Naslov
New rearrangements in the tert-amyl cation

Autori
Vrček, Valerije ; Ljubas, Danijel ; Saunders, Martin ; Kronja, Olga

Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, sažetak, znanstveni

Skup
13th European Symposium of Organic Chemistry

Mjesto i datum
Cavtat, Hrvatska, 10.09.2003. - 15.09.2003

Vrsta sudjelovanja
Poster

Vrsta recenzije
Međunarodna recenzija

Ključne riječi
carbocation; rearrangement; computational chemistry

Sažetak
13C NMR spectroscopy of the 2-methyl-2-butyl-1-13C cation (13C-labeled tert-amyl cation) indicates that interchange of the inside and outside carbons occurs via a barrier of 19.5 ( 2.0 kcal/mol. A plausible mechanism involves hydride migration in the proposed 2-pentyl cation 4 to form 3-pentyl cation 5. Via the protonated cyclopropane intermediate 6, which undergoes degenerate corner-to-corner hydride shift, the secondary 3-pentyl cation 5¢ with the label shifted to the central carbon atom is formed. The tert-amyl cation obtained from 5¢ in the reverse process has the 13C label on an inside carbon atom. All intermediates and transition structures were located on the PES theoretically at the MP2/6-31G(d, p) level of theory. The rearrangement rate of the doubly labeled tert-amyl cation (methyl-13C-butyl-1-13C cation), followed by means of 13C NMR, revealed that the process that interchanges inside and outside carbons has the highest barrier. Comparison of the initial rates revealed that isotopomer 1e arises considerably more slowly than other isotopomers, indicating that in the overall rearrangement process transition structure 5-TS has the highest energy.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA