Reactions of 2-sulfanylethanol with mucochloric acid and its derivatives

Article abstract of DOI:10.1134/S1070428008080204

Mucochloric acid reacted with 2-sulfanylethanol in the presence of triethylamine to give 3-chloro-5-hydroxy-4-(2-hydroxyethylsulfanyl)furan-2(5H)- one which underwent acid-catalyzed cyclization to 7-chloro-2,3,4a,6- tetrahydrofuro[2,3-b][1,4]oxathiin-6-on

Full text of DOI:10.1134/S1070428008080204

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 8, pp. 1225–1232. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © N.F. Devyatova, L.S. Kosolapova, A.R. Kurbangalieva, E.A. Berdnikov, O.A. Lodochnikova, I.A. Litvinov, G.A. Chmutova, 2008,
published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 8, pp. 1237–1244.
Reactions of 2-Sulfanylethanol with Mucochloric Acid
and Its Derivatives
N. F. Devyatovaa, L. S. Kosolapovaa, A. R. Kurbangalievaa, E. A. Berdnikova,
O. A. Lodochnikovab, I. A. Litvinovb, and G. A. Chmutovaa
a Kazan State University, ul. Kremlevskaya 18, Kazan, 420008 Tatarstan, Russia
b Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
e-mail: Almira.Kurbangalieva@ksu.ru
Received August 2, 2007
Abstract—Mucochloric acid reacted with 2-sulfanylethanol in the presence of triethylamine to give 3-chloro-
5-hydroxy-4-(2-hydroxyethylsulfanyl)furan-2(5H)-one which underwent acid-catalyzed cyclization to
7-chloro-2,3,4a,6-tetrahydrofuro[2,3-b][1,4]oxathiin-6-one. Likewise, reactions of 5-alkoxy-3,4-dichlorofuran-
2(5H)-ones with 2-sulfanylethanol in the presence of triethylamine involved replacement of chlorine in position
4 of the furan ring with formation of the corresponding 4-(2-hydroxyethylsulfanyl) derivatives. The reaction of
mucochloric acid with 2-sulfanylethanol in excess aqueous potassium hydroxide resulted in the formation of
an acyclic product, 3-(2-hydroxyethylsulfanyl)-2-chloroprop-2-enoic acid. The structure of 7-chloro-2,3,4a,6-
tetrahydrofuro[2,3-b][1,4]oxathiin-6-one and 3-(2-hydroxyethylsulfanyl)-2-chloroprop-2-enoic acid was proved
by X-ray analysis.
DOI: 10.1134/S1070428008080204
Development of the chemistry of unsaturated
γ-lactones is related to their occurrence in nature, vast
synthetic potential, and wide scope of application in
medicine and agriculture due to their versatile biolog-
ical activity [1–4]. Mucochloric acid [I, 3,4-dichloro-
5-hydroxyfuran-2(5H)-one] is among such chemically
and biologically active heterocyclic compounds. In the
recent time, it has attracted considerable attention as
an accessible starting material [5–8]. Mucochloric acid
(I) is capable of undergoing ring–chain tautomerism
[9, 10], and its molecule possesses several reaction
centers, so that it may be regarded as α,β-unsaturated
acid, α,β-unsaturated aldehyde, tetrasubstituted Z-ole-
fin, vinyl halide, latent hemiacetal, or pseudolactone.
Therefore, the lactone ring in I can be modified via
introduction of various functional substituents with
a view to obtain new heterocyclic compounds possess-
ing practically useful properties.
(acid or base catalysis), as well as of the order of mix-
ing of the reactants, ensures selective formation of dif-
ferent nucleophilic replacement products, the corre-
sponding α-, β-, and γ-arylsulfanyl derivatives [11].
The goal of the present work was to study reactions
of mucochloric acid (I) and some its derivatives with
2-sulfanylethanol under different conditions. The use
in these reactions of a sulfur-containing binucleophile
seemed to be promising from the viewpoint of obtain-
ing new sulfur-containing products having both mono-
and bicyclic structure.
Zanker and Reicheneder [13] and Gumulka and
Kokosinski [14] previously reported on the formation
of different types of substitution products in the reac-
tions of compound I with 2-sulfanylethanol under
basic and acidic conditions. Under the conditions
ensuring replacement of the 4-chlorine atom by the
action of aliphatic and aromatic thiols (base catalysis),
compound II having a free hydroxy group in the side
chain was obtained [13] (Scheme 1). The reaction of I
with 2-sulfanylethanol at a ratio of 2:1 on heating in
benzene in the presence of sulfuric acid gave product
III [14]. Unfortunately, no reliable spectral parameters
of compounds II and III were given in [13, 14].
While studying the synthesis, structure, and prop-
erties of sulfur- and selenium-containing derivatives of
biologically active heterocycles, we previously report-
ed on the reactions of mucochloric acid (I) with
aromatic and heterocyclic thiols [11] and selenols [12].
We showed that variation of the reaction conditions
1225

