JP2008019265A - METHOD FOR PRODUCING beta-HYDROXYHYDROPEROXIDE AND CATALYST FOR THE SAME - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing β-hydoxyhydroperoxides more industrially advantageously by oxidizing an internally disubstituted olefins with hydrogen peroxide. <P>SOLUTION: This method for producing the β-hydoxyhydroperoxides is characterized by reacting the internally disubstituted olefins with hydrogen peroxide in an organic solvent in the presence of a metal oxide catalyst obtained by reacting at least 1 kind of a metal selected from a group consisting of tungsten metal, molybdenum metal, a tungsten compound consisting of the tungsten with an element of the IIIb group, the IVb group, the Vb group or the VIb group excluding oxygen, and a molybdenum compound consisting of the molybdenum with an element of the IIIb group, the IVb group, the Vb group or the VIb group excluding the oxygen, with hydrogen peroxide. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a process for producing β-hydroxyhydroperoxides and a catalyst thereof.

  β-Hydroxy hydroperoxides are important compounds as various chemical products and synthetic intermediates thereof, and are particularly important compounds as synthesis precursors of aldehydes and diols.

  Such β-hydroxyhydroperoxides 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 that is inexpensive, easy to handle, and harmless water after the reaction.

  As a method for producing β-hydroxyhydroperoxides by oxidizing internal disubstituted substituted olefins with hydrogen peroxide, for example, a method using a tetrakis (oxodiperoxotungsto) phosphate catalyst (Non-patent Document 1) is known. However, this method is a two-stage method in which an internal disubstituted olefin and hydrogen peroxide are reacted to convert them into a corresponding epoxide, and then the epoxide and hydrogen peroxide are further reacted. In addition, the preparation of the catalyst is relatively complicated and cannot always be said to be an efficient method.

  Known methods for obtaining aldehydes from β-hydroxyhydroperoxides include, for example, a method using a base (Non-patent Document 2), a method using an acid (Non-Patent Document 3), and a thermal decomposition method (Patent Document 1). However, development of a more industrially advantageous method has been desired.

  Examples of methods for producing aldehydes from internal disubstituted olefins include a method using a methylrhenium trioxide catalyst (Patent Document 2), a method using heteropolyacids and magnesium sulfate as a catalyst (Patent Document 3), a tungsten compound and boron. A method using a compound as a catalyst (Patent Document 4), a method using a heteropolyacid containing phosphorus or germanium as a catalyst (Patent Document 5), a heteropolyacid containing phosphorus or germanium, and a metal salt of Group Ia or IIa of the periodic table A method using a catalyst (Patent Document 6), a method using a heteropolyacid and magnesium sulfate as a catalyst (Patent Document 3), a method using a tungsten oxide synthesized from sodium tungstate as a catalyst (Non-Patent Document 4), etc. are known. However, both methods use relatively expensive catalysts and reagents. In that the yield is low, not necessarily industrially advantageous method.

  As a method for producing diols by reducing β-hydroxyhydroperoxides, for example, a method using triphenylphosphine as a reducing agent (Non-Patent Document 1) is known. However, triphenylphosphine is expensive, and It was not an advantageous method in that an operation for separating the produced diols and by-product triphenylphosphine oxide was necessary.

  As a method for producing diols from internal disubstituted olefins, for example, a method using a complex catalyst composed of tungstophosphoric acid and a quaternary ammonium salt (Non-Patent Document 5) is known. This is not always an efficient method.

JP 58-121234 A WO98 / 47847 Japanese Patent Publication No. 8-19027 Japanese Patent Publication No. 63-56207 Japanese Examined Patent Publication No. 6-84324 Japanese Examined Patent Publication No. 6-99355 J. et al. Org. Chem. 63, 7190 (1998) J. et al. Org. Chem. , 43, 1760 (1978) J. et al. Chem. Soc. , Chem. Comm. , 1976, 507 Tetrahedron, 48, 3503 (1992) Synthesis, 295 (1989)

  Under such circumstances, the present inventor has intensively studied to develop a method for producing β-hydroxyhydroperoxides more advantageously industrially by oxidizing internal disubstituted olefins with hydrogen peroxide. However, tungsten metals, molybdenum metals, tungsten compounds such as tungsten boride, and other metal oxides obtained by reacting molybdenum compounds such as molybdenum boride with hydrogen peroxide are easily oxidized with internal disubstituted olefins. In the reaction of hydrogen, it shows good catalytic activity, and β-hydroxyhydroperoxides can be obtained by reacting internal disubstituted olefins with hydrogen peroxide in the presence of the metal oxide catalyst, By treating the obtained β-hydroxy hydroperoxides with a specific metal compound, the β-hydroxy hydride is obtained. Decomposition of peroxides proceeds by reduction treatment that aldehydes can be obtained and the β- hydroxy hydroperoxides, found that diol is obtained, leading to the present invention.

