III International Conference

PP-I-35and an opportunity of catalytic management of process with the help of UV - irradiations. It isestablished, that photochemical reaction of partial convertible reduction of molybdenum (VI)in complexes with polyvinyl alcohol proceeds in an oscillatory mode in direct as well as onreverse direction. It, apparently, plays a positive role for catalytic activity of thesecompositions. Also proceeding from this, the most rational mode of the UV-irradiation of thereactionary solution for providing maximal catalytic activity is represented in a periodicmode. Compositions are used as water solutions. Catalytic reaction of oxidation the alpha -pinene proceeds in that case most intensively near to border of the unit of phases of the waterand organic solution containing substrate. After reaction the catalyst mass be easily separatedfrom compound and used cyclically practically without loss of catalytic activity.In reaction of oxidation of trimethylphenole were used homogeneous complexes of Co(II) both giving a signal in EPR-spectrum, justifying about convertible bonding of oxygen,and not giving a signal in the EPR-spectrum. Nevertheless in test reaction of oxidationtrimethylphenole appeared active on data GC both complexes. It is possible, that themechanism of oxidation, despite of similarity of a structure of the given compounds, appearedvarious. Rate consumption of dioxygen was measured also volumetrically.TableComparison of catalytic activity of homogeneous catalysts in reaction of oxidation of2,3,6-trimetylphenoleCatalyst Mol.ratio:2,3,6--V 0 ,-V sp ,TMPh:solvent:Met mol/l•min mol/l•min•[Met]C 16 H 14 N 2 O 2 Co 1:46,7:0,03 0,00075 12,8C 12 H 12 F 6 N 2 O 2 Co 1:46,7:0,03 0,00036 6,18C 12 H 12 F 6 N 2 O 2 Co 1:66,7:0,01 0,00010 4,96This work is supported by RFBR (grant 02-03-32777)References1. Rothenberg G., Yatziw Y., Sasson Y. Tetrahedron. 1998. Vol.54. P.5932. Kuznetsova N.I., Kuznetsova L.I., Kirilova N.V. etc. Rus.Chem.Bull. 2003. P.14623. Menshikov S.Yu., Sennikov M.Yu., Romanova Yu.B. etc. J.Org.Chem. (Rus) Vol.40. N 6. P.8304. Menshikov S.Yu., Vurasko A.V., Molochnikov L.S. etc. J.Mol.Catal. A: Chemical Vol.158.2000. P.44771