Science of Synthesis

Aitken, K. M.; Aitken, R. A., Science of Synthesis, (2007) 31, 1226.

The dinitrogen tetroxide complexes of transition metal nitrates are used to mono- or dinitrate phenols, with good yields.[‌175‌–‌177‌] The complexes Fe(NO3)3•1.5N2O4 and Cu(NO3)2•N2O4,[‌175‌] as well as Cr(NO3)3•2N2O4,[‌176‌] mononitrate p-cresol and halophenols in acetone at room temperature and give dinitrated products when stirred under reflux in ethyl acetate. All three complexes can also be used to nitrate 4-hydroxybenzaldehyde and (4-hydroxyphenyl)ethanone at room temperature, with prolonged reaction times (2–3.5 h) (‌Scheme 55‌).

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References