  That is, the present invention relates to a tungsten compound comprising internal disubstituted olefins and hydrogen peroxide, tungsten metal, molybdenum metal, tungsten and a group IIIb, group IVb, group Vb or group VIb element excluding oxygen. And a metal obtained 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, a group IVb, a group Vb or a group VIb element excluding oxygen. The present invention provides a process for producing a β-hydroxyhydroperoxide characterized by reacting in an organic solvent in the presence of an oxide catalyst and the catalyst.

  According to the method of the present invention, internal disubstituted olefins and inexpensive hydrogen peroxide are added in the presence of easily available tungsten metal such as tungsten metal, molybdenum metal, tungsten boride, and molybdenum compound such as molybdenum boride. By reacting, β-hydroxyhydroperoxides can be easily obtained, and diols and aldehydes can be easily obtained from the β-hydroxyhydroperoxides, which is industrially advantageous.

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

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

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

  Among these metal compounds, tungsten metal, molybdenum metal, tungsten boride, molybdenum boride, tungsten sulfide, and molybdenum sulfide are preferable. Such metal compounds may be used alone or in combination of two or more.

  As 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 it is preferable to use aqueous hydrogen peroxide in terms of easy handling. The concentration of hydrogen peroxide in the 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. When using a hydrogen peroxide solution, a commercially available product may be used as it is or after adjusting the concentration by dilution, concentration or the like as necessary. When an organic solvent solution of hydrogen peroxide is used, a solution prepared by, for example, extracting hydrogen peroxide solution with an organic solvent or distilling hydrogen peroxide solution in the presence of an organic solvent is used. Use it.

  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 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 and tetrahydrofuran, ester solvents such as ethyl acetate, alcohol solvents such as methanol, ethanol and tert-butanol, nitrile solvents such as acetonitrile and propionitrile, etc. You may implement in the organic solvent of this, or the mixed solvent of this organic solvent and water.

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

  The preparation temperature at the time of metal oxide preparation is usually −10 to 100 ° C.

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

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

  Internal disubstituted olefins include olefinic carbon-carbon double bonds, and one hydrogen atom and one substituent are bonded to each carbon atom forming the double bond. If it is. A cyclic olefin containing the carbon-carbon double bond may be formed by combining two substituents bonded to each carbon atom forming the carbon-carbon double bond of the olefin. .

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

(In the formula, R ¹ and R ² are the same or different and each may be an alkyl group which may be substituted, an alkoxy group which may be substituted, an aryl group which may be substituted, or a substituent which may be 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.)
And olefins represented by

Examples of the alkyl group which may be substituted include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms such as decyl group, cyclopropyl group, 2,2-dimethylcyclopropyl group, cyclopentyl group, cyclohexyl group and menthyl group, and these alkyl groups Is substituted with a substituent such as an alkoxy group, an aryloxy group, an aralkyloxy group, a halogen atom, an acyl group, a carboalkoxy group, a carboaryloxy group, a carboaralkyloxy group, or a carboxyl group described below, for example, a chloromethyl group , Fluoromethyl group, trifluoromethyl group, methoxymethyl group, ethoxymethyl group, Tokishiechiru group, carbomethoxymethyl group, 1-carbethoxy-2,2-dimethyl-3-cyclopropyl group and the like.

  Examples of the optionally substituted alkoxy group include those composed of the optionally substituted alkyl group and an oxygen atom. For example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n -Butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, n-decyloxy group, cyclopentyloxy group, cyclohexyloxy group, menthyloxy group, etc. Cyclic C1-C20 alkoxy groups and these alkoxy groups substituted with substituents such as halogen atoms and alkoxy groups, for example, chloromethoxy group, fluoromethoxy group, trifluoromethoxy group, methoxymethoxy group, ethoxy A methoxy group, a methoxyethoxy group, etc. are mentioned.

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

  Examples of the optionally substituted aralkyl group include those composed of the optionally substituted aryl group and the optionally substituted alkyl group, such as a benzyl group, a 4-chlorobenzyl 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, Examples include 3,5,6-tetrafluoro-4-methoxybenzyl group and 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl group. Examples of the optionally substituted aralkyloxy group include those composed of the optionally substituted aralkyl group and an oxygen atom, such as a benzyloxy group, 4-chlorobenzyloxy group, 4- Methylbenzyloxy group, 4-methoxybenzyloxy group, 3-phenoxybenzyloxy group, 2,3,5,6-tetrafluorobenzyloxy group, 2,3,5,6-tetrafluoro-4-methylbenzyloxy group 2,3,5,6-tetrafluoro-4-methoxybenzyloxy group, 2,3,5,6-tetrafluoro-4-methoxymethylbenzyloxy group and the like.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

  Examples of the optionally substituted acyl group include a carbonyl group and the optionally substituted alkyl group, a carbonyl group and the optionally substituted aryl group, and a carbonyl group and the optionally substituted aralkyl group. Examples thereof include carbomethyl group, carboethyl group, carbophenyl group, carbobenzyl group and the like.

