JP2003292460A - Method for producing carbonyl compound and catalyst for the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for simply producing a carboxylic acid from a chain state 1,2-diol. <P>SOLUTION: This method for producing the carboxylic acid is characterized by performing a reaction of the chain state 1,2-diol with hydrogen peroxide in the presence of a metal oxide catalyst obtained by performing a reaction of hydrogen peroxide with at least 1 kind selected from a group consisting of tungsten metal, molybdenum metal, a tungsten compound consisting of the tungsten and an element of IIIb group, IVb group, Vb group or VIb group except for oxygen, and a molybdenum compound consisting of the molybdenum and an element of IIIb, IVb, Vb or VIb except for oxygen. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a carbonyl compound and its catalyst.

[0002]

BACKGROUND OF THE INVENTION Carbonyl compounds represented by carboxylic acids are important compounds as various chemical products and synthetic intermediates thereof. As a method for producing them, chain 1,2-diols are reacted with hydrogen peroxide. The method is known. For example, a method using a tris (cetylpyridinium) tungstophosphoric acid catalyst (J. Org. Chem., 5
3 , 3587 (1988)), a method of reacting under the condition of pH = 2 using a catalytic amount of sodium tungstate and a phosphoric acid catalyst (J. Org. Chem., 51 , 1).
599 (1986)) and the like, but the former method requires complicated catalyst preparation, and the latter method has
Since the adjustment operation is essential, the chain-like 1,2-
It has been desired to develop a method for producing a carbonyl compound from diols.

[0003]

Under these circumstances, the present inventors have earnestly studied a method for producing a carbonyl compound from a chain 1,2-diol in a simpler manner, and found that it was available. A metal oxide obtained by reacting an easy tungsten metal, a tungsten compound such as tungsten boride, a molybdenum metal, a molybdenum compound such as molybdenum boride with hydrogen peroxide is a chain 1,2-diol and hydrogen peroxide. In the reaction with, it was found that good catalytic activity was exhibited, and the present invention was achieved.

[0004]

That is, the present invention relates to tungsten metal, molybdenum metal, tungsten and IIIb.
Group III, Group IVb, Group Vb or Group VIb elements excluding oxygen and tungsten compounds and molybdenum and Group IIIb
Group, group IVb, group Vb or a group VIb element other than oxygen, and at least one selected from the group consisting of molybdenum compounds, and hydrogen peroxide in the presence of a metal oxide catalyst, the chain The present invention provides a method for producing a carbonyl compound, which comprises reacting hydrogenated 1,2-diols with hydrogen peroxide, and a catalyst therefor.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION First, a metal oxide catalyst used when reacting a chain 1,2-diol with hydrogen peroxide will be described. As the catalyst, tungsten metal, molybdenum metal, tungsten and Group IIIb, IVb
Tungsten compounds consisting of Group VIb, Group Vb or Group VIb elements other than oxygen, and molybdenum and Group IIIb, IVb
A metal oxide catalyst obtained by reacting at least one selected from the group consisting of molybdenum compounds consisting of Group VIb group or VIb group elements excluding oxygen (hereinafter abbreviated as metal compound) with hydrogen peroxide. Is used.

The tungsten compound containing tungsten and a Group IIIb element is, for example, tungsten boride, and the tungsten compound containing tungsten and a Group IVb element is, for example, tungsten carbide, tungsten silicide, etc. Examples of the tungsten compound including the group Vb element include tungsten nitride and the like, and examples of the tungsten compound including the tungsten and the group VIb element excluding oxygen include tungsten sulfide and the like.

As the molybdenum compound composed of molybdenum and a Group IIIb element, for example, molybdenum boride,
Examples of molybdenum compounds containing molybdenum and Group IVb elements include molybdenum carbide and molybdenum silicide, and examples of molybdenum compounds containing molybdenum and Group Vb elements include molybdenum nitride and the like, excluding molybdenum and oxygen. Examples of the molybdenum compound containing the Group VIb element include molybdenum sulfide and the like.

Among these metal compounds, tungsten metal, tungsten boride, tungsten carbide and tungsten sulfide are preferable. These metal compounds may be used alone or in combination of two or more. In addition, it is preferable to use a metal compound having a small particle size, because it facilitates the preparation of a metal oxide that is a catalyst.

