Steric strain and reactivity: electrophilic bromination of trans-(1-methyl-2-adamantylidene)-1-methyladamantane
trans-(1-Methyl-2-adamantylidene)-1-methyladamantane (DMAD, 1b) reacts with Br(2) 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 pi-complex having K(f) = 1.85(0.19) x 10(3) M(-)(1) at 25 degrees 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 pi-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.
Chiappe
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Dipartimento Chimica Bioorganica e Biofarmacia, Universita di Pisa, via Bonanno 33, Pisa 56126, Italy, Institut fur Organische Chemie und Biochemie, Technische Universitat Munchen, Lichtenbergstrasse 4, D-85747 Garching, Germany, and Institut fu.
De Rubertis A
Lemmen
P
Lenoir
D