JP2003292465A - Method for producing carbonyl compound and catalyst for the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a carbonyl compound easily by performing a reaction of a chain state vicinal diol (except for a chain state 1,2-diol) with hydrogen peroxide. <P>SOLUTION: This method for producing the carbonyl compound is characterized by performing a reaction of the chain state vicinal diol (except for 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]

Carbonyl compounds such as diketones obtained by oxidizing linear vicinal diols are important compounds as various chemical products and synthetic intermediates thereof (eg, Tetrahedron. Lett., 3).
6, 1523 (1995)), as a manufacturing method thereof,
For example, a method of reacting linear vicinal diols with tert-butyl hydroperoxide in the presence of a molybdenum oxide acetylacetonate complex catalyst (Chem. L.
ett. , 1295 (1988)) is known,
Since tert-butyl hydroperoxide requires careful handling, it was not always an industrially satisfactory method.

On the other hand, hydrogen peroxide has recently been attracting attention as a clean and excellent oxidizing agent that is inexpensive, easy to handle, and becomes harmless water after the reaction. A method of reacting hydrogen peroxide to produce a carbonyl compound is also known. For example, (a) a method using a tris (cetylpyridinium) tungstophosphoric acid catalyst (J. Org. Chem., 53 , 3587).
(1988)), (b) tris (cetylpyridinium)
Method of reacting chain vicinal diol with an oxidizing agent prepared from tungstophosphoric acid catalyst and hydrogen peroxide in 1,2-dichloroethane (Tetrahedron. Let
t. , 36, 1523 (1995)) and the like are known, but in any of the methods, the preparation of the catalyst is complicated, and the method (b) has problems in terms of environment and occupational safety and health. There was a problem that the reaction had to be carried out using dichloroethane as a solvent.

[0004]

Under these circumstances, the present inventors have found that chain vicinal diols (provided that
Excludes linear 1,2-diols. ) And hydrogen peroxide to make it easier to produce a carbonyl compound. As a result, readily available tungsten metal, tungsten compound such as tungsten boride,
The inventors have found that a metal oxide obtained by reacting a molybdenum compound such as molybdenum metal or molybdenum boride with hydrogen peroxide exhibits a good oxidation catalytic activity, and thus reached the present invention.

[0005]

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 a linear vicinal diol (excluding a chain 1,2-diol) with hydrogen peroxide, and a catalyst therefor.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION First, a metal oxide catalyst used when reacting chain vicinal diols (excluding chain 1,2-diols) with hydrogen peroxide will be described. . As the catalyst, tungsten metal, molybdenum metal, tungsten and group IIIb, group IVb, group Vb
Tungsten compounds consisting of Group VIb elements other than oxygen or molybdenum and Group IIIb, Group IVb, or Group Vb
At least one selected from the group consisting of molybdenum compounds consisting of Group VIb elements other than oxygen or Group VIb elements (hereinafter,
It is abbreviated as a metal compound. ) And hydrogen peroxide are reacted with each other to use a metal oxide catalyst.

The tungsten compound composed of tungsten and a Group IIIb element is, for example, tungsten boride, and the tungsten compound composed of 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 tungsten phosphide, and examples of the tungsten compound including the tungsten and the group VIb element excluding oxygen include tungsten sulfide.

Examples of molybdenum compounds composed of molybdenum and Group IIIb elements include molybdenum boride and the like.
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 molybdenum phosphide. Examples of the molybdenum compound composed of a group VIb element excluding oxygen and oxygen 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 used to react 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 a tertiary alcohol solvent such as rt-butanol, in an organic solvent such as a nitrile solvent such as acetonitrile or propionitrile, or in 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, chain vicinal diols (excluding chain 1,2-diols; hereinafter abbreviated as chain vicinal diols) using the metal oxide as a catalyst and hydrogen peroxide. The reaction of is explained.

The chain vicinal diols used in the present invention are chain diols excluding the chain 1,2-diols, wherein a hydroxyl group is bonded to any two adjacent carbon atoms, There is no particular limitation as long as at least one of the carbon atoms is a secondary carbon atom.

