JP2002069079A - Catalyst compound, catalyst composition and method for producing epoxy compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst compound having high selectivity of epoxy compound and enabling easy recovery and reuse, a catalyst composition containing the catalyst compound and a method for producing an epoxy compound from an olefin by using the catalyst composition and easily available and handleable dilute hydrogen peroxide solution. SOLUTION: The catalyst compound is a ketone compound expressed by general formula (1); -Si(R1R2)-Y-A-CO-B-X (Si is silicon atom; R1 and R2 are each the same or different lower alkyl; Y is (CH2)nO, PhO or PhCH2O; (n) is an integer of 1-10; Y is bonded to A through oxygen atom; A and B are each benzene ring or CH(R3R4); R3 and R4 are each the same or different H, a halogen or a lower alkyl; and X is a halogen atom, CN or amide group) wherein the terminal Si of the ketone compound is supported on activated carbon or inorganic carrier through the oxygen atom of the activated carbon or the inorganic carrier. The invention further provides a catalyst composition containing the catalyst compound and hydrotalcite and a method for producing an epoxy compound from an olefin by using the catalyst composition and hydrogen peroxide solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel catalyst compound in which a specific ketone compound is supported on activated carbon or an inorganic carrier, a catalyst composition, and a method for producing an epoxy compound using the same. More specifically, the present invention relates to an epoxidation reaction from an olefin produced by using a low-concentration hydrogen peroxide solution to produce an epoxy compound useful as a synthetic intermediate for an epoxy resin raw material, an organic chemical, a medicine, an agricultural chemical, or the like. The present invention relates to a catalyst compound having a specific ketone compound supported on activated carbon or an inorganic carrier, a catalyst composition, and a method for producing an epoxy compound using the catalyst compound, which is useful for various reactions of the above.

[0002]

2. Description of the Related Art Epoxy compounds are useful as raw materials for epoxy resins and as synthetic intermediates for various organic chemicals, medicines, agricultural chemicals and the like. In the epoxidation reaction of olefins with hydrogen peroxide used as a method for producing these epoxy compounds, it is generally known that both the conversion of olefins and the selectivity to epoxides are low.

[0003] The conversion is low because hydrogen peroxide remains unreacted in low-temperature reactions, decomposes at high temperatures to generate oxygen, and is not effectively consumed in the reaction. In addition, the low selectivity to epoxide is due to water introduced into the reaction system together with hydrogen peroxide and water generated by the reaction, and a polyol is by-produced by a hydrolysis reaction.

Heretofore, in producing the corresponding epoxide by reacting olefins with hydrogen peroxide, there has been proposed a method of using a specific catalyst to solve the above problems [KA Jorg (KA Jorg).
ensen), Chemical Rev., 89
No. 431, 1989]. For example, there is a method using a ketone catalyst (MCA van Vliet, et al., Chemical Communication (Chem. Commun.,), P. 263, 1999).
Year〕.

However, the conventional method for producing an epoxide requires the use of a high concentration (60%) aqueous hydrogen peroxide solution in which it is difficult to recover the catalyst used in the reaction.
Low catalyst efficiency (turnover number is 20 or less),
There have been various problems from an industrial point of view, such as the need for a buffer, and from the viewpoint of protecting the global environment.

[0006]

The problem to be solved by the present invention is to provide a catalyst compound having high selectivity to an epoxy compound and easy to recover and reuse, a catalyst composition using the catalyst compound, and An object of the present invention is to provide a method for producing an epoxy compound from an olefin using these and a low-concentration aqueous hydrogen peroxide solution which is easily available and handled.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, a catalyst compound in which a ketone compound having a specific structure is supported on activated carbon or an inorganic solid; By reacting olefins and low-concentration hydrogen peroxide in an organic solvent using a catalyst composition consisting of and hydrotalcite, a type of layered clay mineral, only epoxides can be selectively produced. The present inventors have found that it is easy to collect and reuse the same, and have completed the present invention.

That is, the present invention relates to (1) a compound represented by the general formula (1) wherein —Si at the terminal of the ketone compound is activated carbon or an inorganic carbon, A catalyst compound bonded to a silicon atom and supported on activated carbon or an inorganic carrier;

General formula (1)

## STR4 ## -Si (R ₁ R ₂ ) -YA-CO-BX

(Wherein, Si is a silicon atom, R ₁ and R ₂ are the same or different lower alkyl groups, Y is — (CH ₂ ) n O—, Ph
O— or PhCH ₂ O—, n is an integer of 1 to 10, Y is bonded to A via an oxygen atom, A and B are a benzene ring or —CH (R ₃ R ₄ ), Where R ₃ and R ₄
Are the same or different and are each a hydrogen atom, a halogen atom or a lower alkyl group, and X is a halogen atom, -CN
Group or amide group)

(2) The catalyst compound according to (1), wherein the inorganic carrier is at least one selected from the group consisting of alumina, silica gel, florisil, celite, and molecular sieves;

(3) reacting the ketone compound represented by the general formula (2) with one or more carriers selected from the group consisting of activated carbon, alumina, silica gel, florisil, celite, and molecular sieves;

General formula (2)

## STR00005 ## -X ₁ -Si (R ₁ R ₂ ) -YA-CO-BX ₂

(Wherein, Si is a silicon atom, R ₁ and R ₂ are the same or different lower alkyl groups, Y is — (CH ₂ ) nO—,
PhO- or PhCH ₂ is O-, n is an integer of 1 to 10, Y is bonded to A through an oxygen atom, A and B are benzene rings, or -CH (R ₃ R _4), R ₃ and R ₄ are the same or different and are each a hydrogen atom, a halogen atom or a lower alkyl group, X ₁ is a halogen atom or an alkoxy group, and X ₂ is a halogen atom, a —CN group, or an amide group. is there)

A ketone compound represented by the general formula (1):

