JPH10298131A - Production of aromatic ketone - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for easily producing an aromatic ketone useful as a raw material for emulsifiers, oiling agents, perfumes, medicines, agrochemicals, base agents for cosmetics, etc., at a low cost and in a high yield, wherein a rare earth element catalyst used by the method can easily be recovered and reutilized after the reaction is finished. SOLUTION: The method for producing an aromatic ketone comprises reacting an aromatic compound having at least one substitutable hydrogen atom on the aromatic ring with a carboxylic acid ester as an acylating agent in the presence of a Broensted acid and a rare earth element-based catalyst selected from a compound of the formula: M(OSO2 R<f> )3 (M is a rare earth element atom; R<f> is a perfluoroalkyl group or a perfluoroalkoxy group) and a rare earth element wholly fluorinated sulfonic acid ionomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a base for cosmetics and the like,
The present invention relates to a method for producing aromatic ketones useful as raw materials for emulsifiers, oils, fragrances, medicines, agricultural chemicals and the like in high yield.

[0002]

2. Description of the Related Art Conventionally, in the synthesis of aromatic ketones, a Friedel-Crafts reaction using a Lewis acid such as aluminum chloride, titanium chloride or tin chloride as a catalyst and an acid anhydride or an acid halide as an acylating agent has been carried out. (G.
A. Olah, "Friedel-Crafts Chemistry,", Wiley-Inters
cience, New York (1973)]. However, such a method requires a stoichiometric amount or more of a Lewis acid, and the Lewis acid is reacted with water after the reaction is completed, and is separated from the product (aromatic ketone) as a water-soluble substance. Is difficult, and the disposal cost is high even when discarded.
There are difficulties in mass-producing industrially.

A rare earth metal trifluoromethanesulfonate (triflate) recently developed as a new Lewis acid [S. Kobayashi, Chem. Lett., 2087 (1992)
1)] is attracting attention as a solution to this problem. Unlike rare Lewis acids, this rare earth metal triflate has the characteristics that it is stable in water, the reaction proceeds quickly at less than the stoichiometric amount, and can be easily recovered and reused. Application to the synthesis of ketones is also known [A. Kawada, S. Mitamura, S. Kobayashi, J.
Chem. Soc., Chem. Commun., 1157 (1993), A. Kawada,
S. Mitamura, S. Kobayashi, J. Chem. Soc., Chem. Co
mmun., 183 (1996), JP-A-5-320089, JP-A-7-22
No. 3990].

However, in the above-mentioned technique, it is necessary to use conventional highly reactive acid anhydrides and acid chlorides as acylating agents, and these must be synthesized from the corresponding carboxylic acids, and the operation is complicated. It was also a problem in terms of cost.

On the other hand, recently, a method has been developed in which a rare earth metal triflate is used as a catalyst and an aromatic ketone is obtained by directly using a carboxylic acid as an acylating agent [Preprints of the 70th Annual Meeting of the Chemical Society of Japan II. 1097 (1996)].

[0006]

However, even in the above method, there is a problem that the yield is low depending on the combination of the raw materials and under moderate conditions such as room temperature, and it is difficult to say that it is suitable for industrial production. Met.

Accordingly, an object of the present invention is to provide a method for producing an aromatic ketone inexpensively, easily, and in a high yield under milder conditions.

[0008]

Under such circumstances, the present inventors have conducted intensive studies. As a result, when a specific rare earth compound is used as a catalyst, low reactivity or low catalyst activity is used as an acylating agent. Carboxylic acid esters that could not be used conventionally can be used due to the problem of decomposition, and aromatic ketones can be easily synthesized while recovering and reusing the catalyst.Moreover, the presence of Bronsted acid in this system allows The present inventors have found that the yield can be significantly improved, and that milder reaction conditions can be selected, and the present invention has been completed.

