JP5339361B2 - Process for producing hydroxyaromatic derivatives - Google Patents

Description

  The present invention relates to a method for efficiently producing a hydroxyaromatic derivative compound.

Hydroxy aromatic derivative compounds such as alkylphenols are widely used as basic raw materials for chemicals, agricultural chemicals, fragrances, disinfectants, electronic materials, and other important chemical products.
As a main production method of alkylhydroxy aromatic compounds, Friedel-Crafts type reaction of hydroxyaromatic compounds using an acidic catalyst has been known. As an example of a reactive agent for a hydroxy aromatic compound, an example using an olefin or an alcohol is known, but in an example using an alcohol, water produced as a by-product may inhibit the progress of the reaction. Therefore, in the production of alkylphenols, a method of performing a reaction while removing water stepwise or continuously from a reaction system has been proposed (see, for example, Patent Documents 1 and 2), but the process is complicated. Therefore, there is a need for a method that allows the reaction to proceed efficiently with a simpler process.
Moreover, as a method for producing an alkyl derivative of phenols, a method of reacting under a condition in which an alcohol is in a supercritical state has been proposed (see Patent Documents 3 to 5). There is a problem that a high pressure condition is necessary (for example, methanol is 240 ° C. or more and 8 MPa or more, butanol is 287 ° C. or more and 4.8 MPa or more), and a special reaction vessel / equipment for that purpose is required.

  On the other hand, as a method for producing a phenol derivative having an acylalkyl group, a method in which an alcohol having an acylalkyl group (4-hydroxy-2-butanone) is reacted with phenol using a cation exchange resin as a catalyst is known. (See, for example, Patent Document 6) Usually, a long reaction time of several hours or more (for example, 15 hours at 70 ° C. or 3 hours at 120 ° C.) is required, and a more efficient method has been demanded. . In this reaction system, a method using a metal cation-containing montmorillonite catalyst (see Non-patent Document 1) or a zeolite catalyst (see Non-Patent Document 2) instead of a cation exchange resin has been studied. However, usually, a long reaction time (for example, 12 to 48 hours at 100 ° C.) is required, and this is not an industrially advantageous method.

JP 2004-123723 A JP 2004-203861 A JP 2001-335523 A Japanese Patent Laid-Open No. 2002-3425 Japanese Patent Laid-Open No. 2002-30015 JP 55-151530 A

J. et al. Org. Chem. 59, p. 5901 (1994) Appl. Catal. A: General 241, p. 247 (2003)

  The present invention has been made in view of the above circumstances, and provides a method for efficiently producing a hydroxyaromatic derivative compound such as an alkylphenol in a short time without going through complicated steps. It is for the purpose.

  As a result of intensive studies to solve the above problems, the present inventors have found that alcohols and specific solid acid catalysts have a property of easily absorbing microwaves, and water produced as a by-product in the reaction is microscopic. We found that it was very easy to absorb waves and was easily released from the reaction system when heated to a high temperature. As a result, the dehydrating Friedel-Crafts-type reaction between hydroxy aromatic compounds and alcohols in the presence of a solid acid catalyst is greatly accelerated by microwave irradiation and is not accompanied by reaction inhibition by by-product water. The present inventors have found a novel fact that a hydroxy aromatic derivative compound can be produced with good yield in a short time, and the present invention has been completed.

That is, according to the present invention, the following inventions are provided.
[1] The following general formula (I)
HO-R-H (I)
(In the formula, R represents a divalent aromatic ring group, and a part of hydrogen atoms on the ring may be substituted with a group not participating in the reaction.)
In the hydroxy aromatic compound represented by the following general formula (II)
R'OH (II)
(In the formula, R ′ represents a monovalent alkyl group, an aralkyl group or an acylalkyl group.)
The in represented by alcohols, in the presence of a sulfonic acid group-containing polymer catalysts, which comprises reacting by microwave irradiation, the following general formula (III)
HO-R-R "(III)
And / or the following general formula (IV)
R "O-R-H (IV)
(In these formulas, R has the same meaning as described above, and R ″ represents an alkyl group, an aralkyl group or an acylalkyl group in which the alkyl group portion has the same carbon number as R ′.)
The manufacturing method of the hydroxy aromatic derivative compound represented by these.

