JPH1087549A - Production of aromatic ketone - Google Patents

Abstract

PROBLEM TO BE SOLVED: To facilitate the recovery and reutilization of a catalyst and make it possible to obtain an aromatic ketone useful as a base for cosmetics, etc., and a raw material for emulsifying agents, oil agents, etc., from an inexpensive acylating agent, by using a specific catalyst and the specified acylating agent. SOLUTION: (A) An aromatic compound having one or more substitutable hydrogens in the aromatic ring is reacted with (B) an acylating agent which is a carboxylic acid (ester) such as a compound represented by the formula A-COOH [A is a (substituted) 1-36C aliphatic, alicyclic or aromatic group] or a compound represented by the formula A-COO-B (B is A) by using (C) a catalyst that is a compound represented by the formula M(OSO2 Rf )3 [M is a rare earth atom; Rf is a perfluoroalkyl(oxy)] to afford an aromatic ketone. Furthermore, the reaction is preferably carried out by using (D) a cocatalyst that is a compound represented by the formula D-OH (D is A) in order to promote the reaction and improve the yield.

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 an aromatic ketone which can be used as a raw material for an emulsifier, an oil, a fragrance, a medicine, a pesticide and the like.

[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 chloride as an acylating agent is carried out. (GA Olah,
“Friedel-Crafts Chemistry,” Wiley-Interscience,
New York (1973)). However, such a method requires a stoichiometric amount of Lewis acid or more, and after the reaction is completed, the Lewis acid is reacted with water to produce a product (aromatic ketone) as a water-soluble substance.
Is very difficult to regenerate,
Furthermore, when the Lewis acid is discarded, the processing cost increases,
There are difficulties in mass-producing industrially.

In order to solve such a problem, a rare earth metal trifluoromethanesulfonate (triflate) (S. Kobayashi, Chem.
Lett., 2087 (1991)). The triflate is water-stable, unlike conventional Lewis acids,
In addition, the reaction proceeds quickly at a stoichiometric amount or less, and has characteristics that it can be easily recovered and reused. For example, JP-A-5-320089 and JP-A-7-223990 disclose techniques using such a technique.

[0004]

However, in the above-mentioned technique, a conventional acid anhydride or acid chloride having high reactivity is used as an acylating agent. Such acid anhydrides and acid chlorides had to be synthesized from the corresponding carboxylic acids, which involved complicated operations and cost problems. Therefore, the present invention does not require the synthesis of such acid anhydrides and acid chlorides, the reaction proceeds rapidly with a stoichiometric or less Lewis acid, and the collection and reuse of the Lewis acid are easy. It is an object to provide a method for producing an aromatic ketone.

[0005]

Means for Solving the Problems In view of such circumstances, the present inventors have conducted intensive studies and as a result, by using a specific rare earth catalyst as a catalyst, the conventional catalyst can be decomposed or the reactivity as an acylating agent is reduced. When using a carboxylic acid or a carboxylic acid ester which could not be used as an acylating agent because of its low content, it was found that an aromatic ketone could be easily synthesized, and when a carboxylic acid or a carboxylic acid ester was used as an acylating agent In addition, it has been found that the recovery and reuse of the rare earth catalyst after the completion of the reaction is easy,
The present invention has been completed.

[0006] That is, the present invention provides an aromatic ring having at least one
In a method for producing an aromatic ketone by reacting an aromatic compound having two displaceable hydrogens with an acylating agent using a catalyst, a catalyst represented by the general formula M (OSO ₂ Rf) ₃
(Wherein M represents a rare earth atom, Rf represents a perfluoroalkyl group or a perfluoroalkoxyl group), and a carboxylic acid or a carboxylic ester is used as an acylating agent. The present invention provides a method for producing an aromatic ketone.

