JPH0741452A - Production of 4-(3-oxoalkyl)phenol - Google Patents

Abstract

PURPOSE:To efficiently obtain 4-(3-oxoalkyl)phenol useful as intermediate of an agrochemical, a perfume, etc., in a high yield by reacting phenol with beta- hydroxyketone in the presence of a specific catalyst. CONSTITUTION:The compound of formula II (R1 is R2) is obtained by reacting (A) phenol with (B) a beta-hydroxyketone of formula I [R2 is 1-7C (branched) alkyl] in the presence of (C) a heteropolyacid catalyst in liquid phase. Further, in the production of the objective compound, an alkyl vinyl ketone of formula III (R3 is R2) may be used in stead of the compound of formula I as the reaction component B. The catalyst component C is preferably a heteropolyacid which has the configuration of the condensate of an oxide selected from among molybdenum oxide, tungsten oxide and vanadium oxide with the oxiacid of an element selected from among P, Si and Ge at atomic ratio of the former to the latter of 1-12.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing 4- (3-oxoalkyl) phenol by reacting phenol with β-hydroxyketone or alkyl vinyl ketone.

The 4- (3-oxoalkyl) phenol according to the present invention is a compound useful as an intermediate raw material for various agricultural chemicals, medicines, and fragrances, or as a fragrance. For example, 4- (3-oxobutyl) phenol is a perfume known as raspberry ketone.

[0003]

2. Description of the Related Art Conventionally, as a method for producing 4- (3-oxoalkyl) phenol, for example, a method for producing 4- (3-oxobutyl) phenol from phenol and 4-hydroxy-2-butanone, concentrated hydrochloric acid and concentrated hydrochloric acid are used. It is known to use sulfuric acid, aluminum chloride, zinc chloride (Industrial Chemistry Magazine, 57 , 42 (1954)), sulfuric acid, phosphoric acid, hydrochloric acid gas (German Patent 2145308). In all of these conventional methods, since a soluble strong acid is used as a catalyst, it is necessary to use a special material having high corrosion resistance as a material of the reactor.
Furthermore, in order to remove the catalyst used from the reaction mixture,
It was not economical because it required a large-scale purification process.

Therefore, in order to overcome these drawbacks, an H-type cation exchange resin has recently been used as a catalyst. For example, JP-B-57-27096 discloses a method of using H-type cation exchange resin as a catalyst for producing 4- (3-oxobutyl) phenol from phenol and 4-hydroxy-2-butanone, and JP-A-64-64. -34941 discloses 4- (3-oxobutyl) from phenol and methyl vinyl ketone.
A method of using a H-type cation exchange resin as a catalyst for producing phenol has been shown. However, in the method using such an H-type cation exchange resin, 4-hydroxy-2-butanone or methyl vinyl ketone used as a raw material is polymerized during the reaction to produce a polymer, and the polymer is a catalyst of the H-type cation exchange resin. It has the drawback of deteriorating the resin and shortening the life of the catalyst, and also has the drawback of causing mechanical destruction of the exchange resin, which is the catalyst.

[0005]

DISCLOSURE OF THE INVENTION The present inventors use a reaction apparatus of a special material when reacting phenol with β-hydroxyketone or alkyl vinyl ketone to produce 4- (3-oxoalkyl) phenol. We have earnestly studied a manufacturing method that does not require the catalyst used in the reaction, can be easily recovered and reused, and has a small amount of waste such as ion-exchange resin as a catalyst and washing water. As a result, it was found that the objective can be achieved by using a heteropolyacid as a catalyst when reacting phenol with β-hydroxyketone or alkyl vinyl ketone to produce 4- (3-oxoalkyl) phenol, and based on this finding The present invention has been completed. As is clear from the above description, the object of the present invention is to react phenol with β-hydroxyketone or alkyl vinyl ketone,
-When producing (3-oxoalkyl) phenol, it is not necessary to use a reactor with a special material, and the catalyst used in the reaction can be easily collected and reused, and the ion-exchange resin as catalyst and water for washing are discarded. It is to provide a method for producing 4- (3-oxoalkyl) phenol, which is low in product.

