Synthesis of new monoterpene sulfonic acids and their derivatives

Article abstract of DOI:10.1134/S1070428017060082

The oxidation of monoterpene thiols with chlorine dioxide afforded new water-soluble sulfonic acids and their derivatives (sulfonothioates and sulfonyl chlorides). The reaction of terpene thiols with ClO₂ gave the corresponding trisulfides. Sulfonothioates with a pinane skeleton showed antibacterial and antifungal activity.

Full text of DOI:10.1134/S1070428017060082

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2017, Vol. 53, No. 6, pp. 860–868. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © O.N. Grebyonkina, O.M. Lezina, E.S. Izmest’ev, D.V. Sudarikov, S.V. Pestova, S.A. Rubtsova, A.V. Kutchin, 2017, published in
Zhurnal Organicheskoi Khimii, 2017, Vol. 53, No. 6, pp. 844–852.
Synthesis of New Monoterpene Sulfonic Acids
and Their Derivatives
O. N. Grebyonkina, O. M. Lezina,* E. S. Izmest’ev, D. V. Sudarikov, S. V. Pestova,
S. A. Rubtsova, and A. V. Kutchin
Institute of Chemistry, Komi Scientific Center, Ural Branch, Russian Academy of Sciences,
ul. Pervomaiskaya 48, Syktyvkar, 167982 Russia
*e-mail: lezina-om@yandex.ru
Received March 17, 2017
Abstract—The oxidation of monoterpene thiols with chlorine dioxide afforded new water-soluble sulfonic
acids and their derivatives (sulfonothioates and sulfonyl chlorides). The reaction of terpene thiols with ClO2
gave the corresponding trisulfides. Sulfonothioates with a pinane skeleton showed antibacterial and anti-
fungal activity.
DOI: 10.1134/S1070428017060082
Alkane- and arenesulfonic acids and -sulfonyl
chlorides are intermediate products in organic synthe-
sis and in the manufacture of some pharmaceuticals.
The presence of a sulfo group in a drug molecule
endows it with somewhat different biological activity
and higher solubility in water, which reduces the
toxicity and facilitates design of injection dosage
forms. Sulfonothiates are known to exhibit bactericidal
and fungicidal activity [1].
sulfonate was obtained by reaction of β-pinene with
sodium hydrogen sulfite and potassium nitrate [4]. The
reaction was carried out on heating to 110°C under
reduced pressure (4 h), and it involved transformation
of the pinane skeleton to menthane.
We have proposed a procedure for the synthesis of
new water-soluble monoterpene sulfonic acids and
their derivatives via oxidation of the corresponding
thiols with chlorine dioxide (ClO2). Depending on the
conditions, several concurrent reaction pathways are
possible. Chlorine dioxide is a large-scale product used
for bleaching of cellulose and disinfection of water,
and its application as oxidant seems to be promising
and economically reasonable. Unlike other oxidants,
chlorine dioxide molecule possesses an unpaired elec-
tron and two reaction centers, chlorine and oxygen
atoms. It works well in different media due to good
solubility in water and organic solvents.
Physiological activity of terpenes includes bacteri-
cidal, analgesic, and expectorant effects, as well as
fungicidal and antiviral properties. Introduction of
a sulfo group into terpene molecule extends the spec-
trum of its biological activity [1] and the scope of its
application due to improved solubility in water. For
example, camphorsulfonic acid is used in the manu-
facture of coronary vasodilator drugs, antibacterial
agents, and analgesics (sulfocamphocaine, semisyn-
thetic penicillins and cephalosporins) [2].
The product structure in the reactions of ClO2 with
various thiols and disulfides is determined mainly by
the substrate structure, and the yields depend on the
reactant ratio, solvent nature, and order of addition of
the reactants [5–11]. Reactions of ClO2 with thiols
generally produce disulfides, sulfonothioates, sulfonyl
chlorides, and sulfonic acids; trisulfides, sulfinyl
chlorides, ketones, and esters are formed less
frequently [5–11].
Functionalization of terpene compounds according
to known sulfonation methods (reaction with concen-
trated sulfuric acid, oleum, or chlorosulfonic acid) is
complicated due to high lability of the terpene frag-
ment. Under these conditions, most terpenes undergo
numerous rearrangements and tarring. Therefore, only
a few terpene sulfonic acids have been reported. Cam-
phorsulfonic acid was synthesized in 27–42% yield by
reaction of camphor with acetic anhydride and concen-
trated sulfuric acid [2, 3]. Sodium p-menth-1-ene-7-
As starting compounds we used optically pure
thiols with pinane (1a–1d), bornane (1e, 1f), carane
860

SYNTHESIS OF NEW MONOTERPENE SULFONIC ACIDS
861
Scheme 1.
O
O
O
ClO2
ClO2
RSSSR
S
S
R
Cl
R
Cl
7f, 7j
9f, 9j
3a, 3b, 3h–3j, 3l
ClO2
ClO2
H2O
pyridine
ClO2 –ROClO
–C5H5N·HCl
O
O
S
O
O
O
O
ClO2
ClO2
–Cl–
H2O, pyridine
Pyridine
C5H5NH
RSH
RSSR
S
S
O–
5c, 5d, 5l
–C5H5N·HCl
R
SR
R
OH
R
1a–1j
6a–6j
8a, 8b, 8d, 8g, 8j
2a–2l
R=O
4c
OH
10
10
1
Me
Me
2
8
OH
OH
Me 6
1
R =
(a),
(b),
(c),
Me
Me
(d),
(e),
(f),
Me
Me
3
4
2
7
7
8
9
6
3
Me
Me
Me
Me
Me
Me 5
9
Me
4
5
Me7
Me
10Me
3
Me
Me
OH
OH
4
5
2
4
2
1
4
3
6
1
(k),1
1
7
H
(l).