Another object of the present invention is to provide a method for producing an aromatic ketone in which after the reaction is completed, the rare earth catalyst used is recovered and the recovered rare earth catalyst is reused as a catalyst.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION As the aromatic compound which can be used in the present invention, any aromatic compound having at least one substitutable hydrogen in the aromatic ring can be used, and any known compounds can be used. But preferably 4 to 20 carbon atoms
Monocyclic aromatic compounds, condensed polycyclic aromatic compounds, ring-assembled aromatic compounds, condensed heterocyclic aromatic compounds and the like. Specifically, for example, as a monocyclic aromatic compound, benzene, furan, pyrrole, pyridine, thiophene, etc.
As fused polycyclic aromatic compounds, 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., condensed heterocyclic aromatic compounds, indole, isoindole, quinoline,
Isoquinoline, quinazoline, purine, xanthene, carbazole, acridine, phenanthroline and the like. Of these, preferred are monocyclic aromatic compounds and condensed polycyclic aromatic compounds, and particularly preferred are benzene,
Naphthalene.

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, an alkoxyl group, an amino group, a thio group, a hydroxyl group and the like, and a plurality of these may be substituted. Preferred are an alkyl group having 1 to 3 carbon atoms, an alkoxyl group, and a hydroxyl group.

The carboxylic acid which can be used in the present invention is not particularly limited, but in the carboxylic acid of the general formula A-COOH, A is an aliphatic group having 1 to 36 carbon atoms which may have a substituent. , An alicyclic or aromatic group. Specifically, for example, as an aliphatic monocarboxylic acid, 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 and unsaturated such as crotonic acid and oleic acid,
Straight-chain, branched-chain aliphatic monocarboxylic acids, as alicyclic carboxylic acids, cyclohexane carboxylic acids, etc., as aliphatic polycarboxylic acids, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, Saturated or unsaturated aliphatic polycarboxylic acids such as fumaric acid and pentaritic acid,
Examples of the aromatic carboxylic acid include monocyclic and condensed polycyclic aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, cinnamic acid, and naphthoic acid. Of these, preferred are aliphatic carboxylic acids, particularly preferred are aliphatic monocarboxylic acids having 1 to 5 carbon atoms, and most preferred is acetic acid.

The carboxylic acid 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, an alkoxyl group, an acyl group, an amino group, a thio group, an amide group, a halogen atom, a nitro group, and a hydroxyl group. This may be replaced by a plurality. Specific examples of such compounds include acetoacetic acid, glycolic acid, glyceric acid, toluic acid, salicylic acid, and the like.

The carboxylic acid ester which can be used in the present invention is not particularly limited.
In the carboxylate ester of OB, A and B are preferably an aliphatic, alicyclic or aromatic group having 1 to 36 carbon atoms which may have a substituent.

Specifically, for example, aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, pivalic acid, lauric acid, myristyl acid, palmitic acid, stearic acid, acrylic acid, propiolic acid, Saturated and unsaturated such as methacrylic acid, crotonic acid and oleic acid,
As linear or branched aliphatic monocarboxylic acids and aliphatic polycarboxylic acids, saturated or unsaturated oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, pentaritic acid, etc. Aliphatic polycarboxylic acids, as alicyclic carboxylic acids, such as cyclohexanecarboxylic acid,
Examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthoic acid, and cinnamic acid (the carboxylic acid compound may have an appropriate substituent.
The substituent is not particularly limited as long as it does not inhibit the reaction, and examples thereof include an alkyl group, an alkoxyl group, an acyl group, an amino group, a thio group, an amide group, a halogen atom,
Examples thereof include a nitro group and a hydroxyl group, and specific examples include acetoacetic acid, glycolic acid, glyceric acid, toluic acid, and salicylic acid. ), Preferably aliphatic carboxylic acids, particularly preferably aliphatic monocarboxylic acids having 1 to 5 carbon atoms, most preferably acetic acid, e.g. methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, tert- Butanol, isobutanol, heptanol, hexanol, octanol, ethylhexanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, pentaerythritol, sorbitol, glycerin, polyglycerins, phenol, naphthol, dihydroxybenzene, trihydroxy Benzene and the like (the above alcohols and phenols may have a suitable substituent, or may have a plurality of these. For example, an alkyl group, an alkoxyl group, an acyl group, an amino group Thio group,
Amide group, nitro group, halogen group, sulfonic acid group and the like, specifically, cholesterol, cholestanol,
Fluorophenol, chlorophenol, bromophenol, iodophenol, difluorophenol, dichlorophenol, dibromophenol, diiodophenol, trifluorophenol, trichlorophenol, tribromophenol, triiodophenol, nitrophenol, dinitrophenol, trinitrophenol, Cresol, dimethylphenol, trimethylphenol, phenolsulfonic acid and the like can be mentioned. ), Preferably a carboxylic acid ester obtained by dehydrating and condensing an aromatic group which may have a substituent, particularly preferably a phenol or naphthol substituted with a halogen or an alkyl group.

