JP4374838B2 - Process for producing lactones, esters or carboxylic acids and catalyst thereof - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a process for producing lactones, esters or carboxylic acids and a catalyst thereof.
[0002]
[Prior art]
Lactones, esters, or carboxylic acids are important compounds as pharmaceuticals, fragrances, dyes, organic synthetic intermediates, resin raw materials, and the like (for example, JP-A-2000-256342). A method of reacting organic peracids such as peracetic acid and perbenzoic acid (so-called Bayer-Villiger reaction) is known, but organic peracids are relatively expensive, and post-treatment after the reaction is troublesome. There was a problem.
[0003]
On the other hand, a method for producing lactones, esters or carboxylic acids from ketones using hydrogen peroxide, which is inexpensive and harmless water after the reaction as an oxidizing agent, has also been reported. For example, (1) a method using a molybdenum complex catalyst (J. Chem. Soc. Chem. Commun., 888 (1978)), (2) a method using a methyl rhenium trioxide catalyst (Euro. J. Org. Chem., 1767 (1999)) has been reported, but the method (1) is difficult to obtain industrially, and it is necessary to use a high-concentration hydrogen peroxide solution of 90% by weight, which is problematic in terms of safety. In addition, in the method (2), the catalyst is expensive, and none of them is sufficiently satisfactory from an industrial viewpoint.
[0004]
[Problems to be solved by the invention]
Under these circumstances, the present inventors have earnestly studied a method for industrially advantageously producing lactones, esters or carboxylic acids by reacting ketones with hydrogen peroxide. The tungsten oxide aqueous solution obtained by reacting an inexpensive tungsten metal, tungsten boride, a tungsten compound such as tungstic acid or tungsten oxide, and hydrogen peroxide water in the reaction between ketones and hydrogen peroxide. The inventors have found that the catalyst has good catalytic activity, and have reached the present invention.
[0005]
[Means for Solving the Problems]
That is, the present invention is selected from the group consisting of tungsten metal, a tungsten compound composed of tungsten and a group IIIb element, a tungsten compound composed of tungsten and a group IVb element, and a tungsten compound composed of tungsten and a group VIb element. at least one tungsten compound with an aqueous hydrogen peroxide in the presence of the tungsten oxide solution comprising by reacting lactones which comprises reacting a ketone and hydrogen peroxide, the production of esters or carboxylic acids A method and an aqueous catalyst solution are provided.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
First, the catalyst of the present invention will be described. As the catalyst, the tungsten oxide solution comprising by reacting and hydrogen peroxide solution tungsten compound.
[0007]
Examples of the tungsten compound include at least one selected from the group consisting of tungsten metal, a tungsten compound composed of tungsten and a Group IIIb element, a tungsten compound composed of a Group IVb element, and a tungsten compound composed of a Group VIb element. Can be mentioned.
[0008]
Tungsten and as the tungsten compound consisting of a Group IIIb element, for example, tungsten boride and the like, tungsten and a tungsten compound comprising a group IVb element, such as tungsten carbide, tungsten silicide or the like, data tungsten and the VIb Examples of the tungsten compound composed of a group element include tungsten oxide, tungstic acid, tungsten sulfide, and the like.
[0009]
Among such tungsten compounds, tungsten metal, tungsten boride, tungsten carbide, tungsten oxide, tungstic acid, and tungsten sulfide are preferable. Such tungsten compounds may be used alone or in combination of two or more. In addition, it is preferable to use a tungsten compound having a small particle diameter in terms of facilitating preparation of a tungsten oxide as a catalyst.
[0010]
While such hydrogen peroxide concentration of tungsten compound and reacted peroxide Motosuichu is not particularly limited, considering the volume efficiency, safety, etc., is practically 1 to 60% by weight. As the hydrogen peroxide solution, a commercially available one may be used as it is or after adjusting the concentration by dilution, concentration or the like, if necessary .
[0011]
The amount of hydrogen peroxide to be reacted with the tungsten compound is usually 3 mol times or more, preferably 5 mol times or more with respect to the tungsten compound, and there is no particular upper limit.