That is, the present invention provides an aromatic compound having at least one substitutable hydrogen atom on an aromatic ring, and a carboxylic acid ester as an acylating agent, represented by the following general formula:
(1) M (OSO ₂ R ^f ) ₃ (1) [wherein M represents a rare earth atom, and R ^f represents a perfluoroalkyl group or a perfluoroalkoxyl group. And a method for producing an aromatic ketone, characterized in that the reaction is carried out in the presence of a rare earth catalyst selected from a compound represented by the formula (I) and a rare earth perfluorinated sulfonic acid ionomer and a Bronsted acid.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION As the aromatic compound which can be used in the present invention, any compound having at least one substitutable hydrogen atom on an aromatic ring may be used. Although any of conventionally known compounds may be used regardless of cyclic aromatic compounds, ring-assembled aromatic compounds, and condensed heterocyclic aromatic compounds, those having 4 to 20 carbon atoms are preferred. Specifically, for example, as a monocyclic aromatic compound, benzene, furan, pyrrole, pyridine, thiophene, etc., as a condensed polycyclic aromatic compound, naphthalene, anthracene, naphthacene, pentacene, indene, azulene, heptalene, Indacene, acenaphthylene, fluorene, phenalene, phenanthrene, triphenylene, pyrene, chrysene, perylene, etc., as ring-assembled aromatic compounds, biphenyl, terphenyl, etc., as condensed heterocyclic aromatic compounds, indole, isoindole, quinoline, isoquinoline , Quinazoline, pudding,
Xanthene, carbazole, acridine, phenazine,
Phenanthroline and the like. Of these, monocyclic aromatic compounds and condensed polycyclic aromatic compounds, particularly benzene and naphthalene, are preferred.

Further, the aromatic compound may have a suitable substituent. The substituent is not particularly limited as long as it does not inhibit the reaction, and examples thereof include an alkyl group,
One or two or more substituents such as an alkoxyl group, an amino group, a mercapto group, and a hydroxyl group are exemplified.
Preferred are an alkyl group, an alkoxyl group, and a hydroxyl group.

The carboxylic acid ester usable in the present invention is not particularly limited.
(2) A-COO-B (2) [In the formula, A and B are the same or different and each may have a substituent and may have a heterooxygen atom and may have 1 to 36 carbon atoms. Represents an aromatic, alicyclic or aromatic hydrocarbon group. ] Is preferable. Specifically, a carboxylic acid represented by the following general formula A-COOH,
Carboxylic acid esters in the form of dehydration-condensation with alcohols or phenols represented by the general formula B-OH are mentioned.

The carboxylic acid A-COOH includes, for example, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, pivalic acid, lauric acid, myristyl acid, palmitic acid, stearic acid, acrylic acid, propiolic acid, methacrylic acid, Saturated or unsaturated linear or branched aliphatic monocarboxylic acids such as crotonic acid and oleic acid; alicyclic carboxylic acids such as cyclohexanecarboxylic acid; aromatic monocarboxylic acids such as benzoic acid, naphthoic acid, and cinnamic acid Acids.
The substituents that these carboxylic acids may have are not particularly limited as long as they do not inhibit the reaction.
For example, one or more substituents such as an alkyl group, an alkoxyl group, an acyl group, an amino group, a mercapto group, an amide group, a halogen atom, a nitro group, a hydroxyl group, an oxo group, and a carboxyl group are exemplified. Specific examples of the substituted carboxylic acid include acetoacetic acid, glycolic acid, glyceric acid, toluic acid, salicylic acid and the like, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid,
Examples include polycarboxylic acids such as pentalitic acid, phthalic acid, isophthalic acid, and terephthalic acid. Among these carboxylic acids, aliphatic carboxylic acids are preferable, aliphatic monocarboxylic acids having 1 to 5 carbon atoms are more preferable, and acetic acid is particularly preferable.