  The optionally substituted carboalkoxy group includes a carbonyl group and the optionally substituted alkoxy group, and the optionally substituted carboaryloxy group includes a carbonyl group and the substituted As the carboaralkyloxy group which is composed of an optionally substituted aryloxy group, the carboaralkyloxy group which is optionally substituted is composed of a carbonyl group and the optionally substituted aralkyloxy group, respectively. Examples thereof include carbomethoxy group, carboethoxy group, carbophenoxy group, carbobenzyloxy group and the like.

Examples of the ring structure when R ¹ and R ² together form a part 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, and 3,5-dimethyl. Cyclopentene, 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-2- (1-propenyl) cyclo Methyl Ropankarubon acid, 3,3-dimethyl-2- (1-propenyl) ethyl cyclopropanecarboxylate and the like.

  Some olefins have an asymmetric carbon in the molecule and have optical isomers, but in the present invention, any one or a mixture of optical isomers can be used. .

  In this reaction, olefins and hydrogen peroxide are reacted in the presence of the metal oxide catalyst described above, and β-hydroxy hydroperoxides in which the carbon-carbon double bonds of the olefins are oxidized are generated. .

（式中、Ｒ¹およびＲ²は上記と同一の意味を表わす。）
で示されるβ−ヒドロキシヒドロペルオキシド類および／または一般式（３）

（式中、Ｒ¹およびＲ²は上記と同一の意味を表わす。）
で示されるβ−ヒドロキシヒドロペルオキシド類が生成する。なお、本反応においては、オレフィン類の別の酸化生成物であるジオール類やβ−ヒドロキシヒドロペルオキシド類が分解したアルデヒド類が副生成物として生成することがある。上記一般式（１）で示されるオレフィン類を用いた場合には、一般式（４）

（式中、Ｒ¹およびＲ²は上記と同一の意味を表わす。）
で示されるジオール類や一般式（７）

（式中、Ｒ¹は上記と同一の意味を表わす。）
で示されるアルデヒド類および一般式（８）

（式中、Ｒ²は上記と同一の意味を表わす。）
で示されるアルデヒド類が副生物として生成する。 When the olefin represented by the general formula (1) is used as the olefin, the general formula (2) in which the carbon-carbon double bond is oxidized.

(In the formula, R ¹ and R ² represent the same meaning as described above.)
Β-hydroxy hydroperoxides represented by the general formula (3)

(In the formula, R ¹ and R ² represent the same meaning as described above.)
The β-hydroxy hydroperoxides represented by In this reaction, diols, which are other oxidation products of olefins, and aldehydes decomposed by β-hydroxyhydroperoxides may be produced as by-products. When the olefins represented by the general formula (1) are used, the general formula (4)

(In the formula, R ¹ and R ² represent the same meaning as described above.)
Diols represented by the general formula (7)

(In the formula, R ¹ represents the same meaning as described above.)
And aldehydes represented by the general formula (8)

(Wherein R ² represents the same meaning as described above.)
Is generated as a by-product.

  More specifically, taking specific olefins as an example, for example, when cyclopentene is used as the raw material olefins, 1-hydroperoxy-2-hydroxycyclopentane is obtained, and 2-hexene is used as the raw material olefins. Is used, 2-hydroperoxy-3-hydroxyhexane and / or 3-hydroperoxy-2-hydroxyhexane are obtained.

  The amount of metal oxide catalyst used in the reaction between olefins and hydrogen peroxide is usually 0.001 mol times or more with respect to olefins, and there is no particular upper limit, but considering the economic aspect, Practically, it is 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 hydrogen peroxide concentration in the hydrogen peroxide solution or the organic solvent solution is not particularly limited, but is practically 1 to 60% by weight in consideration of volume efficiency, safety and the like. As the hydrogen peroxide solution, a commercially available one is usually used as it is or after adjusting the concentration by dilution, concentration or the like as necessary. The organic solvent solution of hydrogen peroxide can be prepared, for example, by a means such as extraction treatment of hydrogen peroxide solution with an organic solvent or distillation treatment of hydrogen peroxide solution in the presence of the organic solvent.

  The amount of hydrogen peroxide used is usually 1 mol times or more with respect to olefins, and there is no particular upper limit on the amount of use, but considering the economic aspect, practically for olefins 10 mol times or less. In addition, when using the preparation liquid containing a metal oxide as a catalyst, you may set the usage-amount of hydrogen peroxide including the amount of hydrogen peroxide in this preparation liquid.

