Sulfides, sulfones, and sulfoxides of the furan-2(5H)-one series. synthesis and structure

Article abstract of DOI:10.1134/S1070428014040149

A number of 4- and 5-R-sulfanylfuran-2(5H)-one derivatives were synthesized, and their oxidation with various reagents was studied. The corresponding sulfones were obtained using hydrogen peroxide in acetic acid. 4-R-sulfanyl derivatives were selectively oxidized to sulfoxides with m-chloroperoxybenzoic acid. The molecular and crystal structures of some new sulfones and sulfoxides were determined by X-ray analysis.

Full text of DOI:10.1134/S1070428014040149

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 4, pp. 521–534. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © L.Z. Latypova, E.Sh. Saigitbatalova, D.R. Chulakova, O.A. Lodochnikova, A.R. Kurbangalieva, E.A. Berdnikov, G.A. Chmutova,
2014, published in Zhurnal Organicheskoi Khimii, 2014, Vol. 50, No. 4, pp. 532–545.
Sulfides, Sulfones, and Sulfoxides of the Furan-2(5H)-one Series.
Synthesis and Structure
L. Z. Latypovaa, E. Sh. Saigitbatalovaa, D. R. Chulakovaa, O. A. Lodochnikovab,
A. R. Kurbangalievaa, E. A. Berdnikova, and G. A. Chmutovaa
a Butlerov Institute of Chemistry, Kazan (Volga Region) Federal University,
ul. Lobachevskogo 1/29, Kazan, 420008 Tatarstan, Russia
b Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
e-mail: Almira.Kurbangalieva@ksu.ru
Received January 14, 2014
Abstract—A number of 4- and 5-R-sulfanylfuran-2(5H)-one derivatives were synthesized, and their oxidation
with various reagents was studied. The corresponding sulfones were obtained using hydrogen peroxide in acetic
acid. 4-R-sulfanyl derivatives were selectively oxidized to sulfoxides with m-chloroperoxybenzoic acid. The
molecular and crystal structures of some new sulfones and sulfoxides were determined by X-ray analysis.
DOI: 10.1134/S1070428014040149
The chemistry of organosulfur compounds, namely
sulfides, sulfoxides, and sulfones, attracts increased
attention due to importance of these compounds from
the practical viewpoint, their biological activity, and
broad synthetic potential [1–6]. Sulfur-containing frag-
ments are present in many natural compounds involved
in a number of biologically important processes, as
well as in synthetic medicinal agents exhibiting diverse
physiological activity [1, 4–6]. Sulfoxides and sulfones
are widely used in fundamental studies and preparative
organic chemistry for building up C−C bonds via
cycloaddition and Michael addition reactions and in
various stereocontrolled transformations of functional
groups. Insofar as sulfonyl and sulfinyl groups are
capable of stabilizing carbanionic centers, sulfones
and sulfoxides readily react with various electrophiles
[1–3, 5–7].
and agriculture; they are also useful as dyes, plasti-
cizers, detergents, etc. [1, 4, 5, 9].
Sulfoxides and sulfones of the furan-2(5H)-one
series are potential biologically active compounds. The
presence in their molecules of a sulfonyl or sulfinyl
group in combination with the pharmacophoric unsatu-
rated γ-lactone fragment [10, 11] is expected to extend
the scope of application of such heterofunctional com-
pounds and endow them with new kinds of biological
activity. Published data on sulfonyl and sulfinyl deriva-
tives of furan-2(5H)-one are fairly few in number
[12–17]. Their synthesis via oxidation of the corre-
sponding sulfides with m-chloroperoxybenzoic acid-
based systems and Oxone (potassium peroxymono-
sulfate) has been reported. The anti-inflammatory drug
Vioxx acting as highly selective cyclooxygenase-2
inhibitor is one of the most shining examples of com-
pounds comprising a furan-2(5H)-one fragment and
a sulfonyl group [12, 13].
We previously developed methods for selective
introduction of sulfur-containing substituents into posi-
tions 3, 4, and 5 of furan-2(5H)-one derivatives. Reac-
tions of 3,4-dichloro-5-hydroxyfuran-2(5H)-one (I,
mucochloric acid) with a number of aromatic thiols
[18] and 2-sulfanylacetic acid [19] under base or acid
catalysis afforded various sulfides of the furanone
series, whereas analogous reactions with 2-sulfanyl-
Being ambident nucleophiles, sulfoxides form com-
plexes with transition and non-transition metal cations
and therefore attract interest as extractants for salts
derived from metals and acids [3, 7, 8]. Chiral sulf-
oxides ensure efficient asymmetric induction and are
widely used in numerous practically important asym-
metric reactions and syntheses of biologically active
molecules [1, 6, 7]. Sulfonyl group inhibits various
enzymatic processes, and many compounds containing
a sulfonyl group are used in medicine, engineering,
521

LATYPOVA et al.
522
ethanol [20] and ethane-1,2-dithiol [21], apart from the
corresponding sulfides and bis-sulfides, produced vari-
ous sulfur-containing bicyclic compounds. The prod-
ucts of these reactions are very attractive as stable and
accessible substrates for their subsequent transforma-
tion into sulfinyl and sulfonyl derivatives. In this work
we examined oxidation of various 4- and 5-R-sulfanyl-
substituted furan-2(5H)-ones with a view to develop
preparative procedures for the synthesis of new
sulfones and sulfoxides and study their structure and
properties.
presence of a catalytic amount of concentrated sulfuric
acid. Reactions of acid I with benzenethiols in benzene
under acidic conditions produced 5-arylsulfanylfura-
nones IVa–IVc. All sulfides II–IV are stable solids;
compounds IId, IIe, and IIIa–IIId were not described
previously.
Oxidation of R-sulfanyl-substituted furan-2(5H)-
ones to sulfones. In order to obtain the corresponding
sulfones from 4- and 5-R-sulfanylfuran-2(5H)-ones,
the latter were subjected to oxidation with a classical
oxidizing system, a solution of hydrogen peroxide in
acetic acid. It is well known that this oxidant, in ad-
dition to its accessibility and efficiency and simplicity
of the experimental procedure, offers such advantages
as the possibility for carrying out the reactions at room
temperature and the absence of inorganic by-products
(except for water) [1–3, 22–24].
The initial sulfides were prepared from muco-
chloric acid (I) according to the procedures described
previously in the presence of acids or bases [18]. By
reactions of I with aromatic thiols and phenylmeth-
anethiol in the presence of triethylamine we obtained
4-R-sulfanyl derivatives IIa–IIf (Scheme 1), some of
which were converted into 5-alkoxy derivatives IIIa–
IIId by heating in boiling ethanol or propan-2-ol in the
Treatment of compounds IIa–IIf, IIIa–IIId, and
IVa–IVc with excess 33% hydrogen peroxide in acetic
Scheme 1.
O
O
RS
Cl
Cl
Cl
S
Cl
R
ii
iv
R'O
O
R'O
O
O
O
IIIa–IIId
VIa–VId
O
O
RS
Cl
S
R
i
iv
HO
O
HO
O
O
O
IIa–IIf
Va–Vf
O
Cl
Cl
S
R
v
HO
O
HO
O
O
O
O
I
VIIIa–VIIIe
Cl Cl
Cl
Cl
iii
iv
R
RS
O
S
O
O
O
O
IVa–IVc
VIIa–VIIc
II, V, R = 4-MeC6H4 (a), 4-ClC6H4 (b), 4-BrC6H4 (c), 3,5-(t-Bu)2-4-HO-C6H2 (d), PhCH2 (e), 1-naphthyl (f); III, VI: R′ = Et, R =
4-MeC6H4 (a), 4-BrC6H4 (b), PhCH2 (c); R = 4-MeC6H4, R′ = i-Pr (d); IV, VII, R = 4-MeC6H4 (a), 4-ClC6H4 (b), 4-BrC6H4 (c);
VIII, R = 4-MeC6H4 (a), 4-ClC6H4 (b), 4-BrC6H4 (c), 3,5-(t-Bu)2-4-HO-C6H2 (d), PhCH2 (e). Reagents and conditions: i: RSH, Et3N,
Et2O, 20°C; ii: excess ROH, concd. H2SO4, reflux; iii: RSH, concd. H2SO4, PhH, 80°C [18]; iv: excess 33% H2O2, AcOH, 20°C;
v: 3-ClC6H4CO3H, Et2O, –12°C.
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SULFIDES, SULFONES, AND SULFOXIDES OF THE FURAN-2(5H)-ONE SERIES
523
acid at room temperature led to the formation of the
corresponding sulfonyl derivatives Va–Vf, VIa–VId,
and VIIa–VIIc (Scheme 1). The products were isolat-
ed from the reaction mixtures as colorless crystalline
substances (yield 60–80%) by precipitation with water,
followed by recrystallization.
pattern from the OCH2CH3 group, a triplet at δ 0.9–
1.4 ppm from the methyl protons and a multiplet at
δ 3.1–4.1 ppm from the diastereotopic methylene
protons (Fig. 1). We calculated the chemical shifts and
coupling constants for protons of the 5-ethoxy group in
IIIa–IIIc and VIa–VIc. The smallest nonequivalence
of the diastereotopic protons was found for compound
VIb having a p-bromophenylsulfonyl group on C4
(ΔδAB = 0.004 ppm; cf. ΔδAB = 0.35 ppm for initial
sulfide IIIb in acetone-d6).