[0012]
The reaction between the tungsten compound and hydrogen peroxide is usually carried out in an aqueous solution. Of course, for example, an ether solvent such as diethyl ether and methyl tert-butyl ether, a tertiary alcohol solvent such as tert-butanol, an organic solvent such as a nitrile solvent such as acetonitrile and propionitrile, or the organic solvent and water. You may implement in the mixed solvent.
[0013]
The reaction between the tungsten compound and hydrogen peroxide is usually carried out by mixing and contacting the two, and the tungsten compound is sufficiently dispersed in the tungsten oxide preparation solution to improve the contact efficiency between the tungsten compound and hydrogen peroxide. It is preferable to carry out the reaction while stirring. In addition, for example, a tungsten compound having a small particle diameter such as a powdery tungsten compound is preferably used in order to increase the contact efficiency between the tungsten compound and hydrogen peroxide and to facilitate control during preparation of the tungsten oxide.
[0014]
The preparation temperature at the time of preparation of tungsten oxide is usually −10 to 100 ° C.
[0015]
By reacting the tungsten compound and hydrogen peroxide in water or an organic solvent, all or part of the tungsten compound is dissolved, and a homogeneous solution or suspension containing tungsten oxide can be prepared. The tungsten 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 it is as a catalyst.
[0016]
Next, the reaction between ketones and hydrogen peroxide using the tungsten oxide as a catalyst will be described.
[0017]
As the ketones, as long as carbon substituents such as an optionally substituted alkyl group, an optionally substituted aryl group, and an optionally substituted aralkyl group are bonded to both ends of the carbonyl group, There is no particular limitation. The carbon substituents bonded to both ends of the carbonyl group may be the same or different, and the carbon substituents may be bonded to form a part of the ring structure.
[0018]
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 such as a hexyl group, an n-octyl group, an isooctyl group, an n-nonyl group, an n-decyl group, a cyclopentyl group or a cyclohexyl group, and such an alkyl group One or more hydrogen atoms are, for example, alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group and n-butoxy group, for example, halogen atoms such as fluorine atom, chlorine atom and bromine atom, etc. For example, chloromethyl group, fluoromethyl group, trifluoromethyl group, methoxymethyl group, methoxyethyl group And the like.
[0019]
Examples of the optionally substituted aryl group include a phenyl group, a naphthyl group, and the like, and a hydrogen atom of an aromatic ring constituting the phenyl group, naphthyl group, and the like, for example, the alkyl group, for example, the alkoxy group, for example, the halogen atom. Substituted with a substituent such as an acyl group such as an acetyl group or a propionyl group, for example, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2-chlorophenyl group, a 3-chlorophenyl group, 4- Examples include chlorophenyl group, 2-bromophenyl group, 2-methylphenyl group, 4-methylphenyl group, 4-methoxyphenyl group and the like.
[0020]
Examples of the aralkyl group which may be substituted include those composed of the alkyl group and the aryl group, such as benzyl group, phenylethyl group, 4-fluorobenzyl group, 4-methoxybenzyl group, 2- A chlorobenzyl group etc. are mentioned.
[0021]
In addition, when the carbon substituents together form a part of the ring structure, examples of the ring structure include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, Examples include a cyclodecane ring, a cyclododecane ring, a benzene ring, and the like, and the ring may be substituted with the alkyl group, the alkoxy group, the halogen atom, or the like.
[0022]
Examples of such ketones include acetone, methyl ethyl ketone, 2-pentanone, methyl isopropyl ketone, 2-hexanone, methyl isobutyl ketone, methyl sec-butyl ketone, methyl tert-butyl ketone, 2-octanone, diethyl ketone, ethyl isopropyl ketone, methyl cyclohexyl. Ketone, methyl phenyl ketone, methyl (p-tolyl) ketone, methyl (2-pyridyl) ketone, cyclohexyl phenyl ketone, dicyclohexyl ketone, cyclopropanone, cyclobutanone, 3-methylcyclobutanone, 3-phenylcyclobutanone, cyclopentanone, 2 -Methylcyclopentanone, 2-phenylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2-phenylcyclohexanone, 4-methyl Le cyclohexanone, 4-phenylcyclohexanone, 4-chlorocyclohexanone, cycloheptanone, cyclooctanone, cyclodecanone, cyclododecanone, 1,4-cyclohexanedione, chain or cyclic ketones such as adamantanone and the like.