  By using the manufacturing method of this invention, there exists an advantage that hydroxy aromatic derivative compounds, such as alkylphenol, can be obtained more efficiently compared with the conventional method.

Hereinafter, the present invention will be described in detail.
The production method of the present invention is characterized in that a hydroxy aromatic compound is irradiated with microwaves in the presence of a solid acid catalyst to react with an alcohol.

In the present invention, the hydroxy aromatic compound used as a raw material is represented by the following general formula (I):
HO-R-H (I)
It is an aromatic compound represented by these.
In the formula, R represents a divalent aromatic ring group, and specific examples of the aromatic compound serving as a base include benzene, naphthalene, anthracene, phenanthrene, etc., and the divalent aromatic ring group includes a phenylene group. Naphthylene group, anthrylene group, phenanthrylene group and the like. Some of the hydrogen atoms on the ring of R may be substituted with groups that do not participate in the reaction. Specific examples of these groups include alkyl groups such as methyl, isopropyl and hexyl groups, and methoxy groups. In addition to alkoxy groups such as ethoxy group, isopropoxy group and hexyloxy group, there can be mentioned oxyethylene group and oxyethyleneoxy group which are divalent groups for bonding two carbon atoms on the ring. .

In addition, the alcohol to be reacted with the hydroxy aromatic compound is represented by the following general formula (II)
R'OH (II)
It is represented by
In the formula, R ′ represents a monovalent alkyl group, an aralkyl group or an acylalkyl group. When R ′ is an alkyl group, the carbon number thereof is preferably 1-20, more preferably 1-16. Specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-methylpropyl group, pentyl group, 1-methylbutyl group, hexyl. Group, 1-methylpentyl group, octyl group, 1-methylheptyl group, nonyl group, decyl group, hexadecyl group and the like. Specific examples of alcohols having these alkyl groups include methanol, ethanol, propanol, 2 -Propanol, butanol, sec-butanol, hexanol, octanol, hexadecanol and the like can be mentioned. When R ′ is an aralkyl group, the carbon number is preferably 7 to 22, more preferably 7 to 18. Specific examples thereof include phenylmethyl group, phenylethyl group, phenylbutyl group, phenyloctyl group, phenyldodecyl group, phenyloctadecyl group, etc. Specific examples of alcohols having these aralkyl groups include phenylmethanol. , 2-phenylethanol, 4-phenylbutanol, 8-phenyloctanol, 18-phenyloctadecanol group and the like. Further, when R ′ is an acylalkyl group, the carbon number thereof is preferably 2 to 20, more preferably 2 to 16. Specific examples thereof include acetyl group, 2-acetylethyl group, 2-propionylethyl group, 2-hexanoylethyl group, 2-decanoylethyl group, 3-acetylpropyl group, 4-acetylbutyl group and the like. Specific examples of the alcohol having an acylalkyl group include 4-hydroxy-2-butanone, 1-hydroxy-3-pentanone, 1-hydroxy-3-dodecanone, 5-hydroxy-2-pentanone, 6- Hydroxy-2-hexanone and the like can be mentioned.

  The molar ratio of the aromatic compound to the alcohol can be arbitrarily selected, but is usually 0.5 or more and 200 or less in consideration of the yield of the target product with respect to the alcohol.

By the reaction of the above general formulas (I) and (II), the following general formula (III)
HO-R-R "(III)
And / or the following general formula (IV)
R "O-R-H (IV)
(In these formulas, R has the same meaning as described above, and R ″ represents an alkyl group, an aralkyl group or an acylalkyl group in which the alkyl group portion has the same carbon number as R ′.)
The hydroxy aromatic derivative compound represented by these is manufactured.

