JP2003246783A - Method for manufacturing 3-(3'-oxobutyl)-4,4- dimethylbutyrolactone - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an efficient, environmentally friendly industrial method for manufacturing 3-(3'-oxobutyl)-4,4-dimethylbutyrolactone. <P>SOLUTION: This method for manufacturing 3-(3'-oxobutyl)-4,4- dimethylbutyrolactone comprises reacting α-terpineol with hydrogen peroxide in the presence of a metal oxide catalyst obtained by reacting at least one substance selected from the group consisting of a tungsten metal, a molybdenum metal, tungsten compounds and molybdenum compounds with hydrogen peroxide. <P>COPYRIGHT: (C)2003,JPO

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing 3- (3′-oxobutyl) -4,4-dimethylbutyrolactone. [0002] 3- (3'-oxobutyl) -4,4-
Dimethylbutyrolactone is an important compound as a synthetic intermediate of a pyrethroid compound useful as a household epidemic preventive and an insecticide (for example, see Non-Patent Document 1). Is known as a raw material. For example, a method of oxidizing α-terpineol with ozone followed by Jones oxidation (for example, see Non-Patent Document 2) and a method of oxidizing α-terpineol with potassium permanganate and then performing chromic acid oxidation (for example, Non-Patent Document 3) See, for example). However, any of these methods involves performing the oxidation reaction twice, which is not an efficient production method, and also requires heavy equipment such as ozone, potassium permanganate, and chromic anhydride, which require special equipment in consideration of disaster prevention. Since the compound is used in an amount exceeding the stoichiometric amount, the production method has environmental problems. [Non-Patent Document 1] Synthetic Communication, 12 , 995
(1982) [Non-Patent Document 2] Org. Chem. , 46 , 4279 (1981) [Non-Patent Document 3] Liebigs. Ann. Chem. , 275 , 150 (189
3) Under such circumstances, the present inventors have proposed 3- (3′-oxobutyl) -4,4.
-After diligent studies to develop an efficient and environmentally friendly industrial production method of dimethylbutyrolactone, hydrogen peroxide was reacted with at least one selected from the group consisting of tungsten metal, molybdenum metal, tungsten compound and molybdenum compound. By reacting α-terpineol with hydrogen peroxide in the presence of a metal oxide catalyst, 3- (3′-oxobutyl)-
The inventors have found that 4,4-dimethylbutyrolactone can be obtained, and have reached the present invention. [0005] That is, the present invention relates to a metal oxide catalyst obtained by reacting at least one selected from the group consisting of tungsten metal, molybdenum metal, a tungsten compound and a molybdenum compound with hydrogen peroxide. Reacting α-terpineol with hydrogen peroxide in the presence of 3- (3′-oxobutyl)-
It is intended to provide a method for producing 4,4-dimethylbutyrolactone. DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a catalyst for the reaction between α-terpineol and hydrogen peroxide will be described. As the catalyst, a metal oxide obtained by reacting at least one selected from the group consisting of a tungsten metal, a molybdenum metal, a tungsten compound and a molybdenum compound (hereinafter abbreviated as a metal compound) with hydrogen peroxide is used. Examples of the tungsten compound include tungsten oxides such as tungsten oxide and tungstic acid; alkali metal tungstates such as sodium tungstate and potassium tungstate; alkaline earth metal tungstates such as magnesium tungstate; For example, tungstophosphoric acid, heteropolyacid containing tungsten such as tungstosilicic acid as a constituent element, for example, tungsten boride, tungsten carbide,
Tungsten silicide, tungsten nitride, tungsten phosphide, tungsten sulfide, and the like can be given. Examples of the molybdenum compound include molybdenum oxides such as molybdenum oxide and molybdic acid, alkali metal molybdates such as sodium molybdate and potassium molybdate, alkaline earth metal molybdates such as magnesium molybdate, and the like. For example, heteropolyacids containing molybdenum such as molybdophosphoric acid and molybdenum silicic acid as constituent elements, for example, molybdenum boride, molybdenum carbide, molybdenum silicide, molybdenum nitride, molybdenum phosphide, molybdenum sulfide and the like can be mentioned. Such a tungsten compound and a molybdenum compound may be an anhydride or a hydrate. These metal compounds may be used alone or in combination of two or more. Further, it is preferable to use a