22707-48-8Relevant articles and documents
Substituent effects on the solvolysis rates and gas phase stabilities of 1,2,2-trimethyl-1-phenylpropyl and 1,2,2-trimethyl-1-(2-methylphenyl)propyl systems
Nakata, Kazuhide,Fujio, Mizue,Mishima, Masaaki,Nomura, Hideyuki,Tsuno, Yuho,Nishimoto, Kichisuke
, p. 581 - 590 (2007/10/03)
Substituent effects on the solvolysis rates of 1,2,2-trimethyl-1- phenylpropyl chlorides in 80% (v/v) aq acetone at 45 °C and 1,2,2-trimethyl- 1-(2-methylphenyl)propyl p-nitrobenzoates in 50% (v/v) aq ethanol at 75 °C were correlated with the Yukawa-Tsuno
Solvolysis of 2-Aryl-3,3-dimethyl-2-butyl p-Nitrobenzoates. β-Deuterium Kinetic Isotope Effects and the Linear Free Energy Relationships
Liu, Kwang-Ting,Kuo, Mann-Yan
, p. 3523 - 3530 (2007/10/02)
Solvolysis of 2-aryl-3,3-dimethyl-2-butyl p-nitrobenzoates (4a-4d) and the 1,1,1-trideuterio derivatives (5a,5b,5c) in HFIP exhibited a high kinetic isotope effect, k(CH3)/k(CD3) = 1.90 at 60 deg C for the deactivating substrates 4c vs 5c.This effect decreased significantly with increasing electron releasing of the substituent on the aryl ring.Hammett-Brown treatment of the rate data for 4 yielded excellent linear relationships (r = 0.999) with ρ+ = -3.48.It is evident that the contribution of the α-methyl group to the stabilization of the cationic transition state is not constant.The approximation in the linear free energy relationship is discussed.