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

In the present invention, the charge ratio of the aromatic compound to the carboxylic acid or carboxylic acid ester is not particularly limited, but is preferably, for example, 1:10 to 10: 1 (molar ratio), particularly preferably. 3:10 to 10: 3
It is.

In the present invention, a co-catalyst represented by the general formula D
—OH (wherein D represents a carbon atom 1 which may have a substituent)
(Indicating an aliphatic, alicyclic or aromatic group of from 36 to 36) is preferred for promoting the reaction and improving the yield. Specifically, for example, methanol, ethanol,
Propanol, isopropanol, n-butanol, s
ec-butanol, tert-butanol, isobutanol, heptanol, hexanol, octanol, ethylhexanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, phenol, naphthol, etc. Examples thereof include an alkyl group, an alkoxyl group, an acyl group, an amino group, a thio group, an amide group, a nitro group, a halogen, a sulfonic acid group, a hydroxyl group, and the like. Specifically, dihydroxybenzene, trihydroxybenzene, pentaerythritol, sorbitol, glycerin, polyglycerins, cholesterol, cholestanol, fluorophenol,
Chlorophenol, bromophenol, iodophenol, difluorophenol, dichlorophenol, dibromophenol, diiodophenol, trifluorophenol, trichlorophenol, tribromophenol, triiodophenol, nitrophenol, dinitrophenol, trinitrophenol, cresol, dimethyl Phenol, trimethylphenol, phenolsulfonic acid and the like can be mentioned. )

Among the above cocatalysts, those having an aromatic group which may have a substituent, particularly those substituted with a halon, an alkyl group, a sulfonic acid group or a nitro group, are most preferable. Examples are chlorophenol,
Trichlorophenol, nitrophenol, trimethylphenol and phenolsulfonic acid.

The amount of the co-catalyst that can be used in the present invention is not particularly limited, but is, for example, 0.01 to 300 mol%, preferably 0.1 to 100 mol%, based on carboxylic acid or carboxylic acid ester. It is. The amount of co-catalyst is 0.01 to carboxylic acid or carboxylic acid ester.
By setting the content to 300 mol%, the reaction time can be shortened, and it is economically advantageous.

As the rare earth catalyst represented by the general formula M (OSO ₂ Rf) ₃ which can be used as a catalyst in the present invention, for example, M is scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, Gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutesium, etc., preferably scandium, ytterbium, particularly preferably scandium, and Rf is a carbon such as a trifluoromethyl group, a pentafluoroethyl group, a nonafluorobutyl group Examples include perfluoroalkyl groups of Formulas 1 to 6 and those having a perfluoroalkoxy group on the side chain of a polymer such as a Nafion resin, and are preferably perfluoroalkyl groups and particularly preferred. Ku is a trifluoromethyl group. The rare earth catalyst may be used alone or as a mixture of two or more kinds. Further, a product synthesized from a mixture of rare earth compounds before purification that has been produced may be used as such as a mixture of rare earth catalysts.

