JP2002201156A - METHOD FOR PRODUCING beta-HYDROXYHYDROPEROXIDE COMPOUNDS AND CARBOXYLIC ACID COMPOUNDS AND CATALYST THEREFOR - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for profitably producing a β- hydroxyhydroperoxide compound and a carboxylic acid compound by oxidizing an internally di-substituted olefin compound with hydrogen peroxide. SOLUTION: This method for producing the β-hydroxyhydroperoxide compound and the carboxylic acid compound is characterized by reacting the internally di-substituted olefin compound with the hydrogen peroxide in the presence of a metal oxide catalyst prepared by reacting hydrogen peroxide with at least one metal compound selected from the group consisting of tungsten metal, molybdenum metal, tungsten compounds comprising tungsten and the group IIIb elements, the group IVb elements, the group Vb elements or the group VIb elements excluding oxygen, and molybdenum compounds comprising molybdenum and the group IIIb elements, the group IVb elements, the group Vb elements or the group VIb elements excluding oxygen.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing β-hydroxyhydroperoxides and carboxylic acids and a catalyst thereof.

[0002]

2. Description of the Related Art β-Hydroxyhydroperoxides and carboxylic acids are important compounds as various chemical products and synthetic intermediates thereof. Particularly, β-hydroxyhydroperoxides are precursors for the synthesis of aldehydes and diols. Is a very important compound.

[0003] Such β-hydroxyhydroperoxides and carboxylic acids can be obtained by oxidizing olefins, and various oxidizing agents have been studied. Among them, hydrogen peroxide has recently attracted attention as a clean and excellent oxidizing agent which is inexpensive, easy to handle, and becomes harmless water after the reaction.

As a method for producing β-hydroxyhydroperoxide and carboxylic acids by oxidizing an internally disubstituted olefin with hydrogen peroxide, for example, a method using a tetrakis (oxodiperoxotungsto) phosphoric acid catalyst (J. Org. Chem., 63, 7190 (19
98)) is known, but such a method involves reacting an internal disubstituted olefin with hydrogen peroxide to convert the epoxide to a corresponding epoxide, and then further reacting the epoxide with hydrogen peroxide. This is a two-stage method, and the preparation of the catalyst is relatively complicated, and thus cannot always be said to be an efficient method.

As a method for producing carboxylic acids by oxidizing internal disubstituted olefins with hydrogen peroxide, for example, (1) a method using tungstic acid and a nitrogen-containing aromatic carboxylic acid as a catalyst (JP-A-8-295649) No.),
(2) Method using heteropolyacid and cetylpyridinium chloride as catalysts (J. Org. Chem., 53 , 3)
587 (1988)), (3) a method using a dicarboxylic acid complex of tungstic acid as a catalyst (Green Che
m. , 275 (1999)), (4) a method using a tungstic acid and a quaternary ammonium hydrogensulfate as a catalyst (Japanese Patent Laid-Open No. 2000-86574), and (5) tert.
-Method using heteropoly acid as catalyst in butanol (Ch
em. Lett. , 857 (1989)) and the like. However, the methods for producing carboxylic acids described in the above (1) to (3) are not limited to tungstic acid, but also include relatively expensive nitrogen-containing aromatic carboxylic acid and cetylpyridinium chloride. Alternatively, a dicarboxylic acid must be used, which is not always satisfactory from an economic and industrial viewpoint. In the method (4), a relatively expensive quaternary ammonium hydrogen sulfate is used. When the catalyst is recycled, the quaternary ammonium hydrogen sulfate needs to be added, and the reaction time is reduced. However, industrially, it was not satisfactory. Furthermore, the method (5) has a long reaction time, and the yield of carboxylic acid is not satisfactory.

As a method for obtaining aldehydes from β-hydroxyhydroperoxides, for example, a method using a base (J. Org. Chem., 43 , 1760 (19)
78), a method using an acid (J. Chem. Soc., C.
hem. Comm. , 1976, 507), and a method of pyrolysis (Japanese Patent Application Laid-Open No. 58-112234), and the like, but development of a more industrially advantageous method has been desired.

As methods for producing aldehydes from internal disubstituted olefins, for example, a method using a methylrhenium trioxide catalyst (WO98 / 47847), a method using a heteropoly acid and magnesium sulfate as a catalyst (Japanese Patent Publication No. Hei 8- 19027), a method using a tungsten compound and a boron compound as a catalyst (Japanese Patent Publication No. 63-56207), and a method using a heteropolyacid containing phosphorus or germanium (Japanese Patent Publication No. 6-84).
No. 324), a method using a heteropolyacid containing phosphorus or germanium and a metal salt of Group Ia or IIa of the periodic table as a catalyst (Japanese Patent Publication No. 6-99355), a method using a heteropolyacid and magnesium sulfate as a catalyst ( JP-B 8-19027), a method using a tungsten oxide synthesized from sodium tungstate as a catalyst (T
etrahedron, 48 , 3503 (1992))
However, these methods are not necessarily industrially advantageous in that relatively expensive catalysts and reagents are used and the yield is low.

As a method for producing diols by reducing β-hydroxyhydroperoxides, for example, a method using triphenylphosphine as a reducing agent (J. Org.
Chem. , 63 , 7190 (1998)), which is advantageous in that triphenylphosphine is expensive and requires an operation of separating formed diols and by-produced triphenylphosphine oxide. I couldn't say.

As a method for producing a diol from an internally disubstituted olefin, for example, a method using a complex catalyst comprising tungstophosphoric acid and a quaternary ammonium salt (S
syntheses, 295 (1989)), but it is necessary to adjust the catalyst separately, and it is not always an efficient method.

[0010]

Under these circumstances, the present inventors have oxidized internal disubstituted olefins with hydrogen peroxide to produce β-hydroxyhydroperoxides and carboxylic acids more industrially. After intensive studies to develop an advantageous manufacturing method, a metal obtained by reacting a readily available tungsten metal, molybdenum metal, a tungsten compound such as tungsten boride, a molybdenum compound such as molybdenum boride with hydrogen peroxide, and the like. The oxide shows a good catalytic activity in the reaction between the internal disubstituted olefins and hydrogen peroxide, and reacts the internal disubstituted olefins with hydrogen peroxide in the presence of the metal oxide catalyst. that β-hydroxyhydroperoxides and carboxylic acids are obtained, and that the obtained β-hydroxyhydroperoxy By treating a compound with a specific metal compound, the decomposition reaction of the β-hydroxyhydroperoxide proceeds, and an aldehyde is obtained. By reducing the β-hydroxyhydroperoxide, a diol is obtained. Is found to be obtained,
The present invention has been reached.

[0011]

That is, the present invention relates to a method for converting an internally disubstituted olefin and hydrogen peroxide to tungsten metal, molybdenum metal, tungsten and group IIIb, group IV,
Group B, Vb or a tungsten compound comprising a Group VIb element excluding oxygen and molybdenum and Group IIIb, Group IVb
At least one metal compound selected from the group consisting of molybdenum compounds consisting of a group IV, group Vb or group VIb element excluding oxygen and hydrogen peroxide, and reacting in the presence of a metal oxide catalyst It is intended to provide a process for producing β-hydroxyhydroperoxides and carboxylic acids, and a catalyst thereof.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION First, a metal oxide catalyst used for reacting an internally disubstituted olefin with hydrogen peroxide will be described. Catalysts include tungsten metal, molybdenum metal, tungsten and group IIIb, group IVb
Group, Vb or a tungsten compound comprising a group VIb element excluding oxygen and molybdenum and a group IIIb, group IVb
A metal oxide obtained by reacting hydrogen peroxide with at least one metal compound selected from the group consisting of a molybdenum compound consisting of a group Vb group or a group VIb element excluding oxygen is used.

Examples of the tungsten compound comprising tungsten and a Group IIIb element include tungsten boride and the like. Examples of the tungsten compound comprising tungsten and a Group IVb element include tungsten carbide and tungsten silicide. Tungsten nitride, tungsten phosphide, and the like can be given as examples of the tungsten compound containing a Group Vb element, and tungsten sulfide, for example, can be given as an example of a tungsten compound containing tungsten and a Group VIb element other than oxygen.

