JPH11349561A - Production of peracid compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To safely obtain a peracid compound is high yield by reacting a carboxylic acid compound with hydrogen peroxide in the presence of a specific amount of sulfuric acid. SOLUTION: This peracid compound is obtained by reacting (B) a carboxylic acid compound, e.g. a >=5C carboxylic acid compound (e.g. benzoic acid, etc.), with (C) hydrogen peroxide (preferably, a hydrogen peroxide solution having <=90 wt.% concentration is used.) in the presence of sulfuric acid. In the said reaction, <=100 mole % of the ingredient A is used to the ingredient B. The ratio of the ingredients B to C is preferably brought to (the molar number of the ingredient C)/(the molar number of the ingredient B)=0.05-100. The said reaction is preferably carried out in an organic solvent selected from halogenated hydrocarbons (chloroform, dichloromethane, etc.), alcohols (ethanol, 1-propanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), and aromatic compounds (benzene, toluene, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a peroxy acid compound by oxidizing a carboxylic acid compound with hydrogen peroxide. Peracid compounds are useful compounds mainly used as oxidizing agents in the production of epoxy compounds, quinone compounds, lactone compounds and the like.

Conventionally, various methods for producing peracid compounds, particularly peracetic acid, have been known. For example, as a method for producing a peracid compound, a method of reacting carboxylic acid with hydrogen peroxide in the presence of an acid catalyst (J. Am. Chem. Soc., Vol. 77, p. 4037 (1955
J. Org. Chem., Vol. 27, p. 1336 (1962); JP-A-53-1
19813), a method of reacting hydrogen peroxide with a carboxylic anhydride or chloride (Bull. Soc. Chim. Fran)
ce, 1959, p. 1401), a method of reacting dialloyl peroxide with sodium methoxide (Org. Synth., Coll. 1, vol. 431).
Page (1946)), Method by autoxidation of aldehyde (JA
m.Chem.Soc., vol. 79, p. 5882 (1957); J. Org. Chem., vol. 23, 1
923 (1958); Chem, & Ind., Vol. 62, Vol. 1962).

[0003] However, these methods are all methods for producing a peracid compound by oxidizing a carboxylic acid compound having 4 or less carbon atoms (for example, butyric acid, isobutyric acid, propionic acid, acetic acid and the like). It has been difficult to oxidize a carboxylic acid compound having a number of 5 or more, particularly a carboxylic acid compound having a high oxidation-reduction potential, such as benzoic acid, by the above method to produce a peracid compound.

As a method for producing a peracid from a carboxylic acid compound having 5 or more carbon atoms, for example, benzoic acid is suspended in methanesulfonic acid used as a solvent, and then suspended in methanesulfonic acid.
A method for producing perbenzoic acid by dropping 0% by weight aqueous hydrogen peroxide is known (J. Org. Chem., Vol. 27, p. 1336 (19).
62)). However, this method requires a large amount of methanesulfonic acid, is difficult to handle, and is uneconomical.

[0005] Further, as a method for producing peracid from a carboxylic acid compound having 5 or more carbon atoms, a method in which sulfuric acid is added in an amount three times the amount of sulfuric acid to dodecadioic acid is used.
A method for producing diperoxide decadioic acid by dropwise addition of a 10% aqueous hydrogen peroxide solution has been disclosed (JP-A-53-1).
19813). In this method, since the oxidation reaction occurs by absorbing the water in the hydrogen peroxide water and the water generated by the decomposition of the hydrogen peroxide itself with sulfuric acid having a dehydrating action, the amount of sulfuric acid used is In addition to the number of moles of hydrogen peroxide and the number of moles of water in the hydrogen peroxide water,
Further, it is considered that hydrogen peroxide and a carboxylic acid compound react stoichiometrically. However, the use of such large amounts of sulfuric acid is uneconomical. Further, the reaction heat of the reaction between sulfuric acid and water is large, which is extremely disadvantageous in terms of safety when considering production on an industrial scale.

[0006]

The present invention relates to a method for producing a peracid compound by oxidizing a carboxylic acid compound with hydrogen peroxide, wherein the carboxylic acid compound has 5 carbon atoms.
It is an object of the present invention to provide a method capable of easily and inexpensively and safely producing a peracid compound even when the above-mentioned compounds are used.

[0007]

Means for Solving the Problems The present inventor has made intensive studies to solve the above-mentioned problems of the prior art. As a result, they have found that the above problem can be solved by allowing 100 mol% or less of sulfuric acid based on the carboxylic acid compound to be present in the system in which the carboxylic acid compound reacts with hydrogen peroxide.
The present invention has been completed.

