157096-63-4Relevant articles and documents
Photochemical Nitration by Tetranitromethane. XV. Formation of Adducts and their Secondary Products in the Photochemical Reaction between Benzene and Tetranitromethane
Eberson, Lennart,Calvert, Jane L.,Hartshorn, Michael P.,Robinson, Ward T.
, p. 347 - 355 (2007/10/02)
Photolysis of benzene/tetranitromethane in dichloromethane or acetonitrile with light of λ>435 nm gives four main product categories, namely, in dichloromethane at +20 deg C (relative yield, products): adducts 1 of hydroxy/trinitromethyl type (total 54percent, see below), nitro substitution products (total 8percent, nitrobenzene, 1,3-dinitrobenzene and 1,3,5-trinitrobenzene), trinitromethyl substitution products (26percent, trinitromethylbenzene, 1-nitro-4-trinitromethylbenzene, 1,3-dinitro-5-trinitromethylbenzene) and phenols (total 12percent, 2,4- and 2,6-dinitrophenol, 2,4,6-trinitrophenol). In acetonitrile at +20 deg C the same product groups comprised 15, 24, 39 and 18percent, respectively, and, in addition, a low yield (1.7percent) of what is formally a cycloaddition product between 4-nitrobenzonitrile N-oxide and acetonitrile, 5-methyl-3-(4-nitrophenyl)-1,2,4-oxadiazole 2. The structure of 2 was determined by single crystal X-ray analysis. The main adducts were assigned the structures of a cis/trans pair of 1-hydroxy-4-trinitromethylcyclohexa-2,5-diene (NMR). Their formation in both dichloromethane and acetonitrile shows that adduct formation from photolysis of tetranitromethane/aromatics is not only confined to polycyclic aromatics but can occur with a maximally resonance-stabilized system, like benzene itself. The high complexity of the product mixture can be explained partly by elimination reactions of adducts, combined with further thermal and photochemical transformations.