(g),
(h),
(i),
(j),
6
8
Me
Me
5
Me
Me
6
7
8
OH
Me
Me
10
Me
9
Me9
Me
Me
Me
Me
(1g–1i), and p-menthane structures (1j), which were
prepared according to known procedures, namely
3-sulfanylmyrtanol (1a) [12], 10-sulfanylisopinocam-
pheol (1b) [13], trans-thioverbenol (1c) [14], thio-
myrtenol (1d) [15], 10-sulfanylisoborneol (1e) [16],
thioisoborneol (1f) [17], carane-4-thiol (1g) [18],
(3S)- and (3R)-4-sulfanylcaran-3-ols 1h and 1i [19],
and (3S)-p-menthane-3-thiol (1j) [20].
Sulfonic acids 2a, 2b, 2e, 2f, and 2l were synthe-
sized in up to 96% yield by oxidation of the corre-
sponding thiols with excess ClO2 in aqueous pyridine
[10, 11] (Scheme 1). Compounds 2c, 2d, and 2g–2k
were later prepared according to the same procedure in
76–96% yield. Basic pyridine or DMF was used as
solvent to bind free protons and reduced reagent
species (chloride, chlorate, and chlorite ions, etc.)
formed during the reaction, which favored selective
formation of sulfonic acids. For example, in the reac-
tion of 1e with ClO2 in methylene chloride the major
products were sulfonic acid 2l and sulfonyl chloride 3l
(Scheme 1) due to catalysis of camphene rearrange-
ment by free protons [11]. The oxidation of 1g in
aqueous methanol or methylene chloride was accom-
panied by opening of the three-membered ring, assum-
ingly with formation of hydroxy sulfonic acid 2k, as
followed from the sharp downfield shift of the C7
signal (δC 73.45 ppm) relative to the corresponding
signals of initial thiol 1g and sulfonic acid 2g (δC 17.71
and 17.80 ppm, respectively, downfield shift of the C6
signal (δC 48.01 against 31.59 ppm for 1g), appearance
of an additional methylene carbon signal (C1H2) in the
13C JMOD spectrum, and disappearance of C1H signal.
Conservation of the cyclohexane ring in structure 2k
was confirmed by the presence of ion peaks with
m/z 97 and 111 due to C7H13 and C8H15 fragments in
the mass spectrum. Pyridine as solvent favored forma-
tion of acids 2e (57%) and 2g (95%).
In the reactions of 1c with ClO2, pyridine stabilized
final product 2c, while the reaction in methylene
chloride or methanol gave verbenone 4c as a result of
desulfurization. The yields of sulfonic acids in the
oxidation of the other thiols in the system methylene
chloride–water did not exceed 40%.
1
The atom numbering of the precursor (1g) was conserved.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 6 2017

GREBYONKINA et al.
862
Unsaturated thiols 1c and 1d reacted with ClO2 in
The yield of 7j reached 56%, depending on the con-
ditions. The formation of 7j was favored by gradual
addition of the oxidant to excess thiol. If the oxidant
was present in excess with respect to thiol, the major
products were sulfonothioate 8j, sulfonyl chloride 3j,
sulfonic acid 2j, etc.
aqueous pyridine to give acids 2c and 2d together with
pyridinium salts 5c and 5d with a selectivity of up to
86 and 35%, respectively. Camphenesulfonic acid was
isolated as pyridinium salt 5l [11]. Presumably, the
presence of a C=C double bond contiguous to the sulfo
group increases the acidity of 2c, 2d, and 2l. In the
1H NMR spectra of 5c and 5d, the signal intensity ratio
of the pyridine protons and protons of the terpene
fragment was 1 :1. The C10 signal in the 13C NMR
spectrum of 5d was observed in a weaker field
(δC 65.97 ppm) relative to the corresponding signal of
2d (δC 58.37 ppm). The mass spectra of 5c, 5d, and 5l
recorded under mild chemical ionization (positive ion
detection) displayed the molecular ion peaks [M + H]+
with the maximum intensity (100%); in the negative
ion mass spectra of the same compounds, the base
peaks were those belonging to anions of the corre-
sponding acids 2c, 2d, and 2l [M – H]–. The yields of
pyridinium salts in the oxidation of the other thiols
were insignificant (up to 10%).
The reactions of thiol 1j with ClO2 were not selec-
tive as compared to thiols with pinane (1a–1d) and
bornane skeletons (1e–1f). The use of VO(acac)2 as
catalyst, which showed previously [7] good results in
reactions of diphenyl disulfide with ClO2, did not
improve the selectivity. In the oxidation of 1j with
2 equiv of ClO2 in methylene chloride, the yield of
sulfonothioate 8j did not exceed 30% (according to the
1H NMR data). We failed to isolate pure compound 8j,
but the presence of SO2 stretching bands in the IR
spectrum (1321 and 1120 cm–1), downfield shift of the
C1 signal (δC 71.42 ppm against δC 40.20 ppm for thiol
1j), and the presence of double set of signals in the
NMR spectra (indicating unsymmetrical structure) left
no doubt concerning its structure.
Conjugation of lone electron pair on the sulfur atom
with C=C double bond hampers oxidation of thiols 1c
and 1d in less polar solvents. In the oxidation of 1b,
1c, and 1d with ClO2 in hexane–water (substrate-to-
oxidant ratio 1:0.5), the conversion of 1c and 1d in
0.5 h did not exceed 40%, whereas the conversion of
1b was complete.
The oxidation of 1j in a more polar solvent such as
anhydrous acetonitrile afforded sulfonyl chloride 3j
through unstable intermediate diastereoisomeric sul-
13
finyl chlorides 9j (de 54%). The C NMR spectrum
displayed one set of signals from each diastereoisomer,
and the C1 signals were located at δC 70.48 and
72.71 ppm. The S(=O)Cl group gave rise to absorption
band at 1128 cm–1 in the IR spectrum. The oxidation of
9j with 2 equiv of ClO2 gave 3j which showed one set
of signals in the NMR spectra and downfield shift of
the C1 signal in the 13C NMR spectrum (δC 77.92 ppm).