  This reaction is usually carried out in an organic solvent. Examples of the organic solvent include ether solvents such as diethyl ether, methyl tert-butyl ether and tetrahydrofuran, ester solvents such as ethyl acetate, alcohol solvents such as methanol, ethanol and tert-butanol, acetonitrile, propionitrile and the like. A nitrile-type solvent etc. are mentioned. The amount of the organic solvent used is not particularly limited, but is practically 100 weight times or less with respect to the olefins in consideration of volumetric efficiency and the like.

  In this reaction, it is preferable to carry out the reaction under anhydrous conditions. Examples of the method for carrying out the reaction under anhydrous conditions include a method in which a dehydrating agent is allowed to coexist in the reaction system. Examples of the dehydrating agent include anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous boric acid, polyphosphoric acid, diphosphorus pentoxide and the like, and the amount used is more than the amount capable of dehydrating and removing water present in the reaction system. I just need it.

  If the reaction temperature is too low, the reaction is difficult to proceed, and if the reaction temperature is too high, side reactions such as polymerization of raw olefins may proceed, so the practical reaction temperature is in the range of 0 to 200 ° C. It is.

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

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

  Further, this reaction may be carried out in the presence of a boron compound such as boric anhydride. Examples of the boron compound include boric anhydride, metaboric acid, normal boric acid, alkali metal metaborate, alkali earth metal borate, alkali metal normal borate, and alkaline earth metal borate. The amount used is not particularly limited, but if it is too much, it is economically disadvantageous, and therefore, practically, it is usually 1 mole or less with respect 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, followed by concentration treatment, crystallization treatment, and the like to take out the desired aldehydes. be able to. Moreover, aldehydes can also be taken out by adding water and / or an organic solvent insoluble in water to the reaction solution as necessary, performing an extraction treatment, and concentrating the resulting organic layer. The extracted aldehydes may be further purified by means such as distillation or 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, ether ethers such as diethyl ether, methyl-tert-butyl ether, and tetrahydrofuran. Examples of the solvent include ester solvents such as ethyl acetate, and the amount used is not particularly limited.

  In addition, the aqueous layer obtained by extracting the filtrate or reaction solution after the target β-hydroxyhydroperoxides have been extracted by crystallization treatment contains the metal oxide catalyst of this reaction, and it is necessary or necessary. Depending on the concentration, it can be used again for this reaction after concentration treatment or the like.

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

  Examples of the β-hydroxyhydroperoxides thus obtained include 1-hydroperoxy-2-hydroxycyclopentane, 1-hydroperoxy-2-hydroxycyclohexane, 1-hydroperoxy-2-hydroxycycloheptane, 1-hydroperoxy- 2-hydroxycyclooctane, 1-hydroperoxy-2-hydroxy-3-methylcyclopentane, 1-hydroperoxy-2-hydroxy-4-methylcyclopentane, 1-hydroperoxy-2-hydroxy-3,4-dimethyl Cyclohexane, 1-hydroperoxy-2-hydroxy-3,4,5-trimethylcyclohexane, 2-hydroperoxy-3-hydroxyhexane, 3-hydroperoxy-2-hydroxyhexane, bicyclo [2.2.1] hept 2-hydroperoxy-3-ol, methyl 3,3-dimethyl-2- (1-hydroxy-2-hydroperoxypropyl) cyclopropanecarboxylate, 3,3-dimethyl-2- (2-hydroxy-1) -Hydroperoxypropyl) methyl cyclopropanecarboxylate, ethyl 3,3-dimethyl-2- (1-hydroxy-2-hydroperoxypropyl) cyclopropanecarboxylate, 3,3-dimethyl-2- (2-hydroxy-1) -Hydroperoxypropyl) ethyl cyclopropanecarboxylate and the like.

（式中、Ｒ¹は上記と同一の意味を表わす。）
で示されるアルデヒド類および一般式（８）

（式中、Ｒ²は上記と同一の意味を表わす。）
で示されるアルデヒド類が得られる。具体的な化合物を例にしてさらに詳しく説明すると、例えばシクロペンテンから得られる１−ヒドロキシ−２−ヒドロペルオキシシクロペンタンからは、グルタルアルデヒドが生成する。 The produced β-hydroxyhydroperoxides can be subjected to alkali treatment or heat treatment to decompose the β-hydroxyhydroperoxides to obtain the corresponding aldehydes. 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)

(In the formula, R ¹ represents the same meaning as described above.)
And aldehydes represented by the general formula (8)

(Wherein R ² represents the same meaning as described above.)
Is obtained. More specifically, taking a specific compound as an example, glutaraldehyde is produced from, for example, 1-hydroxy-2-hydroperoxycyclopentane obtained from cyclopentene.

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

  Further, the produced β-hydroxy hydroperoxides are Group Va element compound, Group VIIa element compound, Group VIII element compound, Group Ib element compound, Group IIb element compound, Group IIIb element compound, Group IVb. By acting at least one compound selected from the group consisting of group element compounds, group Vb element compounds and lanthanide compounds, the β-hydroxyhydroperoxides can be decomposed to obtain aldehydes.

