New rearrangements in the tert-amyl cation (CROSBI ID 614586)
Prilog sa skupa u zborniku | sažetak izlaganja sa skupa | međunarodna recenzija
Podaci o odgovornosti
Vrček, Valerije ; Ljubas, Danijel ; Saunders, Martin ; Kronja, Olga
engleski
New rearrangements in the tert-amyl cation
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.
carbocation; rearrangement; computational chemistry
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Podaci o prilogu
2003.
objavljeno
Podaci o matičnoj publikaciji
Podaci o skupu
13thEuropean Symposium of Organic Chemistry
poster
10.09.2003-15.09.2003
Cavtat, Hrvatska