As a molybdenum compound composed of molybdenum and a Group IIIb element, for example, molybdenum boride and the like can be mentioned.
Molybdenum compounds composed of molybdenum and Group IVb elements include, for example, molybdenum carbide and molybdenum silicide.Molybdenum compounds composed of molybdenum and Group Vb elements include, for example, molybdenum nitride and molybdenum phosphide. As a molybdenum compound composed of and a Group VIb element excluding oxygen, for example, molybdenum sulfide and the like can be mentioned.

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.

As the hydrogen peroxide to be reacted with such a metal compound, an aqueous solution is usually used. Of course, an organic solvent solution of hydrogen peroxide may be used, but from the viewpoint of easy handling, it is preferable to use a hydrogen peroxide solution. The concentration of hydrogen peroxide in the aqueous hydrogen peroxide solution or the organic solvent solution of hydrogen peroxide is not particularly limited, but is practically 1 to 60% by weight in consideration of volume efficiency, safety and the like. In the case of using aqueous hydrogen peroxide, a commercially available one may be used as it is, or one whose concentration has been adjusted by dilution, concentration or the like as necessary. When an organic solvent solution of hydrogen peroxide is used, for example, a solution prepared by extracting hydrogen peroxide solution with an organic solvent or distilling hydrogen peroxide solution in the presence of an organic solvent is used. It may be used.

The amount of hydrogen peroxide to be reacted with the metal compound is usually at least 3 mol times, preferably at least 5 mol times, 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 in an aqueous solution. Of course, ether solvents such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran and the like, for example, ester solvents such as ethyl acetate, for example, methanol, ethanol, tert-
It may be carried out in an organic solvent such as an alcoholic solvent such as butanol, a nitrile solvent such as acetonitrile and propionitrile, or a mixed solvent of the organic solvent and water.

The reaction between the metal compound and hydrogen peroxide is usually performed by mixing and contacting the two, and in order to further improve the contact efficiency between the metal compound and hydrogen peroxide,
It is preferable to carry out the reaction with stirring so that the metal compound is sufficiently dispersed in the metal oxide preparation liquid. In addition, it is preferable to use a metal compound having a small particle size, such as a powdery metal compound, from the viewpoint of increasing the contact efficiency between the metal compound and hydrogen peroxide and making the control during preparation of the metal oxide easier.

The preparation temperature for preparing the metal oxide is usually -1.
0-100 ° C.

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

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

The internal disubstituted olefin has an olefinic carbon-carbon double bond, and one hydrogen atom and one substituent are bonded to each carbon atom forming the double bond. Any olefin may be used. Two substituents bonded to each carbon atom forming a carbon-carbon double bond of the olefin may be combined to form a cyclic olefin containing the carbon-carbon double bond. .

Such internal disubstituted olefins include:
For example, general formula (1) (Wherein, R ¹ and R ² are the same or different and are each independently an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, or an optionally substituted Aryloxy group, aralkyl group which may be substituted, aralkyloxy group which may be substituted, acyl group which may be substituted, carboalkoxy group which may be substituted, carboaryl which may be substituted Represents an oxy group, an optionally substituted carboaralkyloxy group, a carboxyl group or a halogen atom, and R ¹ and R ² may together form a part of a ring structure. Olefins.

Examples of the alkyl group which may be substituted include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and an n-pentyl group. Group, n-decyl group, cyclopropyl group, 2,2-dimethylcyclopropyl group, cyclopentyl group, cyclohexyl group, menthyl group, etc.
0 alkyl group and these alkyl groups are an alkoxy group, an aryloxy group, an aralkyloxy group,
For example, a chloromethyl group, a fluoromethyl group, a trifluoromethyl group, a methoxymethyl group, an ethoxy group substituted with a substituent such as a halogen atom, an acyl group, a carboalkoxy group, a carboaryloxy group, a carboaralkyloxy group, and a carboxyl group. Methyl group, methoxyethyl group, carbomethoxymethyl group, 1-carbethoxy-2,2-
And a dimethyl-3-cyclopropyl group.

Examples of the optionally substituted alkoxy group include those composed of the above-mentioned optionally substituted alkyl group and an oxygen atom, such as methoxy, ethoxy, n-propoxy and isopropoxy. Group, n-
Butoxy group, isobutoxy group, sec-butoxy group, t
linear, branched or cyclic C1-C20 alkoxy groups such as ert-butoxy group, n-pentyloxy group, n-decyloxy group, cyclopentyloxy group, cyclohexyloxy group, and menthyloxy group; Examples thereof include a chloromethoxy group, a fluoromethoxy group, a trifluoromethoxy group, a methoxymethoxy group, an ethoxymethoxy group, and a methoxyethoxy group in which an alkoxy group is substituted with a substituent such as a halogen atom or an alkoxy group.

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

Examples of the optionally substituted aralkyl group include those composed of the aforementioned optionally substituted aryl group and the aforementioned optionally substituted alkyl group, such as a benzyl group and a 4-chloro group. Benzyl group, 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-
Examples include a methoxybenzyl group and a 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl group. Examples of the aralkyloxy group which may be substituted include those composed of an aralkyl group which may be substituted and an oxygen atom. Examples thereof include a benzyloxy group, a 4-chlorobenzyloxy group and a 4-chlorobenzyloxy group. Methylbenzyloxy group, 4-methoxybenzyloxy group, 3-phenoxybenzyloxy group, 2,3,5,6-tetrafluorobenzyloxy group, 2,3,5,6-tetrafluoro-4-methylbenzyloxy group A 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.

The acyl group which may be substituted includes:
A carbonyl group and an optionally substituted alkyl group,
Examples include a carbonyl group and the optionally substituted aryl group and a carbonyl group and an optionally substituted aralkyl group, such as a carbomethyl group, a carboethyl group, a carbophenyl group, and a carbobenzyl group. Is mentioned.

Examples of the optionally substituted carboalkoxy group include those composed of a carbonyl group and the aforementioned optionally substituted alkoxy group, and examples of the optionally substituted carboaryloxy group include a carbonyl group. And the above-mentioned optionally substituted aryloxy group, the optionally substituted carboaralkyloxy group comprises a carbonyl group and the above-mentioned optionally substituted aralkyloxy group And a carbomethoxy group, a carboethoxy group, a carbophenoxy group, a carbobenzyloxy group, and the like.

When R ¹ and R ² together form a part of a ring structure, examples of the ring structure include a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, and a cyclohexene ring.

Examples of such internally disubstituted olefins (hereinafter abbreviated as olefins) include cyclopentene, cyclohexene, cycloheptene, cyclooctene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 5-dimethylcyclopentene, 3,4,5-trimethylcyclopentene, 3-chlorocyclopentene, 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3,5-dimethylcyclohexene,
3,4,5-trimethylcyclohexene, 2-hexene, 3-hexene, 5-dodecene, norbornene, phenanthrene, 1,2,3,6-tetrahydrophthalic anhydride, dicyclopentadiene, indene, 3,3-dimethyl- Methyl 2- (1-propenyl) cyclopropanecarboxylate, ethyl 3,3-dimethyl-2- (1-propenyl) cyclopropanecarboxylate, and the like.

Some olefins have an asymmetric carbon in the molecule and have optical isomers. In the present invention, either the optical isomers alone or a mixture thereof is used. be able to.

In this reaction, an olefin is reacted with hydrogen peroxide in the presence of the above-mentioned metal oxide catalyst.
-Hydroxyhydroperoxides and carboxylic acids in which the carbon-carbon double bond of olefins is oxidatively cleaved are formed.

When the olefin represented by the above general formula (1) is used as the olefin, the olefin represented by the general formula (2) in which the carbon-carbon double bond is oxidized is used. (In the formula, R ¹ and R ² represent the same meaning as described above.)
Β-hydroxyhydroperoxides represented by the general formula (3) (In the formula, R ¹ and R ² represent the same meaning as described above.)
A β-hydroxyhydroperoxide represented by the general formula (5) in which a carbon-carbon double bond is oxidatively cleaved: (Wherein R ¹ has the same meaning as described above) and a carboxylic acid represented by the general formula (6): (Wherein, R ² has the same meaning as described above). In this reaction,
Other oxidation products of olefins such as diols and β-
Aldehydes decomposed by hydroxyhydroperoxides may be formed as by-products. When the olefin represented by the general formula (1) is used, the olefin represented by the general formula (4) is used. (In the formula, R ¹ and R ² represent the same meaning as described above.)
Or a diol represented by the general formula (7): (Wherein, R ¹ has the same meaning as described above) and a compound represented by the general formula (8) (Wherein R ² has the same meaning as described above), which is produced as a by-product.

