JPH06199718A - Production of hydroxyaromatic compound - Google Patents

Abstract

PURPOSE:To produce the subject compound useful as an intermediate for agrichemicals, pharmaceuticals, etc., by decomposing a hydroxyperoxide compound with an acid in the presence of a specific acid catalyst such as tetrafluoroboric acid and preferably heating the reaction system in two stages. CONSTITUTION:A hydroxyaromatic compound of formula II is produced by the acid decomposition of a hydroperoxide compound of formula I (n is 1 or 2; Ar is n-valent aromatic hydrocarbon group) using an acid catalyst selected from tetrafluoroboric acid, hexafluorosilicic acid and hexafluorophosphoric acid. Preferably, the acid decomposition reaction is carried out in a 1st reactor at 50-95 deg.C and the obtained reaction mixture is transferred to a 2nd reactor and subjected to acid decomposition reaction at 80-120 deg.C. The hydroperoxide compound is especially cumene hydroperoxide, cymene hydroperoxide or diisopropylbenzene dihydroperoxide. The hydroxyaromatic compound is useful as a production intermediate for synthetic resins, agrichemicals, dyes, pharmaceuticals, etc. The process is effective for suppressing the by-production of hydroxyacetone.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a process for producing a hydroxy aromatic compound which is useful as an intermediate for producing synthetic resins, agricultural chemicals, dyes, pharmaceuticals and the like.

[0002]

2. Description of the Related Art As one of the industrial production methods of hydroxyaromatic compounds, a method of producing hydroperoxides by decomposing them in the presence of an acid catalyst is known. Conventionally, sulfuric acid is generally used as the acid catalyst in this method, but various acid catalysts have already been proposed in addition to sulfuric acid.

For example, JP-A-50-50311 proposes a method using trifluoromethanesulfonic acid as an acid catalyst. In addition to this, for example, U.S. Pat.No. 4,898,995 proposes an ion exchange resin containing a sulfonic acid group, and European Patent 125,065 proposes various zeolites. There is. In addition, U.S. Pat.
Lewis acid catalysts such as tin chloride, antimony chloride, sulfur tetrafluoride, silicon tetrafluoride, and tungsten hexafluoride have been proposed, and U.S. Pat.No. 4,267,379 describes boron trifluoride and boron trifluoride. Lewis acid catalysts such as etherate have also been proposed.

Decomposition of hydroperoxides with acid catalysis produces coketones with hydroxyaromatic compounds. When the hydroxyperoxides represented by the general formula (I) are acid-decomposed, acetone is also produced as a ketone. At that time, according to the conventional method, hydroxyacetone is easily produced as a by-product by the reaction between the produced acetone and the raw material hydroperoxides.
Problems have arisen in the industrial production of hydroxyaromatic compounds and acetone by decomposition of hydroperoxides using conventional acid catalysts as described above.

The first problem is a decrease in the yield of hydroxyaromatic compounds and acetone. The second problem is that the water solubility of hydroxyacetone results in wastewater pollution. A third problem is that, depending on the type of hydroxyaromatic compound, hydroxyacetone is mixed in the product, resulting in a decrease in its purity.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems in the conventional methods in the production of hydroxyaromatic compounds and acetone by the decomposition of hydroxyperoxides using an acid catalyst. So, by suppressing the by-product of hydroxyacetone,
It is an object of the present invention to provide a method capable of obtaining a hydroxy aromatic compound in high yield.

[0007]

The method for producing a hydroxyaromatic compound according to the present invention has the general formula (I):

[0008]

[Chemical 5]

(In the formula, n represents an integer of 1 or 2, and Ar
Represents an n-valent aromatic hydrocarbon group. ) Is hydrolyzed with a hydroperoxide represented by the general formula (II)

[0010]

[Chemical 6]

In the method for producing a hydroxyaromatic compound represented by the formula (wherein Ar and n are the same as above), tetrafluoroboric acid is used as an acid catalyst.
It is characterized by using hexafluorosilicic acid or hexafluorophosphoric acid.