The alcohols or phenols represented by the general formula B-OH include, for example, alcohols such as methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, 2-methyl-2-propanol, Isobutanol, heptanol, hexanol, octanol, ethylhexanol, decanol,
Dodecanol, tetradecanol, hexadecanol,
Octadecanol, cyclohexanol and the like,
Examples of phenols include phenol and naphthol. Examples of the substituent which the alcohols or phenols may have include, for example, an alkyl group, an alkoxyl group, an acyl group, an amino group, a mercapto group, an amide group, a nitro group, a halogen atom, a sulfonic acid group, a hydroxyl group and the like. And one or more substituents of the above. Specific examples of substituted alcohols and substituted phenols include cholesterol, cholestanol, fluorophenol, chlorophenol, bromophenol, iodophenol,
Difluorophenol, dichlorophenol, dibromophenol, diiodophenol, trifluorophenol, trichlorophenol, tribromophenol,
Examples include triiodophenol, nitrophenol, dinitrophenol, trinitrophenol, cresol, dimethylphenol, trimethylphenol, phenolsulfonic acid, pentaerythritol, sorbitol, glycerin, polyglycerins, dihydroxybenzene, trihydroxybenzene, and the like. Among these alcohols and phenols, phenols which may have a substituent, particularly phenol and naphthol substituted with a nitro group, a halogen atom or an alkyl group, are preferred.

The carboxylic acid ester is easily produced by a known method such as dehydration condensation or transesterification of the corresponding carboxylic acid with an alcohol or the like.

Particularly preferred examples of the carboxylic acid ester include p-nitrophenyl acetate, 4-chlorophenyltetradecanoate, and 2,4,6-trimethylphenyl acetate.

In the present invention, the charge ratio of the reaction between the aromatic compound and the carboxylic acid ester is not particularly limited, but is preferably from 1:10 to 10: 1, more preferably from 3:10 to 10: 3, by molar ratio.

In the rare earth catalyst used in the present invention, the rare earth atom represented by M in the general formula (3) includes:
Scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, particularly scandium, lanthanum, erbium, thulium, lutetium, ytterbium are preferred. Examples of the perfluoroalkyl group or perfluoroalkoxyl group represented by R ^f include a trifluoromethyl group, a pentafluoroethyl group, a nonafluorobutyl group, a trifluoromethoxyl group, a pentafluoroethoxyl group, and a nonafluorobutoxyl group. Among them, a perfluoroalkyl group is preferable, and furthermore,
~ 12 perfluoroalkyl groups, especially trifluoromethyl groups, are preferred. Examples of the rare earth perfluorinated sulfonic acid ionomer include those obtained from Nafion resin (manufactured by DuPont) and the above rare earth elements.
Of these rare earth catalysts, trifluoromethanesulfonate of rare earth metal (rare earth triflate) is particularly preferred. These rare earth catalysts can be used alone or in combination of two or more. Further, a product synthesized from the mixture of rare earth compounds before purification that has been produced can also be used as such as a mixture of rare earth catalysts.

The amount of the rare earth catalyst used in the present invention is preferably 0.01 to 300 mol%, more preferably 0.1 to 100 mol%, particularly preferably 1 to 20 mol%, based on the carboxylic acid ester. If the amount is less than 0.01 mol%, the reaction time becomes longer, and
Exceeding the mole percentage does not actually reduce the reaction time much.

In the present invention, the presence of a Bronsted acid in the reaction system can significantly improve the yield of the aromatic carboxylic acid, and can further reduce the reaction conditions. . The Bronsted acid used in the present invention is not particularly limited, and any known one may be used as long as it coordinates with a rare earth catalyst to form a stable complex anion, and may be alcoholic or phenolic. Those having no hydroxyl group are preferred. More preferred Bronsted acids include the following general formula (3): R ^f SO ₂ OH (3) wherein R ^f has the same meaning as described above. And a perfluorinated sulfonic acid ionomer (for example, one derived from the aforementioned Nafion resin), and trifluoromethanesulfonic acid is particularly preferred.

The amount of the Brönsted acid used in the present invention is preferably from 0.01 to 300 mol%, particularly preferably from 0.1 to 100 mol%, based on the carboxylic acid ester. If the amount is less than 0.01 mol%, the reaction time is prolonged, and if it exceeds 300 mol%, the reaction time is not substantially shortened.

In order to promote the reaction, a compound having a function as a dehydrating agent, for example, magnesium sulfate,
Other additives such as sodium sulfate, calcium chloride, molecular sieve, and the like, or lithium perchlorate and sodium perchlorate having an activating effect of the acylating agent may be added. The amount of such other additives is not particularly limited, but is preferably 1 to 1000 mol%, particularly preferably 100 to 400 mol%, based on the carboxylic acid ester.