The amount of the rare earth catalyst is not particularly limited, but may be, for example, 0.01 to 300 mol%, preferably 0.1 to 300 mol%, based on carboxylic acid or carboxylic acid ester.
100 mol%. By setting the amount of the rare earth catalyst to 0.01 to 300 mol% based on the carboxylic acid or carboxylic acid ester, the reaction time can be shortened,
It is also economically advantageous.

In order to promote the reaction, a compound having a function as a dehydrating agent such as magnesium sulfate, sodium sulfate, calcium chloride, molecular sieve, or the like, or lithium perchlorate or perchlorine having an activating effect of an acylating agent Other additives such as sodium acid may be added. The addition amount of such other additives is not particularly limited, but is, for example, 1 to 1000 mol%, preferably 100 to 40 mol% based on carboxylic acid or carboxylic acid ester.
0 mol%.

The reaction can be carried out without a solvent, but an organic solvent can also be used to sufficiently mix the raw materials. Such organic solvents include, for example, carbon disulfide, carbon tetrachloride, 1,2-dichloroethane, hexane, diethyl ether, tetrahydrofuran, dichloromethane, acetonitrile, nitromethane, chloroform, cyclohexane, and the like. 0.1-200 times by weight, preferably 1-5
It is preferable to use 0 times by weight. This solvent may be used alone or as a mixture of two or more.

The reaction can be carried out in the air, but is preferably carried out in an inert gas, for example, in a nitrogen or argon atmosphere in order to suppress the formation of by-products. The reaction temperature is -100 to 250C, preferably -20 to 200.
C., particularly preferably at 0 to 150 C. By setting the reaction temperature to -100 to 250 ° C., the reaction rate can be increased and the coloring of the product can be prevented. The reaction time varies depending on the reaction conditions, but is generally from 10 minutes to 100 hours.

The order of the reaction is not particularly limited. For example, a rare earth catalyst and / or a co-catalyst and a carboxylic acid or a carboxylic acid ester are mixed to prepare a reactive species in advance, and an aromatic compound is added dropwise to this solution. A method of adding a carboxylic acid or a carboxylic acid ester to a mixture of an aromatic compound and a rare earth catalyst and / or a co-catalyst; and a method of adding a rare earth catalyst and / or a mixture of an aromatic compound and a carboxylic acid or a carboxylic acid ester. Alternatively, there is a method of adding a co-catalyst, and any of them may be used.

After completion of the reaction, the desired aromatic ketone can be obtained from the reaction solution by a method such as neutralization, filtration, distillation, extraction and the like. In order to recover and reuse the rare earth catalyst represented by the general formula M (OSO ₂ Rf) ₃ , extraction is preferably performed. 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. By removing, the rare earth catalyst can be recovered. If necessary, the catalyst is further purified, and the rare earth catalyst can be reused as the reaction catalyst of the present invention. Further, the reaction product may be purified, if necessary, according to a conventional method such as silica gel column chromatography, distillation and recrystallization.

[0026]

EXAMPLES Next, examples of the present invention will be described, but the present invention is not limited to the following examples.

Example 1 Scandium triflate, a rare earth catalyst (general formula M) at 25 ° C. under a nitrogen atmosphere
(OSO ₂ Rf) ₃ in which M is scandium and Rf is a trifluoromethyl group;
g (0.080 mmol) and 17.7-naphthol 57.7
mg (0.40 mmol) was placed in a reactor and stirred for 10 minutes. Next, acetic acid was added to 2.0 ml of toluene.
0 mg (0.40 mmol) dissolved solution was added, and 10
Stirred at 0 ° C. for 6 hours. As a result of analyzing the reaction solution by gas chromatography, 2-acetyl-1-naphthol was added.
It was confirmed that 22 mmol (54% yield) had been produced.