DEVYATOVA et al.
1226
Scheme 1.
OH
Cl
Cl
S
HSCH2CH2OH
Et3N, Me2CO
S
Concd. H2SO4, PhH
O
O
OH
O
O
O
Cl
Cl
II
IV
HO
O
Cl
O
O
O
1/2HSCH2CH2OH
H2SO4, PhH
Cl
S
I
O
Cl
O
O
Cl
III
Therefore, first of all we made an attempt to reproduce
the reactions described therein. In fact, the product ob-
tained in benzene in the presence of sulfuric acid had
the structure of 3,4-dichloro-5-[2-(3,4-dichloro-5-oxo-
2,5-dihydrofuran-2-ylsulfanyl)ethoxy]furan-2(5H)-one
(III); it was formed as a mixture of two diastereoiso-
mers. When the reaction was performed under basic
conditions (triethylamine, acetone), we isolated not
only 3-chloro-5-hydroxy-4-(2-hydroxyethylsulfanyl)-
furan-2(5H)-one (II) but also previously unknown bi-
cyclic compound IV, depending on the procedure for
treatment of the reaction mixture.
The 1H NMR spectrum of IV contained a singlet at
δ 6.11 ppm from 5-H, while no signals assignable to
hydroxy protons were present. Methylene protons in
the OCH2CH2S fragment resonated as an ABXY spin
system: the OCH2 group gave a multiplet in the region
δ 4.2–4.5 ppm, while the SCH2 protons appeared as
a multiplet at δ 3.2–3.4 ppm. The structure of bicyclic
compound IV in crystal was characterized by the
X-ray diffraction data (Fig. 1). The six-membered ring
in molecule IV adopts a chair conformation: the
C4C5C6C7 fragment is planar within 0.01 Å, and the
O5 and S4 atoms deviate from that plane by –0.70 and
0.57 Å, respectively.
tetrahydrofuro[2,3-b][1,4]oxathiin-6-one. As far as we
know, there are no published data on the synthesis of
sulfur-containing bicyclic compounds on the basis of
mucochloric acid and its derivatives. Hartke and
Rauschen [15] reported on the formation of tricyclic
sulfur-containing compound in the reaction of 3,4-di-
bromo-5-methoxyfuran-2(5H)-one with disodium
2-oxo-1,3-dithiole-4,5-dithiolate.
O
S
S
O
O
S
S
OMe
Acyclic product II was isolated when the reaction
mixture was treated with water, while bicyclic com-
pound IV was isolated by treatment of the reaction
mixture (in another experiment) with butanol. We pre-
sumed that compound IV is formed via intramolecular
cyclization of II in the presence of traces of triethyl-
amine hydrochloride. This assumption was based on
the known ability of mucochloric acid to undergo nu-
cleophilic attack on C5 in the presence of mineral acids
[11, 14] and was confirmed by special experiments. By
heating compound II in boiling benzene in the pres-
ence of sulfuric acid we obtained furo[2,3-b][1,4]oxa-
thiine IV, whereas no intramolecular cyclization
occurred when pure sulfide II was recrystallized from
anhydrous butanol. Facile intramolecular dehydration
of II with formation of bicyclic compound IV also
follows from the results of quantum-chemical calcula-
tions. The Gibbs energy ΔΔG298 of this reaction was
estimated at –1.29 kkal/mol in terms of the density
functional theory [B3LYP/6-31G(d,p)].
Compound IV is the first representative of a new
sulfur-containing fused heterocyclic system, 2,3,4a,6-
O1
O5
O2
C2
C5
C6
C3
C4
C7
Cl1
S4
2-Sulfanylethanol reacted with 3-(p-tolylsulfanyl)-
substituted furanone V and 5-alkoxy derivatives VI–
VIII in the presence of triethylamine to give the corre-
sponding sulfides IX–XII as a result of nucleophilic
Fig. 1. Structure of the molecule of 7-chloro-2,3,4a,6-tetra-
hydrofuro[2,3-b][1,4]oxathiin-6-one (IV) according to the
X-ray diffraction data.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 8 2008