The oxidation of 5-R-sulfanyl-substituted furanones
IVa–IVc was accompanied by a side process, cleavage
of the C5–S bond, with formation of a small amount of
1
mucochloric acid (I). The H NMR spectrum of the
reaction mixture obtained in the oxidation of IVa with
3 equiv of H2O2 contained signals belonging to sulfone
VIIa, mucochloric acid I, and p-toluenesulfonic acid,
whose ratio was estimated at 10:1:1. In another ex-
periment, sulfide IVa was stirred for 6 days in glacial
acetic acid at room temperature without addition of
H2O2, and no hydrolysis of the initial compound was
observed (only signals of IVa were present in the
1H NMR spectrum of the mixture).
The molecular and crystal structures of some newly
synthesized sulfones were determined by X-ray anal-
ysis. We recently performed a detailed study of the
crystallization of 4-arylsulfonylfuran-2(5H)-ones Va–
Vc. It was found that crystallization of sulfone Va
from chloroform solution is accompanied by spontane-
ous resolution of enantiomers and that compounds Vb
and Vc crystallized as racemates [27]. The conforma-
tions of molecules Va–Vc in crystal are almost iden-
tical. The five-membered furan ring is planar, and the
hydroxy group and aromatic ring appear at one side
with respect to the heterocycle plane. The substituents
on C4 and S1 are arranged so that their configuration
with respect to the C4–S1 bond is staggered, i.e., the
aromatic and furan rings are almost orthogonal. Such
conformation favors conjugation of the S=O bonds
with both π-electron system of the aromatic ring and
C3=C4 bond in the heteroring. This assumption is sup-
ported by almost equal lengths of the C4–S1 and S1–C6
bonds [for example, 1.748(6) Å in molecule Va] [27].
Mucochloric acid (I) was also isolated previously in
preparative electrochemical oxidation of sulfide IVa in
MeCN/Bu4NBF4 [25]. Furthermore, the results of
quantum chemical calculations showed that dissocia-
tion of the C5–S bond with formation of arenesulfanyl
radical and 3,4-dichloro-5-oxofuran-2-yl cation is
energetically favorable; the subsequent reaction of the
cation with water gives acid I [25]. Hydrolysis was
also observed when the reaction mixture obtained from
a solution of 5-ethoxy derivative IIIb in acetic acid
and excess 33% aqueous hydrogen peroxide was kept
1
for a long time (3 months). According to the H NMR
5-Alkoxyfuryl sulfones VIa and VId crystallized in
a conformation similar to sulfones Va–Vc: staggered
conformation along the C4–S1 bond, dihedral angle
between the furan and benzene ring planes ~94° in
both structures (Fig. 2). The alkoxy group and p-tolyl
fragment reside at the same side of the heterocycle
plane. Compound VIa in crystal featured disordering
of the ethyl group by two positions with a population
ratio of 40:60, whereas no disordering was observed
for the isopropyl group in sulfone VId. Both sulfones
VIa and VId crystallized as racemates (centrosym-
metric space group P21/c for VIa and P21/n for VId).
data, the reaction mixture contained sulfones VIb and
Vc at a ratio of 4:1.
The structure of new sulfonyl derivatives Va–Vf,
VIa–VId, and VIIa–VIIc was proved by IR spectros-
copy and NMR. These compounds displayed in the IR
spectra strong narrow peaks corresponding to stretch-
ing vibrations of the sulfonyl group at 1310–1357
(antisymmetric vibrations) and 1140–1165 cm–1 (sym-
metric vibrations) [26]. The number of signals in the
1H and 13C NMR spectra of oxidation products V–VII
was the same as in the spectra of initial sulfides II–IV.
In the spectra of 4-R-sulfonyl derivatives, all signals in
the 1H and 13C NMR spectra were displaced downfield.
Analogous pattern was observed in the spectra of
5-R-sulfonyl derivatives VIIa–VIIc; an exception was
the 5-H signal which appeared in a stronger field
(Δδ ~0.05 ppm in acetone-d6 and ~0.33 ppm in CDCl3).
5-Arylsulfonyl derivatives VIIa–VIIc crystallized
as racemates in monoclinic crystal system, and con-
formations of their molecules in crystal differed from
those observed for compounds Va–Vc: the conforma-
tion along the C5–S1 bond is gauche, and the dihedral
angle between the furan and benzene ring planes is
~30° (Fig. 3a). Presumably, different conformations of
4- and 5-sulfones V and VII are related to the lack of
1
The H NMR spectra of 5-ethoxyfuranones IIIa–
IIIc and VIa–VIc characteristically showed an ABX3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 4 2014

LATYPOVA et al.
524
7.26
O
Cl
HA
HB
O
S
HA
HB
Me
O
O
O
7.38
1.41
6.08
ΔδAB = 0.07 ppm
4.49 4.42
ΔδAB = 0.14 ppm
4.12 3.98
5.30
1.00
6.0
2.14
2.12
4.0
3.21
7.0
5.0
3.0
2.0
δ, ppm
Fig. 1. 1H NMR spectrum of 4-benzylsulfonyl-3-chloro-5-ethoxyfuran-2(5H)-one (VIc) in CDCl3.
conjugation between the S=O bond and endocyclic
C3=C4 bond in the latter. Correspondingly, the C5–S1
bond in VIIa–VIIc is considerably longer than the S1–
C6 and S1–C4 bonds in Va–Vc.
with the same chirality. Neighboring chains formed by
molecules with opposite chiralities are also linked to
each other through analogous Carom–H···O=S contacts.
Oxidation of R-sulfanyl-substituted furan-2(5H)-
ones to sulfoxides. Unlike oxidation to sulfones,
which is achieved fairly readily, selective oxidation of
sulfides to sulfoxides is much more difficult to accom-
plish. Although several tens of various oxidants were
successfully used in the synthesis of sulfoxides [1–3,
The crystal packing of 5-arylsulfonylfuranones
VIIa–VIIc is characterized by intermolecular interac-
tions C–H···O involving the sulfonyl oxygen atoms
and aromatic hydrogen atoms (Fig. 3b). These interac-
tions give rise to infinite parallel chains of molecules
(a)
(b)
C12
C12
C9
C9
C10
C10
C8
C8
C11
C11
C7
C7
C6
C6
C14
S1
C14A
C14B
S1
O6
O6
O5
O7
C3
O5
O7
C3
13B
C13
C
Cl1
Cl1
C4
C4
C13A
C5
C5
C15
O1
C2
O2
C2
O1
O2
Fig. 2. Structure of the molecules of (a) 3-chloro-5-ethoxy-4-(4-methylphenylsulfonyl)furan-2(5H)-one (VIa) and (b) 3-chloro-5-
isopropoxy-4-(4-methylphenylsulfonyl)furan-2(5H)-one (VId) in crystal.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 4 2014

SULFIDES, SULFONES, AND SULFOXIDES OF THE FURAN-2(5H)-ONE SERIES
525
O4
(a)
C10
C9
C11
C8
O3
6, 22–24], there is no general procedure ensuring
formation of sulfoxides without overoxidation to
sulfone and undesirable side reactions. Analysis of
different available procedures showed that selective
synthesis of sulfoxides from sulfides requires thorough
selection of reaction conditions in each particular case
and strict adherence to these conditions, including the
nature of oxidant and solvent, reactant ratio, tempera-
ture, reaction time, addition of other compounds, etc.
Furthermore, the substrate structure is very important.
This was demonstrated by us in the oxidation of
sulfides containing RS substituent in position 4 or 5 of
the furan ring.
C6
C7
S1
C5
C12
Cl2
C4
C3
O1
C2
Cl1
(b)
O2
O3
O4
With a view to develop a selective method for the
synthesis of R-sulfinyl-substituted furan-2(5H)-one
derivatives, we studied oxidation of sulfides IIa and
IVa with different oxidants, namely with hydrogen
peroxide, m-chloroperoxybenzoic acid, Oxone, sodium
periodate, and tert-butyl hydroperoxide. The oxidation
of IIa with an equimolar amount of 33% hydrogen
peroxide in acetic acid gave a mixture of sulfone Va
and sulfoxide VIIIa. The use of such oxidants as
sodium periodate in aqueous alcohol and Oxone in
aqueous acetone in the oxidation of sulfides IIa–IIf is
limited due to poor solubility of the substrates in
aqueous–organic media at reduced or room tempera-
ture. The solubility problem can be solved by raising
the temperature, but in this case a mixture of IIa, Va,
and VIIIa was obtained.
Fig. 3. (a) Molecular structure and (b) a fragment of crystal
packing of sulfone VIIa. Analogous patterns were observed
for sulfones VIIb and VIIc.
1
In the H NMR spectra of VIIIa–VIIId in acetone-d6,
the positions of 5-H signals from different diastereo-
isomers were very similar (Δδ = 0.01–0.04 ppm),
while the difference in the chemical shifts of 5-H
in sulfoxide VIIIe was appreciably larger (Δδ =
0.26 ppm). Diastereotopic methylene protons of one
diastereoisomer of benzylsulfinyl derivative VIIIe
1
resonated in the H NMR spectrum as an AB quadru-
plet (ΔδAB = 0.09 ppm), while those of the second dia-
stereoisomer gave rise to a singlet (ΔδAB = 0.0 ppm).