<Example 2> Under a nitrogen atmosphere, scandium triflate, which is a rare earth catalyst, was heated at 25 ° C at 49.7 m.
g (0.10 mmol) and 1-naphthol.
5 mg (2.0 mmol) and 1.20 g of acetic acid (2
0 mmol) and stirred under reflux for 24 hours. As a result of analyzing the reaction solution by gas chromatography, 1.16 mmol of 2-acetyl-1-naphthol was obtained.
(58% yield) was confirmed to have been produced.

Example 3 A rare earth catalyst ytterbium triflate (general formula M) at 25 ° C. under a nitrogen atmosphere
In (OSO ₂ Rf) ₃ , M is ytterbium, Rf
Is a trifluoromethyl group) of 62.0 mg (0.
10 mmol) and 289.2 mg of 1-naphthol
(2.0 mmol) and 1.20 g (20 mmol) of acetic acid.
l) was placed in a reactor and stirred for 24 hours while refluxing. As a result of analyzing the reaction solution by gas chromatography,
It was confirmed that 0.56 mmol (yield 28%) of 2-acetyl-1-naphthol was produced.

<Comparative Example 1> 11.4 mg of a catalyst boron trifluoride ether complex at 25 ° C under a nitrogen atmosphere.
(0.080 mmol) and 57.7 of 1-naphthol
mg (0.40 mmol) was placed in a reactor and stirred for 10 minutes. Next, 24.0 mg of acetic acid was added to 2.0 ml of toluene.
(0.40 mmol) dissolved solution was added and stirred at 100 ° C. for 6 hours. As a result of analyzing the reaction solution by gas chromatography, formation of 2-acetyl-1-naphthol was not confirmed.

Comparative Example 2 20.8 mg (0.080 mmol) of the catalyst tin tetrachloride was added at 25 ° C. under a nitrogen atmosphere.
57.7 mg (0.40 mmol) of 1-naphthol was placed in a reactor and stirred for 10 minutes. Next, toluene 2.0
A solution in which 24.0 mg (0.40 mmol) of acetic acid was dissolved in 100 ml was added, and the mixture was stirred at 100 ° C. for 6 hours. As a result of analyzing the reaction solution by gas chromatography, 2-acetyl-
It was confirmed that 1-naphthol was generated in a trace amount (1% or less).

<Example 4> Under a nitrogen atmosphere, scandium triflate, a rare earth catalyst, was added at 40.0 m at 25 ° C.
g (0.08 mmol) and 2.0 ml of anisole
(18 mmol) and acetic acid (24.9 mg, 0.41 m
mol)) and stirred at 100 ° C. for 4 hours. As a result of analyzing the reaction solution by gas chromatography,
It was confirmed that 0.012 mmol (yield 3%) of 4-methoxyacetophenone was generated.

Comparative Example 3 11.4 mg of boron trifluoride ether complex in a nitrogen atmosphere at 25 ° C.
(0.080 mmol) and 2.0 ml of anisole
(18 mmol) and 24.0 mg of acetic acid (0.40 m
mol)) and stirred at 100 ° C. for 16 hours. As a result of analyzing the reaction solution by gas chromatography,
The production of 4-methoxyacetophenone was not confirmed.

Comparative Example 4 20.8 mg (0.080 mmol) of the catalyst tin tetrachloride was added at 25 ° C. under a nitrogen atmosphere.
2.0 ml (18 mmol) of anisole and 2 parts of acetic acid
4.0 mg (0.40 mmol) and 1
Stirred at 00 ° C. for 16 hours. As a result of analyzing the reaction solution by gas chromatography, generation of 4-methoxyacetophenone was not confirmed.