The IR spectrum of 3j contained SO2 stretching bands
at 1369 and 1167 cm–1.
In the first stage, regardless of the solvent nature,
all thiols are oxidized with ClO2 to disulfides 6a–6j
[11] whose further transformations are determined by
the conditions and substrate structure. Increase of the
amount of ClO2 or solvent polarity (e.g., in going to
methanol) promoted unexpected transformation of 6f
and 6j to trisulfides 7f and 7j in 56–78% yield. Com-
pounds 7 are likely to be formed according to the
scheme proposed in [10] for the formation of 7f.
Although the reactions in pyridine selectively
afforded the corresponding sulfonic acid, their separa-
tion from solvates and pyridinium salts (hydro-
chlorides, chlorates, and chlorites resulting from reac-
tion of pyridine with the reduced oxidant species) is
a difficult problem since almost all reaction products
are readily soluble both in water and in organic sol-
vents. Therefore, apart from pyridine, aqueous aceto-
nitrile was tested as solvent to find optimal conditions
for the synthesis and isolation of sulfonic acid 2j. In
this case, we succeeded in improving the yield of 2j
from 35 to 80% (in comparison with the reaction in
methylene chloride) and isolating it in the pure state by
extraction (in comparison with the reaction in pyri-
dine). In the 13C NMR spectrum of 2j, the C1 signal
was observed in a weaker field (δC 59.72 ppm) relative
Trisulfide 7j showed in the mass spectrum the
molecular ion peak with m/z 374, as well as fragment
ion peaks with m/z 236 and 171 corresponding to
terpene fragments bearing three and one sulfur atom,
respectively. The IR spectrum of 7j was similar to the
spectrum of 6j. In the 13C NMR spectrum of 7j, the
C1 signal appeared in a weaker field (δC 54.97 ppm)
relative to the C1 signal of 6j (δC 52.60 ppm), and the
1-H proton signal also shifted downfield (δ 3.58
against 3.26 ppm for 6j). The cis arrangement of the
SH and isopropyl groups was retained, as shown by
using two-dimensional NMR techniques (HSQC,
COSY, NOESY, HMBC). The elemental composition
of 7j was consistent with the assumed structure.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 6 2017

SYNTHESIS OF NEW MONOTERPENE SULFONIC ACIDS
863
to the corresponding signal of thiol 1j (δC 40.20 ppm),
and a new signal appeared in the 1H NMR spectrum at
δ 9.35 ppm due to the OH proton. The IR spectrum of
2j showed SO2 stretching bands at 1228, 1197, 1172,
1053, and 1022 cm–1. The mass spectrum of 2j con-
tained ion peak with m/z 219.22 [M – 1]–.
In summary, the oxidation of terpene thiols with
pinane, p-menthane, bornane, and carane structures
with chlorine dioxide afforded the corresponding sul-
fonic acids in high yields (76–96%) and their deriva-
tives (28–85%). Monofunctional thiols of the p-men-
thane and bornane series characteristically gave rise to
the corresponding trisulfides as the major products.
Nitrogen-containing aprotic solvents favored smooth
transformation of thiols to sulfonic acids and prevented
acid-catalyzed rearrangements in the reactions with
bornane and carane thiols and desulfurization in the
oxidation of thioverbenol.
Under analogous conditions, thiol 1d was selec-
tively oxidized to sulfonothioate 8d. The 13C NMR
spectrum of 8d contained a double set of signals, and
the C10 signal was shifted downfield (δC 69.95 ppm)
relative to the corresponding signals of 6d (δC 45.72
ppm) and 1d (δC 30.56 ppm). The IR spectrum of 8d
showed SO2 bands at 1325 and 1128 cm–1.
EXPERIMENTAL
The oxidation of carane thiols 1g–1i with ClO2 was
accompanied by opening of the cyclopropane ring.
Thiol 1i reacted with 2 equiv of ClO2 in aqueous
acetonitrile in the presence of VO(acac)2 to give
sulfonyl chloride 3i with a selectivity of up to 70%;
however, the product was isolated in less than 30%
yield due to its instability during chromatographic
purification. In the oxidation of 1h, the corresponding
sulfonyl chloride was formed with a selectivity of
~40%. The formation of 3h and 3i followed from the
position of the C4 signals in the 13C NMR spectra
(δС 85.80 and 84.42 ppm, respectively) and the pres-
ence of SO2 stretching bands in the IR spectra (1369
and 1161 cm–1). The oxidation of 1g under similar
conditions gave sulfonothioate 8g in a poor yield
(16%). The NMR spectra of 8g contained a double set
of signals, the C4 signal was shifted downfield
(δC 70.48 ppm), and SO2 stretching bands were ob-
served in the IR spectrum at 1320 and 1122 cm–1.
