JPH0645566B2 - Method for producing acylphenols - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to a novel method for producing acylphenols.

[Industrial application field]

Acylphenols are compounds useful as agricultural chemicals, photographic agents, UV absorbers and the like.

[Prior art]

Regarding the conventional method for producing an acylphenol, for example, a phenol is reacted with a carboxylic acid using a catalyst such as sulfuric acid or an ion exchange resin to form an esterified product, and the esterified product is then reacted with aluminum chloride, polyphosphoric acid, or the like. A method of performing Fries rearrangement using a catalyst is described in Journal of Chemical Society (J. Chem. Soc. (C)) p. 650 (19
71). In these conventionally known methods,
Since the esterification reaction and the Fries rearrangement are separately performed, the reaction operation is complicated and cannot be said to be an industrially advantageous method.

[Object of the Invention]

The present inventors have examined the industrially practical new production method of acylphenols, and as a result, by using the following method, acylphenols can be obtained in one step by a very simple method unlike the conventional method. They have found that they can be manufactured and have completed the present invention.

[Configuration of the invention] That is, according to the present invention, in the presence of an ion-exchange type layered clay catalyst ion-exchanged with aluminum ions, indium ions, gallium ions, titanium ions, nickel ions, or zirconium ions, with phenols A method for producing an acylphenol by reacting a carboxylic acid is provided.

The ion-exchange type layered clay catalyst referred to in the present invention refers to ion-exchange type synthetic mica, montmorillonite, vermiculite, etc. which are ion-exchanged with each of the above-mentioned ions. Synthetic mica is generally a layered compound whose main component is silicon dioxide, and silicon is a series of hexagonal mesh plates based on a SiO ₄ tetrahedron. Alkali metal ions, alkaline earth metal ions, etc. exist as interlayer ions X, and the general formula is X _{1/3 to 1} Y _{2 to 3} Z ₄ O ₁₀ F ₂ (where X is a cation having a coordination number of 12). , Y is a cation having a coordination number of 6, and Z is a cation having a coordination number of 4). In the above general formula, X is Na ⁺ , K ⁺ , Ca ²⁺ ,
Ba ²⁺ , Rb ⁺ , Cs ⁺ , Sr ^2+, etc. are exemplified, and Y is Mg ²⁺ , F
e ²⁺ , Ni ²⁺ , Mn ²⁺ , Al ³⁺ , Fe ³⁺ , Ti ⁴⁺ , Zr ²⁺ , In ³⁺ , Ga
Examples are cations such as ³⁺ and Li ⁺ , Z is Al ³⁺ , Si ⁴⁺ , G
Examples are cations such as e ⁴⁺ , Fe ³⁺ and B ³⁺ . Such synthetic mica is specifically represented by 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 Teniolite XMg ₂ Li (Si ₄ O ₁₀ ) F ₂ (where X is K, Na or Li), etc. Usually, synthetic mica is different from natural mica in comparison with the above X, Y and Z. The synthetic mica catalyst that can be used in the present invention is the above synthetic mica, which is an interlayer ion among ion-exchangeable interlayer ions. Is usually ion-exchanged at 10 mol% or more, preferably 30 to 100 mol% .The base of the synthetic mica catalyst used in the present invention is preferably the above-mentioned tetrasilicon mica or teniolite. Ions used for ion exchange of the layered clay catalyst in the present invention Examples thereof include aluminum ion, indium ion, gallium ion, titanium ion, nickel ion, or zirconium ion, and ion exchange with these ions is preferable because of high yield of acylphenols. In order to prepare a catalyst composed of tetrasilicon mica or teniolite as the synthetic mica catalyst used in, the above-mentioned Na-type, Li-type, K-type, etc. tetrasilicon-mica or Na-type, Li-type, K-type, etc. exchanges of teniolite Usually, 10 mol% or more of each possible interlayer cation may be exchanged with the above-mentioned ion, for example, in order to exchange Na-type tetrafluorosilicon mica or Na-type teniolite with aluminum ion, any known ion-exchange method is adopted. Among them, it is preferable that a suspension of purified Na-type tetrasilicon mica or Na-type teniolite is mixed with al sulfate. The amount of aluminum ion added to the aqueous solution of aluminum, aluminum nitrate or aluminum chloride is about 0.5 to 5 times gram ion equivalent, preferably about 0.8 to 2 times gram ion equivalent to the amount of Na ion to be ion-exchanged. In addition, the mixture is usually stirred at a temperature range of 0 to 200 ° C., preferably room temperature to 80 ° C. for about 1 to 60 minutes, or left to stand for ion exchange treatment, and the solid phase is filtered or centrifuged. At room temperature to about 10 ° C., then washed with water and / or ethanol, then under reduced pressure or atmospheric pressure.
A method of drying at a temperature of 0 ° C. is exemplified. This ion exchange treatment may be repeated a plurality of times if necessary. Aluminum-exchanged tetra-silicon mica, or aluminum-exchanged teniolite is in powder form, and in the present invention, it may be used as it is as a catalyst, if necessary, tablet form, spherical form, tablet form or ring form such as columnar shape, It can also be formed into a honeycomb shape and used. The catalyst composed of these synthetic mica has good metal dispersibility and high activity per unit metal. In addition, the catalyst composed of these synthetic mica,
It can be prepared by a simple operation. Montmorillonite is a mineral that constitutes clay and is a phyllosilicate mineral that has a layered structure. Its composition is represented by the general formula M _1/3 (X, Y) _{2 to 3} (Si, Al) ₄ O ₁₀ (OH) ₂ · mH ₂ O (wherein M is an alkali metal such as K or Na or Ca).
Alkaline earth metal such as, X is Al, Fe, Mn or Cr,
Y is Mg, Fe, Mn, Ni, Zn or Li, and m is a positive integer) and is a layered clay with ion-exchange ability that constitutes the main components of bentonite, hectorite, acid clay, etc. Ions can be exchanged with the above-mentioned ions by the same treatment as in the case of mica. The catalyst can be used in the form of powder or in any shape. Among these ion-exchange type clay catalysts used in the method of the present invention, it is particularly preferable to use the above synthetic mica since the yield and the selectivity of the acylphenols are high.

