77748-61-9Relevant academic research and scientific papers
A Study of Cations Generated from 1- and 3-Methyl- and 1,3- and 1,7-Dimethyl-2-arylbicycloheptan-2-ols
Coxon, James M.,Steel, Peter J.
, p. 2455 - 2466 (2007/10/02)
The 13C n.m.r. spectrum of the 2-(4'-methoxyphenyl)-1-methylbicyclohept-2-yl cation is reported and indicates a significant reduction in ?-delocalization of charge into the aryl ring on introducing a C1-methyl group.The endo-3-methyl-2-phenylbicyclohept-2-yl cation in strong acid undergoes epimerization at C3 and does not afford the tetracyclic or dimeric compounds. 1,exo-3-Dimethyl-endo-2-phenylbicycloheptan-exo-2-ol on reaction with HSO3F gave the exo-3,endo-6-dimethyl-2-phenylbicyclohept-2-yl cation at temperatures above -50 deg C.This is the first alcohol containing a C1-methyl, C2-aryl system which does not undergo a WM; 6,2H, WM rearrangement.Reaction of 1,syn-7-dimethyl-endo-2-phenylbicycloheptan-exo-2-ol gave the parent 1,syn-7-dimethyl cation which at -50 deg C gave the exo-5,endo-6-dimethyl-2-phenylbicyclohept-2-yl cation but not the WM; 6,2H; WM product.The structural features which determine the pathway of rearrangement of these bicyclic cations are discussed.