Experiments with m-chloroperoxybenzoic acid
showed that the best results (with respect to the yield
of sulfoxide VIIIa and side formation of sulfone Va)
were achieved by stirring a mixture of sulfide IIa and
m-chloroperoxybenzoic acid (1.2 equiv) in diethyl
ether at –12°C (3 h). Increase of the reaction time and
temperature led to overoxidation to sulfone Va.
Electrochemical oxidation of compound IIa afforded
only 16% of sulfoxide VIIIa.
The IR spectra of VIIIa–VIIIe contained absorp-
tion bands due to stretching vibrations of the endo-
cyclic C=C bond and hydroxy and carbonyl groups,
and a strong narrow peak at 1043–1052 cm–1, which is
typical of stretching vibrations of sulfinyl group [26].
The OH stretching vibration band in the spectra of
VIII was located at lower frequencies as compared to
the corresponding band in the spectra of sulfones V
(3146–3260 and 3363–3473 cm–1, respectively). This
difference may be attributed to the formation of
a stronger intermolecular hydrogen bond between the
OH hydrogen atom and oxygen atom of the sulfinyl
group, which was confirmed by the X-ray diffraction
data for compounds VIIIa and VIIIc.
Using m-chloroperoxybenzoic acid as oxidant,
sulfides IIa–IIe were converted into the corresponding
sulfoxides VIIIa–VIIIe (Scheme 1). According to the
1H NMR spectra of the reaction mixtures, sulfoxides
VIIIa–VIIIe were formed as two diastereoisomers at
a ratio of 1:1. By recrystallization and (in some cases)
by column chromatography we succeeded in obtaining
samples slightly enriched in one stereoisomer. Some
signals in the 1H and 13C NMR spectra of VIIIa–VIIIe
were doubled due to the presence of diastereoisomers,
and their ratio was determined from the intensities of
two singlets due to 5-H in the region δ 6.38–6.64 ppm.
Crystals of sulfoxides VIIIa and VIIIc have similar
structures. The conformation of their molecules
(Fig. 4a) is analogous to the conformation of struc-
turally related sulfones Va–Vc [27]. Sulfoxides VIIIa
and VIIIc crystallize in P21 chiral space group but are
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LATYPOVA et al.
526
Table 1. Parameters of hydrogen bonds in the crystal structure of sulfoxides VIIIa and VIIIc
Compound no.
Hydrogen bond
O5–H5, Å
H5···O6′, Å
O5···O6′, Å
∠O5H5O6′, deg
VIIIa
O5A–H5A···O6B
O5B–H5B···O6A
O5A–H5A···O6B
O5B–H5B···O6A
00.84(3)
0.9(1)
01.89(4)
2.1(1)
02.673(7)
02.697(7)
2.65(2)
155(3)0
130(11)
148(13)
152(8)0
VIIIc
0.8(1)
1.9(2)
0.9(1)
1.9(1)
2.67(2)
represented by two independent molecules A and B
that constitute an enantiomer pair (molecules A and B
have opposite configurations of both chiral centers);
therefore, spontaneous resolution of enantiomers does
not occur. Enantiomeric molecules of sulfoxides VIIIa
and VIIIc are linked in pairs to form H-bonded dimers
(Fig. 4b); the parameters of the S1=O6 ···H5–O5 hy-
drogen bonds indicate stability of the dimers (Table 1).
The dimers are linked through so-called halogen bonds
C=O···Cl to produce infinite zigzag chains along the b
axis. Here, molecule B with the R-configured sulfur
atom donates the carbonyl oxygen atom (lone electron
pair donor), and molecule A (S configuration of the
sulfur atom) provides the chlorine atom (electron pair
acceptor).
acetone resulted in the formation of a complex mixture
of products (Scheme 2) among which we identified by
1H NMR and GC/MS unreacted initial compound IVa,
sulfoxide IX, and sulfone VIIa. In addition, muco-
chloric acid (I), disulfide X, and p-toluenesulfonic acid
(XI) were detected, which were formed via cleavage of
the C5–S bond in IVa. When m-chloroperoxybenzoic
acid was used as oxidant, the major components were
compounds IVa and VIIa, whereas only traces of sulf-
oxide IX and furanone I were present. The oxidation
with silica-supported tert-butyl hydroperoxide was
almost inefficient. As with 4-R-sulfanyl derivatives,
sodium periodate in MeCN–H2O or MeOH–H2O
cannot be used as oxidant because of poor solubility of
sulfide IVa in aqueous–organic media.
We also performed a series of experiments on
oxidation of 5-(p-tolylsulfanyl) derivative IVa with
different oxidants, the reaction conditions being varied
over a wide range. The oxidation of IVa with an equi-
molar amount of hydrogen peroxide in acetic acid or
The oxidation of IVa with an equimolar amount of
another inorganic oxidant, Oxone, in aqueous acetone
gave sulfoxide IX in the largest amount, as compared
to other experiments, but the reaction mixture also
contained furanones IVa and I and traces of sulfone
(a)
(b)
C12
C9
A
C10
C11
C8
C7
Cl1
A
O2
a
C6
B
O6
S1
O5
B
B
Cl1
C4
C3
A
C5
O1
O2
C2
b
0
Fig. 4. (a) Structure of the molecule of 3-chloro-5-hydroxy-4-(4-methylphenylsulfinyl)furan-2(5H)-one (VIIIa) in crystal according
to the X-ray diffraction data and (b) zigzag chains formed by hydrogen-bonded dimers of sulfoxide VIIIa via halogen bonds along
the b axis. Hydrogen bonds are shown with dashed lines, and C=O···Cl interactions are shown with dash–dotted lines. Analogous
pattern was observed for sulfoxide VIIIc.
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SULFIDES, SULFONES, AND SULFOXIDES OF THE FURAN-2(5H)-ONE SERIES
527
Scheme 2.
Me
Me
Me
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
[O]
+
+
S
O
S
O
S
O
HO
O
O
O
O
O
O
O
O
IVa
VIIa
IX
I
Me
S
+
+
SO3H
Me
S
Me
X
XI
VIIa. In all cases, work-up of the reaction mixture was
complicated due to similar solubilities of oxidation
products VIIa and IX in many organic solvents and
very close Rf values of compounds I, IX, and XI in
different eluent systems, so that we failed to isolate
target sulfoxide IX as pure substance by recrystalliza-
tion or column chromatography.
yses were carried out on a Shimadzu GCMS-QP2010
Ultra instrument (HP-1 MS column; carrier gas
helium, flow rate 5 mL/min, split ratio 100; injector
temperature 250°C, oven temperature programming
from 80 to 300°C; electron impact, 70 eV). The X-ray
diffraction data were obtained on a Bruker SMART
Apex II diffractometer (λMoKα 0.71073 Å, graphite
monochromator, ω-scanning) at 293 K. The crystallo-
graphic data and structure refinement parameters are
collected in Table 2. Absorption by the crystals was
taken into account semiempirically using SADABS
program [30]. The structures were solved by the direct
method using SHELXS program, and the positions of
non-hydrogen atoms were refined first in isotropic and
then in anisotropic approximation using SHELXL-97
[31]. Single crystals of VIIIa and VIIIc were very
small needles; the crystal structure of VIIIa was
refined as a twin crystal with the twinning matrix
(1 0 0 0 –1 0 0 0 –1 n = 2); the structure of VIIIc was
refined as a combined (general and racemic) twin with
analogous matrix (n = –4), which enabled acceptable
results to be obtained. Hydrogen atoms attached to
carbons were placed into calculated positions which
were refined according to the riding model. Hydrogen
atoms in the hydroxy groups were localized from
the difference Fourier map, and their positions were
refined in isotropic approximation at the final step.
All calculations were carried out using WinGX [32]
and APEX2 [33]. The molecular structures were
plotted with the aid of PLATON [34]. The X-ray dif-
fraction data were deposited to the Cambridge
Crystallographic Data Centre; the corresponding entry
numbers are given in Table 2.
Preliminary tests of chlorine- and sulfur-containing
furan-2(5H)-ones for antibacterial activity showed that
some compounds at a concentration of 1 μg/mL con-
siderably inhibited the growth of Gram-positive bac-
teria [28]. Search for new antimicrobial agents and
inhibitors of bacterial biofilm formation among the
synthesized sulfides, sulfones, and sulfoxides of the
furan-2(5H)-one series will be continued.
EXPERIMENTAL
Commercial 3,4-dichloro-5-hydroxyfuran-2(5H)-
one (I) was recrystallized from water, mp 127°C [29].
4-Arylsulfanyl-3-chloro-5-hydroxyfuran-2(5H)-ones
IIa–IIc, IIf, and IVa–IVc were synthesized according
to the procedures described in [18].