More specifically, taking concrete olefins as an example, for example, when cyclopentene is used as a starting olefin, 1-hydroperoxy-
When 2-hydroxycyclopentane and glutaric acid are obtained, and 2-hexene is used as a starting olefin, 2-hydroperoxy-3-hydroxyhexane and / or 3-hydroperoxy-2-hydroxyhexane and acetic acid are used. And butanoic acid are obtained.

The amount of the metal oxide catalyst used in the reaction between the olefins and hydrogen peroxide is
It is usually 0.001 mol times or more, and there is no particular upper limit. However, considering the economic aspect, it is practically 1 mol times or less 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 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 volumetric efficiency, safety and the like. The hydrogen peroxide solution is usually used as it is or after adjusting the concentration by diluting or concentrating as needed.
The organic solvent solution of hydrogen peroxide can be prepared by, for example, extracting hydrogen peroxide solution with an organic solvent, or distilling the hydrogen peroxide solution in the presence of the organic solvent.

The amount of hydrogen peroxide used is usually at least 1 mole times the amount of the olefin, and there is no particular upper limit to the amount of the hydrogen peroxide. To 10 mol times or less. When a preparation solution containing a metal oxide is used as the catalyst, the amount of hydrogen peroxide used may be set, including the amount of hydrogen peroxide in the preparation solution.

This reaction is usually carried out in an aqueous solvent, an organic solvent or a mixed solvent of an organic solvent and water. As the organic solvent, for example, ether solvents such as diethyl ether, methyl-tert-butyl ether and tetrahydrofuran, ester solvents such as ethyl acetate, methanol, ethanol, alcohol solvents such as tert-butanol,
Examples thereof include nitrile solvents such as acetonitrile and propionitrile. The amount of water or organic solvent used is not particularly limited, but is practically not more than 100 times the weight of the olefins in consideration of volumetric efficiency and the like.

In the present reaction, the production ratio of the product varies depending on the reaction conditions. Therefore, the reaction conditions may be appropriately selected according to the desired product. For example, in the case of β-hydroxyhydroperoxides, the reaction is preferably performed in an organic solvent, and in the case of carboxylic acids, the reaction is preferably performed in an aqueous solvent. When β-hydroxyhydroperoxides are intended, the reaction is preferably carried out under anhydrous conditions. Examples of a method for carrying out the reaction under anhydrous conditions include a method in which a dehydrating agent coexists in the reaction system. Examples of the dehydrating agent include anhydrous magnesium sulfate, anhydrous sodium sulfate, boric anhydride, polyphosphoric acid,
Diphosphorus pentoxide and the like may be used, and the amount of use may be any amount as long as the amount of water present in the reaction system can be dehydrated and removed.

If the reaction temperature is too low, the reaction hardly proceeds, and if the reaction temperature is too high, a side reaction such as polymerization of the starting olefins may proceed. It is in the range of ° C.

In this reaction, the production ratio of β-hydroxyhydroperoxides and carboxylic acids varies depending on the reaction temperature, the structure of the olefins, etc., and may be appropriately selected according to the target compound. For example, in the case of β-hydroxyhydroperoxides, the reaction is preferably carried out in an organic solvent, and in the case of carboxylic acids, the reaction is preferably carried out in an aqueous solvent. When β-hydroxyhydroperoxides are intended, the reaction is preferably carried out under anhydrous conditions. Examples of a method for carrying out the reaction under anhydrous conditions include a method in which a dehydrating agent coexists in the reaction system. Examples of the dehydrating agent include, for example, anhydrous magnesium sulfate, anhydrous sodium sulfate, boric anhydride, polyphosphoric acid, diphosphorus pentoxide, and the like, and the amount of the dehydrating agent is not less than an amount capable of dehydrating and removing water present in the reaction system. I just need.

This reaction is usually carried out by contacting and mixing an olefin, hydrogen peroxide and a metal oxide catalyst, but the order of mixing is not particularly limited. Further, for example, a metal compound, hydrogen peroxide and an olefin may be contacted and mixed, and the preparation operation of the metal oxide catalyst and the reaction between the olefin and the hydrogen peroxide may be performed simultaneously.

This reaction may be carried out under normal pressure conditions or under pressurized conditions. The progress of the reaction can be confirmed by ordinary analytical means such as gas chromatography, high performance liquid chromatography, thin layer chromatography, NMR and IR.

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, orthoboric acid, alkali metal metaborate, alkaline earth metal metaborate, alkali metal orthoborate, alkaline earth metal borate, and the like. , Its usage is not particularly limited,
If it is too much, it is economically disadvantageous. Therefore, practically, it is usually 1 mole or less relative to olefins.

After completion of the reaction, the reaction solution is left as it is or, if necessary, the remaining hydrogen peroxide is decomposed with a reducing agent such as sodium sulfite, and then concentrated and crystallized to obtain the desired aldehyde. And carboxylic acids can be removed. Further, if necessary, water and / or an organic solvent insoluble in water is added to the reaction solution, extraction is performed, and the obtained organic layer is subjected to concentration treatment.
Aldehydes and carboxylic acids can also be removed. The aldehydes and carboxylic acids taken out may be further purified by means such as distillation and column chromatography.

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, diethyl ether, methyl-tert-
Examples thereof include ether solvents such as butyl ether and tetrahydrofuran, and ester solvents such as ethyl acetate, and the amount thereof is not particularly limited.

The aqueous layer obtained by extracting the filtrate or the reaction solution after removing the desired β-hydroxyhydroperoxides and carboxylic acids by crystallization treatment contains the metal oxide catalyst of this reaction. It can be used again in the reaction as it is or after necessary concentration treatment or the like.

Further, depending on the type of the olefin used, the carboxylic acid to be formed may be unstable. In such a case, for example, a decarboxylation reaction of the carboxylic acid occurs in the reaction system. A carboxylic acid having one less carbon number may be obtained.

When an optically active substance is used as the olefin, an optically active product is obtained.

The β-hydroxyhydroperoxides thus obtained include, for example, 1-hydroperoxy-
2-hydroxycyclopentane, 1-hydroperoxy-2-hydroxycyclohexane, 1-hydroperoxy-2-hydroxycycloheptane, 1-hydroperoxy-2-hydroxycyclooctane, 1-hydroperoxy-2-hydroxy-3-methyl Cyclopentane,
1-hydroperoxy-2-hydroxy-4-methylcyclopentane, 1-hydroperoxy-2-hydroxy-3,4-dimethylcyclohexane, 1-hydroperoxy-2-hydroxy-3,4,5-trimethylcyclohexane, -Hydroperoxy-3-hydroxyhexane, 3-hydroperoxy-2-hydroxyhexane, bicyclo [2.2.1] heptane-2-hydroperoxy-3-ol, 3,3-dimethyl-2- (1-hydroxy Methyl-2-hydroperoxypropyl) cyclopropanecarboxylate, 3,3-dimethyl-2- (2-
Methyl hydroxy-1-hydroperoxypropyl) cyclopropanecarboxylate, 3,3-dimethyl-2- (1
-Hydroxy-2-hydroperoxypropyl) cyclopropanecarboxylate, 3,3-dimethyl-2-
Ethyl (2-hydroxy-1-hydroperoxypropyl) cyclopropanecarboxylate and the like.

Examples of the carboxylic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, 2-methylglutaric acid, and 3-methylglutaric acid. Acid, 3-chloroglutaric acid, 2,3-dimethylglutaric acid, 2,4-dimethylglutaric acid, 2-methyladipic acid, 3-methyladipic acid, 2,3-dimethyladipic acid, 2,4-dimethyladipine Acid, 3,4-dimethyladipic acid, 2,3,4-trimethylglutaric acid,
Cyclopentane-1,3-dicarboxylic acid, biphenyl-
2,2'-dicarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, benzoic acid, 1- (carboxymethyl)
Cyclopentane-2,3,4-tricarboxylic acid, homophthalic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, 3,3-dimethyl-2-carbomethoxycyclopropanecarboxylic acid, 3,3-dimethyl -2-carboethoxycyclopropanecarboxylic acid and the like.