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

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

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

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

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

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

  Examples of aldehydes thus obtained include acetaldehyde, propionaldehyde, butyraldehyde, pentylaldehyde, hexylaldehyde, heptylaldehyde, undecanaldehyde, benzaldehyde, glutaraldehyde, adipaldehyde, heptanedialdehyde, octanedialdehyde, 2-chloroglutar Aldehyde, 2-methyl glutaraldehyde, 3-methyl glutaraldehyde, 2,3-dimethyl glutaraldehyde, 2,4-dimethyl glutaraldehyde, 2,3,4-trimethyl glutaraldehyde, 2-methyl adipaldehyde, 3-methyl Adipaldehyde, 2,3-dimethyladipaldehyde, 2,4-dimethyladipaldehyde, 2,3,4-dimethyladipaldehyde, cyclopentane- , 3-dicarbaldehyde, diphenyl-2,2′-dicarbaldehyde, 1- (formylmethyl) cyclopentane-2,3,4-tricarbaldehyde, 1,2-bis (formylmethyl) succinic anhydride 1,4-diformylbutane-2,3-dicarboxylic acid, methyl 3,3-dimethyl-2-formylcyclopropanecarboxylate, ethyl 3,3-dimethyl-2-formylcyclopropanecarboxylate, and the like.

（式中、Ｒ¹およびＲ²はそれぞれ上記と同一の意味を表わす。）
で示されるジオール類が生成する。 Also, diols can be obtained by reducing β-hydroxyhydroperoxides with a reducing agent. When β-hydroxyhydroperoxides represented by the general formula (2) and / or β-hydroxyhydroperoxides represented by the general formula (3) are reduced with a reducing agent, the general formula (4)

(In the formula, R ¹ and R ² each have the same meaning as described above.)
Is produced.

  The reduction treatment is usually carried out by mixing β-hydroxyhydroperoxides and a reducing agent, and 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 1 mol or more with respect to β-hydroxyhydroperoxides, and there is no particular upper limit, but considering practicality, 5 mol with respect to β-hydroxyhydroperoxides. Is less than double.

  The temperature of the reduction treatment is usually in the range of 10 to 100 ° C. This reduction treatment is also usually performed in the presence of a solvent in which β-hydroxyhydroperoxides are dissolved. In the case of using a reaction liquid containing β-hydroxyhydroperoxides obtained by oxidizing olefins with, for example, tungsten metal, tungsten boride or the like, the reaction liquid may be directly mixed with a reducing agent. In many cases, unreacted hydrogen peroxide and other oxidizing substances remain in the reaction solution, so that β-hydroxyhydroperoxides are extracted from the reaction solution by extraction or the like and then mixed with a reducing agent. It is preferable in terms of economy.

  Examples of the diol include 1,2-dihydroxycyclopentane, 1,2-dihydroxycyclohexane, 1,2-dihydroxycycloheptane, 1,2-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, methyl 3,3-dimethyl-2- (1,2-dihydroxypropyl) cyclopropanecarboxylate, 3,3-dimethyl-2- (1,2-dihydroxypropyl) Examples include ethyl cyclopropanecarboxylate.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples.

  The conditions for gas chromatography analysis (hereinafter abbreviated as GC analysis) and high performance liquid chromatography analysis (hereinafter abbreviated as LC analysis) are as follows.

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

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

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

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

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

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

Example 3 <Preparation of oxide by reaction of tungsten sulfide and hydrogen peroxide>
In Example 2, it replaced with the tungsten boride powder, and it implemented similarly to Example 2 except having used 5.4 g of tungsten sulfide and having changed the quantity of water to 12 g, and obtained 10.1 g of pale yellow solid.

UV spectrum of solution before concentration λ ^H2O _max : 200,240 (s) nm
IR spectrum of colorless solution before concentration (aqueous solution; 4000-750 cm ⁻¹ )
ν _max : 3373, 1187, 1044, 974, 878, 837 cm ⁻¹
IR spectrum (KBr) of the obtained solid
ν _max : 3435, 3359, 1730, 1632, 1320, 1285, 1178, 1103, 1070, 1008, 981, 887, 839, 851, 660, 615, 578 cm ⁻¹
Elemental analysis value; W: 35.3, O: 47.7, H: 3.0, S: 12.4

Example 4 <Preparation of Oxide by Reaction of Molybdenum Metal with Hydrogen Peroxide>
In Example 2, instead of tungsten boride powder, 2.1 g of molybdenum metal was used, the amount of water was 12 g, and the amount of 60 wt% aqueous hydrogen peroxide was 12 g. Carried out 4.0 g of yellow solid.

