Reaction of 1-Bromoadamantane with Diphenylphosphide and Diphenylarsenide Ions by the SRN1 Mechanism. Facile Nucleophilic Substitution at the Bridgehead Position

ROSSI R. A.; PALACIOS S. M.; SANTIAGO A. N.

AMER CHEMICAL SOC

Año: 1982 vol. 47 p. 4654 - 4654

p class="MsoNormal" style="MARGIN: 0cm 0cm 0pt; mso-layout-grid-align: none">The photostimulated reaction of 1-bromoadamantane (1) with diphenylphosphide (2) and diphenylarsenide (6) ions in liquid ammonia afforded good yields of the substitution products, together with small amounts of adamantane (4) and 1,l'-biadamantyl (5) as byproducts. The reaction of 1 with 2 in the dark did not occur, but stimulation with solvated electrons gives a small amount of the substitution product and 5, with a large amount of 4. The photostimulated reaction of 1 with 2 is inhibited by p-dinitrobenzene and di-tert-butyl nitroxide. All these results suggest that these reactions occur by the SRN1 mechanism of substitution, where radical and radical anions are intermediates.