentane, 3-methyl-3-hydroperoxy-2-hydroxyhexane and 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, 3,3
-Dimethyl-2- (2-methyl-2-hydroperoxy-1-hydroxypropyl) cyclopropanecarboxylate, 3,3-dimethyl-2- (2-methyl-2-hydroperoxy-1-hydroxypropyl) cyclo Ethyl propanecarboxylate, 3,3-dimethyl-2- (2-
Methyl-2-hydroperoxy-1-hydroxypropyl) cyclopropanecarboxylate isopropyl, 3,3-
Dimethyl-2- (2-methyl-2-hydroperoxy-
1-hydroxypropyl) cyclopropanecarboxylic acid t
ert-butyl, 3,3-dimethyl-2- (2-methyl-2-hydroperoxy-1-hydroxypropyl) cyclopropanecarboxylic acid cyclohexyl, 3,3-dimethyl-2- (2-methyl-2-hydroperoxy) -1-
Menthyl hydroxypropyl) 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-hydroperoxy-
1-hydroxypropyl) cyclopropanecarboxylic acid (2,3,5,6-tetrafluorobenzyl), 3,3
-Dimethyl-2- (2-methyl-2-hydroperoxy-1-hydroxypropyl) cyclopropanecarboxylic 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) cyclopropanecarboxylic acid (3-phenoxybenzyl), 3,3-dimethyl-2-
Methyl (2-methyl-2-hydroxy-1-hydroperoxypropyl) cyclopropanecarboxylate, 3,3-
Dimethyl-2- (2-methyl-2-hydroxy-1-hydroperoxypropyl) cyclopropanecarboxylate ethyl ester, 3,3-dimethyl-2- (2-methyl-2-hydroxy-1-hydroperoxypropyl) cyclopropane Isopropyl carboxylate, 3,3-dimethyl-2-
Examples include tert-butyl (2-methyl-2-hydroxy-1-hydroperoxypropyl) cyclopropanecarboxylic acid.

The β-hydroxyperoxides (1) have an asymmetric carbon in the molecule,
Although some optical isomers exist, either a single optical isomer or a mixture of optical isomers can be used in the present invention.

These β-hydroxyhydroperoxides (1) are represented by the general formula (5) in the presence of a tungsten oxide catalyst obtained by reacting a tungsten compound such as tungsten metal with hydrogen peroxide. (Wherein R ¹ , R ² and R ³ have the same meanings as described above) and hydrogen peroxide and trisubstituted olefins (hereinafter abbreviated as trisubstituted olefins (5)). It can be obtained by reacting. In the reaction of such tri-substituted olefins with hydrogen peroxide, in addition to the target β-hydroxyhydroperoxides (1), a compound represented by the general formula (2) (In the formula, R ³ has the same meaning as above.), An aldehyde represented by the general formula (3) (In the formula, R ¹ and R ² have the same meanings as described above.)
And a general formula (6) (Wherein R ¹ , R ² and R ³ have the same meanings as described above), and the diols are obtained at 0 to 65 ° C.
By carrying out the reaction within the range, β-hydroxyhydroperoxides (1) can be obtained with good selectivity.

Examples of such trisubstituted olefins (5) include 2-methyl-2-pentene and 3-methyl-2.
-Hexene, 1-methylcyclopentene, 1,3-dimethylcyclopentene, 1,3,5-trimethylcyclohexene, 3-carene, 3,3-dimethyl-2- (2-methyl-1-propenyl) -cyclopropanecarboxylic acid Methyl, ethyl 3,3-dimethyl-2- (2-methyl-1-propenyl) -cyclopropanecarboxylate, 3,3-
Isopropyl dimethyl-2- (2-methyl-1-propenyl) -cyclopropanecarboxylate, tert-butyl 3,3-dimethyl-2- (2-methyl-1-propenyl) -cyclopropanecarboxylate, 3,3- Dimethyl-2
Cyclohexyl- (2-methyl-1-propenyl) -cyclopropanecarboxylate, 3,3-dimethyl-2- (2
-Methyl-1-propenyl) -menthyl cyclopropanecarboxylate, 3,3-dimethyl-2- (2-methyl-1)
-Propenyl) -benzyl cyclopropanecarboxylate and the like.