The resulting β-hydroxyhydroperoxide is subjected to an alkali treatment or a heat treatment, whereby the β-hydroxyhydroperoxide is decomposed to obtain a corresponding aldehyde. For example, from the β-hydroxyhydroperoxides represented by the general formula (2) and / or the β-hydroxyhydroperoxides represented by the general formula (3), the general formula (7) (Wherein, R ¹ has the same meaning as described above) and a compound represented by the general formula (8) (Wherein, R ² has the same meaning as described above). To explain in more detail by taking a specific compound as an example, for example, glutaraldehyde is produced from 1-hydroxy-2-hydroperoxycyclopentane obtained from cyclopentene.

Examples of the alkali for the alkali treatment include alkali metal alcoholates such as sodium methylate. The amount of the alkali used is usually 0.01 mol times or more based on the β-hydroxyhydroperoxide. There is no particular upper limit. The temperature for the heat treatment is usually from 60 to 200 ° C.

The produced β-hydroxyhydroperoxides are a Group Va element compound, a Group VIIa element compound, a Group VIII element compound, a Group Ib element compound, a Group IIb element compound, and a Group IIIb element compound. By reacting at least one compound selected from the group consisting of a Group IVb element compound, a Group Vb element compound and a lanthanide compound, the β-hydroxyhydroperoxide is decomposed to give an aldehyde. .

Examples of the Group Va element compound include vanadium metal, vanadium oxide, ammonium vanadate,
Vanadium oxides and vanadium compounds such as vanadium carbonyl complexes formed by reacting vanadium metal with hydrogen peroxide, for example, niobium metals, niobium oxide, niobium compounds such as niobium chloride (V) (NbCl ₅ ) and niobium carbonyl complexes. Can be 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 (aca).
c) Ruthenium compounds such as ₃ , RuCl ₂ (PPh ₃ ) ₃ , for example, cobalt metal, cobalt acetate, cobalt compounds such as [Co ₂ (CO) ₈ ] ₂ , for example, rhodium metal, rhodium chloride, Rh ₄ (CO) ₁₂
Rhodium compounds such as iridium metal, iridium compounds such as iridium chloride, such as nickel metal, Ni
Nickel compounds such as (CO) _{4 and the} like, for example, palladium compounds such as palladium metal, palladium acetate and palladium carbon are exemplified.

Examples of the Group Ib element compound include copper metals, for example, copper compounds such as cuprous chloride, cupric chloride, cuprous bromide, and cupric bromide. Examples of the Group IIb element compound include zinc metal, for example, a zinc compound such as zinc chloride. Group IIIb element compounds include:
For example, boron compounds such as boron trifluoride, aluminum compounds such as aluminum metal and aluminum chloride and the like can be mentioned. Examples of the Group IVb element compound 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 ), and antimony compounds such as antimony metal and antimony chloride (V) (SbCl ₅ ) and antimony chloride (III) (SbCl ₃ ) And the like. Examples of the lanthanide compound include samarium compounds such as samarium metal and samarium triflate (Sm (OTf) ₂ ); gadolinium compounds such as gadolinium metal; and dysprosium compounds such as dysprosium metal and dysprosium triflate (Dy (OTf) ₃ ). And a dysprosium compound is preferred.

Among these compounds, vanadium compounds, copper compounds, ruthenium compounds, palladium compounds and mixtures thereof are preferred. These compounds may be used alone or as a mixture.

The amount of the compound to be used is usually 0.001 mol times or more with respect to β-hydroxyhydroperoxides, and there is no particular upper limit. It is not more than molar times.

The action of the compound on β-hydroxyhydroperoxides may be performed by mixing both of them, and the mixing temperature is usually -20 to 100 ° C. The reaction is usually carried out in the presence of a solvent in which β-hydroxyhydroperoxides are soluble. Such solvents include, for example, diethyl ether, methyl tert-butyl ether,
Ether solvents such as tetrahydrofuran and the like, ester solvents such as ethyl acetate and the like, alcohol solvents such as methanol, ethanol, tert-butanol and the like, for example, nitrile solvents such as acetonitrile and propionitrile, and the like are used. It is sufficient that the β-hydroxyhydroperoxide is dissolved, and there is no particular upper limit. However, in consideration of volumetric efficiency and the like, the amount is practically 100 times or less the β-hydroxyhydroperoxide.

When a reaction solution containing β-hydroxyhydroperoxides obtained by oxidizing olefins with, for example, tungsten metal or tungsten boride is used, the compound is allowed to act on the reaction solution as it is. Alternatively, the compound may be allowed to act after the β-hydroxyhydroperoxides are extracted from the reaction solution by an extraction treatment or the like.

The aldehydes thus obtained include:
For example, acetaldehyde, propionaldehyde, butyraldehyde, pentylaldehyde, hexylaldehyde, heptylaldehyde, undecanealdehyde, benzaldehyde, glutaraldehyde, adipaldehyde, heptanedialdehyde, octanedialdehyde,
-Chloroglutaraldehyde, 2-methylglutaraldehyde, 3-methylglutaraldehyde, 2,3-dimethylglutaraldehyde, 2,4-dimethylglutaraldehyde, 2,3,4-trimethylglutaraldehyde, 2-methyladipaldehyde, 3-methyladipaldehyde, 2,3-dimethyladipaldehyde, 2,4
-Dimethyladipaldehyde, 2,3,4-dimethyladipaldehyde, cyclopentane-1,3-dicarbaldehyde, diphenyl-2,2'-dicarbaldehyde, 1- (formylmethyl) cyclopentane-2, 3,
4-tricarbaldehyde, 1,2-bis (formylmethyl) succinic anhydride, 1,4-diformylbutane-
Examples thereof include 2,3-dicarboxylic acid, methyl 3,3-dimethyl-2-formylcyclopropanecarboxylate, and ethyl 3,3-dimethyl-2-formylcyclopropanecarboxylate.

Diols can also be obtained by reducing β-hydroxyhydroperoxides with a reducing agent. When the β-hydroxyhydroperoxide represented by the general formula (2) and / or the β-hydroxyhydroperoxide represented by the general formula (3) are reduced with a reducing agent, the general formula (4) (Wherein, R ¹ and R ² each have the same meaning as described above).

The reduction treatment is usually carried out by mixing a β-hydroxyhydroperoxide with a reducing agent.
Examples of the reducing agent include inorganic reducing agents such as sodium thiosulfate, and sulfides such as dimethyl sulfide. The amount of the reducing agent to be used is usually at least 1 mole times the β-hydroxyhydroperoxide, and there is no particular upper limit.
-5 mole times or less based on hydroxyhydroperoxides.

The temperature for 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 dissolve.
When a reaction solution containing β-hydroxyhydroperoxides obtained by oxidizing olefins with, for example, the above-mentioned tungsten metal, tungsten boride or the like is used, the reaction solution may be directly mixed with a reducing agent. Since unreacted oxidizing substances such as hydrogen peroxide often remain in the reaction solution, β
After taking out the hydroxyhydroperoxides, it is preferable in terms of economy to mix with a reducing agent.

Examples of the diols include 1,2-dihydroxycyclopentane, 1,2-dihydroxycyclohexane, 1,2-dihydroxycycloheptane,
2-dihydroxycyclooctane, 1,2-dihydroxy-3-methylcyclopentane, 1,2-dihydroxy-4-methylcyclopentane, 1,2-dihydroxy-
3,4-dimethylcyclohexane, 1,2-dihydroxy-3,4,5-trimethylcyclohexane, 2,3-
Dihydroxyhexane, bicyclo [2.2.1] heptane-2,3-diol, 3,3-dimethyl-2- (1,
Examples thereof include methyl 2-dihydroxypropyl) cyclopropanecarboxylate and ethyl 3,3-dimethyl-2- (1,2-dihydroxypropyl) cyclopropanecarboxylate.