In the method of the present invention, the above general formula (I)
In the above, n represents an integer of 1 or 2, and Ar represents an n-valent aromatic hydrocarbon group. Therefore, as a specific example of Ar, n is 1
When it is, for example, a substituted phenyl group such as a phenyl group, a tolyl group, an isopropylphenyl group, a t-butylphenyl group, a diisopropylphenyl group, a phenylphenyl group, a methoxyphenyl group, a phenoxyphenyl group, a naphthyl group, a methylnaphthyl group, Examples thereof include substituted naphthyl groups such as isopropylnaphthyl group. Also, n is 2
In this case, specific examples of Ar include a substituted phenylene group such as a phenylene group, a methylphenylene group and an isopropylphenylene group, a substituted naphthalene group such as a naphthalene group, a methylnaphthalene group and an isopropylnaphthalene group.

Therefore, as the hydroxyperoxides represented by the general formula (I) which can be preferably used in the method of the present invention, for example, cumene hydroxyperoxide, cymen hydroxyperoxide, diisopropylbenzene monohydroperoxide, triisopropylbenzene can be mentioned. Examples thereof include monohydroperoxide, isopropylnaphthalene hydroxyperoxide, methylisopropylnaphthalene monohydroxyperoxide, diisopropylnaphthalene monohydroxyperoxide, diisopropylbenzene dihydroperoxide, triisopropylbenzene dihydroperoxide, diisopropylnaphthalene dihydroxyperoxide and the like. These hydroxyperoxides can be prepared by oxidizing the corresponding isopropyl-substituted aromatic compound with air or molecular oxygen.

The hydroxyaromatic compound represented by the general formula (II) produced by the method of the present invention is
Depending on the hydroxyperoxides used, for example, phenol, cresol, isopropylphenol, diisopropylphenol, naphthol, methylnaphthol, isopropylnaphthol, resorcin, hydroquinone, isopropylresorcin, dihydroxynaphthalene and the like can be mentioned.

A feature of the method of the present invention is that tetrafluoroboric acid (HBF ₄ ) is used as an acid catalyst when decomposing hydroxyperoxides in the presence of an acid catalyst.
Hexafluorosilicic acid (H ₂ SiF ₆ ) or hexafluorophosphoric acid (HPF ₆ ) is used.

Further, in the present invention, since the above-mentioned protonic acid containing a fluorine atom has a high acid decomposition rate, it is general to use a purified one, but in some cases,
Unpurified ones may be used. As a specific example of the unpurified product, for example, in the case of tetrafluoroboric acid, a theoretical amount of hydrofluoric acid (HF) and boric acid (H ₃ BO ₃ ) are mixed in an aqueous solvent at room temperature. The reaction mixtures mentioned can be mentioned.

In the present invention, these acid catalysts are generally added in the reaction system as an aqueous solution or diluted with a solvent inert to the reaction such as acetone. The amount of these acid catalysts used is usually 20% as the concentration in the reaction mixture.
ppm to 5% by weight, preferably 100 ppm to 2% by weight. The optimum amount used depends on the type of acid catalyst, the type of reaction solvent, the reaction temperature, the amount of water in the reaction system, the reaction time, and the like.

In the present invention, a reaction solvent may not be used, but ketones such as acetone, aromatic hydrocarbons such as benzene, toluene and cumene, aliphatic hydrocarbons such as hexane, heptane and octane, cyclohexane. Alicyclic hydrocarbons such as methylcyclohexane and cyclooctane, halogenated hydrocarbons such as dichloroethane and chlorobenzene, phenols such as phenol and cresol,
Compounds which are stable under the reaction conditions of the process according to the invention can also be used as reaction solvents. These solvents may be used as a mixture. When a reaction solvent is used in the present invention, the amount used is relative to the hydroxyperoxides.
Usually, 0.1 to 5 times by weight is suitable.

In the present invention, the reaction may be carried out batchwise or continuously. When the reaction is carried out in a continuous manner, according to the present invention, the reactor may be of a one-tank type, a multi-tank type or a tubular type. Further, a tank reactor and a tubular reactor may be used in combination.

Regarding the reaction temperature, when the reaction is carried out in a batch system, or even when it is a continuous system, it is usually carried out in a one-tank system.
20 ° C to 150 ° C, preferably 50 ° C to 140 ° C
The reaction time is usually in the range of 1 minute to 1 hour.

