JP4000816B2 - Method for producing 3-methyladipic acid - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing 3-methyladipic acid.
[0002]
[Prior art]
3-methyl adipic acid is useful as a raw material for synthetic materials such as pharmaceuticals, agricultural chemicals, and physiologically active substances, and liquid crystal polymers. As a method for producing such 3-methyladipic acid, for example, (1) a method of reacting pulegone with potassium permanganate (J. Chem. Edu., 70, 951 (1993)), (2) in the presence of a ruthenium catalyst. A reaction of pulegone and sodium periodate (J. Org. Chem., 52, 689 (1987)), (3) plegon and oxone (registered trademark of DuPont) in the presence of a ruthenium catalyst; (J. Org. Chem., 66, 4814 (2001)) and the like are known.
The method (1) uses potassium permanganate at a stoichiometric amount or more with respect to plegon, and the metal waste after the reaction must be treated, so there is a problem in terms of economy and environment. In addition, the methods (2) and (3) use an expensive catalyst and an oxidizing agent, and are disadvantageous economically.
[0003]
On the other hand, hydrogen peroxide is attracting attention as a clean and excellent oxidant that is inexpensive, easy to handle and harmless after the reaction. Thus, no method for producing 3-methyladipic acid has been reported so far.
[0004]
[Problems to be solved by the invention]
Under such circumstances, the present inventors diligently studied a method for producing 3-methyladipic acid by reacting pulegone and hydrogen peroxide. As a result, tungsten metal, molybdenum metal, tungsten compound, and molybdenum were obtained. A metal oxide obtained by reacting hydrogen peroxide with at least one metal compound selected from the group consisting of compounds exhibits good oxidation catalytic activity in the reaction between pulegone and hydrogen peroxide. It has been found that adipic acid can be obtained and has led to the present invention.
[0005]
[Means for Solving the Problems]
That is, the present invention provides pulegone and peroxidation in the presence of a metal oxide catalyst obtained by reacting at least one metal compound selected from the group consisting of tungsten metal, molybdenum metal, tungsten compound and molybdenum compound with hydrogen peroxide. The present invention provides a method for producing 3-methyladipic acid characterized by reacting with hydrogen.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, plegon may be an optically active substance alone or a mixture of optically active substances.
[0007]
Examples of the tungsten compound include a tungsten compound composed of a Group IIIb element such as tungsten boride and tungsten, for example, a tungsten compound composed of a Group IVb element such as tungsten carbide and tungsten silicide, and tungsten, such as tungsten nitride, phosphorus Tungsten compounds composed of Group Vb elements such as tungsten fluoride and tungsten, for example, tungsten compounds composed of Group VIB elements such as tungsten sulfide, tungsten oxide, tungstic acid and tungsten, such as sodium tungstate, potassium tungstate, tungstic acid Examples thereof include tungstates such as magnesium.
[0008]
As the molybdenum compound, for example, a molybdenum compound composed of a Group IIIb element such as molybdenum boride and molybdenum, for example, a molybdenum compound composed of a Group IVb element such as molybdenum carbide and molybdenum silicide, and molybdenum, such as molybdenum nitride, phosphorus Tungsten compounds composed of Group Vb elements such as molybdenum fluoride and molybdenum, for example, molybdenum compounds composed of Group VIb elements such as molybdenum sulfide, molybdenum oxide, and molybdic acid, and molybdenum, such as molybdenum such as sodium molybdate and potassium molybdate. Examples include acid salts.
[0009]
These tungsten metal, molybdenum metal, tungsten compound and molybdenum compound may be used alone or in combination of two or more.
[0010]
By reacting such a metal compound with hydrogen peroxide, pulegone is oxidized to prepare a metal oxide that serves as a catalyst for producing 3-methyladipic acid. The reaction between the metal compound and hydrogen peroxide is usually carried out in an aqueous solvent. Of course, ether solvents such as diethyl ether, methyl tert-butyl ether and tetrahydrofuran, ester solvents such as ethyl acetate, tertiary alcohol solvents such as tert-butanol, nitrile solvents such as acetonitrile and propionitrile, etc. It may be carried out in an organic solvent such as, or in a mixed solvent of the organic solvent and water.
[0011]
Hydrogen peroxide is usually used as an aqueous solution, but an organic solvent solution may be used. In view of easier handling, it is preferable to use hydrogen peroxide. 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.
[0012]
The amount of hydrogen peroxide used in preparing the metal oxide is usually 3 mol times or more, preferably 5 mol times or more with respect to the metal compound, and the upper limit thereof is not particularly limited. Considering it, it is 50 mol times or less practically.
[0013]
The reaction between the metal compound and hydrogen peroxide is usually performed by mixing and contacting the two, and in order to improve the contact efficiency between the metal compound and hydrogen peroxide, the metal compound is added in the metal oxide preparation solution. It is preferable to carry out stirring with sufficient dispersion. In addition, it is possible to use a metal compound having a small particle diameter, such as a powdered metal oxide, in order to further increase the contact efficiency between the metal compound and hydrogen peroxide and to facilitate control during preparation of the metal oxide. preferable. The preparation temperature of the metal oxide is usually −10 to 100 ° C.
[0014]
By reacting the metal compound and hydrogen peroxide in water or an organic solvent, all or part of the metal compound is dissolved, and a uniform solution or suspension containing the metal oxide can be prepared. The obtained preparation liquid may be concentrated, for example, to extract the metal oxide and used as a catalyst, or the preparation liquid may be used as a catalyst as it is.