Carbon atoms constituting the chain vicinal diols other than the carbon atom to which the hydroxyl group is bonded are substituted with a substituent such as an alkyl group, an aryl group, an aralkyl group, an alkoxy group, a silyl group or a halogen atom. May be.

The alkyl group includes, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group and the like having 1 to 1 carbon atoms.
4 lower alkyl group, and the aryl group includes
Examples thereof include a phenyl group and a naphthyl group. Examples of the aralkyl group include those composed of the alkyl group and the aryl group, and examples thereof include a benzyl group. Examples of the alkoxy group include those composed of the aforementioned alkyl group and oxygen atom, and include, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert-butoxy group and the like carbon. Examples include lower alkoxy groups of the numbers 1 to 4. Examples of the silyl group include a trimethylsilyl group, a methyldiphenylsilyl group, a dimethylphenylsilyl group, and the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom,
A bromine atom etc. are mentioned.

Examples of such chain vicinal diols include:
Examples thereof include 2,3-butanediol, 2,3-hexanediol, 3,4-hexanediol, 4,5-nonanediol and 2-methyl-2,3-heptanediol.

In this reaction, a linear vicinal diol is reacted with hydrogen peroxide in the presence of the metal oxide catalyst to form a carbonyl compound. As the chain vicinal diols, for example, when chain vicinal diols such as 2,3-butanediol in which two carbon atoms to which a hydroxyl group is bonded are both secondary carbon atoms, One obtains diketones in which one alcohol site is oxidized, and carboxylic acids in which the alcohol site is oxidized and the carbon-carbon bond between two carbon atoms having two hydroxyl groups is also cleaved. Further, as the chain vicinal diols, for example, of the two carbon atoms to which a hydroxyl group such as 2-methyl-2,3-heptanediol is bonded, one is a secondary carbon atom and the other is a tertiary carbon atom. When a chain vicinal diol that is an atom is used,
Ketones in which a secondary carbon atom site to which a hydroxyl group is bound are oxidized, and ketols are oxidized, and a carbon-carbon bond between two carbon atoms in which two hydroxyl groups are bound is also cut, and ketones Carboxylic acids are obtained.

Taking a specific compound as an example, a more detailed description will be made. When 2,3-butanediol is used, a mixture of 2,3-butanedione and acetic acid can be obtained.
When using -methyl-2,3-heptanediol, a mixture of 2-hydroxy-2-methylheptan-3-one, acetone and pentanoic acid is obtained.

The amount of the metal oxide catalyst used is
Usually 0.001 to the chain vicinal 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.

A carbonyl compound can be obtained by reacting a chain vicinal diol with hydrogen peroxide.
As described above, the carbonyl compound produced differs depending on the structure of the chain vicinal diol, and in the case of the chain vicinal diol in which the two carbon atoms to which the hydroxyl groups are bonded are both secondary carbon atoms, In the case of a chain vicinal diol in which a mixture of diketones and carboxylic acids is obtained, and one of two carbon atoms having a hydroxyl group bonded is a secondary carbon atom and the other is a tertiary carbon atom For example, a mixture of ketols, ketones and carboxylic acids can be obtained.

The production ratio of each component in the obtained mixture is
In the case of chain vicinal diols in which the two carbon atoms to which the hydroxyl groups are bonded are both secondary carbon atoms, which varies depending on the amount of hydrogen peroxide used, the amount of hydrogen peroxide used is 1. 6 times or more the molar amount of diols, 2.
When the amount is less than 5 mol times, diketones are easily obtained as a main product, and when the amount of hydrogen peroxide used is 2.5 mol times or more with respect to the chain vicinal diols, carboxylic acids are generated. Easily obtained as the main product. In the case of chain vicinal diols in which one of the two carbon atoms to which the hydroxyl group is bonded is a secondary carbon atom and the other is a tertiary carbon atom, the amount of hydrogen peroxide used is 0.8 mol times or more relative to the vicinal diols,
When the amount is less than 1.5 mol times, ketol is easily obtained as the main product, and the amount of hydrogen peroxide used is
When the molar amount of chain vicinal diol is 1.5 times or more, carboxylic acids and ketones are easily obtained as main products. Therefore, the amount of hydrogen peroxide used may be appropriately selected depending on the structure of the chain vicinal diols as the raw material and the target compound.

