JP2003300950A - Method for producing sulfone compound of sulfoxide compound and catalyst therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for more industrially and advantageously producing a sulfone compound or a sulfoxide compound by reacting a sulfide compound with hydrogen peroxide. <P>SOLUTION: The method for producing the sulfone compound or sulfoxide compound is carried out as follows. The sulfide compound is reacted with the hydrogen peroxide in the presence of a metal oxide catalyst prepared by reacting at least one kind selected from the group consisting of tungsten metal, molybdenum metal, a tungsten compound composed of tungsten and a group IIIb element, a group IVb element, a group Vb element or a group VIb element except oxygen and molybdenum, a molybdenum compound composed of the group IIIb element, the group IVb element, the group Vb element or the group VIb element except oxygen with the hydrogen peroxide. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a sulfone compound or a sulfoxide compound and a catalyst therefor.

[0002]

2. Description of the Related Art Sulfone compounds or sulfoxide compounds are important compounds as various chemical products and synthetic intermediates thereof (see, for example, Non-Patent Document 1), and as a method for producing them, a sulfide compound and hydrogen peroxide are used. A method of reacting is known. Hydrogen peroxide has recently been attracting attention as a clean and excellent oxidizing agent that is cheap, easy to handle, and becomes harmless water after the reaction. The method of reacting to produce a sulfone compound or a sulfoxide compound is important.

As a method for producing a sulfone compound or a sulfoxide compound by reacting a sulfide compound with hydrogen peroxide, for example, a method using a sodium tungstate catalyst is known (see Non-Patent Document 2, for example). However, the method uses 2-phenylmercaptoethanol, which is a sulfide compound having a relatively high reactivity, and there is a problem that the reaction hardly progresses even if such a method is applied to a sulfide compound having a low reactivity. Therefore, a method using a quaternary ammonium hydrogensulfate and phenylphosphonic acid in addition to the sodium tungstate catalyst (see, for example, Non-Patent Document 1) has been developed, but an expensive phenylphosphonic acid is used. However, it was not always a method that was industrially satisfactory. Further, a method using a cetylpyridinium tungstophosphoric acid catalyst (for example, see Non-Patent Document 3) and a method using a methylrhenium trioxide catalyst (see, for example, Non-Patent Document 4) have been developed. In addition to complicated catalyst preparation, as a reaction solvent,
The latter method is not necessarily satisfactory from an industrial point of view, since it uses chloroform, which is problematic in terms of environment and occupational safety and health, and the catalyst is expensive. There wasn't.

[0004]

[Non-Patent Document 1] Tetrahedoron, 57 , 2
469 (2001)

[Non-Patent Document 2] J. Org. Chem. , 28 , 11
40 (1963)

[Non-Patent Document 3] Chem. Lett. , 1 (199
4)

[Non-Patent Document 4] Bull. Chem. Soc. Jp
n. , 69 , 2955 (1996)

[0005]

Under the circumstances, the present inventors have made a method for producing a sulfone compound or a sulfoxide compound industrially advantageously by reacting a sulfide compound with hydrogen peroxide. As a result of extensive studies to develop a metal oxide, a metal oxide obtained by reacting readily available tungsten metal, molybdenum metal, a tungsten compound such as tungsten boride and / or a molybdenum compound such as molybdenum boride with hydrogen peroxide is found. , Showing good catalytic activity in the reaction between a sulfide compound and hydrogen peroxide, and obtaining a sulfone compound or a sulfoxide compound by reacting the sulfide compound with hydrogen peroxide in the presence of the metal oxide catalyst. By controlling the amount of hydrogen peroxide used. Found that it is possible to selectively produce, we have completed the present invention.

[0006]

That is, the present invention relates to tungsten metal, molybdenum metal, tungsten and IIIb.
Group V element, Group IVb element, Group Vb element or V excluding oxygen
At least one selected from the group consisting of a tungsten compound composed of an Ib group element and molybdenum and a molybdenum compound composed of a molybdenum group IIIb element, a group IVb element, a group Vb element or a group VIb element other than oxygen, and hydrogen peroxide. The present invention provides a method for producing a sulfone compound or a sulfoxide compound, which comprises reacting a sulfide compound with hydrogen peroxide in the presence of a metal oxide catalyst obtained by reacting with.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The catalyst used in the present invention will be described first. The present invention includes a tungsten compound containing tungsten metal, molybdenum metal, tungsten and a Group IIIb element, a Group IVb element, a Group Vb element or a Group VIb element except oxygen, and molybdenum and a Group IIIb element, IVb. A metal oxide formed by reacting at least one selected from the group consisting of molybdenum compounds consisting of Group V elements, Group Vb elements or Group VIb elements excluding oxygen (hereinafter abbreviated as metal compound) with hydrogen peroxide. Physical catalyst is used.

Examples of the tungsten compound composed of tungsten and a Group IIIb element include tungsten boride and the like, and examples of the tungsten compound composed of tungsten and a Group IVb element include tungsten carbide and tungsten silicide. 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 such metal compounds, tungsten metal, tungsten boride, tungsten sulfide and molybdenum metal are preferable, and tungsten metal and tungsten sulfide are particularly preferable. Further, such metal compounds may be used alone or in combination of two or more.

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 hydrogen peroxide solution is preferably used from the viewpoint of easy handling. 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. When hydrogen peroxide water is used, a commercially available product may be used as it is, or one whose concentration has been adjusted by diluting, concentrating, etc., if necessary. When an organic solvent solution of hydrogen peroxide is used, for example, a solution prepared by a method such as extracting hydrogen peroxide solution with an organic solvent or distilling hydrogen peroxide solution in the presence of an organic solvent is used. You can use it.

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, for example, ether solvents such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran, etc., ester solvents such as ethyl acetate, eg, methanol, ethanol, tert-
It may be carried out in an organic solvent such as an alcohol solvent such as butanol, a nitrile solvent such as acetonitrile or propionitrile, 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 both of them, in order to further improve the contact efficiency between the metal compound and hydrogen peroxide,
It is preferable to carry out the reaction in the metal oxide preparation liquid while stirring so that the metal compound is 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 facilitating the control during preparation of the metal oxide.

The temperature for preparing the metal oxide is usually -1.
It is 0 to 100 ° C.

By reacting the metal compound with hydrogen peroxide in water, an organic solvent or a mixed solvent of an organic solvent and water, a part or all of the metal compound is dissolved to contain a metal oxide. Although a homogeneous solution or suspension can be prepared, 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. .

Then, in the presence of the above metal oxide catalyst,
A method for producing a sulfone compound or a sulfoxide compound by reacting a sulfide compound with hydrogen peroxide will be described.

The sulfide compound used in the present invention is not particularly limited as long as it has two substituents bonded to a sulfur atom.

Examples of the sulfide compound include those represented by the general formula (1) (In the formula, R ¹ and R ² are the same or different and each is an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group or an optionally substituted group. It represents an alkenyl group, and R ¹ and R ² may combine to form a part of a ring structure).