[0006]

The present invention includes the following (1)-
It has the configuration of (3). (1) 4- (3-oxoalkyl) represented by the following chemical formula 4
Phenol and the following chemicals 5
The β-hydroxyketone represented by the formula (4)-(3) is characterized in that it is subjected to a liquid phase reaction in the presence of a heteropolyacid catalyst.
-Oxoalkyl) phenol production method. (2) 4- (3-oxoalkyl) represented by the following chemical formula 4
In producing phenol, the following chemical formula
The method for producing 4- (3-oxoalkyl) phenol according to (1) above, which comprises subjecting the alkyl vinyl ketone represented by the formula (4) to a liquid phase reaction in the presence of a heteropolyacid catalyst. (3) The heteropolyacid of the catalyst is condensed with at least one oxide selected from molybdenum oxide, tungsten oxide and vanadium oxide and an oxyacid of one element selected from phosphorus, silicon and germanium. The method according to any one of (1) or (2) above, which is a heteropolyacid having a structure and an atomic ratio of the former to the latter is 1 to 12.

[Chemical 4] (In the formula, R ₁ represents a linear or branched alkyl group having 1 to 7 carbon atoms.)

[Chemical 5] (In the formula, R ₂ represents a linear or branched alkyl group having 1 to 7 carbon atoms.)

[Chemical 6] (In the formula, R ₃ represents a linear or branched alkyl group having 1 to 7 carbon atoms.)

The structure and effect of the present invention will be described below. The production method of the present invention is a production method for producing 4- (3-oxoalkyl) phenol by stirring phenol and β-hydroxyketone or alkyl vinyl ketone in the presence of a heteropolyacid.

Specific examples of the β-hydroxyketone represented by Chemical formula 5 used in the present invention include the following, but the invention is not limited thereto. That is, 4-hydroxy-2-butanone, 1-hydroxy-3-pentanone, 1-hydroxy-3-hexanone, 1-hydroxy-3-heptanone and the like can be mentioned.

Specific examples of the alkyl vinyl ketone represented by Chemical formula 6 used in the present invention include the following, but are not limited thereto. That is, methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, butyl vinyl ketone and the like can be mentioned.

The amount of phenol used is 2 to 10 with respect to 1 mol of β-hydroxyketone or alkyl vinyl ketone.
It is selected in mol, preferably in the range of 2 to 5 mol.
Since the reaction is usually carried out in the presence of excess phenol, the use of a solvent is not particularly required, but toluene, xylene or the like inert to the reaction may be added.

The method of the present invention essentially requires the use of a heteropolyacid as a catalyst. The heteropolyacid referred to in the present invention is molybdenum oxide, tungsten oxide, at least one oxide selected from vanadium oxide and oxyacid of one element selected from phosphorus, silicon and germanium are condensed. And the former atomic ratio to the latter is 1 to 12 in the heteropoly acid. Specific examples of these heteropolyacids include:
Phosphomolybdic acid, phosphotungstic acid, phosphomolybdotungstic acid, phosphomolybdovanadic acid, phosphomolybdotungstovanadic acid, silicotungstic acid, silicomolybdic acid, silicomolybdotungstic acid, silicolybdoungstvanadic acid, germanium tungsten Such as acids. Of these, phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, and germanium tungstic acid are preferable.

The commercially available heteropolyacid can be used as it is, but it is also possible to use a heteropolyacid salt in which a part of the protons of the heteropolyacid is replaced with an alkali metal, an alkaline earth metal element or the like to make it insoluble or hardly soluble. It is possible. The substitution element is not limited to these, and a heteropolyacid salt widely substituted with a transition metal element or the like can be used. Similarly, a nitrogen-containing compound such as ammonia or an amine compound in which a part of the protons of the heteropoly acid is replaced can be used.

