JPH058178B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a novel method for producing acylphenols.

[Industrial application field]

Acylphenols are compounds useful as pesticides, photographic drugs, UV absorbers, etc.

[Prior art]

A conventional method for producing acylphenols includes, for example, a method in which an ester is subjected to Fries rearrangement using a Friedel-Crafts type catalyst such as aluminum chloride. c)) 650 pages (1971)
It is described in. In these conventionally known methods, the catalyst is used in an amount equal to or more than the amount of the reactant, so a large amount of catalyst is required, and the separation and purification process is complicated due to the hydrolysis process after the reaction. do not have.

[Purpose of the invention]

The present inventors investigated a new industrially practical production method for acylphenols, and found that
The inventors have discovered that, unlike conventional methods, acylphenols can be produced with high selectivity by using the method described below, and have completed the present invention.

[Structure of the invention]

That is, according to the present invention, aromatic carboxylic esters are reacted in the presence of an ion-exchange layered clay catalyst ion-exchanged with aluminum ions, indium ions, gallium ions, titanium ions, nickel ions, or zirconium ions. A method for producing acylphenols is provided.

The ion exchange type layered clay catalyst referred to in the present invention is:
Refers to ion-exchanged synthetic mica, montmorillonite, vermiculite, etc. that have been ion-exchanged with each of the above ions. Synthetic mica is generally a layered compound whose main component is silicon dioxide, and silicon is connected in a hexagonal network plate shape based on SiO ₄ regular tetrahedrons.
These plate-like bodies overlap in multiple layers, and alkali metal ions, alkaline earth metal ions, etc. exist between the layers as interlayer ions X, and the general formula is: X _1/3~1 Y _2~3 Z ₄ O ₁₀ F ₂ (However, X is a cation with a coordination number of 12, Y is a cation with a coordination number of 6, and Z is a cation with a coordination number of 4.)
This is shown in . In the above general formula,
Examples of X include Na ⁺ , K ⁺ , Ca ²⁺ , Ba ²⁺ , Rb ⁺ , Cs ⁺ , Sr ²⁺ , and Y include Mg ²⁺ , Fe ²⁺ , Ni ²⁺ , Mn ²⁺ ,
Cations such as Al ³⁺ , Fe ₃₊ , Ti ⁴⁺ , Zr ₂₊ , In ³⁺ , Ga ³⁺ , Li ⁺ are exemplified, and Z is Al ³⁺ , Si ⁴⁺ , Ge ⁴⁺ ,
Examples include cations such as Fe ³⁺ and B ³⁺ . Specifically, such synthetic mica is fluorine phlogopite [XMg _2.5 (AlSi ₃ O ₁₀ )] F ₂ (where X is K), tetrasilicon mica XMg _2.5 (Si ₄ O ₁₀ ) F ₂ (where X is K, Na or Li) Taeniolite XMg ₂ Li (Si ₄ O ₁₀ ) F ₂ (X is K, Na or Li). Generally, synthetic mica can be obtained or prepared in which X, Y, and Z are composed of a single element in a relatively pure manner compared to naturally produced mica, but the synthetic mica catalyst that can be used in the present invention is In the above-mentioned synthetic mica, it is desirable that the interlayer ions of the interlayer ions that can be ion-exchanged are usually 10 mol % or more, preferably 30 to 100 mol %. The base of the synthetic mica catalyst used in the present invention is preferably the aforementioned tetrasilicon mica or taeniolite. In the present invention, aluminum ions, indium ions, gallium ions, titanium ions, nickel ions, or zirconium ions are used for ion exchange of the layered clay catalyst, and when ion exchange is performed with these ions, the yield of acylphenols is reduced. It is preferable because it has a high rate. In order to prepare a catalyst made of tetrasilicon mica or taeniolite as a synthetic mica catalyst used in the present invention, the above-mentioned tetrasilicon mica such as Na type, Li type, or K type, or taeniolite such as Na type, Li type, or K type is used. Generally, 10 mol % or more of each exchangeable interlayer cation may be exchanged with the ion.
For example, to exchange Na-type fluorine tetrasilicon mica or Na-type taeniolite with aluminum ions,
Any known ion exchange method can be employed. Among these, preferably, an aqueous solution of aluminum sulfate, aluminum nitrate, or aluminum chloride is added to a suspension of purified Na-type tetrasilicon mica or Na-type taeniolite, so that the amount of aluminum ions added is equal to the amount of Na ions to be ion-exchanged. 0.5 to 5 times the gram ion equivalent, preferably about 0.8 to 2 times the gram ion equivalent, and usually at a temperature range of 0 to 200°C, preferably room temperature to 80° for about 1 to 60 minutes. The solid phase is separated by filtration or centrifugation after stirring or standing for ion exchange treatment, followed by water and/or
Alternatively, a method of washing with ethanol and then drying at a temperature of room temperature to about 100° under reduced pressure to normal pressure is exemplified. This ion exchange treatment may be repeated multiple times as necessary. Aluminum-exchanged tetrasilicon mica or aluminum-exchanged taeniolite is in powder form, and in the present invention, it may be used as a catalyst as it is, and if necessary, it may be shaped into tablets, spheres, cylinders, etc., rings, etc. It can also be used by forming it into a honeycomb shape.
Catalysts made of these synthetic mica have good metal dispersibility and high activity per unit metal. Further, catalysts made of these synthetic mica can be prepared by simple operations. Montmorillonite is a mineral that constitutes clay, and is a phyllosilicate mineral with a layered structure. Its composition is expressed by the general formula: M _1/3 (X, Y) _2~3 (Si, Al) ₄ O ₁₀ (OH) ₂ mH ₂ O (where M is an alkali metal such as K or Na, or even Ca alkaline earth metals such as, X is Al,
Fe, Mn or Cr, Y is Mg, Fe, Mn, Ni,
Zn or Li, m is a positive integer),
It is a layered clay with ion-exchange ability that is mainly composed of bentonite, hectorite, acid clay, etc., and can be ion-exchanged with the above-mentioned ions by the same treatment as in the case of synthetic mica. The catalyst can be used in powder form or in any desired shape. Among these ion-exchange clay catalysts used in the method of the present invention, it is particularly preferable to use the synthetic mica, since the yield and selectivity of acylphenols are high.