Among the sulfide compounds represented by the general formula (1), examples of the sulfide compound in which R ¹ and R ² are bonded to each other to form a part of the ring structure include, for example, the general formula (2) (In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group or an optionally substituted group. Aryl group, optionally substituted aryloxy group, optionally substituted aralkyl group, optionally substituted aralkyloxy group, optionally substituted alkenyl group, optionally substituted arylalkenyl group An optionally substituted arylalkynyl group,
Optionally substituted silyl group, halogen atom, nitro group, cyano group, optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted amide group, optionally substituted Represents a good imido group, a carboxyl group or an optionally substituted carboalkoxy group. Here, R ³ and R ⁴ , R ⁴ and R ^5, or R ⁵ and R ⁶ may combine to form a part of the ring structure. ).

Among the sulfide compounds represented by the general formula (2), examples of the sulfide compound in which R ³ and R ⁴ and R ⁵ and R ⁶ are bonded to each other to form a part of the ring structure include (3) (In the formula, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are the same or different and each is a hydrogen atom, an optionally substituted alkyl group, or a substituted group. Optionally alkoxy group, optionally substituted aryl group, optionally substituted aryloxy group, optionally substituted aralkyl group, optionally substituted aralkyloxy group, optionally substituted Alkenyl group, optionally substituted arylalkenyl group, optionally substituted arylalkynyl group, optionally substituted silyl group, halogen atom, nitro group, cyano group, optionally substituted acyl group, Optionally substituted acyloxy group, optionally substituted amide group, optionally substituted imide group, carboxyl group or optionally substituted carbo group Represents an alkoxy group. Here, R ⁷ and R ^8, R ⁸ and R ^9, R ⁹ and R ^{1 0,} R ¹¹ and R ^12, R ¹² and R ¹³ or R ¹³ and R ¹⁴ are bonded ring structure May form a part of the).

The alkyl group which may be substituted includes, 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. Group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, 3,7-
Dimethyloctyl group, lauryl group, cyclopropyl group,
A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms such as a 2,2-dimethylcyclopropyl group, a cyclopentyl group, a cyclohexyl group and a menthyl group, and one or more of these alkyl groups Examples thereof include those in which a hydrogen atom is substituted with a substituent such as an alkoxy group, an aryloxy group, an aralkyloxy group, a halogen atom, an acyl group, a carboalkoxy group, a carboaryloxy group, a carboaralkyloxy group, and a carboxyl group. .

Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group,
n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, cyclopropyloxy Group, 2,2-dimethylcyclopropyloxy group,
Examples thereof include alkoxy groups having 1 to 20 carbon atoms such as cyclopentyloxy group, cyclohexyloxy group and menthyloxy group.

The aryloxy group is, for example, an unsubstituted aryloxy group such as a phenoxy group, a 1-naphthyloxy group or a 2-naphthyloxy group, and one or two aromatic rings constituting these unsubstituted aryloxy groups. One or more hydrogen atoms are substituted with a substituent such as the alkyl group, the alkoxy group, or a halogen atom, for example, 4-methylphenoxy group, 4-ethylphenoxy group, 1,3,5-
Trimethylphenoxy group, 2-methoxyphenoxy group,
An aryloxy group having 6 to 60 carbon atoms such as a pentafluorophenoxy group can be mentioned.

The aralkyloxy group includes, for example, benzyloxy group, 2-phenylethoxy group, 4-phenylbutoxy group, 5-phenylpentyloxy group, 6-phenylhexyloxy group, 7-phenylheptyloxy group, 8-phenyl. Examples thereof include an aralkyloxy group having 7 to 60 carbon atoms, which is composed of the above alkoxy group such as an octyloxy group and an unsubstituted or substituted aryl group.

Examples of the halogen atom include a fluorine atom and a chlorine atom, and examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group and a pentafluoro group. 2 to 2 carbon atoms such as benzoyl group
0 acyl group can be mentioned. Examples of the carboalkoxy group include a carboalkoxy group having a carbon number of 2 to 20 composed of a carbonyl group such as a carbomethoxy group and a carboethoxy group and the above alkoxy group. A carboaryloxy group having 7 to 60 carbon atoms, which is composed of a carbonyl group such as a group and the aryloxy group, and a carboaralkyloxy group includes, for example, a carbonyl group such as a carbobenzyloxy group and the above aralkyloxy group. Examples thereof include a carboaralkyloxy group having 8 to 60 carbon atoms.

Specific examples of the alkyl group substituted with such a substituent include fluoromethyl group, chloromethyl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group. , Methoxymethyl group, ethoxymethyl group,
Examples thereof include a methoxyethyl group and a carbomethoxymethyl group.

Examples of the optionally substituted aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group and 9
One or more hydrogen atoms of the aromatic ring constituting the anthracenyl group and these phenyl groups and the like, the optionally substituted alkyl group, the aryl group, the aralkyl group described later, the alkoxy group, the An aryloxy group, the aralkyloxy group, the halogen atom,
The acyl group, acylamido group, nitro group, cyano group,
Examples thereof include an aryl group having 6 to 60 carbon atoms, which is substituted with a substituent such as a carboxyl group and the carboalkoxy group.
Specific examples of the aryl group substituted with such a substituent include 2-methylphenyl group, 4-methylphenyl group, 2
-Ethylphenyl group, 2,4-dimethylphenyl group,
2,4,6-trimethylphenyl group, 2-methyl-4-
Ethylphenyl group, 4-decylphenyl group, 4-chlorophenyl group, pentafluorophenyl group, 4-methoxyphenyl group, 3-phenoxyphenyl group, 2-nitrophenyl group, 4-cyanophenyl group, 3-carbomethoxyphenyl group Etc.

Examples of the optionally substituted aralkyl group include those which are composed of the optionally substituted aryl group and the optionally substituted alkyl group, and include, for example, benzyl group, 4- Chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group,
3-phenoxybenzyl group, 2,3,5,6-tetrafluorobenzyl group, 2,3,5,6-tetrafluoro-
4-methylbenzyl group, 2,3,5,6-tetrafluoro-4-methoxybenzyl group, 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl group, phenylethyl group, phenylbutyl group, phenyl Hexyl group and the like can be mentioned.

Examples of the optionally substituted alkoxy group include those which are composed of the aforementioned optionally substituted alkyl group and oxygen atom. In particular,
Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert
-Butoxy group, n-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyl group, n
-Nonyloxy group, n-decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyloxy group, perfluorooctyloxy group, methoxy Examples thereof include a methoxy group and a 2-methoxyethoxy group.

Examples of the optionally substituted aryloxy group include those which are composed of the optionally substituted aryl group and an oxygen atom. Specifically, phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 2-methylphenoxy group, 4-methylphenoxy group, 2-ethylphenoxy group, 2,4-dimethylphenoxy group, 2,4. 6-trimethylphenoxy group,
2-methyl-4-ethylphenoxy group, 4-decylphenoxy group, 4-chlorophenoxy group, 4-methoxyphenoxy group, 3-phenoxyphenoxy group, 2-nitrophenoxy group, 4-cyanophenoxy group, 3-carbomethoxy Examples thereof include a phenoxy group and a pentafluorophenoxy group.