## STR6 ## -Si (R ₁ R ₂ ) -YA-CO-BX

(Wherein, Si is a silicon atom, R ₁ R ₂ are the same or different lower alkyl groups, Y is — (CH ₂ ) n O—, P
hO- or PhCH ₂ is O-, n is an integer of 1 to 10, Y is bonded to A through an oxygen atom, A and B are benzene rings, or -CH (R ₃ R _4), Where R ₃ and R ₄
Are the same or different and each is a hydrogen atom, a halogen atom or a lower alkyl group, and X is a halogen atom, -CN
Group or amide group)

A method for producing a catalyst compound supported on activated carbon or an inorganic carrier, wherein -Si at the terminal is bonded to a carbon atom of activated carbon or a silicon atom of an inorganic carrier via an oxygen atom in activated carbon or an inorganic carrier,

(4) A catalyst composition comprising (A) the catalyst compound described in (1) or (2) above and (B) hydrotalcite.

(5) The weight ratio of the catalyst compound (A) described in the above (1) or (2) to the hydrotalcite (B) is 0.2 to 1.2. A catalyst composition of

(6) A method for producing an epoxy compound from an olefin, using the catalyst compound according to the above (1) or (2) and hydrogen peroxide;

(7) A method for producing an epoxy compound from an olefin using the catalyst composition according to the above (4) or (5) and hydrogen peroxide;

(8) For 1 mol of the olefin,
The method for producing an epoxy compound from the olefins according to (6), wherein the catalyst compound according to (1) or (2) is used in an amount of 0.0005 mol to 0.5 mol,

(9) For 1 mol of the olefin,
(7) The method for producing an epoxy compound from olefins according to (7), wherein 0.0005 mol to 0.5 mol of the catalyst compound in the catalyst composition according to (4) or (5) is used.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The catalyst compound of the present invention comprises a ketone compound represented by the following general formula (2):

General formula (2)

Embedded image —X ₁ —Si (R ₁ R ₂ ) -YA-CO-BX ₂

(Wherein, Si is a silicon atom, R ₁ and R ₂ are the same or different lower alkyl groups, Y is — (CH ₂ ) nO—,
PhO- or PhCH ₂ is O-, n is an integer of 1 to 10, Y is bonded to A through an oxygen atom, A and B are benzene rings, or -CH (R ₃ R _4), R ₃ and R ₄ are the same or different and are each a hydrogen atom, a halogen atom or a lower alkyl group, X ₁ is a halogen atom or an alkoxy group, and X ₂ is a halogen atom, a —CN group, or an amide group. is there)

Reaction with one or more carriers selected from the group consisting of activated carbon, alumina, silica gel, florisil, celite and molecular sieves, the -Si at the terminal of the ketone compound represented by the general formula (1) is activated carbon or By bonding to a carbon atom of activated carbon or a silicon atom of an inorganic carrier via an oxygen atom in an inorganic carrier, a catalyst compound supported on activated carbon or an inorganic carrier and a catalyst composition comprising the catalyst compound and hydrotalcite is there.

General formula (1)

## STR8 ## -Si (R ₁ R ₂ ) -YA-CO-BX

(Wherein, Si is a silicon atom, R ₁ and R ₂ are the same or different lower alkyl groups, Y is — (CH ₂ ) nO—,
PhO- or PhCH ₂ is O-, n is an integer of 1 to 10, Y is bonded to A through an oxygen atom, A and B are benzene rings, or -CH (R ₃ R _4), Here, R ₃ and R ₄ are the same or different and are each a hydrogen atom, a halogen atom or a lower alkyl group, and X is a halogen atom, -C
N group or amide group)

In the general formula (2), X ₁ is a halogen atom or an alkoxy group, preferably a halogen atom having high reactivity with activated carbon and an inorganic solid, particularly preferably a chlorine atom or a bromine atom. R ₁ and R ₂ is a lower alkyl group such as methyl group, ethyl group, is a propyl group, since there is no significant difference in the reactivity of the olefin by the difference R ₁ and R _2, and R ₁ R ₂ is not particularly limited. R ₁ and R ₂ may be different groups or the same group.

Y is-(CH ₂ ) nO-, PhO- or PhCH ₂ O-, and n is an integer of 1-10. n
Is preferably 5 to 10, and particularly preferably 7 to 10. A and B are benzene rings, or _{-CH (R 3 R 4),} R 3
And R ₄ are a hydrogen atom, a halogen atom or a lower alkyl group. A and B may be the same or different, and it is preferable that zero to all of the hydrogen atoms bonded to the benzene ring are substituted with halogen atoms, particularly fluorine atoms, and those in which all hydrogen atoms are substituted with fluorine atoms are preferred. Most preferred.

R ₃ and R ₄ are a hydrogen atom, a halogen atom or a lower alkyl group. As the halogen atom, chlorine and fluorine are preferred, and fluorine is particularly preferred. Examples of the lower alkyl group include a methyl group, an ethyl group, and a propyl group, but R ₃ and R ₄ are not particularly limited because there is no significant difference in the reactivity of the olefin due to the difference between R ₃ and R _4. is not. R ₃ and R ₄ may be different groups or the same group.

X ₂ is a halogen atom, a —CN group, or an amide group. As the halogen atom, a bromine atom and a fluorine atom are preferable, and a fluorine atom is particularly preferable. The amide group is not particularly limited as long as it does not react with hydrogen peroxide.

The method for preparing the ketone compound represented by the general formula (2) is not particularly limited, but a halosilane is reacted with a compound obtained by condensation of a hydroxybenzophenone derivative with a halogenated olefin. The method is simple and recommended. [CW Frank, Journal of American Chemical Society (J. Am. Chem. Soc.,) No. 121
No., 8766, 1999].

