The nitration of multiply deactivated aromatic compounds usually requires heating with fum-HNO
3/conc-H
2SO
4 at elevated temperature. However, a combination of NO
2 and O
3 was found to exhibit a powerful nitrating ability toward such deactivated aromatic systems in the presence of MeSO
3H/FeCl
3 as catalyst. Using this reagent system, isophthalonitrile was converted to 5-intro derivative in acetonitrile even at -10 oC and no amide formation was observed under the conditions employed. With moderately deactivated aromatic systems such as tolunitriles and naphthonitriles, nitration can be successfully effected using a NO
2-O
2 system in the presence of zeolite. A remarkable feature of this type of nitration is high and unique regioselectivity. Thus, the nitration of 2-naphthonitrile with the NO
2-O
2 system in acetonitrile at room temperature gave a product in which the 5-nitro/8-nitro isomer ratio was reversed against ordinary nitration based on HNO
3-H
2SO
4 (1.33 versus 0.72).
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