The optionally substituted aralkyloxy group includes, for example, those composed of the aforementioned optionally substituted aralkyl group and an oxygen atom. Specifically, benzyloxy group, 4-chlorobenzyloxy group, 4-methylbenzyloxy group, 4-methoxybenzyloxy group, 3-phenoxybenzyloxy group, 2,
3,5,6-tetrafluorobenzyloxy group, 2,
3,5,6-Tetrafluoro-4-methylbenzyloxy group, 2,3,5,6-tetrafluoro-4-methoxybenzyloxy group, 2,3,5,6-tetrafluoro-
4-methoxymethylbenzyloxy group, phenylethoxy group, phenylbutoxy group, phenylhexyloxy group and the like can be mentioned.

Examples of the alkenyl group which may be substituted include ethenyl group, 1-propenyl group, 2-propenyl group, 1-methylethenyl group, 1-butenyl group and 2-
Butenyl group, 3-butenyl group, 1-methyl-1-propenyl group, 2-methyl-1-propenyl group, 1-methyl-
C2-C12 alkenyl such as 2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 1-hexenyl group, 1-decenyl group, 2-cyclopentenyl group and 2-cyclohexenyl group. Group and one or more hydrogen atoms of these alkenyl groups are, for example, an alkoxy group, an aryloxy group, an aralkyloxy group,
Examples thereof include those substituted with a substituent such as a halogen atom, an acyl group, a carboalkoxy group, a carboaryloxy group, a carboaralkyloxy group and a carboxyl group.

Examples of the optionally substituted arylalkenyl group include those which are composed of the optionally substituted alkenyl group and the optionally substituted aryl group. Specifically, a styryl group and the like can be mentioned. Examples of the optionally substituted arylalkynyl group include those which are composed of an alkynyl group having 2 to 12 carbon atoms and the above aryl group. Specifically, a phenylethynyl group and the like can be mentioned.

As the silyl group which may be substituted,
For example, a silyl group substituted with 1 to 3 substituents selected from the group consisting of the optionally substituted alkyl group, the optionally substituted aryl group, and the optionally substituted aralkyl group is Examples thereof include trimethylsilyl group, triethylsilyl group, tri (n-propyl) silyl group, triisopropylsilyl group, dimethylisopropylsilyl group, diethylisopropylsilyl group,
Examples thereof include a tert-butyldimethylsilyl group, a pentyldimethylsilyl group, a hexyldimethylsilyl group, a triphenylsilyl group, a tribenzylsilyl group, a diphenylmethylsilyl group, a dimethylphenylsilyl group, and a tert-butyldiphenylsilyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the optionally substituted acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group and a pivaloyl group. Group, benzoyl group, trifluoroacetyl group,
What is composed of the optionally substituted alkyl group such as a pentafluorobenzoyl group and a carbonyl group,
Examples thereof include those composed of the above-mentioned optionally substituted aryl group and carbonyl group, those composed of the above-mentioned optionally substituted aralkyl group and carbonyl group, and the like.

Examples of the optionally substituted acyloxy group include those which are composed of the aforementioned optionally substituted acyl group and oxygen atom. In particular,
Examples thereof include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetoxy group and a pentafluorobenzoyloxy group. Examples of the optionally substituted amide group include a formamide group,
Acetamide group, propioamide group, butyroamide group,
Examples thereof include a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group, a ditrifluoroacetamide group and a dipentafluorobenzamide group.

As the imide group which may be substituted,
For example, the groups shown below may be mentioned (in the following groups, · represents a binding site).

Examples of the optionally substituted carboalkoxy group include those which are composed of the aforementioned optionally substituted alkoxy group and carbonyl group.
Specific examples include a carbomethoxy group, a carboethoxy group, a carbopropoxy group, and a carbohexyloxy group.

Examples of the sulfide compound used in the present invention include dimethyl sulfide, diethyl sulfide, di (n-propyl) sulfide, di (n-butyl).
Sulfide, di (n-amyl) sulfide, di (n-hexyl) sulfide, di (n-heptyl) sulfide,
Di (n-octyl) sulfide, di (n-nonyl) sulfide, di (n-decyl) sulfide, di (n-dodecyl) sulfide, di (isopropyl) sulfide, di (isobutyl) sulfide, di (sec-butyl) Sulfide, di (tert-butyl) sulfide, di (isoamyl) sulfide, methyl butyl sulfide, dicyclopentyl sulfide, dicyclohexyl sulfide,
Dicyclododecyl sulfide, diphenyl sulfide,
Dibenzyl sulfide, methylphenyl sulfide, ethylphenyl sulfide, di (4-chlorophenyl) sulfide, di (3-methoxyphenyl) sulfide, di (2,4-dichlorophenyl) sulfide, di (4-trifluoromethylphenyl) sulfide, Di (4-nitrophenyl) sulfide, (4-fluorophenyl)
(4-tolyl) sulfide, (3-chlorophenyl)
(4-tolyl) sulfide, (4-nitrophenyl)
(4-chloromethylphenyl) sulfide, (2-nitrophenyl) phenyl sulfide, (4-chloromethylphenyl) phenyl sulfide,

9H-thioxanthen-9-one, 3-acetamido-9H-thioxanthen-9-one, 3-carbomethoxy-9H-thioxanthen-9-one, phenoxathiin, 1-ethylphenoxathiin, 3- (2
-Trifluoromethylethoxy) phenoxathine,
(2-hydroxyethyl) phenyl sulfide, (chloromethyl) phenyl sulfide, (carbomethoxymethyl) phenyl sulfide, tetrahydrothiophene, benzo [b] thiophene, 3-chlorobenzo [b] thiophene, 3,5-dibromobenzo [b] Thiophene, 3,
4-dichlorobenzo [b] thiophene, 5-methylbenzo [b] thiophene, 4,7-dimethoxybenzo [b]
Thiophene, 3-octyloxybenzo [b] thiophene, 5-octyloxybenzo [b] thiophene, 3,
5-dioctyloxybenzo [b] thiophene, 3,4
-Dioctyloxybenzo [b] thiophene, 4,7-
Dioctyloxybenzo [b] thiophene,

Dibenzothiophene, 2,3-dioctyldibenzothiophene, 2,8-dioctyldibenzothiophene, 2,3-dioctyloxydibenzothiophene, 2,8-dioctyloxydibenzothiophene,
1,9-dioctyloxydibenzothiophene, 4,6
-Dioctyloxydibenzothiophene, 1,2,8,
9-tetraoctyloxydibenzothiophene, 1,
4,6,9-Tetraoctyloxydibenzothiophene, 1,2,4,6,8,9-hexaoctyloxydibenzothiophene, 1,3-dioctyloxydibenzothiophene, 1,2,9-trioctyloxydibenzothiophene , 3,4-dioctyloxydibenzothiophene, 1,2,3,4,6,9-hexaoctyloxydibenzothiophene, 2,3-dichlorodibenzothiophene, 2,8-dichlorodibenzothiophene, 2,3-
Difluorodibenzothiophene, 2,8-difluorodibenzothiophene, 2,3-diphenyldibenzothiophene, 2,8-diphenyldibenzothiophene, 2,3
-Diphenoxydibenzothiophene, 2,8-diphenoxydibenzothiophene, 2,3-dibenzyldibenzothiophene, 2,8-dibenzyldibenzothiophene,
2,3-dibenzyloxydibenzothiophene, 2,8
-Dibenzyloxydibenzothiophene,

