engleski

New rearrangements in the tert-amyl cation

Two rearrangement processes that rapidly interchange chemically different hydrogens have been reported in the stable tert-amyl ion. These two processes do not interchange the two inside carbons with the methyl carbons. However, if the 3-pentyl cation is formed, it could rearrange so as to interchange an inside and an outside carbon atom. To see whether this scrambling process does occur, we labeled a methyl group of tert-amyl with 13C. We report here observing its rearrangement to the inside carbon positions by means of 13C NMR spectroscopy. Quantum chemical calculations (at the MP4/6-31G(d, p)//MP2/6-31G(d, p) level of theory) concerning the pathway are also presented.

carbocation rearrangement; NMR spectroscopy; quantum-chemical calculations

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