Some of the tri-substituted olefins (5) have an asymmetric carbon atom in the molecule and have optical isomers, and the optical isomers may be used alone or as a mixture. Can be used.

The catalyst used for producing the β-hydroxyhydroperoxides (1) is, for example, tungsten metal, tungsten boride, tungsten carbide, tungstic acid, tungsten oxide, a tungsten compound such as sodium tungstate, and hydrogen peroxide. Tungsten oxide obtained by reacting with is used, and the amount thereof is usually 0.001 mol times or more based on the trisubstituted olefin (5), and there is no particular upper limit,
Considering economical aspects, it is practically 1 mol times or less with respect to the tri-substituted olefin (5).

Hydrogen peroxide is usually used as hydrogen peroxide, but hydrogen peroxide / organic solvent solution may be used. The amount of hydrogen peroxide used is trisubstituted olefins (5)
On the other hand, it is usually 2 mol times or more, and there is no particular upper limit of the amount used, but in view of economic aspects, practically, it is 10 mol times or less with respect to the tri-substituted olefin (5). is there.

After reacting the tri-substituted olefins (5) with hydrogen peroxide, the reaction liquid is subjected to β-
The hydroxyhydroperoxides (1) may be taken out and used in the present invention. Further, if necessary, water and / or an organic solvent insoluble in water is added to the reaction solution, the mixture is subjected to extraction treatment, the obtained organic layer is concentrated, and β-hydroxyhydroperoxides (1) are taken out and It may be used in the invention. Of course, the taken out β-hydroxyhydroperoxides (1) may be used after further purification by means such as column chromatography.

Subsequently, the group VIa elemental compound is allowed to act on the β-hydroxyhydroperoxides (1) to give a compound represented by the general formula (2): (In the formula, R ³ has the same meaning as above.) And an aldehyde (hereinafter abbreviated as aldehyde (2)) and a general formula (3). (In the formula, R ¹ and R ² have the same meanings as described above.)
A method for producing a ketone represented by (hereinafter abbreviated as ketone (3)) will be described.

By reacting the β-hydroxyhydroperoxides (1) with the group VIa element compound, the carbon-carbon bond is cleaved to obtain the aldehydes (2) and the ketones (3).

Examples of the group VIa element compound are tungsten compounds such as tungsten metal, tungsten oxide, tungstic acid, sodium tungstate, tungsten sulfide, tungsten boride, and tungstophosphoric acid, for example, molybdenum metal, molybdenum oxide, molybdic acid, Examples thereof include potassium molybdate, sodium molybdate, ammonium molybdate, molybdenum chloride, molybdenum sulfide, molybdenum dioxobis (acetylacetonato), molybdenum hexacarbonyl, molybdophosphoric acid, and other molybdenum compounds. Among such compounds, molybdenum compounds are preferable. Such VIa
The group element compounds may be used alone or in combination.

The amount of the group VIa element compound used is β
It is usually 0.001 mol times or more with respect to -hydroxyhydroperoxides (1), and there is no particular upper limit, but in view of economical aspects, β-hydroxyhydroperoxides (1 ) To 1 mol times or less.

The β-hydroxyhydroperoxides (1) are allowed to react with the group VIa element compound by mixing both of them. The reaction temperature of this reaction is usually 0 to
120 degreeC, Preferably it is 20-100 degreeC.

This reaction is usually carried out in a solvent in which β-hydroxyhydroperoxides (1) are dissolved. Examples of the solvent include water, alcohols such as methanol, ethanol, tert-butanol, etc., such as acetonitrile, nitrile solvents such as propionitrile, such as diethyl ether, methyl tert-butyl ether, ether solvents such as tetrahydrofuran,
For example, an ester solvent such as ethyl acetate, for example, an aromatic hydrocarbon solvent such as toluene and xylene, for example, a halogenated hydrocarbon solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, etc., alone or mixed. Solvents may be mentioned.
The amount of the β-hydroxyhydroperoxides (1) may be dissolved, and there is no particular upper limit. However, in consideration of volumetric efficiency, practically, the amount of β-hydroxyhydroperoxides (1) is Therefore, it is 100 times or less by weight.

In order to make the reaction proceed more smoothly,
For example, a phase transfer catalyst such as trioctylmethylammonium hydrogensulfate or tetrabutylammonium chloride may be used.

