JP2003201288A - METHOD FOR PRODUCING gamma-BUTYROLACTONE AND CATALYST FOR THE SAME - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for industrially and advantageously producing γ-butyrolactone by oxidizing a 1,4-diol with hydrogen peroxide. <P>SOLUTION: This method for producing the γ-butyrolactone is to react the 1,4-diol with hydrogen peroxide in the presence of a metal oxide catalyst. The metal oxide catalyst is prepared by reacting at least one species selected from a group consisting of tungsten compounds and molybdenum compounds with hydrogen peroxide. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing γ-butyrolactones.

[0002]

2. Description of the Related Art γ-Butyrolactones are important compounds as various chemical products and synthetic intermediates thereof. As a method for producing them, for example, 1,4-diols are potassium permanganate and potassium dichromate. It is known to oxidize using heavy metal oxides such as, but in terms of using a metal oxide whose waste treatment is complicated, in a stoichiometric amount or more, it has a high environmental load, There was a problem.

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. As a method for producing γ-butyrolactones by reacting with hydrogen, for example, a method using a triscetylpyridinium 12-molybdophosphoric acid catalyst (J. Or.
g. Chem. , 53 , 3587 (1988)). However, such a method is not necessarily industrially advantageous because the preparation of the catalyst is complicated.

[0004]

Under these circumstances, the present inventors have made 1,4-diols oxidizable with hydrogen peroxide to make γ-butyrolactones more industrially advantageous. As a result of diligent study on the production method, a readily available tungsten compound such as tungsten metal or tungsten boride, a metal oxide easily prepared from a molybdenum compound such as molybdenum metal or molybdenum boride, and hydrogen peroxide are preferable. It was found that γ-butyrolactones can be obtained by reacting 1,4-diols with hydrogen peroxide in the presence of the metal oxide catalyst, which has achieved various oxidation catalytic activities, and has reached the present invention. .

[0005]

That is, the present invention relates to tungsten metal, molybdenum metal, tungsten and IIIb.
Tungsten compounds consisting of group IV, IVb, Vb or VIb elements and molybdenum and IIIb, IVb
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 Vb or Group VIb elements with hydrogen peroxide,
The present invention provides a method for producing γ-butyrolactones, which comprises reacting 1,4-diols with hydrogen peroxide, and a catalyst therefor.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The 1,4-diols are diols having two hydroxyl groups in the molecule, and the two hydroxyl groups are bonded via a carbon chain having 4 carbon atoms. There is no particular limitation as long as it is a diol in which at least one of both ends to which a hydroxyl group of a carbon chain is bonded is a methylene group. Here, among the carbon atoms constituting the carbon chain,
A carbon atom other than the carbon atom forming the methylene group to which a hydroxyl group is bonded may have a substituent.

Examples of the carbon chain having 4 carbon atoms include a tetramethylene group. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, an alkoxy group, a silyl group and a halogen atom.

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group. Examples thereof include linear, branched or cyclic alkyl groups such as n-octyl group, isooctyl group, n-nonyl group, n-decyl group, cyclopentyl group and cyclohexyl group. Such an alkyl group may have a substituent, and as the substituent,
Examples thereof include alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group and n-butoxy group, silyl groups such as trimethylsilyl group, halogen atoms such as fluorine atom, chlorine atom and bromine atom. Examples of the alkyl group having such a substituent include a chloromethyl group, a fluoromethyl group, a trifluoromethyl group, a methoxymethyl group, a methoxyethyl group and a trimethylsilylmethyl group.

As the aryl group, for example, a phenyl group,
Examples of the naphthyl group and the like, such an aryl group may have a substituent, and as the substituent, for example, the alkyl group, for example, the alkoxy group, for example, the silyl group described later, for example, the halogen atom described below, for example, acetyl is used. Base,
Examples thereof include an acyl group such as a propionyl group, and examples of the aryl group substituted with such a substituent include a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2-chlorophenyl group and a 3-chlorophenyl group. Group, 4-chlorophenyl group, 2-bromophenyl group,
Examples thereof include a 2-methylphenyl group, a 4-methylphenyl group, a 4-methoxyphenyl group, a 4-acetylphenyl group.