The IR spectra were recorded on a Shimadzu IR
Prestige 21 spectrometer with Fourier transform. The
melting points were determined on a Gallenkamp-
1
13
Sanyo melting point apparatus. The H and C NMR
spectra were recorded on a Bruker Avance-300 spec-
trometer at 300.17 and 75.48 MHz, respectively, using
CDCl3 as solvent and reference or D2O as solvent with
addition of sodium 4,4-dimethyl-4-silapentane-1-sul-
1
fonate (DSS) as internal standard. The H and 13C
NMR signals were assigned using two-dimensional
1
homo- (1H–1H COSY, H–1H NOESY) and hetero-
nuclear experiments (1H–13C HSQC, HMBC). The
mass spectra were obtained on a Thermo Finnigan
LCQ Fleet HPLC/MS instrument using MeOH and
MeCN as solvents and on a Thermo Fisher Scientific
TRACE DSQ GC/MS system (electrospray ionization,
capillary voltage 5 kV) with positive (3–9) and nega-
tive (2) ion detection. The optical rotations were meas-
ured on a Kruss P3002RS automated digital polarim-
eter. Thin-layer chromatography was performed on
Sorbfil plates with petroleum ether–ethyl acetate (1:1)
(1a–1d) and CHCl3 (1e–1g) as eluents; spots were
visualized by treatment with a solution of phospho-
molybdic acid in ethanol, a solution of KMnO4, or
a 0.2% solution of Bromocresol Green in ethanol (for
sulfinyl and sulfonyl chlorides). The elemental anal-
yses were obtained with an EA 1110 CHNS-O
automated analyzer.
Hydroxypinane sulfonothioates 8a and 8b [11]
were tested for antimicrobial activity against five
bacterial strains (Escherichia coli, Klebsiella
pneumoniae, Acinetobacter baumannii, Pseudomonas
aeruginosa, Staphylococcus aureus) and antifungal
activity against two fungal strains (Candida albicans,
Cryptococcus neoformans). These bacteria showed
multiple resistance to antibiotics. Colistin and Vanco-
mycin were used as reference drugs for gram-negative
and gram-positive bacteria, respectively, and Fluco-
nazole was used as reference drug for fungi. Bacterial
growth inhibition was evaluated by measuring the
optical density at λ 530–600 nm, depending on the
particular strain. A compound was assumed to be
active if the bacterial growth inhibition was higher
than 80%. The results showed that sulfonothioates 8a
and 8b are active against Candida albicans, while
compound 8a also showed activity against Staphylo-
coccus aureus and Cryptococcus neoformans.
All reactions were carried out in freshly distilled
solvents. The products were isolated by column chro-
matography on silica gel (0.06–0.2 mm, Alfa Aesar)
using the same solvent systems as in TLC. The yields
1
were determined by H NMR from the intensities of
4-H for 1c and 1g–1k and of 1-H for 1j.
Aqueous solution of chlorine dioxide is a com-
mercial product; the concentration of ClO2 was deter-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 6 2017

GREBYONKINA et al.
864
mined by titration according to the procedure de-
scribed in [21]. Solutions of ClO2 in organic solvents
were prepared by extraction from an aqueous solution,
the extract was dried over, and the concentration of
ClO2 was determined by titration [21].
spectrum, m/z (Irel, %): 215.29 (100) [M – H]–, 97.00
(48) [C7H13].
(1S,3R,4S,6R)-3,7,7-Trimethylbicyclo[4.1.0]-
heptane-4-sulfonic acid (2g). Yield 84% (a). IR spec-
trum (KBr), ν, cm–1: 3437 br (O–H), 2983, 1467, 1386,
1215 s (SO2), 1153 s (SO2), 1026 s (SO2), 990, 885,
Samples for biological screening were prepared and
applied to microplates with Caliper Zephyr and
Biomek NX automated liquid handling systems.
Fungal strains were cultivated on yeast extract peptone
dextrose (YEPD) agar. The optical densities at
λ 600 nm (OD600) were measured with Tecan M1000
Pro (bacteria) and Biotek Synergy HTX (fungi) micro-
plate readers.
1
664, 619. H NMR spectrum (CDCl3), δ, ppm: 0.40–
0.51 m (1H, 1-H), 0.69 q (1H, 6-H, J = 8.4 Hz), 0.79–
0.95 m (H, 5-H), 0.91 s and 0.93 s (6H, 8-H, 9-H),
1.02 d (3H, 10-H, J = 7.2 Hz), 0.97–1.23 m (1H, 2-H),
1.89–2.04 m (1H, 5-H), 2.05–2.23 m (2H, 2-H, 3-H),
13
2.73–2.89 m (1H, 4-H), 8.76 s (OH). C NMR spec-
trum (CDCl3), δC, ppm: 15.06 (C8), 17.60 (C10), 17.73
(C7), 18.62 (C2), 19.41 (C1), 22.33 (C6), 26.34 (C3),
26.43 (C5), 28.11 (C9), 59.20 (C4). Mass spectrum, m/z
(Irel, %): 434.94 (5) [2M – H]–, 217.19 (100) [M – H]–,
97.03 (13) [C7H13].
Oxidation of thiols with chlorine dioxide (general
procedures). The overall volume of the reaction mix-
ture was calculated for a thiol concentration of 0.02 M
(sample weight 0.05–0.1 g). The progress of reactions
was monitored by TLC.
(1S,3S,4S,6R)-3-Hydroxy-3,7,7-trimethylbicyclo-
[4.1.0]heptane-4-sulfonic acid (2h). Yield 92% (a).
IR spectrum (KBr), ν, cm–1: 3423 br (O–H), 2983,
1485, 1249 s (SO2, asym.), 1207 s (SO2, asym.), 1157 s
(SO2, asym.), 1035 s (SO2, sym.), 999 s (SO2, sym.),
a. A solution of chlorine dioxide in water or organic
solvent was added to a solution of thiol 1 in pyridine,
DMF, or acetonitrile to a substrate-to-oxidant ratio of
1 : (2–3).2 The mixture was stirred for 1–3 h and
extracted with chloroform or methylene chloride to
isolate neutral compounds, and the aqueous phase was
additionally treated with benzene or hexane and
evaporated. The dry residue contained 76–96% of
sulfonic acid 2.