[0069]

EXAMPLES 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 gas chromatography analysis (hereinafter referred to as “gas chromatography analysis”)
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. (heating rate:
2 ° C./min, holding time at 180 ° C .: 0 min) → 300 ° C.
(Heating rate: 10 ° C./min, holding time at 300 ° C .: 15)
Min) Inlet temperature: 200 ° C, detector temperature: 250 ° C

<LC Analysis Conditions> Column: SUMIPAX ODS A-212 (5 μm, φ6 mm × 15 cm) Mobile phase: A solution; 0.1% by volume trifluoroacetic acid aqueous solution B solution; 0.1% by volume trifluoroacetic acid / acetonitrile Solution The composition was changed linearly from solution A / solution B = 90/10 (volume ratio) to solution A / solution B = 10/90 (volume ratio) in 40 minutes, and solution A / solution B = 10/90 (volume ratio). (Volume ratio) and held for 20 minutes. Flow rate: 1.0 mL / min, sample injection volume: 10 μL, detection wavelength: 220 nm

Example 1 <Preparation of oxide by reaction of tungsten metal with hydrogen peroxide and evaluation of activity> 4 g of tungsten metal powder was added to a beaker, 50 g of a 15% by weight aqueous hydrogen peroxide solution was further added, and the mixture was stirred at room temperature. I let it. While generating the oxygen gas, the tungsten metal powder was dissolved (the internal temperature was raised to 60 ° C.), and a uniform transparent liquid colored pale yellowish brown was obtained. The solution was cooled to room temperature, and the remaining hydrogen peroxide was decomposed using a platinum mesh, and then water was distilled off from the solution using a rotary evaporator at room temperature to remove a pale yellow solid (tungsten oxide). Obtained. The solid was dried at room temperature in an open-air system until a constant weight was obtained, to obtain 5.8 g of a solid.

UV spectrum of uniform transparent liquid before concentration λ ^H2O _max : 204,238 nm IR spectrum of uniform transparent liquid before concentration (aqueous solution: 400
0 to 750 cm ^-1 ) ν _max : 3342,1275,1030,967,83
IR spectrum (KBr) of the solid obtained at 7 cm ^-1 ν _max : 3531,3452,2945,1653,1
619, 973, 906, 638, 551 cm ^-1 Elemental analysis; W: 63.9, O: 31.2, H: 1.6

50 mL with magnetic rotor and reflux condenser
A flask was charged with 2 g of a 30% by weight aqueous hydrogen peroxide solution and 140 mg of the solid obtained above, and the internal temperature was raised to 60 ° C.
After stirring and maintaining at the same temperature for 0.5 hour, 4 g of cyclohexene and 25.8 g of 30% by weight aqueous hydrogen peroxide were added dropwise over 20 minutes. After completion of the dropping, the mixture was heated and stirred in an oil bath at an internal temperature of 100 ° C. for 6 hours. The internal temperature of the reaction solution is 9
The temperature rose to 5 ° C. After the completion of the reaction, the internal temperature is cooled to 5 ° C,
The precipitated crystals were filtered and dried to obtain 5.3 g of white crystals. The crystals were analyzed by ¹ H-NMR to confirm that they were high-purity adipic acid. GC analysis of filtrate (internal standard method)
As a result, adipic acid contained in the filtrate was 1.4 g.
Met. Total adipic acid yield: 94%.

Example 2 <Preparation of oxide by reaction of tungsten boride with hydrogen peroxide> In 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 placed.
, And 18 g of a 60% by weight aqueous hydrogen peroxide solution was added dropwise over 2 hours while stirring at an internal temperature of 40 ° C. The mixture was further kept 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 mesh, water was distilled off from the solution using a rotary evaporator at room temperature to obtain a white solid (oxide). This was dried at room temperature in an open air system until the weight became constant, 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)
７750 cm ⁻¹ ) ν _max : 3350,2836,1275,1158,9
65,836Cm ^-1 resulting solid IR spectrum (KBr) ν _max: 3527,3220,2360,2261,1
622, 1469, 1196, 973, 904.5, 8
84, 791, 640, 549 cm ^-1 elemental analysis; 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, instead of tungsten boride powder,
10. A pale yellow solid was obtained in the same manner as in Example 2 except that 5.4 g of tungsten sulfide was used and the amount of water was changed to 12 g.
1 g was obtained.

UV spectrum of solution before concentration λ ^H2O _max : 200,240 (s) nm IR spectrum of colorless solution before concentration (aqueous solution: 4000)
７750 cm ⁻¹ ) ν _max : 3373,1187,1044,974,87
IR spectrum (KBr) of the solid obtained at 8,837 cm ^-1 ν _max : 3435, 3359, 1730, 1632, 1
320, 1285, 1178, 1103, 1070, 1
008,981,887,839,851,660,6
15,578 cm ^-1 elemental analysis; W: 35.3, O: 47.7, H: 3.
0, S: 12.4

Example 4 <Preparation of oxide by reaction of molybdenum metal and hydrogen peroxide> In Example 2, instead of tungsten boride powder,
Using 2.1 g of molybdenum metal, the amount of water was 12 g,
The same operation as in Example 2 was carried out except that the amount of the 60% by weight aqueous hydrogen peroxide solution used was changed to 12 g, to obtain 4.0 g of a yellow solid.

UV spectrum of solution before concentration λ ^H2O _max : 207,300 nm IR spectrum of colorless solution before concentration (aqueous solution: 4000)
７750 cm ⁻¹ ) ν _max : 3359, 2480, 1372, 974, 86
IR spectrum (KBr) of the solid obtained at 6 cm ^-1 ν _max : 3530,1621,964,927,90
2,840,633,557,530,522 cm ^-1 elemental analysis; Mo: 47.8, O: 46.2, H: 2.
1

Example 5 <Preparation of oxide by reaction of molybdenum boride with hydrogen peroxide> In Example 2, instead of tungsten boride powder,
5.2 g of yellow solid was carried out in the same manner as in Example 2, except that 2.3 g of molybdenum boride was used, the amount of water was 12 g, and the amount of the 60% by weight aqueous hydrogen peroxide solution was 12 g.
I got

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, 2262.1
620,1463,1439,1195,965,92
7,887,840,799,674,634,54
7,529 cm ^-1 elemental analysis; Mo: 35.5, O: 51.0, H: 2.
9, B: 4.1

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

UV spectrum of solution before concentration λ ^H2O _max : 210,250 (s) nm IR spectrum of solution before concentration (aqueous solution; 4000-7)
50 cm ^-1 ) ν _max : 3400, 2833, 1355, 967, 83
IR spectrum (KBr) of the solid obtained at 6 cm ^-1 ν _max : 3416, 1623, 1385, 975, 88
0,839,749,700,643,625,550
cm ^-1 elemental analysis; W: 63.9, O: 31.2, H: 1.6 These spectral data were obtained by the reaction of the tungsten metal obtained in Example 1 with hydrogen peroxide. Compared to the oxide, it was a different oxide.

The activity was evaluated in the same manner as in Example 1 except that 140 mg of the solid obtained above was used. However, after the reaction, cyclohexene remained, and the reaction solution remained in two layers. 5
After cooling to ℃, there was no precipitation of adipic acid.

Example 6 Into a 1 L flask equipped with an induction stirrer and a reflux condenser, 30
A 20% by weight aqueous hydrogen peroxide solution and 895 mg of tungsten metal powder were charged, and the internal temperature was raised to 60 ° C. After stirring and maintaining at the same temperature for 0.5 hour, 40 g of cyclohexene and 228 g of 30% by weight hydrogen peroxide solution were added dropwise over 20 minutes. After completion of the dropwise addition, the mixture was heated and stirred in an oil bath at an internal temperature of 100 ° C. for 8 hours. The internal temperature of the reaction solution rose from 72 ° C to 95 ° C. After the completion of the reaction, the mixture was cooled to an internal temperature of 5 ° C., and the precipitated crystals were collected by filtration and dried to obtain 57.3 g of white crystals. The crystals were analyzed by ¹ H-NMR to confirm that they were high-purity adipic acid. When the melting point of the crystal was measured,
152 ° C. When the filtrate was analyzed by GC (internal standard method), the filtrate contained 9.6 g of adipic acid. The total adipic acid yield obtained by combining the obtained adipic acid crystals and the adipic acid in the filtrate was 94%.

Example 7 The filtrate obtained in Example 6 was concentrated to 188 g. In a 1 L flask equipped with an induction stirrer and a reflux condenser,
The concentrated filtrate was charged, and 40 g of cyclohexene and 250 g of a 30% by weight hydrogen peroxide solution were added dropwise over 20 minutes. Thereafter, the mixture was heated and stirred in an oil bath at an internal temperature of 100 ° C. for 9 hours. The internal temperature of the reaction solution rose from 72 ° C to 95 ° C. After completion of the reaction, the mixture was cooled to an internal temperature of 0 ° C., and the precipitated crystals were collected by filtration and dried to obtain 57.2 g of adipic acid white crystals. Melting point: 151-152 [deg.] C. The filtrate was concentrated to 130 g, cooled to an internal temperature of 0 ° C., and the precipitated crystals were collected by filtration.
After drying, 5.0 g of white crystals of adipic acid were obtained. Melting point: 151-152 [deg.] C. The yield of the obtained adipic acid crystals was 87.5%.