Examples of the aralkyl group which may be substituted include those composed of the above alkyl group and the above aryl group, and examples thereof include a benzyl group, a phenylethyl group, a 4-fluorobenzyl group and a 4-methoxybenzyl group. , 2-chlorobenzyl group and the like.

Examples of the silyl group include a trimethylsilyl group, a triethylsilyl group and a dimethylphenylsilyl group, and examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

Further, such a substituent may be bonded to form a part of a ring structure, and examples of the ring structure include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, Examples thereof include a cyclononane ring, 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 silyl group, the halogen atom, or the like.

Examples of such 1,4-diols include 1,4-butanediol, 1,4-pentanediol, 2-methyl-1,4-butanediol, 2-methyl-1,4-pentanediol, 3-methyl-1,4-pentanediol, 4-methyl-1,4-pentanediol, 2,2-dimethyl-1,4-butanediol, 2,
3-dimethyl-1,4-butanediol, 1,4-hexanediol, 2-ethyl-1,4-butanediol,
1,4-heptanediol, 1,4-octanediol, 1,4-nonanediol, 1,4-decanediol, 1,4-undecanediol, 1,4-dodecanediol, 1-phenyl-1, 4-butanediol, 2-
Phenyl-1,4-butanediol, 2- (2-fluorophenyl) -1,4-butanediol, 2- (3-fluorophenyl) -1,4-butanediol, 2- (4
-Fluorophenyl) -1,4-butanediol, 2-
(2-chlorophenyl) -1,4-butanediol, 2
-(2-bromophenyl) -1,4-butanediol,
2-chloro-1,4-butanediol, 2- (4-methoxyphenyl) -1,4-butanediol, 2- (4-
Acetylphenyl) -1,4-butanediol, benzene-1,2-dimethanol and the like can be mentioned.

The catalyst used in the present invention includes tungsten metal, molybdenum metal, tungsten and Group IIIb, Group IV.
At least one selected from the group consisting of a tungsten compound containing a b-group, a Vb group or a VIb group element and a molybdenum compound containing a molybdenum and a IIIb group, IVb group, a Vb group or a VIb group element (hereinafter , Abbreviated as a metal compound) and hydrogen peroxide.

Examples of the tungsten compound composed of tungsten and the element IIIb include tungsten boride and the like, and examples of the tungsten compound composed of tungsten and the element IVb include tungsten carbide and tungsten silicide, and the combination of tungsten and the element Vb. Examples of the tungsten compound containing the group element include tungsten nitride and tungsten phosphide, and examples of the tungsten compound containing the tungsten and the group VIb element include tungsten oxide, tungstic acid and tungsten sulfide.

Examples of the molybdenum compound containing molybdenum and the element IIIb include molybdenum boride, and examples of the molybdenum compound containing molybdenum and the element IVb include molybdenum carbide and molybdenum silicide.
Examples of the molybdenum compound composed of molybdenum and a Group Vb element include molybdenum nitride and molybdenum phosphide, and examples of the molybdenum compound composed of molybdenum and a Group VIb element include molybdenum oxide and molybdic acid.
Examples thereof include molybdenum sulfide.

The metal compound is preferably tungsten metal, tungsten boride, tungsten carbide, tungsten sulfide, tungsten oxide, or tungstic acid. These metal compounds may be used alone or in combination of two or more.

By reacting the metal compound with hydrogen peroxide, the 1,4-diols are oxidized to give γ
-A metal oxide is prepared which serves as a catalyst for the production of butyrolactones. 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, tertiary alcohol solvents such as tert-butanol, nitrile solvents such as acetonitrile and propionitrile. It may be carried out in an organic solvent such as or a mixed solvent of the organic solvent and water.

Hydrogen peroxide is usually used as an aqueous solution, but an organic solvent solution may be used. It is preferable to use an aqueous hydrogen peroxide solution because it is easier to handle. The hydrogen peroxide concentration in the aqueous hydrogen peroxide solution or the organic solvent solution 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 aqueous solution, a commercially available aqueous solution may be used as it is, or if necessary, after the concentration is adjusted by diluting, concentrating or the like. Further, the organic solvent solution of hydrogen peroxide can be prepared by means such as extraction treatment of an aqueous hydrogen peroxide solution with an organic solvent, or distillation treatment in the presence of an organic solvent.