[0015]
By reacting pulegone and hydrogen peroxide in the presence of the metal oxide catalyst thus obtained, 3-methyladipic acid can be obtained, and hydrogen peroxide 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 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 solution may be used as it is or after adjustment of the concentration by dilution, concentration or the like, if necessary. What is necessary is just to use what was prepared by means, such as extracting with a solvent or carrying out distillation in presence of an organic solvent.
[0016]
The amount of hydrogen peroxide used is usually 2 mol times or more with respect to plegon, and there is no particular upper limit, but it is economically disadvantageous if it is too much, so it is practically 10 mol times or less. .
[0017]
The usage-amount of a metal oxide is 0.001-0.95 mol times normally with respect to a plegon.
[0018]
For example, when water is present in a reaction system such as hydrogen peroxide that reacts in an aqueous solvent, a quaternary ammonium salt may coexist in the reaction system. Examples of the quaternary ammonium salt include sulfuric acid. Hydrogen quaternary ammonium salts such as tetra (n-butyl) ammonium hydrogen, tetra (n-hexyl) ammonium hydrogen sulfate, methyl tricetylammonium hydrogen sulfate, and quaternary ammonium salts such as benzyltriethylammonium chloride Can be mentioned. The amount used in the case of using such a quaternary ammonium salt is usually 0.001 to 1 mole times that of Pregon. Further, such a quaternary ammonium salt may be added in advance when preparing a metal oxide as a catalyst.
[0019]
In the case of using tungsten oxide obtained by reacting tungstate and hydrogen peroxide and / or molybdenum oxide obtained by reacting molybdate and hydrogen peroxide as the catalyst, for example, hydrochloric acid, sulfuric acid, phosphoric acid. It is preferable to carry out the reaction by adding an acid such as boric acid to the reaction system. When the acid is added to the reaction system, the amount used is usually 1 mol times or more with respect to the tungsten oxide and / or molybdenum oxide. Such an acid may be added in advance when preparing a metal oxide as a catalyst.
[0020]
When the reaction is carried out in a two-layer system of water and an organic solvent, a dehydrating agent may coexist in the reaction system, and examples of the dehydrating agent include anhydrous magnesium sulfate and anhydrous sodium sulfate. The amount used in the case of using a dehydrating agent is not particularly limited, but a sufficient amount of dehydrating agent is usually used to remove water present in the reaction system.
[0021]
The reaction between plegon and hydrogen peroxide may be carried out without a solvent, or in water or an organic solvent. Examples of the organic solvent include halogenated hydrocarbon solvents such as carbon tetrachloride, chloroform, dichloroethane, chlorobenzene, and dichlorobenzene, aromatic hydrocarbon solvents such as toluene, xylene, and nitrobenzene, such as diethyl ether and methyl tert-butyl ether. And ether solvents such as tetrahydrofuran, ester solvents such as ethyl acetate, alcohol solvents such as methanol, ethanol and tert-butanol, and nitrile solvents such as acetonitrile and propionitrile.
[0022]
The amount of water or organic solvent to be used is not particularly limited, but considering volume efficiency and the like, it is practically 100 weight times or less with respect to plegon.
[0023]
This reaction is usually performed by mixing and contacting a metal oxide catalyst, plegon and hydrogen peroxide. For example, a metal oxide catalyst, hydrogen peroxide and plegon are mixed and contacted to prepare a metal oxide catalyst. In addition, the reaction between plegon and hydrogen peroxide may be performed simultaneously.
[0024]
The reaction temperature is usually 50 to 130 ° C. In addition, this reaction is usually performed under normal pressure conditions, but may be performed under reduced pressure or pressurized conditions.
[0025]
As the reaction proceeds, 3-methyladipic acid is 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.
[0026]
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 3-methyladipic acid. be able to. Moreover, 3-methyladipic acid can also be taken out by adding water and / or the organic solvent insoluble in water to a reaction liquid as needed, performing an extraction process, and concentrating the obtained organic layer. The taken-out 3-methyladipic acid may be further purified by an ordinary purification method such as distillation, recrystallization, column chromatography and the like.
[0027]
The filtrate and reaction solution after extraction of 3-methyladipic acid by crystallization treatment is extracted, and the aqueous layer after removal of the organic layer contains a metal oxide catalyst and is concentrated as it is or as necessary. After the treatment, etc., it can be reused in this reaction.
[0028]
When optically active pulegone is used, optically active 3-methyladipic acid is obtained.
[0029]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
[0030]
Example 1
A 50 mL Schlenk tube equipped with a reflux condenser was replaced with nitrogen, and at room temperature, 23 mg of tungsten metal and 2.4 g of 30 wt% hydrogen peroxide solution were charged and stirred at an internal temperature of 60 ° C. for 1 hour to prepare a catalyst solution. The catalyst solution was charged with 1.9 g of plegon and 4.7 g of 30% by weight hydrogen peroxide solution and stirred and held at an internal temperature of 100 ° C. for 5 hours. The obtained reaction solution was cooled, added with 50 mL of ethanol, shaken sufficiently, and then analyzed by high performance liquid chromatography. Production amount of 3-methyladipic acid: 1.38 g, yield 69% (based on pulegone).
[0031]
【The invention's effect】
According to the present invention, a metal oxide obtained by reacting hydrogen peroxide with at least one metal compound selected from the group consisting of tungsten metal, molybdenum metal, tungsten compound and molybdenum compound, which is easily available, is used as a catalyst. Thus, 3-methyladipic acid can be obtained from the reaction of pulegone and hydrogen peroxide, which is industrially advantageous.

Claims (1)

Pregon and hydrogen peroxide are reacted in the presence of a metal oxide catalyst obtained by reacting at least one metal compound selected from the group consisting of tungsten metal, molybdenum metal, tungsten compound and molybdenum compound with hydrogen peroxide. A process for producing 3-methyladipic acid,