The reaction can be carried out without a solvent, but an organic solvent can also be used to sufficiently mix the raw materials. Examples of such organic solvents include carbon disulfide, carbon tetrachloride, 1,2-dichloroethane, hexane, diethyl ether, tetrahydrofuran, dichloromethane, acetonitrile, nitromethane, chloroform, cyclohexane, and the like. 0.1 to 200 times by weight, particularly preferably 1 to 50 times by weight. These organic solvents can be used alone or in combination of two or more.

The reaction can be carried out in air, but is preferably carried out in an inert gas such as nitrogen or argon for the purpose of suppressing the formation of by-products. The reaction temperature is from -100 to 2 from the viewpoint of increasing the reaction rate and preventing coloring of the product.
50 ° C, more preferably -20 to 200 ° C, particularly preferably 0 to 150 ° C. The reaction time varies depending on the reaction conditions.
Ends in 10 minutes to 100 hours.

After completion of the reaction, the desired aromatic ketone can be obtained from the reaction solution by a commonly used isolation and purification method such as neutralization, filtration, distillation, extraction, and recrystallization.

The rare earth catalyst used in the reaction can be recovered by, for example, extraction and reused. That is, a solvent amount of water is added to the reaction mixture, unreacted aromatic compounds, acylating agents, and aromatic ketones are separated from the aqueous solution by a solvent extraction method or the like, an aqueous solution containing a rare earth catalyst is recovered, and the water is distilled. Then, if necessary, further purification is performed, and the rare earth catalyst can be recovered. The recovered rare earth catalyst can be reused as the reaction catalyst of the present invention.

[0027]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 Under nitrogen atmosphere, scandium triflate (78.9 mg, 0.16
mmol), 145.4 mg of p-nitrophenyl acetate (0.80 mmo
l), anisole 4.0 ml (37 mmol) and trifluoromethanesulfonic acid 24.0 mg (0.16 mmol) were charged into a reactor, and 25
Stirred at C for 3 hours. As a result of analyzing the reaction solution by gas chromatography, 4-methoxyacetophenone 0.32 mmol
(40% yield) was confirmed to have been produced.

Comparative Example 1 Scandium triflate 78.9 mg (0.16
mmol), p-nitrophenyl acetate 144.9mg (0.80mmo
l) and 4.0 ml (37 mmol) of anisole were charged into a reactor,
Stirred at 25 ° C. for 3 hours. As a result of analyzing the reaction solution by gas chromatography, 4-methoxyacetophenone 0.032 mmo
It was confirmed that 1 (yield 4%) was produced.

Example 2 94.8 mg (0.16 mmo) of lanthanum triflate under a nitrogen atmosphere
l), p-nitrophenyl acetate 145.3mg (0.80mmo
l), anisole 4.0 ml (37 mmol) and trifluoromethanesulfonic acid 21.2 mg (0.14 mmol) were charged into a reactor, and 25
Stirred at C for 3 hours. As a result of analyzing the reaction solution by gas chromatography, 4-methoxyacetophenone 0.14 mmol
(18% yield) was confirmed to have been produced.

Comparative Example 2 94.8 mg (0.16 mmo) of lanthanum triflate under a nitrogen atmosphere
l), 145.3 mg (0.80 mmol) of p-nitrophenyl acetate
And 4.0 ml (37 mmol) of anisole were charged into a reactor, and 25
Stirred at C for 3 hours. As a result of analyzing the reaction solution by gas chromatography, 4-methoxyacetophenone 0.01 mmol
(Yield 1.3%) was confirmed to have been produced.

Example 3 98.2 mg (0.16 mm) of erbium triflate under a nitrogen atmosphere
ol), p-nitrophenyl acetate 144.7mg (0.80mmo
l), anisole 4.0 ml (37 mmol) and trifluoromethanesulfonic acid 20.4 mg (0.14 mmol) were charged into a reactor, and 10
Stirred at 0 ° C. for 3 hours. As a result of analyzing the reaction solution by gas chromatography, 4-methoxyacetophenone 0.32 mmol
(40% yield) was confirmed to have been produced.

