III International Conference

METHOD FOR PREPARATION OF DICICLOPENTADIENE EPOXIDES BYHYDROGEN PEROXIDE OXIDATIONPP-I-71Miloslavsky D.G., Miloslavsky A.G., Ahmedianova R.A., Liakumovich A.G.Kazan, RussiaE-mail: basdimg@mail.ruMethod for preparation of dicyclopentadiene epoxides by hydrogen peroxide oxidation inpresence of phase transfer catalyst was developed. Dicyclopentadiene epoxides can beapplied in polyesters, laprols productions and for fine chemistry. Epoxidation was prepared in20 to 70 o C temperature interval, without any sort of organic solvents. There was noted thatbest yields of dicyclopentadiene epoxides is obtained at reaction temperature below 65 o C,higher temperatures lead to significant part of byproducts in reaction mixture.Dicyclopentadiene is formed from cyclopentadiene upon its dimerisation.Cyclopentadiene is one of the byproducts of pyrolysis process. Dicyclopentadiene epoxidescan be applied in polyesters, laprols productions and for fine chemistry. The use of oxygen,peroxides and peracids for direct oxidation of alkenes to epoxides is the main method forindustrial applications. Epoxidation with oxygen is only used for ethylene oxide production.This method is not efficient for other alkenes due to large amount of byproducts. A lot ofepoxides are produced by the metal catalysed liquid phase oxidation of alkenes using organichydroperoxides produced by hydrocarbon autoxidation. Homogeneous Mo(VI) andheterogeneous Ti(IV) are used as efficient catalysts for epoxidation with hydroperoxide.Epoxidation of substituted alkenes can be widely used in fine chemicals industry successfullyachieved by peracids method. But peracids epoxidation is not a pure method because acidwastes are produced. The safety is associated with handling peracids is also a matter forconcern. The employment of hydrogen peroxide is an attractive option both on environmentaland economic grounds. It is cheap, readily available and gives water as the only byproduct.Many catalytic systems based on different metals such as tungsten, manganese, rhenium andtitanium have been reported for the epoxidation using hydrogen peroxide. One of the mosteffective catalytic systems using hydrogen peroxide is peroxotungstate catalytic system. Anactive complex as rule is formed in situ from sodium tungstate phosphoric acid (or theirsanalogs) in hydrogen peroxide medium and phase transfer agent (in most cases it is lipophilicammonium or phosphonium salts). For dicyclopentadiene epoxidation we used sodiumtungstate dihydrate and phosphoric acid as cocatalysts, tertiary ammonium salt as phasetransfer agent and 35 % aqueous hydrogen peroxide as oxidant. Despite the fact, that in the133