Thermal rearrangement of spiro[naphthalene(naphthopyranofurazan)]oxides to spiro[naphthalene(phenalenofurazan)oxides. A probable furazan oxide triggered tandem isomerisation process

Abstract

Thermal rearrangement of (±)-spiro{naphthalene-1(2H),4′- (naphtho-[2′,1′:2,3]pyrano[4,5-c]furazan)}-2-one-11′-oxides in DMF or acetic anhydride at 140°C gave an isomeric mixture of (±)-spiro{naphthalene-1(2H),1′-(5′-hydroxyphenalene[1,2-c] furazan)}-2-one-2′-oxides and 4′-oxides. The rearranged structure was confirmed from X-ray analysis and was consistent with the through space NOE data. The rearrangement is suggested to be an overall tandem isomerization process. Using variable temperature 1H NMR spectroscopy the lower limit for the isomerisation barrier for a pair of tautomers was calculated to be 22 kcal mol-1 at 423 K. The isomerisation equilibrium for a pair of isomers was studied by variable temperature 1H NMR. The lower limit for the isomerisation barrier was calculated to be 22 kcal mol-1 at 423 K. This low value may be indicative of the difficulty encountered in separating the isomers by chromatography. Semi-empirical AM1 and molecular mechanics calculations suggest that the (±)-spiro{naphthalene-1(2H), 1′-(5′-hydroxyphenalene[1,2-c]furazan)}-2-one-2′-oxides are more stable than their 4′-oxide counterparts, in accordance to the X-ray structure. The lower population of the 4′-oxide isomers relative to that of the 2′-oxide isomers was explained in terms of an unfavourable intramolecular steric interaction found in the low energy structure of the former. © 2005 Elsevier Ltd. All rights reserved