JPH0348636A - Production of acyl group-substituted aromatic compound - Google Patents

Abstract

PURPOSE:To efficiently produce an acyl group-substituted aromatic compound useful as an agricultural chemical, photographic chemical, UV absorber, etc., by reacting an aromatic compound with carboxylic acids using a highly active fluorine-containing aromatic sulfonic acid catalyst. CONSTITUTION:An aromatic compound expressed by formula II (R is H, alkyl, alkoxy or halogen: (m) is 1-3; both P and Q are H, either thereof is phenyl and the other is H or both are hydrocarbons required to link and form naphthalene or tetralin ring) is reacted with carboxylic acids using a fluorine-containing aromatic sulfonic acid catalyst expressed by formula I (X<1> is F or 1-14C fluorine- containing alkyl which may contain ethereal oxygen atom; Ar<1> is aryl; (n) is 1-5; (m) is 1-3) as a catalyst to afford an acyl group-substituted aromatic compound (e.g. methylbenzophenone). A high yield can be attained by using the aforementioned catalyst even if water is present in the reaction system.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel method for producing an acyl group-substituted aromatic compound, which is a compound useful as an agricultural chemical, a photographic drug, a UV absorber, etc.

[Conventional technology]

In a method for producing acyl group-substituted aromatic compounds from aromatic compounds and carboxylic acids, a method using ion-exchange layered clay as a catalyst has been proposed (Japanese Patent Application Laid-Open No. 1983-1993).
-152636). This method is easy to operate;
Although suitable for industrial production, there is a need for a method for efficiently producing acyl group-substituted aromatic compounds using a highly active catalyst.

[Problem to be solved by the invention]

An object of the present invention is to propose a method for producing an acyl-substituted aromatic compound using a highly active catalyst and capable of producing the acyl-substituted aromatic compound in high yield even in the presence of water.

[Means to solve the problem]

The present invention relates to the following - Noshiro (1) (wherein R is a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, m is an integer of 1 to 3, P and Q are both hydrogen atoms, or either - is a phenyl group and the other is a hydrogen atom, or both are bonded to a hydrocarbon group necessary to form a substituted or unsubstituted naphthalene ring or tetralin ring) In a method for producing an acyl group-substituted aromatic compound by reacting a group compound with a carboxylic acid,
As a catalyst, the following - Noshiro [■] (X'+-A r'-(
So, H).

...(II) (wherein xl is a fluorine-containing alkyl group having 1 to 14 carbon atoms which may contain a fluorine atom or an ether oxygen atom, Ar" is an aryl group, n is an integer of 1 to 5, m is 1
Indicates an integer between ~3. When n is 2 or more, xl may be the same or different. ), or the following -Noshiro (m, 1 (X2)-Ar2-(SOLH)II...[■]) (where x2 does not contain a fluorine atom or an ether oxygen atom) an optional fluorine-containing alkyl group having 1 to 14 carbon atoms, A
r" is an aryl group, n is an integer of 1 to 5, m is an integer of 1 to 3, and when n is 2 or more, x2 may be the same or different.) A substituted aryl group represented by This is a method for producing an acyl group-substituted aromatic compound, characterized by using a bonded fluorine-containing aromatic sulfonic acid catalyst.

The aromatic compound used as a starting material in the present invention is the aromatic compound represented by -Noshiro (1) above.

Specific examples of the aromatic compound represented by -Noshiro [1) include benzene, toluene, o, and at.

P-xylene, mesitylene, pseudocumene, 1.2゜4.5-tetramethylbenzene, ethylbenzene, n
- Alkylbenzenes such as propylbenzene, isopropylbenzene, butylbenzene, diethylbenzene, diisopropylbenzene; anisole, methylmethoxybenzene, ethylmethoxybenzene, ethoxybenzene,
Methyl ethoxybenzene.

Alkoxybenzenes such as propoxybenzene; halogenated benzenes such as chlorobenzene, methylchlorobenzene, methoxychlorobenzene, bromobenzene, methylbromobenzene, iodobenzene, and fluorobenzene; biphenyl; naphthalene, α-methylnaphthalene, β
-Naphthalenes such as methylnaphthalene, 2,6-dimethylnaphthalene, methylchloronaphthalene, and methoxynaphthalene; examples include tetralin. Among these, it is preferable to use toluene+0ell+P-xylene, mesitylene, anisole, naphthalene, methylnaphthalene, dimethylnaphthalene, methoxynaphthalene, etc. because the reaction yield is high.