The ketone compound represented by the general formula (2) was prepared by using activated carbon, alumina, silica gel, florisil,
When reacting with one or more supports selected from the group consisting of celite and molecular sieves, usually, the ketone compound represented by the general formula (2) is previously converted into a suitable solvent (hereinafter, this solvent is referred to as a catalyst preparation solvent). ), And then a carrier is added thereto, and the mixture is vigorously stirred at a predetermined temperature, and then the solvent is distilled off and dried.

The predetermined temperature during stirring is from room temperature to 120 ° C.
Although it is about ° C., the temperature is not limited to this, and may be any value as long as it is lower than the boiling point of the catalyst preparation solvent used. The stirring time at this time is not particularly limited, but is usually 10 minutes.
Minutes to about 7 hours. The drying temperature is not particularly limited as long as the catalyst preparing solvent used can be removed, but if the drying temperature is too high, the catalyst activity may be reduced or deactivated. It is preferably slightly higher than the boiling point of the solvent for preparation. The drying step may be performed not only under normal pressure but also under reduced pressure, and may be performed under an atmosphere of an inert gas such as argon other than air or nitrogen.

The hydrotalcite constituting the catalyst composition of the present invention is a kind of basic layered clay mineral, and is, for example, represented by the following general formula (3)

[Omitted] ^{_{[M 1 2+ 1? X M}} 2 3+ x (OH) 2] x + [X n? X / n mH 2 O] x? ( In the formula, M ₁ and M ₂ is Mg (magnesium atom ) And Al
A metal atom such as (aluminum atom), X is a nitrate ion, a chloride ion, a sulfate ion, etc., m is an integer of 2 or 3, and a small letter x represents the valence of the ion). Clay Minerals (Clays Clay M
iner.,) "(No. 28, p. 50, 1980).

[0038] Specific examples of these hydrotalcites, _{e.g., Mg 10 Al 2 (OH)} 2 4 CO 3, Mg 5 Al
(OH) ₁₁ CO ₃ , Mg ₆ Al ₂ (OH) ₁₆ CO ₃ , Mg ₆
Al ₂ (OH) ₁₆ SO ₄ , Mg ₆ Al ₂ (OH) ₁₆ Cl, M
g ₆ Al ₂ (OH) ₁₆ NO _{3 and the} like.

The olefins in the present invention are represented by the following general formula (4)

[0040]

Embedded image

(Wherein R ₁ ′, R ₂ ′, R ₃ ′ and R ₄ ′ are monovalent hydrocarbon groups which may have a double bond,
R ₁ ′ and R ₂ ′ or R ₃ ′ and R ₄ ′ together represent a divalent hydrocarbon group which may have a double bond, or R ₁ ′ and R ₃ ′ or R ₂ ′ and R ₄ ′ together represent a divalent hydrocarbon group which may have a double bond).

In the general formula (4), R ₁ ′, R ₂ ′, R
₃ ′ and R ₄ ′ are a monovalent hydrocarbon group which may have a double bond, and examples of the hydrocarbon group include an aliphatic hydrocarbon group, for example, a linear or branched hydrocarbon group having 1 to 30 carbon atoms. An alkyl group or an alkenyl group; an alicyclic hydrocarbon group, for example,
Examples thereof include a cycloalkyl group, a cycloalkenyl group, or a polycycloalkyl group having 3 to 12 carbon atoms which may be branched; and an aromatic hydrocarbon group, for example, an aryl group or an alkaliol group.

R ₁ ′ and R ₂ ′ or R ₃ ′ and R ₄ ′ may be taken together as a divalent hydrocarbon group which may have a double bond, a group having 3 to 11 carbon atoms ( Alkylene group, alkenylene group, etc.). R ₁ ′ and R ₃ ′ or
Examples of the divalent hydrocarbon group which may have a double bond together with R ₂ ′ and R ₄ ′ include a group having 1 to 10 carbon atoms (such as an alkylene group and an alkenylene group).

Specific examples of the olefin represented by the general formula (4) are as follows. A. Aliphatic olefinic hydrocarbon (1) Alkene Ethylene, propylene, butene, pentene, 1-hexene, 3-hexene, 1-heptene, 1-octene, 1-
Nonene, 1-undecene, 1-dodecene, 1-tridecene, 1-etradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-icosene, diisobutylene, and propylene Mers, etc.

(2) Terpene such as polyene myrcene; polybutadiene; B. Aromatic olefin hydrocarbons Styrene, α-methylstyrene, divinylbenzene, stilbene and the like.

C. Alicyclic olefinic hydrocarbons cycloalkenes or cyclopolyenes such as cyclopentene, cyclohexene, 1-phenyl-1-cyclohexene, 1-methyl-1-cyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclopentadiene, Cyclooctadiene, cyclododecatriene and the like;
Dicycloalkapolyenes, for example, dicyclopentadiene, tetrahydroindene and the like; alkylenecycloalkanes, for example, methylenecyclopropane, methylenecyclopentane, methylenecyclohexene and the like;

Vinylcycloalkenes such as vinylcyclohexene; cyclic terpenes such as α-limonene, pyrene and camphene; norbornene compounds such as norbornene, methylnorbornene, ethylnorbornene, vinylnorbornene and ethylidene norbornene. The olefins used in the present invention are not limited to the compounds exemplified here. The above olefins can be used as a mixture of two or more.

The hydrogen peroxide used in the present invention may be a general-purpose hydrogen peroxide, and an aqueous solution having a concentration of usually 3 to 70% by weight can be used. When using hydrogen peroxide at a concentration of 35% or more, the reaction time is shortened, but the selectivity of the epoxide is reduced by a side reaction. Is preferred. When using hydrogen peroxide having a concentration of 35% or more, it is possible to selectively synthesize an epoxide by lowering the reaction temperature.

