Reaction of 1-methyl-2-terpenylsulfanylimidazoles with chlorine dioxide

Full text of DOI:10.1134/S1070428012110127

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 11, pp. 1490−1492. © Pleiades Publishing, Ltd., 2012.
Original English Text © M.Ya. Demakova, D.V. Sudarikov, S.A. Rubtsova, I.V. Gruzdev, A.V. Kuchin, 2012, published in Zhurnal Organicheskoi Khimii, 2012,
Vol. 48, No. 11, pp. 1510−1512.
SHORT
COMMUNICATIONS
Reaction of 1-Methyl-2-terpenylsulfanylimidazoles
with Chlorine Dioxide
M. Ya. Demakovaa, D. V. Sudarikova, S. A. Rubtsovaa,
I. V. Gruzdeva, and A. V. Kuchina
aInstitute of Chemistry, Komi Scientific Center, Ural Division, Russian Academy of Sciences, Syktyvkar, 167982 Russia
e-mail: my-demakova@rambler.ru
bInstitute of Biology, Komi Scientific Center, Ural Branch, Russian Academy of Sciences, Syktyvkar, Russia
Received March 22, 2012
DOI: 10.1134/S1070428012110127
It was formerly established that chlorine dioxide
oxidized chemoselectively organosulfur compounds (tri-
azole-, tetrazole-, benzimidazole-containing sulfides) af-
fording the corresponding sulfoxides without any forma-
tion of chlorinated products [1]. It was also reported that
monoterpene imidazole- and benzimidazole-containing
sulfides were selectively oxidized by achiral oxidants
and also under the conditions of chiral catalysis [2, 3].
The main products of the reaction between N-sub-
stituted 1-methyl-2-terpenylsulfanylimidazoles Ia–Id
and chlorine dioxide in diverse solvents (chloroform,
ethyl ether, benzene) were chlorinated products IIa–IId
(yields 76–84%).
The process was accompanied with the formation of
insignificant quantities of the corresponding sulfoxides
of low diastereoselectivity (yields 6–17%, de 4–8%).
In continuation of the research on the reactivity of
ClO2 in the oxidation of monoterpene sulfanylimidazoles
and benzimidazoles we established that the unsubstituted
imidazole- and benzimidazole-containing sulfide with
menthane, carane, and pinane fragments were oxidized
to the corresponding sulfoxides in 71–91% yields and de
10–37%. In these reactions the terpene and heterocyclic
fragments remained intact.
The Beilstein test showed the presence of chlorine in
compounds IIa–IId. The composition and structure of
compounds IIa–IId was proved by GC-MS and NMR
methods. The mass spectra contained the molecular ion
peaks corresponding to the structures of compounds
IIa–IId, and the main fragment ions were consistent with
the fragmentation of the molecular ions. The 13C NMR
JMOD spectra of compounds IIa–IId in the region
O
S
N
N
N
N
N
ClO2
4'
5'
Terp
S
Terp
Terp
S
+
CHCl3, 5oC
N 6'
Cl
Me
IIа_IId
Me
IIIа_IIId
Me
Iа_Id
10
1
7
∗
∗
10
2
∗
3
Terp =
1
(d).
(а),
(b),
(c),
1
6
8
2
∗
7
8
9
8
1490

REACTION OF 1-METHYL-2-TERPENYLSULFANYLIMIDAZOLES
1491
(C 0.23, CHCl3). IR spectrum, ν, cm–1: 802.39 (C–Cl).
1H NMR spectrum, δ, ppm: 0.90 d (1H, H7α, J 9.7 Hz),
1.02 s (3H, Me8), 1.19 s (3H, Me9), 1.54–1.62 m (1H,
H3α), 1.84–2.11 m (5H, H4α, H4β, H5, H1, H3β), 2.24–
2.43 m (2H, H2, H7β), 3.08–3.22 m (2H, H10α, H10β),
3.56 s (3H, Me6’), 6.99 s (1H, H4’). 13C NMR spectrum,
δ, ppm: 21.79 (C3), 23.23 (C8), 26.06 (C4), 27.91 (C9),
31.00 (C6`), 33.24 (C7), 38.66 (C6), 41.00 (C2), 41.04
(C10), 41.16 (C5), 45.36 (C1), 118.60 (C5’), 125.56 (C4’),
141.80 (C2’). Mass spectrum, m/z (Irel, %): 285 (100)
[M]+, 251 (41), 237 (63), 148 (100).