Carboxylic acids used in the method for producing acyl-substituted aromatic compounds of the present invention include fatty acids such as formic acid, acetic acid, propionic acid, stearic acid, lauric acid, acrylic acid, methacrylic acid, oxalic acid, succinic acid, and maleic acid. Group carboxylic acids; phenylacetic acid.

Aliphatic carboxylic acids substituted with substituted or unsubstituted aromatic hydrocarbons such as cinnamic acid; benzoic acid, toluic acid, ethylbenzoic acid, phenylbenzoic acid, hydroxybenzoic acid, methoxybenzoic acid, arylbenzoic acid, chloro Aromatic carboxylic acids such as benzoic acid, nitrobenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthoic acid, naphthalene dicarboxylic acid; acid anhydrides such as acetic anhydride, propionic anhydride, benzoic anhydride, phthalic anhydride; chloride Acetyl.

Examples include acid halides such as benzoyl chloride; ketocarboxylic acids such as pyruvic acid.

In the present invention, the catalyst is a fluorine-containing aromatic sulfonic acid catalyst represented by the above-mentioned -Noshiro (Il) (hereinafter referred to as "Il").

(sometimes abbreviated as catalyst 1), or -Noshiro (m
) A fluorine-containing aromatic sulfonic acid catalyst having a substituted aryl group bonded to a matrix (hereinafter sometimes abbreviated as catalyst 2) is used.

Catalyst 1 consists of a fluorine-containing aromatic sulfonic acid obtained by substituting an aromatic compound with a fluorine atom or a fluorine-containing alkyl group and a sulfonic acid group. Catalyst 2 is one in which such a fluorine-containing aromatic sulfonic acid is bonded to a matrix.

In the above-Noshiro (If) and (m), Ar1, A
Examples of the aryl group represented by r2 include a phenyl group, a naphthyl group, an anthryl group, and the like.

In the above-Noshiro (II) and (II[), x”
, x'' is a fluorine-containing alkyl group,
Specifically -CF3. -CF2CF, -CF2CF
2CF.

-CH2C71, -CHaC+Fs--CHxCsFx
x, -CH2C7Fxs.

-C1lzCsFtt, -cH,c,F,,, -c
H,c1oF2. .

-C1l,C)I,CF,, -CH,CH2C,F,
, -CH2CH,C,F,.

-C) lzCHzC4Fs, -CHzCHzCsFxn
t-CHzC)I2CtFts.

-CH2C)H2C,F,, -Cl(2C82C,
Fi,, -C11,C)1. C. F...

-CH2(CFZ), 11. -CIl2(CF2)4H
, -CIl2(CF2), 11°-C)1z(CFz)
sHl-C1la (CF, a) to H2-C11 (CF
3) 2゜-cll□CF, cH[7CF,, -CH
zCFzCHF(CF2)s't-C11,CF(CF
3) CHFCF(CF, ), -C)12CF(C,
F,)C)l(CF,),.

-CHaCsHFz*, -CcHFia, -CHz
CtaHF*o.

-C)I, C3F1. )I, −(C11,)SOCF
(CF3)2゜-(CHz)zxOcF(CFi)z
--CHz (CF2)zOcF3゜-CIl, (C
F2 >2QC,F, l-cHz (CFP)2
0C3F? .

For example, As Xl and X2, a fluorine atom or 10F is preferable.

As the catalyst 1, the fluorine-containing aromatic sulfonic acid may be used as it is, or may be physically supported on a carrier such as activated carbon.

Catalyst 1 includes a method of fluorinating an aromatic compound corresponding to the above Ar'' with a fluorinating agent and then sulfonating it with a sulfonating agent, and a method of hydrolyzing a fluorine-containing aromatic sulfochloride sulfonated with a sulfonating agent. As the fluorinating agent used for fluorination, known fluorinating agents such as xenon fluoride and fluorine gas can be used, and as the sulfonating agent used for sulfonation,
For example, known sulfonating agents such as chlorosulfuric acid and concentrated sulfuric acid can be used.

The matrix to which the substituted aryl group represented by the general formula (III) is bonded in the catalyst 2 is not particularly limited, as long as it can chemically bond to Ar2. Specific examples of such a matrix include, for example, polysiloxane; cyclodextrin; ion exchange resin;
Examples include polymers such as polystyrene; metal compounds such as zirconium, aluminum, and titanium; clays such as bentonite, montmorillonite, and mica; and silica and alumina. Specific examples of the metal compound include zirconium phosphate. Among these, polysiloxane, zirconium compounds, mica, and montmorillonite are preferably used.