That is, the present invention relates to a method of preparing a carboxylic acid compound and hydrogen peroxide in an amount of 100 mol% based on the carboxylic acid compound.
The present invention relates to a method for producing a peracid compound, which comprises reacting in the presence of the following sulfuric acid.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION As the carboxylic acid compound used in the present invention, various organic carboxylic acid compounds having about 2 to 40 carbon atoms can be used without any particular limitation. Such carboxylic acid compounds include, for example, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, caprylic acid, stearic acid, oleic acid, eicosahexadienoic acid, and the like. Such as aliphatic monocarboxylic acids and derivatives thereof; succinic acid, glutaric acid, adipic acid, aliphatic dicarboxylic acids such as pimelic acid and derivatives thereof; benzoic acid, aromatic monocarboxylic acids such as naphthoic acid and derivatives thereof, Aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, and derivatives thereof, and the like. The present invention is particularly applicable to carboxylic acid compounds having 5 or more carbon atoms, particularly aromatic carboxylic acids and derivatives thereof, which have been difficult to apply to the production of peracid compounds among these carboxylic acid compounds. It is advantageous. In addition, the said derivative means what substituted the hydrocarbon group of the carboxylic acid compound with various functional groups, such as an alkyl group, a hydroxyl group, a carboxyl group, an amino group, an alkoxy group, and a halogen group.

The hydrogen peroxide used in the present invention is usually a solution obtained by diluting hydrogen peroxide with water or an organic solvent (hereinafter referred to as a hydrogen peroxide solution). The organic solvent is preferably an alcohol or ketone that dissolves hydrogen peroxide and is not oxidized by the hydrogen peroxide. Specifically, alcohols such as methanol, ethanol,
-Or 2-propanol, 1-, 2-, 3- or te
Examples of rt-butanol and the like, and examples of ketones include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, and ethyl butyl ketone. In addition, as the alcohols and ketones, those in which these compounds are substituted with various functional groups such as an alkyl group, a hydroxyl group, a carboxyl group, an amino group, an alkoxy group, and a halogen group can also be used.

The concentration of the hydrogen peroxide solution is not particularly limited, and various types can be used from various commercially available concentrations to high concentrations exceeding 90% by weight. Generally, a concentrated hydrogen peroxide solution of more than 90% by weight is
Since there is a high risk of explosion, it is desirable to use a hydrogen peroxide solution having a concentration of 90% by weight or less, and more preferably a concentration of 75% by weight or less in consideration of safety. On the other hand, a low concentration hydrogen peroxide solution has no effect on the reaction, but considering the amount of the hydrogen peroxide solution used to generate a certain amount of the peroxide compound, the hydrogen peroxide solution is It is desirable to use those having a concentration of 5% by weight or more, and more preferably those having a concentration of 25% by weight or more.

The ratio of the carboxylic acid compound to hydrogen peroxide is not particularly limited. However, considering the efficiency and safety of the reaction, the value obtained by dividing the number of moles of hydrogen peroxide by the number of moles of carboxylic acids is 0.05. A range of １００100 is desirable. Further, the value is desirably 10 or less, and desirably 0.5 or more.

In the present invention, when the carboxylic acid compound is reacted with hydrogen peroxide to produce a peracid compound, 100 parts of the carboxylic acid compound are used as an acid catalyst in the reaction system.
Up to mol% sulfuric acid is present. Sulfuric acid has been conventionally used as an acid catalyst for the production of peracid compounds. However, the present invention makes it possible to use a large amount of sulfuric acid by controlling the amount of use to 100 mol% or less based on the carboxylic acid compound. This solves the problem of the conventional method used. Further, the lower limit of the amount of sulfuric acid used is desirably 10 mol% in consideration of a reduction in reaction rate and reaction time. In the conventional method, sulfuric acid used in a large amount was also used to absorb water in the reaction system by dehydration, but in the present invention, the amount of sulfuric acid used was extremely small compared to the conventional method. Therefore, the sulfuric acid of the present invention cannot exert a sufficient dehydrating action. From this, it is considered that the sulfuric acid of the present invention has a different function due to a different function from the sulfuric acid used in the conventional method.

The production of the peracid compound of the present invention is carried out by oxidizing the carboxylic acid compound with hydrogen peroxide in the presence of the specified amount of sulfuric acid. Usually, it is carried out by dropping a hydrogen peroxide solution into a system containing the carboxylic acid compound and a specific amount of sulfuric acid.

In such a reaction, when the carboxylic acid compound to be subjected to the reaction is liquid at the reaction temperature, the carboxylic acid compound also acts as a solvent, so that the use of a solvent is not particularly required. Is a solid at the reaction temperature, the reaction is carried out in the presence of an organic solvent in which the carboxylic acid compound is dissolved. In addition,
Even when the carboxylic acid compound to be subjected to the reaction is liquid at the reaction temperature, an appropriate amount of an organic solvent can be added for the purpose of improving the compatibility with water in the hydrogen peroxide solution.