The reaction of chain vicinal diols with hydrogen peroxide is usually carried out in a water solvent. The reaction may be carried out in an organic solvent or a mixed solvent of water and an organic solvent, but from the economical viewpoint, the reaction is preferably carried out in a water solvent. Examples of the organic solvent include diethyl ether and methyl te.
Examples thereof include ether solvents such as rt-butyl ether, tetrahydrofuran, and diglyme, ester solvents such as ethyl acetate, tertiary alcohol solvents such as tert-butanol, and nitrile solvents such as acetonitrile and propionitrile. .

This reaction is usually carried out by bringing a metal oxide catalyst, a chain vicinal diol and hydrogen peroxide into contact with each other and mixing them. For example, a metal compound, hydrogen peroxide and a chain vicinal diol are brought into contact with each other. Alternatively, the operation of preparing the metal oxide catalyst and the reaction of the chain vicinal diols and hydrogen peroxide may be carried out in parallel at the same time.

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 the 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 concentrated or crystallized 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 this reaction,
As it is or after performing concentration treatment etc. as necessary,
It can be reused in this reaction again.

Examples of the carbonyl compound thus obtained include carboxylic acids such as acetic acid, propionic acid, butyric acid, pentanoic acid and heptanoic acid, such as 2,3-butanedione, 2,3-hexanedione and 3,4-hexanedione. Diketones such as 4,5-nonanedione, for example 2-
Examples thereof include ketols such as hydroxy-2-methylheptan-3-one.

[0034]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The analysis 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 catalyst solution. 2, in the catalyst liquid
1.8 g of 3-butanediol and 4.7 g of 30 wt% hydrogen peroxide solution were 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 dimethyl sulfoxide was added, and the mixture was shaken sufficiently to obtain a solution containing 2,3-butanedione. The yield of 2,3-butanedione is
It was 65% (based on 2,3-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 catalyst solution. 2, in the catalyst liquid
1.8 g of 3-butanediol and 7.4 g of 30 wt% hydrogen peroxide solution were 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 dimethyl sulfoxide was added, and the mixture was shaken sufficiently to obtain a solution containing acetic acid. The yield of acetic acid was 100% (the yield was 100% when 2 mol of acetic acid was produced from 1 mol of 2,3-butanediol, based on 2,3-butanediol).

Example 3 The same procedure as in Example 1 was repeated except that molybdenum metal (the amount used was equimolar to tungsten metal) was used in place of tungsten metal, and 2,3-butanedione was added. , With a yield of 27% (based on 2,3-butanediol).

Example 4 The same procedure as in Example 1 was repeated except that molybdenum boride (the amount used was equimolar to tungsten metal) was used in place of the tungsten metal, and 2,3-butanedione was used. Was obtained in a yield of 30% (based on 2,3-butanediol).

Example 5 The procedure of Example 2 was repeated, except that tungsten boride (the amount used was equimolar to tungsten metal) was used in place of the tungsten metal, and acetic acid was obtained in a yield of 89% (based on 2,3-butanediol, the yield was 100% when 2 mol of acetic acid was produced from 1 mol of 2,3-butanediol).

Example 6 The procedure of Example 2 was repeated except that tungsten metal was used in place of the tungsten metal (the amount used was equimolar to the amount of tungsten metal), and acetic acid was produced in a yield of 9
2% (based on 2,3-butanediol, the yield was 100% when 2 mol of acetic acid was produced from 1 mol of 2,3-butanediol).

Example 7 The procedure of Example 2 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 acetic acid was produced in a yield of 9
2% (based on 2,3-butanediol, the yield was 100% when 2 mol of acetic acid was produced from 1 mol of 2,3-butanediol).

Example 8 The procedure of Example 2 was repeated except that molybdenum metal (the amount used was equimolar to tungsten metal) was used instead of tungsten metal, and acetic acid was produced in a yield of 64.
% (Based on 2,3-butanediol, the yield was 100% when 2 mol of acetic acid was produced from 1 mol of 2,3-butanediol).