Example 8 A 1 L flask equipped with an induction stirrer and a reflux condenser was charged with 122 g of the filtrate obtained in the above Example 7, and further 40 g of cyclohexene and 250 g of a 30% by weight hydrogen peroxide solution.
Was added dropwise over 20 minutes. After dropping, internal temperature 100 ° C
The mixture was heated and stirred in an oil bath for 11.5 hours. The internal temperature of the reaction solution rose from 72 ° C to 95 ° C. After the completion of the reaction, the mixture was cooled to an internal temperature of 0 ° C., and the precipitated crystals were collected by filtration and dried to obtain 57.5 g of adipic acid white crystals. Melting point: 151-15
2 ° C. The filtrate was concentrated to 128 g, cooled to an internal temperature of 0 ° C., and the precipitated crystals were collected by filtration and dried to obtain 5.2 g of adipic acid white crystals. Melting point: 151-152 [deg.] C. The yield of the obtained adipic acid crystals was 88.2%.

Example 9 A 1 L flask equipped with an induction stirrer and a reflux condenser was charged with 103 g of the filtrate obtained in the above Example 8, and further 40 g of cyclohexene and 250 g of 30% by weight hydrogen peroxide solution.
Was added dropwise over 20 minutes. Thereafter, the mixture was heated and stirred in an oil bath at an internal temperature of 100 ° C. for 10.5 hours. The internal temperature of the reaction solution is
The temperature rose from 72 ° C to 95 ° C. After the reaction is completed, the internal temperature is 0 ° C
The precipitated crystals were collected by filtration and dried to obtain 55.7 g of adipic acid white crystals. Melting point: 151-152 [deg.] C.
When the filtrate was analyzed by GC (internal standard method), the amount of adipic acid contained in the filtrate was 11.6 g. The yield of adipic acid was 88.9% (excluding the adipic acid content contained in 103 g of the filtrate obtained in Example 8 above).

Example 10 In a 50 mL flask equipped with a magnetic rotor and a reflux condenser,
2 g of 30% by weight aqueous hydrogen peroxide and 97 mg of tungsten metal powder were charged, and the internal temperature was raised to 60 ° C. After stirring and maintaining at the same temperature for 0.5 hour, 4 g of cyclohexene and 25.8 g of 30% by weight aqueous hydrogen peroxide were added dropwise over 20 minutes. After completion of the dropping, the mixture was heated and stirred in an oil bath at an internal temperature of 100 ° C. for 6 hours. The internal temperature of the reaction solution rose from 72 ° C to 95 ° C. After completion of the reaction, the mixture was cooled to an internal temperature of 5 ° C., and the precipitated crystals were filtered and dried to obtain 5.3 g of white crystals. The crystals were analyzed by ¹ H-NMR to confirm that they were high-purity adipic acid. When the filtrate was analyzed by GC (internal standard method), the filtrate contained 1.4 g of adipic acid. Total adipic acid yield: 94%.

Example 11 The procedure of Example 10 was repeated, except that 96 mg of tungsten carbide was used instead of 97 mg of tungsten metal powder, to obtain 4.5 g of adipic acid crystals. Adipic acid contained in the filtrate was 1.2 g,
The total adipic acid yield was 80%.

Example 12 The procedure of Example 10 was repeated, except that 96 mg of tungsten boride was used instead of 97 mg of tungsten metal powder, to obtain 3.6 g of adipic acid crystals. Yield: 51%.

Example 13 The procedure of Example 10 was repeated, except that 121 mg of tungsten sulfide was used instead of 97 mg of tungsten metal powder, to obtain 5.0 g of adipic acid crystals. The adipic acid contained in the filtrate was 1.12 g.
Met. Total adipic acid yield: 86%.

Example 14 The procedure of Example 10 was repeated, except that 3.2 g of cyclopentene was used instead of 4 g of cyclohexene, to obtain 4.2 g of glutaric acid crystals. The amount of glutaric acid contained in the filtrate was 0.93 g. The total glutaric acid yield obtained by combining the obtained glutaric acid crystals and glutaric acid contained in the filtrate was 80%.

Example 15 A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 1.1 g of 30% by weight hydrogen peroxide solution and 46 mg of tungsten metal, and the internal temperature was raised to 60 ° C. Stir and hold for .5 hours. Add oleic acid 7.1
g and 30% by weight of hydrogen peroxide solution (13.1 g) were charged. Thereafter, the reaction solution was heated and stirred for 7 hours in an oil bath at an internal temperature of 95 ° C. Further, 14.2% by weight of 30% by weight hydrogen peroxide solution
g was added and the mixture was heated and stirred at 95 ° C. for 11 hours. After completion of the reaction, the mixture was cooled to an internal temperature of 25 ° C. and subjected to LC analysis (internal standard method).
%) And 1.71 g of azelaic acid (yield 36.4%).

Example 16 A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 2.4 g of 30% by weight hydrogen peroxide solution and 46 mg of tungsten metal, and the internal temperature was raised to 60 ° C. Stir and hold for hours. After charging 2.9 g of indene and 7.1 g of water thereto, 4.7 g of a 30% by weight hydrogen peroxide solution was charged. Thereafter, the reaction solution was heated and stirred in an oil bath at an internal temperature of 100 ° C. for 8 hours. After the reaction is completed, internal temperature 2
When cooled to 5 ° C and subjected to LC analysis (internal standard method),
3.2 g (yield 71%) of homophthalic acid was produced.

Example 17 A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 1.1 g of a 30% by weight aqueous hydrogen peroxide solution and 46 mg of tungsten metal, and the internal temperature was raised to 60 ° C. Stir and hold for .5 hours. This is cis-1,2,
A solution obtained by adding water to 3.8 g of 3,6-tetrahydrophthalic anhydride and dissolving it, and 13.1 g of a 30% by weight aqueous hydrogen peroxide solution
Was charged. Thereafter, the reaction solution was heated and stirred in an oil bath at an internal temperature of 95 ° C. for 20 hours. After the completion of the reaction, the mixture was cooled to an internal temperature of 25 ° C. and subjected to LC analysis (internal standard method).
3.4 g of 1,2,3,4-tetracarboxylic acid was produced. Yield: 58%.

Example 18 A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 2.4 g of 30% by weight hydrogen peroxide solution and 23 mg of tungsten metal, and the internal temperature was raised to 60 ° C. Stir and hold for .5 hours. 2.1 g of cis-5-norbornene-2,3-dicarboxylic anhydride and 4.7 g of a 30% by weight hydrogen peroxide solution were charged therein. Thereafter, the reaction solution was cooled to room temperature, and heated and stirred at room temperature for 12 hours. After the completion of the reaction, LC analysis (internal standard method) revealed that 2.6 g of cyclopentane-1,2,3,4-tetracarboxylic acid was produced. Yield: 81%.

Example 19 A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 200 mg of 30% by weight aqueous hydrogen peroxide, 1.5 g of tert-butanol and 40 mg of tungsten metal powder.
And heated to an internal temperature of 60 ° C., and stirred at the same temperature for 1 hour,
Held. The solution was cooled to 25 ° C., and 530 mg of anhydrous magnesium sulfate was added.
g, tert-butanol 1.5 g and a 30 wt% aqueous hydrogen peroxide solution (350 mg) were added dropwise over 20 minutes. After stirring and maintaining at an internal temperature of 25 ° C. for 16 hours, 5 g of water was added, and the mixture was extracted twice with 5 g of methyl-tert-butyl ether to obtain a methyl-tet-butyl ether solution.
When the solution was analyzed by LC, 1-hydroperoxy-
2-Hydroxycyclopentane was produced, but glutaraldehyde was not produced.