REACTIONS OF 2-SULFANYLETHANOL WITH MUCOCHLORIC ACID
1227
Scheme 2.
HO
Cl
S
S
S
4-MeC6H4SH
KOH, H2O
HSCH2CH2OH
Et3N, Me2CO
Me
Me
HO
O
HO
O
O
O
V
IX
I
OH
Cl
Cl
Cl
S
HSCH2CH2OH
Et3N, Me2CO
ROH, concd. H2SO4
RO
O
O
OR
O
O
VI–VIII
X–XII
VI, X, R = Me; VII, XI, R = Et; VIII, XII, R = i-Pr.
replacement of chlorine in position 4 of the furan ring
(Scheme 2). Compounds X–XII characteristically
showed in the H NMR spectra a group of multiplets
lowed by intramolecular cyclization, also occurred on
heating in benzene in the presence of a catalytic
amount of concentrated sulfuric acid; in these cases,
bicyclic product IV was isolated.
1
from protons in the SCH2CH2OH fragment (ABMXY
system, Fig. 2).
As we showed previously [11], mucochloric acid
(I) reacted with 4-methylbenzenethiol in excess aque-
ous potassium hydroxide to give product of chlorine
replacement at C3. According to [9–11], alkaline medi-
um promotes cleavage of the lactone ring in molecule
I, nucleophilic attack is directed at the α-carbon atom
with respect to the carboxy group, and cyclic product
is isolated after acidification of the reaction mixture. In
The reactions of furanones V–VII with 2-sulfanyl-
ethanol (heating in boiling acetone in the presence of
triethylamine) required a longer time than analogous
reaction of mucochloric acid (I). We also found that
recrystallization of compounds X and XI from water is
accompanied by dealkylation with formation of com-
pound II. Dealkylation of compounds X–XII, fol-
HX
HM
HA
O
Cl
S
HY
HB
O
O
O
Me
Me
4.4
4.2
4.0
3.8
3.6
3.4
δ, ppm
6.12
1.00
2.18
3
1.01
4
2.10
0.99
6
5
2
δ, ppm
Fig. 2. 1H NMR spectrum of 3-chloro-4-(2-hydroxyethylsulfanyl)-5-isopropoxyfuran-2(5H)-one (XII) in acetone-d6.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 8 2008

