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Solvolysis of 2-aryl-3,3-dimethyl-2-butyl p-nitrobensoates : β -Deuterium kinetic isotope effects and the linear free energy relationships

✍ Scribed by Kwang-Ting Liu; Mann-Yan Kuo

Publisher: Elsevier Science
Year: 1988
Tongue: French
Weight: 553 KB
Volume: 44
Category: Article
ISSN: 0040-4020
DOI: 10.1016/s0040-4020(01)85982-2

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✦ Synopsis

Abmtraota Solvolyaim of 1-•ryl-3,3-diaethyl-2-butyl p-nitrobsnroates (68-64) and tha l,l,l-trfdautario derivatives (58, Sb, la) in HlTP exhibited a h&h kinetic isotope offeat, k(M3)/k(CDj) -1.90 at 60°C for the doaotivating substrates 40 vs So. This effect dacreamed significantly vfth incraa8ing electron rolea8fng of tha substftuent on the arylring. Hanett-Brown treatment of ths rat0 data for 4 yielded excellent linear relationships (r -0.999) vith p' --3.48. Itis evident that the contribution of the d-~sthyl group to the 8tabiliration of the cationia transition stats is not constant. Thr approximation in the linear free anergy relationship is discussad.

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