According to the present invention, the first stage of the reaction is carried out in a continuous tank reactor at a temperature of 50 ° C to 95 ° C, and the second stage of the reaction is carried out in a tubular reactor at a temperature of 80 ° C to 120 ° C. This is preferable because the by-product of hydroxyacetone can be suppressed particularly effectively, and the target hydroxyaromatic compound can be obtained in a higher yield.

Particularly, in the method of the present invention, when the reaction is carried out in two steps as described above, the residual hydroperoxide concentration is 1% by weight or less, preferably 0.5.
When the amount of the hydroperoxide was reduced to less than 10% by weight, the reaction of the first stage was stopped, and then the reaction of the second stage was stopped at a residual hydroperoxide concentration of 0.
Particularly desirable results can be obtained by carrying out the treatment at a content of 1% by weight or less.

The reaction pressure may be any of reduced pressure, normal pressure and increased pressure in any of the above methods. After completion of the reaction, the hydroxyaromatic compound can be isolated by removing the acid catalyst from the reaction mixture by neutralization or washing with water, and then performing concentration, distillation and crystallization.

The present invention is described below with reference to examples, but the present invention is not limited to these examples.

Reference Example 1 Cumene was added in an amount of 100 to 11 in the presence of an aqueous sodium carbonate solution.
Air oxidize at 0 ° C., then oil-water separation, concentration,
A cumene hydroperoxide (CHP) solution having the composition shown in was prepared.

[0026]

[Table 1]

Example 1 A stainless steel one-tank continuous reactor having a hold-up capacity of 60 ml equipped with a stirrer, a water condenser, a hot water jacket, a temperature detector, a raw material introduction pipe, a catalyst introduction pipe and a reaction mixture withdrawal pipe, 1 CHP solution prepared in Reference Example 1
A 1.0 wt% acetone solution of tetrafluoroboric acid (42% aqueous solution) was added as an acid catalyst at a rate of 20 ml / hour and at a rate of 52 ml / hour. In this method, the concentration of tetrafluoroboric acid in the reaction mixture was 1200 ppm. In this way, the reaction was carried out with the residence time of 20 minutes while maintaining the temperature of the reaction solution at 75 ° C.

After the reaction mixture continuously extracted was neutralized with sodium carbonate powder, phenol and hydroxyacetone in the supernatant were quantitatively analyzed by gas chromatography. The yield of phenol (raw material CHP and dicumyl peroxide) was analyzed. Yield with respect to the total number of moles of (DCP),
same as below. ) Was 97 mol%, and the amount of by-product of hydroxyacetone (weight ratio to phenol, hereinafter the same) was 390 ppm.

Examples 2 and 3 and Comparative Examples 1 to 5 Reaction and analysis were carried out in the same manner as in Example 1 except that the catalyst shown in Table 1 was used instead of tetrafluoroboric acid. Done. The results are shown in Table 2.

[0030]

[Table 2]

Example 4 and Comparative Examples 6 to 7 In Example 1, as the raw hydroperoxide,
The reaction and analysis were carried out in the same manner as in Example 1 except that a cymen solution of cymen hydroperoxide was used and the catalyst shown in Table 3 was used. The results are shown in Table 3.

[0032]

[Table 3]

Example 5 and Comparative Examples 8 and 9 In Example 1, m was used as the starting hydroperoxide.
-M- of diisopropylbenzene dihydroperoxide
The reaction and analysis were performed in the same manner as in Example 1 except that the diisopropylbenzene solution was used and the catalyst shown in Table 4 was used. The results are shown in Table 4.

[0034]

[Table 4]

Example 6 A continuous tank type reactor made of stainless steel having a hold-up capacity of 100 ml equipped with a stirrer, a water condenser, a hot water jacket, a temperature detector, a raw material introduction pipe, a catalyst introduction pipe and a reaction mixture withdrawal pipe (No. 1). 1 reactor), the CHP solution prepared in Reference Example 1 at a rate of 260 g / hour, and 0.15
Acetone solutions containing wt% tetrafluoroboric acid and 1.6 wt% water were added at a rate of 40.9 g / hr, respectively. In this method, the concentration of tetrafluoroboric acid in the reaction mixture was 200 ppm. In this way, while maintaining the temperature of the reaction solution at 84 ° C., the residence time was 20
The reaction was done in minutes.