118–135 ppm contained the signals of two quaternary
and one methine carbon atom in contrast to the initial
sulfides which had two methine and one quaternary car-
bon atoms thus indicating the substitution of one of the
methine protons. In the heteronuclear HMBC spectra of
compounds IIa–IId cross-peaks were observed between
methyl protons N–CH36’ and the quaternary carbon atom
C5’–Cl indicating that the substitution occurred in the
position 5’.
The chlorinating agents (sulfuryl chloride, N-chloro-
succinimide) also lead to the substitution of the methine
protons for chlorine in the N-substituted imidazoles. The
compounds of this kind are promising as insecticides [4].
2-{[(1R,2R,5R)-6,6-Dimethylbicyclo[3.1.1]heptyl-2]
methylsulfanyl}-1-methyl-5-chloro-1H-imidazole
(IIc). Viscous dark-orange fluid. Yield 77%, [α]D20 +5.1
(C 0.41, CHCl3). IR spectrum, ν, cm–1: 802.39 (C–Cl). 1H
NMR spectrum, δ, ppm: 0.82 s (3H, 9-Me), 1.23 s (3H,
8-Me), 1.30–1.40 m (2H, H4α, H7α), 1.72–1.83 m (3H,
H3α, H3β, H4β), 1.85–1.96 m (2H, H1, H5), 2.03–2.13 m
The characteristics of sulfinyl derivatives IIIa–IIId
are reported in [2, 3].
Oxidation of sulfide with chlorine dioxide. Chlorine
dioxide was extracted from water solution into chloroform
by repeated shaking of equal volumes of ClO2 water
solution and the extraction agent. The concentration of
the oxidant was determined as described in [5]. The ClO2
solution in chloroform (1 mmol) was added dropwise to
5 ml of a solution containing 1 mmol of sulfide, and the
mixture was stirred at 5°C for 2–6 h. The mixture was
washed with water, the water layer was extracted with
chloroform (2 × 10 ml), the combined organic extracts
were dried with MgSO4, the solvent was distilled off in
a vacuu, the residue was subjected to column chroma-
tography (eluent chloroform–ethyl ether, 50 : 1, with
subsequent increase in the ether content).
(1H, H7β), 2.15–2.26 m (1H, H2), 2.93–3.07 m (2H, H10α
,
H10β), 3.55 s (3H, Me6’), 6.98 s (1H, H4’). 13C NMR
spectrum, δ, ppm: 20.10 (C9), 21.93 (C4), 23.35 (C7),
24.20 (C3), 26.66 (C8), 30.91 (C6’), 35.04 (C2), 39.52
(C6), 40.28 (C10), 40.80 (C1), 44.93 (C5), 118.46 (C5’),
125.75 (C4’), 141.95 (C2’). Mass spectrum, m/z (Irel, %):
285 (100) [M]+, 251 (87), 237 (47), 148 (77).
1-Methyl-2-{[(1R,3S,4R,6S)-4,7,7-trimethylbi-
cyclo[4.1.0]heptyl]sulfanyl}-5-chloro-1H-imidazole
(IId). Viscous dark-orange fluid. Yield 84%, [α]D20 +32.8
(C 0.12, CHCl3). IR spectrum, ν, cm–1: 804.32 (C–Cl).
