3-Nitro-9-nitrosocarbazole

[5393-41-9]  · C12H7N3O3  · 3-Nitro-9-nitrosocarbazole  · (MW 241.22)

(mild nitrosating reagent1)

Physical Data: mp 166-168 °C.

Solubility: sol benzene; insol methanol.

Form Supplied in: brown-yellow needles.

Analysis of Reagent Purity: IR (KBr, cm-1) 3050, 1530, 1440, 1310, 840, 780, 760, 725; MS (m/e (intensity)) 242 (3.8), 241 (M+, 13.5), 222 (11.5), 211 (90.4), 210 (86.5), 204 (9.6), 181 (32.7), 167 (13.5), 166 (52.9), 165 (28.8), 153 (46.1), 150 (13.5), 149 (100.0).

Preparative Methods: an aqueous solution of Sodium Nitrite (1.5 g, 22 mmol) is added to a suspension of carbazole (3.0 g, 18 mmol) in nitrobenzene (30 mL), and HCl (2 mL) is then introduced dropwise for 1 h. The reaction mixture is kept at 15 °C for 1 h. To the resulting solution of 9-nitrosocarbazole is added HNO3 (1 mL) slowly for 30 min, and the solution is kept for 1.5 h. Crystalline 3-nitro-9-nitrosocarbazole (3.5 g, 14 mmol) is obtained when the solvent is evaporated.2 3-Nitro-9-nitrosocarbazole (6.65 g, 28 mmol) is also prepared by the reaction of 3-nitrocarbazole (6.39 g, 30 mmol) and sodium nitrite (2.76 g, 40 mmol) in acetic acid (120 mL) at 70 °C.3

Purification: recrystallization from acetone or 2-butanone.

Nitrosation.1

3-Nitro-9-nitrosocarbazole is a mild nitrosating reagent, which is suitable for nitrosating secondary amines. N-Methylaniline (1) reacts with 3-nitro-9-nitrosocarbazole (2) in refluxing benzene to afford N-nitrosomethylaniline (3) in 55% yield (eq 1). 3-Nitrocarbazole (4) is obtained as a byproduct. However, attempted nitrosation of aziridine (5) by (2) does not produce N-nitrosoaziridine. Instead, ethylene (42%) and nitrous oxide (50%) are isolated; these might arise from decomposition of N-nitrosoazirine (eq 2).


1. Bumgardner, C. L.; McCallum, K. S.; Freeman, J. P. JACS 1961, 83, 4417.
2. Shishkina, V. I.; Omel'chenko, S. I.; Soshin, V. A. Trudy Ural. Politekh. Inst. im. S. M. Kirova 1960, 96, 19 (CA 1961, 55, 24 715e). See also: Parakka, J. P.; Nugara, P. N.; Lakshmikantham, M. V.; Belmore, K. A.; Cava, M. P. Synth. Met. 1992, 47, 141.
3. Kyziol, J. B.; Daszkiewicz, Z. T 1984, 40, 1857.

Sangho Koo

Emory University, Atlanta, GA, USA



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