The reaction mixture continuously withdrawn from the first reactor was neutralized with sodium carbonate powder, and the composition of the supernatant was quantitatively analyzed by gas chromatography. The results are shown in Table 5.

[0037]

[Table 5]

Next, the reaction mixture continuously withdrawn from the first reactor was fed through a pressure pump to a coiled stainless steel pipe (second reactor) having an inner diameter of 4 mm equipped with a temperature detector and a pressure gauge. The coiled stainless steel pipe was immersed in a heated oil bath and heated, and the internal volume of the immersed part was 20 ml. In this way, the internal temperature is 1
The reaction was carried out with a residence time of 4 minutes while maintaining the temperature at 16 ° C.

The reaction mixture continuously withdrawn from the second reactor through the water cooling jacket and the exhaust pressure valve was neutralized with sodium carbonate powder, and the composition of the supernatant was quantitatively analyzed by gas chromatography. The results are shown in Table 6.

[0040]

[Table 6]

As a result of carrying out the acid decomposition through the first reactor and the second reactor in this manner, the yield of phenol was 9
It was 9%. From the analysis results of the other components in Table 6, the amount of hydroxyacetone by-product was 240 ppm.

Comparative Example 10 Reaction and analysis were carried out in the same manner as in Example 6 except that sulfuric acid was used instead of tetrafluoroboric acid. As a result, the yield of phenol was 97%, and the amount of hydroxyacetone by-product was 2000 ppm.

[0043]

INDUSTRIAL APPLICABILITY As described above, in the production of hydroxyaromatic compounds and acetone by the decomposition of hydroxyperoxides using an acid catalyst, according to the method of the present invention, tetrafluoroboric acid, hexafluoro By using silicic acid or hexafluorophosphoric acid, a hydroxy aromatic compound can be obtained in a high yield while well suppressing the by-product of hydroxyacetone.

In particular, according to the present invention, the above-mentioned acid decomposition reaction is divided into a first stage and a second stage, and the first stage of the reaction is carried out in the first stage.
In a reactor of 50 to 95 ° C. and the reaction mixture obtained is led to a second reactor in which the second stage of the reaction is carried out at a temperature of 80 to 120 ° C. Then, by effectively suppressing the by-product of hydroxyacetone,
The target hydroxyaromatic compound can be obtained in an even higher yield.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location C07C 39/08 8930-4H // C07B 61/00 300 (72) Inventor Isamu Hashimoto Kazuki Waki-cho, Kuga-gun, Yamaguchi Prefecture 6-6-2 Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Mitsuaki Mukaiyama 1-15-18 Minamiogikubo, Suginami-ku, Tokyo

Claims (3)

[Claims] 1. A compound represented by the general formula (I): (In the formula, n represents an integer of 1 or 2, and Ar represents an n-valent aromatic hydrocarbon group.) Hydroperoxides are acid-decomposed in the presence of an acid catalyst to give a compound represented by the general formula (II ) [Chemical 2] (In the formula, Ar and n are the same as above.) In the method for producing the hydroxy aromatic compound, tetrafluoroboric acid, hexafluorosilicic acid or hexafluorophosphoric acid is used as the acid catalyst. A method for producing a hydroxy aromatic compound, which is characterized. 2. A compound represented by the general formula (I): (In the formula, n represents an integer of 1 or 2, and Ar represents an n-valent aromatic hydrocarbon group.) Hydroperoxides are acid-decomposed in the presence of an acid catalyst to give a compound represented by the general formula (II ) [Chemical 4] (In the formula, Ar and n are the same as above.) In the method for producing the hydroxyaromatic compound, tetrafluoroboric acid, hexafluorosilicic acid or hexafluorophosphoric acid is used as the acid catalyst, The acid decomposition reaction is carried out in the first reactor at a temperature of 50 ° C to 95 ° C.
And the reaction mixture obtained is carried out in the second reactor at a temperature of 80 ° C to 120 ° C. 3. The method for producing a hydroxyaromatic compound according to claim 1, wherein the hydroperoxide is cumene hydroperoxide, cymen hydroperoxide or diisopropylbenzene dihydroperoxide.