The IR spectra of solid compounds were recorded
on a Bruker Tensor-27 spectrometer from samples
dispersed in Nujol and placed between KBr plates. The
1H and 13C NMR spectra were measured on Varian
1
Unity-300 (299.94 MHz for H) and Bruker Avance
1
III 400 spectrometers (400.17 MHz for H and
100.62 MHz for 13C) at 25°C; the chemical shifts were
determined relative to the residual proton signals of the
deuterated solvent. Silufol UV-254 plates were used
for thin-layer chromatography (eluent acetone–ben-
zene or acetone–toluene). Column chromatography
was performed on Silicagel 60 (Fluka, 70–230 mesh,
0.063–0.200 mm). The melting points were measured
on an OptiMelt Stanford Research Systems MPA100
automated melting point apparatus and were not cor-
rected. Gas chromatographic/mass spectrometric anal-
3-Chloro-4-(3,5-di-tert-butyl-4-hydroxyphenyl-
sulfanyl)-5-hydroxyfuran-2(5H)-one (IId). A solu-
tion of 4.24 g (17.8 mmol) of 2,6-di-tert-butyl-4-sul-
fanylphenol in 15 mL of diethyl ether was added
dropwise under vigorous stirring to a solution of 3 g
(17.8 mmol) of mucochloric acid (I) in 25 mL of di-
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LATYPOVA et al.
528
Table 2. Crystallographic data and parameters of X-ray diffraction experiments for compounds VIa, VId, VIIa–VIIc,
VIIIa, and VIIIc
Parameter
Formula
VIa
C13H13ClO5S C14H15ClO5S C11H8Cl2O4S C10H5Cl3O4S C10H5BrCl2O4S C11H9ClO4S C10H6BrClO4S
316.74 330.77 307.13 327.55 372.01 272.69 337.57
Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic
VId
VIIa
VIIb
VIIc
VIIIa
VIIIc
Molecular weight
Crystal system
Space group
a, Å
P21/c
P21/n
P21/c
10.447(3)
08.095(3)
15.660(5)
107.03(3)
1266.3(7)
4 (1)
P21/n
07.894(1)
15.477(3)
10.344(2)
91.406(2)
1263.4(4)
4 (1)
P21/n
07.8645(9)
15.851(2)
10.425(1)
91.618(1)
1299.0(3)
4 (1)
P21
P21
08.919(2)
11.167(2)
15.379(3)
10.281(3)
08.275(2)
18.644(5)
04.964(2)
23.23(1)0
10.277(5)
90.248(5)
1184.8(9)
4 (2)
04.902(4)
22.74(2)0
10.603(8)
90.130(10)
1182(2)
4 (2)
b, Å
c, Å
β, deg
V, Å3
105.167(2) 94.522(4)
1478.5(5)
4 (1)
1581.2(8)
4 (1)
Z (Z′)
d
calc, g/cm3
1.423
1.389
1.611
1.722
1.902
1.529
01.897
μ, cm–1
4.140
3.900
6.790
8.910
37.37
4.970
38.790
Scan range (θ, deg)
2.28–27.99 2.19–26.00 2.72–26.28 2.37–27.00
2.34–25.99
1.98–26.00 2.12–25.99
Total number of
reflections measured
(Rint)
16451
(0.023)
11465
(0.04)
2638
(0.016)
10019
(0.036)
9689
(0.023)
8633
(0.077)
11167
(0.17)
Number of reflections
2498
2050
1693
2192
2066
2945
2663
with I ≥ 2σ(I)
Number of variables
R1 [I ≥ 2σ(I)]
2030
0.0466
0.1343
968537
1930
0.0497
0.1328
968539
1630
0.047
1640
0.034
1630
0.031
3180
0.0609
0.1450
968540
3160
0.1149
0.1920
968541
wR2 (all reflections)
CCDC entry no.
0.179
0.092
0.084
968542
968543
968544
ethyl ether, and a solution of 2.48 mL (17.8 mmol) of
triethylamine in 15 mL of diethyl ether was then
added. The mixture slightly warmed up, and triethyl-
amine hydrochloride separated as white solid. The
mixture was stirred for 1 h at room temperature, the
precipitate was filtered off and washed with diethyl
ether, the filtrate was evaporated under reduced pres-
sure to dryness, and the yellow oily residue was recrys-
tallized from benzene. Yield 4.75 g (72%), colorless
powder, mp 180–187°C (decomp.), Rf 0.38 (acetone–
toluene, 1:6). IR spectrum, ν, cm−1: 3615 (4′-OH),
2.78 mL (23.7 mmol) of phenylmethanethiol using
3.30 mL (23.7 mmol) of triethylamine. Yield 4.20 g
(69%), colorless crystals, mp 122°C (from benzene),
Rf 0.46 (acetone–toluene, 1:6). IR spectrum, ν, cm−1:
3150–3500 br (OH), 1753 (C=O), 1582, 1493
1
(C=Carom). H NMR spectrum (300 MHz), δ, ppm: in
CDCl3: 4.40 m and 4.47 m (1H each, SCH2, AB
quartet, 2JAB = 13.2 Hz), 6.02 s (1H, 5-H), 7.29–7.43 m
(5H, Harom); in acetone-d6: 4.57 m and 4.59 m (1H
2
each, SCH2, AB quartet, JAB = 12.7 Hz), 6.38 d (1H,
3
5-H, JHH = 7.0 Hz), 7.26–7.53 m (5H, Harom). Found,
1
3445 (5-OH), 1750 (C=O), 1589 (C=Carom). H NMR
%: C 51.35; H 3.48; Cl 13.97; S 12.72. C11H9ClO3S.
Calculated, %: C 51.47; H 3.53; Cl 13.81; S 12.49.
spectrum (acetone-d6, 300 MHz), δ, ppm: 1.44 s (18H,
3
CH3), 5.93 d (1H, 5-H, JHH = 8.5 Hz), 6.60 s (1H,
3-Chloro-5-ethoxy-4-(4-methylphenylsulfanyl)-
furan-2(5H)-one (IIIa). Concentrated sulfuric acid,
0.025 mL (0.46 mmol), was added to a solution of
1.18 g (4.6 mmol) of sulfide IIa and 27 mL (0.46 mol)
of ethanol in 30 mL of benzene, and the mixture was
heated under reflux until initial sulfide IIa disappeared
completely (70 h, TLC). The mixture was cooled and
evaporated under reduced pressure to dryness, and the
3
4′-OH), 7.00 d (1H, 5-OH, JHH = 8.5 Hz), 7.49 s
(2H, Harom). Found, %: C 58.01; H 6.16; Cl 9.72;
S 8.79. C18H23ClO4S. Calculated, %: C 58.29; H 6.25;
Cl 9.56; S 8.65.
4-Benzylsulfanyl-3-chloro-5-hydroxyfuran-
2(5H)-one (IIe) was synthesized in a similar way from
4.00 g (23.7 mmol) of mucochloric acid (I) and
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SULFIDES, SULFONES, AND SULFOXIDES OF THE FURAN-2(5H)-ONE SERIES
529
yellow oily residue was treated with 20 mL of hexane
and kept at –7°C for crystallization. Yield 0.93 g
(71%), colorless crystals, mp 43–44°C, Rf 0.65
(acetone–benzene, 1:6). IR spectrum, ν, cm–1: 1767
1782, 1769 (C=O), 1595 (C=Carom). 1H NMR spectrum
(300 MHz), δ, ppm: in (CDCl3: 1.32 t (3H, CH3, X part
3
3
of ABX3, JAX = JBX = 7.1 Hz), 3.70 m (1H, OCH2, B
2
3
part of ABX3, JAB = –9.2, JBX = 7.1 Hz), 3.88 m (1H,
2
3
1
OCH2, A part of ABX3, JAB = –9.2, JAX = 7.1 Hz),
4.36 m and 4.40 m (1H each, CH2S, AB quartet, 2JAB
13.2 Hz), 5.77 s (1H, 5-H), 7.29–7.45 m (5H, Har3om); in
(C=O), 1596, 1493 (C=Carom). H NMR spectrum
=
(CDCl3, 300 MHz), δ, ppm: 1.04 t (3H, CH3, X part of
3
3
ABX3, JAX = JBX = 7.1 Hz), 2.40 s (3H, 4′-CH3),
3.16 m (1H, OCH2, A part of ABX3, 2JAB = –9.2, 3JAX
=
=
acetone-d6: 1.30 t (3H, CH3, X part of ABX3, JAX
=
3JBX = 7.1 Hz), 3.87 m (1H, OCH2, B part of ABX3,
2
7.1 Hz), 3.63 m (1H, OCH2, B part of ABX3, JAB
2JAB = –9.5, JBX = 7.1 Hz), 3.92 m (1H, OCH2, A part
3
3
–9.2, JBX = 7.1 Hz), 5.46 s (1H, 5-H), 7.23 m and
2
3
3
5
of ABX3, JAB = –9.5, JAX = 7.1 Hz), 4.55 m and
4.57 m (1H each, CH2S, AB quartet, JAB = 12.5 Hz),
7.48 m (4H, Harom, AA′BB′, JAB + JAB′ = 8.0 Hz).
Found, %: C 54.72; H 4.63; Cl 12.45; S 11.22.
C13H13ClO3S. Calculated, %: C 54.83; H 4.60;
Cl 12.45; S 11.26.