As described above, one of the features of the present invention is that the reaction proceeds efficiently by using hydrogen peroxide having a concentration of 35% or less which is inexpensive and easy to handle as compared with the conventional method. One. In reacting the olefins with hydrogen peroxide, the ratio between the olefins and hydrogen peroxide may be equimolar, but one of the raw materials may be too small or too large. That is, for producing an epoxy compound from the olefins of the present invention, usually about 0.1 to 5 mol of hydrogen peroxide, more preferably 0.1 to 5 mol per mol of olefin.
7 to 2 moles of hydrogen peroxide are used.

The amount of the ketone catalyst used in the production of the epoxy compound from the olefin of the present invention is 1
0.0005 to 0.5 mol, preferably 0.001 to 0.1 mol, more preferably 0.0
04 to 0.05 mol.

The terminal -Si of the ketone compound represented by the general formula (1) is bonded to the carbon atom of the activated carbon or the silicon atom of the inorganic carrier via an oxygen atom in the activated carbon or the inorganic carrier to form the activated carbon or the inorganic carrier. The catalyst compound supported on is a ketone compound represented by the general formula (2) in an amount of 5 mmol to 100 g of at least one support selected from the group consisting of activated carbon, alumina, silica gel, florisil, celite, and molecular sieves. It can be obtained by reacting in the range of 150 mmol, preferably in the range of 30 to 130 mmol, and more preferably in the range of 50 to 110 mmol.

The amount of hydrotalcite used in the catalyst composition of the present invention together with the catalyst compound represented by the general formula (1) in which the ketone compound is supported on activated carbon or an inorganic carrier is 5 g per mole of olefin. To 100 g, preferably 10 g to 80 g, more preferably 20 g to 50 g.
g. The weight ratio between the ketone catalyst and the hydrotalcite is in the range of 0.2 to 1.2.

The solvent used in the production of the epoxy compound from the olefins of the present invention is an organic solvent, and the amount of the organic solvent used is arbitrary. Usually, about 100 ml to 5000 ml per 1 mol of the olefin. is there. As the organic solvent, one that is as inert as possible to the reactants (olefins, hydrogen peroxide) and the produced epoxide is used.

For example, alcohols (primary, secondary and tertiary alcohols having 1 to 6 carbon atoms, for example, methanol,
Ethanol, normal or isopropanol, tertiary butanol, amyl alcohol, cyclohexanol, etc., polyhydric alcohols (ethylene glycol, propylene glycol, glycerin, etc.), polyhydric alcohol derivatives (ethylene oxide, oligomers of propylene oxide such as diethylene glycol, triethylene) Glycol, dipropylene glycol; ethers of this oligomer, for example, dimethoxyethylene glycol, diethoxyethylene glycol, dimethoxydiethylene glycol, etc.),

Ethers (eg, ethyl ether, isopropyl ether, dioxane, tetrahydrofuran), nitrogen compounds (eg, dimethylformamide, nitromethane), phosphorus compounds (eg, phosphoric acid esters such as triethyl, trioctyl, and diethylhexyl esters), and halogenated carbons Hydrogen (chloroform, dichloromethane, ethylene dichloride, etc.), aliphatic hydrocarbons (normal hexane, normal heptane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), alicyclic hydrocarbons (cyclohexane, cyclopentane, etc.), etc. Can be used.

Among these, preferred solvents are alcohols and ethers which are hydrophilic solvents, and alcohol is particularly preferred. These solvents may be used alone or in combination of two or more.

The reaction is carried out in an oxygen-containing gas atmosphere or an inert gas atmosphere. When the reaction scale is large, there is a danger of explosion in the oxygen-containing gas atmosphere. It is preferable to carry out. Also,
The order in which the raw materials such as olefins, catalyst, reaction solvent, hydrogen peroxide and the like are charged into the reaction tank (order of charging) is arbitrary, and they may be charged all at once or sequentially.

In the case of epoxidation of olefins having low reactivity, the reaction can be efficiently advanced by dropping olefins into a mixture of a catalyst, a reaction solvent and hydrogen peroxide. . The reaction temperature is usually 0 to
The temperature is 120 ° C, preferably 20 to 110 ° C.
When the reaction temperature is higher than 110 ° C., the self-decomposition of hydrogen peroxide is remarkable, and the selectivity of the epoxide is reduced. If the temperature is lower than 0 ° C., the reaction becomes slow.

The reaction time varies depending on the catalyst, solvent, olefin, hydrogen peroxide concentration and the like used, but is usually from several minutes to 24 hours. After the reaction, the catalyst can be easily catalyzed by filtration, and after separating the catalyst, the desired epoxy compound can be obtained by removing water and the solvent by extraction or / and distillation. The catalyst separated by filtration can be repeatedly used by washing and drying.

The catalyst compound represented by the general formula (1) of the present invention, in which the ketone compound is supported on activated carbon or an inorganic carrier, and the catalyst composition containing the catalyst compound and hydrotalcite, are obtained from olefins. Not only the production of epoxy compounds, but also various oxidation reactions, such as the synthesis of carboxylic acids by oxidation of aldehydes, the synthesis of quinones by oxidation of phenol derivatives, benzene derivatives or naphthalene derivatives, and the nitrones by oxidation of tertiary amines It is useful for the synthesis of sulfone, the synthesis of sulfone by oxidation of sulfide, the synthesis of sulfoxide by oxidation of sulfone, and is particularly useful for the synthesis of sulfone by oxidation of sulfide.

[0061]

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

(Example 1) [CW Frank, Journal of American Chemical Society (J. Am. Chem. Soc.,) No. 121;
8766, 1999] and referring to the synthesis method of the ketone compound “4- (3′-chlorodimethylsilyl) proproxybenzophenone”, the ketone compound “4- (3′-chlorodimethylsilyl) octyloxy”. -4'-fluorobenzophenone "was synthesized.