2,3-bis (trimethylsilyl) dibenzothiophene, 2,8-bis (trimethylsilyl) dibenzothiophene, 2,3-bis (triphenylsilyl)
Dibenzothiophene, 2,8-bis (triphenylsilyl) dibenzothiophene, 2,3-bis (tribenzylsilyl) dibenzothiophene, 2,8-bis (tribenzylsilyl) dibenzothiophene, 2,3-diacetyldibenzothiophene, 2,8-diacetyldibenzothiophene, 2,3-diacetoxydibenzothiophene,
2,8-diacetoxydibenzothiophene, 2,3-bis (diacetylamino) dibenzothiophene, 2,8-
Bis (diacetylamino) dibenzothiophene, 2,3
-Bis (styryl) dibenzothiophene, 2,8-bis (styryl) dibenzothiophene, 2,3-bis (phenylethynyl) dibenzothiophene, 2,8-bis (phenylethynyl) dibenzothiophene, 2,3-dicyanodibenzothiophene , 2,8-dicyanodibenzothiophene, dinaphtho [2,1-b: 1 ', 2'-d] dibenzothiophene, dianthro [2,1-b: 1', 2 '
-D] dibenzothiophene and the like.

By reacting the sulfide compound with hydrogen peroxide in the presence of the metal oxide catalyst, the sulfur atom of the sulfide compound is oxidized to produce a sulfone compound or a sulfoxide compound.

When the sulfide compound represented by the general formula (1) is used, the general formula (4) (In the formula, R ¹ and R ² have the same meanings as described above.)
Or a general formula (5) (In the formula, R ¹ and R ² have the same meanings as described above.)
A sulfoxide compound represented by is obtained.

When the sulfide compound represented by the general formula (2) is used, the general formula (6) (Wherein R ³ , R ⁴ , R ⁵ and R ⁶ have the same meanings as described above) or the general formula (7). (In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ have the same meanings as described above.) A sulfoxide compound represented by the formula is obtained.

When the sulfide compound represented by the general formula (3) is used, the general formula (8) (Wherein R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ have the same meanings as described above) or the general formula (9). (In the formula, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ have the same meanings as described above.) A sulfoxide compound represented by the following formula is obtained.

The amount of the metal oxide used in the reaction of the sulfide compound and hydrogen peroxide is usually 0.0005 mol times or more with respect to the sulfide compound, and there is no particular upper limit, but in view of economic aspects. Then, practically, it is 1 mol times or less with respect to the sulfide compound.

As the hydrogen peroxide, hydrogen peroxide solution is usually used. Of course, hydrogen peroxide / organic solvent solution may be used. The concentration of hydrogen peroxide in the 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 solution, a commercially available product is usually used as it is or after adjusting the concentration by diluting, concentrating or the like as necessary. The solution of hydrogen peroxide in an organic solvent can be prepared, for example, by means of extracting hydrogen peroxide solution with an organic solvent, or distilling hydrogen peroxide solution in the presence of the organic solvent.

The amount of hydrogen peroxide used is usually 0.8 mole times or more the amount of the sulfide compound, and the upper limit thereof is not particularly limited. However, if it is too much, it is economically disadvantageous, so it is practical. Specifically, it is 10 mol times or less with respect to the sulfide compound. In this reaction,
By controlling the amount of hydrogen peroxide used, either the sulfone compound or the sulfoxide compound can be selectively produced. For example, when hydrogen peroxide is used in an amount of 1.5 moles or more with respect to the sulfide compound, a sulfone compound is selectively formed and 0.8 moles or more, 1.5 or more with respect to the sulfide compound. When using less than the molar amount of hydrogen peroxide, the sulfoxide compound is selectively produced. When a preparation liquid containing a metal oxide is used as the catalyst, the amount of hydrogen peroxide used may be set including the amount of hydrogen peroxide in the preparation liquid.

This reaction is usually carried out in water, an organic solvent or a mixed solvent of an organic solvent and water. Examples of the organic solvent include ether solvents such as diethyl ether, methyl tert-butyl ether, and tetrahydrofuran,
For example, ester solvents such as ethyl acetate, for example, methanol, ethanol, alcohol solvents such as tert-butanol, for example, acetonitrile, nitrile solvents such as propionitrile, for example, aromatic hydrocarbon solvents such as toluene, xylene, chlorobenzene, etc., Examples include aliphatic hydrocarbon solvents such as cyclohexane and n-heptane. The amount of water or organic solvent used is not particularly limited, but practically, it is 100 times or less the weight of the sulfide compound in view of volume efficiency and the like.

If the reaction temperature is too low, the reaction is difficult to proceed, and if the reaction temperature is too high, side reactions such as decomposition of the raw material sulfide compound or the produced sulfone compound or sulfoxide compound may proceed, so that it is practical. The reaction temperature is in the range of -20 to 100 ° C.

This reaction is usually carried out by mixing and contacting a sulfide compound, hydrogen peroxide and a metal oxide catalyst, and the mixing order is not particularly limited. Further, for example, a metal compound, hydrogen peroxide and a sulfide compound may be mixed and brought into contact with each other to carry out the operation of preparing the metal oxide catalyst and the reaction of the sulfide compound and hydrogen peroxide at the same time.

This reaction may be carried out in the presence of a phase transfer catalyst, and examples of the phase transfer catalyst include quaternary ammonium salts, quaternary phosphonium salts and macrocyclic polyethers. Quaternary ammonium salts are preferred.

Examples of the quaternary ammonium salt include trioctylmethylammonium chloride, trioctylethylammonium chloride, dilauryldimethylammonium chloride, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride,
Lauryldimethylbenzylammonium chloride, tricaprylmethylammonium chloride, tridecylmethylammonium chloride, trihexylmethylammonium chloride, tridodecylmethylammonium chloride, tetrabutylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, N-laurylpyridinium chloride , N-cetylpyridinium chloride, quaternary ammonium chlorides such as N-laurylpicolinium chloride, and chlorine ions constituting the quaternary ammonium chlorides, quaternary ammonium bromides in which bromine ions are replaced, Chloride ions that make up quaternary ammonium chlorides are quaternary ammonium iodides that have replaced iodine ions, Chlorine ion constituting the quaternary ammonium chloride is a quaternary ammonium sulfite salt replacing sulfite ion, chlorine ion constituting the quaternary ammonium chloride is a quaternary ammonium sulfate replacing sulfate ion. Examples thereof include salts and quaternary ammonium hydrogensulfates in which the chlorine ions constituting the quaternary ammonium chlorides are replaced with hydrogensulfate ions.