Example 5 Under a nitrogen atmosphere, scandium triflate, a rare earth catalyst, was added at 39.6 m at 25 ° C.
g (0.081 mmol), 74.8 mg (0.40 mmol) of 1-naphthyl acetate, and 2.0 ml (18 mmol) of anisole were placed in a reactor.
Stirred at C for 1 hour. The reaction mixture was analyzed by gas chromatography to find that 4-methoxyacetophenone 0.17
It was confirmed that mmol (yield 43%) was produced.

<Example 6> Under a nitrogen atmosphere, scandium triflate, a rare earth catalyst, was added at 79.0 m at 25 ° C.
g (0.16 mmol) and 147.0 mg (0.83 mmol) of 2,4,6-trimethylphenyl acetate.
l) and 4.0 ml (36 mmol) of anisole were put into a reactor and stirred at 100 ° C. for 4 hours. As a result of analyzing the reaction solution by gas chromatography, it was confirmed that 0.29 mmol (yield 35%) of 4-methoxyacetophenone was generated.

Example 7 Under a nitrogen atmosphere, scandium triflate, a rare earth catalyst, was added at 25 ° C. for 78.7 m.
g (0.16 mmol) and 192.6 mg (0.80 mmol) of 2,4,6-trichlorophenyl acetate.
l) and 4.0 ml (36 mmol) of anisole were put in a reactor and stirred at 100 ° C. for 2 hours. As a result of analyzing the reaction solution by gas chromatography, it was confirmed that 0.39 mmol (yield 49%) of 4-methoxyacetophenone was generated.

Example 8 Under a nitrogen atmosphere, scandium triflate, a rare earth catalyst, was added at 78.7 m at 25 ° C.
g (0.16 mmol), 137.9 mg (0.81 mmol) of 4-chlorophenylacetate, and 4.0 ml (36 mmol) of anisole were put into a reactor,
Stirred at 100 ° C. for 8 hours. As a result of analyzing the reaction solution by gas chromatography, it was confirmed that 0.31 mmol (yield 38%) of 4-methoxyacetophenone was generated.

<Comparative Example 5> 11.4 mg of boron trifluoride ether complex in a nitrogen atmosphere at 25 ° C.
(0.080 mmol) and 2.0 ml of anisole
(18 mmol) and 68.2 mg (0.40 mmol) of 4-chlorophenylacetate were placed in a reactor,
Stirred at 100 ° C. for 16 hours. As a result of analyzing the reaction solution by gas chromatography, generation of 4-methoxyacetophenone was not confirmed.

Comparative Example 6 20.8 mg (0.080 mmol) of the catalyst tin tetrachloride was added at 25 ° C. under a nitrogen atmosphere.
2.0 ml (18 mmol) of anisole and 68.4 mg (0.40 mmol) of 4-chlorophenylacetate
1) was placed in a reactor and stirred at 100 ° C. for 16 hours.
As a result of analyzing the reaction solution by gas chromatography, 4-
No formation of methoxyacetophenone was confirmed.

Example 9 Under a nitrogen atmosphere, scandium triflate, which is a rare earth catalyst, was heated at 25 ° C. in an amount of 79.2 m.
g (0.16 mmol) and 4-chlorophenol in 1
44.4 mg (0.81 mmol) and 48.2 mg of acetic acid
mg (0.80 mmol) and 4.0 ml of anisole
(36 mmol) was placed in a reactor and stirred at 100 ° C. for 16 hours. As a result of analyzing the reaction solution by gas chromatography, 0.080 mmol of 4-methoxyacetophenone was obtained.
It was confirmed that 1 (yield 10%) was produced.

Example 10 Under nitrogen atmosphere, scandium triflate, a rare earth catalyst, was added at 78.9 at 25 ° C.
mg (0.16 mmol), 21.8 mg (0.16 mmol) of 2,4,6-trimethylphenol, 52.5 mg (0.87 mmol) of acetic acid, and 4.0 ml (36 mmol) of anisole Put in a container, 10
Stirred at 0 ° C. for 16 hours. The reaction mixture was analyzed by gas chromatography to find that 4-methoxyacetophenone 0.1.
It was confirmed that 043 mmol (yield 5%) was produced.