Further, in order to make it possible to easily separate and recover the catalyst after the reaction, it is also possible to impregnate and carry a heteropolyacid on a carrier for use in the reaction. In this case, a carrier that is stable to heteropolyacid and has a large specific surface area is preferable, and it is preferable to use one or more of silica, alumina, titania, activated carbon and the like. Further, it is also possible to use a catalyst immobilized by wrapping a heteropolyacid or a heteropolyacid salt with SiO ₂ or Al ₂ O ₃ by a coprecipitation method or a cogelling method. The subsequent separation and recovery of the catalyst becomes easy. In the production method of the present invention, a homogeneous reaction using a free heteropolyacid as a catalyst, a heteropolyacid salt insoluble in a raw material and a reactant, or a heteropolyacid or an immobilized heteropolyacid supported on the above-mentioned carrier is used as a catalyst. It does not matter which method of the heterogeneous reaction used as
The heterogeneous reaction is preferable because the catalyst can be easily separated and recovered.

The amount of the heteropolyacid to be used is not particularly limited, but if the amount of the heteropolyacid present in the reaction system is small, the reaction rate will be low, so the amount of the heteropolyacid is 1 mol of β-hydroxyketone or alkyl vinyl ketone. 0.0001 mol to 0.05 mol, preferably 0.0
It is used in the range of 01 mol to 0.01 mol. The amount of the heteropoly acid used is, for example, as an aqueous solution after the reaction is completed.
Alternatively, since it can be collected by filtration and reused, it is not always necessary to use a small amount, but rather, in order to proceed the reaction stably, it is preferable to use a relatively large amount and to collect and reuse it to achieve an advantage.

The reaction of phenol with β-hydroxyketone or alkyl vinyl ketone is usually carried out in an inert gas atmosphere under atmospheric pressure to about 5 atm at a temperature of 20-1.
It is carried out at 00 ° C, preferably 30 to 80 ° C. If the reaction temperature is too low, the reaction activity of the catalyst is not sufficiently exhibited, and further, the reaction rate is greatly reduced by the water produced by the reaction, so that the reaction rate becomes extremely slow as the reaction proceeds. Further, when the reaction temperature is too high, a large amount of a polymer of β-hydroxyketone or an alkyl vinyl ketone and other by-products are produced and the yield is lowered.

The reaction time varies depending on the amount of catalyst and the reaction temperature, but is usually about 1 to 20 hours in the case of a batch reaction using a stirred tank reactor. The reaction format is
A commonly used one such as a tank type or a tower type is used. It can be carried out by either a batch system or a continuous system.

After the completion of the reaction, as a method of separating the catalyst from the reaction solution, when a free heteropolyacid is used, it is possible to extract the heteropolyacid with water, recover it, and reuse it. . When used as a partial salt, a supported product, or an immobilized product, the reaction solution is filtered to recover the catalyst,
It can be reused.

Isolation of the desired product, 4- (3-oxoalkyl) phenol, is carried out by a conventional method. For example, crude 4- (3-oxoalkyl) phenol is obtained by distilling and separating water, a low-boiling-point by-product, and phenol, and further known purification operations such as distillation and crystallization are performed to obtain pure 4- (3-oxoalkyl) phenol. Phenol can be obtained.

The 4- (3-oxoalkyl) phenol represented by the above formula 4 obtained by the method of the present invention is, for example, 4- (3-oxobutyl) phenol, 4- (3-oxopentyl) phenol, 4- (3-oxohexyl). Examples thereof include phenol and 4- (3-oxoheptyl) phenol, but the invention is not limited thereto.

[0020]

The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

In the reaction solutions in the examples, phenol and 4- (3-oxoalkyl) phenol were quantified by the internal standard method, and the selectivity for phenol and β-hydroxyketone or alkyl vinyl ketone was as defined below. To do.

