Reaction of guaiazulene with o-formylbenzoic acid in diethyl ether (or methanol) in the presence of hexafluorophosphoric acid: comparative studies on 1H and 13C NMR spectral properties of 3-guaiazulenylmethylium- and 3-guaiazulenium-ion structures

Abstract

Reaction of guaiazulene ( 1) with o-formylbenzoic acid ( 2) in diethyl ether in the presence of hexafluorophosphoric acid at 25 °C for 90 min gives the corresponding monocarbenium-ion compound, [2-(carboxy)phenyl](3-guaiazulenyl)methylium hexafluorophosphate ( 3), quantitatively, which upon treatment with aq NaHCO 3 leads to 3-(3-guaiazulenyl)-2-benzofuran-1(3 H)-one ( 5) in 96% isolated yield. Similarly, reaction of 1 with 2 in methanol under the same conditions as the above reaction affords two kinds of inseparable monocarbenium-ion compounds, 3 and (3-guaiazulenyl)[2-(methoxycarbonyl)phenyl]methylium hexafluorophosphate ( 4) with an equilibrium between them, which upon reaction with a solution of NaBH 4 in ethanol at 25 °C for 30 min leads to 5 in 46% isolated yield and (3-guaiazulenyl)[2-(methoxycarbonyl)phenyl]methane ( 6) in 37% isolated yield. Along with the 1H and 13C NMR spectral properties of a solution of 5 in trifluoroacetic acid- d 1 at 25 °C, whose molecular structure is converted to a ca. 1:1 equilibrium mixture of 7 possessing a partial structure of the 3-guaiazulenylmethylium-ion and 8 possessing a partial structure of the 3-guaiazulenium-ion, comparative studies on the 1H and 13C NMR spectral properties of 7 and 8 with those of the monocarbenium-ion compound, (3-guaiazulenyl)[4-(methoxycarbonyl)phenyl]methylium hexafluorophosphate ( A), 5, and 6 are reported. From these NMR studies, it can be inferred that the positive charge of the 3-guaiazulenylmethylium-ion part of 7 apparently is transferred to the seven-membered ring, generating a resonance form of the 3-guaiazulenylium-ion structure η′, and the same result can be inferred for the previously documented monocarbenium-ion compounds A– I. Moreover, referring to a comparative study on the C–C bond lengths of A observed by the X-ray crystallographic analysis with those of the optimized (3-guaiazulenyl)[4-(methoxycarbonyl)phenyl]methylium-ion structure for A calculated by a WinMOPAC (Ver. 3.0) program using PM3, AM1, or MNDOD as a semiempirical Hamiltonian, the optimized [2-(carboxy)phenyl](3-guaiazulenyl)methylium-ion structure for 3 calculated using PM3 is described.