Example 11 Under a nitrogen atmosphere, scandium triflate, a rare earth catalyst, was added at 25 ° C. to 39.4.
mg (0.080 mmol), 54.5 mg (0.40 mmol) of 2,4,6-trimethylphenol,
24.8 mg (0.41 mmol) of acetic acid and 2.0 ml (18 mmol) of anisole were put into a reactor, and 1
Stirred at 00 ° C. for 8 hours. The reaction mixture was analyzed by gas chromatography to find that 4-methoxyacetophenone 0.1.
It was confirmed that 029 mmol (yield 7%) was produced.

Example 12 Under a nitrogen atmosphere, scandium triflate, a rare earth catalyst, was added at 25 ° C. at 79.4.
mg (0.16 mmol), 28.9 mg (0.17 mmol) of p-phenolsulfonic acid, and 5% of acetic acid.
2.0 mg (0.87 mmol) and anisole in 4.
0 ml (36 mmol) was placed in the reactor and stirred at 100 ° C. for 16 hours. The reaction mixture was analyzed by gas chromatography to find that 4-methoxyacetophenone 0.064
It was confirmed that mmol (yield 7%) was produced.

Example 13 Scandium triflate as a rare earth catalyst was 39.4 at 25 ° C. in a nitrogen atmosphere.
mg (0.080 mmol) and 1-naphthol
7.7 mg (0.40 mmol) and 144 mg (1.2 mmol) of magnesium sulfate were put into a reactor, and 10
Stirred for minutes. Next, 24.0 ml of acetic acid was added to 2.0 ml of toluene.
mg (0.40 mmol) was added, and 10
Stirred at 0 ° C. for 4 hours. As a result of analyzing the reaction solution by gas chromatography, 2-acetyl-1-naphthol was added.
It was confirmed that 21 mmol (yield 53%) was produced.

EXAMPLE 14 Under a nitrogen atmosphere, scandium triflate, a rare earth catalyst, was added at 78.7 at 25 ° C.
mg (0.16 mmol), 136.5 mg (0.80 mmol) of 4-chlorophenylacetate, 4.0 ml (36 mmol) of anisole, and 288 mg (2.4 mmol) of magnesium sulfate were placed in a reactor. Stirred at C for 4 hours. As a result of analyzing the reaction solution by gas chromatography, it was confirmed that 0.32 mmol (yield 40%) of 4-methoxyacetophenone was generated.

<Example 15> Under a nitrogen atmosphere, scandium triflate, which is a rare earth catalyst, at 25 ° C. was used at 79.2.
mg (0.16 mmol), 104.4 mg (0.81 mmol) of 4-chlorophenol and 48.
2 mg (0.80 mmol) and anisole 4.0 m
l (36 mmol) and 288 mg of magnesium sulfate
(2.4 mmol) was placed in a reactor and stirred at 100 ° C. for 8 hours. As a result of analyzing the reaction solution by gas chromatography, 4-methoxyacetophenone 0.081 mmol
It was confirmed that 1 (yield 10%) was produced.

Example 16 After the reaction operation performed in Example 1, 20 ml of ether and 20 ml of water were added to perform an extraction operation. The obtained aqueous layer was concentrated under reduced pressure, and the residue was dried under reduced pressure at 200 ° C. for 24 hours to obtain scandium triflate.
3 mg was recovered. Then, 39.3 mg (0.080 mg) of the scandium triflate was added at 25 ° C. under a nitrogen atmosphere.
mmol) and 57.8 mg (0.4 mm) of 1-naphthol.
0 mmol) was stirred in the reactor for 10 minutes. Next, 24.2 mg (0.40 mg) of acetic acid was added to 2.0 ml of toluene.
(mmol) dissolved solution and stirred at 100 ° C. for 6 hours. As a result of analyzing the reaction solution by gas chromatography, 0.21 mmol of 2-acetyl-1-naphthol was obtained.
(Yield 53%) was confirmed to have been produced. That is, it was confirmed that the rare earth catalyst recovered after the reaction was able to be reused.