[0023]
In this reaction, a ketone and hydrogen peroxide are reacted in the presence of the above-described tungsten oxide catalyst to produce a corresponding lactone, ester or carboxylic acid. When water is used as a reaction solvent, carboxylic acids are easily obtained. When chain ketones are used, esters or carboxylic acids are obtained, and when cyclic ketones are used, lactones or carboxylic acids are obtained.
[0024]
The usage-amount of a tungsten oxide catalyst is 0.001-0.95 mol times normally with respect to ketones as a metal, Preferably it is 0.005-0.1 mol times.
[0025]
As hydrogen peroxide, an aqueous solution is usually used. Of course, an organic solvent solution of hydrogen peroxide may be used. 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. As the hydrogen peroxide solution, a commercially available one may be used as it is or after adjusting the concentration by dilution, concentration or the like, if necessary. As the organic solvent solution of hydrogen peroxide, for example, a solution prepared by a means such as extraction treatment of aqueous hydrogen peroxide with an organic solvent or distillation treatment in the presence of an organic solvent may be used.
[0026]
The amount of hydrogen peroxide used is usually 0.8 mol times or more, preferably 1 mol times or more, relative to ketones. The upper limit is not particularly limited, but if it is too much, it tends to be economically disadvantageous, so it is practically 10 mole times or less. In addition, when using the preparation liquid containing tungsten oxide as a catalyst, you may set the usage-amount of hydrogen peroxide in consideration of the quantity of hydrogen peroxide contained in this preparation liquid.
[0027]
The reaction between the ketones and hydrogen peroxide may be performed without a solvent, or may be performed in an aqueous solvent, an organic solvent, or a mixed solvent of water and an organic solvent. Examples of the organic solvent include ether solvents such as diethyl ether, methyl tert-butyl ether and diglyme, tertiary alcohol solvents such as tert-butanol, and nitrile solvents such as acetonitrile and propionitrile.
[0028]
This reaction is generally tungsten oxide solution, ketones and contacting hydrogen peroxide, Ru done by mixing.
[0029]
The reaction temperature is usually 50 to 130 ° C. and is usually carried out under normal pressure conditions, but may be carried out under reduced pressure or pressurized conditions.
[0030]
As the reaction proceeds, lactones, esters, or carboxylic acids are produced. The progress of the reaction can be confirmed by ordinary analytical means such as gas chromatography, high performance liquid chromatography, thin layer chromatography, NMR, IR, and the like. it can.
[0031]
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, etc. Or carboxylic acids can be removed. In addition, lactones, esters or carboxylic acids may be taken out by adding water and / or an organic solvent insoluble in water to the reaction solution as necessary, subjecting to extraction, and concentrating the resulting organic layer. it can. The extracted lactones, esters, or carboxylic acids may be further purified by a conventional purification method such as distillation, column chromatography, recrystallization, and the like.
[0032]
The filtrate and reaction liquid after the lactones, esters or carboxylic acids are removed by crystallization treatment are extracted, and the aqueous layer after the organic layer is taken out contains the tungsten oxide catalyst of this reaction. Alternatively, it can be reused in the reaction again after concentration treatment or the like as necessary.