In order to produce catalyst 2, any method can be adopted as long as it provides a structure in which the substituted aryl group represented by the general formula (m) is bonded to these matrices, but as a specific example, The following manufacturing methods 1 to 5 are mentioned. In addition, in each manufacturing method, -A and B each represent a reactive group. Furthermore, Ar2 and xl have the same meanings as in the above general formula [old] 6 Manufacturing method 1 A-8 Matrix -A + B-Ar"~x"-1 → Manufacturing method 3 In this method, the aromatic group of the matrix into which has been introduced is sulfonated with a sulfonating agent, and then fluorinated with a fluorinating agent.

Production method 4 In this method, a fluorine-containing aromatic group is first introduced into a matrix, and then this is sulfonated with a sulfonating agent.

Manufacturing method 2 A-8 Matrix-A + B-Ar"-3o3H->
In this method, a sulfonic acid group-containing aromatic group is first introduced into a matrix, and then this is fluorinated with a fluorinating agent.

In this method, an aromatic group in a matrix into which an aromatic group has already been introduced is fluorinated with a fluorinating agent, and then sulfonated with a sulfonating agent.

Production Method 5 2 AB Matrix-A+B-Ar2-9o31+->Catalyst 2 This method is a method of introducing an aromatic group to which fluorine and a sulfonic acid group are bonded into a matrix.

In each production method, known fluorinating agents such as xenon fluoride and fluorine gas can be used as fluorinating agents for fluorination, and examples of sulfonating agents used for sulfonation include chlorosulfuric acid, concentrated sulfuric acid, etc. Known sulfonating agents such as can be used.

Catalyst 1 and Catalyst 2 used in the present invention both contain fluorine atoms with large electron-withdrawing properties, so the acid strength of the sulfonic acid group is strengthened, and they also have excellent water repellency because they have fluorine atoms. .

Therefore, in the method of the present invention, even if water is present in one reaction system, the catalyst is not poisoned by water, and high activity is continuously exhibited. Compounds can be produced in high yield.

The amount of these catalysts 1.2 to be used varies somewhat depending on the raw material compounds and reaction conditions, but is usually 0.1 to 100 parts by weight per 100 parts by weight of the aromatic compounds and carboxylic acids charged as raw materials. , preferably 1 to 30 parts by weight.

In the present invention, an acyl group-substituted aromatic compound is obtained by reacting the aromatic compound with the carboxylic acid in the presence of Catalyst 1 or Catalyst 2. Specifically, the acyl group-substituted aromatic compounds produced include alkylphenyl ketones such as benzaldehyde, acetophenone, ethyl phenyl ketone, n-propylphenyl ketone, propylphenyl ketone, and butylphenyl ketone; 2-methylbenzaldehyde, 4 -Methylacetophenone, 2,4-dimethylacetophenone, 2,4
゜6-Dolimethylacetophenone, 2-ethylacetophenone, 4-methoxyacetophenone, 4-ethoxyacetophenone, 2.4-dimethylphenylethyl ketone, 2,4.6-dolimethylphenylethyl ketone, 2.
4. Alkylarylketones such as 6-drimethylphenylpropylketone and 4-methoxyphenylbutylketone; benzophenone, 2-methylbenzophenone, 4-methoxyphenylbutylketone, etc.
-ethylbenzophenone, 2,4-dimethylbenzophenone, 3.4-dimethylbenzophenone, 2.5-dimethylbenzophenone, 2,4.6-1-dimethylbenzophenone, 2,4.6-trimethyl-4'-methylbenzophenone, 2,4-diethyl-4'-methylbenzophenone, 2,4-dimethyl-4'-methoxybenzophenone, 4-methoxybenzophenone, 4-methoxy-
Diaryl ketones such as 4'-methylbenzophenone and 4,4'-dimethoxybenzophenone; l-naphthyl ethyl ketone, 2-naphthyl methyl ketone, 1-naphthyl ethyl ketone, ■-naphthylpropyl ketone, 1-(6
Alkylnaphthyl ketones such as -methylnaphthyl)methylketone, 2-(l-methoxynaphthyl)methylketone, and 2-(1-methoxynaphthyl)ethylketone; phenyl-1-naphthylketone, phenyl-2-naphthylketone, phenyl-1- (2-methylnaphthyl)ketone,
Phenyl-1-(6-methylnaphthyl)ketone, Phenyl-1-(2,6-dimethylnaphthyl-1-(6-
ethylnaphthyl)ketone, phenyl-1-(6-
Phenylnaphthyl ketones such as propylnaphthyl)ketone, phenyl-2-(2-methylnaphthyl)ketone, phenyl-2-(6-methylnaphthyl)ketone, and phenyl-2-(1-methoxynaphthyl)ketone; tolyl-1 −
naphthylketone, triluene, naphthylketone, 2.
4-dimethylphenyl-1'-naphthylketone, 2,4
-dimethylphenyl-2'-naphthylketone, 2,4.

