Synthesis structure and reactivity of a symmetrically substituted 9-phosphatriptycene oxide and its derivatives

Novel 9-phosphatriptycenes were synthesized by utilizing ortho-lithiation of a triarylphosphine oxide as a key step. The structural analysis of the 9-phosphatriptycene oxide revealed its highly distorted structure around the phosphorus atom, which is consistent with the up-field shift in the P-31 NMR spectrum. The 9-phosphatriptycene and its chalcogenides were synthesized by ordinary methods, and the spectral comparisons of these chalcogenides indicated the large s-character of the lone-pair orbital or the phosphorus-chalcogen sigma bonds of those species. The 9-phosphatriptycene oxide was reacted with lithium naphthalenide to give the ring-opened products. (C) 2004 Wiley Periodicals, Inc.