[0033]
Examples of lactones thus obtained include β-propiolactone, γ-butyrolactone, β-methyl-γ-butyrolactone, β-phenyl-γ-butyrolactone, δ-valerolactone, ε-valerolactone, and α-phenyl-δ. -Valerolactone, δ-phenyl-δ-valerolactone, ε-caprolactone, α-methyl-ε-caprolactone, ε-methyl-ε-caprolactone, α-phenyl-ε-caprolactone, ε-phenyl-ε-caprolactone, etc. Can be mentioned. Examples of the esters include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, hexyl acetate, ethyl propionate, isopropyl propionate, cyclohexyl acetate, and phenyl acetate. , Acetic acid (4-methyl) phenyl, acetic acid (2-pyridyl), phenyl cyclohexanecarboxylate, cyclohexyl benzoate, cyclohexyl cyclohexanecarboxylate and the like. Examples of carboxylic acids include glutaric acid, 5-oxohexanoic acid, 1-phenyl-1-oxopentanoic acid, adipic acid, 6-oxoheptanoic acid, 3-methyladipic acid, heptane-1,7-dicarboxylic acid, and suberin. An acid etc. are mentioned.
[0034]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples at all.
[0035]
Example 1
A 100 mL Schlenk tube equipped with a reflux condenser was purged with nitrogen, and at room temperature, 0.044 g of tungsten metal and 4.8 g of 30 wt% hydrogen peroxide solution were charged and stirred at an internal temperature of 50 ° C. for 15 minutes. An aqueous solution was prepared. To the aqueous solution, 0.56 g of cyclobutanone was added dropwise over 15 minutes at an internal temperature of 10 ° C., and the mixture was stirred and held at the same temperature for 2 hours to be reacted. When 50 mL of ethanol was added to the resulting reaction liquid and sufficiently shaken, and analyzed by gas chromatography, γ-butyrolactone was produced in a yield of 92% (based on cyclobutanone).
[0036]
Example 2
A 100 mL Schlenk tube equipped with a reflux condenser was purged with nitrogen, and at room temperature, 0.15 g of tungsten metal and 5.8 g of 30% by weight hydrogen peroxide were charged and stirred at an internal temperature of 50 ° C. for 15 minutes. An aqueous solution was prepared. To this aqueous solution was charged 3.9 g of 2-methylcyclopentanone, and the mixture was stirred and held at an internal temperature of 60 ° C. for 6 hours to be reacted. The obtained reaction liquid was cooled, added with 50 mL of ethanol, shaken sufficiently, and analyzed by gas chromatography. As a result, δ-caprolactone and 5-oxohexanoic acid were produced. The yield of δ-caprolactone was 18%, and the yield of 5-oxohexanoic acid was 33% (all based on 2-methylcyclopentanone).
[0037]
Example 3
A 100 mL Schlenk tube equipped with a reflux condenser was purged with nitrogen, and at room temperature, 0.15 g of tungsten metal and 5.8 g of 30% by weight hydrogen peroxide were charged and stirred at an internal temperature of 50 ° C. for 15 minutes. An aqueous solution was prepared. To this aqueous solution, 4.5 g of 2-methylcyclohexanone was charged, and the mixture was stirred and held at an internal temperature of 60 ° C. for 6 hours to be reacted. The obtained reaction liquid was cooled, added with 50 mL of ethanol, sufficiently shaken, and analyzed by gas chromatography. As a result, methyl-ε-caprolactone and 6-oxoheptanoic acid were produced. The yield of methyl-ε-caprolactone was 3%, and the yield of 6-oxoheptanoic acid was 68% (all based on 2-methylcyclohexanone).
[0038]
Example 4
A 100 mL Schlenk tube equipped with a reflux condenser was purged with nitrogen, and at room temperature, 0.15 g of tungsten metal and 11.5 g of 30 wt% hydrogen peroxide solution were added and stirred at an internal temperature of 50 ° C. for 15 minutes. An aqueous solution was prepared. The aqueous solution was charged with 3.4 g of cyclopentanone, and stirred and held at an internal temperature of 60 ° C. for 6 hours for reaction. The obtained reaction solution was cooled, added with 50 mL of ethanol, shaken sufficiently, and analyzed by gas chromatography. As a result, δ-valerolactone was produced in a yield of 28% (based on cyclopentanone).