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 there is no particular upper limit.

The reaction between the metal compound and hydrogen peroxide is usually carried out by mixing both of them, and in order to improve the contact efficiency between the metal compound and hydrogen peroxide, the metal compound is sufficiently added in the metal oxide preparation liquid. It is preferable to carry out the reaction while stirring so as to disperse. In addition, it is preferable to use a metal compound having a small particle size, such as a powdery metal oxide, from the viewpoint of increasing the contact efficiency between the metal compound and hydrogen peroxide and facilitating the control during the preparation of the metal oxide. The preparation temperature during preparation of the metal oxide is usually -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. The metal oxide may be taken out from the preparation liquid by, for example, concentration treatment and used as the catalyst, or the preparation liquid may be directly used as the catalyst.

By reacting 1,4-diols with hydrogen peroxide in the presence of the metal oxide catalyst thus obtained, γ-butyrolactones can be obtained. Is used. Of course, an organic solvent solution of hydrogen peroxide may be used. The hydrogen peroxide concentration in the hydrogen peroxide aqueous solution or the hydrogen peroxide organic solvent solution is not particularly limited, but is practically 1 to 60% by weight in view of volume efficiency, safety and the like.

The amount of hydrogen peroxide used is usually 1.5 mol times or more, preferably 2 mol times or more, with respect to 1,4-diols, and there is no particular upper limit, but if too much, it is economical. Since it is likely to be disadvantageous, it is practically 10 mol times or less.

The amount of the metal oxide catalyst used is
Usually 0.001-0.9 for 1,4-diols
It is 5 times by mole, preferably 0.005 to 0.1 times by mole.

The reaction of 1,4-diols and hydrogen peroxide may be carried out without solvent, in a water solvent, an organic solvent or a mixed solvent of water and an organic solvent. Examples of the organic solvent include diethyl ether and methyl tert.
-Ethyl solvents such as 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 with a metal oxide catalyst, 1,4-
It is carried out by contacting and mixing diols and hydrogen peroxide. For example, a metal compound, hydrogen peroxide and 1,4-diols are contacted and mixed to prepare a metal oxide catalyst, and 1,4 -The reaction between the diols and hydrogen peroxide may be carried out simultaneously in parallel.

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.

With the progress of the reaction, γ-butyrolactones are produced, and the progress of such reaction can be confirmed by a usual analytical means such as gas chromatography, high performance liquid chromatography, thin layer chromatography, NMR, IR and the like. .

After the completion of the reaction, the reaction solution is left as it is or, if necessary, the 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 objective. It is possible to take out γ-butyrolactones. In addition, γ-butyrolactone can be taken out by adding water and / or an organic solvent insoluble in water to the reaction liquid, if necessary, and subjecting the resulting organic layer to concentration processing. Γ taken out
-Butyrolactones may be further purified by conventional purification methods such as distillation, recrystallization and column chromatography.

The filtrate or the reaction solution after the γ-butyrolactone has been 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, Alternatively, it can be reused in this reaction again after performing concentration treatment or the like as necessary.

Examples of the γ-butyrolactone thus obtained include γ-butyrolactone and α-methyl-γ-
Butyrolactone, β-methyl-γ-butyrolactone, γ
-Methyl-γ-butyrolactone, α, β-dimethyl-γ
-Butyrolactone, α, γ-dimethyl-γ-butyrolactone, β, γ-dimethyl-γ-butyrolactone, γ, γ
-Dimethyl-γ-butyrolactone, α, α-dimethyl-
γ-butyrolactone, β, β-dimethyl-γ-butyrolactone, α-ethyl-γ-butyrolactone, β-ethyl-γ-butyrolactone, γ-ethyl-γ-butyrolactone, α- (n-propyl) -γ-butyrolactone, γ-
(N-Propyl) -γ-butyrolactone, γ- (n-butyl) -γ-butyrolactone, γ- (n-pentyl)-
γ-butyrolactone, γ- (n-hexyl) -γ-butyrolactone, γ- (n-heptyl) -γ-butyrolactone, γ- (n-octyl) -γ-butyrolactone,