2
6.27 s (1H, 5-H), 7.22–7.57 m (5H, Harom); in ben-
zene-d6: 0.84 t (3H, CH3, X part of ABX3, 3JAX = 3JBX
=
=
2
7.1 Hz), 3.06 m (1H, OCH2, B part of ABX3, JAB
Compounds IIIb–IIId were synthesized in a simi-
lar way.
3
–9.3, JBX = 7.1 Hz), 3.28 m (1H, OCH2, A part of
2
3
ABX3, JAB = –9.3, JAX = 7.1 Hz), 3.77 s (2H, SCH2),
5.14 s (1H, 5-H), 6.94–7.12 m (5H, Harom). 13C–{1H}
NMR spectrum (CDCl3, 100 MHz), δC, ppm: 15.00
(CH3), 34.67 (SCH2), 64.76 (OCH2), 100.27 (C5),
117.56 (C3); 128.31, 128.69, 129.08, 134.99 (Carom);
154.81 (C4), 164.36 (C2). Found, %: C 54.65; H 4.58;
Cl 12.57; S 11.02. C13H13ClO3S. Calculated, %:
C 54.83; H 4.60; Cl 12.45; S 11.26.
4-(4-Bromophenylsulfanyl)-3-chloro-5-ethoxy-
furan-2(5H)-one (IIIb) was synthesized from 4.0 g
(12.4 mmol) of furanone IIc and 20 mL (0.34 mol) of
ethanol using 0.066 mL (1.24 mmol) of concentrated
sulfuric acid. Yield 3.62 g (83%), colorless crystals,
mp 63–65°C (from petroleum ether), Rf 0.65 (acetone–
toluene, 1:6). IR spectrum, ν, cm–1: 1765 (C=O), 1587
1
(C=Carom), 1567 (C3=C4). H NMR spectrum (ace-
3-Chloro-5-isopropoxy-4-(4-methylphenylsul-
fanyl)furan-2(5H)-one (IIId) was synthesized from
1.18 g (4.6 mmol) of sulfide IIa and 35 mL (0.46 mol)
of propan-2-ol using 0.025 mL (0.46 mmol) of concd.
H2SO4. The yellow oily residue was crystallized from
hexane. Yield 1.18 g (86%), colorless crystals, mp 65–
66°C, Rf 0.40 (acetone–toluene, 1:6). IR spectrum, ν,
cm–1: 1764 (C=O), 1628 (C3=C4), 1600 (C=Carom).
1H NMR spectrum (CDCl3, 400 MHz), δ, ppm: 0.73 d
tone-d6, 300 MHz), δ, ppm: 1.00 t (3H, CH3, X part of
ABX3, 3JAX = 3JBX = 7.1 Hz), 3.28 m (1H, OCH2, A part
2
3
of ABX3, JAB = –9.4, JAX = 7.1 Hz), 3.63 m (1H,
2
3
OCH2, B part of ABX3, JAB = –9.4, JBX = 7.1 Hz),
5.89 s (1H, 5-H), 7.69 m and 7.73 m (4H, Harom
,
3
3
4
4
5
AA′BB′, JAB = JA′B′ = 7.8, JAA′ = JBB′ = 2.1, JAB′
=
5JA′B = 1.0 Hz). 13C–{1H} NMR spectrum (acetone-d6,
100 MHz), δC, ppm: 15.87 (CH3), 67.24 (OCH2),
102.51 (C5), 118.73 (C3); 126.52, 126.54, 134.48,
138.87 (Carom); 156.42 (C4), 165.37 (C2). 13C NMR
spectrum (acetone-d6, 100 MHz), δC, ppm: 15.86 q.t
(CH3, 1JCH = 126.81, 2JCH = 2.4 Hz), 67.24 d.d.q (CH2,
3
3
(3H, CH3, JHH = 6.2 Hz), 1.10 d (3H, CH3, JHH
=
6.2 Hz), 2.36 s (3H, CH3C6H4), 3.53 sept (1H, CH,
3JHH = 6.2 Hz), 5.60 s (1H, 5-H), 7.21 m and 7.44 m
3
5
(4H, Harom, AA′BB′, JAB + JAB′ = 8.2 Hz). 13C NMR
2
3
1JCH = 144.3, JCH = JCH = 4.6 Hz), 102.50 d.t (C5,
3
3
1JCH = 179.4, JCH = 2.9 Hz), 118.69 d (C3, JCH
=
spectrum (CDCl3, 100 MHz), δC, ppm: 20.90 q.q.d and
1
2
3
1.9 Hz), 126.52 t (Ci, Cp, JCH = 8.9 Hz), 134.47 d.d
3
22.77 q.q.d (CH3, JCH = 126.5, JCH = 0.9, JCH
=
=
=
1
3
1
3
4.8 Hz), 21.16 q.t (4′-CH3, JCH = 127.1, JCH
(Carom, JCH = 169.8, JCH = 5.2 Hz), 138.87 d.d (Carom
,
1
3
3
1JCH = 168.2, JCH = 5.8 Hz), 156.43 s (C4), 165.37 d
4.4 Hz), 73.85 d.d.sept (OCH, JCH = 143.8, JCH
4.3 Hz), 99.45 d.d (C5, JCH = 176.4, JCH = 3.6 Hz),
1
3
3
(C2, JCH = 2.9 Hz). Found, %: C 41.49; H 2.89;
116.91 d (C3, JCH = 2.2 Hz), 121.86 t (Ci, JCH
=
3
3
Br 23.01; Cl 10.43; S 9.38. C12H10BrClO3S. Calculat-
ed, %: C 41.22; H 2.88; Br 22.85; Cl 10.14; S 9.17.
9.7 Hz), 130.22 d.m (Cm, 1JCH = 161.4 Hz), 135.22 d.m
(Co, JCH = 158.5 Hz), 140.91 q.t (Cp, JCH = JCH
=
1
2
3
4-Benzylsulfanyl-3-chloro-5-ethoxyfuran-2(5H)-
one (IIIc) was synthesized from 0.72 g (2.8 mmol) of
sulfide IIe and 20 mL (0.34 mol) of ethanol using
0.015 mL (0.28 mmol) of concd. H2SO4. The solid
residue was recrystallized from hexane–benzene (3:1).
Yield 0.57 g (71%), colorless crystals, mp 81–83°C,
Rf 0.55 (acetone–toluene, 1:6). IR spectrum, ν, cm–1:
6.3 Hz), 155.80 s (C4), 163.64 d (C2, JCH = 3.3 Hz).
Found, %: C 56.24; H 5.09; Cl 11.79; S 10.70.
C14H15ClO3S. Calculated, %: C 56.28; H 5.06;
Cl 11.87; S 10.73.
3
3-Chloro-5-hydroxy-4-(4-methylphenylsulfonyl)-
furan-2(5H)-one (Va). Sulfide IIa, 0.60 g (2.3 mmol),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 4 2014

LATYPOVA et al.
530
3
was dissolved in 20 mL of glacial acetic acid, 0.57 mL
(5.8 mmol) of 33% hydrogen peroxide was added
under stirring, and the mixture was stirred for 4 days at
room temperature (TLC). When the reaction was com-
plete, the mixture was diluted with 30 mL of water,
and the precipitate was filtered off, dried, and recrys-
tallized from appropriate solvent. Yield 0.50 g (74%),
colorless crystals, mp 155°C (from benzene), Rf 0.68
(acetone–benzene, 1:6). IR spectrum, ν, cm–1: 3363
(OH), 1801 (C=O), 1623 (C3=C4), 1594 (C=Carom),
6.59 d (1H, 5-H, JHH = 8.4 Hz), 7.56 d (1H, OH,
3JHH = 8.4 Hz), 7.94 m and 8.03 m (4H, Harom, AA′BB′,
3JAB = JA′B′ = 8.4, JAA′ = JBB′ = 2.2, JAB′ = JA′B
=
3
4
4
5
5
0.4 Hz). 13C–{1H} NMR spectrum (acetone-d6,
100 MHz), δC, ppm: 98.69 (C5); 132.06, 134.16,
140.05 (C3, Ci, Cp); 132.53 and 134.83 (Co, Cm),
153.40 (C4), 164.69 (C2). Found, %: C 34.23; H 1.40;
Br 22.91; Cl 10.32; S 9.27. C10H6BrClO5S. Calculated,
%: C 33.97; H 1.71; Br 22.60; Cl 10.03; S 9.07.
3-Chloro-4-(3,5-di-tert-butyl-4-hydroxyphenyl-
sulfonyl)-5-hydroxyfuran-2(5H)-one (Vd) was syn-
thesized by oxidation of 0.60 g (1.62 mmol) of sulfide
IId with 0.50 mL (5.15 mmol) of 33% H2O2. Yield
0.45 g (69%), colorless powder, mp 221–223°C (from
benzene), Rf 0.44 (acetone–benzene, 1:6). IR spec-
trum, ν, cm–1: 3603 (4′-OH), 3473 (5-OH), 1805
(C=O), 1622 (C3=C4), 1576 (C=Carom), 1322 (SO2,
1
1334 (SO2, asym.), 1144 (SO2, sym.). H NMR spec-
trum, δ, ppm: in acetone-d6 (300 MHz): 2.49 s (3H,
3
CH3), 6.57 d (1H, 5-H, JHH = 8.2 Hz), 7.58 d (1H,
3
OH, JHH3 = 8.2 Hz), 7.54 m and 7.98 m (4H, Harom
,
5
AA′BB′, JAB + JAB′ = 8.3 Hz); in CDCl3 (400 MHz):
2.48 s (3H, CH3), 4.46 br.s (1H, OH), 6.45 s (1H, 5-H),
3
5
7.42 m and 7.95 m (4H, Harom, AA′BB′, JAB + JAB′
=
8.3 Hz). Found, %: C 45.84; H 2.83; Cl 12.43; S 11.26.
C11H9O5ClS. Calculated, %: C 45.76; H 3.14;
Cl 12.28; S 11.11.