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

After the completion of the reaction, the ketones and aldehydes can be separated and taken out from the reaction liquid by subjecting the reaction liquid to concentration treatment, column chromatography treatment, or the like. If necessary, water and / or an organic solvent insoluble in water is added to the reaction solution, extraction treatment is carried out, and the obtained organic layer is concentrated treatment, whereby these products can be separated and taken out. The taken out ketones and aldehydes can be further separated and purified by means such as distillation and column chromatography.

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

When, for example, β-hydroxyhydroperoxides (1) obtained by reacting trisubstituted olefins (5) with hydrogen peroxide are used as a raw material for this reaction, trisubstituted olefins (5) The diols represented by the general formula (6) and the like, which are by-produced by the reaction of hydrogen peroxide with hydrogen peroxide, may be used as they are. The diols represented by the general formula (6) hardly decompose even when a Group VIa group element compound is acted on and remain in the reaction solution.
Hydroxyhydroperoxides (1) and general formula (6)
When a mixture with a diol represented by is used as the raw material of the present invention, after the reaction is completed, the reaction solution is treated with, for example, sodium periodate (eg, Tetrah).
edron, 53 , 16277 (1997), etc.) to decompose the diols represented by the general formula (6) and convert them into aldehydes (2) and ketones (3).

The aldehydes (2) thus obtained include, for example, acetaldehyde, propionaldehyde, butyraldehyde, pentylaldehyde, 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-
Oxoheptyl aldehyde,

2,2-dimethyl-3- (2-oxopropyl) cyclopropane acetaldehyde, 2,2-dimethyl-3- (3-oxobutyl) cyclopropyl aldehyde, 2,2-dimethyl-3- (2-oxoethyl) ) Cyclobutane acetaldehyde, 3,3-dimethyl-2-
Methyl formylcyclopropanecarboxylate, Ethyl 3,3-dimethyl-2-formylcyclopropanecarboxylate, Isopropyl 3,3-dimethyl-2-formylcyclopropanecarboxylate, 3,3-Dimethyl-2-formylcyclopropanecarboxylic acid tert-butyl, 3,3
-Cyclohexyl dimethyl-2-formylcyclopropanecarboxylate, Menthyl 3,3-dimethyl-2-formylcyclopropanecarboxylate, 3,3-Dimethyl-2-
Benzyl formylcyclopropanecarboxylate, (4-chlorobenzyl) -3,3-dimethyl-2-formylcyclopropanecarboxylate, (2,3,5,6-tetrafluorobenzyl) -3,3-dimethyl-2- Formyl cyclopropanecarboxylate, (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,

Examples of the ketones (3) include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, acetophenone and the like.

[0034]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The analysis is carried out by gas chromatography (hereinafter abbreviated as GC) and high performance liquid chromatography (hereinafter abbreviated as LC), and each condition of GC analysis and LC analysis is as follows.

<GC analysis conditions> Column: DB-1 (φ0.25 μm × 30 m, film thickness 1.
Carrier gas: Helium (flow rate: 1 m / min) Split ratio: 1/10, sample injection amount: 1 μL Column temperature: 100 ° C. (0 min) → 180 ° C. (heating rate:
2 ° C / min, holding time at 180 ° C: 0 minutes) → 300 ° C
(Rise rate: 10 ° C / min, holding time at 300 ° C: 15
Min) inlet temperature: 200 ℃, detector temperature: 250 ℃

[0036] <LC analysis conditions>   Column: SUMPIPAX ODS A-212 (5 μm, φ6 mm × 15 cm)   Mobile phase: Solution A; 0.1% by volume aqueous trifluoroacetic acid solution           Solution B: 0.1% by volume trifluoroacetic acid / acetonitrile solution   A liquid / B liquid = 90/10 (volume ratio), linearly in 40 minutes, A liquid / B liquid = 10 Composition ratio of liquid A / liquid B = 10/90 (volume ratio) by changing the composition to / 90 (volume ratio) Then, hold for 20 minutes.   Flow rate: 1.0 mL / min, sample injection amount: 10 μL, detection wavelength: 220 nm