The amount of the ion-exchange layered clay catalyst used in the present invention is based on the amount of aromatic carboxylic esters.
Per 100 parts by weight, usually 0.1 to 100 parts by weight,
Preferably it is 1 to 30 parts by weight.

Specifically, the aromatic carboxylic esters used in the method of the present invention include phenyl acetate, tolyl acetate, nitrophenyl acetate, chlorophenyl acetate, hydroxyphenyl acetate, dihydroxyphenyl acetate, phenyl propionate, and hydroxyphenyl propionate. aliphatic carboxylic acid phenyl esters such as naphthyl acetate, hydroxynaphthyl acetate, naphthyl propionate, hydroxynaphthyl propionate, phenyl benzoate, tolyl benzoate, nitrophenyl benzoate, benzoic acid Aromatic carboxylic acid phenyl esters such as chlorophenyl, hydroxyphenyl benzoate, dihydroxyphenyl benzoate, phenyl hydroxybenzoate, phenyl terephthalate, phenyl naphthoate, hydroxyphenyl naphthoate, dihydroxyphenyl naphthoate, benzoate Examples include aromatic carboxylic acid naphthyl esters such as naphthyl acid, hydroxynaphthyl benzoate, and naphthyl naphthoate; among these, phenyl benzoate, tolyl benzoate, hydroxyphenyl benzoate, phenyl hydroxybenzoate, and naphthyl benzoate. , phenyl naphthoate, phenyl acetate, tolyl acetate, hydroxyphenyl acetate are preferably used.