1
asym.), 1140 (SO2, sym.). H NMR spectrum (ace-
tone-d6, 400 MHz), δ, ppm: 1.47 s (18H, CH3), 6.56 d
(1H, 5-H, JHH = 8.2 Hz), 7.28 s (1H, 4′-OH), 7.55 d
3
3
Compounds Vb–Vf, VIa–VId, VIIa–VIIc, and
VIIIc–VIIIe were synthesized in a similar way.
(1H, 5-OH, JHH = 8.2 Hz), 7.95 s (2H, Harom).
13C–{1H} NMR spectrum (acetone-d6, 100 MHz), δC,
ppm: 31.05 (CH3), 36.46 [C(CH3)3], 98.83 (C5),
128.43 (Co); 130.73, 131.97, 139.97 (C3, Ci, Cm);
155.27 and 162.21 (Cp, C4), 165.10 (C2). Found, %:
C 53.31; H 5.83; Cl 8.92; S 8.13. C18H23ClO6S. Cal-
culated, %: C 53.66; H 5.75; Cl 8.80; S 7.96.
3-Chloro-4-(4-chlorophenylsulfonyl)-5-hydroxy-
furan-2(5H)-one (Vb) was synthesized by oxidation
of 0.57 g (2.1 mmol) of sulfide IIb with 1.00 mL
(10.9 mmol) of 33% H2O2. Yield 0.53 g (83%), color-
less crystals, mp 139–141°C (from benzene), Rf 0.36
(acetone–toluene, 1:6). IR spectrum, ν, cm–1: 3395
(OH), 1801 (C=O), 1625 (C3=C4), 1575 (C=Carom),
4-Benzylsulfonyl-3-chloro-5-hydroxyfuran-
2(5H)-one (Ve) was synthesized by oxidation of 0.90 g
(3.51 mmol) of sulfide IIe with 1.62 mL (16.7 mmol)
of 33% H2O2. Yield 0.75 g (74%), colorless crystals,
mp 167–169°C (from benzene), Rf 0.42 (acetone–
toluene, 1:6). IR spectrum, ν, cm–1: 3405 (OH), 1800
(C=O), 1629 (C3=C4), 1495 (C=Carom), 1310 (SO2,
asym.), 1156 (SO2, sym.). H NMR spectrum (CDCl3,
300 MHz), δ, ppm: 4.47 m and 4.56 m (1H each, SCH,
AB quartet, JAB = 14.1 Hz), 6.38 br.s (1H, 5-H),
1
1338 (SO2, asym.), 1147 (SO2, sym.). H NMR spec-
trum, δ, ppm: in CDCl3 (300 MHz): 6.48 br.s (1H,
3
5-H), 7.60 m and 8.01 m (4H, Harom, AA′BB′, JAB
+
5JAB′ = 8.7 Hz); in acetone-d6 (400 MHz): 6.59 d (1H,
3
3
5-H, JHH = 8.6 Hz), 7.57 d (1H, OH, JHH = 8.6 Hz),
3
3
1
7.78 m and 8.11 m (4H, Harom, AA′BB′, JAB = JA′B′
=
8.5, 4JAA′ = 4JBB′ = 2.3, 5JAB′ = 5JA′B = 0.3 Hz). 13C–{1H}
NMR spectrum (acetone-d6, 100 MHz), δC, ppm: 98.71
(C5), 131.81 and 132.58 (Co, Cm); 134.14, 139.59,
143.29 (C3, Ci, Cp); 153.47 (C4), 164.71 (C2). Found,
%: C 38.65; H 1.78; Cl 23.06; S 10.45. C10H6Cl2O5S.
Calculated, %: C 38.85; H 1.96; Cl 22.94; S 10.37.
2
7.41 br.s (5H, Harom). Found, %: C 45.41; H 3.33;
Cl 12.36; S 11.23. C11H9ClO5S. Calculated, %:
C 45.76; H 3.14; Cl 12.28; S 11.11.
3-Chloro-5-hydroxy-4-(naphthalen-1-ylsulfonyl)-
furan-2(5H)-one (Vf) was synthesized by oxidation of
0.44 g (1.50 mmol) of sulfide IIf with 0.84 mL
(9.18 mmol) of 33% H2O2. Yield 0.28 g (58%), yellow
powder, mp 183–186°C (from benzene), Rf 0.46
(acetone–benzene, 1:6). IR spectrum, ν, cm–1: 3350
(OH), 1796 (C=O), 1621 (C3=C4), 1591, 1507
(C=Carom), 1318 (SO2, asym.), 1154 (SO2, sym.).
1H NMR spectrum (acetone-d6, 300 MHz), δ, ppm:
6.56 br.s (1H, 5-H), 7.41 br.s (1H, OH), 7.66–8.83 m
4-(4-Bromophenylsulfonyl)-3-chloro-5-hydroxy-
furan-2(5H)-one (Vc) was synthesized by oxidation of
1.50 g (4.66 mmol) of sulfide IIc with 1.75 mL
(18 mmol) of 33% H2O2. Yield 1.27 g (77%), colorless
crystals, mp 141–142°C (from benzene), Rf 0.46
(acetone–benzene, 1:6). IR spectrum, ν, cm–1: 3394
(OH), 1798 (C=O), 1623 (C3=C4), 1569, 1507
(C=Carom), 1333 (SO2, asym.), 1142 (SO2, sym.).
1H NMR spectrum (acetone-d6, 400 MHz), δ, ppm:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 4 2014

SULFIDES, SULFONES, AND SULFOXIDES OF THE FURAN-2(5H)-ONE SERIES
531
(7H, Harom). Found, %: C 51.56; H 2.92; Cl 10.84;
S 10.05. C14H9ClO5S. Calculated, %: C 51.78; H 2.79;
Cl 10.92; S 9.87.
(acetone-d6, 100 MHz), δC, ppm: 16.10 (CH3), 69.05
(OCH2), 103.19 (C5); 132.17, 132.53, 134.83, 139.86
(C3, Carom); 151.81 (C4), 164.53 (C2). Found, %:
C 37.71; H 2.51; Br 20.95; Cl 9.14; S 8.37.
C12H10BrClO5S. Calculated, %: C 37.77; H 2.64;
Br 20.94; Cl 9.29; S 8.40.
3-Chloro-5-ethoxy-4-(4-methylphenylsulfonyl)-
furan-2(5H)-one (VIa) was synthesized by oxidation
of 0.39 g (1.36 mmol) of furanone IIIa with 0.44 mL
(4.80 mmol) of 33% H2O2. Yield 0.26 g (61%),
colorless crystals, mp 63°C (from hexane), Rf 0.48
(acetone–toluene, 1:6). IR spectrum, ν, cm–1: 1800
(C=O), 1625 (C3=C4), 1593 (C=Carom), 1343 (SO2,
4-Benzylsulfonyl-3-chloro-5-ethoxyfuran-2(5H)-
one (VIc) was synthesized by oxidation of 0.34 g
(1.21 mmol) of furanone IIIc with 0.38 mL (3.6 mmol)
of 33% H2O2. Yield 0.19 g (50%), colorless crystals,
mp 79–81°C (from hexane), Rf 0.52 (acetone–toluene,
1:6). IR spectrum, ν, cm–1: 1808 (C=O), 1623 (C3=C4),
1497 (C=Carom), 1330 (SO2, asym.), 1153 (SO2, sym.).