Example 17 After the reaction operation performed in Example 8, 20 ml of ether and 20 ml of water were added to perform an extraction operation. The obtained aqueous layer was concentrated under reduced pressure, and the residue was dried under reduced pressure at 200 ° C. for 24 hours to obtain scandium triflate.
4 mg were collected. Next, 78.4 mg (0.16 m 2) of the scandium triflate was added at 25 ° C. under a nitrogen atmosphere.
mol) and 4-chlorophenyl acetate.
4 mg (0.80 mmol) and 4.0 m of anisole
(36 mmol) was placed in a reactor and stirred at 100 ° C. for 8 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. That is, it was confirmed that the rare earth catalyst recovered after the reaction was able to be reused.

Example 18 After the reaction operation performed in Example 9, 20 ml of ether and 20 ml of water were added to perform an extraction operation. The obtained aqueous layer was concentrated under reduced pressure, and the residue was dried under reduced pressure at 200 ° C. for 24 hours.
9.0 mg was recovered. Then, at 25 ° C. under a nitrogen atmosphere, 79.0 mg (0.16 mg) of the scandium triflate was used.
mmol) and 102.4 mg of 4-chlorophenol.
(0.80 mmol) and 48.0 mg (0.8
0 mmol) and 4.0 ml (36 mmol) of anisole.
1) was placed in a reactor and stirred at 100 ° C. for 16 hours.
As a result of analyzing the reaction solution by gas chromatography, 4-
0.084 mmol of methoxyacetophenone (yield 10
%) Was confirmed to be formed. That is, it was confirmed that the rare earth catalyst recovered after the reaction was able to be reused.

[0051]

By using a specific rare earth catalyst, a carboxylic acid or a carboxylic acid ester which could not be used because of its low reactivity as an acylating agent can be converted into an aromatic ketone by the use of an aromatic ketone. Can be used for synthesis. This effect is further improved by using an alcohol or phenol as a co-catalyst. Even when a carboxylic acid or a carboxylic acid ester is used as the acylating agent, the rare earth catalyst after the completion of the reaction can be easily recovered, and the recovered rare earth catalyst can be reused. According to the present invention, bases such as cosmetics, emulsifiers, oils,
Aromatic ketones that can be used as raw materials for fragrances, medicines, agricultural chemicals and the like can be easily produced at low cost.

Claims (5)

[Claims] 1. A method for producing an aromatic ketone by reacting an aromatic compound having at least one substitutable hydrogen in an aromatic ring with an acylating agent using a catalyst, wherein the catalyst is a compound of the general formula M Using a rare earth catalyst represented by (OSO ₂ Rf) ₃ (where M represents a rare earth atom and Rf represents a perfluoroalkyl group or a perfluoroalkoxyl group), and using a carboxylic acid or a carboxylic ester as an acylating agent A method for producing an aromatic ketone, comprising: 2. The carboxylic acid of the general formula A-COOH
(In the formula, A has 1 to 36 carbon atoms which may have a substituent.
The aliphatic, alicyclic or aromatic group of the formula (1). 3. The carboxylic acid ester represented by the general formula A-
The compound represented by COO-B (wherein A and B represent an aliphatic, alicyclic or aromatic group having 1 to 36 carbon atoms which may have a substituent). the method of. 4. A co-catalyst further using a general formula D-OH (wherein D is a group having 1 to 1 carbon atoms which may have a substituent).
36 aliphatic, cycloaliphatic or aromatic groups).
The method according to any one of claims 1 to 3. 5. The method according to claim 1, wherein after the completion of the reaction, the used rare earth catalyst is recovered, and the recovered rare earth catalyst is reused as a catalyst.