Hydrogen Participation vs. Elimination. The Role and Fate of Neighboring Hydrogen in Solvolysis of Neomenthyl Tosylate

Article abstract of DOI:10.1021/jo01305a003

Product composition and α-d1 and β-d3 isotope effects in the solvolysis of neomenthyl tosylate (8-OTs) were determined in 70 percent aqueous trifluoroethanol and 70 percent aqueous ethanol.Both trifluoroethanolysis and ethanolysis gave 1-2 percent neomenthol (97percent d3), 12-13percent cis-4-menthanol (100percent d3), 2-3percent trans-4-menthanol (100percent d3), 66-70percent 3-p-menthene (83percent d3 and 17percent d2), and 5-9percent 4,8-p-menthene (97percent d3), respectively.These results and the high value of the β-d3 isotope effect (k_H/k_D=2.45) were interpreted in terms of rate-determining hydride shift followed by elimination which accounts for 75percent of all products.In 85percent of the elimination productsthe migrating hydrogen (deuterium) is not the one being eliminated.