UV spectrum of solution before concentration λ ^H2O _max : 207,300 nm
IR spectrum of colorless solution before concentration (aqueous solution; 4000-750 cm ⁻¹ )
ν _max : 3359, 2480, 1372, 974, 866 cm ⁻¹
IR spectrum (KBr) of the obtained solid
ν _max : 3530, 1621, 964, 927, 902, 840, 633, 557, 530, 522 cm ⁻¹
Elemental analysis value; Mo: 47.8, O: 46.2, H: 2.1

Example 5 <Preparation of oxide by reaction of molybdenum boride and hydrogen peroxide>
In Example 2, instead of tungsten boride powder, 2.3 g of molybdenum boride was used, the amount of water was 12 g, and the amount of 60 wt% aqueous hydrogen peroxide solution was 12 g. To obtain 5.2 g of a yellow solid.

UV spectrum of the solution before concentration λ ^H2O _max : 200,310 nm
IR spectrum (KBr) of the obtained solid
ν _max : 3221, 2520, 2361, 2262, 1620, 1463, 1439, 1195, 965, 927, 887, 840, 799, 674, 634, 547, 529 cm ⁻¹
Elemental analysis value; Mo: 35.5, O: 51.0, H: 2.9, B: 4.1

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

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

Example 6
A 50 mL flask equipped with a magnetic rotor and reflux condenser was charged with 200 mg of 30 wt% hydrogen peroxide, 1.5 g of tert-butanol and 40 mg of tungsten metal powder, and the temperature was raised to 60 ° C. Stir and hold for hours. This solution was cooled to 25 ° C., 530 mg of anhydrous magnesium sulfate was added, and a mixed solution of 150 mg of cyclopentene, 1.5 g of tert-butanol and 350 mg of 30 wt% hydrogen peroxide was 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-tert-butyl ether solution. When the solution was analyzed by LC, 1-hydroperoxy-2-hydroxycyclopentane was produced, but glutaraldehyde was not produced.

GC analysis of the solution revealed that 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 as the yield of 1-hydroperoxy-2-hydroxycyclopentane.
Yield of 1-hydroperoxy-2-hydroxycyclopentane: 80.7%

Example 7
The methyl-tert-butyl ether solution containing 1-hydroperoxy-2-hydroxycyclopentane obtained in Example 6 above was charged into a 50 mL flask equipped with a magnetic rotor and a reflux condenser, and 50 mg of vanadium pentoxide was further charged. The mixture was stirred and held at an internal temperature of 60 ° C. for 4 hours. When the obtained reaction liquid was analyzed by LC, the peak of 1-hydroperoxy-2-hydroxycyclopentane disappeared and the peak of glutaraldehyde was detected. As a result of GC analysis (internal standard method), 170 mg of glutaraldehyde was contained. Glutaraldehyde yield: 77% (based on 1-hydroperoxy-2-hydroxycyclopentane).

Example 8
The reaction was conducted in the same manner as in Example 6 to obtain 11 g of a tert-butanol solution containing 940 mg of 1-hydroperoxy-2-hydroxycyclopentane. 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 liquid was analyzed by LC, the peak of 1-hydroperoxy-2-hydroxycyclopentane disappeared and the peak of glutaraldehyde was detected. As a result of GC analysis (internal standard method), 398 mg of glutaraldehyde was contained. Yield: 50% (based on 1-hydroperoxy-2-hydroxycyclopentane).

Example 9
A reaction solution containing 279 mg of glutaraldehyde was obtained in the same manner as in Example 8 except that 350 mg of palladium acetate was used instead of bismuth chloride in Example 8. Yield: 35% (based on 1-hydroperoxy-2-hydroxycyclopentane).

Example 10
A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 200 mg of 30 wt% hydrogen peroxide, 1.5 g of tert-butanol, 20 mg of boric anhydride and 40 mg of tungsten metal powder, and the temperature was raised to 60 ° C. The mixture was stirred and held at the same temperature for 1 hour. This solution was cooled to 25 ° C., 530 mg of anhydrous magnesium sulfate was added, and a mixed solution of 180 mg of cyclohexene, 1.5 g of tert-butanol and 350 mg of 30 wt% hydrogen peroxide was 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 was formed, and formation of adipaldehyde could not be confirmed. As a result of GC analysis, 1-hydroperoxy-2-hydroxycyclohexane was thermally decomposed at the inlet and detected as adipaldehyde. Therefore, the yield of adipaldehyde was determined by GC analysis. -The yield was hydroperoxy-2-hydroxycyclohexane. Yield: 54.7%.