When the solution was analyzed by GC, 1-hydroperoxy-2-hydroxycyclopentane was thermally decomposed at the injection port and detected as glutaraldehyde. Therefore, the yield of glutaraldehyde was determined by GC analysis (internal standard). Method) The yield was calculated from the results, and the yield was defined as the yield of 1-hydroperoxy-2-hydroxycyclopentane. Yield of 1-hydroperoxy-2-hydroxycyclopentane: 80.7%

Example 20 A methyl-tert-butyl ether solution containing 1-hydroperoxy-2-hydroxycyclopentane obtained in the above Example 19 was charged into a 50 mL flask equipped with a magnetic rotor and a reflux condenser, and was then charged with pentoxide. Vanadium 50mg
Was further charged and stirred and maintained at an internal temperature of 60 ° C. for 4 hours.
When the obtained reaction solution was analyzed by LC, the peak of 1-hydroperoxy-2-hydroxycyclopentane disappeared and the peak of glutaraldehyde was detected. According to GC analysis (internal standard method), glutaraldehyde 17
0 mg was included. Glutaraldehyde yield: 7
7% (based on 1-hydroperoxy-2-hydroxycyclopentane).

Example 21 By reacting in the same manner as in Example 19, 1-hydroperoxy-
Ter containing 940 mg of 2-hydroxycyclopentane
11 g of t-butanol solution was obtained. This solution was charged with 363 mg of bismuth chloride and stirred at an internal temperature of 25 ° C. for 6 hours. When the obtained reaction solution was analyzed by LC, the peak of 1-hydroperoxy-2-hydroxycyclopentane disappeared and the peak of glutaraldehyde was detected. G
C analysis (internal standard method) revealed that it contained 398 mg of glutaraldehyde. Yield: 50% (based on 1-hydroperoxy-2-hydroxycyclopentane).

Example 22 A reaction solution containing 279 mg of glutaraldehyde was obtained in the same manner as in Example 20, except that 350 mg of palladium acetate was used instead of bismuth chloride. Yield: 35% (based on 1-hydroperoxy-2-hydroxycyclopentane).

Example 23 A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 200 mg of a 30% by weight aqueous hydrogen peroxide solution, 1.5 g of tert-butanol, 20 mg of boric anhydride, and 40 mg of tungsten metal powder. Temperature to 60 ° C,
The mixture was stirred and maintained at the same temperature for 1 hour. The solution was cooled to 25 ° C., and after adding 530 mg of anhydrous magnesium sulfate, 180 mg of cyclohexene and 1.5 mg of tert-butanol were added.
g and a mixed solution of 350 mg of a 30% by weight aqueous hydrogen peroxide solution were added dropwise over 20 minutes. After stirring and holding at an internal temperature of 25 ° C. for 16 hours, LC analysis revealed that 1-hydroperoxy-2-hydroxycyclohexane had been produced, and production of adipaldehyde could not be confirmed. According to GC analysis, 1-hydroperoxy-2-hydroxycyclohexane was thermally decomposed at the injection port and detected as adipaldehyde. Therefore, the yield of adipaldehyde was determined by GC analysis, and the yield was 1%. -The yield of hydroperoxy-2-hydroxycyclohexane. Yield: 54.7
%.

Example 24 A 100-mL flask equipped with a magnetic rotor and a reflux condenser was charged with 400 mg of tungsten metal powder.
After adding 2.5 g of a hydrogen peroxide aqueous solution by weight little by little, 30
And stirred at room temperature to obtain a colorless homogeneous solution. After adding 3.0 g of 60% by weight aqueous hydrogen peroxide, 30 g of tert-butanol, and 5.3 g of anhydrous magnesium sulfate to this solution, stirring at room temperature for 30 minutes, 2.0 g of cyclohexene,
A mixed solution of 15 g of tert-butanol was added dropwise over 30 minutes. After stirring and maintaining at an internal temperature of 25 ° C. for 16 hours, 30 g of toluene and 20 g of water were added to the reaction solution, and the mixture was stirred and separated to obtain 82.7 g of a toluene solution. As a result of LC analysis of this solution, 1-hydroperoxy-2-hydroxycyclohexane was produced, and production of adipaldehyde could not be confirmed. According to GC analysis, 1-hydroperoxy-2-hydroxycyclohexane was thermally decomposed at the injection port and detected as adipaldehyde. Therefore, the yield of adipaldehyde was determined by GC analysis, and the yield was 1%. −
The yield of hydroperoxy-2-hydroxycyclohexane was determined. Yield: 54.0%. Further, 1,2-dihydroxycyclohexane was produced at a yield of 26.0%.

Example 25 In a 50 mL flask equipped with a magnetic rotor and a reflux condenser, 390 mg of copper (II) chloride was charged, and the above Example 24 was added.
41 g of a toluene solution containing 1-hydroperoxy-2-hydroxycyclohexane obtained in 1 was added, and the mixture was stirred at an internal temperature of 25 ° C for 16 hours. When the obtained reaction solution was analyzed by LC, the peak of 1-hydroperoxy-2-hydroxycyclohexane disappeared and the peak of adipaldehyde was detected. As a result of GC analysis (internal standard method), 783 mg of adipaldehyde was contained. Adipaldehyde yield: 56% (based on cyclohexene).

Example 26 The 1-hydroperoxy-2 obtained in Example 24 was placed in a 500 mL flask equipped with a magnetic rotor and a reflux condenser.
41 g of a toluene solution containing hydroxycyclohexane
50 g of a 10% by weight aqueous sodium thiosulfate solution was added, and the mixture was stirred at an internal temperature of 25 ° C. for 16 hours.
50 g of rt-butyl ether was added, and the mixture was subjected to an extraction treatment to obtain 95.7 g of an organic layer. When the organic layer was analyzed by GC, no adipaldehyde peak was detected and 1,2-
Dihydroxycyclohexane was detected. Yield of 1,2-dihydroxydichlorohexane: 81% (based on cyclohexene).

Example 27 In Example 23, 370 mg of 5-dodecene was used instead of 180 mg of cyclohexene, and 4 parts of tungsten metal powder 4 were used.
Example 23 was carried out in the same manner as in Example 23 except that 22 mg of tungsten boride was used instead of 0 mg, and the mixture was stirred and maintained at an internal temperature of 25 ° C for 39 hours. When the reaction solution was analyzed by GC, peaks of 1-heptylaldehyde and 1-pentylaldehyde were detected, and the respective yields were 44%. From the results of 5-dodecene, 5-hydroperoxy-6-hydroxydodecane was obtained. And / or 6-hydroperoxy-5-hydroxydodecane was found to be obtained in a yield of 44%.

Example 28 A 100 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 200 mg of molybdenum metal powder, and 3.0 g of a 30% by weight aqueous hydrogen peroxide solution was added little by little.
The mixture was stirred at room temperature to obtain a yellow homogeneous solution. In this solution, 6
After adding 3.5 g of 0 wt% hydrogen peroxide, 15 g of methyl-tert-butyl ether and 5.3 g of anhydrous magnesium sulfate, the mixture was stirred at room temperature for 30 minutes, and then norbornene 2.0 was added.
g and 15 g of methyl-tert-butyl ether were added dropwise over 30 minutes. After stirring and maintaining the internal temperature at 25 ° C for 4 hours, the mixture was further stirred at 50 ° C for 6 hours. 30 g of toluene and 20 g of water were added to the reaction solution, and the mixture was stirred and separated to obtain 82.7 g of a toluene solution. After the solvent was distilled off from the toluene solution, the residue was purified using 20 g of silica gel (eluent: ethyl acetate: n-hexane = 1: 5 (volume ratio)), and the obtained solution was concentrated to give a colorless oily substance. 2.6g
I got As a result of GC analysis, the purity was 82%.
This colorless oily substance was analyzed by ¹ H-NMR, ¹³ C-NMR, M
From the S spectrum, it was found that bicyclo [2.2.1] heptane-
Identified as 2-hydroperoxy-3-ol.

¹ H-NMR: 10.4 ppm and 9.9
The peak (b) derived from the hydroperoxy group was found at 5 ppm.
s) Yes ¹³ C-NMR: 89.2 ppm and 86.6 ppm
Has a peak derived from the carbon atom to which the hydroperoxy group is bonded

Example 29 A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 100 mg of the colorless oil obtained in Example 28 and 5 g of methyl-tert-butyl ether.
5 g of a 0% by weight aqueous sodium thiosulfate solution was added, and the internal
After stirring at 5 ° C. for 16 hours, the layers were separated, and the obtained organic layer was concentrated to give 95 mg of a colorless oily substance. As a result of GC analysis, the purity was 95%. This colorless oil contains ¹
The compound was identified as bicyclo [2.2.1] heptane-2,3-diol from 1 H-NMR, ¹³ C-NMR and MS spectra.

