from first principles PP-I-1

PP-I-5Mathematical Modeling of Reactivity of Olefinic and AcetylenicCompounds in Catalytic Reaction of CycloaluminationGubaidullin I.M. 1 , Ramazanov I.R. 1 , Kadikova R.N. 1 , Nurislamova L.F. 21 Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, Ufa, Russia2 Bashkir State University, Ufa, RussiaNurislamova_LF@mail.ruAmong the many methods for the synthesis of organoaluminum compounds the greatestdistribution was found of reactions of hydro-, carbo-and cycloalumination. Cycloaluminationis relatively new and perspective direction, which requires a detailed study of the boundariesof the reaction application and its mechanism [1]. Now it is a little known about behavior inthis reaction of functionally substituted olefins and acetylenes, and also no comparative dataon the reactivity of different classes of olefinic and acetylenic compounds. The kinetics of thereaction and the influence of the nature of the unsaturated compounds on the mechanism oftransformation were not studied. Thus, the problem is new and actual.In this work the kinetic models of complex reactions of olefins and acetylenescycloalumination by AlEt 3 in the presence of Cp 2 ZrCl 2 catalyst in to aluminacyclopentane hasbeen constructed [2]. On the basis of computer experiment, two stages were added in thescheme of chemical reactions, reversibility of the first stage was established (catalystconversion), the key complex of the reaction was identified.On the basis of the developed kinetic models:a) mathematical conditions of origin and development of the induction period of the reactionof olefins cycloalumination were formulated; high parametrical sensitivity of the inductionperiod to the temperature of carrying out of the reaction and the quantity of the catalyst wasshown.b) the numerical analysis of the reactivity of olefins and acetylenes was carried out for thecycloalumination reaction; the obtained dependence of the rate of unsaturated compoundinsertion in studied reaction from time completely coincide with the experiment.References:[1] R. Ramazanov, R. N. Kadikova, and U. M. Dzhemilev. Cp 2 ZrCl 2 _Catalyzed cycloalumination ofacetylenic alcohols and propargylamines by Et 3 Al. Russian Chemical Bulletin, International Edition,Vol. 60, No. 1, pp. 99—106, January, 2011[2] Gubaidullin I.M., Spivak S.I. Information-analytical system of inverse chemical kinetics problems// Control system and information technologies. – N 1.1(31), 2008 (in Russian).120