Steric Strain and Reactivity:  Electrophilic Bromination of trans-(1-Methyl-2-adamantylidene)-1-methyladamantane

• Published in: Journal of organic chemistry 2000-03, Vol.65 (5), p.1273-1279
• Main Authors: Chiappe, Cinzia, De Rubertis, Antonietta, Lemmen, Peter, Lenoir, Dieter
• Format: Article
• Language: English
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo9910076

trans-(1-Methyl-2-adamantylidene)-1-methyladamantane (DMAD, 1b) reacts with Br2 in chlorinated hydrocarbon solvents to give either a bromonium polybromide ion pair or a substitution product, depending on bromine concentration. The first intermediate is a 1:1 π-complex having K f = 1.85(0.19) × 103 M-1 at 25 °C, which rapidly evolves to the bromonium tribromide ion pair. At high bromine concentration, which shifts all equilibria involving the counteranion of the ion pair intermediate toward the pentabromide species, this bromonium ion is stable and unable to further evolve into products. Temperature-dependent NMR spectra indicate chemical exchange of Br+ between the sides of the plane containing the two carbons of the bromonium ion. At very low bromine concentration, no ionic intermediate is detected and the reaction rapidly yields a rearranged substitution product, identified as 10. Under these conditions the disappearance of the π-complex follows a first-order rate law, and the observed rate constant increases with increasing olefin concentration, showing that product formation implies Br- as counteranion of the ionic intermediate, whose formation is a reversible process. A comparison of the results reported here for the bromination of 1b with those previously found for the parent olefin, adamantylideneadamantane (1a), shows that steric strain markedly affects the reactivity of the double bond.