1-nitrocyclohexene and 3-methyl-4-nitro-3-thiolene 1,1-dioxide in reactions with benzoylhydrazine and its analogs

Full text of DOI:10.1134/S1070363210110277

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 11, pp. 2393–2395. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © M.I. Vakulenko, L.V. Lapshina, S.I. Grishchenko, I.E. Efremova, V.M. Berestovitskaya, 2010, published in Zhurnal Obshchei
Khimii, 2010, Vol. 80, No. 11, pp. 1930–1932.
LETTERS
TO THE EDITOR
1-Nitrocyclohexene and 3-Methyl-4-nitro-3-thiolene
1,1-Dioxide in Reactions with Benzoylhydrazine and Its Analogs
M. I. Vakulenko, L. V. Lapshina, S. I. Grishchenko, I. E. Efremova, and V. M. Berestovitskaya
Herzen Russian State Pedagogical University, nab. r. Moiki 48, St. Petersburg, 191186 Russia
e-mail: kohrgpu@yandex.ru
Received April 8, 2010
DOI: 10.1134/S1070363210110277
Reactions of nitroalkenes with hydrazine and its
derivatives occur ambiguously: depending on the
reaction conditions and reagents nature the products of
addition [1–3], transalkenylation [4] or hetero-
cyclization [5, 6] are formed. Aiming at revealing the
features of the chemical behavior of carbo- and
heterocyclic nitroalkenes (of the thiolene 1,1-dioxide
series) in similar reactions, we studied a reaction of 1-
nitrocyclohexene I and 3-methyl-4-nitro-3-thiolene
1,1-dioxide II with benzoic acid hydrazide and its
analogs containing various substituents in the aromatic
ring.
H
N−NH
O2N
R = H, X = (CH2)2
Ar
1
2
O
3
6
O2N
R
5
4
H2NNHC(O)Ar
III−VI
X
I, II
H
N
O2N
CH3
Ar
R = CH3, X = SO2
4
5
3
2
N
H
O
S
O
O
VII−X
Ar = C6H5 (III, VII), o-CH3C6H4 (IV, VIII), m-CH3OC6H4 (V, IX), p-ClC6H4 (VI, X).
The selected N-nucleophiles react readily with the
multiplets at 4.47 and 3.36 ppm, respectively; hyd-
razide fragment (–NHNHСО–) protons give rise to
singlets at 4.76 and 8.33 ppm, in agreement with the
published data for N-alkylsubstituted hydrazides [7]. In
the spectra of aminonitrosulfolane derivatives VII–X
the signals of the corresponding proton groups are
shifted downfield.
nitroalkenes I, II at room temperature in ethanol
medium to give adducts III–X. The condensation
involving nitrosulfolene II completed rapidly (in 1 h).
In the case of nitrocyclohexene I the keeping for 24 h
was required, and the reaction with p-chlorobenzoic
acid hydrazide required an additional heating.
The structure of compounds III–X was established
The IR spectra of compounds III–X contain
absorption bands of the nonconjugated nitro group
(1379–1386, 1551–1559 cm–1), amide carbonyl (1624–
1648 cm–1), aromatic multiple bonds (1580–1602 cm–1),
and NH groups (3248–3312 cm–1); in the spectra of
hydrazinonitrothiolane 1,1-dioxides there are addi-
1
1
using Н NMR and IR spectroscopy. The Н NMR
spectra contain signals of the protons of all structural
fragments of molecules III–X and prove its stereo-
homogeneity. Thus, methine protons at С1 and С2
atoms of cyclohexane ring of compound III appear as
2393