Specifically, the acylphenols obtained by the method of the present invention include hydroxybenzophenones such as hydroxybenzophenone, dihydroxybenzophenone, and trihydroxybenzophenone, hydroxyphenylnaphthyl ketone, and dihydroxyphenylnaphthyl. Hydroxyphenylnaphthyl ketones such as ketones, hydroxyphenyl alkyl ketones such as hydroxyacetophenone, chlorohydroxyacetophenone, dihydroxyacephenone, hydroxyphenylpropyl ketone, hydroxynaphthyl phenyl ketone, hydroxynaphthyl methyl ketone Examples include hydroxynaphthyl phenyl ketones and hydroxynaphthylalkyl ketones, among which hydroxybenzophenone, dihydroxybenzophenone, hydroxyphenylnaphthyl ketone, and hydroxynaphthyl phenyl ketone are preferred.

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. In that case, the reaction may be carried out without a solvent, but it is also possible to carry out the reaction using a solvent. When a solvent is used, the solvent is:
For example, benzene, toluene, ethylbenzene,
Aromatic hydrocarbons such as mesitylene, cumene, cymene, chlorobenzene, dichlorobenzene, bromobenzene, biphenyl and terphenyl;
Examples include aromatic ethers such as diphenyl ether, benzofuran and dibenzofuran, and aromatic ketones such as acetophenone and benzophenone. When a solvent is used, the amount of the solvent used is usually 0.1 to 100 parts by weight per 1 part by weight of the aromatic carboxylic ester.

In the method of the present invention, phenols can be used as reaction solvents in addition to the above-mentioned solvents, if necessary. Examples of the phenols in this case include compounds in which the acyl groups in the acyl phenols are replaced with hydrogen atoms, and among these, it is preferable to use phenols corresponding to the target acyl phenols as the solvent. The amount of the phenol used is usually 0.01 to 10 parts by mole per 1 part by mole of the aromatic carboxylic ester.

The reaction temperature used in the method of the present invention is usually 100 to 350°C, preferably 150 to 250°C, and the reaction is carried out in this temperature range by adopting either a liquid phase method or a gas phase method as necessary. Can be implemented. The reaction time at this time is appropriate, but especially in the case of a liquid phase method, it is usually sufficient to carry out the reaction for 0.1 to 10 hours. When a liquid phase method is adopted, a batch method, a semi-batch method, or a continuous method such as a tubular reaction method can be used as necessary; when a gas phase method is adopted, a fixed bed method or a fluidized reaction method can be used. A reaction method such as a layer method can be used. The catalyst used in this reaction may be used in either a liquid phase method or a gas phase method, and may be used in the form of a powder or in the above-mentioned specific shape, if necessary. The reaction can be carried out under reduced pressure, atmospheric pressure or increased pressure as required.

After the reaction is completed, the catalyst can be separated from the reaction mixture by a method such as filtration, and the acylphenols can be obtained by a distillation method, a crystallization method, an extraction method, or the like.

[Effects of the Invention] By employing the method of the present invention, acylphenols can be obtained with simpler operations and in higher yields than conventional methods.

〔Example〕

The present invention will be explained in more detail below using Examples.

Example 1 Sodium tetrasilismic mica (NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ ), a synthetic mica manufactured by Topy Industries, Ltd.
100 g of a 10 wt% aqueous solution was added to the water in Step 1, and while stirring well, 200 ml of 5% Al(NO ₃ ) ₃ was added to perform aluminum ion exchange. After washing with water, drying (40
℃, 50 mmHg, 10 hours) and used as a catalyst. 0.8 g of this aluminum ion-exchanged synthetic mica, 3.0 g of phenyl benzoate, and 6 g of phenol were placed in a reactor and reacted with stirring at 180° C. for 4 hours to obtain hydroxybenzophenone with a selectivity of 99%. The conversion rate of phenyl benzoate at this time was 45%.

Example 2 A reaction was carried out under the same conditions as in Example 1 except that 3.0 g of phenyl benzoate was replaced with 3.0 g of phenyl α-naphthoate to obtain hydroxyphenyl α-naphthyl ketone with a selectivity of 99%. The conversion rate of phenyl α-naphthoate at this time was 38%.

Example 3 In Example 1, 3.0 g of phenyl benzoate was
The reaction was carried out under the same conditions except that 3.0 g of α-naphthyl benzoate was used and 6 g of phenol was replaced with 9 g of α-naphthol, and the following results were obtained.