Α-phenyl-γ-butyrolactone, β-
Phenyl-γ-butyrolactone, γ-phenyl-γ-butyrolactone, α- (2-fluorophenyl) -γ-butyrolactone, β- (2-fluorophenyl) -γ-butyrolactone, α- (3-fluorophenyl) -γ -Butyrolactone, β- (3-fluorophenyl) -γ-butyrolactone, α- (4-fluorophenyl) -γ-butyrolactone, β- (4-fluorophenyl) -γ-butyrolactone, α- (2-chlorophenyl)- γ-butyrolactone, β- (2-chlorophenyl) -γ-butyrolactone, α- (2-bromophenyl) -γ-butyrolactone, β- (2-bromophenyl) -γ-butyrolactone, α- (4-methoxyphenyl) -Γ-butyrolactone, β- (4-methoxyphenyl) -γ-butyrolactone, α- (4-acetylphenyl) γ- butyrolactone, beta-(4-acetylphenyl)-.gamma.-butyrolactone, phthalide, and the like.

[0034]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 A 100 mL Schlenk tube (with nitrogen substitution) equipped with a reflux condenser was charged with 0.074 g of tungsten metal powder and 1.1 g of 30% by weight hydrogen peroxide at room temperature, and the internal temperature was 5
The catalyst liquid was prepared by stirring at 0 ° C. for 15 minutes. 1.8 g of 1,4-butanediol and 30% by weight were added to the catalyst liquid.
11 g of hydrogen peroxide water was charged, and the mixture was stirred and held at an internal temperature of 90 ° C. for 4 hours. The obtained reaction liquid is cooled and ethanol 5 is added.
After adding 0 mL and shaking thoroughly, it was analyzed by gas chromatography to confirm the production of γ-butyrolactone. Production amount of γ-butyrolactone: 0.88 g, yield:
51% (based on 1,4-butanediol).

Example 2 In a 100 mL Schlenk tube equipped with a reflux condenser (nitrogen substituted), at room temperature, 0.1 g of tungstic acid, 30% by weight was added.
12.1 g of hydrogen peroxide solution and 1.8 g of 1,4-butanediol 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, added with 50 mL of ethanol, shaken sufficiently, and then analyzed by gas chromatography to confirm the production of γ-butyrolactone. Production amount of γ-butyrolactone: 0.96 g, yield: 56%
(Based on 1,4-butanediol).

Example 3 A 100 mL Schlenk tube (with nitrogen substitution) equipped with a reflux condenser was charged with 0.074 g of tungsten metal powder and 1.1 g of 30% by weight hydrogen peroxide at room temperature, and the internal temperature was 5
A catalyst solution was prepared by stirring and holding at 0 ° C for 15 minutes. To the catalyst solution, 2.4 g of benzene-1,2-dimethanol and 9.5 g of 30 wt% hydrogen peroxide solution were charged, and the internal temperature was 90 ° C.
The mixture was stirred and held for 4 hours. The obtained reaction liquid was cooled, 50 mL of ethanol was added, and the mixture was shaken sufficiently and then analyzed by gas chromatography to confirm the formation of phthalide. Amount of phthalide produced: 2.3 g, yield: 97% (based on benzene-1,2-dimethanol).

Example 4 The same procedure as in Example 2 was repeated except that tungsten oxide (the amount used was equimolar to tungstic acid) was used in place of tungstic acid, and γ-butyrolactone was collected. Obtained at a rate of 51% (based on 1,4-butanediol).

Example 5 γ-butyrolactone was prepared in the same manner as in Example 1 except that tungsten boride (the amount used was equimolar to tungsten metal) was used instead of tungsten metal. Obtained in a yield of 39% (based on 1,4-butanediol).

Example 6 γ-butyrolactone was collected in the same manner as in Example 1 except that tungsten carbide (the amount used was equimolar to tungsten metal) was used in place of tungsten metal. It was obtained at a rate of 53% (based on 1,4-butanediol).

Example 7 The procedure of Example 1 was repeated except that tungsten sulfide (the amount used was equimolar to tungsten metal) was used instead of tungsten metal, and γ-butyrolactone was collected. The yield was 56% (based on 1,4-butanediol).