2394
VAKULENKO et al.
tionally absorption bands belonging to sulfonyl group
(1126–1129, 1316–1318 cm–1).
(5Н, Ph), 8.53 d (1Н, NHСО). Found, %: N 13.27.
C12H15N3O5S. Calculated, %: N 13.41.
The initial 1-nitrocyclohexene I and 3-methyl-4-
nitro-3-thiolene 1,1-dioxide II were obtained by the
modified procedures [8] and [9], respectively.
3-Methyl-4-nitro-3-(о-tolylhydrazino)thiolane-
1,1-dioxide (VIII). Yield 49%, mp 115–117°С
(ethanol). IR spectrum, ν, cm–1: 1129, 1316 (SO2),
1386, 1558 (NO2), 1602 (C=CAr), 1638 (С=O), 3264,
2-(Benzoylhydrazino)-1-nitrocyclohexane (III).
Yield 78%, mp 133–136°С (ethanol–water, 1:1). IR
spectrum, ν, cm–1: 1381, 1559 (NO2), 1580 (C=CAr),
1
3290 (NH). Н NMR spectrum, δ, ppm: 1.35 s (3H,
CH3), 2.39 s (3H, CH3), 3.43 m (2Н, С2Н2), 3.83 m,
4.03 m (2Н, С5Н2), 5.33 m (1H, С4Н), 5.52 d (1Н,
NH), 7.27 m, 7.35 m, 7.41 m (4Н, С6Н4), 8.33 d (1Н,
NHСО). Found, %: N 12.64. C13H17N3O5S. Cal-
culated, %: N 12.84.
1
1627 (С=O), 3297, 3312 (NH). Н NMR spectrum, δ,
ppm: 1.30–1.73 m (6Н, С3Н2, С4Н2, С5Н2), 1.93–2.05
m (2Н, С6Н2), 3.36 m (1H, С2Н), 4.47 m (1H, С1Н),
4.76 br.s (1Н, NH), 7.45 m, 7.53 m, 7.69 m (5Н, Ph),
8.33 s (1Н, NHСО). Found, %: N 16.19. C13H17N3O3.
Calculated, %: N 15.97.
3-(m-Anisoylhydrazino)-3-methyl-4-nitrothiolane-
1,1-dioxide (IX). Yield 75%, mp 123–125°С
(ethanol). IR spectrum, ν, cm–1: 1126, 1318 (SO2),
1386, 1558 (NO2), 1583 (C=CAr), 1648 (С=O), 3296
1-Nitro-2-(о-tolylhydrazino)cyclohexane
(IV).
Yield 44%, mp 122–124°С (ethanol–water, 1:1). IR
1
spectrum, ν, cm–1: 1380, 1559 (NO2), 1597 (C=CAr),
(NH). Н NMR spectrum, δ, ppm: 1.36 s (3H, CH3),
3.42 m (2Н, С2Н2), 3.83 s (3H, OCH3), 3.86 m, 4.03 m
(2Н, С5Н2), 5.31 m (1H, С4Н), 5.53 d (1Н, NH), 7.12
m, 7.34 m, 7.39 m (4Н, С6Н4), 8.58 (1Н, NHCO).
Found, %: N 12.37. C13H17N3O6S. Calculated, %: N
12.24.
1
1624 (С=O), 3253, 3280 (NH). Н NMR spectrum, δ,
ppm: 1.31–1.78 m (6Н, С3Н2, С4Н2, С5Н2), 1.82–2.04
m (2Н, С6Н2), 2.20 s (3H, CH3), 3.55 m (1H, С2Н),
4.45 m (1H, С1Н), 4.90 br.s (1Н, NH), 7.23 m, 7.29 m,
(4Н, С6Н4), 7.97 s (1Н, NHСО). Found, %: N 15.11.
C14H19N3O3. Calculated, %: N 15.16.
3-Methyl-4-nitro-3-(p-chlorobenzoylhydrazino)-
thiolane 1,1-dioxide (X). Yield 62%, mp 128–130°С
(ethanol). IR spectrum, ν, cm–1: 1126, 1317 (SO2),
1386, 1559 (NO2), 1596 (C=CAr), 1646 (С=O), 3289
2-(m-Anisoylhydrazino)-1-nitrocyclohexane (V).
Yield 48%, mp 105–107°С (ethanol–water, 1:1). IR
spectrum, ν, cm–1: 1382, 1558 (NO2), 1585 (C=CAr),
1
1
1627 (С=O), 3266, 3297 (NH). Н NMR spectrum, δ,
(NH). Н NMR spectrum, δ, ppm: 1.38 s (3H, CH3),
ppm: 1.31–1.76 m (6Н, С3Н2, С4Н2, С5Н2), 1.79–2.04
m (2Н, С6Н2), 3.35 m (1H, С2Н), 3.79 s (3H, OCH3),
4.46 m (1H, С1Н), 5.04 br.s (1Н, NH), 7.07 m, 7.20 m,
7.32 m, (4Н, С6Н4), 8.32 s (1Н, NHСО). Found, %: N
14.41. C14H19N3O4. Calculated, %: N 14.33.
3.45 m (2Н, С2Н2), 3.90 m, 4.08 m (2Н, С5Н2), 5.35 m
(1H, С4Н), 5.55 d (1Н, NH), 7.50 m, 7.80 m (4Н,
С6Н4), 8.85 d (1Н, NHСО). Found, %: N 11.76.
C12H14ClN3O5S. Calculated, %: N 12.09.
1
The Н NMR spectra were registered on a Jeol
1-Nitro-2-(p-chlorobenzoylhydrazino)cyclohexane
(VI). Yield 19%, mp 132–134°С (ethanol). IR spec-
trum, ν, cm–1: 1379, 1551 (NO2), 1594 (C=CAr), 1635
ECX400A spectrometer at operating frequencies
399.78 MHz in CD3CN using the signals of the
residual protonated solvents as reference signals. The
IR spectrum was taken on a Shimadzu IR-21 Prestige
Fourier-spectrometer from KBr. The elemental analysis
was performed on a Eurovector EA3028 analyzer. The
reaction progress was monitored by TLC on Silufol
UV-254 plates with detection on a chromatoscope.
1
(С=O), 3248, 3303 (NH). Н NMR spectrum, δ, ppm:
1.31–1.73 m (6Н, С3Н2, С4Н2, С5Н2), 1.80–2.07 m
(2Н, С6Н2), 3.35 m (1H, С2Н), 4.46 m (1H, С1Н), 4.70
br.s (1Н, NH), 7.45 m, 7.67 m (4Н, С6Н4), 8.38 s (1Н,
NHСО). Found, %: N 13.68. C13H16ClN3O3. Cal-
culated, %: N 14.11.
REFERENCES
3-(Benzoylhydrazino)-3-methyl-4-nitrothiolane-
1,1-dioxide (VII). Yield 56%, mp 135–137°С
(ethanol). IR spectrum, ν, cm–1: 1127, 1317 (SO2),
1385, 1556 (NO2), 1580 (C=CAr), 1647 (С=O), 3294
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