In a 100 mL round bottom flask,
-Fluoro-4'-hydroxybenzophenone (4.3
2 g, 20 mmol), 8-bromo-1-octene
(4.20 g, 22 mmol), potassium carbonate (3.04).
g, 22 mmol) and acetone (12 ml).
The mixture was refluxed for 8 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was cooled to room temperature, distilled water (8 ml) was added, and dichloromethane (20 ml) was added.
mL × 3). After washing with a 10% aqueous sodium hydroxide solution (50 ml), anhydrous magnesium sulfate was added and dried.

The concentrate was recrystallized from methanol (30 ml) to give 4-fluoro-4'-7-octenoxybenzophenone as a pale yellow solid (6.33 g, 97%). In a 100 ml round bottom flask, at room temperature, 4-fluoro-4'-7-octenoxybenzophenone (3.26 g, 10 mmol), chlorodimethylsilane (19 g, 200 mmol) and 10% by weight
Pt-C (10 mg) was added, and the mixture was refluxed for 5 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was cooled to room temperature, and excess chlorodimethylsilane was distilled off under reduced pressure to give 4-
(3'-chlorodimethylsilyl) octyloxy-4'-
Fluorobenzophenone was obtained as a colorless liquid (4.
21 g, 100%).

In a 100 ml round bottom flask,
-(3'-chlorodimethylsilyl) octyloxy-4 '
-Fluorobenzophenone (2.11 g, 5 mmol
l), triethylamine (0.557 g, 5.5 mmol)
l), silica gel (5 g) and toluene (50 ml) were added, and the mixture was refluxed for 5 hours under a nitrogen atmosphere. After the completion of the reaction, the mixture was cooled to room temperature and filtered. The solid filtered off is mixed with toluene (50
After washing with (ml × 2), the resultant was dried under reduced pressure at 100 ° C. for 5 hours to obtain a target catalyst (hereinafter, referred to as ketone 1 catalyst).

In a 10 ml round bottom flask, at room temperature, Mg
₁₀ Al ₂ (OH) ₂₄ CO ₃ (100 mg), cyclohexene (0.246 g, 3 mmol), ketone 1 catalyst (42
mg, 1 mol%), 30% hydrogen peroxide aqueous solution (1.3
6 g, 12 mmol) and methanol (2 ml), and the mixture was vigorously stirred at 80 ° C. for 8 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was cooled to room temperature and filtered. A saturated aqueous solution of sodium thiosulfate (10 ml) and dichloromethane (10 mL) were added to the filtrate.
ml), the aqueous phase and the organic phase were separated, and the aqueous phase was extracted with dichloromethane (10 ml × 2) and combined with the filtrate.

After adding anhydrous magnesium sulfate and drying, the mixture was concentrated, and the concentrated solution was analyzed by gas chromatography. As a result, the conversion of cyclohexene was 72%, and the desired epoxide (cyclohexene oxide) was obtained.
Was> 99%. Gas chromatography measurement conditions: O
V-1 column (0.258 mm × 30 m), column temperature 40 ° C. to 250 ° C. (heating rate, 5 ° C./min).

Comparative Example 1 In the epoxidation reaction described in Example 1, ketone 1 catalyst (42 mg, 1 mol
%) Instead of 4- (3′-chlorodimethylsilyl) octyloxy-4′-fluorobenzophenone (13 m
g, 1 mol%) except that the reaction was carried out in the same manner as in Example 1. As a result of analyzing the concentrated solution of the extract using gas chromatography, the conversion of cyclohexene was 29.
%, And the selectivity of the target epoxide (cyclohexene oxide) was 68%.

Comparative Example 2 In the epoxidation reaction described in Example 1, Mg ₁₀ Al ₂ (OH) ₂₄ CO ₃ (100
mg)), except that sodium hydroxide (100 mg) was used. As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of cyclohexene was 5%, and the selectivity of the target epoxide (cyclohexene oxide) was 58%.
%Met.

Comparative Example 3 In the epoxidation reaction described in Example 1, Mg ₁₀ Al ₂ (OH) ₂₄ CO ₃ (100
mg), the reaction was carried out in the same manner as in Example 1 except that potassium hydroxide (100 mg) was used. As a result of analyzing the concentrated solution of the extract using gas chromatography,
The conversion of cyclohexene was 6%, and the selectivity of the target epoxide (cyclohexene oxide) was 62%.

Comparative Example 4 In the epoxidation reaction described in Example 1, Mg ₁₀ Al ₂ (OH) ₂₄ CO ₃ (100
The reaction was carried out in the same manner as in Example 1 except that triethylamine (100 mg) was used instead of (mg). As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of cyclohexene was 3%, and the selectivity of the target epoxide (cyclohexene oxide) was 73%.
%Met.

(Example 2) In the epoxidation reaction described in Example 1, Mg ₁₀ Al ₂ (OH) ₂₄ CO ₃ (100
The reaction was carried out in the same manner as in Example 1 except that mg) was not added. As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of cyclohexene was 7%, and the target epoxide (cyclohexene oxide) was obtained.
Was 98%.

Example 3 In the epoxidation reaction described in Example 1, Mg ₁₀ Al ₂ (OH) ₂₄ CO ₃ (100
mg), Mg ₅ Al (OH) ₁₁ CO ₃ (100 m
The reaction was carried out in the same manner as in Example 1 except that g) was used.
As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of cyclohexene was 66%, and the selectivity of the target epoxide (cyclohexene oxide) was> 99%.

(Example 4) In the epoxidation reaction described in Example 1, Mg ₁₀ Al ₂ (OH) ₂₄ CO ₃ (100
mg), Mg ₆ Al ₂ (OH) ₁₆ CO ₃ (100
The reaction was carried out in the same manner as in Example 1 except that mg) was used. As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of cyclohexene was 59%, and the target epoxide (cyclohexene oxide) was obtained.
Was> 99%.