Comparative Example 3 98.2 mg (0.16 mm) of erbium triflate under a nitrogen atmosphere
ol), p-nitrophenyl acetate 144.7mg (0.80mmo
l) and 4.0 ml (37 mmol) of anisole were charged into a reactor,
The mixture was stirred at 100 ° C. for 3 hours. As a result of analyzing the reaction solution by gas chromatography, 4-methoxyacetophenone 0.03 mm
It was confirmed that ol (yield 3.8%) was produced.

Example 4 98.6 mg (0.16 mmo) of thulium triflate in a nitrogen atmosphere
l), p-nitrophenyl acetate 145.5mg (0.80mmo
l), anisole 4.0 ml (37 mmol) and trifluoromethanesulfonic acid 20.4 mg (0.14 mmol) were charged into a reactor, and 10
Stirred at 0 ° C. for 3 hours. As a result of analyzing the reaction solution by gas chromatography, 4-methoxyacetophenone 0.39 mmol
(Yield 48%) was confirmed to have been produced.

Comparative Example 4 98.6 mg (0.16 mmo) of thulium triflate in a nitrogen atmosphere
l), p-nitrophenyl acetate 145.5mg (0.80mmol)
And 4.0 ml (37 mmol) of anisole were charged into a reactor, and 100
Stirred at C for 3 hours. As a result of analyzing the reaction solution by gas chromatography, 4-methoxyacetophenone 0.032 mmol
(Yield 4.2%) was confirmed to have been produced.

Example 5 99.9 mg of ytterbium triflate (0.
16mmol), p-nitrophenyl acetate 145.5mg (0.80m
mol), anisole 4.0 ml (37 mmol) and trifluoromethanesulfonic acid 21.0 mg (0.14 mmol) were charged into a reactor,
The mixture was stirred at 100 ° C. for 3 hours. As a result of analyzing the reaction solution by gas chromatography, 4-methoxyacetophenone 0.38 mm
It was confirmed that ol (yield 47%) was produced.

Comparative Example 5 Under nitrogen atmosphere, 99.9 mg of ytterbium triflate (0.
16mmol), p-nitrophenyl acetate 145.5mg (0.80m
mol) and 4.0 ml (37 mmol) of anisole were charged into a reactor and stirred at 100 ° C. for 3 hours. As a result of analyzing the reaction solution by gas chromatography, 4-methoxyacetophenone was added.
It was confirmed that 029 mmol (yield 3.6%) had been produced.

Example 6 99.6 mg of lutetium triflate (0.16 mm
ol), 145.2 mg (0.80mmo) of p-nitrophenyl acetate
l), anisole 4.0 ml (37 mmol) and trifluoromethanesulfonic acid 20.9 mg (0.14 mmol) were charged into a reactor, and 10
Stirred at 0 ° C. for 3 hours. As a result of analyzing the reaction solution by gas chromatography, 4-methoxyacetophenone 0.28 mmol
(35% yield) was confirmed to have been produced.

Comparative Example 6 99.6 mg of lutetium triflate (0.16 mm
ol), 145.2 mg (0.80mmo) of p-nitrophenyl acetate
l) and 4.0 ml (37 mmol) of anisole were charged into a reactor,
The mixture was stirred at 100 ° C. for 3 hours. As a result of analyzing the reaction solution by gas chromatography, 4-methoxyacetophenone 0.02 mm
It was confirmed that ol (yield 2.5%) was produced.

Example 7 Under a nitrogen atmosphere, scandium triflate 80.1 mg (0.16 mg) was used.
mmol), 271.7 mg of 4-chlorophenyltetradecanoate
(0.80 mmol), 4.0 ml (37 mmol) of anisole and 24.0 mg (0.16 mmol) of trifluoromethanesulfonic acid were charged into a reactor and stirred at 25 ° C. for 3 hours. As a result of analyzing the reaction solution by gas chromatography, it was confirmed that 0.35 mmol (44% yield) of 4-methoxytetradecanone was produced.

Comparative Example 7 Under a nitrogen atmosphere, scandium triflate 80.1 mg (0.16 mg) was used.
mmol), 271.7 mg of 4-chlorophenyltetradecanoate
(0.80 mmol) and 4.0 ml (37 mmol) of anisole were charged into a reactor and stirred at 25 ° C. for 3 hours. As a result of analyzing the reaction solution by gas chromatography, it was confirmed that 0.03 mmol (yield 3.8%) of 4-methoxytetradecanone was produced.