Example 8 The procedure of Example 1 was repeated except that molybdenum metal (the amount used was equimolar to tungsten metal) was used in place of tungsten metal, and γ-butyrolactone was collected. It was obtained at a rate of 23% (based on 1,4-butanediol).

Example 9 γ-butyrolactone was prepared in the same manner as in Example 1 except that molybdenum boride (the amount used was equimolar to tungsten metal) was used in place of tungsten metal. Obtained in a yield of 21% (based on 1,4-butanediol).

Example 10 A phthalide was prepared in the same manner as in Example 3 except that tungsten boride (the amount used was equimolar to tungsten metal) was used in place of tungsten metal.
The yield was 79% (based on benzene-1,2-dimethanol).

Example 11 The procedure of Example 3 was repeated except that tungsten carbide (the amount used was equimolar to tungsten metal) was used in place of the tungsten metal, and phthalide was obtained in a yield of 81. % (Based on benzene-1,2-dimethanol).

Example 12 The procedure of Example 3 was repeated except that tungsten sulfide (the amount used was equimolar to tungsten metal) was used in place of the tungsten metal, and phthalide was produced in a yield of 75. % (Based on benzene-1,2-dimethanol).

Example 13 The procedure of Example 3 was repeated except that molybdenum metal (the amount used was equimolar to tungsten metal) was used in place of tungsten metal, and phthalide was obtained in a yield of 74. % (Based on benzene-1,2-dimethanol).

Example 14 The procedure of Example 3 was repeated except that molybdenum boride (the amount used was equimolar to the amount of tungsten metal) was used instead of tungsten metal, and phthalide was obtained in a yield of phthalide. Obtained in 77% (based on benzene-1,2-dimethanol).

[0049]

EFFECTS OF THE INVENTION According to the present invention, at least one selected from the group consisting of readily available tungsten metal, tungsten compound such as tungsten boride and molybdenum compound such as molybdenum metal, and hydrogen peroxide can be easily prepared. A metal oxide showing a good oxidation catalytic activity can be prepared,
By using the metal oxide as a catalyst and reacting 1,4-diols with hydrogen peroxide, γ-butyrolactone can be produced, which is industrially advantageous.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C07B 61/00 300 C07D 307/32 FF term (reference) 4C037 EA03 RA01 4G069 AA06 AA08 BB01C BB02C BB04A BB04B BB20C BC15C BC20C BC24C BC59A BC59B BC59C BC60A BC60B BC60C BD01C BD02C BD03C BD04C BD05C BD06C BD07C BD08C BD09C BD10C CB07 DA02 FA01 FB41 FB77 FC02 FC04 4H039 CA42 CG10

Claims (7)

[Claims] 1. A tungsten compound containing tungsten metal, molybdenum metal, tungsten and an element of group IIIb, IVb, Vb or VIb, and molybdenum and
1,4 in the presence of a metal oxide catalyst obtained by reacting hydrogen peroxide with at least one selected from the group consisting of molybdenum compounds consisting of Group IIIb, Group IVb, Group Vb or Group VIb elements. -A method for producing γ-butyrolactone, which comprises reacting a diol with hydrogen peroxide. 2. The method for producing γ-butyrolactone according to claim 1, wherein the Group IIIb element is boron. 3. The method for producing γ-butyrolactone according to claim 1, wherein the Group IVb element is carbon. 4. The method for producing γ-butyrolactone according to claim 1, wherein the Group Vb element is nitrogen or phosphorus. 5. The method for producing γ-butyrolactone according to claim 1, wherein the Group VIb element is oxygen or sulfur. 6. The method for producing γ-butyrolactone according to claim 1, wherein the 1,4-diol is 1,4-butanediol. 7. A tungsten compound composed of tungsten metal, molybdenum metal, tungsten and an element of group IIIb, IVb, Vb or VIb and molybdenum and
By oxidizing at least one selected from the group consisting of molybdenum compounds consisting of Group IIIb, Group IVb, Group Vb or Group VIb elements and hydrogen peroxide, 1,4-diols are oxidized, A catalyst for producing γ-butyrolactones.