DERIVATIVES OF THE PHOSPHAALKYNE TETRAMER 1,2,5,6-TETRAPHOSPHATRICYCLO [4.2.0.0(2,5)]OCTADIENE - PHOSPHONIUM IONS OF ALKYLATION (ETOTF) AND ACYLATION (MECO(+) SBCL6-), AND MONO- AND DIPROTONATION WITH SUPERACIDS - SYNTHESIS OF THE 1-MONOOXO, 1-MONOTH

摘要

Tricyclooctadiene 5 reacts with ethyl triflate and acetyl cation hexachloroantimonate at room temperature to give the corresponding P-ethylated and P-acylated phosphonium salts 6 and 8. P-Adamantylation (with 1-AdCl/SbCl5 complex) is not chemoselective, forming 7 in a mixture. The low temperature protonation of 5 with FSO3H/SO2ClF and FSO3H/SbF5 (1:1)''magic acid''/SO2ClF gave the mono- and diphosphonium ions 9 and 10, respectively. The monooxo and monothioxo derivatives of 5 (11 and 12) were prepared by oxygenation with (TMS)(2)O-2 and sulfuration with S-8/Et(3)N, respectively. Finally the Staudinger reaction of 5 with 1 and 2 equiv of p-tosyl azide gave the mono- and 1,5-bis(p-tosylimino) derivatives 13 and 14, respectively. Multinuclear NMR data of the resulting compounds are discussed and compared. [References: 15]