6-drimethylphenyl-1'-naphthylketone, 2,
4.

6-drimethylphenyl-2'-naphthylketone, 2,
4-dimethylphenyl-1'-(4'-methylnaphthyl)kene, 2,4.6-trimethylphenyl-
1'-(6'-methylnaphthyl)ketone, 4-methoxyphenyl-1'-naphthylketone, 4-methoxyphenyl-2-naphthylketone, 4-methoxyphenyl-2'
-Arylnaphthyl ketones such as (6'-methoxynaphthyl)ketone;1,1'-dinaphthyl ketone, 1.2
'-dinaphthyl ketone, 2.

2'-dinaphthyl ketone, 1-(2-methylnaphthyl)
-1'-naphthyl ketone, ■-(5-methylnaphthyl)
-t'-naphthylketone, l-(6-methylnaphthyl)
-1'-naphthyl ketone, 1-(4.6-dimethylnaphthyl)-1'-naphthyl ketone, 1-(5-ethylnaphthyl)-1'-naphthyl ketone, l-naphthyl-1'-
(6'-methylnaphthyl)ketone, L-(4-methylnaphthyl)-1'-(6'-methylnaphthyl)ketone,
1-(4-methylnaphthyl)-2'-naphthyl ketone,
1-(6-propylnaphthyl)-2'-naphthyl ketone, ■-naphthyl-2'-(6'-methylnaphthyl) ketone, 1-(6-methylnaphthyl)-2'-(4'-methylnaphthyl) ketone , 2-(6-methylnaphthyl)-
2'-(4',7'-dimethylnaphthyl)ketone, 2
-(1-methoxynaphthyl)-1'-naphthyl ketone,
2-(1-methoxynaphthyl)-1,'-(6'-methylnaphthyl)ketone, 2-(1-methoxynaphthyl)-
Examples include dinaphthyl ketones such as 1'-(4'-methoxynaphthyl)ketone.

Among the above acyl group-substituted aromatic compounds, in particular, diaryl ketones such as methylbenzophenone, dimethylbenzophenone, trimethylbenzophenone, and methoxybenzophenone; alkylaryl ketones such as methylacetophenone and dimethylacetophenone; phenylnaphthyl ketones such as phenylnaphthyl ketone and phenylmethoxynaphthyl ketone ;Methoxyphenylnaphthylketone, arylnaphthylketones of phenylmethoxynaphthylketone;
When producing alkyl naphthyl ketones such as methoxy naphthyl methyl ketone, it is preferable to use the method of the present invention because the reaction yield will be high.

Although the reaction according to the method of the present invention can be carried out using either a liquid phase method or a gas phase method, it is particularly preferable to carry out the reaction using a liquid phase method in terms of efficiency.

The reaction can be carried out without using a solvent or with a solvent. Examples of the solvent include halogen-substituted aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, and bromobenzene. The amount of the solvent used is preferably 0.1 to 100 parts by weight based on 1 part by weight of the aromatic compounds and carboxylic acids charged as raw materials.

In the method of the present invention, 100% of the raw aromatic compound
Carboxylic acids can usually be used in an amount of 1 to 1000 moles per mole, but it is preferable to use 10 to 50 moles of carboxylic acids and conduct the reaction under conditions where the aromatic compound is in excess when selecting an acyl group-substituted aromatic compound. This is preferable from the viewpoint of increasing the ratio.

The reaction temperature of the acylation reaction of the present invention is usually room temperature to 350°C.
, preferably from 100 to 250°C, and the reaction can be carried out by either a liquid phase method or a gas phase method as required within the temperature range. Although the reaction time at this time is appropriate, particularly in the case of a liquid phase method, it is usually sufficient to carry out the reaction for 0.1 to 20 hours.