Selectivity to phenol = (generated 4- (3
-Mol of (oxoalkyl) phenol) / (mol of charged phenol-mol of unreacted phenol) vs. β-hydroxyketone or alkyl vinyl ketone selectivity = mol of 4- (3-oxoalkyl) phenol produced / consumed Number of moles of β-alkyl ketone or alkyl vinyl ketone

Example 1 A glass four-necked round flask having an internal volume of 100 ml, which had been replaced with nitrogen, was equipped with a Dimroth condenser and a dropping funnel, and was charged with 60.0 g (0.638 mol) of phenol. Acid (H ₄ SiW ₁₂ O ₄₀・ 24
H ₂ O) 3 g (0.906 mmol) was added, and the temperature was 60 ° C.
Heat and stir at 4-hydroxy-2-butanone 11.2
g (0.128 mol) was added dropwise from the dropping funnel over 2 hours. Then, the mixture was stirred at 60 ° C. for 3 hours, and the disappearance of 4-hydroxy-2-butanone was confirmed by analysis by gas chromatography. The solution after the reaction was analyzed by gas chromatography. The analysis conditions of the gas chromatography are as follows: a column of 1 m in length, 1 wt% of FPAP (FFAP) as a packing material, a helium gas as a carrier gas at a flow rate of 50 ml / min, and a heating rate of 10 ° C. per minute. The temperature was raised from 80 ° C to 240 ° C. A hydrogen ionization detector was used as the detector. as a result,
The conversion of 4-hydroxy-2-butanone was 100 mol%, and the selectivities of 4- (3-oxobutyl) phenol, the target product, for phenol and 4-hydroxy-2-butanone were 64.8 mol% and 63.2 mol%, respectively. . The reaction conditions are shown in Table 1 and the results are shown in Table 2.

Example 2 Using the catalyst obtained by extracting and recovering the silicotungstic acid used in Example 1 as a catalyst, the reaction was carried out again according to Example 1. The reaction conditions are shown in Table 1 and the results are shown in Table 2.

Example 3 18.7 g of starting material 4-hydroxy-2-butanone
(0.213 mol) and the reaction was carried out in accordance with Example 1 except that the catalyst was replaced by an ammonium salt of silicotungstic acid. As the ammonium salt of silicotungstic acid, a salt of silicotungstic acid, to which a specified amount of aqueous ammonia solution was added, was stirred at room temperature for 6 hours and then dried at 60 ° C. by an evaporator. The reaction conditions are shown in Table 1 and the results are shown in Table 2.

Example 4 The reaction was carried out in the same manner as in Example 3 except that a catalyst having 15% by weight of silicotungstic acid supported on silica was used as the catalyst. The catalyst was prepared by putting silica gel (Fuji Silica gel type B, manufactured by Fuji Davison Co., Ltd.) in a silicotungstic acid aqueous solution, supporting it by an impregnation method, and drying at 60 to 70 ° C., and then at 300 ° C. under reduced pressure to 3 kPa before use. It was baked and used. The reaction conditions are shown in Table 1 and the results are shown in Table 2.

Example 5 The reaction was carried out in the same manner as in Example 3 except that a catalyst prepared by supporting 15% by weight of silicotungstic acid on activated carbon was used as the catalyst, and the reaction was conducted after dropping for 2 hours and stirring for 8 hours. As the catalyst, activated carbon (Calgon F-300) was placed in an aqueous solution of silicotungstic acid, supported by an impregnation method, filtered, and washed with warm water.
Dry at 60-70 ° C and reduce pressure to 3 kPa before use 30
It was used after firing at 0 ° C. The reaction conditions are shown in Table 1 and the results are shown in Table 2.
It was shown to.

Example 6 The procedure of Example 1 was repeated except that 13 g (0.127 mol) of 1-hydroxy-3-pentanone was used as a raw material instead of 4-hydroxy-2-butanone, and silicotungstic acid was changed to 4 g (1.208 mmol). . Then, stirring was continued at 60 ° C. for 4 hours until the disappearance of 1-hydroxy-3-pentanone could be confirmed by analysis by gas chromatography. After completion of the reaction, analysis by gas chromatography was performed by the internal standard method. Analysis by gas chromatography was in accordance with Example 1. As a result, the conversion rate of 1-hydroxy-3-pentanone was 100 mol%, and the selectivity of 4- (3-oxopentyl) phenol, the target product, to phenol and 1-hydroxy-3-pentanone was 62.5 mol% and 61.3 mol%, respectively. Met. The reaction conditions are shown in Table 1 and the results are shown in Table 2.

