JPS5938236B2 - Production method of γ,γ-undecamethylene butyrolactone - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new method for producing γ,γ-undecamethylene butyrolactone.

γ,γ-Undecamethylene butyrolactone has various uses as a starting material for perfumes, pharmaceuticals, agricultural chemicals, and the like.

Conventionally, as a method for producing γ-alkyl-γ-lactone, for example, Japanese Patent Publication No. 50-12423 discloses a method for producing γ-methyl-γ-decalactone in which acrylic acid ester and 2-octanol are heated and reacted in the presence of a radical initiator. A method of manufacturing is disclosed.

However, in a heated reaction in the presence of a radical reaction initiator as in this method, when alcohol is applied to cyclododecanol, the yield of the corresponding lactone, γ, γ-undecamethylene butyrolactone, is 20 to 40%. The degree is extremely bad. Therefore, the conventionally known method for producing γ-alkyl-γ-lactone from acrylic ester and alcohol has not been used industrially for producing γ,γ-undecamethylene butyrolactone. The reality is that it is not.

In view of this situation, the present inventors aimed to establish a method for producing γ,γ-undecamethylene butyrolactone from acrylic acid ester and cyclododecanol in high yield. In order to find out what kind of substance should be present in the reaction system, we conducted an intensive search for the effects of various compounds.

As a result, if an alkali metal or alkaline earth metal phosphate and/or sulfate is present in addition to ditertiary butyl peroxide in the reaction system, γ, γ-undecamethylene can be produced in high yield. The present invention was completed based on the discovery that butyrolactone can be produced. That is, the present invention
acrylic ester and cyclododecanol in the presence of (a) di-tert-butyl peroxide (b) an alkali metal or alkaline earth metal phosphate and/or sulfate; This invention relates to a new method for producing γ, γ-undecamethylene butyrolactone.

The acrylic ester used as a starting material in the present invention is
It means a lower alkyl ester having 1 to 5 carbon atoms, and representative examples include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and pentyl acrylate.

The amount of these acrylic esters used is 0.05 to 0.4 times by mole per mole of cyclododecanol used.
Preferably, it is sufficient to use 0.10 to 0.25 mole times. Next, the phosphates and sulfates used in the present invention include sodium, potassium, calcium, magnesium, barium, zinc, aluminum, zirconium, lead, chromium, manganese, nickel, iron, ammonium, and other phosphoric or sulfuric acid salts. Examples include salts, hydrogen salts, sodium ammonium hydrogen phosphate, and hydrates of these salts, and mixtures of these salts can also be used effectively.

If the amount of these alkali metal or alkaline earth metal phosphates and/or sulfates used is too small, the reaction rate will be slow and the yield of the desired product will be reduced, and if the amount is too large, side reactions may occur. Since there is a risk of corroding the equipment, 0.0% per 100 parts by weight of acrylic ester
It is advisable to use 1 to 10 parts by weight, preferably 0.5 to 6 parts by weight. The amount of di-tertiary butyl peroxide used is
0.01 to 0.5 mol, preferably 0.04 to 0.2 mol is used per 1 mol of acrylic ester, and the reaction temperature is 140 to 200°C, preferably 150 to 180°C.
If the reaction is carried out for 2 to 10 hours, the desired product can be effectively produced, and the desired product γ, γ
- Undecamethylene butyrolactone can be recovered by appropriately employing conventionally known methods such as distillation, solvent extraction, recrystallization, gas chromatography, and the like. Next, examples of the present invention and comparative examples will be given.

Example: Put 920f of cyclododecanol and 1.6f of dipotassium hydrogen phosphate into a 12t separable flask and
While heating and maintaining at 65°C and stirring, add 1 liter of this medium, 86 t of methyl acrylate, and 14.67 t of di-tert-butyl peroxide.
A mixed solution was added dropwise over a period of 7 hours.

Stirring was continued at the same temperature for an additional hour. After the reaction is completed, unreacted cyclododecanol is distilled off from the reaction solution, and then distilled under reduced pressure to a boiling point of 175-177°C/4TT.
tmHf γ,γ-undecamethylene butyrolactone 1
Obtained 82V. Examples 2 to 7 Instead of dipotassium hydrogen phosphate in Example 1,
An experiment was conducted in the same manner as in Example 1, except that 0.97% of the phosphate or sulfate shown in the table was used.

Comparative Example 1 An experiment was conducted in the same manner as in Example 1, except that dipotassium hydrogen phosphate in Example 1 was not used.

Next, Table 1 shows the yields and yields of γ,γ-undecamethylene butyrolactone obtained in the experiments of Examples 1 to 7 and Comparative Example 1.

Examples 8 and 9 The amount of dipotassium hydrogen phosphate used in Example 1 was changed to 4
, 3t (Example 8), 0.6V (Example 9), and the reaction temperature was approximately 155° C., but an experiment was conducted in the same manner as in Example 1.

As a result, γ,γ-undecamethylene butyrolactone was obtained in Example 8 with 1807 (yield 76(f) based on methyl acrylate) and in Example 9 with 176V (yield 74% with respect to methyl acrylate). Example 10 The same procedure as in Example 1 was carried out except that ethyl acrylate was used in place of methyl acrylate in Example 1, and the amount of ditertiary butyl peroxide was changed to 11.0f. I conducted an experiment.

Claims (1)

[Claims] 1. Acrylic acid ester and cyclododecanol (
γ,γ-Undecamethylene butyrolactone, characterized in that it is subjected to a heating reaction in the presence of a) ditert-butyl peroxide (b) an alkali metal or alkaline earth metal phosphate and/or sulfate. manufacturing method.