The reaction can be carried out under reduced pressure, atmospheric pressure or increased pressure as required. Further, in the method of the present invention, it is preferable to carry out the reaction while removing generated water from the system as necessary, since the reaction proceeds easily.

After the reaction is completed, an acyl group-substituted aromatic compound can be obtained by a distillation method, a crystallization method, an extraction method, or the like.

〔Effect of the invention〕

According to the present invention, since a fluorine-containing aromatic sulfonic acid catalyst having a fluorine atom or a fluorine-containing alkyl group and a sulfonic acid group is used as a catalyst, acyl group substitution can be achieved in high yield even in the presence of water. Aromatic compounds can be produced.

〔Example〕

Examples of the present invention will be described below.

Example 1 0.2 g of p-fluorobenzenesulfonic acid (hereinafter abbreviated as FIBSA), 5.6 g of benzoic anhydride, and m
-Xylene 20+aQ was placed in a reaction vessel and reacted for 2 hours under m-xylene reflux to perform an acylation reaction of m-xylene. The results are shown in Table 1.

Example 2 The reaction was carried out under the same conditions as in Example 1 except that the catalyst was changed to pentafluorobenzenesulfonic acid (hereinafter abbreviated as F5BSA). The results are shown in Table 1.

Comparative Examples 1 to 3 Same conditions as in Example 1 except that the catalyst was changed to sulfonated polyphenylsiloxane (Comparative Example 1), p-toluenesulfonic acid (Comparative Example 2), or silica/alumina (Comparative Example 3) The reaction was carried out. The results are shown in Table 1.

Table 1 Example 3 8.0 g of chlorotrie-1-xysilane was added to 100 g of ether
n+Q and stirred on a triice-acetone bath. Next, P-fluorophenylmagnesium bromide F
20 mQ of a 2.0M ether solution of (F 8 M g Br ) was added dropwise to perform one reaction. The pale yellow oil obtained by distilling off the ether was dissolved in ethanol 100n+Q,
20 g of tetraethoxysilane and 0. IN hydrochloric acid 35m
fi was added thereto, heated at 120°C, and ethanol was distilled off while stirring for 2 hours.

Add 100 mρ of cyclohexane and 60 mρ of ethanol to the residue.
After adding +all, it was added dropwise to distilled water 5001 with strong stirring, and then aqueous ammonia IQOmQ was added.

After 8 hours, the generated solids were filtered, washed with water, and
It was dried at .degree. C. for 8 hours to obtain 14 g of fluorine-containing polyphenylsiloxane in the form of a white powder.

After adding 13 g of the obtained powder to 50 d of chloroform,
A 5:1 (volume ratio) mixed solution 1100a of chloroform and CQSO,H was added dropwise to perform sulfonation. After filtering, washing with water, and drying at 100° C., 11 g of the desired fluorine-containing sulfonated polyphenylsiloxane catalyst was obtained. As a result of elemental analysis, the composition of this fluorine-containing sulfonated polyphenylsiloxane is F: 2.6 wt%, S: 3.5
wt%, C: 12.0wt%, Si: 33.0w
t%. 0.2 g of the fluorine-containing sulfonated polyphenylsiloxane catalyst obtained as above, mesitylene (1,3,
5-trimethylbenzene) and 0.5 [5-trimethylbenzene] were placed in a 50 mA flask and heated at 1110°C for 5
The reaction was carried out for a period of time, and the acylation reaction of mesitylene was carried out.

The results are shown in Table 2.

Comparative Examples 4 and 5 The acylation reaction of mesitylene was carried out under the same conditions as in Example 3 except that the catalyst was changed to Nafion-11 (manufactured by DuPont, trademark) (Comparative Example 4) or silica/alumina (Comparative Example 5). went. The results are shown in Table 2.

Example 4 Commercially available sulfonic acid type ion exchange resin (ROHM & Co., Ltd.)
After adding 5 g of Amberlyst 15 (trademark) manufactured by Haas Corporation to 50 g of carbon tetrachloride, 2.5 g of xenon fluoride was added at room temperature and the reaction was carried out for 3 hours to obtain fluorine-containing Amberlyst 15.

Using this fluorine-containing Amberlyst 15 as a catalyst,
The same reaction as in Example 3 was carried out. The results are shown in Table 2.

Comparative Example 6 The reaction was carried out under the same conditions as in Example 4 except that the catalyst was changed to Anno List 15 before fluorination. The results are shown in Table 2.

