Mathematisch-Naturwissenschaftliche Fakultät

Leibniz-Institut für Katalyse e.V. an der Universität Rostock

Fachgebiet: Optical in situ spectroscopy

Betreuer: Prof. Dr. Angelika Brückner / Dr. Ursula Bentrup

Diplom-Chemiker Leif Robin Knöpke
(e-mail: )

Reaction monitoring in multiphase systems: Application of coupled in situ spectroscopic techniques in organic synthesis

The benefit of coupling different in situ spectroscopic methods (ATR-FTIR / UV-vis / Raman spectroscopy) is exemplarily demonstrated by the means of two reactions as application examples: the Lewis acid mediated formal [3+3] cyclocondensation reaction of a diene with a keteneacetale and the heterogeneously catalysed enantioselective hydrogenation of imines. For both reactions new reactors (deep-temperature cell, probe autoclave) have been developed enabling in situ measurements under real reaction conditions

For the [3+3] cyclocondensation reaction it was demonstrated that the nature of the formed product depends on the different intermediates formed between the ketenacetal and the acids (complexation or acid catalysed rearrangement reaction). Furthermore the mechanisms of similar reactions (including other Lewis acids like AlCl3, Al2O3 and TiO2 or substrates like N-salicylideneaniline) could be successfully elucidated.

The effectiveness of the hydrogenation depends on the specific interaction of the tested ketimines with the phosphoric acid ester used as chiral modifer. This interaction is mainly influenced by the used solvent and leads to the formation of a carbocation (CH3OH) or a contact ion pair in (CH2Cl2, CF3CH2OH). Furthermore, the detected strong adsorption of imines and modifier on the Pt/Al2O3 catalyst affect their efficiency and acitivity in the reaction.