[Tris(trimethylsllyl)methyl](dimethyl)silyl cyanate. The cyanate to isocyanate isomerization, and the high activity of cyanate as a leaving group in solvolysis

Abstract

The isomerization of the cyanate (Me₃Si)₃CSiMe₂(OCN), (1), to the isocyanate (i) in Ph₂O at 195 °C is second order in (1), (ii) in CCl₄ is catalysed by ICI, and (iii), in MeOH is catalysed by NaOMe; in solvolysis in MeOH, (1) is comparable in reactivity to the corresponding trifluoromethanesulphonate, and shows an abnormally high selectivity for reaction with the water in slightly aqueous MeOH.