An aqueous solution is usually used as the hydrogen peroxide reacted with the metal compound. Of course, an organic solvent solution of hydrogen peroxide may be used, but it is preferable to use hydrogen peroxide solution because it is easy to handle. The concentration of hydrogen peroxide in the hydrogen peroxide solution or the solution of hydrogen peroxide in the organic solvent 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 hydrogen peroxide solution may be used as it is, or as necessary, the concentration of which is adjusted by dilution, concentration or the like. The organic solvent solution of hydrogen peroxide may be prepared by means such as extraction of hydrogen peroxide solution with an organic solvent or distillation in the presence of an organic solvent.

The amount of hydrogen peroxide to be reacted with the metal compound is usually 3 mol times or more, preferably 5 mol times or more with respect 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 and methyl tert-butyl ether, ester solvents such as ethyl acetate, such as te.
It may be carried out in an organic solvent such as a tertiary alcohol solvent such as rt-butanol, for example, acetonitrile, a nitrile solvent such as propionitrile, or a mixed solvent of the organic solvent and water.

The reaction between the metal compound and hydrogen peroxide is usually carried out by mixing and contacting both, and in order to improve the contact efficiency between the metal compound and hydrogen peroxide, the metal compound is prepared in the metal oxide preparation liquid. It is preferable to carry out the reaction while stirring so as to sufficiently disperse. Further, from the viewpoint of increasing the contact efficiency between the metal compound and hydrogen peroxide and facilitating the control at the time of preparing the metal oxide, it is preferable to use a metal compound having a small particle size such as a powdery metal compound.

The temperature for preparing the metal oxide is usually −
It is 10 to 100 ° C.

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

Next, the reaction of the chained 1,2-diols with hydrogen peroxide using the metal oxide as a catalyst will be described.

The chain-shaped 1,2-diol used in the present invention is particularly preferably a chain-shaped diol in which a hydroxyl group is respectively bonded to a terminal carbon atom in the molecule and a carbon atom adjacent to the terminal carbon. Without limitation, for example, 1-phenyl-
1,2-ethanediol, 1,2-propanediol,
1-phenyl-2,3-propanediol, 1,2-butanediol, 3-methyl-1,2-butanediol,
1,2-Pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, 2-methyl-1,2- Heptanediol etc. are mentioned.

In this reaction, chain 1,2-diols are reacted with hydrogen peroxide in the presence of the above-mentioned metal oxide catalyst, and the alcohol portion is oxidized to form the chain 1,2 as a raw material. A carbonyl compound having one carbon number less than that of the 2-diol is produced. As the chain 1,2-diol, for example, when the chain 1,2-diol in which the carbon atom to which the 2-hydroxy group such as 1,2-octanediol is bonded is a secondary carbon atom is used, As the carbonyl compound, carboxylic acids having one less carbon number than the chain 1,2-diols can be obtained. Further, as the chain 1,2-diol, for example, a carbon atom to which a 2-position hydroxyl group such as 2-methyl-1,2-heptanediol is bonded is
When a chain 1,2-diol having a tertiary carbon atom is used, a ketone having a carbon number one less than that of the chain 1,2-diol is obtained as a carbonyl compound.

Taking a specific compound as an example, a more detailed description will be made. When 1,2-octanediol was used, heptanoic acid was obtained, and when 2-methyl-1,2-heptanediol was used, 2-heptanic acid was obtained. Heptanone is obtained.

The amount of the metal oxide catalyst used is
Usually 0.001 to chain 1,2-diols
It is 0.95 mol times, preferably 0.005 to 0.1 mol times.

An aqueous solution is usually used as hydrogen peroxide. Of course, an organic solvent solution of hydrogen peroxide may be used. The concentration of hydrogen peroxide in the hydrogen peroxide solution or the solution of hydrogen peroxide in the organic solvent 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 hydrogen peroxide solution may be used as it is, or as necessary, the concentration of which is adjusted by dilution, concentration or the like. The organic solvent solution of hydrogen peroxide may be prepared by means such as extraction of hydrogen peroxide solution with an organic solvent or distillation in the presence of an organic solvent.

The amount of hydrogen peroxide used is usually 2 mol times or more, preferably 4 mol times or more, with respect to the chained 1,2-diols, and there is no particular upper limit, but it is economical if too much. However, it is practically 10 mol times or less. When a preparation liquid containing a metal oxide is used as a catalyst, the amount of hydrogen peroxide used may be set in consideration of the amount of hydrogen peroxide contained in the preparation liquid.