  The production ratio of the compound (III) having an alkyl group introduced into an aromatic ring and the compound (IV) having an alkyl group introduced into a hydroxyl group can be controlled by reaction conditions such as temperature, time, catalyst, etc. When it is desired to produce more), it is preferable to use reaction conditions of high temperature and long time.

  In the present invention, various conventionally known solid acid catalysts used in Friedel-Crafts type reactions can be used. Specific examples thereof include sulfonic acid group-containing polymer catalysts, zeolite catalysts, montmorillonite catalysts, and the like.

  As sulfonic acid group-containing polymer catalysts, Dowex (registered trademark) available from Dow Chemical Co., Nafion (registered trademark) available from DuPont, available from Rohm & Hass Cation exchange resins such as Amberlite (registered trademark) and Amberlyst (registered trademark) available from Rohm & Hass are available, with various degrees of crosslinking, shapes and sizes Can be used. Among these, as for Dowex, 50WX2 (crosslinking degree 2%), 50WX4 (crosslinking degree 4%), 50WX8 (crosslinking degree 8%), etc. can be used, and for Nafion, a pellet form like NR50 is used. In various shapes and forms, such as those supported on silica such as SAC-13, can be used.

  Examples of the zeolite catalyst include zeolite catalysts having a protic hydrogen atom or a metal cation (aluminum, titanium, gallium, iron, cerium, etc.). As the zeolite, those having a basic skeleton such as Y-type, beta-type, mordenite-type, ZSM-5-type, and SAPO-type can be used. Among these zeolites, the proton type is represented by HY type, H-beta type, H-mordenite type, H-ZSM-5 type and the like. Regarding the silica / alumina ratio of these zeolites, various ratios can be selected depending on the reaction conditions, but are usually 2 to 400.

  Further, as the montmorillonite-based catalyst, those containing metal cations such as tin, aluminum, iron, zirconium, titanium, indium, gallium, copper, cerium, and lanthanum can be used. These metal cation-containing montmorillonites can be obtained, for example, by treating sodium cation type montmorillonite with an aqueous solution of an appropriate metal cation.

The amount of the catalyst for the raw material alcohol or hydroxyaromatic compound can be arbitrarily determined, but is usually about 0.0001 to 10, preferably about 0.001 to 8, more preferably 0.001 in terms of weight ratio. It is about ~ 6.
In the present invention, in order to heat the reaction system more efficiently, a heating material (susceptor) that absorbs microwaves and generates heat can be added to the reaction system. As the kind of the heating material, various conventionally known materials such as activated carbon, graphite, silicon carbide, titanium carbide and the like can be used. Further, a molded catalyst obtained by mixing the catalyst described above and the heating material powder and calcining using an appropriate binder such as sepiolite or holmite can also be used.

  The reaction of the present invention can be carried out in a liquid phase or gas phase depending on the reaction temperature and reaction pressure. Moreover, as a form of a reaction apparatus, it can carry out with various forms conventionally known, such as a batch type and a flow type. The reaction temperature is −10 ° C. or higher, preferably 0 to 350 ° C., more preferably 10 to 300 ° C. Furthermore, the reaction pressure is usually 0.1 to 100 atm, preferably 0.1 to 80 atm, and more preferably 0.1 to 60 atm. Although the reaction time depends on the reaction temperature, the amount of catalyst, the form of the reaction apparatus, etc., it is about 1 to 240 minutes, preferably about 1 to 200 minutes, more preferably about 1 to 160 minutes.

  Further, when the reaction is carried out in a liquid phase system, it can be carried out with or without a solvent, but when a solvent is used, hydrocarbons such as decalin (decahydronaphthalene) and decane, chlorobenzene, 1,2- or 1, Various solvents other than those that react with raw materials such as halogenated hydrocarbons such as 3-dichlorobenzene and 1,2,4-trichlorobenzene, ethers such as dibutyl ether, etc. can be used. You can also. Moreover, when performing reaction in a gaseous phase, it can also react by mixing inert gas, such as nitrogen.