1H NMR spectrum (300 MHz), δ, ppm: in CDCl3:
1.41 t (3H, CH3, X part of ABX3, 3JAX = 3JBX = 7.1 Hz),
1
asym.), 1159 (SO2, sym.). H NMR spectrum
(300 MHz), δ, ppm: in CDCl3: 1.28 t (3H, CH3, X part
3
3
of ABX3, JAX = JBX = 7.1 Hz), 2.48 s (3H, CH3),
3.87 m (1H, OCH2, B part of ABX3, 2JAB = –9.4, 3JBX
=
=
2
7.1 Hz), 3.95 m (1H, OCH2, A part of ABX3, JAB
3
3.98 m (1H, OCH2, B part of ABX3, 2JAB = –9.5, 3JBX
=
=
–9.4, JAX = 7.1 Hz), 6.15 s (1H, 5-H), 7.40 m (2H,
3
3
4
2
m-H, AA′ part of AA′BB′X3, JAB = JA′B′ = 8.0, JAA′
=
7.1 Hz), 4.12 m (1H, OCH2, A part of ABX3, JAB
5
5
5
5
3
1.8, JAB′ = JA′B = 0.2, JAX = JA′X = 0.0 Hz), 7.92 m
–9.5, JAX = 7.1 Hz), 4.42 m and 4.49 m (1H each,
3
3
2
(2H, o-H, BB′ part of AA′BB′X3, JAB = JA′B′ = 8.0,
CH2, AB quartet, JAB = 14.0 Hz), 6.08 s (1H, 5-H),
4JBB′ = 1.8, 5JBA′ = 5JB′A = 0.2, 4JBX <0.5, 4JB′X <0.5 Hz);
7.33–7.49 m (5H, Harom); in acetone-d6: 1.38 t (3H,
3
3
3
in acetone-d6: 1.24 t (3H, CH3, X part of ABX3, JAX
=
CH3, X part of ABX3, JAX = JBX = 7.1 Hz), 4.04 m
3JBX = 7.1 Hz), 2.49 s (3H, CH3), 3.89 q (2H, OCH2,
(1H, OCH2, B part of ABX3, 2JAB = –9.7, 3JBX = 7.1 Hz),
3JHH = 7.1 Hz), 6.36 s (1H, 5-H), 7.56 m and 7.97 m
4.11 m (1H, OCH2, A part of ABX3, 2JAB = –9.7, 3JAX
=
3
5
(4H, Harom, AA′BB′, JAB + JAB′ = 8.3 Hz); in ben-
7.1 Hz), 4.65 m and 4.71 m (1H each, CH2, AB quartet,
3
3
2JAB = 14.0 Hz), 6.33 s (1H, 5-H), 7.36–7.54 m (5H,
zene-d6: 0.82 t (3H, CH3, JAX = 7.1, JBX = 7.0 Hz),
1.80 s (3H, CH3), 3.20 m (1H, OCH2, B part of ABX3,
Harom); in C6D6: 0.83 t (3H, CH3, X part of ABX3, 3JAX
=
2JAB = –9.4, JBX = 7.0 Hz), 3.33 m (1H, OCH2, A part
3
3JBX = 7.1 Hz), 3.19 m (1H, OCH2, B part of ABX3,
of ABX3, 2JAB = –9.4, 3JAX = 7.1 Hz), 5.46 s (1H, 5-H),
3
2JAB = –9.6, JBX = 7.1 Hz), 3.41 m (1H, OCH2, A part
3
5
6.69 m and 7.81 m (4H, Harom, AA′BB′, JAB + JAB′
=
2
3
of ABX3, JAB = –9.6, JAX = 7.1 Hz), 3.78 m and
8.3 Hz). 13C–{1H} NMR spectrum (acetone-d6,
100 MHz), δC, ppm: 15.62 (CH3CH2), 22.19 (4′-CH3),
68.41 (OCH2), 102.80 (C5), 130.32 and 131.56 (Co,
Cm); 133.24, 137.22, 148.34 (C3, Ci, Cp); 152.26 (C4),
164.24 (C2). Found, %: C 49.44; H 4.17; Cl 10.95;
S 10.27. C13H13ClO5S. Calculated, %: C 49.29; H 4.14;
Cl 11.19; S 10.12.
2
3.95 m (1H each, CH2, AB quartet, JAB = 13.9 Hz),
5.29 s (1H, 5-H), 6.84–7.11 m (5H, Harom). Found, %:
C 49.41; H 4.46; Cl 10.96; S 10.23. C13H13ClO5S.
Calculated, %: C 49.29; H 4.14; Cl 11.19; S 10.12.
3-Chloro-5-isopropoxy-4-(4-methylphenylsul-
fonyl)furan-2(5H)-one (VId) was synthesized by
oxidation of 0.60 g (2.00 mmol) of furanone IIId with
1.10 mL (12.0 mmol) of 33% H2O2. Yield 0.43 g
(65%), colorless crystals, mp 76°C (from benzene–
CCl4, 1:1), Rf 0.65 (acetone–toluene, 1:6). IR spec-
trum, ν, cm–1: 1794 (C=O), 1626 (C3=C4), 1594, 1493
(C=Carom), 1340 (SO2, asym.), 1164 (SO2, sym.).
1H NMR spectrum (CDCl3, 300 MHz), δ, ppm: 1.24 d
4-(4-Bromophenylsulfonyl)-3-chloro-5-ethoxy-
furan-2(5H)-one (VIb) was synthesized by oxidation
of 1.46 g (4.16 mmol) of furanone IIIb with 2.80 mL
(30.4 mmol) of 33% H2O2. Yield 1.00 g (63%),
colorless crystals, mp 107–108°C (from CCl4), Rf 0.65
(acetone–toluene, 1:6). IR spectrum, ν, cm–1: 1790
(C=O), 1622 (C3=C4), 1575 (C=Carom), 1344 (SO2,
3
1
and 1.33 d (3H each, CH3, JHH = 6.2 Hz), 2.46 s (3H,
asym.), 1165 (SO2, sym.). H NMR spectrum
4′-CH3), 4.16 sept (1H, CH, 3JHH = 6.2 Hz), 6.24 s (1H,
(acetone-d6, 400 MHz), δ, ppm: 1.24 t (3H, CH3,
3
3
3
5-H), 7.39 m and 7.91 m (4H, Harom, AA′BB′, JAB
+
X part of ABX3, JAX = JBX = 7.1 Hz), 3.918 m (1H,
5JAB′ = 8.2 Hz). Found, %: Cl 11.01; S 9.97.
2
2
OCH2, B part of ABX3, JAB = 2.5, JBX = 7.1 Hz),
3.922 m (1H, OCH2, A part of ABX3, 2JAB = 2.5, 3JAX
7.1 Hz), 6.40 s (1H, 5-H), 7.95 m and 8.02 m (4H,
C14H15ClO5S. Calculated, %: Cl 10.72; S 9.69.
=
3,4-Dichloro-5-(4-methylphenylsulfonyl)furan-
2(5H)-one (VIIa) was obtained by oxidation of 2.08 g
(7.57 mmol) of furanone IVa with 2.28 mL
3
3
4
4
H
arom, AA′BB′, JAB = JA′B′ = 8.4, JAA′ = JBB′ = 2.0,
5JAB′ = JA′B = 0.4 Hz). 13C–{1H} NMR spectrum
5
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 4 2014

LATYPOVA et al.
532
1
(24.88 mmol) of 33% H2O2. According to the 1H NMR
data, the reaction mixture contained sulfone VIIa,
mucochloric acid (I), and p-toluenesulfonic acid (XI)
at a ratio of 10:1:1. Compound VIIa was precipitated
with water and recrystallized from carbon tetrachlo-
ride. Yield 1.92 g (83%), colorless crystals, mp 106–
107°C, Rf 0.28 (acetone–benzene, 1:9). IR spectrum,
ν, cm–1: 1800 (C=O), 1616 (C3=C4), 1595, 1494
(C=Carom), 1340 (SO2, asym.), 1158 (SO2, sym.).
1H NMR spectrum (400 MHz), δ, ppm: in CDCl3:
2.48 s (3H, CH3), 5.69 s (1H, 5-H), 7.40 m and 7.80 m
1357 (SO2, asym.), 1166 (SO2, sym.). H NMR spec-
trum (acetone-d6, 400 MHz), δ, ppm: 6.61 s (1H, 5-H),
3
5
7.92 m and 7.98 m (4H, Harom, AA′BB′, JAB + JAB′
=
8.8 Hz). 13C–{1H} NMR spectrum (acetone-d6,
100 MHz), δC, ppm: 92.77 (C5); 126.79, 132.69,
135.46 (C3, Ci, Cp); 133.40 and 134.95 (Co, Cm),
146.44 (C4), 164.41 (C2). Found, %: C 32.41; H 1.07;
Br 21.78; Cl 18.86; S 8.75. C10H5BrCl2O4S. Calculat-
ed, %: C 32.29; H 1.35; Br 21.48; Cl 19.06; S 8.62.
3-Chloro-5-hydroxy-4-(4-methylphenylsulfinyl)-
furan-2(5H)-one (VIIIa). A solution of 0.40 g
(1.6 mmol) of sulfide IIa in 22 mL of diethyl ether was
cooled to –15°C, a cold solution of 0.32 g (1.9 mmol)
of m-chloroperoxybenzoic acid in 8 mL of diethyl
ether was added dropwise, and the mixture was stirred
for 3 h at –12°C and evaporated to dryness under
reduced pressure. The solid residue containing sulf-
oxide VIIIa and m-chlorobenzoic acid was washed on
a Schott filter with hexane–diethyl ether (3:1). The
undissolved material was recrystallized from carbon
tetrachloride–benzene (4:1) to isolate a mixture of two
diastereoisomers at a ratio of 1:1. Yield 0.27 g (64%),
colorless crystals, mp 138–142°C; published data [25]:
mp 138°C. The spectral parameters of the product
were consistent with those given in [25].
3
5
(4H, Harom, AA′BB′, JAB + JAB′ = 8.2 Hz); in ace-
tone-d6: 2.49 s (3H, CH3), 6.51 s (1H, 5-H), 7.56 m
3
5
and 7.84 m (4H, Harom, AA′BB′, JAB + JAB′ = 8.2 Hz).