1
756, 682. H NMR spectrum (CDCl3), δ, ppm: 0.61 t
(1H, 1-H, J = 8.5 Hz), 0.77–0.98 m (2H, 5-H, 6-H),
0.84 s (3H, 8-H), 0.91 s (3H, 9-H), 1.24 d.d (1H, 2-H,
J = 15.7, 6.3 Hz), 1.38 s (3H, 10-H), 2.00 d.d (1H,
2-H, J = 16.0, 8.8 Hz), 2.22–2.35 m (1H, 5-H),
2.95 d.d (1H, 4-H, J = 12.0, 2.0 Hz), 10.57 br.s (1H,
11-H). 13C NMR spectrum (CDCl3), δC, ppm: 14.84
(C8), 17.81 (C1), 18.59 (C7), 20.74 (C5), 23.62 (C6),
26.47 (C10), 27.85 (C9), 35.44 (C2), 67.81 (C4), 71.15
(C3). Mass spectrum, m/z (Irel, %): 233.21 (100)
[M – H]–, 97.03 (8) [C7H13].
b. Thiol 1 was dissolved in an organic solvent,
10 mol % of VO(acac)2 was added, and a solution of
chlorine dioxide in water or organic solvent was
added. The aqueous and organic phases were separated
and evaporated on a rotary evaporator. The dry residue
from the organic phase was subjected to column
chromatography.
(1S,3R,4R,6R)-3-Hydroxy-3,7,7-trimethylbicyclo-
[4.1.0]heptane-4-sulfonic acid (2i). Yield 96% (a). IR
spectrum (KBr), ν, cm–1: 3410 br (O–H), 2933 s, 1487,
1249 s (SO2), 1211 s (SO2), 1161 s (SO2), 1035 (SO2),
Compounds 2a, 2b, 2e, 2l, 3a, 3b, 3l, 5l, 6a, 6b, 6e,
8a, 8b [11], 2f, 6f, 7f, 9f [10], 6c, 6d [22], and 4c [23]
were described previously.
1
1001 (SO2), 756, 682 s, 601. H NMR spectrum
{(1S,5R)-6,6-Dimethylbicyclo[3.1.1]hept-2-en-
2-yl}methanesulfonic acid (2d). Yield 74% (a). IR
(CDCl3), δ, ppm: 0.60 t (1H, 1-H, J = 8.5 Hz), 0.75 t.d
(1H, 6-H, J = 9.2, 5.2 Hz), 0.92 s (3H, 8-H), 0.96 s
(3H, 9-H), 1.20 d.d (1H, 2-H, J = 14.3, 3.9 Hz), 1.39 s
(3H, 10-H), 1.93 d.d (1H, 2-H, J = 14.0, 10.2 Hz),
2.10–2.26 m and 2.27–2.43 m (1H each, 5-H), 2.70 d.d
(1H, 4-H, J = 11.8, 7.4 Hz). 13C NMR spectrum
(CDCl3), δC, ppm: 15.33 (C8), 17.78 (C7), 18.30 (C1),
19.77 (C6), 20.97 (C5), 22.39 (C10), 28.46 (C9), 35.53
(C2), 64.46 (C4), 70.53 (C3). Mass spectrum, m/z (Irel,
%): 233.21 (100) [M – H]–, 97.03 (11) [C7H13].
1
spectrum (KBr), ν, cm–1: 1325, 1128 (SO2). H NMR
spectrum (D2O), δ, ppm: 0.84 s (3H, 9-H), 1.21–
1.34 m (1H, 7-H), 1.26 s (3H, 8-H), 2.11–2.19 m (2H,
1-H, 5-H), 2.27–2.54 m (3H, 4-H, 7-H), 3.53–3.65 m
(2H, 10-H), 5.21 s (1H, 3-H), 10.3 br.s (1H, OH).
13C NMR spectrum (D2O), δC, ppm: 20.53 (C9), 25.67
(C8), 31.06, 31.34 (C7, C4), 38.23 (C6), 39.85 (C5),
45.67 (C1), 58.37 (C10), 124.66 (C3), 138.79 (C2). Mass
2
(1S,2S,5R)-5-Methyl-2-(propan-2-yl)cyclohex-
ane-1-sulfonic acid (2j). Yield 78% (a; MeCN, H2O).
Variation of the organic solvent-to-water ratio from 5:1 to 5:2
had no appreciable effect on the results.
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SYNTHESIS OF NEW MONOTERPENE SULFONIC ACIDS
865
IR spectrum (KBr), ν, cm–1: 3410 br (O–H), 2953 s,
1182 s (SO2), 1070 (SO2), 1014, 885, 582. H NMR
1.30–1.48 m (1H, 2-H), 1.53 s (3H, 10-H), 1.68–
1.85 m (1H, 6-H), 2.10 d.d (1H, 2-H, J = 14.9, 9.4 Hz),
2.41 d.d (1H, 5-H, J = 15.1, 8.0 Hz), 2.64 d.d.d (1H,
5-H, J = 15.0, 11.1, 8.5 Hz), 3.28 s (1H, OH), 3.67 d.d
(1H, 4-H, J = 11.0, 8.3 Hz). 13C NMR spectrum
(CDCl3), δС, ppm: 15.28 (C8), 18.29 (C1), 18.46 (C7),
19.29 (C6), 21.65 (C5), 23.38 (C10), 27.96 (C9), 35.97
(C2), 73.08 (C3), 84.42 (C4). Mass spectrum, m/z
(Irel, %): 253.06 (65) [M + H]+, 137.13 (100) [C10H17]+.
Found, %: C 47.62; H 6.80; S 12.86. C10H17ClO3S.
Calculated, %: C 47.52; H 6.78; S 12.68.
1
spectrum (D2O), δ, ppm: 0.83 d (3H, 7-H, J = 6.1 Hz),
0.90 d (3H, 10-H, J = 6.6 Hz), 0.88–0.97 m (1H, 4-H),
0.99 d (3H, 9-H, J = 6.6 Hz), 1.13–1.38 m (2H, 2-H,
6-H), 1.62–1.95 m (5H, 3-H, 4-H, 5-H, 8-H), 2.25 d.d
(1H, 6-H, J = 13.8, 2.2 Hz), 3.39–3.45 m (1H, 1-H).