(Example 5) In the epoxidation reaction described in Example 1, Mg ₁₀ Al ₂ (OH) ₂₄ CO ₃ (100
mg), Mg ₆ Al ₂ (OH) ₁₆ SO ₄ (100
The reaction was carried out in the same manner as in Example 1 except that mg) was used. As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of cyclohexene was 53%, and the target epoxide (cyclohexene oxide) was obtained.
Was> 99%.

Example 6 According to the catalyst preparation method described in Example 1, the catalyst described in Example 1 was replaced with 4-
(3'-chlorodimethylsilyl) octyloxy-4'-
A catalyst having chlorobenzophenone immobilized on silica gel was prepared (Ketone 2 catalyst).

In the epoxidation reaction described in Example 1, ketone 1 catalyst (42 mg, 1 mol%) was used in place of ketone 1 catalyst.
The reaction was carried out in the same manner as in Example 1 except that ketone 2 catalyst (42 mg, 1 mol%) was used. As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of cyclohexene was 49%, and the selectivity of the target epoxide (cyclohexene oxide) was> 99%.

Example 7 According to the catalyst preparation method described in Example 1, the catalyst described in Example 1 was replaced with 4-
A catalyst in which (3′-chlorodimethylsilyl) octyloxybenzophenone was immobilized on silica gel was prepared (ketone 3 catalyst).

In the epoxidation reaction described in Example 1, ketone 1 catalyst (42 mg, 1 mol%) was used instead of
The reaction was carried out in the same manner as in Example 1 except that ketone 3 catalyst (41 mg, 1 mol%) was used. As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of cyclohexene was 29%, and the selectivity of the target epoxide (cyclohexene oxide) was> 99%.

Example 8 According to the catalyst preparation method described in Example 1, the catalyst described in Example 1 was replaced with 4-
(3'-chlorodimethylsilyl) octyloxy-4'-
A catalyst in which fluorobenzophenone was immobilized on alumina was prepared (ketone 4 catalyst).

In the epoxidation reaction described in Example 1, the ketone 1 catalyst (42 mg, 1 mol%) was replaced with
The reaction was carried out in the same manner as in Example 1 except that ketone 4 catalyst (42 mg, 1 mol%) was used. As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of cyclohexene was 71%, and the selectivity of the target epoxide (cyclohexene oxide) was> 99%.

Example 9 According to the catalyst preparation method described in Example 1, the catalyst described in Example 1 was replaced with 4-
(3'-chlorodimethylsilyl) octyloxy-4'-
A catalyst in which fluorobenzophenone was immobilized on Florisil was prepared (Ketone 5 catalyst).

In the epoxidation reaction described in Example 1, the ketone 1 catalyst (42 mg, 1 mol%) was replaced with
The reaction was carried out in the same manner as in Example 1 except that ketone 5 catalyst (42 mg, 1 mol%) was used. As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of cyclohexene was 72%, and the selectivity of the target epoxide (cyclohexene oxide) was> 99%.

Example 10 According to the catalyst preparation method described in Example 1, the catalyst described in Example 1 was replaced with 4-
(3'-chlorodimethylsilyl) octyloxy-4'-
A catalyst in which fluorobenzophenone was immobilized on Celite was prepared (ketone 6 catalyst).

In the epoxidation reaction described in Example 1, the ketone 1 catalyst (42 mg, 1 mol%) was replaced with
The reaction was carried out in the same manner as in Example 1 except that ketone 6 catalyst (42 mg, 1 mol%) was used. As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of cyclohexene was 71%, and the selectivity of the target epoxide (cyclohexene oxide) was> 99%.

Example 11 According to the catalyst preparation method of Example 1, the catalyst described in Example 1 was used instead of 4- (3'-
A catalyst in which chlorodimethylsilyl) octyloxy-4′-fluorobenzophenone was immobilized on molecular sieves was prepared (ketone 7 catalyst).

In the epoxidation reaction described in Example 1, the ketone 1 catalyst (42 mg, 1 mol%) was replaced with
The reaction was carried out in the same manner as in Example 1 except that ketone 7 catalyst (42 mg, 1 mol%) was used. As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of cyclohexene was 72%, and the selectivity of the target epoxide (cyclohexene oxide) was> 99%.

(Example 12) In the epoxidation reaction described in Example 1, a 30% aqueous hydrogen peroxide solution (1.36%) was used.
g, 12 mmol) and a 15% aqueous hydrogen peroxide solution (2.72 g, 12 mmol), and the reaction was carried out in the same manner as in Example 1 except that the reaction time was changed to 20 hours instead of 7 hours. . As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of cyclohexene was 6%.
5%, and the selectivity of the target epoxide (cyclohexene oxide) was> 99%.

Example 13 The epoxidation reaction described in Example 1 was carried out in the same manner as in Example 1 except that ethanol (2 ml) was used instead of methanol (2 ml). As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of cyclohexene was found to be 7%.
0%, and the selectivity of the target epoxide (cyclohexene oxide) was> 99%.

Example 14 In the epoxidation reaction described in Example 1, the reaction was carried out in the same manner as in Example 1 except that propanol (2 ml) was used instead of methanol (2 ml). As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of cyclohexene was 69%, and the selectivity of the target epoxide (cyclohexene oxide) was> 99%.

Example 15 The procedure of Example 1 was repeated, except that in the epoxidation reaction described in Example 1, methanol (2 ml) was replaced by etrahydrofuran (2 ml).
The reaction was carried out in the same manner as described above. As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of cyclohexene was 45%, and the selectivity of the target epoxide (cyclohexene oxide) was> 99%.

(Example 16) In the epoxidation reaction described in Example 1, Mg ₁₀ Al ₂ (OH) ₂₄ CO ₃ (10
0 mg) instead of Mg ₁₀ Al ₂ (OH) ₂₄ CO ₃ (50
The reaction was carried out in the same manner as in Example 1 except that mg) was used. As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of cyclohexene was 50%, and the target epoxide (cyclohexene oxide) was obtained.
Was> 99%.