13C–{1H} NMR spectrum (acetone-d6, 100 MHz), δC,
ppm: 22.69 (CH3), 92.92 (C5); 126.47, 131.65, 132.15,
133.04, 146.86, 149.24 (C3, C4, Carom); 164.56 (C2).
Found, %: C 42.95; H 2.35; Cl 22.80; S 10.46.
C11H8Cl2O4S. Calculated, %: C 43.01; H 2.63;
Cl 23.09; S 10.44.
Signals of p-toluenesulfonic acid (XI) in the
1H NMR spectrum of the reaction mixture (acetone-d6,
400 MHz), δ, ppm: 2.43 s (3H, CH3), 7.41 m and
7.78 m (4H, Harom, AA′BB′, 3JAB + 5JAB′ = 8.1 Hz).
3,4-Dichloro-5-(4-chlorophenylsulfonyl)furan-
2(5H)-one (VIIb) was synthesized in a similar way by
oxidation of 0.80 g (2.70 mmol) of furanone IVb with
0.63 mL (6.5 mmol) of 33% H2O2. Yield 0.61 g (68%),
colorless crystals, mp 115°C (from CCl4), Rf 0.61
(acetone–benzene, 1:6). IR spectrum, ν, cm–1: 1796
(C=O), 1613 (C3=C4), 1573 (C=Carom), 1353 (SO2,
Compounds VIIIb–VIIIe were synthesized in
a similar way.
3-Chloro-4-(4-chlorophenylsulfinyl)-5-hydroxy-
furan-2(5H)-one (VIIIb) was synthesized by reaction
of 0.44 g (1.6 mmol) of furanone IIb with 0.33 g
(1.9 mmol) of m-chloroperoxybenzoic acid. According
to the 1H NMR data, the solid residue contained initial
compound IIb and sulfoxide VIIIb at a ratio of
1:5 and m-chlorobenzoic acid. Sulfoxide (VIIIb) was
isolated by column chromatography on silica gel
(gradient elution with acetone–toluene, 1:6, to pure
acetone). Yield 0.28 g (59%), colorless crystals,
mp 118–121°C (from benzene), Rf 0.20 (acetone–
toluene, 1:6). IR spectrum, ν, cm–1: 3167 (OH), 1790
(C=O), 1630 (C3=C4), 1572 (C=Carom), 1045 (S=O).
1H NMR spectrum (acetone-d6, 300 MHz), δ, ppm:
1
asym.), 1166 (SO2, sym.). H NMR spectrum
(300 MHz), δ, ppm: in acetone-d6: 6.64 s (1H, 5-H),
3
5
7.83 m and 8.00 m (4H, Harom, AA′BB′, JAB + JAB′
8.9 Hz); in CDCl3: 5.70 s (1H, 5-H), 7.61 m and
=
3
5
7.88 m (4H, Harom, AA′BB′, JAB + JAB′ = 8.8 Hz).
Found, %: C 36.61; H 1.19; Cl 32.36; S 9.47.
C10H5O4Cl3S. Calculated, %: C 36.67; H 1.54;
Cl 32.47; S 9.79.
5-(4-Bromophenylsulfonyl)-3,4-dichlorofuran-
2(5H)-one (VIIc) was synthesized by oxidation of
1.20 g (3.53 mmol) of furanone IVc with 1.03 mL
3
6.44 d (1H, 5-H, JHH = 8.5 Hz), 6.46 d (1H, 5-H,
3JHH = 8.4 Hz), 7.39 d (1H, OH, 3JHH = 8.4 Hz), 7.44 d
1
(10.6 mmol) of 33% H2O2. According to the H NMR
3
(1H, OH, JHH = 8.5 Hz), 7.69, 7.90 m (4H, Harom
AA′BB′, JAB + JAB′ = 8.7 Hz), 7.70 m and 7.92 m
(4H, Harom, AA′BB′, JAB + JAB′ = 8.5 Hz). Found, %:
Cl 24.35; S 11.13. C10H6Cl2O4S. Calculated, %:
Cl 24.19; S 10.94.
,
data, the reaction mixture contained sulfone VIIc,
mucochloric acid (I), and 4-bromobenzenesulfonic
acid at a ratio of 7:1:1. Sulfone VIIc was precipitated
with water and recrystallized from carbon tetrachlo-
ride. Yield 1.04 g (79%), colorless crystals, mp 103–
105°C, Rf 0.66 (acetone–benzene, 1:6). IR spectrum,
ν, cm–1: 1795 (C=O), 1615 (C3=C4), 1570 (C=Carom),
3
5
3
5
4-(4-Bromophenylsulfinyl)-3-chloro-5-hydroxy-
furan-2(5H)-one (VIIIc) was synthesized by oxida-
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SULFIDES, SULFONES, AND SULFOXIDES OF THE FURAN-2(5H)-ONE SERIES
533
tion of 0.40 g (1.2 mmol) of furanone IIc with 0.26 g
(1.5 mmol) of m-chloroperoxybenzoic acid. Yield
0.28 g (71%), colorless crystals, mp 147–149°C (from
CCl4–benzene, 3:1), Rf 0.27 (acetone–benzene, 1:6).
IR spectrum, ν, cm–1: 3176 (OH), 1792 (C=O), 1626
Cl 12.96; S 11.72. C11H9ClO4S. Calculated, %:
C 48.45; H 3.33; Cl 13.00; S 11.76.
This study was performed under financial support
by the subsidy of the Russian Government to support
the Program of Competitive Growth of Kazan Federal
University among World’s Leading Academic Centers,
by the Russian Foundation for Basic Research (project
no. 12-03-00898-a), and by the Kazan (Volga Region)
Federal University (grant for student’s research).
1
(C3=C4), 1594 (C=Carom), 1045 (S=O). H NMR spec-
trum (acetone-d6, 400 MHz), δ, ppm: 6.42 d (1H, 5-H,
3JHH = 8.8 Hz), 6.46 d (1H, 5-H, 3JHH = 8.4 Hz), 7.34 d
3
3
(1H, OH, JHH = 8.4 Hz), 7.39 d (1H, OH, JHH
=
8.8 Hz), 7.80–7.88 m (8H, Harom). 13C–{1H} NMR
spectrum (acetone-d6, 100 MHz), δC, ppm: 97.97 and
98.60 (C5); 128.07, 128.22, 128.96, 129.31, 134.63,
134.69, 140.84, 142.26, 142.59 (C3, Carom); 159.83
(C4), 164.84 (C2). Found, %: C 35.87; H 1.53.
C10H6BrClO4S. Calculated, %: C 35.58; H 1.79.
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peroxybenzoic acid. The mixture was evaporated to
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using hexane–diethyl ether (1:3) as eluent to isolate
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0.26 g (60%) of sulfoxide VIIId (Rf 0.22). Yellow
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(C=O), 1626 (C3=C4), 1579 (C=Carom), 1043 (S=O).
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3
3
5-H, JHH = 9.0 Hz), 6.42 d (1H, 5-H, JHH = 8.2 Hz),
6.89 s (1H, 4′-OH), 6.90 s (1H, 4′-OH), 7.41 d (1H,
3
3
5-OH, JHH = 9.0 Hz), 7.53 d (1H, 5-OH, JHH
=
8.2 Hz), 7.73 s (2H, Harom), 7.79 s (2H, Harom). Found,
%: C 55.96; H 6.12; Cl 9.13; S 8.12. C18H23ClO5S.
Calculated, %: C 55.88; H 5.99; Cl 9.16; S 8.29.
11. Bellina, F. and Rossi, R., Curr. Org. Chem., 2004,
4-Benzylsulfinyl-3-chloro-5-hydroxyfuran-
2(5H)-one (VIIIe) was synthesized by oxidation of
0.22 g (0.8 mmol) of furanone IIe with 0.17 g
(1.0 mmol) of m-chloroperoxybenzoic acid. The pre-
cipitate was filtered off and washed with diethyl ether
(the product was not recrystallized). Yield 0.16 g
(66%), colorless crystals, mp 130°C, Rf 0.24 (acetone–
benzene, 1:6). IR spectrum, ν, cm–1: 3146 (OH), 1781
(C=O), 1625 (C3=C4), 1500 (C=Carom), 1052 (S=O).
vol. 8, p. 1089.
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1H NMR spectrum (acetone-d6, 300 MHz), δ, ppm:
2
4.49 m and 4.58 m (1H each, CH2, AB quartet, JAB
=
=
3
13.1 Hz), 4.70 s (2H, CH2), 6.38 d (1H, 5-H, JHH
16. Farina, F., Martin, M.V., Martin-Aranda, R.M., and
7.3 Hz), 6.64 d (1H, 5-H, 3JHH = 6.6 Hz), 7.36–7.52 m
Guerenu, A.M., Synth. Commun., 1993, vol. 23, p. 459.
3
(10H, Harom), 7.67 d (1H, OH, JHH = 7.3 Hz), 8.07 d
17. Frischmuth, K., Muller, D., and Welzel, P., Tetrahedron,
3
(1H, OH, JHH = 6.6 Hz). Found, %: C 48.59; H 3.61;
1998, vol. 54, p. 3401.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 4 2014

LATYPOVA et al.
534
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