L. Eberson, F. Radner
1991
Citations
0
Influential Citations
16
Citations
Journal
Journal of the American Chemical Society
Abstract
The photolysis of naphtalene or 1-methoxynaphthalene together with tetranitromethane in dichloromethane, using light with a cuttof at λ<435 nm, has been investigated. It is shown that naphthalene, a representative of less reactive aromatics, predominantly (85-90%) reacts to give nitro compounds with a low α/β ratio (ca. 1.5) via a photochemical addition/elimination mechanism, the remaining part being formed via thermal, NO 2 -promoted nitration (α/β ratio ca. 20). The adducts are formed by photochemical excitation of the CT complex between naphthalene and tetranitromethane, resulting in formation of the triad [ArH .+ NO 2 (NO 2 ) 3 C − ] from which the observed chemistry develops by attack of trinitromethanide upon the radical cation. For 1-methoxynaphthalene, a representative of more highly reactive aromatics, the reaction is again photochemically initiated and again adducts seem to be responsible for the further development of thermal nitration reactions, apart from the NO 2 -induced reaction