The amount of the ion-exchange type layered clay catalyst used in the present invention is somewhat different depending on the starting compounds and reaction conditions, but is usually 0.1 to 100 parts by weight of the phenols and carboxylic acids charged as the starting materials. It is 100 parts by weight, preferably 1 to 30 parts by weight.

The phenols used in the method of the present invention have the general formula [I] (In the formula, R represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an aryl group, a nitro group or a halogen atom, m represents an integer of 1, 2 or 3, and X and Y are both hydrogen atoms. Or both of them represent a hydrocarbon group necessary for bonding to form a substituted or unsubstituted naphthalene ring). Specific examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, 2,6-xylenol, 2,4-xylenol, 2,3,6-trimethylphenol, o-ethylphenol, m. -Ethylphenol, p-ethylphenol, n-propylphenol, isopropylphenol, butylphenol, cyclohexylphenol, phenylphenol, benzylphenol, chlorophenol, nitrophenol, methoxyphenol, ethoxyphenol,
Catechol, resorcin, hydroquinone, methylresorcin, butylresorcin, benzylresorcin, methoxyresorcin, ethoxyresorcin, methylhydroquinone, butylhydroquinone, benzylhydroquinone, chlororesorcin, chlorohydroquinone, phloroglucin,
Methyl phloroglucin, naphthol, methylnaphthol, ethylnaphthol, methoxynaphthol, ethoxynaphthol, dihydroxynaphthalene can be exemplified,
Of these, the use of phenol, cresol, chlorophenol, nitrophenol, resorcin, catechol, hydroquinone, phloroglucin, naphthol, dihydroxynaphthalene is preferable.

As the carboxylic acids used in the method of the present invention, formic acid, acetic acid, propionic acid, stearyl acid, acrylic acid,
Methacrylic acid, oxalic acid, succinic acid, aliphatic carboxylic acids such as maleic acid, phenylacetic acid, aliphatic carboxylic acids substituted with a substituted or unsubstituted aromatic hydrocarbon such as cinnamic acid,
Benzoic acid, toluic acid, ethylbenzoic acid, phenylbenzoic acid, hydroxybenzoic acid, methoxybenzoic acid, arylbenzoic acid, chlorobenzoic acid, nitrobenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthoic acid, naphthalenedicarboxylic acid, etc. Examples thereof include aromatic carboxylic acids, acid anhydrides such as acetic anhydride and benzoic acid, acid halides such as acetyl chloride and benzoyl chloride, and ketocarboxylic acids such as pyruvic acid.

In the reaction according to the method of the present invention, the acylphenols are obtained by reacting the phenols with the carboxylic acids in the presence of the ion exchange type layered clay catalyst. Specific examples of the acylphenols include hydroxybenzophenone, trihydroxybenzophenone, hydroxyphenylnaphthyl ketone, dihydroxyphenylnaphthyl ketone, hydroxynaphthylphenyl ketone,
Examples include hydroxyacetophenone, chlorohydroxyacetophenone, dihydroxyacetophenone, hydroxyphenylpropyl ketone, hydroxynaphthylphenyl ketone, and hydroxynaphthylmethyl ketone.
Hydroxybenzophenone, dihydroxybenzophenone, hydroxyphenyl naphthyl ketone and hydroxynaphthyl phenyl ketone are preferred.