Example 11
A 100 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 400 mg of tungsten metal powder, 2.5 g of 30 wt% hydrogen peroxide was added little by little, and then stirred at room temperature for 30 minutes to give a colorless homogeneous solution. Obtained. To this solution was added 3.0 g of 60% by weight hydrogen peroxide, 30 g of tert-butanol, and 5.3 g of anhydrous magnesium sulfate, followed by stirring at room temperature for 30 minutes, and then mixing of 2.0 g of cyclohexene and 15 g of tert-butanol. The liquid was added dropwise over 30 minutes. After stirring and holding 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, followed by liquid separation after stirring to obtain 82.7 g of a toluene solution. When this solution was analyzed by LC, 1-hydroperoxy-2-hydroxycyclohexane was formed, and formation of adipaldehyde could not be confirmed. As a result of GC analysis, 1-hydroperoxy-2-hydroxycyclohexane was thermally decomposed at the inlet and detected as adipaldehyde. Therefore, the yield of adipaldehyde was determined by GC analysis. -The yield was hydroperoxy-2-hydroxycyclohexane. Yield: 54.0%. Further, 1,2-dihydroxycyclohexane was produced in a yield of 26.0%.

Example 12
A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 390 mg of copper (II) chloride, and 41 g of a toluene solution containing 1-hydroperoxy-2-hydroxycyclohexane obtained in Example 11 was added. Stir at 16 ° C. for 16 hours. When the obtained reaction liquid 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 13
A 500 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 41 g of a toluene solution containing 1-hydroperoxy-2-hydroxycyclohexane obtained in Example 11 above, and 50 g of a 10 wt% aqueous sodium thiosulfate solution was added. After stirring at 25 ° C. for 16 hours, 50 g of methyl-tert-butyl ether was added and extraction treatment was performed to obtain 95.7 g of an organic layer. GC analysis of the organic layer revealed that no adipaldehyde peak was detected and 1,2-dihydroxycyclohexane was detected. Yield of 1,2-dihydroxy chlorohexane: 81% (based on cyclohexene).

Example 14
Example 10 Example 10 was carried out in the same manner as Example 10 except that 370 mg of 5-dodecene was used instead of 180 mg of cyclohexene, 22 mg of tungsten boride was used instead of 40 mg of tungsten metal powder, and the mixture was stirred and maintained at an internal temperature of 25 ° C. for 39 hours. did. When the reaction solution was analyzed by GC, the peaks of 1-heptylaldehyde and 1-pentylaldehyde were detected, and the respective yields were 44%. From 5-dodecene, 5-hydroperoxy-6-hydroxydodecane And / or 6-hydroperoxy-5-hydroxydodecane was found to be obtained in 44% yield.

Example 15
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 30 wt% hydrogen peroxide was added little by little, and then stirred at room temperature for 30 minutes to obtain a yellow uniform solution. Obtained. To this solution were added 60 g of hydrogen peroxide solution (3.5 g), methyl-tert-butyl ether (15 g) and anhydrous magnesium sulfate (5.3 g), followed by stirring at room temperature for 30 minutes, and then norbornene (2.0 g), methyl-tert- A mixed liquid of 15 g of butyl ether was added dropwise over 30 minutes. The mixture was stirred and maintained at an internal temperature of 25 ° C. for 4 hours, and 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 separated after stirring to obtain 82.7 g of a toluene solution. After evaporating the toluene solution, the residue was purified using 20 g of silica gel (eluent: ethyl acetate: n-hexane = 1: 5 (volume ratio)), and the resulting solution was concentrated to a colorless oily substance. 2.6 g was obtained. As a result of GC analysis, the purity was 82%. This colorless oily substance was identified as bicyclo [2.2.1] heptan-2-hydroperoxy-3-ol from ¹ H-NMR, ¹³ C-NMR and MS spectra.

¹ H-NMR: peaks (bs) derived from hydroperoxy group at 10.4 ppm and 9.95 ppm
¹³ C-NMR: Peaks derived from the carbon atom to which the hydroperoxy group is bonded at 89.2 ppm and 86.6 ppm

Example 16
A 50 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 100 mg of the colorless oily substance obtained in Example 15 and 5 g of methyl tert-butyl ether, and 5 g of 10 wt% sodium thiosulfate aqueous solution was added. After stirring for 16 hours, liquid separation was performed, and the resulting organic layer was concentrated to obtain 95 mg of a colorless oily substance. As a result of GC analysis, the purity was 95%. This colorless oily substance was identified as bicyclo [2.2.1] heptane-2,3-diol from ¹ H-NMR, ¹³ C-NMR and MS spectra.

