The stepwise carbonylation of 2,3-diazidonaphthalene catalyzed by rhodium(I) complexes: Synthesis of new heterocyclic organic derivatives

Abstract

By carbonylation at atmospheric pressure and 45 °C of 2,3-diazidonapthalene ( A) catalyzed by [Rh(DPP)(CO)Cl] 2 (DPP = Ph 2P(CH 2) 3PPh 2) or by RhCl(CO)(PPh 3) 2 heterogenized with a polymeric phosphine, 2-azido-3-isocyanatonaphthalene ( I) has been obtained. ( I) reacted with aniline to give N-phenyl- N 1[2(3-azido)naphthyl]urea ( II), which in the presence of carbon monoxide and of the homogeneous catalyst [Rh(DPP)(CO)Cl] 2 gave 1-phenylaminocarbonyl-1 H-2,3-dihydronaphth[2,3-d]imidazolin-2-one ( III). Compound ( III) was also obtained by the direct catalytic carbonylation of ( A) carried out in the presence of aniline. The reaction of ( I) with carbon monoxide in the presence of the homogeneous catalyst did not allow the isolation of any heterocyclic product when diethylamine was used, 2,3- N, N-diethylureidonaphthalene ( IV) being formed. The catalytic carbonylation of ( I) in the presence ofethanol gave 1-ethoxycarbonyl-1 H-2,3-dihydronaphth-[2,3-d]imidazolin-2-one ( V). Compounds I– V have been characterized by elemental analyses, spectroscopic data and mass spectrometry. The results reported here confirm the usefulness of rhodium( I) catalysts in the carbonylation of aromatic azides, allowing the selective synthesis under mild conditions of organic products which appear to be difficult to prepare by conventional routes.