The reaction according to the method of the present invention can be carried out by using either a liquid phase method or a gas phase method, but among them, the liquid phase method is preferable in terms of efficiency. In that case, no solvent may be used, but it is also possible to carry out the reaction using a solvent. When the solvent is used, examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, mesitylene, cumene, cymen, chlorobenzene, dichlorobenzene, bromobenzene, biphenyl and terphenyl, diphenyl ether, benzofuran. And aromatic ethers such as dibenzofuran, aromatic ketones such as acetophenone and benzophenone, and the amount of the solvent used in this case is 1 part by weight of the total of the phenols and the carboxylic acids. On the other hand, it is usually 0.1 to 100 parts by weight.

In the method of the present invention, the carboxylic acid can be usually used in an amount of 1 to 1000 parts by mole with respect to 100 parts by mole of the phenol, but preferably 10 to 50 parts by mole of the carboxylic acid and the phenol are in excess. It is preferable that the reaction is carried out in order to increase the selectivity of acylphenols.

The reaction temperature used in the method of the present invention is usually 100 to 350 ° C., preferably 150 to 250 ° C., and the liquid phase method or the gas phase method is adopted in the temperature range as necessary to carry out the reaction. Can be implemented. The reaction time at this time is appropriate, but particularly in the case of the liquid phase method, it is usually sufficient to carry out the reaction for 0.1 to 10 hours. When liquid phase method is adopted, continuous method such as batch method, semi-batch method or tubular reaction method can be used as needed, and when gas phase method is adopted, fixed method or flow method can be used. A reaction method such as a layer method can be used. The catalyst used in the present reaction may be used in either a liquid phase method or a gas phase method, if necessary, by molding it into a powder or a specific shape as described above. The reaction pressure may be reduced pressure, atmospheric pressure or increased pressure as required. Further, in the method of the present invention, when the above-mentioned phenols and carboxylic acids are used as the raw materials for producing the acylphenols, the reaction is easily carried out by removing the generated water outside the system, if necessary. Is preferable because

After completion of the reaction, 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.

〔The invention's effect〕

When the method of the present invention is adopted, acylphenols can be obtained in a high yield with a simple operation as compared with the conventional method.

〔Example〕

 Hereinafter, the present invention will be described more specifically with reference to Examples.

Example 1 100 g of a 10 wt% aqueous solution of sodium tetrasilica mica (NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ ) which is a synthetic mica manufactured by Topy Industries, Ltd.
5% Al (NO ₃ ) ₃ while stirring well with water
Aluminum ion exchange was performed by adding 200 ml of the aqueous solution. After washing with water, it was dried (40 ° C., 50 mmHg, 10 hours) to obtain a catalyst. 0.7 g of this aluminum ion-exchange type synthetic mica, 3.5 g of phenol and 1.0 g of benzoic acid were placed in a glass reactor and reacted at 180 ° C. for 5 hours with stirring to obtain hydroxybenzophenone. The conversion rate of benzoic acid at this time is 100%
And the selectivity of hydroxybenzophenone was 47% (based on benzoic acid). In addition, phenyl benzoate was produced with a selectivity of 52% (based on benzoic acid).

Example 2 The reaction was performed under the same conditions as in Example 1 except that the gallium ion-exchanged synthetic mica was used in place of the aluminum ion-exchanged synthetic mica to obtain hydroxybenzophenone with a selectivity of 42% (based on benzoic acid). The conversion rate of benzoic acid at this time is 100%
In addition, phenyl benzoate was produced with a selectivity (based on benzoic acid) of 56%.

Example 3 0.7 g of aluminum ion-exchange type synthetic mica, resorcin
1.5 g, benzoic acid 3.3 g, and mesitylene 15 ml were put into a reactor equipped with a Dean-Stark water collection trap and reacted for 3 hours under reflux of mesitylene to select 2,4-dihydroxybenzophenone at a selectivity of 56% (resorcin standard). ) Obtained in. At this time, the conversion rate of resorcin was 85%, and hydroxyphenyl benzoate was produced at a selectivity of 41% (resorcin standard).

Example 4 0.8 g of aluminum ion-exchange type synthetic mica, phenol
2.2 g of p-hydroxybenzoic acid and 2.9 g of p-hydroxybenzoic acid were reacted under the same conditions as in Example 1 to obtain dihydroxybenzophenone with a selectivity of 27% (based on p-hydroxybenzoic acid). At this time, the conversion rate of p-hydroxybenzoic acid was 96%.
Phenyl p-hydroxybenzoate was produced with a selectivity of 72% (based on p-hydroxybenzoic acid).

Example 5 Aluminum ion-exchange type synthetic mica 0.8 g, phenol
The reaction was carried out under the same conditions as in Example 1 using 1.7 g and 1.0 g of α-naphthoic acid to obtain 40% hydroxyphenyl naphthyl ketone.
Was obtained (based on α-naphthoic acid). Α at this time
-The conversion of naphthoic acid was 94%, and α-naphthoic acid phenyl was also produced with a selectivity of 59% (based on α-naphthoic acid).

