1186
LAPSHINA et al.
methylene protons of nitroethyl moieties are mani-
fested as two triplets at 3.83–3.93 and 4.93–4.98 ppm
with the spin-spin coupling constant JHH 6.41 Hz,
which is typical for the vicinal protons with a free
rotation around the σ-bonds [6]. The NH-protons resonate
as a singlet in the weak field (9.21–10.77 ppm).
In the 13C NMR spectra of hydrazones III and IV
there are the signals in the weak field at 134.37–
137.90 ppm corresponding to the azomethine carbon
atoms, as well as the signals at 68.79, 68.70 ppm,
which are characteristic of the primary carbon atoms
bonded with the nitro groups [6]. The assignment of
the signals of C2' and C1 (62.00, 61.83 ppm) and
C1' (48.50, 48.61 ppm) was made on the basis of the
1H–13C HMQC experiment.
trum, ν, cm–1: 1320, 1130 (SO2), 1560, 1390 (NO2),
1
1600 (C=N), 3360 (NH). Н NMR spectrum, δ, ppm
3
3
(J, Hz): 1.98 s (3Н, СН3), 3.88 t (2Н, С1'Н2, J 6.41),
3
4.23 s (2Н, С1Н2), 4.98 t (2Н, С2'Н2, J 6.41), 6.72 m,
7.08 m, 7.15 m (5H, Ph), 9.21 s (1H, NН). 13С NMR
spectrum, δС, ppm: 62.00 (C1), 134.37 (C2), 17.41
(СН3), 48.50 (C1'), 68.79 (C2'), 113.20, 119.76, 129.40,
146.07 (С6Н5). Found, %: C 46.63; H 5.52; N 14.79.
C11H15N3O4S. Calculated, %: С 46.31; H 5.30; N
14.73.
1
1
The H, 13C–{1H}, H–13C HMQC NMR spectra
were recorded on a Jeol ECX400A spectrometer
operating at 399.78 (1H) and 100.525 MHz (13C) in
(CD3)2SO, using the residual signals of the non-
deuterated solvent as an internal standard. The IR
spectra were obtained on a Shimadzu IR-21 Prestige
Fourier spectrometer (KBr). The elemental analysis
was performed on an Eurovector EA3028 analyzer.
The starting 3-methyl-4-nitro-3-thiolene 1,1-dioxide
I was obtained by a modified method [7].
(2-Nitroethylsulfonyl)propanone benzoylhydrazone
(II). Yield 21%, mp 154–156°C (ethanol). IR spec-
trum, ν, cm–1: 1310, 1120 (SO2), 1555, 1370 (NO2),
REFERENCES
1
1. Perekalin, V.V., Lipina, E.S., Berestovitskaya, V.M.,
and Efremov, D.A., Nitroalkenes (Conjugated Nitro
Compounds), New York; London: Willey & Sons, 1994.
2. Berestovitskaya, V.M., Zh. Obshch. Khim., 2000, vol. 70,
no. 9, p. 1512.
1620 (C=N), 1660, 1520 (C(O)NH), 3335 (NH). Н
NMR spectrum, δ, ppm (J, Hz): 2.10 s (3Н, СН3), 3.93
3
t (2Н, С1'Н2), 4.33 s (2Н, С1Н2), 4.98 t (2Н, С2'Н2, J
6.41), 7.44 m, 7.50 m, 7.81 m (5H, Ph), 10.77 s (1H,
NН). Found, %: C 46.34; H 5.01; N 13.20. C12H15N3O5S.
Calculated, %: С 46.00; H 4.83; N 13.41.
3. Vakulenko, M.I., Lapshina, L.V., Grishchenko, S.I.,
Efremova, I.E., and Berestovitskaya, V.M., Zh. Obshch.
Khim., 2010, vol. 80, no. 11, p. 1930.
(2-Nitroethylsulfonyl)propanone semicarbazone
(III). Yield 80%, mp 128–131°C (ethanol). IR spec-
trum, ν, cm–1: 1300, 1140 (SO2), 1550, 1390 (NO2),
1630 (C=N), 1710, 1570 [C(O)NH], 3530, 3410, 3210
4. Bulatova, N.N. and Suvorov, N.N., Khim. Geterotsikl.
Soed., 1969, no. 5, p. 813.
1
(NH). Н NMR spectrum, δ, ppm (J, Hz): 1.90 s (3Н,
5. Aboskalova, N.I., Smirnova, N.N., Kataeva, O.N., Bai-
churin, R.I., Fel’gendler, A.V., Berkova, G.A., and Bere
stovitskaya, V.M., Zh. Obshch. Khim., 2008, vol. 78,
no. 9, p. 1479.
3
СН3), 3.83 t (2Н, С1'Н2, J 6.41), 4.13 s (2Н, С1Н2),
4.93 t (2Н, С2'Н2, 3J 6.41), 6.39 br. s (2H, NH2), 9.44 s
(1H, NН). 13С NMR spectrum, δС, ppm: 61.83 (C1),
137.90 (C2), 17.35 (CН3), 48.61 (C1'), 68.70 (C2'),
157.35 (С=О). Found, %: C 28.30; H 4.83; N 22.48.
C6H12N4O5S. Calculated, %: С 28.57; H 4.80; N 22.22.
6. Pretsch, E., Bullman, P., and Affolter, C., Structure
Determination of Organic Compounds: Tables of
Spectral Data, Heidelberg: Springer, 2000.
7. Berestovitskaya, V.M. and Perekalin, V.V., Zh. Obshch.
Khim., 1993, vol. 63, no. 2, p. 241.
(2-Nitroethylsulfonyl)propanone phenylhydrazone
(IV). Yield 44%, mp 125–127°C (ethanol). IR spec-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 6 2012