The reaction of the chain 1,2-diols with hydrogen peroxide may be carried out without solvent or in a water solvent, an organic solvent or a mixed solvent of water and an organic solvent. Good. Examples of the organic solvent include ether solvents such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran and diglyme, ester solvents such as ethyl acetate, tertiary alcohol solvents such as tert-butanol, such as acetonitrile and propio. Examples thereof include nitrile solvents such as nitrile.

This reaction is usually carried out using a metal oxide catalyst, a chain 1,
It is carried out by contacting and mixing 2-diols and hydrogen peroxide. For example, the metal compound, hydrogen peroxide and chain-shaped 1,2-diols are contacted and mixed to prepare a metal oxide catalyst. The chain 1,2-diols and hydrogen peroxide may be simultaneously and concurrently reacted.

The reaction temperature is usually 50 to 130 ° C.,
Usually, it is carried out under normal pressure conditions, but it may be carried out under reduced pressure or increased pressure.

A carbonyl compound is produced with the progress of the reaction, and the progress of such a reaction can be confirmed by a usual analytical means such as gas chromatography, high performance liquid chromatography, thin layer chromatography, NMR and IR.

After completion of the reaction, the reaction solution is left as it is, or if necessary, residual hydrogen peroxide is decomposed with a reducing agent such as sodium sulfite, and then subjected to concentration treatment, crystallization treatment, etc. to obtain the desired carbonyl. The compound can be removed. Further, the carbonyl compound can also be taken out by adding water and / or an organic solvent insoluble in water to the reaction solution as necessary, subjecting it to an extraction treatment, and subjecting the resulting organic layer to a concentration treatment. The carbonyl compound taken out may be further purified by an ordinary purification method such as distillation, column chromatography, recrystallization and the like.

The filtrate or the reaction solution after the carbonyl compound is taken out by the crystallization treatment is subjected to the extraction treatment, and the aqueous layer after taking out the organic layer contains the metal oxide catalyst of the present reaction,
As it is or after performing concentration treatment etc. as necessary,
It can be reused in this reaction again.

The carbonyl compound thus obtained includes, for example, carboxylic acids such as benzoic acid, acetic acid, phenylacetic acid, propionic acid, 2-methylpropionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid and nonanoic acid. For example, ketones such as 2-butanone, 2-pentanone and 2-heptanone can be mentioned.

[0029]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The analysis was performed by gas chromatography.

Example 1 A 100 mL Schlenk tube equipped with a reflux condenser was replaced with nitrogen, and then 0.074 g of tungsten metal and 1.1 g of 30% by weight hydrogen peroxide were charged at room temperature, and the internal temperature was 50 ° C.
The mixture was stirred for 15 minutes to prepare a tungsten oxide catalyst aqueous solution. The aqueous solution was charged with 1.8 g of 1,2-butanediol and 7.6 g of 30% by weight hydrogen peroxide solution, and the internal temperature was adjusted to 9
The mixture was stirred and maintained at 0 ° C for 4 hours. The obtained reaction liquid was cooled, 50 mL of ethanol was added, and the mixture was shaken sufficiently to obtain a solution containing propionic acid. The yield of propionic acid is 7
It was 8% (based on 1,2-butanediol).

Example 2 A 100 mL Schlenk tube equipped with a reflux condenser was replaced with nitrogen, and then 0.074 g of tungsten metal and 1.1 g of 30% by weight hydrogen peroxide were charged at room temperature, and the internal temperature was 50 ° C.
The mixture was stirred for 15 minutes to prepare a tungsten oxide catalyst aqueous solution. 1.5 g of 1,2-octanediol was added to the aqueous solution.
Then, 3.2 g of 30 wt% hydrogen peroxide solution was charged, and the mixture was stirred and held at an internal temperature of 90 ° C. for 4 hours. The obtained reaction solution was cooled, 50 mL of ethanol was added, and the mixture was shaken sufficiently to obtain a solution containing heptanoic acid. The yield of heptanoic acid is 85%
Was (based on 1,2-octanediol).

Example 3 The procedure of Example 1 was repeated, except that tungsten boride (the amount used was equimolar to tungsten metal) was used in place of tungsten metal, and propionic acid was collected. It was obtained at a rate of 80% (based on 1,2-butanediol).

