Phenyl boronic acid (Sigma Aldrich)
Bismuth nitrate (Sigma Aldrich), ACS reagent, ≥98.0%
Toluene anhydrous, 99.8% (Sigma Aldrich)
Ethyl acetate (SD Fine Chemicals Ltd), directly used without drying
Dichloromethane (SD Fine Chemicals Ltd), directly used without drying

The mixture of phenyl boronic acid (50 mg, 1 mmol) and bismuth (III) nitrate (397 mg, 2 mmol) in toluene (2 mL) was refluxed for 1.5 h. Reaction mixture was allowed to cool to room temperature and was filtered through filter paper. Residue was washed with ethyl acetate followed by dichloromethane. The combined organic layer was evaporated on rotary evaporator. Purified by silica gel column chromatography (mesh 100-200) using EtOAc-hexane (5: 95) as mobile phase gave nitrobenzene as yellowish liquid (45.5 mg, 90% yield). The product was characterized by comparison of NMR data with literature values (Manna, S.; Maity, S.; Rana, S.; Agasti, S.; Maiti, D. Org. Lett. 2012, 14, 1736-1739. http://dx.doi.org/10.1021/ol300325t)

The present protocol is catalyst-free, making it more ecofriendly, economical, and feasible for large scale synthesis of nitroarenes (For details, see: Tetrahedron Lett. 2012, 53, 5958-5960. http://dx.doi.org/10.1016/j.tetlet.2012.08.121)

Nitrobenzene: Yellowish liquid;
¹H NMR (CDCl₃, 400 MHz) δ ppm: 8.18 (d, J = 1.2 Hz, 2H), 7.75-7.68 (m, 1H), 7.56-7.49 (m, 2H);
IR (CHCl₃): 3435, 3077, 2860, 2929, 1524, 1348 cm^-1;
GC-MS (EI) m/z (%): 124 (M⁺+1, 8.24), 123 (M⁺, 76.23), 107 (11.43), 93.1 (100), 91.1 (23.27), 78.1 (7.65), 77.1 (46.90), 65.10 (70.93), 51.1 (5.57).

Yadav, R. R.; Bharate, S. B.; Vishwakarma, R. A. Catalyst-free Ipso-nitration of arylboronic acids using bismuth nitrate.Tetrahedron Lett. 2012, 53, 5958-5960. http://dx.doi.org/10.1016/j.tetlet.2012.08.121

• Salzbrunn, S.; Simon, J.; Prakash, G. K. S.; Petasis, N. A.; Olah, G. A. Synlett 2000, 1485-1487. http://dx.doi.org/10.1055/s-2000-7642
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