13C NMR spectrum (D2O), δC, ppm: 20.87 (C10), 21.39
(C9), 21.84 (C7), 23.74 (C3), 26.07 (C5), 29.10 (C8),
34.90 (C4), 37.78 (C6), 47.29 (C2), 58.82 (C1). Mass
spectrum, m/z (Irel, %): 219.20 (100) [M – H]–, 97.00
(35) [C7H13]. Found, %: C 54.62; H 9.80; S 13.86.
C10H20O3S. Calculated, %: C 54.51; H 9.15; S 14.55.
(1S,2S,5R)-5-Methyl-2-(propan-2-yl)cyclohex-
ane-1-sulfonyl chloride (3j). Yield 28% (b; reaction
time 2 h, MeCN, CHCl3; 1j–ClO2 1:6), viscous liquid.
IR spectrum (film), ν, cm–1: 1369 (SO2), 1166 (SO2).
13C NMR spectrum (CDCl3), δC, ppm: 21.51 (C10),
21.80 (C9), 22.13 (C7), 24.83 (C3), 26.02 (C5), 30.21
(C8), 34.77 (C4), 37.86 (C6), 50.51 (C2), 77.89 (C1).
Mass spectrum, m/z (Irel, %): 239.04 (49) [M + H]+,
139.17 (100) [C10H19]+. Found, %: C 49.82; H 7.89;
S 12.96. C10H19ClO2S. Calculated, %: C 50.30;
H 8.02; S 13.43.
(1S,2R,5S)-5-(2-Hydroxypropan-2-yl)-2-methyl-
cyclohexane-1-sulfonic acid (2k). Selectivity 68%
(a; MeCN, H2O). IR spectrum (film), ν, cm–1: 3423 br
1
(O–H), 1172 (SO2), 1051 (SO2). H NMR spectrum
(D2O), δ, ppm: 0.78 d (3H, 10-H, J = 7.2 Hz), 0.93–
0.97 m (1H, 1-H), 0.96 s (6H, 8-H, 9-H), 1.12–1.39 m
(3H, 2-H, 6-H), 1.39–1.61 m (2H, 5-H), 1.64–1.83 m
(1H, 1-H), 2.00–2.31 m (1H, 3-H), 2.57–2.90 m (1H,
13
4-H). C NMR spectrum (D2O), δС, ppm: 12.14 (C10),
19.92 (C2), 21.54 (C1), 25.29 (C8, C9), 28.24 (C3),
32.53 (C5), 48.01 (C6), 62.55 (C4), 73.45 (C7). Mass
spectrum, m/z (Irel, %): 235.21 (45) [M – H]–, 111.06
(26) [C8H15], 97.03 (100) [C7H13].
Pyridinium (1R,4S,5R)-2,6,6-trimethylbicyclo-
[3.1.1]hept-2-ene-4-sulfonate (5c). Yield 86% (a). IR
spectrum (KBr), ν, cm–1: 3431 br (O–H), 3061, 2515
br (N+–H), 1631, 1537, 1485, 1294 s (SO2), 1151 s
(SO2), 1051, 1028 s (SO2), 819, 758, 721, 684.
1H NMR spectrum (CDCl3), δ, ppm: 0.84 s (3H, 8-H),
0.96–1.09 (1H, 7-H), 1.15 s (3H, 9-H), 1.68 s (3H,
10-H), 1.94–2.06 m (2H, 1-H, 7-H), 2.30–2.40 m (1H,
5-H), 5.29–5.35 m (1H, 3-H), 5.49–5.57 m (H, 4-H),
8.02 t (2H, Py, J = 6.87 Hz), 8.44 t (1H, Py, J =
7.97 Hz), 9.00 d (2H, Py, J = 5.5 Hz), 14.64 s (1H,
NH). 13C NMR spectrum (CDCl3), δC, ppm: 19.70
(C8), 22.80 (C10), 25.00 (C7), 25.49 (C9), 46.32 (C1),
46.86 (C6), 48.15 (C5), 71.00 (C4), 109.45 (C3), 127.82
(CPy), 142.95 (CPy), 145.08 (CPy), 156.70 (C2). Mass
spectrum, m/z (Irel, %): 591 (23) [2M + H]+, 296.24
(100) [M + H]–. Found, %: C 62.01; H 7.30; N 4.84;
S 10.66. C10H16SO3·C5H5N. Calculated, %: C 60.99;
H 7.17; N 4.74; S 10.85.
(1S,3S,4S,6R)-3-Hydroxy-3,7,7-trimethylbicyclo-
[4.1.0]heptane-4-sulfonyl chloride (3h). Reaction
time 1 h (b; MeCN, H2O), selectivity 38–44%; viscous
liquid. IR spectrum (film), ν, cm–1: 3402 br (O–H),
1373 s (SO2), 1163 s (SO2), 1111 s (C–O). The NMR
spectra were obtained by subtracting the signals analo-
gous to 3i from the spectrum of mixture 3h/6h.
1H NMR spectrum (CDCl3), δ, ppm: 0.67–0.90 m (1H,
1-H), 1.04 s (3H, 8-H), 1.10 s (3H, 9-H), 1.19–1.40 m
(1H, 2-H), 1.55 s (3H, 10-H), 1.68–1.83 m (1H, 6-H),
2.15 d.d (1H, 2-H, J = 16.0, 8.3 Hz), 2.30–2.48 d.d
(1H, 5-H), 2.64 d.d.d (1H, 5-H, J = 14.3, 7.7, 3.3 Hz),
3.30 s (1H, OH), 3.89 d.d (1H, 4-H, J = 12.4, 3.0 Hz).