Reference Example 1 A 2 L four-necked flask equipped with a stirrer and a reflux condenser was charged with 10 g of tungsten metal powder and 75 g of water, and 36.7 g of 60% by weight hydrogen peroxide solution at an internal temperature of 40 ° C. while stirring. Was added dropwise over 1 hour, and the mixture was further stirred at the same temperature for 1 hour and reacted to obtain a uniform solution containing tungsten oxide. Next, 6.8 g of boric acid was charged, the solution was cooled to room temperature, and tert-butyl alcohol 380 was added.
g and 19 g of 60 wt% hydrogen peroxide solution were charged. Next, 133 g of anhydrous magnesium sulfate was charged over 30 minutes, and the mixture was stirred at an internal temperature of 20 ° C. for 2 hours. Trans-3,3-dimethyl-2- (2-
A mixture of 100 g of methyl-1-propenyl) cyclopropanecarboxylate and 120 g of tert-butyl alcohol and 41 g of 60% by weight hydrogen peroxide solution were simultaneously added dropwise over 4 hours, and the mixture was stirred at an internal temperature of 20 ° C. for 18 hours. It was made to react. After that, 600 g of water is added, and toluene 500 is added.
Extraction treatment was performed twice with g to obtain 1688 g of a toluene solution.
LC analysis of the toluene solution revealed that trans-3,
Methyl 3-dimethyl-2- (1-hydroxy-2-hydroperoxy-2-methylpropyl) cyclopropanecarboxylate, trans-3,3-dimethyl-2- (1-hydroperoxy-2-hydroxy-2-methyl) Methyl propyl) cyclopropanecarboxylate (hereinafter, these two compounds will be collectively referred to as β-hydroxyhydroperoxide compound) and 3,3-dimethyl-2-
It was confirmed that methyl formylcyclopropanecarboxylate was contained.

GC analysis of the toluene solution revealed that β-
Since the hydroxyhydroperoxide compound was thermally decomposed at the injection port and detected as methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate, β
The yields of hydroxy hydroxyperoxide compound and methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate were calculated using both GC and LC analysis.

The content of β-hydroxyhydroperoxide compound in the toluene solution was 4.5%, and the yield was
It was 60%. Trans-3,3-in toluene solution
The content of methyl dimethyl-2-formylcyclopropanecarboxylate was 0.1%, and the yield was 2.4%.

Example 1 To 300 g of a toluene solution containing the β-hydroxyhydroperoxide compound obtained in Reference Example 1 was added 1.0 g of dioxobis (acetylacetonato) molybdenum,
The mixture was stirred at the reflux temperature for about 10 hours for reaction. The insoluble matter was filtered off from the reaction solution while washing with toluene, and the obtained filtrate was partially concentrated under reduced pressure to give trans-3,3-
264 g of a toluene solution containing methyl dimethyl-2-formylcyclopropanecarboxylate was obtained. GC analysis of the toluene solution revealed that trans-3,3-dimethyl-
The content of methyl 2-formylcyclopropanecarboxylate was 3.4%, and the yield was 94% (based on β-hydroxyhydroperoxide compound).

Example 2 A 100 mL four-necked flask equipped with a stirrer and a reflux condenser was placed in a toluene solution containing the β-hydroxyhydroperoxide compound obtained in the same manner as in Reference Example 1 (content of β-hydroxyhydroperoxide compound). : 4.1%, content of methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate: 0.15%) 79 g, water 1
g and 0.13 g of molybdenum sulfide powder were charged, and the mixture was refluxed and reacted for 7 hours while stirring. After cooling, the insoluble matter is filtered off, and 78 g of a toluene solution containing methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate is added.
Got When the toluene solution was analyzed by GC, the content of methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 3.0% and the yield was 9%.
It was 9% (based on β-hydroxyhydroperoxide compound).

Example 3 Toluene solution containing β-hydroxyhydroperoxide compound (content of β-hydroxyhydroperoxide compound: 4.1%, content of methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate: 0.15
%) 80 g, water 1 g and molybdenum chloride powder 0.22
g was charged, and the mixture was refluxed and reacted for 7 hours with stirring. After cooling, insoluble matter was filtered off and trans-3,3-dimethyl-
78 g of a toluene solution containing methyl 2-formylcyclopropanecarboxylate was obtained. When the toluene solution was analyzed by GC, the content of methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 2.4%, and the yield was 80% (β-hydroxyhydroperoxide compound Criteria).