Example 9 The procedure of Example 2 was repeated except that molybdenum boride (the amount used was equimolar to the amount of tungsten metal) was used instead of tungsten metal, and acetic acid was obtained in a yield of 5
The yield was 6% (based on 2,3-butanediol, the yield was 100% when 2 mol of acetic acid was produced from 1 mol of 2,3-butanediol).

Example 10 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 wt% 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, 2.4 g of 2-methyl-2,3-heptanediol 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 was 60% (2-methyl-2,
3-Heptanediol standard).

[0045]

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. A carbonyl compound is obtained by reacting a chain vicinal diol (excluding the chain 1,2-diol) with hydrogen peroxide, and the amount of hydrogen peroxide used is selected. As a result, diketones or ketols can be mainly obtained, or carboxylic acids and ketones can be obtained mainly, which is advantageous from an industrial viewpoint.

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI Theme Coat (Reference) C07C 49/12 C07C 49/12 51/285 51/285 53/08 53/08 // C07B 61/00 300 C07B 61/00 300 F term (reference) 4G069 AA02 AA08 BB01C BB04A BB04B BB09C BB11C BB13C BB15C BB18C BC59A BC59B BC59C BC60A BC60B BC60C ACBA32 BA46BA32 BA46BA32 BA34BA32BA34BA34BA32BA46ABA4ABA4A4A4A4A0 CA65 CC20 CC40 CD90 CE50

Claims (10)

[Claims] 1. A tungsten compound containing tungsten metal, molybdenum metal, tungsten and a group IIIb, IVb, Vb or a VIb group element except oxygen, and molybdenum and a group IIIb, IVb or Vb. In the presence of a metal oxide catalyst prepared by reacting at least one selected from the group consisting of molybdenum compounds consisting of group VIb elements other than oxygen with group VIb with hydrogen peroxide, chain vicinal diols (however, A method for producing a carbonyl compound, which comprises reacting hydrogen peroxide with chain-shaped 1,2-diols). 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 or phosphorus. 5. The method for producing a carbonyl compound according to claim 1, wherein the Group VIb element other than oxygen is sulfur. 6. A chain vicinal diol is a chain vicinal diol in which both of the two carbon atoms to which a hydroxyl group is bonded are secondary carbon atoms, and the amount of hydrogen peroxide used is The method for producing a carbonyl compound according to claim 1, wherein the amount is 1.6 mol times or more and less than 2.5 mol times with respect to the chain vicinal diols, and the carbonyl compound is a diketone. 7. The chain vicinal diol is a chain vicinal diol in which each of the two carbon atoms to which a hydroxyl group is bonded is a secondary carbon atom, and the amount of hydrogen peroxide used is The method for producing a carbonyl compound according to claim 1, wherein the amount is 2.5 times or more the amount of the chain vicinal diol, and the carbonyl compound is a carboxylic acid. 8. A chain vicinal diol is a chain vicinal diol in which one of two carbon atoms having a hydroxyl group bonded is a secondary carbon atom and the other is a tertiary carbon atom. The amount of hydrogen peroxide used is in the range of 0.8 mole times or more and less than 1.5 mole times the chain vicinal diols, and the carbonyl compound is a ketol. A method for producing the described carbonyl compound. 9. A chain vicinal diol is a chain vicinal diol in which, of two carbon atoms having a hydroxyl group bonded, one is a secondary carbon atom and the other is a tertiary carbon atom. The carbonyl compound according to claim 1, wherein the amount of hydrogen peroxide used is in a range of 1.5 times or more the amount of the chain vicinal diol, and the carbonyl compound is a ketone or a carboxylic acid. Manufacturing method. 10. A tungsten compound containing tungsten metal, molybdenum metal, tungsten and a group IIIb group, IVb group, Vb group or a VIb group element except oxygen, and molybdenum and a group IIIb group, IVb group, Vb group. Chain vicinal diols (provided that chain 1,2-diols are 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 A catalyst for producing a carbonyl compound by reacting hydrogen peroxide with hydrogen peroxide.