Physical Sciences and Mathematics Commons^™

Photochemical Generation Of 2-Methoxy-2methylpropylidene And Its Rearrangement Pathways, Stanislav Presolski

Honors Theses

2-methoxy-2-methylpropylidene was photochemically generated from a non-nitrogenous precursor, 1a,9b-Dihydro-IH-cyclopropa[1]phenanthrene-l-etbane 2-methoxy-2-methyl, available in two steps from phenanthrene. Two competing rearrangement pathways were observed for the p-methoxy carbene, 1,2-methyl shift and C-H insertion, which had varying weights depending on the solvent used. Nevertheless, the C-H insertion was always predominant, contrary to the current understanding of B-substituted carbenes, which apparently needs revision. An attempt was also made to measure by LFP the rate constant of rearrangement and lifetime of the stabilized l-chloro-2-methoxy-2-metbylpropylidene.