DEVYATOVA et al.
1228
Scheme 3.
O3
S
HSCH2CH2OH
(1) KOH–H2O; (2) HCl
HO
C6
C5
I
Cl
XIII
COOH
O1
C3
carboxy hydrogen atom of the neighboring molecule
(O1–H1···O3: H1···O3 1.59 Å, ∠O1H1O3 166°), while
the carbonyl oxygen atom is involved in hydrogen
bonding with hydrogen atom in the hydroxy group
(O3–H3···O2: H3···O2 1.77 Å, ∠O3H3O2 166°).
C1
S4
C2
O2
Cl1
Although it is still difficult to discuss the mechan-
ism of formation of acyclic compound XIII, we be-
lieve that it can be formed as shown in Scheme 4.
Fig. 3. Structure of the molecule of 2-chloro-3-(2-hydroxy-
ethylsulfanyl)prop-2-enoic acid (XIII) according to the
X-ray diffraction data.
Excess aqueous alkali promotes generation of thio-
late ion from 2-sulfanylethanol and anion from the
open-chain tautomer of mucochloric acid. Reaction of
these species gives product A as a result of nucleo-
philic replacement of the chlorine atom on C3. Inter-
mediate A takes up hydroxide ion at the carbonyl
group to form adduct B, and subsequent transforma-
tions of the latter may follow two pathways. One of
these involves first decarboxylation of B into C and
then disproportionation of C into E, while the second,
Cannizzaro reaction of B to D and decarboxylation of
D into E. Acidification of E gives acid XIII.
the reaction of mucochloric acid with 2-sulfanyletha-
nol in aqueous potassium hydroxide, after treatment of
the reaction mixture with dilute hydrochloric acid,
we isolated compound XIII which (according to the
spectral data) had acyclic structure (Scheme 3). The IR
spectrum of XIII lacked absorption band assignable to
stretching vibrations of γ-lactone carbonyl, but a strong
sharp peak was present at 1686 cm–1; such absorption
is typical of stretching vibrations of the carbonyl group
1
in carboxylic acid dimers [16]. In the H NMR spec-
trum of XIII we observed an olefinic proton singlet at
δ 8.14 ppm, a broadened signal at δ 4.0–4.5 ppm (OH),
and a multiplet at δ 3.0–4.0 ppm, typical of methylene
protons. The structure of compound XIII as 2-chloro-
3-(2-hydroxyethylsulfanyl)prop-2-enoic acid was
finally proved by X-ray analysis (Fig. 3).
Thus, depending on the conditions (acid or base
catalysis), reactions of mucochloric acid and some its
derivatives with 2-sulfanylethanol result in the forma-
tion of different products, 3-chloro-5-hydroxy(alkoxy)-
4-(2-hydroxyethylsulfanyl)furan-2(5H)-ones, 2,3,4a,6-
tetrahydrofuro[2,3-b][1,4]oxathiin-6-one, or 2-chloro-
3-(2-hydroxyethylsulfanyl)prop-2-enoic acid.
The presence of hydroxy and carboxy groups in
molecule XIII determines specificity of crystal pack-
ing of this compound. Intermolecular hydrogen bonds
in crystal give rise to twinned chains along the a
crystallographic axis (Fig. 4). The oxygen atom in the
hydroxy group of one molecule interacts with the
EXPERIMENTAL
Commercial mucochloric acid (I) was recrystallized
from water, mp 127°C [17]. 4-Chloro-5-hydroxy-3-
(4-methylphenylsulfanyl)furan-2(5H)-one (V) [11],
3,4-dichloro-5-methoxyfuran-2(5H)-one (VI),
3,4-dichloro-5-ethoxyfuran-2(5H)-one (VII) [18], and
3,4-dichloro-5-isopropoxyfuran-2(5H)-one (VIII) [19]
were synthesized by known methods.
a
0
c
The IR spectra (4000–400 cm–1) were recorded
from samples dispersed in Nujol and placed between
KBr plates on a Bruker Tensor-27 spectrometer with
Fourier transform at the Optical Research Laboratory,
Federal Collective Use Center. The NMR spectra were
measured at 25°C from solutions in acetone-d6 on
b
Fig. 4. Crystalline structure of 2-chloro-3-(2-hydroxyethyl-
sulfanyl)prop-2-enoic acid (XIII) according to the X-ray dif-
fraction data.
1
a Varian Unity-300 instrument at 299.94 MHz for H
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 8 2008