Examples of the quaternary phosphonium salt include tetrabutylphosphonium bromide and the like, and examples of macrocyclic polyethers include 12-crown-4, 18-crown-6 and benzo-18-crown-6. To be

The amount of the phase transfer catalyst used is usually 0.0005 mol times or more with respect to the sulfide compound, and there is no upper limit. However, in view of economical aspects, it is practically used. , For sulfide compounds, 1
It is a molar ratio or less. Further, such a phase transfer catalyst may be used when preparing the above-mentioned metal oxide catalyst in advance.

This reaction may be carried out under normal pressure conditions or under elevated pressure conditions. The progress of the reaction can be confirmed by ordinary analytical means such as gas chromatography, high performance liquid chromatography, thin layer chromatography, NMR and IR.

After 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 thiosulfate or sodium bisulfite, and then concentrated or crystallized. The target sulfone compound or sulfoxide compound can be taken out. Further, the reaction solution may contain water and / or
Alternatively, a sulfone compound or a sulfoxide compound can be taken out by adding an organic solvent insoluble in water, subjecting it to extraction treatment, and subjecting the resulting organic layer to concentration treatment. The extracted sulfone compound or sulfoxide compound may be further purified by means of distillation, column chromatography or the like.

Examples of the water-insoluble organic solvent include aromatic hydrocarbon solvents such as toluene, xylene and chlorobenzene, halogenated hydrocarbon solvents such as dichloromethane, dichloroethane and chloroform, such as diethyl ether and methyl tert-butyl ether. Examples thereof include ether solvents such as tetrahydrofuran, and ester solvents such as ethyl acetate, and the amount thereof is not particularly limited.

Further, the aqueous layer obtained by extracting the filtrate or reaction solution after the desired sulfone compound or sulfoxide compound is taken out by the crystallization treatment contains the metal oxide catalyst of this reaction, and as it is. Alternatively, it can be used again in this reaction after concentration treatment and the like if necessary.

Examples of the sulfone compound thus obtained are dimethyl sulfone, diethyl sulfone, di (n-propyl) sulfone, di (n-butyl) sulfone, di (n-amyl) sulfone, di (n-hexyl) sulfone, Di (n-heptyl) sulfone, di (n-octyl) sulfone, di (n-nonyl) sulfone, di (n-decyl) sulfone, di (n-dodecyl) sulfone, di (isopropyl) sulfone, di (isobutyl) Sulfone, di (sec-butyl) sulfone, di (tert-butyl)
Sulfone, di (isoamyl) sulfone, methylbutyl sulfone, dicyclopentyl sulfone, dicyclohexyl sulfone, dicyclododecyl sulfone, diphenyl sulfone, dibenzyl sulfone, methylphenyl sulfone,
Ethylphenyl sulfone, di (4-chlorophenyl) sulfone, di (3-methoxyphenyl) sulfone, di (2,4-dichlorophenyl) sulfone, di (4-trifluoromethylphenyl) sulfone, di (4-nitrophenyl) sulfone , (4-fluorophenyl) (4-tolyl) sulfone, (3-chlorophenyl) (4-tolyl) sulfone, (4-nitrophenyl) (4-chlorophenyl) sulfone, (2-nitrophenyl) phenylsulfone, (4 -Chloromethylphenyl) phenyl sulfone,

10,10-Dioxo-9H-thioxanthen-9-one 10,10-dioxo-3-acetamido-9H-thioxanthen-9-one 10,10-
Dioxo-3-carbomethoxy-9H-thioxanthen-9-one, phenoxathiin-10,10-dioxide, 1-ethylphenoxathiin-10,10-dioxide, 3- (2-trifluoromethylethoxy) phenoxy Sachiin-10,10-dioxide, (2-hydroxyethyl) phenyl sulfone, (chloromethyl) phenyl sulfone, (carbomethoxymethyl) phenyl sulfone,

Tetramethylene sulfone, benzo [b] thiophene sulfone, 3-chlorobenzo [b] thiophene sulfone, 3,5-dibromobenzo [b] thiophene sulfone, 3,4-dichlorobenzo [b] thiophene sulfone, 5-methylbenzo [B] thiophene sulfone,
4,7-dimethoxybenzo [b] thiophene sulfone,
3-octyloxybenzo [b] thiophene sulfone,
5-octyloxybenzo [b] thiophene sulfone,
3,5-dioctyloxybenzo [b] thiophene sulfone, 3,4-dioctyloxybenzo [b] thiophene sulfone, 4,7-dioctyloxybenzo [b] thiophene sulfone,

Dibenzothiophene-5,5-dioxide, 2,3-dioctyldibenzothiophene sulfone,
2,8-dioctyldibenzothiophene sulfone, 2,
3-dioctyloxydibenzothiophene sulfone,
2,8-Dioctyloxydibenzothiophene sulfone, 1,9-Dioctyloxydibenzothiophene sulfone, 4,6-Dioctyloxydibenzothiophene sulfone, 1,2,8,9-Tetraoctyloxydibenzothiophene sulfone, 1,4,6 , 9-Tetraoctyloxydibenzothiophene sulfone, 1,2,4
6,8,9-Hexaoctyloxydibenzothiophene sulfone, 1,3-Dioctyloxydibenzothiophene sulfone, 1,2,9-Trioctyloxydibenzothiophene sulfone, 3,4-Dioctyloxydibenzothiophene sulfone, 1,2, 3,4,6,9-hexaoctyloxydibenzothiophene sulfone, 2,3
-Dichlorodibenzothiophene sulfone, 2,8-dichlorodibenzothiophene sulfone, 2,3-difluorodibenzothiophene sulfone, 2,8-difluorodibenzothiophene sulfone,

2,3-diphenyldibenzothiophene sulfone, 2,8-diphenyldibenzothiophene sulfone, 2,3-diphenoxydibenzothiophene sulfone, 2,8-diphenoxydibenzothiophene sulfone, 2,3-dibenzyldibenzothiophene sulfone. ,
2,8-dibenzyldibenzothiophene sulfone, 2,
3-dibenzyloxydibenzothiophene sulfone,
2,8-dibenzyloxydibenzothiophene sulfone, 2,3-bis (trimethylsilyl) dibenzothiophene sulfone, 2,8-bis (trimethylsilyl) dibenzothiophene sulfone, 2,3-bis (triphenylsilyl) dibenzothiophene sulfone, 2 , 8-bis (triphenylsilyl) dibenzothiophene sulfone,
2,3-bis (tribenzylsilyl) dibenzothiophene sulfone, 2,8-bis (tribenzylsilyl) dibenzothiophene sulfone,

2,3-Diacetyldibenzothiophene sulfone, 2,8-diacetyldibenzothiophene sulfone, 2,3-diacetoxydibenzothiophene sulfone, 2,8-diacetoxydibenzothiophene sulfone, 2,3-bis (diacetylamino) Dibenzothiophene sulfone, 2,8-bis (diacetylamino) dibenzothiophene sulfone, 2,3-bis (styryl) dibenzothiophene sulfone, 2,8-bis (styryl)
Dibenzothiophene sulfone, 2,3-bis (phenylethynyl) dibenzothiophene sulfone, 2,8-bis (phenylethynyl) dibenzothiophene sulfone,
2,3-dicyanodibenzothiophene sulfone, 2,8
-Dicyanodibenzothiophene sulfone, dinaphtho [2,1-b: 1 ', 2'-d] dibenzothiophene sulfone, dianthro [2,1-b: 1', 2'-d] dibenzothiophene sulfone and the like.