13C NMR spectrum (CDCl3), δC, ppm: 14.76 (C8),
17.40 (C1), 19.69 (C7), 21.99 (C5), 22.67 (C6), 24.05
(C10), 27.00 (C9), 33.51 (C2), 73.06 (C3), 85.80 (C4).
Mass spectrum, m/z (Irel, %): 253.06 (52) [M + H]+,
137.13 (100) [C10H17]+.
Bis[(1S,2S,5R)-5-methyl-2-(propan-2-yl)cyclo-
hexyl]trisulfane (7j). Yield 56%, white powder. IR
spectrum (KBr), ν, cm–1: 2949 s, 2918 s, 2870 s, 1450,
1375, 1278, 1238, 860. 1H NMR spectrum (CDCl3), δ,
ppm: 0.83–0.97 m (1H, 4-Hax), 0.93 d (3H, 7-H, J =
6.6 Hz), 0.93 d (3H, 9-H, J = 6.6 Hz), 1.03 d (3H,
10-H, J = 6.6 Hz), 1.08–1.28 m (1H, 6-Hax), 1.09–
1.28 m (1H, 2-H), 1.15–1.28 m (1H, 3-Hax), 1.59–
1.65 m (1H, 8-H), 1.68–1.77 m (1H, 3-Heq), 1.75–
1.78 m (1H, 4-Heq), 1.85–1.95 m (1H, 5-H), 2.40–
(1S,3R,4R,6R)-3-Hydroxy-3,7,7-trimethylbicyclo-
[4.1.0]heptane-4-sulfonyl chloride (3i). Yield 30% (b;
MeCN, H2O), viscous liquid. IR spectrum (film), ν,
cm–1: 3445 (O–H), 1369 (SO2), 1161 (SO2), 1115
1
(C–O). H NMR spectrum (CDCl3), δ, ppm: 0.85–
0.99 m (1H, 1-H), 1.01 s (3H, 8-H), 1.09 s (3H, 9-H),
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GREBYONKINA et al.
866
13
2.45 m (1H, 6-Heq), 3.55–3.60 m (1H, 1-H). C NMR
spectrum, δС, ppm: 20.20 (C9), 20.71 (C10), 21.29 (C7),
26.29 (C5), 26.49 (C3), 29.94 (C8), 35.37 (C4), 39.98
(C6), 48.94 (C2), 54.96 (C1). Mass spectrum, m/z
(Irel, %): 374 (11) [M]+, 236 (6) [С10H19S3H], 171 (8)
[C10H19S], 139 (68) [C10H19], 83 (100). Found, %:
C 64.12; H 10.21; S 25.70. C20H38S3. Calculated, %:
C 64.17; H 10.16; S 25.67.
(C9), 21.51 (C9′), 21.86 (C7), 22.28 (C7′), 25.64 (C3′),
26.15 (C3), 26.25 and 26.42 (C5, C5′), 29.87 and 30.03
(C8, C8′), 34.78 and 35.00 (C4, C4′), 35.24 (C6′), 37.92
(C6), 48.87 (C2′), 50.40 (C2), 53.91 (C1), 71.37 (C1′).
Mass spectrum, m/z (Irel, %): 375.16 (49) [M + H]+,
139.15 (100) [C10H19]+.
(1S,2S,5R)-5-Methyl-2-(propan-2-yl)cyclo-
hexane-1-sulfinyl chloride (9j). Yield 36–45%
(b; CH2Cl2, 1j–ClO2 1:4, reaction time 2 h), mixture of
diastereoisomers A and B (77:23). IR spectrum (film):
S-[(1R,5S)-6,6-Dimethylbicyclo[3.1.1]hept-2-en-
2-yl]methyl (1R,5S)-6,6-dimethyl(bicyclo[3.1.1]-
hept-2-en-2-yl)methanesulfonothioate (8d). Yield
85% (a; MeCN, H2O), white powder, [α]D22 = –3.7° (c =
0.2, CHCl3). IR spectrum (KBr), ν, cm–1: 1325, 1128
(SO2). 1H NMR spectrum (CDCl3), δ, ppm: 0.85 s (3H,
9′-H), 0.91 s (3H, 9-H), 1.15–1.31 m (2H, 7-H, 7′-H),
1.33 s (6H, 8-H, 8′-H), 2.09–2.19 m (2H, 5-H, 5′-H),
2.24 d (1H, 1′-H, J = 5.2 Hz), 2.27–2.54 m (7H, 1-H,
4-H, 4′-H, 7-H, 7′-H), 3.70–3.79 m and 3.82–3.91 m
(1H each, 10′-H), 3.97 q (2H, 10-H, J = 11.5 Hz),
5.65 s (1H, 3′-H), 5.81 s (1H, 3-H). 13C NMR spectrum
(CDCl3), δС, ppm: 21.09 (C9′), 21.21 (C9) 26.05 (C8,
C8′), 31.45 (C7′), 31.74 (C7), 31.88 (C4′), 32.03 (C4),
38.23 (C6), 40.06 (C5′), 40.31 (C5), 42.78 (C10′), 45.15
(C1′), 46.20 (C1), 70.20 (C10), 123.33 (C3′), 129.76
(C3), 135.96 (C2′), 140.95 (C2). Found, %: C 64.69;
H 8.21; S 17.35. C20H30O2S2. Calculated, %: C 65.53;
H 8.25; S 17.49.