metal compound having a small particle size in that the preparation of a metal oxide as a catalyst is facilitated. An aqueous solution is usually used as hydrogen peroxide when preparing a metal oxide. Of course, an organic solvent solution of hydrogen peroxide may be used, but it is preferable to use aqueous hydrogen peroxide because it is easier to handle. The concentration of hydrogen peroxide in the aqueous solution of hydrogen peroxide or in the organic solvent of hydrogen peroxide is not particularly limited, but is practically 1 to 60% by weight in consideration of volumetric efficiency, safety and the like. As the hydrogen peroxide solution, a commercially available one may be used as it is, or one whose concentration has been adjusted by dilution, concentration or the like as needed. The organic solvent solution of hydrogen peroxide may be prepared by, for example, extracting an aqueous hydrogen peroxide solution with an organic solvent, or performing a distillation treatment in the presence of an organic solvent. The amount of hydrogen peroxide used for preparing the metal oxide is usually at least 1 mole 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, for example, 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, and nitrile solvents such as acetonitrile and propionitrile. It may be carried out in an organic solvent 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 the two. In order to improve the contact efficiency between the metal compound and hydrogen peroxide, the metal compound is prepared in a metal oxide preparation solution. It is preferable to carry out the reaction while stirring so that the particles are sufficiently dispersed. In addition, it is preferable to use a metal compound having a small particle size, such as a powdery metal compound, from the viewpoint of increasing the contact efficiency between the metal compound and hydrogen peroxide and making the control during preparation of the metal oxide easier. The preparation temperature at the time of preparing the metal oxide is usually from -10 to 100C. By reacting the metal compound with hydrogen peroxide in water, an organic solvent or a mixed solvent of water and an organic solvent, all or a part of the metal compound is dissolved and a homogeneous solution containing a metal oxide or A suspension can be prepared. The metal oxide may be taken out of the prepared solution by, for example, a concentration treatment and used as a catalyst, or the prepared solution may be used as it is as a catalyst. Subsequently, in the presence of a metal oxide catalyst, α-
Reacting terpineol with hydrogen peroxide to form 3-
A method for producing (3′-oxobutyl) -4,4-dimethylbutyrolactone will be described. Α-Terpineol can be used either as a natural product or as a synthetic product. Further, α-terpineol has an asymmetric carbon in the molecule and has two kinds of optical isomers. In the present invention, any of these optical isomers can be used alone or as a mixture. The amount of the metal oxide used as a catalyst is usually 0.001 to 0.95 mole times based on α-terpineol. Hydrogen peroxide is usually used as an aqueous solution or an organic solvent solution from the viewpoint of safety. The concentration of hydrogen peroxide in the aqueous solution or organic solvent solution is not particularly limited,
Considering volumetric efficiency, safety, etc., practically 1-60
% By weight. The aqueous hydrogen peroxide is usually used as it is or after adjusting the concentration by dilution, concentration or the like as needed. The hydrogen peroxide / organic solvent solution can be prepared by, for example, extracting hydrogen peroxide solution with an organic solvent or distilling it in the presence of an organic solvent. The amount of hydrogen peroxide to be used is usually at least 1 mole times the amount of α-terpineol, and there is no particular upper limit. is there. When a metal oxide preparation liquid is used as a catalyst, the amount of hydrogen peroxide used may be set, including the amount of hydrogen peroxide in the preparation liquid. The reaction between α-terpineol and hydrogen peroxide is usually carried out in water, an organic solvent or a mixed solvent of water and an organic solvent. Examples of the organic solvent include carbon tetrachloride, chloroform, dichloroethane, chlorobenzene,
o-Dichlorobenzene, halogenated hydrocarbon solvents such as m-dichlorobenzene, for example, aromatic hydrocarbon solvents such as benzene, toluene, and nitrobenzene, for example, ether solvents such as diethyl ether, methyl tert-butyl ether, and tetrahydrofuran, for example, Ester solvents such as ethyl acetate, for example, methanol, ethanol, t
