110175-20-7Relevant articles and documents
Photochemical Nitration by Tetranitromethane. X. A Possible Addition/Elimination Pathway to Trinitromethylaromatic Compounds
Eberson, Lennart,Hartshorn, Michael P.,Svensson, Jan Olof
, p. 925 - 934 (2007/10/02)
The photolysis of tetranitromethane and 4-chloroanisole in dichloromethane at +20, -20 and -50 deg C led to the formation of mainly 4-chloro-2-trinitromethylanisole (40-50percent yield) and a pair of adducts (ca. 30percent yield) in which nitrito/trinitromethyl addition had taken place across the 2,5-positions of 4-chloroanisole.Small amounts of a pair of labile adducts (2-3percent yield), assigned the structure of the analogous hydroxy/trinitromethyl adducts were formed in the beginning of the runs.In acetonitrile, the major product from the same reaction was 4-chloro-2-nitroanisole at all three temperatures.Only at -50 deg C were the nitrito/trinitromethyl adducts detectable in low yield (1-2percent).The pair of nitrito/trinitromethyl adducts spontaneously decomposed in acetonitrile to give 4-chloro-2-trinitromethylanisole with rate constants of 7*10-4 min-1 at 0 deg C and 0.020 min-1 at 20 deg C, implying that they should be stable in this solvent at -20 and -50 deg C, if formed.The adducts also decomposed to 4-chloro-2-trinitromethylanisole under photochemical conditions accounting for the formation of this compound in low yield also in acetonitrile.The nitration process predominantly observed in acetonitrile presumably occurs via coupling of 4-chloroanisole radical cation and NO2, both formed in the initial photochemical step.The nitrito/trinitromethyl adducts were thermally and photochemically stable in dichloromethane under the reaction periods employed for photolysis.The conversion into labile hydroxy/trinitromethyl adducts was assumed to occur via acid-catalysed hydrolysis, eventually leading to 4-chloro-2-trinitromethylanisole via acid-promoted elimination of water from the latter adducts.However, only a minor part of this compound can be accounted for in this way.