1
ν 1128 cm–1 (S=O). H NMR spectrum (CDCl3), δ,
ppm: 0.93 d (3H, 10-H, J = 6.1 Hz), 0.95 d (3H, 9-H,
J = 6.6 Hz), 0.97–1.03 m (1H, 4-H), 1.06 d (3H, 7-H,
J = 6.6 Hz), 1.28–1.48 m (2H, 2-H, 6-H), 1.72–2.49 m
(5H, 3-H, 4-H, 5-H, 8-H), 2.96 d.d (1H, 6-H, J = 13.8,
2.2 Hz), 3.68–3.74 m (A) and 3.97–4.01 m (B) (1H,
1-H). 13C NMR spectrum (CDCl3), δC, ppm: 21.55 and
21.10 (C9), 21.68 and 21.55 (C8), 22.34 and 22.78
(C10), 26.08 and 26.01 (C3), 27.68 and 28.06 (C5),
29.84 and 29.15 (C7), 34.77 and 35.31 (C4), 34.81 and
37.42 (C6), 48.32 and 50.31 (C2), 70.48 and 72.71 (C1).
Mass spectrum, m/z (Irel, %): 223.08 (100) [M + H]+,
139.15 (38) [C10H19]+.
Antimicrobial activity. Compounds 8a and 8b
were tested for antimicrobial activity at a concentration
of 32 μg/mL in duplicate. A sample of 8a or 8b was
dissolved in DMSO to a concentration of 10 mg/mL.
The resulting solution was diluted to a concentration of
320 μg/mL with 7% aqueous DMSO and dispensed
over a 384-well polypropylene plate (StorPlate; Perkin
Elmer № 6008690). In a duplicate experiment, 5 μL of
the same solution was dispensed over a 384-well plate
(NBS; Corning № 3640). After addition of biological
media, the concentration of test compounds was
~32 μg/mL, and the concentration of DMSO, 1%.
S-(1R,3S,4R,6S)-4,7,7-Trimethylbicyclo[4.1.0]-
hept-3-yl (1R,3S,4R,6S)-4,7,7-trimethylbicyclo-
[4.1.0]heptane-3-sulfonothioate (8g). Yield 16%
(a; MeCN, H2O; isolated from the organic fraction),
viscous liquid. IR spectrum (film), ν, cm–1: 1320
1
(SO2), 1122 (SO2). H NMR spectrum (DMSO-d6), δ,
ppm: 0.52–0.68 m (4H, 2′-H, 10′-H), 0.68–0.87 m (1H,
6′-H), 0.87–1.33 m (17H, 1′-H, 6-H, 8-H, 8′-H, 9-H,
9′-H, 10-H), 1.45–2.17 m (6H, 1-H, 2′-H, 3′-H, 5-H,
5′-H), 2.20–2.64 m (3H, 2-H, 3-H, 5′-H), 3.43–3.61 m
(1H, 4-H), 3.61–3.87 m (1H, 4′-H). 13C NMR spectrum
(DMSO-d6), δC, ppm: 15.49 (C8′), 16.37 (C8), 16.63
(C7′), 17.86 (C7), 18.30 (C10′), 18.46 (C2), 19.46 (C1′,
C10), 19.65 (C1), 21.47 (C6′), 22.07 (C6), 25.35 (C2′),
27.09 (C5′), 27.44 (C9′), 27.78 (C5), 28.37 (C3), 28.79
(C9), 31.46 (C3′), 52.50 (C4′), 70.48 (C4). Found, %:
C 64.82; H 9.25; S 17.30. C20H34O2S2. Calculated, %:
C 65.20; H 9.20; S 17.49.
Bacterial cultures were grown on a cation-adjusted
Muller–Hinton broth at 37°C. Each culture was then
diluted with 40 volumes of a fresh broth and incubated
for 1.5–2 h at 37°C, and a 45-μL portion was added to
each well containing compounds to be tested; the
concentration of bacteria therein was 5×105 CFU/mL
(determined from OD600). All microplates were capped
and incubated for 18 h at 37°C without shaking.
Bacterial growth inhibition was determined by
measuring the optical density at λ 600 nm for each
well using only broth and bacterial culture without
inhibitor as negative and positive controls, respec-
tively. The inhibition percentage was estimated
through Z-sets with calculation of mean and standard
deviations for wells with samples (without control) in
S-[(1S,2S,5R)-5-Methyl-2-(propan-2-yl)cyclo-
hexyl] (1S,2S,5R)-5-methyl-2-(propan-2-yl)cyclo-
hexane-1-sulfonothioate (8j). Selectivity 30–48% (b).
IR spectrum (film), ν, cm–1: 1321 (SO2), 1120 (SO2).
13C NMR spectrum (from the spectrum of mixture
3j/8j; CDCl3), δC, ppm: 20.51 (C10′), 20.69 (C10), 21.11
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SYNTHESIS OF NEW MONOTERPENE SULFONIC ACIDS
867
each microplate. Samples with an inhibition value of
more than 80% and Z-set ~2.5 in each experiment (n =
2 for different plates) were defined as active.
Scientific Center, Ural Branch, Russian Academy of
Sciences), namely E.N. Zainullina and S.P. Kuznetsov
for recording the NMR spectra, E.U. Ipatova for
recording the IR spectra, S.A. Patov, V.A. Belyi, and
I.V. Gruzdev for recording the mass spectra, S.L. Smo-
leva for performing elemental analyses, and I.A. Dvor-
nikova for measuring the optical rotations, as well
as the Community for Open Antimicrobial Drug
Discovery (Australia) for performing biological tests.
Fungal strains were cultivated for 72 h at 30°C.
A suspension of yeasts containing 106 to 5×106 cells
per milliliter was prepared from 5 colonies. These
cultures were diluted with yeast nitrogen base (YNB)
medium to a final concentration of 2.5×103 CFU/mL
and dispensed over microplates in an amount of 45 μL
per well. The microplates were capped and incubated
for 24 h at 35°C without shaking.
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mean and standard deviations for wells with samples
(without control) in each microplate. Samples with
an inhibition value of more than 80% and Z-set ~2.5 in
each experiment (n = 2 for different plates) were
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