[0113]

According to the method of the present invention, an internal disubstituted olefin can be produced at a low cost in the presence of easily available tungsten metal, molybdenum metal, a tungsten compound such as tungsten boride, and a molybdenum compound such as molybdenum boride. Β-hydroxyhydroperoxides and carboxylic acids can be easily obtained by reacting with hydrogen peroxide, and diols and aldehydes can be easily obtained from the β-hydroxyhydroperoxides. Industrially advantageous.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C07C 35/14 C07C 35/14 35/29 35/29 45/53 45/53 47/12 47/12 51/31 51 / 31 53/126 53/126 55/12 55/12 55/14 55/14 55/18 55/18 55/24 55/24 55/28 55/28 63/14 63/14 407/00 407/00 409/14 409/14 // C07B 61/00 300 C07B 61/00 300 F term (reference) 4G069 AA02 AA08 BB02C BB04A BB04B BB09C BB11C BB13C BB15C BB18C BC15A BC15C BC16A BC20A BC20C BC22A BC24A35 BCA BCBC BC55A BC59A BC59B BC60A BC60B BC61A BC64A BC65A BC66A BC67A BC68A BC69A BC70A BC71A BC72A BC74A BD03A BD03B CB07 CB35 CB70 CB72 CB74 DA02 DA03 FA01 FB41 FC01 4H006 AA02 AC40 AC41 BA32 BA30 BA30 BA30 BA30 BA30 BA30 BA30 BA30 BA30 FE12 4H039 CA62 CA64 CA65 CC40 CH70

Claims (25)

[Claims] 1. A tungsten compound comprising an internal disubstituted olefin and hydrogen peroxide, comprising tungsten metal, molybdenum metal, tungsten and a Group IIIb, IVb, Vb or Group VIb element except oxygen. Metal oxide formed by reacting hydrogen peroxide with at least one metal compound selected from the group consisting of molybdenum and a molybdenum compound consisting of a group IIIb, group IVb, group Vb or group VIb element excluding oxygen A process for producing β-hydroxyhydroperoxides and carboxylic acids, wherein the reaction is carried out in the presence of a catalyst. 2. The method according to claim 1, wherein the internally disubstituted olefin has the general formula (Wherein, R ¹ and R ² are the same or different and are each independently an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, or an optionally substituted Aryloxy group, aralkyl group which may be substituted, aralkyloxy group which may be substituted, acyl group which may be substituted, carboalkoxy group which may be substituted, carboaryl which may be substituted Represents an oxy group, an optionally substituted carboaralkyloxy group, a carboxyl group or a halogen atom, and R ¹ and R ² may together form a part of a ring structure. The method for producing β-hydroxyhydroperoxys and carboxylic acids according to claim 1, which is an olefin. 3. The method for producing β-hydroxyhydroperoxides and carboxylic acids according to claim 1, wherein the Group IIIb element is boron. 4. The method for producing β-hydroxyhydroperoxides and carboxylic acids according to claim 1, wherein the Group IVb element is carbon. 5. The process for producing β-hydroxyhydroperoxides and carboxylic acids according to claim 1, wherein the Group Vb element is nitrogen or phosphorus. 6. The method for producing β-hydroxyhydroperoxides and carboxylic acids according to claim 1, wherein the Group VIb element excluding oxygen is sulfur. 7. The β according to claim 1, wherein a hydrogen peroxide solution is used.
-A process for producing hydroxyhydroperoxides and carboxylic acids. 8. A tungsten compound consisting of tungsten metal, molybdenum metal, tungsten and a group IIIb, group IVb, group Vb or group VIb element excluding oxygen, and molybdenum and a group IIIb, group IVb, group Vb Reacting at least one metal compound selected from the group consisting of a molybdenum compound consisting of a Group VIb element excluding oxygen or oxygen with hydrogen peroxide, and oxidizing an internal disubstituted olefin to obtain β-hydroxy Metal oxide catalyst for producing hydroperoxides and carboxylic acids. 9. A tungsten compound comprising tungsten metal, molybdenum metal, tungsten and a Group IIIb, IVb, Vb or Group VIb element excluding oxygen, and molybdenum and a Group IIIb, Group IVb, Vb Reacting at least one metal compound selected from the group consisting of molybdenum compounds consisting of a Group VIb element excluding oxygen and oxygen with hydrogen peroxide in water, oxidizing an internal disubstituted olefin, An aqueous metal oxide catalyst solution for producing β-hydroxyhydroperoxides and carboxylic acids. 10. A metal oxide comprising the aqueous solution of the metal oxide catalyst according to claim 9 and an organic solvent, for oxidizing an internally disubstituted olefin to produce β-hydroxyhydroperoxides and carboxylic acids. Catalyst solution. 11. A tungsten compound comprising tungsten metal, molybdenum metal, tungsten and a Group IIIb, Group IVb, Group Vb or Group VIb element other than oxygen, and molybdenum and a group IIIb, group IVb, group Vb. At least one metal compound selected from the group consisting of molybdenum compounds consisting of group VIb elements excluding oxygen or oxygen and hydrogen peroxide are reacted in water while stirring so that the metal compound is sufficiently dispersed. A method for preparing an aqueous solution of a metal oxide catalyst for producing β-hydroxyhydroperoxides and carboxylic acids by oxidizing internally disubstituted olefins. 12. A method according to claim 1, wherein the β-hydroxyhydroperoxide is obtained, and then the β-hydroxyhydroperoxide is treated with an alkali or a heat treatment to obtain the β-hydroxyhydroperoxide. A method for producing aldehydes, comprising decomposing aldehydes. 13. The method according to claim 1, wherein a β-hydroxyhydroperoxide is obtained, and the β-hydroxyhydroperoxide is added to a Group Va element compound, a Group VIIa element compound, Group VIII compound,
A group Ib element compound, a group Iib element compound, a group IIIb element compound, a group IVb element compound, a group Vb element compound and at least one compound selected from the group consisting of lanthanide compounds are acted on to obtain the β- A method for producing aldehydes, comprising decomposing hydroxyhydroperoxides. 14. The method for producing aldehydes according to claim 13, wherein the Group Va element compound is a vanadium compound or a niobium compound. 15. The method for producing an aldehyde according to claim 13, wherein the Group VIIa element compound is a rhenium compound. 16. The method for producing aldehydes according to claim 13, wherein the Group VIII element compound is an iron compound, a ruthenium compound, a cobalt compound, a rhodium compound, an iridium compound, a nickel compound or a palladium compound. 17. The method for producing an aldehyde according to claim 13, wherein the Group Ib element compound is a copper compound. 18. The method for producing an aldehyde according to claim 13, wherein the Group IIb element compound is a zinc compound. 19. The method for producing an aldehyde according to claim 13, wherein the Group IIIb element compound is a boron compound or an aluminum compound. 20. The method for producing an aldehyde according to claim 13, wherein the Group IVb element compound is a tin compound. 21. The method for producing an aldehyde according to claim 13, wherein the Group Vb element compound is a bismuth compound or an antimony compound. 22. The method for producing an aldehyde according to claim 13, wherein the lanthanide compound is a dysprosium compound. 23. A diol comprising the steps of obtaining a β-hydroxyhydroperoxide by the method according to any one of claims 1 to 7, and reducing the β-hydroxyhydroperoxide with a reducing agent. Manufacturing method. 24. The general formula (2) (Wherein R ¹ and R ² are the same or different and are each independently an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, or an optionally substituted Aryloxy group, optionally substituted aralkyl group, optionally substituted aralkyloxy group, optionally substituted acyl group, optionally substituted carboalkoxy group, optionally substituted carboaryl And represents an oxy group, an optionally substituted carboaralkyloxy group, a carboxyl group or a halogen atom, and R ¹ and R ² may together form a part of a ring structure. β-hydroxyhydroperoxides and / or general formula (3) (In the formula, R ¹ and R ² represent the same meaning as described above.)
Wherein β-hydroxyhydroperoxides represented by the formula (1) are reduced with a reducing agent. (Wherein, R ¹ and R ² each have the same meaning as described above). 25. The method for producing diols according to claim 23 or 24, wherein the reducing agent is an inorganic reducing agent or a sulfide.