Example 8 Under a nitrogen atmosphere, 79.0 mg (0.16 mg) of scandium triflate was used.
mmol), 2,4,6-trimethylphenyl acetate 147.0mg
(0.83 mmol), 4.0 ml (37 mmol) of anisole and 24.0 mg (0.16 mmol) of trifluoromethanesulfonic acid were charged into a reactor and stirred at 25 ° C. for 3 hours. As a result of analyzing the reaction solution by gas chromatography, 4-methoxyacetophenone
It was confirmed that 0.24 mmol (29% yield) had been produced.

Comparative Example 8 Scandium triflate (79.0 mg, 0.16
mmol), 2,4,6-trimethylphenyl acetate 147.0mg
(0.83 mmol) and 4.0 ml (37 mmol) of anisole were charged into a reactor and stirred at 25 ° C. for 3 hours. As a result of analyzing the reaction solution by gas chromatography, it was confirmed that 0.01 mmol (yield 1.2%) of 4-methoxyacetophenone was produced.

Example 9 Under a nitrogen atmosphere, scandium triflate (78.7 mg, 0.16 mg) was used.
mmol), 192.6 mg of 2,4,6-trichlorophenyl acetate
(0.80 mmol), 4.0 ml (37 mmol) of anisole and 24.1 mg (0.16 mmol) of trifluoromethanesulfonic acid were charged into a reactor and stirred at 25 ° C. for 2 hours. As a result of analyzing the reaction solution by gas chromatography, 4-methoxyacetophenone
It was confirmed that 0.28 mmol (35% yield) had been produced.

Comparative Example 9 Under a nitrogen atmosphere, scandium triflate 78.7 mg (0.16 mg) was used.
mmol), 192.6 mg of 2,4,6-trichlorophenyl acetate
(0.80 mmol) and 4.0 ml (37 mmol) of anisole were charged into a reactor and stirred at 25 ° C. for 2 hours. As a result of analyzing the reaction solution by gas chromatography, it was confirmed that 0.02 mmol (yield 2.5%) of 4-methoxyacetophenone was generated.

Example 10 Under a nitrogen atmosphere, scandium triflate (78.7 mg, 0.16
mmol), 137.9 mg of 4-chlorophenylacetate (0.81 mmo)
l), anisole 4.0 ml (37 mmol) and trifluoromethanesulfonic acid 24.0 mg (0.16 mmol) were charged into a reactor, and 25
Stirred at C for 8 hours. As a result of analyzing the reaction solution by gas chromatography, 4-methoxyacetophenone 0.24 mmol
(Yield 29%) was confirmed to have been produced.

Comparative Example 10 Under a nitrogen atmosphere, scandium triflate 78.7 mg (0.16 mg) was used.
mmol), 137.9 mg of 4-chlorophenylacetate (0.81 mmo)
l) and 4.0 ml (37 mmol) of anisole were charged into a reactor,
Stirred at 25 ° C. for 8 hours. As a result of analyzing the reaction solution by gas chromatography, 4-methoxyacetophenone 0.02 mmol
(Yield 2.5%) was confirmed to have been produced.

Comparative Example 11 24.0 mg of trifluoromethanesulfonic acid under a nitrogen atmosphere
(0.16 mmol), 145.2 mg of p-nitrophenyl acetate
(0.80 mmol) and 4.0 ml (37 mmol) of anisole were charged into a reactor and stirred at 25 ° C. for 3 hours. As a result of analyzing the reaction solution by gas chromatography, it was confirmed that 0.10 mmol (13% yield) of 4-methoxyacetophenone was produced.

Comparative Example 12 24.0 mg of trifluoromethanesulfonic acid under a nitrogen atmosphere
(0.16 mmol), 145.2 mg of p-nitrophenyl acetate
(0.80 mmol) and 4.0 ml (37 mmol) of anisole were charged into a reactor and stirred at 100 ° C. for 3 hours. As a result of analyzing the reaction solution by gas chromatography, it was confirmed that 0.21 mmol (yield 26%) of 4-methoxyacetophenone was produced.