[0039]
Example 5
A 100 mL Schlenk tube equipped with a reflux condenser was purged with nitrogen, and at room temperature, 0.037 g of tungsten metal and 2.7 g of 30% by weight hydrogen peroxide were charged and stirred at an internal temperature of 50 ° C. for 15 minutes. An aqueous solution was prepared. The aqueous solution was charged with 2 g of cyclohexanone and stirred and held at an internal temperature of 70 ° C. for 6 hours for reaction. The obtained reaction solution was cooled, added with 50 mL of ethanol, shaken sufficiently, and analyzed by gas chromatography. As a result, ε-caprolactone was produced in a yield of 12% (based on cyclohexanone).
[0040]
Example 6
In Example 4, it replaced with tungsten metal and implemented similarly to Example 4 except having used tungsten boride (the usage-amount is tungsten metal equimolar), and (delta) -valerolactone was 27% of yield. Obtained (based on cyclopentanone).
[0041]
Example 7
In Example 4, in place of tungsten metal, tungsten carbide (amount used is equimolar with tungsten metal) was used except that tungsten carbide was used, and δ-valerolactone was obtained in a yield of 32%. (Based on cyclopentanone).
[0042]
Example 8
In Example 4, in place of tungsten metal, tungsten sulfide (amount used is equimolar with tungsten metal) was used in the same manner as in Example 4 to obtain δ-valerolactone in a yield of 37%. (Based on cyclopentanone).
[0045]
Example 11
In Example 3, it replaced with tungsten metal, and implemented similarly to Example 3 except having used tungsten boride (the usage-amount is an equimolar amount with a tungsten metal), 6-oxo heptanoic acid was obtained with a yield of 66%. (Based on 2-methylcyclohexanone).
[0046]
Example 12
In Example 3, instead of tungsten metal, tungsten carbide (the amount used is equimolar to tungsten metal) was used except that tungsten carbide was used, and 6-oxoheptanoic acid was obtained in a yield of 56%. Obtained (based on 2-methylcyclohexanone).
[0047]
Example 13
In Example 3, in place of tungsten metal, tungsten sulfide (amount used is equimolar with tungsten metal) was used in the same manner as in Example 3 to obtain 6-oxoheptanoic acid at a yield of 45%. Obtained (based on 2-methylcyclohexanone).
[0050]
【The invention's effect】
According to the present invention, ketones and hydrogen peroxide are reacted in the presence of a tungsten oxide catalyst that can be easily prepared from tungsten compounds such as tungsten metal and tungsten boride and hydrogen peroxide, which are easily available. Can obtain lactones, esters or carboxylic acids, which is industrially advantageous.

Claims (6)

Tungsten compound consisting of tungsten metal, tungsten and the Group IIIb element, at least one tungsten compound selected from tungsten and the group consisting of tungsten compound consisting of tungsten compound and tungsten comprising a Group IVb elemental and the VIb group element A method for producing lactones, esters or carboxylic acids, comprising reacting ketones with hydrogen peroxide in the presence of an aqueous tungsten oxide solution obtained by reacting water with hydrogen peroxide in advance. Tungsten compound consisting of tungsten metal, tungsten and the Group IIIb element, at least one tungsten compound selected from tungsten and the group consisting of tungsten compound consisting of tungsten compound and tungsten comprising a Group IVb elemental and the VIb group element A lactone, ester or carboxylic acid characterized in that a tungsten oxide aqueous solution is prepared by reacting with a hydrogen peroxide solution, and then a ketone and hydrogen peroxide are reacted in the presence of the aqueous solution. Manufacturing method. The method for producing lactones, esters or carboxylic acids according to claim 1 or 2, wherein the Group IIIb element is boron. The method for producing lactones, esters or carboxylic acids according to claim 1 or 2, wherein the Group IVb element is carbon. The method for producing lactones, esters or carboxylic acids according to claim 1 or 2, wherein the Group VIb element is oxygen or sulfur. Tungsten compound consisting of tungsten metal, tungsten and the Group IIIb element, at least one tungsten compound selected from tungsten and the group consisting of tungsten compound consisting of tungsten compound and tungsten comprising a Group IVb elemental and the VIb group element A tungsten oxide aqueous solution for producing lactones, esters or carboxylic acids by reacting ketones with hydrogen peroxide, which is obtained by reacting hydrogen peroxide with water.