Example 5 After adding 10 g of commercially available polystyrene to 50 ml of chloroform, a mixed solution of chloroform, Cl2SO, and H was added dropwise to perform sulfonation. After filtering and washing, 5 g of sulfonated polystyrene was added to 50 g of carbon tetrachloride, and then 2.5 g of fluorinated xenon was added at room temperature and a reaction was carried out for 3 hours to obtain fluorinated sulfonated polystyrene.

The same reaction as in Example 3 was carried out using this fluorinated sulfonated polystyrene as a catalyst. The results are shown in Table 2.

Comparative Example 7 The reaction was carried out under the same conditions as in Example 5 except that the catalyst was changed to sulfonated polystyrene.

The results are shown in Table 2.

Table 2 $I F-5PS; Fluorine-containing sulfonated polyphenylsiloxane A2 obtained in Example 3 F-A15; Fluorine-containing Amberlyst 15*
3 FS-PS; Fluorinated sulfonated polystyrene*
4A15; Amberlyst 15 A55-PS; Sulfonated polystyrene Example 6 0.2 g of the fluorine-containing sulfonated polyphenylsiloxane catalyst obtained in Example 3, 20 mA of m-xylene, and 15.6 g of benzoic anhydride were placed in a reaction vessel. , m-xylene was reacted for 2 hours under reflux to carry out an acylation reaction of m-xylene. The results are shown in Table 3.

Example 7.8 In Example 6, m-xylene was replaced with toluene (Example 7
) or anisole (Example 8), the acylation reaction was carried out under the same conditions. The results are shown in Table 3.

Examples 9 to 11 In Example 6, benzoic anhydride was replaced with benzoic acid (Example 9).
), propionic acid (Example 10) or acetic acid (Example 1)
The acylation reaction of m-xylene was carried out under the same conditions except that the conditions were changed to 1). The results are shown in Table 3.

Comparative Examples 8 to 1O In Example 6, the fluorine-containing sulfonated polyphenylsiloxane catalyst was replaced with fluorine-free sulfonated polyphenylsiloxane (Comparative Example 8), ρ-toluenesulfonic acid (Comparative Example 9), or silica/alumina. (Comparative example 1
The acylation reaction of m-xylene was carried out under the same conditions except that the conditions were changed to 0). The results are shown in Table 3.

Table 3 $IF-5PS; Fluorine-containing sulfonated polyphenylsiloxane obtained in Example 3 25PS; Sulfonated polyphenylsiloxane*3
ρ-TSA; P-toluenesulfonic acid Example 12 A catalyst was prepared under the same conditions as in Example 3 except that P-fluorophenylmagnesium bromide was changed to 3,5-bis(trifluoromethyl).

The composition of the obtained fluorine-containing sulfonated polyphenylsiloxane was as follows: F: 1O, 2wt%, S: 3. lst%
, C: 13.2wt%, Si: 34.6wt%
Met.

Next, in Example 3, an acylation reaction of mesitylene was carried out under the same conditions except that the catalyst was changed to the above-mentioned fluorine-containing sulfonated polyphenylsiloxane catalyst6.As a result,
The conversion rate of caprylic acid was 38%.

Example 13 A 0.5M zirconium oxychloride solution was added to a 1M aqueous phosphoric acid solution, and the mixture was reacted overnight at around 0°C. After filtration, 5
It was reslurried with a wt% phosphoric acid aqueous solution and treated at 40°C for 1 hour. After washing with water, dry at 100℃ for 15 hours.
It was added to a 6M aqueous phosphoric acid solution and heated at about 165°C for 10 hours to obtain crystalline zirconium phosphate.

5 g of the above zirconium phosphate and 20 g of chloromethylfluorobenzenesulfonic acid are reacted in the presence of a base,
A catalyst was obtained in which a fluorine-containing benzenesulfonic acid group was introduced into zirconium phosphate.

0.2E of the above catalyst, 20mQ of mesitylene and 0.5g of caprylic were placed in a 50o+Q flask and heated to 180°C.
The reaction was carried out for 5 hours to carry out the acylation reaction of mesitylene.

As a result, the conversion rate of caprylic acid was 35%.

Comparative Example 11 The acylation reaction of mesitylene was carried out under the same conditions as in Example 13 except that zirconium phosphate was used as a catalyst. As a result, the conversion rate of caprylic acid was 0%.

