JPH11130763A - Method for producing 1,2-epoxy-5,9-cyclododecadiene - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To provide 1,5,9-cyclododecatriene with an organic hydroperoxide so as to obtain 1,5,9-cyclododecatriene with high selectivity.
An object of the present invention is to provide an industrially suitable production method for obtaining 2-epoxy-5,9-cyclododecadiene. The object of the present invention is to monoepoxidize 1,5,9-cyclododecatriene by contacting 1,5,9-cyclododecatriene with an organic hydroperoxide in the presence of molybdenum trioxide. In this case, the problem is solved by a method for producing 1,2-epoxy-5,9-cyclododecadiene, wherein alcohol is used as a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing 1,2-epoxy-5,9-cyclododecadiene by monoepoxidizing 1,5,9-cyclododecatriene with high selectivity.
1,2-Epoxy-5,9-cyclododecadiene has an active epoxy group and a carbon-carbon unsaturated bond, so it can be used not only as a resin component in paints and adhesives, but also as a derivative to cyclododecanone. Is further derived into lactams, lactones or dibasic acids by a known method, so that polyamide, synthetic fibers of polyesters,
It is an important compound that serves as an intermediate material for synthetic resins.

[0002]

2. Description of the Related Art Heretofore, a method for producing 1,2-epoxy-5,9-cyclododecadien has been described in a cyclododecan solvent.
There is a method in which an organic hydroperoxide is brought into contact with 1,5,9-cyclododecatriene using boric acids or molybdenum compounds (Japanese Patent Publication No. 49-40464). The amount of molybdenum compounds is extremely large, and the selectivity of the target product is not satisfactory. There is also a method of oxidizing 1,5,9-cyclododecatriene with formic acid formed from formic acid and hydrogen peroxide in a large amount of formic acid (JP-A-56-104877). It is dangerous because formic acid itself is unstable and easily decomposed. Furthermore, since formic acid is extremely corrosive to equipment and the like, there is a problem as an industrial production method.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and provides a high selectivity by contacting 1,5,9-cyclododecatriene with an organic hydroperoxide.
An object of the present invention is to provide an industrially suitable production method for obtaining 1,2-epoxy-5,9-cyclododecadiene.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide 1,5,9-cyclododecatriene by contacting 1,5,9-cyclododecatriene with an organic hydroperoxide in the presence of molybdenum trioxide. 1,2-epoxy-5,9-, characterized in that, when the monoepoxidation of
The problem is solved by a method for producing cyclododecadiene.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The amount of molybdenum trioxide used in the present invention is preferably 0.001 to 0.5 times mol, more preferably 0.01 to 0.1 times mol of 1,5,9-cyclododecatriene.
It is twice the mole.

[0006] The organic hydroperoxide used in the present invention is an alkyl hydroperoxide having 4 to 12 carbon atoms or an aralkyl hydroperoxide having 8 to 12 carbon atoms. Peroxide, cyclododecyl hydroperoxide, cumyl hydroperoxide and the like. The amount of use is preferably 0.1 to equimolar, more preferably 0.2 to 0.5 mole per 1,5,9-cyclododecatriene.

The alcohol used in the present invention includes, for example, methyl, ethyl, i-propyl, t-
Alcohols having an alkyl group such as a butyl group, a cyclohexyl group, and a cyclododecyl group may be mentioned. used. The amount of the solvent to be used is preferably 0.5 to 50 times by weight, more preferably 1 to 10 times by weight, based on 1,5,9-cyclododecatriene.

The reaction is carried out under normal pressure or under pressure, for example, by dropping an organic hydroperoxide to an alcohol solution of 1,5,9-cyclododecatriene in a nitrogen atmosphere in the presence of molybdenum trioxide. Done in The reaction temperature at that time is preferably 50 to 160 ° C., more preferably 80 to 160 ° C.
~ 120 ° C. Further, the obtained product can be isolated and purified by, for example, distillation or the like.

[0009]

The present invention will be specifically described below with reference to examples and comparative examples.

Example 1 In a 100 ml three-necked flask equipped with a reflux condenser, a dropping funnel and a thermometer, 16.23 g of 1,5,9-cyclododecatriene (0.1 mol
l), 0.29 g (2 mmol) of molybdenum trioxide, 20 ml of t-butanol
And heated to 85 ° C. with stirring under a nitrogen atmosphere. Thereafter, a solution obtained by dissolving 6.50 g (0.05 mol) of t-butyl hydroperoxide (69% aq.) In 5 ml of t-butanol was slowly dropped from the dropping funnel. 3 after dropping
After heating and stirring for an hour, the mixture was cooled to room temperature. Analysis of the resulting reaction solution, the remaining t-butyl hydroperoxide by iodometry, remaining 1,5,9-cyclododecatriene (hereinafter referred to as CDT) and generated 1,2-epoxy-5, 9-Cyclododecadienes (hereinafter referred to as monoepoxides) were performed by gas chromatography. The t-butyl hydroperoxide conversion is 92.6%, the CDT conversion is 44.2%, and the monoepoxide selectivity based on the consumed CDT is 93.
It was 2 mol%.

Examples 2 to 5 The reaction was carried out in the same manner as in Example 1 except that the solvent and / or the organic hydroperoxide was changed, and the results shown in Table 1 were obtained.

Comparative Examples 1 to 8 The reaction was carried out in the same manner as in Example 1 except that the solvent and / or the organic hydroperoxide was changed, and the results shown in Table 1 were obtained.

[0013]

【table 1】

[0014]

According to the present invention, when 1,5,9-cyclododecatriene is brought into contact with an organic hydroperoxide in the presence of molybdenum trioxide to monoepoxidize 1,5,9-cyclododecatriene. In addition, the method using alcohol as a solvent can provide an industrially advantageous production method for obtaining 1,2-epoxy-5,9-cyclododecadiene with high selectivity.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Osamu Yamazaki 5 Ube Kogushi 1978 Kogushi, Ube City, Yamaguchi Prefecture

Claims (3)

[Claims] (1) In the presence of molybdenum trioxide, an organic hydroperoxide is brought into contact with 1,5,9-cyclododecatriene to monoepoxidize 1,5,9-cyclododecatriene. Characterized as a solvent
A method for producing 1,2-epoxy-5,9-cyclododecadiene. 2. The method according to claim 1, wherein the alcohol used has an alkyl group having 1 to 12 carbon atoms.
The method for producing 1,2-epoxy-5,9-cyclododecadiene described in 1 above. 3. The method for producing 1,2-epoxy-5,9-cyclododecadiene according to claim 1, wherein the alcohol used has an alkyl group having 1 to 6 carbon atoms. .