Example 4 A 300 mL flask equipped with a stirrer and a reflux condenser was charged with 15 g of water and 2 g of tungsten metal powder, and 7.4 g of 60% by weight hydrogen peroxide solution was stirred at an internal temperature of 40 ° C. for 20 minutes while stirring. Over a period of 1 hour, and stirred at the same temperature for 1 hour.
The reaction was performed to obtain a tungsten oxide-containing solution. The solution was charged with 1.36 g of boric acid, cooled to room temperature and t
76 g of ert-butyl alcohol, 2 g of 60 wt% hydrogen peroxide solution and 26.6 g of anhydrous magnesium sulfate were charged, and the mixture was further stirred at room temperature for 1.5 hours. To the obtained slurry solution, a mixed solution of 20 g of methyl trans-3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate and 24 g of tert-butyl alcohol and 60% by weight hydrogen peroxide were added. 10 g of water was simultaneously added dropwise over 4 hours, and the mixture was stirred and reacted at an internal temperature of 15 ° C for 24 hours. Then, 120 g of water was added, and 100 g of toluene was added.
It was extracted twice with to obtain 331 g of a toluene solution containing a β-hydroxyhydroperoxide compound and methyl trans-3,3-dimethyl-2- (1,2-dihydroxy-2-methylpropyl) cyclopropanecarboxylate.

1.1 g of dioxobis (acetylacetonato) molybdenum was added to 315 g of the toluene solution, and the mixture was stirred and reacted at reflux temperature for 6 hours. The insoluble matter was filtered off from the reaction solution while washing with insoluble toluene, and trans-3,3 was used.
A solution containing methyl dimethyl-2-formylcyclopropanecarboxylate and methyl trans-3,3-dimethyl-2- (1,2-dihydroxy-2-methylpropyl) cyclopropanecarboxylate was obtained.

32 g of a 15 wt% sodium periodate aqueous solution was added dropwise to the solution at room temperature over 10 minutes, and the mixture was stirred and held for 1 hour. The insoluble matter was washed with toluene from the reaction solution, filtered and separated to obtain an organic layer. After partially concentrating at room temperature under reduced pressure, 100 g of a 5 wt% sodium thiosulfate aqueous solution, 50 g of a 5 wt% sodium hydrogencarbonate aqueous solution, and 50 g of water were further washed to obtain trans
223 g of a toluene solution containing methyl 3,3-dimethyl-2-formylcyclopropanecarboxylate was obtained. As a result of the GC analysis, methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate based on methyl trans-3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate was used. The yield was 74%.

[0046]

INDUSTRIAL APPLICABILITY According to the present invention, β-hydroxyhydroperoxides represented by the general formula (1) are reacted with a Group VIa element compound under mild conditions to give corresponding aldehydes and ketones. Since it is possible to obtain a class, it is industrially advantageous.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4H006 AA02 AC44 AC45 AD17 BA14                       BA65 BB11 BB12 BB14 BB15                       BB21 BB25 BC10 BC34 BC35                       BJ20 BQ20 KA31 KC20                 4H039 CA62 CG90

Claims (3)

[Claims] 1. A general formula (1) (In the formula, R ¹ , R ² and R ³ are the same or different and each is an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group or a substituted Represents an optionally substituted acyl group, an optionally substituted carboalkoxy group, an optionally substituted carboaryloxy group, an optionally substituted carboaralkyloxy group or a carboxyl group.
R ¹ and R ² , R ¹ and R ³ or R ² and R ³ may together form a part of a ring structure. One of X and Y represents a hydroxyl group and the other represents a hydroperoxy group. ) To β-hydroxyhydroperoxides, the VI
General formula (2) characterized by causing a group a element compound to act (In the formula, R ³ has the same meaning as above.) And the general formula (3). (In the formula, R ¹ and R ² have the same meanings as described above.)
A method for producing a ketone represented by: 2. The method for producing ketones and aldehydes according to claim 1, wherein the Group VIa element compound is a molybdenum compound. 3. A β-hydroxyhydroperoxide is
General formula (4) (In the formula, one of X and Y represents a hydroxyl group and the other represents a hydroperoxy group, and R ⁴ represents an optionally substituted alkyl group, an optionally substituted aralkyl group or an optionally substituted group. The method for producing ketones and aldehydes according to claim 1, which is a compound represented by a good aryl group.