Example 14 After gradually adding 200 g of aluminum to an aqueous solution of aluminum monochloride, the mixture was reacted at 50° C. for about 6 hours.

Unreacted aluminum was filtered off to obtain an aqueous solution containing an aluminum chlorohydroxide complex. The amount of aluminum in this aqueous solution was 10.0%it%.

Sodium tetrasilicic mica (NaMgz,s (sx4ox), a synthetic mica manufactured by Topie Co., Ltd.
a) 100 g of a 10 wt% colloidal aqueous solution of F2),
After adding to IQ water and stirring well, 300 g of the aqueous solution containing the above aluminum chlorohydroxide complex was gradually added while stirring to perform ion exchange. After filtering and washing with water, 12
It was dried at 0° C. overnight to obtain a crosslinked synthetic mica.

5 g of the above crosslinked synthetic mica and 20 g of chloromethylfluorobenzenesulfonic acid were reacted in the presence of a base to obtain a catalyst in which a fluorine-containing benzenesulfonic acid group was introduced into the crosslinked synthetic mica.

0.2 g of the above catalyst, mesitylene 20- and caprylic r
Put 0.5g of a into a 50mQ no flask and heat at 180℃ for 5 minutes.
The reaction was carried out for a period of time, and the acylation reaction of mesitylene was carried out.

As a result, the conversion rate of caprylic acid was 41%.

Comparative Example 12 The acylation reaction of mesitylene was carried out under the same conditions as in Example 14 except that crosslinked synthetic mica was used as a catalyst. As a result, the conversion rate of caprylic acid was 0%.

Example 15 A catalyst was prepared in the same manner as in Example 14 except that 100 g of a lQwt% aqueous solution of sodium tetrasilicic mica was replaced with powdered montmorillonite IQg, and an acylation reaction of mesitylene was carried out. As a result, the conversion rate of caprylic acid was 33%.

Comparative Example 13 The acylation reaction of mesitylene was carried out under the same conditions as in Example 15 except that crosslinked montmorillonite was used as a catalyst. As a result, the conversion rate of caprylic acid was 1%.

Claims (8)

[Claims] (1) The following general formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼...[I] (In the formula, R is a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and m is an integer from 1 to 3. , P and Q are both hydrogen atoms, one is a phenyl group and the other is a hydrogen atom, or both combine to form a substituted or unsubstituted naphthalene or tetralin ring. In the method for producing an acyl group-substituted aromatic compound by reacting an aromatic compound represented by
As a catalyst, there are the following general formula [II] ▲ numerical formula, chemical formula, table, etc. ▼... [II] (In the formula, X^1 is a carbon number of 1 to 14 that may contain a fluorine atom or an ether oxygen atom is a fluorine-containing alkyl group, Ar^1 is an aryl group, n is an integer of 1 to 5, m is 1
Indicates an integer between ~3. When n is 2 or more, X^1 may be the same or different. ) A method for producing an acyl group-substituted aromatic compound, which comprises using a fluorine-containing aromatic sulfonic acid catalyst represented by: (2) The following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] (In the formula, R is a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and m is an integer from 1 to 3. , P and Q are both hydrogen atoms, one is a phenyl group and the other is a hydrogen atom, or both combine to form a substituted or unsubstituted naphthalene or tetralin ring. In the method for producing an acyl group-substituted aromatic compound by reacting an aromatic compound represented by
As a catalyst, there are the following general formulas [III] ▲ mathematical formulas, chemical formulas, tables, etc. ▼ ... [III] (wherein, is a fluorine-containing alkyl group, Ar^2 is an aryl group, n is an integer of 1 to 5, m is 1
Indicates an integer between ~3. When n is 2 or more, X^2 may be the same or different. 1. A method for producing an acyl group-substituted aromatic compound, which comprises using a fluorine-containing aromatic sulfonic acid catalyst in which a substituted aryl group represented by the following formula is bonded to a matrix. (3) The manufacturing method according to claim (2), wherein the matrix is polysiloxane. (4) The manufacturing method according to claim (2), wherein the matrix is a zirconium compound. (5) The manufacturing method according to claim (2), wherein the matrix is clay. (6) The manufacturing method according to claim (5), wherein the matrix is crosslinked mica or crosslinked montmorillonite. (7) The manufacturing method according to claim (2), wherein the matrix is an ion exchange resin. (8) The manufacturing method according to claim (2), wherein the matrix is polystyrene.