Piatak, David M.
M.S. (Master of Science)
Department of Chemistry
Ruthenium compounds; Amides; Ruthenium tetroxide; Electrochemistry; Oxidation
The use of ruthenium tetroxide as an oxidant for piperidine and pyrrolidine amide systems, namely 4- methylpiperidine, isonipecotic acid ethyl ester and proline ethyl ester, was explored. The amine group for each substrate was protected by acylation with acetyl chloride, benzoyl chloride, o-chlorobenzoyl chloride, mchlorobenzoyl chloride and p-chlorobenzoyl chloride to gauge what influence each of these groups might have on the course and yield of the reaction. Electrochemical oxidation was performed in a twophase system of saturated aqueous NaCl and CH3CN utilizing catalytic amounts of Ru04 regenerated in situ by CIO'. The CIO' was produced by electrochemical oxidation of an aqueous Cl' solution present in the cell. Varying yields of imides were produced and the time of the reaction proved crucial, especially for the pyrrolidine system. Good yields were obtained for the latter only after 48 hours instead of standard 8 h time period. The oxidation was found not to affect the optical activity of the proline ester since oxidation was favored at the other carbon a to the amine. In general, the hindered o-chloro derivatives proved more resistant to oxidation thereby giving the lowest yields. The best yields were secured when a) the cyclic amine was not substituted with an electron withdrawing ester moiety and b) the ester moiety was placed farther from the amine group. The structures of the products were determined from spectroscopic data and elemental analysis and the assignments of ‘H NMR signals were made available from standard decoupling experiments. The isonipecotic ester derivatives and their corresponding imide products produced *H NMR spectra in which the equatorial and axial protons on the carbons adjacent to the amine were clearly separated from one another owing to shielding/deshielding effects.
Shrivastava, Poornima, "Ruthenium tetroxide catalyzed electrochemical oxidation of substituted five and six membered cyclic amides" (1993). Graduate Research Theses & Dissertations. 4799.
Northern Illinois University
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