JP2003055363A - Method for producing lactone - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an industrially advantageous method for efficiently producing a lactone. SOLUTION: In the method for producing the lactone expressed by general formula (I) (X expresses O or methylene) by reacting an unsaturated carboxylic acid expressed by formula (II) (X expresses the same as described above) with hydrogen peroxide in the presence of formic acid, formic acid is azeotropically distilled away from the reaction mixture by using a hydrocarbon-based solvent.

Description

Description: BACKGROUND OF THE INVENTION [0001] The present invention relates to a compound represented by the general formula (I): (Wherein, X represents an oxygen atom or a methylene group.) The present invention relates to a method for producing a lactone represented by the following formula (hereinafter sometimes abbreviated as lactone (I)). The lactone (I) obtained by the present invention is useful as a raw material for synthesizing a resist material for an argon-fluorine laser. 2. Description of the Related Art Conventionally, methods for producing lactone (I) include the following: (1) General formula (II) (Wherein, X represents an oxygen atom or a methylene group), and an unsaturated carboxylic acid represented by the following formula (hereinafter sometimes abbreviated as unsaturated carboxylic acid (II)) is subjected to peroxidation A method of oxidizing and epoxidizing with hydrogen and directly concentrating the obtained reaction mixture (Carbohydrate. Res.), Vol. 58, 240
Page, 1997; Journal of Chemical Society, Perkin Transaction 1 (J. Che.
m. Soc. , Perkin Trans. 1) 903
1985, Journal of Chemical Society, Perkin Transaction 1 (J. Che.
m. Soc. , Perkin Trans. 1), 10
65, 1998) and (2) the epoxidation of unsaturated carboxylic acids (II) with hydrogen peroxide in the presence of formic acid and the reaction mixture obtained in large quantities in aqueous solution of an inorganic base such as sodium sulfite. And then extraction with an organic solvent such as an ester such as ethyl acetate or a halogenated hydrocarbon solvent such as methylene chloride (JP-A-2000-159858). [0003] In the above method (1), since the thermal stability of lactone (I) is low, lactone (I) is denatured when the reaction mixture is concentrated, and the yield is increased. ,
There were problems such as a decrease in purity. In the above method (2), a metal component such as sodium remains in the obtained lactone (I), which is not preferable as a method for producing a raw material for synthesizing an argon-fluorine laser resist material. Furthermore, since the concentration of lactone (I) in the aqueous solution after the neutralization treatment is reduced by adding an inorganic base as an aqueous solution and generating water by neutralization, the lactone (I) is extracted from the aqueous solution. For this purpose, a large amount of organic solvent is required. [0004] It is, therefore, an object of the present invention to provide an industrially advantageous method for efficiently producing lactone (I). Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies on a method for producing lactone (I). Lactone (I) can be efficiently produced by reacting the resulting reaction mixture with hydrogen peroxide under reduced pressure, and azeotropically distilling formic acid from the obtained reaction mixture using a hydrocarbon solvent. As a result, the present invention has been completed. That is, the present invention relates to a process for producing a lactone (I) by reacting an unsaturated carboxylic acid (II) with hydrogen peroxide in the presence of formic acid. And azeotropically distilling the lactone (I). DETAILED DESCRIPTION OF THE INVENTION As formic acid used in the present invention, those commercially available can be used as they are. Usually, it is preferable to use 85% formic acid. The amount of formic acid used is not particularly limited, but is preferably in the range of 0.2 to 5 equivalents with respect to the unsaturated carboxylic acid (II), and from 0.5 to 3 in terms of operability and economy.
It is more preferably in the range of equivalents, and particularly preferably in the range of 0.5 to 2.5 equivalents. [0008] Hydrogen peroxide is commercially available 1
An aqueous solution of の 60% hydrogen peroxide can be used as it is. Using a high-concentration aqueous solution of hydrogen peroxide
From the viewpoint of reactivity and volumetric efficiency, it is preferable to use a hydrogen peroxide aqueous solution having a concentration of about 30% from the viewpoint of safety. The amount of the aqueous hydrogen peroxide solution is not particularly limited. However, in consideration of the yield and the productivity, the amount of the aqueous hydrogen peroxide solution is usually 0.1 to 10% with respect to the unsaturated carboxylic acid (II) in terms of hydrogen peroxide. It is preferably in the range of 2 to 5 equivalents, more preferably in the range of 0.5 to 3 equivalents, particularly preferably in the range of 0.5 to 2.5 equivalents from the viewpoint of operability and economy. preferable. [0010] The reaction temperature is preferably in the range of 10 to 80 ° C, more preferably in the range of 40 to 70 ° C. When the reaction temperature is lower than 10 ° C., the progress of the reaction tends to be extremely slow, which is not preferable. If the reaction temperature exceeds 80 ° C., self-decomposition of hydrogen peroxide occurs, so that the selectivity per hydrogen peroxide decreases and the product tends to be denatured into a high boiling point compound, which is not preferable. . The reaction may be carried out under normal pressure or under reduced pressure, and may be carried out in either a continuous system or a batch system. Further, the reaction can be carried out in the atmosphere, but from the viewpoint of safety, it is preferable to carry out the reaction in an atmosphere of an inert gas such as nitrogen or argon. The reaction is carried out, for example, by dropwise adding an aqueous solution of hydrogen peroxide to a mixture of unsaturated carboxylic acid (II) and formic acid at a predetermined temperature under an inert gas atmosphere such as nitrogen or argon and stirring the mixture. In the present invention, formic acid is azeotropically distilled from the reaction mixture obtained by the above method using a hydrocarbon solvent. Examples of the hydrocarbon solvent include pentane, hexane, heptane, octane, cyclopentane,