Claims (24)

Internal disubstituted olefins and hydrogen peroxide, tungsten metal, molybdenum metal, tungsten and group IIIb, group IVb, group Vb or a group VIb excluding oxygen and molybdenum and group IIIb In the presence of a metal oxide catalyst obtained by reacting hydrogen peroxide with at least one metal compound selected from the group consisting of molybdenum compounds consisting of Group IVb, Group Vb or Group VIb elements excluding oxygen And a method for producing β-hydroxyhydroperoxides, characterized by reacting in an organic solvent. The process for producing β-hydroxyhydroperoxides according to claim 1, wherein the internal disubstituted olefins and hydrogen peroxide are carried out under anhydrous conditions. The process for producing β-hydroxyhydroperoxides according to claim 1, wherein the internal disubstituted olefins and hydrogen peroxide are used in the presence of a dehydrating agent. The process for producing β-hydroxyhydroperoxides according to claim 3, wherein the dehydrating agent is anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous boric acid, polyphosphoric acid or diphosphorus pentoxide. Internal disubstituted olefins are represented by the general formula (1)

(In the formula, R ¹ and R ² are the same or different and each may be an alkyl group which may be substituted, an alkoxy group which may be substituted, an aryl group which may be substituted, or a substituent which may be 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-hydroxyhydroperoxides according to claim 1, wherein the olefins are represented by the formula: The manufacturing method of (beta) -hydroxy hydroperoxide in any one of Claims 1-5 using hydrogen peroxide water. Tungsten metal, molybdenum metal, tungsten and group IIIb, group IVb, group Vb, or tungsten compound consisting of group VIb elements excluding oxygen and molybdenum and group IIIb, group IVb, group Vb or oxygen are excluded Production of β-hydroxy hydroperoxides by oxidizing internal disubstituted olefins, which are made by reacting hydrogen peroxide with at least one metal compound selected from the group consisting of molybdenum compounds consisting of Group VIb elements Metal oxide catalyst for Tungsten metal, molybdenum metal, tungsten and group IIIb, group IVb, group Vb, or tungsten compound consisting of group VIb elements excluding oxygen and molybdenum and group IIIb, group IVb, group Vb or oxygen are excluded Β-hydroxyhydroperoxide obtained by oxidizing an internal disubstituted olefin by reacting at least one metal compound selected from the group consisting of molybdenum compounds consisting of Group VIb elements with hydrogen peroxide in water. Metal oxide catalyst aqueous solution for producing a catalyst. A metal oxide catalyst solution for producing β-hydroxyhydroperoxides by oxidizing internal disubstituted olefins, comprising the metal oxide catalyst aqueous solution according to claim 8 and an organic solvent. Tungsten metal, molybdenum metal, tungsten and group IIIb, group IVb, group Vb, or tungsten compound consisting of group VIb elements excluding oxygen and molybdenum and group IIIb, group IVb, group Vb or oxygen are excluded It is characterized in that at least one metal compound selected from the group consisting of molybdenum compounds consisting of Group VIb elements and hydrogen peroxide are reacted with stirring in water so that the metal compound is sufficiently dispersed in water. A method for preparing an aqueous metal oxide catalyst solution for producing β-hydroxyhydroperoxides by oxidizing internal disubstituted olefins. A β-hydroxy hydroperoxide is obtained by the method according to claim 1, and then the β-hydroxy hydroperoxide is decomposed by alkali treatment or heat treatment. A process for producing aldehydes characterized by the following. A β-hydroxy hydroperoxide is obtained by the method according to claim 1, and then the β-hydroxy hydroperoxide is added to 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, a group IIIb element compound, a group IVb element compound, a group Vb element compound, and a lanthanide compound, -A process for producing aldehydes, which comprises decomposing hydroxy hydroperoxides. The method for producing an aldehyde according to claim 12, wherein the Group Va element compound is a vanadium compound or a niobium compound. The method for producing aldehydes according to claim 12, wherein the Group VIIa element compound is a rhenium compound. The method for producing an aldehyde according to claim 12, 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. The method for producing aldehydes according to claim 12, wherein the Group Ib element compound is a copper compound. The method for producing aldehydes according to claim 12, wherein the Group IIb element compound is a zinc compound. The method for producing an aldehyde according to claim 12, wherein the Group IIIb element compound is a boron compound or an aluminum compound. The method for producing aldehydes according to claim 12, wherein the Group IVb element compound is a tin compound. The method for producing an aldehyde according to claim 12, wherein the Group Vb element compound is a bismuth compound or an antimony compound. The method for producing aldehydes according to claim 12, wherein the lanthanide compound is a dysprosium compound. A process for producing diols, characterized in that β-hydroxyhydroperoxides are obtained by the method according to any one of claims 1 to 6, and then the β-hydroxyhydroperoxides are reduced with a reducing agent. General formula (2)

(In the formula, R ¹ and R ² are the same or different and each may be an alkyl group which may be substituted, an alkoxy group which may be substituted, an aryl group which may be substituted, or a substituent which may be 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.)
Β-hydroxy hydroperoxides represented by the general formula (3)

(In the formula, R ¹ and R ² represent the same meaning as described above.)
The β-hydroxyhydroperoxides represented by the general formula (4) are reduced with a reducing agent:

(In the formula, R ¹ and R ² each have the same meaning as described above.)
The manufacturing method of diol shown by these. The method for producing a diol according to claim 22 or 23, wherein the reducing agent is an inorganic reducing agent or sulfides.