1H NMR spectrum, δ, ppm: 0.59 t.d (1H, H1, J 8.9,
5.5 Hz), 0.73 t.d (1H, H6, J 8.9, 7.2 Hz), 0.89 d.d.d (1H,
H5α, J 14.7, 10.0, 7.0 Hz), 0.98 d (3H, 10-Me, J 1.2 Hz),
1.00 s (3H, 8-Me), 1.04 s (3H, 9-Me), 1.43 d.d.d (1H,
H2α, J 15.4, 7.5, 5.6 Hz), 1.86 d.d.d (1H, H5β, J 14.6,
9.0, 5.8 Hz) 1.94–2.07 m (1H, H4), 2.25 d.d.d (1H, H2β,
J 15.5, 8.4, 7.2 Hz), 3.56 s (3H, H6'), 3.82 q (1H, H3,
J 7.0 Hz), 6.99 s (1H, H4'). 13C NMR spectrum, δ, ppm:
15.82 (C9), 17.78 (C8), 18.81 (C7), 20.37 (C1), 21.47 (C6),
25.32 (C5), 25.67 (C2), 28.50 (C10), 30.69 (C4), 31.00
(C6'), 49.60 (C3), 118.31 (C5'), 125.83 (C4'), 142.03 (C2').
Mass spectrum, m/z (Irel, %): 284 (21.5) [M]+, 251 (12.5),
192 (22), 149 (78).
2-{[(1S,2S,5R)-2-Isopropyl-5-methylcyclohexyl]
sulfanyl}-1-methyl-5-chloro-1H-imidazole (IIa). Vis-
cous dark-orange fluid. Yield 82%. [α]D20 +47.4 (C 0.23,
CHCl3). IR spectrum, ν, cm–1: 802.39 (C–Cl). 1H NMR
spectrum, δ, ppm: 0.90 d (3H, 7-Me, J 6.5 Hz), 0.95 d
(3H, 10-Me, J 5.0 Hz), 0.97 d (3H, 9-Me, J 5.0 Hz),
1.16–1.24 m (3H, H2, H3a, H4a), 1.26–1.33 m (1H, H6a),
1.62–1.71 m (1H, H5), 1.75–1.87 m (2H, H4e, H3e),
1.89–1.99 m (2H, H6e, H8), 3.57 s (3H, Me6’), 4.10 m
(1H, H1), 7.00 s (1H, H4’). 13C NMR spectrum, δ, ppm:
20.64 (C9), 21.05 (C10), 22.03 (C7), 26.46 (C3), 27.11
(C8), 30.47 (C5), 30.92 (C6`), 35.19 (C4), 41.34 (C6), 48.50
(C2), 51.13 (C1), 118.26 (C5’), 125.88 (C4’), 132.57 (C2’).
Mass spectrum, m/z (Irel, %): 287 (85) [M]+, 285 (48),
250 (30), 243 (17), 148 (100).
1H and 13C NMR spectra were registered on a spec-
trometer Bruker Avence-II-300 (300.17, 75.48 MHz) in
CDCl3 using residual protons of the solvent as internal
reference. The GC-MS measurements were performed
on a mass spectrometer DSQ (Thermo) with a direct ad-
2-{[(1R,2S,5R)-6,6-Dimethylbicyclo[3.1.1]heptyl-2]
methylsulfanyl}-1-methyl-5-chloro-1H-imidazole
(IIb). Viscous dark-orange fluid. Yield 76%. [α]D20 –31.9
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 11 2012

DEMAKOVA et al.
1492
mission of the sample into the ion source. Ionization by
electron impact, ionizing electrons energy 70 eV, ionizing
chamber temperature 200°C. The reaction progress was
monitored by TLC on Sorbfil plates (eluent hexane–Et2O,
1:2, developer phosphomolibdic acid).
registering the NMR spectra.
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ACKNOWLEDGMENTS
The study was carried out under the financial support
of the Russian Foundation for Basic Research (grant
no. 12-03-31338 mol_a) and of the Department of Chem-
istry and Material Science (project no. 12-T-3-1030).
The authors express their gratitude to Research
Fellows of the Laboratory of physicochemical methods
of the Institute of Chemistry of Komi Scientific Center
E.N. Zainullina, S.P. Kuznetsov, A.N. Alekseev for
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 11 2012