Cyclohexane, methylcyclohexane, cycloheptane, cyclooctane and the like can be used. The amount of the hydrocarbon solvent to be used is not particularly limited, but is preferably in the range of 1 to 100 times the weight of formic acid. Is more preferable, and the range of 2 to 30 times the weight is particularly preferable. The method of adding the hydrocarbon solvent is not particularly limited, but is preferably added to the reaction mixture after completion of the reaction from the viewpoint of operability and efficiency. The temperature at which formic acid is distilled off azeotropically is 10 to 60 ° C.
Is preferably within the range. The azeotropic distillation temperature is 10 ° C
If the temperature is less than 60 ° C., it is inefficient because a large amount of energy is required for condensation of the hydrocarbon solvent to be evaporated. If the temperature for azeotropic distillation exceeds 60 ° C., the lactone (I)
From the viewpoint of the stability of The azeotropic distillation of formic acid may be carried out under reduced pressure, normal pressure or increased pressure. When the azeotropic temperature exceeds 60 ° C., it is preferably carried out under reduced pressure. Is lower than 10 ° C., it is preferable to carry out the reaction under pressure. In the azeotropic distillation of formic acid, water in the reaction mixture is also distilled off, so that water may be added to the system if necessary. The method of adding water is not particularly limited, and a method of adding a distillate as needed, a method of adding a necessary amount in advance, and the like can be used. Lactone (I) obtained by the above method
Can be isolated and purified by a method generally used for isolating and purifying organic compounds. For example, the hydrocarbon solvent is removed from the residue after azeotropic distillation of formic acid by liquid separation, and then an organic solvent such as ethyl acetate is added to perform extraction.The obtained organic layer is concentrated, and then recrystallized. Purify by column chromatography or the like. The unsaturated carboxylic acids (II), such as 5-norbornene-2-carboxylic acid, used in the present invention can be easily prepared by the Diels-Alder reaction between cyclopentadiene and acrylic acid (Justig. Liebig Annalen der Chemie (Ann.), 514, 197, 1934); Journal of the American Chemical Society (J. Am. Chem. Soc.), 72, 311.
6, 1950; Journal of the American Chemical Society (J. Am. Chem. So
c. ), 77, 3584, 1955). EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1 138.2 g (1.0 mol) of 5-norbornene-2-carboxylic acid and 54.2 g of 85% formic acid were placed in a 1000 ml three-necked flask equipped with a mechanical stirrer, a thermometer and a dropping funnel. 1.0 mol), and the inside of the system was replaced with nitrogen to prepare a mixed solution. Subsequently, the temperature of the mixture was raised to 50 ° C. while stirring, 124.7 g (1.1 mol) of a 30% aqueous hydrogen peroxide solution was added dropwise over 4 hours, and the mixture was further stirred at the same temperature for 11 hours. The obtained reaction mixture was cooled, and after adding 22.3 g of sodium sulfite, 200 ml of hexane was added and the temperature was raised to 60 ° C.
Formic acid was azeotropically distilled off. The aqueous layer was separated from the obtained residue, and the aqueous layer was extracted three times with 200 ml of ethyl acetate. The extract was concentrated, and 131.5 g of the concentrate was crystallized to give 2%.
-Hydroxy-4-oxatricyclo [4.2.1.0
^3,7 ] nonan-5-one 108.4 g (yield 70.3)
%). Example 2 142 g of 7-oxabicyclo [2.2.1] hept-5-ene-2-carboxylic acid was placed in a three-necked flask equipped with a mechanical stirrer, a thermometer and a dropping funnel and having a capacity of 1000 ml. 1.0 mol), 119.1 g of 85% formic acid
(2.2 mol) and 83 g of water were added, and the inside of the system was replaced with nitrogen to prepare a mixed solution. Subsequently, the temperature of the mixture was raised to 40 ° C. while stirring, and a 30% aqueous hydrogen peroxide solution 14
After 7.4 g (1.3 mol) was added dropwise over 4 hours,
The mixture was further stirred at the same temperature for 11 hours. After cooling the resulting reaction mixture and adding 26.3 g of sodium sulfite,
200 ml of hexane was added and the temperature was raised to 60 ° C., and formic acid was azeotropically distilled off. The aqueous layer was separated from the obtained residue, and the aqueous layer was extracted 10 times with 400 ml of ethyl acetate. The extract was concentrated and crystallized from 124.5 g of the concentrate to give 2-hydroxy-4,8-dioxatricyclo [4.2.1.0.
^3,7 ] nonan-5-one 106.2 g (68.1 yield)
%).

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Claims (1)

Claims: 1. A compound represented by the general formula (II): (Wherein X represents an oxygen atom or a methylene group) by reacting an unsaturated carboxylic acid represented by the formula (I) with hydrogen peroxide in the presence of formic acid. Wherein X is as defined above, wherein formic acid is azeotropically distilled off from the reaction mixture using a hydrocarbon-based solvent. Method.