Example 7 The reaction and analysis were carried out in accordance with Example 1 except that 8.9 g (0.127 mol) of methyl vinyl ketone was used as a raw material instead of 4-hydroxy-2-butanone. As a result, the conversion rate of methyl vinyl ketone was 100 mol%, and the selectivity of 4- (3-oxobutyl) phenol, the target product, to phenol and methyl vinyl ketone was 63.5 mol% and 60.2 mol%, respectively. It was The reaction conditions are shown in Table 1 and the results are shown in Table 2.

Comparative Example 1 Instead of the silicotungstic acid of Example 1, concentrated sulfuric acid (9
The reaction was carried out according to Example 1 except that 1.6 g of (8% by weight) was added. As a result, the conversion rate of 4-hydroxy-2-butanone was 100 mol%, and the desired product 4- (3
The selectivity of -oxobutyl) phenol for phenol and 4-hydroxy-2-butanone was 47 mol% and 48 mol%, respectively. The reaction conditions are shown in Table 1 and the results are shown in Table 2.

Comparative Example 2 In Example 1 except that 18 g of a sulfonic acid type cation exchange resin (Mitsubishi Kasei Kogyo Co., Ltd., trade name Diaion SK-1B) was used in place of the silicotungstic acid of Example 1. The reaction was carried out in a compliant manner. As a result, 4-hydroxy-2
The conversion of -butanone was 100 mol%, and the selectivities of 4- (3-oxobutyl) phenol, the target product, for phenol and 4-hydroxy-2-butanone were 45.1 mol% and 52.2 mol%, respectively. Also,
Due to mechanical destruction due to stirring, the ion exchange resin was finely pulverized, which made it difficult to separate the catalyst, and the reaction liquid was often entrained in the catalyst, resulting in a low acquisition rate. The reaction conditions are shown in Table 1 and the results are shown in Table 2.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

According to the method of the present invention, phenol and β
-When a 4- (3-oxoalkyl) phenol is produced by reacting it with a hydroxyketone or an alkyl vinyl ketone, the use of a specific heteropolyacid as a catalyst allows the 4- (3-oxoalkyl) phenol to be produced more significantly than the conventional method. It can be produced with high selectivity and high yield. In addition, the production method of the present invention does not require the use of a special material in the reaction apparatus, and the catalyst used in the reaction can be easily collected and reused, and the waste of the ion-exchange resin as the catalyst and washing water can be used. It is a small and industrially advantageous manufacturing method.

Claims (3)

[Claims] 1. When producing 4- (3-oxoalkyl) phenol represented by the following chemical formula 1, phenol and a β-hydroxyketone represented by the following chemical formula 2 are subjected to a liquid phase reaction in the presence of a heteropolyacid catalyst. A method for producing 4- (3-oxoalkyl) phenol, which comprises: [Chemical 1] (In the formula, R ₁ represents a linear or branched alkyl group having 1 to 7 carbon atoms.) (In the formula, R ₂ represents a linear or branched alkyl group having 1 to 7 carbon atoms.) 2. A process for producing a 4- (3-oxoalkyl) phenol represented by Chemical formula 1, in which a phenol and an alkyl vinyl ketone represented by the following Chemical formula 3 are subjected to a liquid phase reaction in the presence of a heteropolyacid catalyst. The method for producing 4- (3-oxoalkyl) phenol according to claim 1, wherein [Chemical 3] (In the formula, R ₃ represents a linear or branched alkyl group having 1 to 7 carbon atoms.) 3. The heteropoly acid of the catalyst comprises at least one oxide selected from molybdenum oxide, tungsten oxide and vanadium oxide and an oxyacid of one element selected from phosphorus, silicon and germanium. It has a condensed structure and the former atomic ratio to the latter is 1 to 1
2. The heteropoly acid of 2, which is 2.
Alternatively, the production method according to claim 2.