The Preparation and Acetolyses of 5-Deuteriated exo-2-Norbornyl-p-bromobenzenesulfonates

Autor:	I. Goodwin, R. R. Macdonald, R. E. Massey, J. G. Ballard, A. Walling, Nick Henry Werstiuk, Miss Y. Teruta, R. E. Young, R. W. Ouwehand, Frank P. Cappelli, W. L. Chan, George Timmins
Rok vydání:	1972
Předmět:	Deuterium Chemistry Organic Chemistry Kinetic isotope effect Organic chemistry General Chemistry Solvolysis 2-Norbornyl cation Catalysis
Zdroj:	Canadian Journal of Chemistry. 50:618-626
ISSN:	1480-3291 0008-4042
DOI:	10.1139/v72-097
Popis:	The deuterionorborneols 2a, b, c, and e have been prepared and converted to the brosylates 1a, b, c, and e. The deuterium isotope effects determined spectrophotometrically for solvolysis in HOAc–KOAc are 1.00 ± 0.01, 1.01 ± 0.01, 0.99 ± 0.01, and 1.11 ± 0.01, respectively. These data establish that: (a) a steric deuterium isotope effect does not operate at C-5 and therefore probably not at C-6; (b) hyperconjugative stabilization of the norbornonium ion to the C-5 hydrogens is confirmed to be not important, and (c) provides the first experimental evidence that the hydrogen (deuterium) shift – internal return pathway contribution to the γ-deuterium isotope effects observed for 1d and e is minor.
Databáze:	OpenAIRE
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