Example 6 The reaction was carried out under the same conditions as in Example 1 except that 0.7 g of the aluminum ion-exchange type synthetic mica was replaced with 0.7 g of the aluminum ion-exchange type montmorillonite, and the selectivity of hydroxybenzophenone was 42% (benzoic acid standard). Got with. At this time, the conversion rate of benzoic acid was 100%, and phenyl benzoate was produced at a selectivity of 50% (based on benzoic acid).

Example 7 The reaction was performed under the same conditions as in Example 1 except that benzoic acid (1.0 g) was replaced with benzoic anhydride (0.9 g), and hydroxybenzophenone was obtained with a selectivity of 43% (based on benzoic anhydride). At this time, the conversion rate of benzoic anhydride was 100%, and phenyl benzoate was produced with a selectivity of 55% (based on benzoic anhydride).

Example 8 In Example 1, 1.0 g of benzoic acid was added to 1.2% of benzoyl chloride.
The reaction was performed under the same conditions except that g was replaced with hydroxybenzophenone with a selectivity of 44% (based on benzoyl chloride). At this time, the conversion rate of benzoyl chloride was 100%, and phenyl benzoate was produced at a selectivity of 53% (based on benzoyl chloride).

Example 9 Aluminum ion-exchange type synthetic mica in Example 1
The reaction was carried out under the same conditions as in Example 1 except that 7 g was replaced with 0.7 g of indium ion exchange type synthetic mica. The conversion of benzoic acid was 100% and the selectivity of hydroxybenzophenone was 43%. Phenyl benzoate was also produced with a selectivity of 55%.

Example 10 Aluminum ion exchange type synthetic mica in Example 1
The reaction was carried out under the same conditions as in Example 1 except that 7 g was replaced with 0.7 g of titanium ion (Ti ⁴⁺ ) exchange type synthetic mica. The conversion of benzoic acid was 100% and the selectivity of hydroxybenzophenone was 40%. Phenyl benzoate was also produced with a selectivity of 58%.

Example 11 Aluminum ion exchange type synthetic mica in Example 1
7 g of zirconium ion exchange type montmorillonite 0.7 g
The reaction was carried out under the same conditions as in Example 1 except that The conversion of benzoic acid was 100% and the selectivity of hydroxybenzophenone was 41%. Phenyl benzoate is another
Produced with a selectivity of 57%.

Example 12 Aluminum ion exchange type synthetic mica in Example 1
The reaction was carried out under the same conditions as in Example 1 except that 7 g was replaced with 0.7 g of nickel ion exchange type montmorillonite. The conversion of benzoic acid was 100% and the selectivity of hydroxybenzophenone was 36%. 61% phenyl benzoate
Generated with a selectivity of.

Comparative Example 1 Aluminum ion exchange type synthetic mica in Example 1
The reaction was carried out under the same conditions as in Example 1 except that 7 g was replaced with 0.7 g Na ⁺ -montmorillonite clay. The conversion of benzoic acid is 5% and the selectivity of hydroxybenzophenone is 0.2.
%Met. Phenyl benzoate was also produced with a selectivity of 98%.

Comparative Example 2 Aluminum ion exchange type synthetic mica in Example 1
The reaction was carried out under the same conditions as in Example 1 except that 7 g was replaced with 0.7 g K ⁺ -montmorillonite clay. The conversion rate of benzoic acid is 4%, and the selectivity of hydroxybenzophenone is 0.1%.
%Met. In addition, phenyl benzoate was produced with a selectivity of 99%.

Comparative Example 3 In Example 1, aluminum ion-exchange type synthetic mica was used.
The reaction was carried out under the same conditions as in Example 1 except that 7 g was replaced with 0.7 g Mg ²⁺ -montmorillonite clay. The conversion rate of benzoic acid is 7%, and the selectivity of hydroxybenzophenone is
It was 0.8%. Phenyl benzoate was also produced with a selectivity of 98%.

Comparative Example 4 Aluminum ion exchange type synthetic mica in Example 1
The reaction was carried out under the same conditions as in Example 1 except that 7 g was replaced with 0.7 g K-10 (H ⁺ -montmorillonite). The conversion rate of benzoic acid is 24%, and the selectivity of hydroxybenzophenone is
It was 6.7%. Phenyl benzoate was also produced with a selectivity of 92%.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C07C 69/773 9279-4H 69/78 9279-4H // B01J 21/16 X 8017-4G C07B 61 / 00 300

Claims (1)

[Claims] 1. An aluminum ion, an indium ion,
A method for producing acylphenols by reacting phenols with carboxylic acids in the presence of an ion-exchange type layered clay catalyst ion-exchanged with gallium ions, titanium ions, nickel ions, or zirconium ions.