Example 4 The procedure of Example 1 was repeated, except that tungsten carbide (the amount used was equimolar to the amount of tungsten metal) was used in place of the tungsten metal, and the yield of propionic acid was increased. Obtained at 89% (based on 1,2-butanediol).

Example 5 The procedure of Example 1 was repeated except that tungsten sulfide (the amount used was equimolar to the amount of tungsten metal) was used in place of the tungsten metal, and the yield of propionic acid was increased. Obtained in 79% (based on 1,2-butanediol).

Example 6 Propionic acid was prepared in the same manner as in Example 1 except that molybdenum metal (the amount used was equimolar to tungsten metal) was used in place of tungsten metal.
Obtained in a yield of 47% (based on 1,2-butanediol).

Example 7 The procedure of Example 1 was repeated except that molybdenum boride (the amount used was equimolar to the amount of tungsten metal) was used instead of tungsten metal, and propionic acid was collected. It was obtained at a rate of 31% (based on 1,2-butanediol).

Example 8 After replacing a 100 mL Schlenk tube equipped with a reflux condenser with nitrogen, 0.074 g of tungsten metal and 12 g of 30% by weight hydrogen peroxide solution were charged at room temperature, and the mixture was stirred at an internal temperature of 50 ° C. for 15 minutes. A tungsten oxide catalyst aqueous solution was prepared. To the aqueous solution, 2.9 g of 2-methyl-1,2-heptanediol was charged, and the mixture was stirred and held at an internal temperature of 90 ° C for 4 hours. The obtained reaction liquid was cooled, 50 mL of ethanol was added, and the mixture was shaken sufficiently to obtain a solution containing 2-heptanone. The yield of 2-heptanone was 83% (based on 2-methyl-1,2-heptanediol).

[0038]

INDUSTRIAL APPLICABILITY According to the present invention, a metal oxide catalyst which can be easily prepared from a readily available tungsten compound, a tungsten compound such as tungsten boride, a molybdenum compound such as molybdenum metal, and hydrogen peroxide is used. By reacting the chain 1,2-diols with hydrogen peroxide, a carbonyl compound having one carbon atom less than that of the chain 1,2-diols can be easily obtained. Is also advantageous.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07C 45/29 C07C 45/29 49/04 49/04 A 51/285 51/285 53/08 53/08 53/122 53/122 53/124 53/124 53/126 53/126 57/32 57/32 63/06 63/06 F-term (reference) 4G069 AA02 AA08 BB02C BB04A BB04B BB09C BB11C BB14C BB15C BB18C BC59A BC59B BC59C BC60A BC60B BC60C CB07 CB72 DA08 FA01 FB41 FC02 4H006 AA02 AC44 AC46 BA14 BA31 BA33 BA34 BA36 BB14 BB15 BB25 BB31 BE32 BJ50 BS10 BS30 4H039 CA62 CA65 CC20 CC40 CE50

Claims (6)

[Claims] 1. A tungsten compound composed of tungsten metal, molybdenum metal, tungsten and a group IIIb group, IVb group, Vb group or a VIb group element excluding oxygen, and molybdenum and a group IIIb group, IVb group, Vb group. In the presence of a metal oxide catalyst formed by reacting at least one selected from the group consisting of molybdenum compounds consisting of group VIb elements other than oxygen with hydrogen peroxide with hydrogen peroxide, chain 1,2-diols and A method for producing a carbonyl compound, which comprises reacting with hydrogen peroxide. 2. The method for producing a carbonyl compound according to claim 1, wherein the Group IIIb element is boron. 3. The method for producing a carbonyl compound according to claim 1, wherein the Group IVb element is carbon. 4. The method for producing a carbonyl compound according to claim 1, wherein the Group Vb element is nitrogen. 5. The method for producing a carbonyl compound according to claim 1, wherein the Group VIb element other than oxygen is sulfur. 6. A tungsten compound containing tungsten metal, molybdenum metal, tungsten and a group IIIb group, IVb group, Vb group or a VIb group element other than oxygen, and molybdenum and a group IIIb group, IVb group, Vb group. Group hydrogen or at least one selected from the group consisting of molybdenum compounds consisting of Group VIb elements excluding oxygen is reacted with hydrogen peroxide, and chain 1,2-diols are reacted with hydrogen peroxide, A catalyst for producing a carbonyl compound.