Examples of the sulfoxide compound include dimethyl sulfoxide, diethyl sulfoxide, di (n-propyl) sulfoxide, di (n-butyl) sulfoxide, di (n-amyl) sulfoxide, di (n-hexyl) sulfoxide, di (n-hexyl) sulfoxide and di (n-hexyl) sulfoxide. (N-heptyl) sulfoxide, di (n-octyl) sulfoxide, di (n-nonyl) sulfoxide, di (n-decyl) sulfoxide, di (n-dodecyl) sulfoxide, di (isopropyl) sulfoxide, di (isobutyl) sulfoxide , Di (se
c-butyl) sulfoxide, di (tert-butyl) sulfoxide, di (isoamyl) sulfoxide, methylbutylsulfoxide, dicyclopentylsulfoxide, dicyclohexylsulfoxide, dicyclododecylsulfoxide, diphenylsulfoxide, dibenzylsulfoxide, methylphenylsulfoxide, ethylphenylsulfoxide , Di (4-chlorophenyl) sulfoxide,
Di (3-methoxyphenyl) sulfoxide, di (2,4
-Dichlorophenyl) sulfoxide, di (4-trifluoromethylphenyl) sulfoxide, di (4-nitrophenyl) sulfoxide, (4-fluorophenyl) (4
-Tolyl) sulfoxide, (3-chlorophenyl) (4
-Tolyl) sulfoxide, (4-nitrophenyl) (4
-Chlorophenyl) sulfoxide, (2-nitrophenyl) phenyl sulfone, (4-chloromethylphenyl)
Phenyl sulfoxide,

10-oxo-9H-thioxanthene-9
-One, 10-oxo-3-acetamido-9H-thioxanthen-9-one, 10-oxo-3-carbomethoxy-9H-thioxanthen-9-one, phenoxathiin-10-oxide, 1-ethylphenoxy. Sachiin-
10-oxide, 3- (2-trifluoromethylethoxy) phenoxathiin-10-oxide, (2-hydroxyethyl) phenyl sulfoxide, (chloromethyl)
Phenyl sulfoxide, (carbomethoxymethyl) phenyl sulfoxide, tetramethylene sulfoxide, benzo [b] thiophene sulfoxide, 3-chlorobenzo [b] thiophene sulfoxide, 3,5-dibromobenzo [b] thiophene sulfoxide, 3,4-dichlorobenzo [ b] thiophene sulfoxide, 5-methylbenzo [b] thiophene sulfoxide, 4,7-dimethoxybenzo [b] thiophene sulfoxide, 3-octyloxybenzo [b] thiophene sulfoxide, 5-octyloxybenzo [b] thiophene sulfoxide, 3, 5-
Dioctyloxybenzo [b] thiophene sulfoxide, 3,4-Dioctyloxybenzo [b] thiophene sulfoxide, 4,7-Dioctyloxybenzo [b]
Thiophene sulfoxide,

Dibenzothiophene-5-oxide, 2,
3-dioctyldibenzothiophene sulfoxide, 2,
8-dioctyldibenzothiophene sulfoxide, 2,
3-dioctyloxydibenzothiophene sulfoxide, 2,8-dioctyloxydibenzothiophene sulfoxide, 1,9-dioctyloxydibenzothiophene sulfoxide, 4,6-dioctyloxydibenzothiophene sulfoxide, 1,2,8,9-tetraoctyloxydibenzo Thiophene sulfoxide, 1,4
6,9-Tetraoctyloxydibenzothiophene sulfoxide, 1,2,4,6,8,9-hexaoctyloxydibenzothiophene sulfoxide, 1,3-Dioctyloxydibenzothiophene sulfoxide, 1,2,
9-trioctyloxydibenzothiophene sulfoxide, 3,4-dioctyloxydibenzothiophene sulfoxide, 1,2,3,4,6,9-hexaoctyloxydibenzothiophene sulfoxide,

2,3-dichlorodibenzothiophene sulfoxide, 2,8-dichlorodibenzothiophene sulfoxide, 2,3-difluorodibenzothiophene sulfoxide, 2,8-difluorodibenzothiophene sulfoxide, 2,3-diphenyldibenzothiophene sulfoxide, 2,3. 8-diphenyldibenzothiophene sulfoxide, 2,3-diphenoxydibenzothiophene sulfoxide, 2,8-diphenoxydibenzothiophene sulfoxide, 2,3-dibenzyldibenzothiophene sulfoxide, 2,8-dibenzyldibenzothiophene sulfoxide, 2,3 -Dibenzyloxydibenzothiophene sulfoxide, 2,8-dibenzyloxydibenzothiophene sulfoxide, 2,3-bis (trimethylsilyl) dibenzothi Phensulfoxide, 2,8-bis (trimethylsilyl) dibenzothiophene sulfoxide, 2,3-bis (triphenylsilyl) dibenzothiophene sulfoxide, 2,8-bis (triphenylsilyl) dibenzothiophene sulfoxide, 2,3-bis (tri) Benzylsilyl) dibenzothiophene sulfoxide, 2,8-bis (tribenzylsilyl) dibenzothiophene sulfoxide,

2,3-Diacetyldibenzothiophene sulfoxide, 2,8-diacetyldibenzothiophene sulfoxide, 2,3-diacetoxydibenzothiophene sulfoxide, 2,8-diacetoxydibenzothiophene sulfoxide, 2,3-bis (diacetylamino) Dibenzothiophene sulfoxide, 2,8-bis (diacetylamino) dibenzothiophene sulfoxide, 2,3
-Bis (styryl) dibenzothiophene sulfoxide,
2,8-bis (styryl) dibenzothiophene sulfoxide, 2,3-bis (phenylethynyl) dibenzothiophene sulfoxide, 2,8-bis (phenylethynyl) dibenzothiophene sulfoxide, 2,3-dicyanodibenzothiophene sulfoxide, 2,8 -Dicyanodibenzothiophene sulfoxide, dinaphtho [2,1-
Examples include b: 1 ′, 2′-d] dibenzothiophene sulfoxide, dianthro [2,1-b: 1 ′, 2′-d] dibenzothiophene sulfoxide, and the like.