(Example 17) In the epoxidation reaction described in Example 1, Mg ₁₀ Al ₂ (OH) ₂₄ CO ₃ (10
0 mg) instead of Mg ₁₀ Al ₂ (OH) ₂₄ CO ₃ (70
The reaction was carried out in the same manner as in Example 1 except that mg) was used. As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of cyclohexene was 62%, and the target epoxide (cyclohexene oxide) was obtained.
Was> 99%.

Example 18 In a 1 L round-bottomed flask, at room temperature, Mg ₁₀ Al ₂ (OH) ₂₄ CO ₃ (10 g), cyclohexene (24.6 g, 0.3 mol), ketone 1 catalyst (4.2 g) , 1 mol%), 30% aqueous hydrogen peroxide (136 g, 1.2 mol) and methanol (200 m
l) was added and the mixture was vigorously stirred at 80 ° C. for 12 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was cooled to room temperature and filtered.

To the filtrate was added dichloromethane (500 ml), and the aqueous and organic phases were separated. The aqueous phase was extracted with dichloromethane (200 ml × 2), combined with the organic phase, dried over anhydrous magnesium sulfate, and dried. As a result of analyzing the concentrated solution using gas chromatography, the conversion of cyclohexene was 72%, and the selectivity of the target epoxide (cyclohexene oxide) was> 99%. Gas chromatography measurement conditions: OV-1 column (0.258 mm × 30
m), column temperature 40 ° C to 250 ° C (heating rate, 5 ° C /
Minutes).

Next, the reuse of the recovered solid catalyst and aqueous phase was examined. In a 1 L round bottom flask, add Mg
₁₀ Al ₂ (OH) ₂₄ CO ₃ (10 g), cyclohexene (24.6 g, 0.3 mol), recovered solid catalyst, recovered aqueous phase, 30% aqueous hydrogen peroxide solution (136 g, 1.
2 mol) and methanol (200 ml) were added, and the mixture was vigorously stirred at 80 ° C. for 12 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was cooled to room temperature and filtered. The filtrate contains dichloromethane (50
0 ml) and the aqueous and organic phases were separated. The aqueous phase was extracted with dichloromethane (200 ml × 2), combined with the organic phase, dried over anhydrous magnesium sulfate, and dried.

As a result of analyzing the concentrated solution by gas chromatography, the conversion of cyclohexene was found to be 72%, and the desired epoxide (cyclohexene oxide) was obtained.
Was> 99%. Gas chromatography measurement conditions: O
V-1 column (0.258 mm × 30 m), column temperature 40 ° C. to 250 ° C. (heating rate, 5 ° C./min).

(Example 19) In the epoxidation reaction described in Example 1, cyclohexene (0.246 g, 3
mmol), cycloheptene (0.289 g,
The reaction was carried out in the same manner as in Example 1 except that 3 mmol) was used. As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of cycloheptene was 69%, and the selectivity of the target epoxide (cycloheptene oxide) was> 99%.

Example 20 In the epoxidation reaction described in Example 1, cyclohexene (0.246 g, 3
mmol), cyclooctene (0.331 g,
The reaction was carried out in the same manner as in Example 1 except that 3 mmol) was used. As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of cycloheptene was 98%, and the selectivity of the target epoxide (cyclooctene oxide) was> 99%.

Example 21 In the epoxidation reaction described in Example 1, cyclohexene (0.246 g, 3
mmol) and 1-octene (0.337 g, 3
The reaction was carried out in the same manner as in Example 1 except that (mmol) was used. As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of 1-octene was 27%, and the selectivity of the target epoxide (1,2-epoxyoctane) was> 99%. .

Example 22 In the epoxidation reaction described in Example 1, cyclohexene (0.246 g, 3
mmol) and 1-nonene (0.379 g, 3 m
mol)), except that the reaction was carried out in the same manner as in Example 1. As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of 1-nonene was 30%, and the selectivity of the target epoxide (1,2-epoxynonane) was> 99%. .

Example 23 In the epoxidation reaction described in Example 1, cyclohexene (0.246 g, 3
mmol) instead of 2-methyl-1-octene (0.
The reaction was carried out in the same manner as in Example 1 except that 379 g (3 mmol) was used. As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of 2-methyl-1-octene was 47%, and the target epoxide (2
-Methyl-1,2-epoxyoctane) has a selectivity of> 9
9%.

Example 24 In the epoxidation reaction described in Example 1, cyclohexene (0.246 g, 3
The reaction was carried out in the same manner as in Example 1 except that 1-methyl-1-cyclohexene (0.289 g, 3 mmol) was used instead of (mmol). As a result of analyzing the concentrated solution of the extract using gas chromatography, 1-methyl-1-
The conversion of cyclohexene was 58% and the selectivity of the desired epoxide (1-methyl-1,2-epoxycyclohexane) was> 99%.

(Example 25) In the epoxidation reaction described in Example 1, cyclohexene (0.246 g, 3
The reaction was carried out in the same manner as in Example 1 except that 1-phenyl-1-cyclohexene (0.475 g, 3 mmol) was used instead of (mmol). As a result of analyzing the concentrated solution of the extract using gas chromatography, 1-phenyl-
The conversion of 1-cyclohexene was 60%, and the selectivity of the target epoxide (1-phenyl-1,2-epoxycyclohexane) was> 99%.

Example 26 In the epoxidation reaction described in Example 1, cyclohexene (0.246 g, 3
mmol) and styrene (0.312 g, 3 mm
ol), and the reaction was carried out in the same manner as in Example 1. As a result of analyzing the concentrated solution of the extract using gas chromatography, the conversion of styrene was 51%, and the selectivity of the target epoxide (styrene oxide) was>
It was 99%.