Conversion rate of α-naphthyl benzoate 46% Hydroxynaphthyl phenyl ketone selectivity 99% Example 4 In Example 1, 0.8 g of aluminum ion exchange type synthetic mica was replaced with 0.8 g of gallium ion exchange type synthetic mica.
The reaction was carried out under the same conditions except that the following results were obtained.

Phenyl benzoate conversion rate 42% Hydroxybenzophenone selectivity 99% Example 5 The reaction was carried out under the same conditions as in Example 1 except that 0.8 g of aluminum ion exchange type synthetic mica was replaced with 0.8 g of aluminum ion exchange type montmorillonite. The following results were obtained.

Phenyl benzoate conversion rate 43% Hydroxybenzophenone selectivity 97% Example 6 In Example 1, 3.0 g of phenyl benzoate and 6 g of phenol were converted to 3-hydroxyphenyl benzoate.
The reaction was carried out under the same conditions except that 3.0 g and 8 g of resorcinol were used, and the following results were obtained.

Conversion rate of 3-hydroxyphenyl benzoate 48% Selectivity of 2,4-hydroxybenzophenone 98% Example 7 3.0 g of phenyl acetate, 10 g of phenol, and 0.8 g of aluminum ion-exchanged synthetic mica were charged into an autoclave and heated at 180°C. A time reaction was performed. The reaction results are shown below.

Phenyl acetate conversion rate 32% Hydroxyacetophenone selectivity 96% Example 8 The same procedure as Example 1 was used except that 0.8 g of indium ion exchange type synthetic mica was used instead of 0.8 g of aluminum ion exchange type synthetic mica. I went in the same way. The reaction results were as follows.

Phenyl acetate conversion rate 41% Hydroxybenzophenone selectivity 99% Example 9 Example 1 except that 0.8 g of titanium ion (Ti ⁴⁺ )-exchanged synthetic mica was used instead of 0.8 g of aluminum ion-exchanged synthetic mica. Everything was carried out in the same manner as in Example 1. The reaction results were as follows.

Phenyl acetate conversion rate 37% Hydroxybenzophenone selectivity 98% Example 10 All the same procedures as Example 1 except that 0.8 g of nickel ion exchange type synthetic mica was used instead of 0.8 g of aluminum ion exchange type synthetic mica. I went in the same way. The reaction results were as follows.

Phenyl acetate conversion rate 36% Hydroxybenzophenone selectivity 99% Example 11 Example 1 except that 0.8 g of zirconium ion (Zr ⁴⁺ )-exchanged synthetic mica was used instead of 0.8 g of aluminum ion-exchanged synthetic mica. Everything was carried out in the same manner as in Example 1. The reaction results were as follows.

Phenyl acetate conversion rate 40% Hydroxybenzophenone selectivity 98% Comparative Example 1 In Example 1, 0.8 g of natural montmorillonite, that is, sodium ion type montmorillonite, was used instead of 0.8 g of aluminum ion exchange type synthetic mica.
Everything was carried out in the same manner as in Example 1 except that . The reaction results were as follows.

Phenyl acetate conversion rate 0.2% Hydroxybenzophenone selectivity 97% Comparative Example 2 In Example 1, 0.8 g of non-ion-exchanged synthetic mica, that is, sodium ion-type synthetic mica, is used instead of 0.8 g of aluminum ion-exchanged synthetic mica. Everything else was the same as in Example 1. The reaction results were as follows.

Phenyl acetate conversion rate 0.1% Hydroxybenzophenone selectivity 96% Comparative Example 3 Same conditions as in Example 1 except that 0.8 g of aluminum ion-exchanged synthetic mica was replaced with 0.8 g of aluminum chloride, and 6 g of phenol was replaced with 5 ml of nitrobenzene. The reaction was carried out and the following results were obtained.

Phenyl benzoate conversion rate 28% Hydroxybenzophenone selectivity 91%

Claims (1)

[Claims] 1 Aluminum ion, indium ion, gallium ion, titanium ion, nickel ion,
Alternatively, a method for producing acylphenols by reacting aromatic carboxylic esters in the presence of an ion-exchange layered clay catalyst ion-exchanged with zirconium ions.