SOME GROUP IVB DERIVATIVES OF 1,6-METHANOANNULENE. SYNTHESIS, SUBSTITUENT EFFECTS AND REACTIVITY

Article abstract of DOI:10.1016/0022-328X(86)80191-7

Certain Group IVB derivatives of 1,6-methano<10>annulene have been synthesised, and their 13C nuclear magnetic resonance spectra recorded and assigned, to provide a measure of the substituent effects exerted by metalloid-containing groups in this non-benzenoid aromatic system.Comparisons are made with the corresponding naphthalene and some anthracene derivatives.Protiodemetallations of a number of arylsilanes and -stannanes have been examined, and in protiodestannyletion by CH3CO2H/dioxane at 27 deg C (an electrophilic aromatic substitution) the α- (or 2-) posititon of 1,6-methano<10>annulene is ca. 35 times as reactive as the α (or 1-) position of naphthalene, whereas in protiodesilylation by CF3CO2H/CH3CO2H at 27 deg C it is ca. 700 times the more reactive.