141738-87-6Relevant articles and documents
Photochemical Nitration by Tetranitromethane. Part VI. Predominant Nitro/trinitromethyl Addition to Naphthalene in Dichloromethane and Acetonitrile
Eberson, Lennart,Hartshorn, Michael P.,Radner, Finn
, p. 1793 - 1798 (2007/10/02)
The photochemical reaction between naphthalene and tetranitromethane in dichloromethane or acetonitrile gave predominantly (85-95percent) products of nitro/trinitromethyl addition to the aromatic system, namely cis- and trans-1-nitro-4-trinitromethyl-1,4-dihydronaphthalene and trans-2-nitro-1-trinitromethyl-1,2-dihydronaphthalene.A small amount of trans-2-hydroxy-1-trinitromethyl adduct was also formed, presumably originating from an initial nitrito/trinitromethyl adduct.The minor reaction pathway directly gave product(s) of nitro substitution, the ratio of 1- to 2-nitronaphthalene being high (25) in dichloromethane and in the beginning of the acetonitrile runs (up to ca. 40percent conversion).The temperature dependence of this process suggests that coupling between (naphthalene)cation radical and nitrogen dioxide is the major pathway leading directly to nitro products. 2-Nitronaphthalene, formed after long reaction periods in acetonitrile runs, was presumably formed via elimination of nitroform from the 1,2-adduct. cis-1-Nitro-4-trinitromethyl-1,4-dihydronaphthalene was isolated in pure form and shown to undergo facile base-catalysed elimination of nitroform in dichloromethane and acetonitrile to give 1-nitronaphthalene.It also underwent a slow spontaneous elimination in acetonitrile.It was stable under acidic conditions.GLC of the pure adduct gave exclusively 1-nitronaphthalene at a low injector-port temperature, whereas at higher temperatures a mixture of products was formed (naphthalene, 1- and 2-nitronaphthalene and 1-naphthonitrile).