The organic solvent is preferably one which is not oxidized by a peracid compound. Further, since the substance to be dissolved is a carboxylic acid compound, a substance having polarity is preferable. Examples of such an organic solvent include halogenated hydrocarbons, alcohols, ketones, aromatic compounds and derivatives thereof. In particular,
Examples of the halogenated hydrocarbons include chloroform, dichloromethane, dichloroethane, trichloroethane, 2-chlorobutane, 1,1,2,2-tetrachloropropane and the like. As alcohols, methanol, ethanol, 1- or 2-propanol, 1-, 2-,
3- or tert-butanol, 1-, 2-, 3-, 4-
Or tert-amyl alcohol can be exemplified. Examples of ketones include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, and ethyl butyl ketone. As aromatic compounds, benzene,
Examples include toluene, xylene, and mesitylene. In addition, as these derivatives, those obtained by substituting the compound with various functional groups such as an alkyl group, a hydroxyl group, a carboxyl group, an amino group, an alkoxy group, and a halogen group can also be used. Of these organic solvents, halogenated hydrocarbons and their derivatives are preferred.

In consideration of the efficiency and safety of the reaction, the reaction temperature in the method for producing a peracid compound of the present invention is usually carried out at a temperature lower than a temperature at which the reaction system solidifies and a temperature lower than a temperature at which the reaction system boils. desired. The specific temperature varies depending on the type of the carboxylic acid compound and the organic solvent to be used, but when benzoic acid is used as the carboxylic acid compound and dichloroethane is used as the solvent, practically, the boiling point of dichloroethane is -50 ° C to 87 ° C. It is good to be done in the range. Further, the reaction temperature is preferably -30 ° C or higher from the viewpoint of reaction efficiency, and is preferably 80 ° C or lower from the viewpoint of safety.

The reaction is completed in a short time in most cases.
To complete the reaction, the reaction time can be further extended. Usually, the reaction time is about 5 minutes to 24 hours.

The thus obtained peracid compound can be separated from the production system by means such as distillation, extraction with water or a solvent (using a polar organic solvent which does not mix with the carboxylic acid compound), and column separation.

The apparatus used in the manufacturing method of the present invention is as follows.
A substance that withstands the above-mentioned reaction temperature and does not adhere to a substance that causes rapid decomposition of hydrogen peroxide and a peracid compound, for example, a metal component, a polymer, a chemical substance, or the like, for example, a glass-lined substance is desirable for safety. The material of the reactor is not particularly limited as long as it is not made of a material that withstands the above-mentioned reaction temperature and causes rapid decomposition of hydrogen peroxide and peracid. Further, a device having a stirring device is desirable.

[0021]

According to the production method of the present invention, a carboxylic acid compound is oxidized with hydrogen peroxide under mild conditions,
Peracid compounds can be produced. The production method of the present invention can be suitably applied to carboxylic acid compounds having 5 or more carbon atoms. Further, the peracid compound obtained by the production method of the present invention can be easily separated from the production system.

[0022]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. All percentages are by weight unless otherwise specified.

Example 1 3 g (24.6 mmol) of benzoic acid, 1.9 g (19.7 mmol) of sulfuric acid as an acid catalyst and 20 ml of dichloroethane as a solvent were placed in a 50 ml three-necked glass flask equipped with a reflux tube. Was. While performing magnetic stirring at room temperature (25 ° C.), 1 g (17.6 mmol) of 60% aqueous hydrogen peroxide was added dropwise over 5 minutes. Thereafter, the mixture was left for 5 hours while performing magnetic stirring at room temperature. The reaction solution was titrated with 0.1 mol / l potassium permanganate to determine the amount of hydrogen peroxide. Subsequently, the amount of perbenzoic acid was determined by iodometric titration. As a result, the residual amount of hydrogen peroxide was 5.23 mmol, and the production amount of perbenzoic acid was 12.32 mmol (the yield of perbenzoic acid was 70 mol%).

Claims (4)

[Claims] 1. A method for producing a peracid compound, comprising reacting a carboxylic acid compound with hydrogen peroxide in the presence of 100 mol% or less of sulfuric acid with respect to the carboxylic acid compound. 2. The method according to claim 1, wherein the carboxylic acid compound is a carboxylic acid compound having 5 or more carbon atoms. 3. The method according to claim 2, wherein the carboxylic acid compound having 5 or more carbon atoms is an aromatic carboxylic acid and / or a derivative thereof. 4. The reaction according to claim 1, wherein the reaction is carried out in at least one organic solvent selected from halogenated hydrocarbons, alcohols, ketones and aromatic compounds.
The production method according to any one of the above.