Example 11 Under a nitrogen atmosphere, scandium triflate (78.7 mg, 0.16
mmol), 136.5 mg of 4-chlorophenylacetate (0.80 mmo
l), anisole 4.0 ml (37 mmol), trifluoromethanesulfonic acid 24.1 mg (0.16 mmol) and magnesium sulfate 28
8 mg (2.4 mmol) was charged into a reactor and stirred at 25 ° C. for 4 hours. As a result of analyzing the reaction solution by gas chromatography,
It was confirmed that 0.26 mmol (yield 32%) of 4-methoxyacetophenone was produced.

Example 12 Under a nitrogen atmosphere, scandium triflate (78.9 mg, 0.16 mg) was used.
mmol), 145.4 mg of p-nitrophenyl acetate (0.80 mmo
l), toluene 4.0 ml (38 mmol) and trifluoromethanesulfonic acid 24.0 mg (0.16 mmol) were charged into a reactor, and 100
Stirred at C for 24 hours. As a result of analyzing the reaction solution by gas chromatography, it was confirmed that 0.08 mmol (yield 10%) of 4-methylacetophenone was generated.

Comparative Example 13 Under a nitrogen atmosphere, scandium triflate (78.8 mg, 0.16 mg) was used.
mmol), 145.0 mg of p-nitrophenyl acetate (0.80 mmo
l) and 4.0 ml (38 mmol) of toluene were charged into a reactor, and 10
Stirred at 0 ° C. for 24 hours. As a result of analyzing the reaction solution by gas chromatography, it was confirmed that trace amounts of 4-methylacetophenone were generated (yield 1% or less).

Example 13 After the reaction procedure of Example 1, 20 ml of ether and 20 ml of water were used.
The extraction operation was performed using. The aqueous layer obtained by the extraction operation was concentrated under reduced pressure, and the residue was dried under reduced pressure at 200 ° C. for 24 hours to recover 78.4 mg of scandium triflate. Then, under a nitrogen atmosphere, 78.4 mg of this scandium triflate (0.16 mm
ol), 145.2 mg (0.80mmo) of p-nitrophenyl acetate
l), anisole 4.0 ml (37 mmol) and trifluoromethanesulfonic acid 24.1 mg (0.16 mmol) were charged into a reactor, and 25
Stirred at C for 3 hours. As a result of analyzing the reaction solution by gas chromatography, 0.31 mmol of 4-methoxyacetophenone was obtained.
(39% yield) was confirmed to have been produced.

[0054]

Industrial Applicability According to the present invention, aromatic ketones useful as bases for cosmetics and the like, emulsifiers, oils, fragrances, medicines, agricultural chemicals, and other raw materials can be produced inexpensively and easily in high yield. Also,
The rare earth catalyst used in the method of the present invention can be easily recovered after the completion of the reaction and can be reused.

Claims (6)

[Claims] 1. An aromatic compound having at least one substitutable hydrogen atom on an aromatic ring and a carboxylic acid ester as an acylating agent are represented by the following general formula (1): M (OSO ₂ R ^f ) ₃ ( 1) [In the formula, M represents a rare earth atom, and R ^f represents a perfluoroalkyl group or a perfluoroalkoxyl group. And a rare earth perfluorinated sulfonic acid ionomer, and a reaction in the presence of a Bronsted acid. 2. A carboxylic acid ester represented by the following general formula (2): A-COO-B (2) wherein A and B are the same or different and each may have a substituent, and a hetero oxygen atom Represents an aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 36 carbon atoms which may contain The method according to claim 1, wherein 3. The method according to claim 2, wherein B is an aromatic hydrocarbon group which may have a substituent. 4. The Bronsted acid having no alcoholic or phenolic hydroxyl group.
3. The production method according to any one of 3. 5. The Bronsted acid is represented by the following general formula (3): R ^f SO ₂ OH (3) wherein R ^f represents a perfluoroalkyl group or a perfluoroalkoxyl group. Or the perfluorinated sulfonic acid ionomer. 6. The production method according to claim 1, wherein the rare earth catalyst is recovered and reused after the completion of the reaction.