[0073]

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 Tungsten metal 0.5 was added to 2.6 mL of water under a nitrogen atmosphere.
Add 5 g, stir at room temperature, and add 30 wt% hydrogen peroxide solution 5
g was added and further stirred to prepare a tungsten oxide catalyst aqueous solution. The internal temperature of the aqueous solution was adjusted to 40 ° C., and 1280 mL of ethanol and 44 g of 2,8-dioctyloxydibenzothiophene were added. Further, 25 g of 30 wt% hydrogen peroxide solution was added, and the mixture was stirred and reacted at an internal temperature of 45 ° C. for 5 hours. Then, the mixture was cooled with ice, 1300 mL of a 6 wt% sodium thiosulfate aqueous solution was added, and toluene was added for extraction treatment. The obtained organic layer was washed with water and then concentrated to obtain 47 g of 2,8-dioctyloxydibenzothiophene sulfone. Yield: 99%.

Example 2 A 50 mL Schlenk tube was replaced with nitrogen, and at room temperature, 8 mg of tungsten metal, 20.6 mg of methyltrioctylammonium hydrogensulfate, and 30% by weight hydrogen peroxide solution 6.1.
g, and the mixture was stirred at an internal temperature of 27 ° C. for 30 minutes to prepare a tungsten oxide catalyst aqueous solution. Diphenyl sulfide (4 g) was added dropwise to the aqueous solution over 10 minutes, and the internal temperature was adjusted to 2 ° C at 2 ° C.
The mixture was stirred, maintained, and reacted for a time. On the way, the produced diphenyl sulfone was precipitated as a solid and stirring became impossible. Therefore, 5 mL of ethyl acetate was charged and the reaction was continued. After the reaction was completed, 11.3 g of a 10 wt% sodium hydrogen sulfite aqueous solution was added to the reaction solution, and the mixture was stirred for 30 minutes, then 50 mL of ethyl acetate and n-decane (internal standard substance for analysis) were added, and the mixture was stirred, left standing, and then separated. Liquid treatment was performed, and the obtained organic layer was analyzed by gas chromatography. Diphenyl sulfone yield: 94.5% (based on diphenyl sulfide). Diphenyl sulfoxide yield: 5.4% (based on diphenyl sulfide).

Example 3 A 50 mL Schlenk tube was replaced with nitrogen, and at room temperature, 7.3 mg of tungsten metal and 30 wt% hydrogen peroxide solution were added.
6 g was charged and stirred at an internal temperature of 27 ° C. for 20 minutes to prepare a tungsten oxide catalyst aqueous solution. 14.3 mg of methyltrioctyl ammonium chloride was added to the aqueous solution,
Furthermore, 3.7 g of diphenyl sulfide was added dropwise over 10 minutes, and the mixture was stirred and held at an internal temperature of 27 ° C. for 2 hours to cause a reaction.
After the reaction was completed, 20 mL of ethyl acetate and 10.3 g of a 10 wt% sodium hydrogen sulfite aqueous solution were added, and after stirring for 30 minutes, n-decane (internal standard substance for analysis) was added, and after stirring, leaving still, liquid separation treatment The obtained organic layer was analyzed by gas chromatography. Diphenyl sulfone yield: 96.8% (based on diphenyl sulfide). Diphenyl sulfoxide yield: 3.1% (based on diphenyl sulfide).

Example 4 A 50 mL Schlenk tube was replaced with nitrogen, and at room temperature, 11 mg of tungsten metal and 30% by weight of hydrogen peroxide solution 100 were added.
mg, and the mixture was stirred at an internal temperature of 40 ° C. for 20 minutes to prepare a tungsten oxide catalyst aqueous solution. To the aqueous solution, 3 g of ethanol and 372 mg of diphenyl sulfide were added, and further 500 mg of 30 wt% hydrogen peroxide solution was added dropwise over 10 minutes, and the mixture was stirred and held at an internal temperature of 40 ° C. for 2 hours to be reacted.
After completion of the reaction, 20 mL of ethyl acetate and n-decane (internal standard substance for analysis) were added, and after stirring, the obtained solution was analyzed by gas chromatography. Diphenyl sulfone yield: 99.0% (based on diphenyl sulfide). Diphenyl sulfoxide yield: 1.0% (based on diphenyl sulfide).

Example 5 A 50 mL Schlenk tube was replaced with nitrogen, and at room temperature, 7.8 mg of tungsten metal and 30% by weight of hydrogen peroxide solution were added.
6 g was charged and stirred at an internal temperature of 27 ° C. for 20 minutes to prepare a tungsten oxide catalyst aqueous solution. 7 g of methanol and 3.9 g of diphenyl sulfide were added dropwise to the aqueous solution over 10 minutes, and the mixture was stirred and held at an internal temperature of 27 ° C. for 2 hours to cause a reaction. After the reaction was completed, 20 mL of ethyl acetate and 10.3 g of a 10 wt% sodium hydrogen sulfite aqueous solution were added, and the mixture was stirred for 30 minutes, then n-decane (an internal standard substance for analysis) was added, and the mixture was stirred, allowed to stand, and then subjected to liquid separation treatment. The obtained organic layer was analyzed by gas chromatography. Diphenyl sulfone yield: 18.8% (based on diphenyl sulfide). Diphenyl sulfoxide yield: 80.6% (based on diphenyl sulfide).

Example 6 A 50 mL Schlenk tube was replaced with nitrogen, and at room temperature, 11 mg of tungsten metal and 30% by weight of hydrogen peroxide solution 100 were added.
mg, and the mixture was stirred at an internal temperature of 40 ° C. for 20 minutes to prepare a tungsten oxide catalyst aqueous solution. To the aqueous solution, 3 g of methanol and 268 mg of benzo [b] thiophene were added, and further 500 mg of 30 wt% hydrogen peroxide solution was added over 10 minutes, and the mixture was stirred and reacted at an internal temperature of 40 ° C. for 2 hours. After completion of the reaction, 20 mL of ethyl acetate and n-decane (internal standard substance for analysis) were added, and the mixture was stirred and left standing, and then the organic layer was analyzed by gas chromatography. Benzo [b] thiophene sulfone yield: 99.5% (based on benzo [b] thiophene). Benzo [b] thiophene sulfoxide yield: 0.5%
(Based on benzo [b] thiophene).

Example 7 The same procedure as in Example 4 was carried out except that 15 mg of tungsten sulfide was used in place of 11 mg of tungsten metal and methanol was used in place of ethanol. Diphenyl sulfone yield: 99.5% (based on diphenyl sulfide). Diphenyl sulfoxide yield: 0.5% (based on diphenyl sulfide).

Example 8 Example 8 was repeated except that 12 mg of tungsten boride was used in place of 11 mg of tungsten metal and methanol was used in place of ethanol. Diphenyl sulfone yield: 69.0% (based on diphenyl sulfide). Diphenyl sulfoxide yield: 31.0% (based on diphenyl sulfide).

Example 9 The procedure of Example 4 was repeated, except that 6 mg of molybdenum metal was used in place of 11 mg of tungsten metal and methanol was used in place of ethanol. Diphenyl sulfone yield: 89.0% (based on diphenyl sulfide). Diphenyl sulfoxide yield: 11.0% (based on diphenyl sulfide).