Alcohol solvents such as ert-butanol and the like, and single or mixed solvents such as nitrile solvents such as acetonitrile and propionitrile are exemplified. The mixing ratio of water and the organic solvent in the mixed solvent of water and the organic solvent is not particularly limited. The amount of the water solvent or the organic solvent is not particularly limited, but is practically 100 times by weight or less with respect to α-terpineol in consideration of volumetric efficiency and the like. When water is present in the reaction system, for example, when the reaction is carried out in an aqueous solvent or when using aqueous hydrogen peroxide, the reaction may be carried out in the presence of a quaternary ammonium salt. Preferably, as the quaternary ammonium salt,
Examples thereof include quaternary ammonium hydrogen sulfate such as tetra (n-butyl) ammonium hydrogen sulfate, tetra (n-hexyl) ammonium hydrogen sulfate, and methyltricetyl ammonium hydrogen sulfate. When a quaternary ammonium salt is used, the amount of the quaternary ammonium salt used is usually 0.001 to 1 mol per mol of α-terpineol. When the reaction is carried out in a mixed solvent of an organic solvent and water, the reaction may be carried out in the presence of a dehydrating agent. Examples of the dehydrating agent include magnesium sulfate and sodium sulfate. The amount of the dehydrating agent is not particularly limited, but an amount of a dehydrating agent sufficient to remove water in the reaction system is usually used. When an alkali metal tungstate, an alkali earth tungstate, an alkali metal molybdate or a metal oxide prepared using an alkali earth metal molybdate is used as a catalyst, for example, hydrochloric acid, It is preferable to add an acid such as sulfuric acid, phosphoric acid, boric acid and the like to carry out the reaction under acidic conditions in order to enhance the catalytic activity. In this reaction, α-terpineol, hydrogen peroxide, a metal oxide catalyst and, if necessary, a solvent may be mixed. The mixing order is not particularly limited, but the metal oxide catalyst and hydrogen peroxide are previously mixed. It is preferable to mix and add α-terpineol to the mixture from the viewpoint of the yield of the target compound. Further, for example, by contacting and mixing a metal compound, hydrogen peroxide, water, α-terpineol and a solvent as necessary, the preparation operation of the metal oxide catalyst and the reaction of α-terpineol with hydrogen peroxide are simultaneously performed. It may be performed in parallel.
The reaction temperature of this reaction is generally 0 to 200 ° C, preferably 0 to 200 ° C.
８０80 ° C. This reaction may be carried out in the presence of a boron compound. Examples of the boron compound include boric anhydride,
Metaboric acid, orthoboric acid, alkali metal metaborate, alkaline earth metal metaborate, alkali metal orthoborate, alkaline earth metal borate, and the like, the amount of which is not particularly limited, If it is too much, it is economically disadvantageous. Therefore, practically, it is usually 1 mol times or less with respect to α-terpineol. The progress of the reaction can be confirmed by ordinary analytical means such as gas chromatography, thin-layer chromatography, NMR and IR. After completion of the reaction, if necessary, insolubles are removed by filtration, and for example, the reaction mixture is concentrated to obtain the desired 3- (3'-oxobutyl) -4,4-dimethylbutyrolactone. Can be. Further, if necessary, water and / or an organic solvent insoluble in water are added to the reaction mixture, the mixture is extracted, and the obtained organic layer is concentrated to give 3- (3′-oxobutyl) -4,4.
Dimethylbutyrolactone can also be removed. The extracted 3- (3'-oxobutyl) -4,4-dimethylbutyrolactone may be further purified by a conventional purification means such as distillation and column chromatography. Examples of the organic solvent insoluble in water include aliphatic hydrocarbon solvents such as hexane and heptane, aromatic hydrocarbon solvents such as toluene and xylene, and halogenated carbon solvents such as dichloromethane, chloroform and chlorobenzene. Hydrogen solvents and the like can be mentioned, and the amount of use is not particularly limited. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples. Example 1 A 100 mL flask was charged with 20 mg of tungsten metal and 3 mg of tungsten metal.