Example 27 In the epoxidation reaction described in Example 1, cyclohexene (0.246 g, 3
mmol), norbornene (0.282 g, 3
The reaction was carried out in the same manner as in Example 1 except that (mmol) was used. As a result of analyzing the concentrated solution of the extract using gas chromatography, the conversion of norbornene was 79%, and the selectivity of the target epoxide (exo-2,3-epoxynorbornene) was> 99%. .

Example 28 In the epoxidation reaction described in Example 1, cyclohexene (0.246 g, 3
mmol), trans-stilbene (0.54
The reaction was carried out in the same manner as in Example 1 except that 1 g (3 mmol) was used. As a result of analyzing the concentrate of the extract using gas chromatography, the conversion of trans-stilbene was 37%, and the target epoxide (trans-
The selectivity of (stilbene oxide) was> 99%.

Example 29 In the epoxidation reaction described in Example 1, cyclohexene (0.246 g, 3
mmol), cis-stilbene (0.541
g, 3 mmol), except that the reaction was carried out in the same manner as in Example 1. The concentrate of the extract was analyzed using gas chromatography. 35% conversion of cis-stilbene
And the selectivity of the target epoxide (cis-stilbene oxide) was> 99%.

[0109]

The object of the present invention is to provide a catalyst compound which has a high selectivity to an epoxy compound and is easy to recover and reuse, a catalyst composition using the catalyst compound, and the availability and availability of these catalyst compounds. It is possible to provide a method for producing an epoxy compound from various olefins using a low-concentration aqueous hydrogen peroxide solution that is easy to handle.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) // C07B 61/00 300 C07B 61/00 300 F term (reference) 4C048 AA04 BB01 BC01 CC01 UU03 XX02 XX05 4G069 AA03 BA01A BA01B BA02A BA02B BA10A BA10B BA21A BA21B BA38 BC10B BC16B BD01B BD02B BD04B BE14A BE20A BE32A BE32B BE33A BE33B BE34B BE37A BE37B CB07 CB73 4H039 CA63 CC40 4H049 VN01 VP01 VQ24 VR23 VR24 V24

Claims (9)

[Claims] 1. A compound represented by the general formula (1) in which --Si at a terminal of a ketone compound binds to a carbon atom of an activated carbon or a silicon atom of an inorganic carrier via an oxygen atom in an activated carbon or an inorganic carrier to form an activated carbon or A catalyst compound supported on an inorganic carrier. Formula (1) -Si (R ₁ R ₂ ) -YA-CO-BX (wherein, Si is a silicon atom, R ₁ and R ₂ are the same or different lower alkyl groups, Y It is - (CH ₂₎ nO-, PhO- or Ph
CH ₂ O—, n is an integer of 1 to 10, Y is bonded to A via an oxygen atom, and A and B are a benzene ring, or —C
H (R ₃ R ₄ ), wherein R ₃ and R ₄ are the same or different and are each a hydrogen atom, a halogen atom or a lower alkyl group, and X is a halogen atom, a —CN group or an amide group. is there) 2. The catalyst compound according to claim 1, wherein the inorganic carrier is at least one selected from the group consisting of alumina, silica gel, florisil, celite, and molecular sieves. 3. A method of reacting a ketone compound represented by the general formula (2) with one or more supports selected from the group consisting of activated carbon, alumina, silica gel, florisil, celite, and molecular sieves. 2) embedded image -X ₁ -Si (R ₁ R ₂ ) -YA-CO-B-
X ₂ (wherein, Si is a silicon atom, R ₁ and R ₂ are the same or different lower alkyl groups, Y is — (CH ₂ ) nO—, PhO— or PhCH ₂ O—, and n is 1 to 10 In the integer, Y is bonded to A via an oxygen atom, A and B are a benzene ring or —CH (R ₃ R ₄ ), and R ₃ and R ₄ are the same or different and each represents a hydrogen atom, A halogen atom or a lower alkyl group, X ₁ is a halogen atom or an alkoxy group,
X ₂ is a halogen atom, a —CN group, or an amide group)
Ketone compound represented by the general formula (1) General formula (1) -Si (R ₁ R ₂ ) -YA-CO-BX (wherein, Si is a silicon atom, and R ₁ is R ₂ are the same or different lower alkyl groups, Y is - (CH ₂₎ nO-, PhO- or P
hCH ₂ O—, n is an integer of 1 to 10, Y is bonded to A via an oxygen atom, and A and B are a benzene ring or —CH (R ₃ R ₄ ), where R ₃ and R ₄ are the same or different and are each a hydrogen atom, a halogen atom or a lower alkyl group, and X is a halogen atom, a —CN group or an amide group). A method for producing a catalyst compound which is bonded to a carbon atom of activated carbon or a silicon atom of an inorganic carrier via an oxygen atom of the above and is supported on the activated carbon or the inorganic carrier. 4. A catalyst composition comprising (A) the catalyst compound according to claim 1 or 2 and (B) hydrotalcite. 5. The weight ratio of the catalyst compound (A) according to claim 1 or 2 to hydrotalcite (B) is 0.2 to 0.2.
The catalyst composition according to claim 4, which is 1.2. 6. A method for producing an epoxy compound from an olefin, using the catalyst compound according to claim 1 or 2 and hydrogen peroxide. 7. A method for producing an epoxy compound from olefins, using the catalyst composition according to claim 4 and hydrogen peroxide. 8. The method according to claim 1, wherein 1 mole of the olefin is used.
7. The method for producing an epoxy compound from olefins according to claim 6, wherein 0.0005 mol to 0.5 mol of the catalyst compound according to 2 is used. 9. The method according to claim 4, wherein 1 mole of the olefin is used.
Or the catalyst compound 0.0005 in the catalyst composition according to 5.
The method for producing an epoxy compound from olefins according to claim 7, wherein the molar amount is from 0.5 to 0.5 mol.