[0083]

INDUSTRIAL APPLICABILITY According to the present invention, a sulfide compound and inexpensive hydrogen peroxide are added in the presence of a readily available tungsten metal, molybdenum metal, a tungsten compound such as tungsten boride, or a molybdenum compound such as molybdenum boride. By reacting, a sulfone compound or a sulfoxide compound can be easily obtained, and by controlling the amount of hydrogen peroxide used, either a sulfone compound or a sulfoxide compound can be selectively obtained, Industrially advantageous.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07D 333/76 C07D 333/76 (72) Inventor Takashi Miyawaki 3-1, Kasugadaka, Konohana-ku, Osaka-shi, Osaka No. 98 Sumitomo Chemical Co., Ltd. F term (reference) 4G069 AA02 AA08 BB04B BC15A BC20A BC24A BC59B BC60B BD03B BD08B CB79 FB41 4H006 AA02 AC61 BA09 BA11 BA13 BA14 BA15 BA30 BA31 BA65 BC31 BE32 TA01 TA02 4H039 CA80 CC60

Claims (15)

[Claims] 1. A tungsten compound comprising tungsten metal, molybdenum metal, tungsten and a group IIIb element, a group IVb element, a group Vb element or a group VIb element except oxygen, and molybdenum and a group IIIb element, IVb. Group elements,
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 elements or Group VIb elements excluding oxygen with hydrogen peroxide, sulfide compounds and hydrogen peroxide A method for producing a sulfone compound or a sulfoxide compound, which comprises reacting with 2. A sulfide compound is represented by the general formula (1): (In the formula, R ¹ and R ² are the same or different and each is an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group or an optionally substituted group. Which represents an alkenyl group, and R ¹ and R ² may combine with each other to form a part of a ring structure.), Wherein the sulfone compound or the sulfoxide compound is produced. Method. 3. A sulfide compound is represented by the general formula (2): (In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group or an optionally substituted group. Aryl group, optionally substituted aryloxy group, optionally substituted aralkyl group, optionally substituted aralkyloxy group, optionally substituted alkenyl group, optionally substituted arylalkenyl group An optionally substituted arylalkynyl group,
Optionally substituted silyl group, halogen atom, nitro group, cyano group, optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted amide group, optionally substituted Represents a good imido group, a carboxyl group or an optionally substituted carboalkoxy group. Here, R ³ and R ⁴ , R ⁴ and R ^5, or R ⁵ and R ⁶ may combine to form a part of the ring structure. The method for producing a sulfone compound or a sulfoxide compound according to claim 2, which is a sulfide compound represented by the formula (4). 4. The sulfide compound has the general formula (3): (In the formula, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are the same or different and each is a hydrogen atom, an optionally substituted alkyl group, or a substituted group. Optionally alkoxy group, optionally substituted aryl group, optionally substituted aryloxy group, optionally substituted aralkyl group, optionally substituted aralkyloxy group, optionally substituted Alkenyl group, optionally substituted arylalkenyl group, optionally substituted arylalkynyl group, optionally substituted silyl group, halogen atom, nitro group, cyano group, optionally substituted acyl group, Optionally substituted acyloxy group, optionally substituted amide group, optionally substituted imide group, carboxyl group or optionally substituted carbo group Represents an alkoxy group. Here, R ⁷ and R ^8, R ⁸ and R ^9, R ⁹ and R ^{1 0,} R ¹¹ and R ^12, R ¹² and R ¹³ or R ¹³ and R ¹⁴ are bonded ring structure May be formed as a part of the sulfide compound.) The method for producing a sulfone compound or a sulfoxide compound according to claim 3, which is a sulfide compound. 5. The method for producing a sulfone compound or a sulfoxide compound according to claim 1, wherein the Group IIIb element is boron. 6. The method for producing a sulfone compound or a sulfoxide compound according to claim 1, wherein the Group IVb element is carbon. 7. The method for producing a sulfone compound or a sulfoxide compound according to claim 1, wherein the Vb group element is nitrogen or phosphorus. 8. The method for producing a sulfone compound or a sulfoxide compound according to claim 1, wherein the Group VIb element other than oxygen is sulfur. 9. The method for producing a sulfone compound or a sulfoxide compound according to claim 1, wherein hydrogen peroxide water is used. 10. The method for producing a sulfone compound or a sulfoxide compound according to claim 1, wherein the reaction is carried out in the presence of a phase transfer catalyst. 11. A tungsten compound containing tungsten metal, molybdenum metal, tungsten and a group IIIb element, a group IVb element, a group Vb element or a group VIb element except oxygen, and molybdenum and a group IIIb element, IVb. A sulfide compound in the presence of a metal oxide catalyst formed by reacting hydrogen peroxide with at least one selected from the group consisting of molybdenum compounds consisting of Group V elements, Group Vb elements or Group VIb elements excluding oxygen. A method for producing a sulfone compound by reacting with hydrogen peroxide, comprising using 1.5 mole times or more of hydrogen peroxide with respect to a sulfide compound. 12. A tungsten compound comprising tungsten metal, molybdenum metal, tungsten and a group IIIb element, a group IVb element, a group Vb element or a group VIb element except oxygen, and molybdenum and a group IIIb element, IVb. A sulfide compound in the presence of a metal oxide catalyst formed by reacting hydrogen peroxide with at least one selected from the group consisting of molybdenum compounds consisting of Group V elements, Group Vb elements or Group VIb elements excluding oxygen. A method for producing a sulfoxide compound by reacting with hydrogen peroxide, characterized in that hydrogen peroxide is used in an amount of 0.8 mole times or more and less than 1.5 mole times that of the sulfide compound. Method for producing compound. 13. A tungsten compound containing tungsten metal, molybdenum metal, tungsten and a group IIIb element, a group IVb element, a group Vb element or a group VIb element except oxygen, and molybdenum and a group IIIb element, IVb. A hydrogen peroxide is reacted with at least one selected from the group consisting of molybdenum compounds consisting of Group V elements, Group Vb elements or Group VIb elements excluding oxygen, by reacting sulfide compounds with hydrogen peroxide. A metal oxide catalyst for producing a sulfone compound or a sulfoxide compound. 14. A tungsten compound containing tungsten metal, molybdenum metal, tungsten and a group IIIb element, a group IVb element, a group Vb element or a group VIb element except oxygen, and molybdenum and a group IIIb element, IVb. A sulfide compound and hydrogen peroxide are reacted by reacting at least one selected from the group consisting of molybdenum compounds consisting of Group V elements, Group Vb elements or Group VIb elements excluding oxygen with aqueous hydrogen peroxide. An aqueous metal oxide catalyst solution for producing a sulfone compound or a sulfoxide compound. 15. A metal oxide catalyst solution for producing a sulfone compound or a sulfoxide compound by reacting a sulfide compound and hydrogen peroxide, which comprises the aqueous solution of the metal oxide catalyst according to claim 14 and an organic solvent.