Advent in Organic Methodology
J. Chin. Chem. Soc., Vol. 54, No. 3, 2007 769
analyses of the crude reaction mixtures. The scope of this
nitration was widened by nitration of naphtols to give
mono-nitrated compounds in high yields (Table 1).
The superior regioselectivity of our method is clear
and can be justified by comparison of percentages of ortho
isomers with previously reported protocols (Table 2).
In conclusion, a regioselective ortho nitration of vari-
ous phenols and naphtols using green, available, inexpen-
sive and easy to handle NaNO2/KHSO4 reagent has been
reported. We believe this protocol is an important tool in or-
ganic chemistry.
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Nitration of phenols with NaNO2/KHSO4. Typical
procedure
4-Bromo phenol (0.14 g, 1 mmol), NaNO2 (0.1 g, 1.5
mmol) and KHSO4 (0.27 g, 2 mmol) in acetonitril was
stirred at 50 °C. After the completion of reaction, the reac-
tion mixture was filtered (the progress of the reaction was
monitored by TLC). The residue was washed with aceto-
nitril (2 ´ 5 mL). Anhydrous Na2SO4 (5 g) was added to the
filtrate. The mixture was filtered. The solvent was removed
by distillation using a water bath (35-40 °C). The obtained
crude was pure enough (checked by tlc). For further purifi-
cation, this crude was passed through a small pad of silica
gel using ethyl acetate/pet ether 1:3 to obtain the pure prod-
uct. Yield 0.2 g, (92%), mp 92 °C.
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