Regioselectivity of nucleophilic substitution of the nitro group in 2,4,6-trinitrobenzamide

Under the action of anionic nucleophiles RO− (R=Ph, HCF2CF2CH2), R′S− (R′=Ph, PhCH2, C2H5OC(O)CH2), N3− on 2,4,6-trinitrobenzamide in MeCN or DMF, the ortho-nitro group is substituted with high selectivity. Intramolecular cyclisation involving ortho-positioned fragments SX and -CONH2 (XC2H5OC(O)CH2, Cl) has been achieved with the formation of 2-ethoxycarbonyl-3-hydroxy-4,6-dinitrobenzo[b]thiophene and 4,6-dinitro-2H-benzo[b]isothiazol-3-one correspondingly.