After charging 200 mg of 0% by weight hydrogen peroxide solution,
The temperature was raised to 0 ° C., and the mixture was stirred and maintained at the same temperature for 0.5 hour. After cooling to an internal temperature of 30 ° C., 1.54 g of α-terpineol
Was charged, and 6 g of 30% by weight aqueous hydrogen peroxide was added dropwise over 30 minutes. Then, the internal temperature was raised to 80 ° C., and the mixture was stirred and maintained at the same temperature for 4 hours to be reacted. Cool to room temperature and add methyl te
20 g of rt-butyl ether and 20 g of a 10% by weight aqueous solution of sodium thiosulfate were added, and the mixture was stirred at room temperature overnight, then left standing,
The layers were separated to obtain an organic layer. The organic layer was concentrated to give 3- (3'-
(Oxobutyl) -4,4-dimethylbutyrolactone
8 g were obtained (colorless and transparent oil). Gas chromatography analysis revealed that the area percentage value was 90%. EXAMPLE 2 10 mg of molybdenum metal and 30 mg
After charging 200 mg by weight of hydrogen peroxide solution,
C., and stirred and maintained at the same temperature for 0.5 hour. After cooling to an internal temperature of 30 ° C., 1.54 g of α-terpineol was charged, and 6 g of a 30% by weight aqueous hydrogen peroxide solution was added dropwise over 30 minutes. ,
Hold and react. Cool to room temperature and add methyl tert
20 g of -butyl ether and 20 g of a 10% by weight aqueous sodium thiosulfate solution were added, and the mixture was stirred at room temperature overnight, allowed to stand, and separated to obtain an organic layer containing 3- (3'-oxobutyl) -4,4-dimethylbutyrolactone. Was. As a result of gas chromatography analysis, 3- (3′-oxobutyl) -4,4
-The yield of dimethylbutyrolactone (internal standard method) is 3
5%. Example 3 The procedure of Example 2 was repeated, except that 30 mg of tungsten sulfide was used in place of 10 mg of molybdenum metal, and 3- (3′-oxobutyl) -4,4-dimethylbutyrolactone was used. , With a yield of 56%. Example 4 The procedure of Example 2 was repeated, except that 30 mg of tungstophosphoric acid was used in place of 10 mg of molybdenum metal, to give 3- (3'-oxobutyl) -4,4-dimethylbutyrolactone. Was obtained in a yield of 55%. Example 5 The procedure of Example 1 was repeated, except that tungstic acid was used instead of tungsten metal, to obtain 3- (3′-oxobutyl) -4,4-dimethylbutyrolactone. be able to. Example 6 The procedure of Example 1 was repeated, except that tungsten boride was used instead of tungsten metal, to obtain 3- (3′-oxobutyl) -4,4-dimethylbutyrolactone. Obtainable. Example 7 The procedure of Example 1 was repeated, except that molybdic acid was used instead of tungsten metal, to obtain 3- (3′-oxobutyl) -4,4-dimethylbutyrolactone. be able to. According to the present invention, α-terpineol and inexpensive hydrogen peroxide can be used in the presence of a metal oxide catalyst obtained by reacting readily available tungsten metal or the like with hydrogen peroxide. By reacting, 3- (3′-oxobutyl)-which is important as a synthetic intermediate of pyrethroid compound
4,4-dimethylbutyrolactone can be easily obtained, which is industrially advantageous.

Claims (1)

Claims: 1. An α-catalyst is prepared by reacting at least one selected from the group consisting of tungsten metal, molybdenum metal, a tungsten compound and a molybdenum compound with hydrogen peroxide in the presence of a metal oxide catalyst. 3- (3'-) characterized by reacting terpineol with hydrogen peroxide.
(Oxobutyl) -4,4-dimethylbutyrolactone.