  In the microwave irradiation in the reaction of the present invention, various commercially available devices equipped with a contact type or non-contact type temperature sensor can be used. The output of microwave irradiation, the type of cavity (multimode, single mode), the form of irradiation (continuous, intermittent), etc. can be arbitrarily determined according to the scale and type of reaction. The frequency of the microwave is usually 0.3 to 30 GHz.

  Purification of the hydroxyaromatic derivative compound produced by the method of the present invention can be easily achieved by means usually used in organic chemistry such as distillation, recrystallization and column chromatography.

EXAMPLES Next, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples.
Example 1
Phenol (Ia) 10 mmol, butanol (IIa) 0.5 mmol, 1,2-dichlorobenzene 0.2 ml, ion exchange resin (Dowex, Dowex 50WX4) 151 mg was put in a reaction tube, and the radiation temperature was Using a microwave irradiation apparatus (manufactured by Biotage, single mode type) equipped with a meter, the reaction was carried out at 150 ° C. for 15 minutes while stirring. As a result of analyzing the product with a gas chromatograph and a gas chromatograph mass spectrometer, IIa reacted (87.2% conversion), and 2- and 4-butylphenol (IIIa, 2-butyl body / 4-butyl body = 65). / 35, butyl group is a mixture of n-butyl group and sec-butyl group, n-form / sec-form = 8/92, total 60.5% yield) and butyl phenyl ether (IVa, butyl group is n-form) It was found that a mixture of butyl group and sec-butyl group produced n-form / sec-form = 98/2 (16.5% total yield) (see Table 1).

(Examples 2 to 23)
Table 1 shows the results obtained by performing the reaction and analysis in the same manner as in Example 1 while changing the reaction conditions (catalyst, raw material, temperature, time, etc.) and measuring the yield of the product.

(Comparative Example 1)
As a result of performing the reaction and analysis in the same manner as in the examples except that an oil bath heating device was used instead of the microwave irradiation device, the yields of IIIa and IVa were 36.0% and 13.7%, respectively, Comparing the yield of 49.7% with the total yield of IIIa and IVa of 77.0% obtained in Example 1, it was found that Example 1 was 1.55 times higher (see Table 2). .
These indicate that the method of the present invention using microwave irradiation can efficiently produce the target compound in a higher yield than the method of normal heating with an oil bath at the same reaction temperature and time. Yes.

(Comparative Examples 2 to 11)
As in Comparative Example 1, Table 2 shows the results of the reaction and analysis in the oil bath heating apparatus and the results of comparison with Examples.

  In the production of these hydroxyaromatic derivative compounds, the yield of the corresponding examples is up to 1.58 times larger than that of the comparative examples, and by using microwave irradiation, the purpose is higher than that of the method using normal heating. It has been shown that the compounds can be produced more efficiently.

  Since the hydroxy aromatic derivative compound useful as a basic raw material for various chemical products can be produced more efficiently and safely by the method of the present invention, the utility value of the present invention is high, and its industrial significance is great.

Claims (1)

The following general formula (I)
HO-R-H (I)
(In the formula, R represents a divalent aromatic ring group, and a part of hydrogen atoms on the ring may be substituted with a group not participating in the reaction.)
In the hydroxy aromatic compound represented by the following general formula (II)
R'OH (II)
(In the formula, R ′ represents a monovalent alkyl group, an aralkyl group or an acylalkyl group.)
The in represented by alcohols, in the presence of a sulfonic acid group-containing polymer catalysts, which comprises reacting by microwave irradiation, the following general formula (III)
HO-R-R "(III)
And / or the following general formula (IV)
R "O-R-H (IV)
(In these formulas, R has the same meaning as described above, and R ″ represents an alkyl group, an aralkyl group or an acylalkyl group in which the alkyl group portion has the same carbon number as R ′.)
The manufacturing method of the hydroxy aromatic derivative compound represented by these.