FILIMONOV et al.
922
Presumably, the electrophilicity of nitryl iodide is so
weak that the nitration occurs by the action of nitro-
nium cation and nitrogen oxides arising from homo-
lytic dissociation of the I–N bond.
3,6-Dibromo-1-nitrocarbazole (V). A mixture of
0.5 mmol of carbazole (Ia), 5 ml of acetic acid,
2 mmol of KBr, and 1 mmol of NaNO3 was stirred
for 20 h at 25°C. It was then poured into 70 ml of
a 10% solution of Na2S2O3, and the precipitate was
filtered off, dried, and subjected to column chro-
matography on silica gel using hexane as eluent. Yield
76%, mp 171–173°C (from EtOH). 1H NMR spectrum
(CDCl3), δ, ppm: 7.13 s (1H, 8-H), 7.52 m (4H, 2-H,
4-H, 5-H, 7-H), 8.45 s (1H, NH). Found, %: C 40.1;
H 1.59; Br 44.01; N 7.46. C12H6Br2N2O2. Calculated,
%: C 38.95; H 1.63; Br 43.19; N 7.57.
EXPERIMENTAL
The progress of reactions and the purity of products
were monitored by TLC on Silufol UV-254 plates.
Silica gel L 40/100 µm (Chemapol) was used for
column chromatography. Elemental analysis was per-
formed on an E.A. 1108 CHNS-O instrument. The
melting points were determined on a Boetius device.
The NMR spectra were recorded on a Bruker AC-200
spectrometer in chloroform-d using TMS as internal
reference. The amount of NO2 evolved from solutions
of sodium nitrate in acetic acid was determined by
standard procedure based on NO2 adsorption by a film
sorbent placed in ST 212 tubes, according to GU 25-
1110-039-82 [12]; the procedure includes photometric
determination of NO–2 ion (formed from NO2 and
desorbed into an aqueous solution) via formation of
azo dye with the Griss reagent. Products II, III, IVa,
and IVb were identified by comparing their spectral
parameters and physical constants with those of
authentic samples [5].
This study was performed under financial support
by the Ministry of Education of the Russian Federation
(project no. E02-5.0-176) and by President of the
Russian Federation (grant no. MK-3236.2004.3).
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 7 2004