REACTIONS OF 2-SULFANYLETHANOL WITH MUCOCHLORIC ACID
1229
Scheme 4.
O
O
O
Cl
Cl
Cl
Cl
S
S
OH–
H2O
O–
H
HOCH2CH2S–
–Cl–
HO
O–
H
HO
O–
H
OH–
H
O
O
Cl
Cl
HO
O
OH
O
O
I
A
B
S
HO
H
–CO2
–H–
Cl
O
O
S
HO
C
H+
O
XIII
Cl
O
O
O
S
HO
O
O
E
OH–
–H2O, –H–
H2O
–CO2, –OH–
Cl
D
1
and 75.13 MHz for 13C. The H chemical shifts were
determined relative to the residual proton signal of the
solvent. Thin-layer chromatography was performed on
Silufol UV-254 plates using acetone–benzene (1:4 by
volume) as eluent.
rivative matrix was calculated for all stationary points;
the optimized structures were characterized by only
positive vibration frequencies.
3-Chloro-5-hydroxy-4-(2-hydroxyethylsulfanyl)-
furan-2(5H)-one (II). A solution of 0.42 ml
(5.9 mmol) of 2-sulfanylethanol in 8 ml of acetone was
added dropwise under vigorous stirring to a solution of
1 g (5.9 mmol) of mucochloric acid in 10 ml of ace-
tone. A solution of 0.8 ml (5.9 mmol) of triethylamine
in 4 ml of acetone was then added, the mixture was
heated for 2 h under reflux, the precipitate of triethyl-
amine hydrochloride was filtered off and washed with
acetone, the filtrate was evaporated under reduced
pressure, and the oily residue was crystallized twice
from water. Yield 53%, colorless crystals, mp 123°C;
published data [13]: mp127–128°C; Rf 0.25. IR spec-
trum, ν, cm–1: 3362, 3152 (OH), 1742 (C=O), 1578
(C=C). 1H NMR spectrum, δ, ppm: 3.37 m (1H, SCHA,
JAB = –13.5, JAX = 5.4, JAY = 5.4, JAM = 0.0 Hz), 3.55 m
X-Ray analysis was performed at the X-Ray
Department, Spectral Analytical Collective Use Center,
Russian Foundation for Basic Research, on a Smart
Apex diffractometer at 20°C (MoKα irradiation, multi-
scan mode). The structures were solved by the direct
method using SIR program [20] and were refined first
in isotropic and then in anisotropic approximation
(SHELXL97 [21], WinGX [22]). Hydrogen atoms
were visualized from difference electron density series,
and their positions were refined in isotropic approxi-
mation in the final step. The structures were plotted,
and intermolecular contacts were analyzed, using
PLATON program [23]. X-Ray diffraction data: com-
pound IV: C6H5ClO3S, M 192.61; rhombic crystals,
space group P212121 (no. 19); unit cell parameters: a =
4.1995(5), b = 11.335(1), c = 16.228(2) Å; V =
772.5(2) Å3; compound XIII: C5H7ClO3S, M 182.62;
monoclinic crystals, space group P21/c (no. 14); unit
cell parameters: a = 8.352(5), b = 7.290(5), c =
12.785(5) Å; β = 93.510(5)°; V = 777.0(8) Å3.
(1H, SCHB, JAB = –13.5, JBX = 7.2, JBY = 5.7, JBM
0.0 Hz), 3.86 m (1H, OCHX, JAX = 5.4, JBX = 7.2, JXY
=
=
–11.3, JXM = 5.3 Hz), 3.94 m (1H, OCHY, JAY = 5.4,
JBY = 5.7, JXY = –11.3, JYM = 5.3 Hz), 4.43 t (1H, OHM,
JAM = 0.0, JBM = 0.0, JXM = 5.3, JYM = 5.3 Hz), 6.49 d
(1H, 5-H, J = 8.7 Hz), 7.32 d (1H, 5-OH, J = 8.7 Hz).
Found, %: C 34.50; H 3.23; Cl 16.81; S 15.19.
C6H7ClO4S. Calculated, %: C 34.21; H 3.35; Cl 16.83;
S 15.22. Recrystallization of the oily residue from
butanol gave bicyclic compound IV.
Quantum-chemical calculations were performed at
the DFT B3LYP/6-31G(d,p) level using Gaussian-98
software package [24]; the geometric parameters were
optimized without symmetry restrictions; second de-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 8 2008

DEVYATOVA et al.
1230
then added. The mixture was heated for 30 h under
3,4-Dichloro-5-[2-(3,4-dichloro-5-oxo-2,5-dihy-
reflux (TLC), the precipitate of triethylamine hydro-
chloride was filtered off and washed with acetone, and
the filtrate was evaporated to dryness under reduced
pressure. The oily residue was dissolved in chloro-
form, and the solution was washed with several
portions of water, dried over anhydrous magnesium
sulfate, and evaporated to dryness under reduced pres-
sure. The residue was ground with hexane on cooling,
and the precipitate was filtered off and recrystallized
from petroleum ether–benzene. Yield 46%, mp 101°C,
Rf 0.31. IR spectrum, ν, cm–1: 3327, 3194 (OH), 1740
drofuran-2-ylsulfanyl)ethoxy]furan-2(5H)-one (III).
Concentrated sulfuric acid, 0.16 ml, was added to
a solution of 5.0 g (29.6 mmol) of mucochloric acid
(I) and 1.04 ml (14.8 mmol) of 2-sulfanylethanol in
100 ml of benzene, and the mixture was heated under
reflux until mucochloric acid disappeared completely
(34 h, TLC). The mixture was cooled, washed with
water until neutral washings, dried over magnesium
sulfate, and evaporated under reduced pressure. The
yellow oily residue was crystallized first from carbon
tetrachloride and then from petroleum ether–benzene.
Yield 36%, mp 97–98°C; published data [14]: mp 127–
129°C; Rf 0.69. IR spectrum, ν, cm–1: 1788 (C=O),
1
(C=O), 1548 (C=C), 1490 (C=Carom). H NMR spec-
trum, δ, ppm: 2.29 s (3H, CH3), 3.2–3.6 m (2H, SCH2),
3.7–4.0 m (2H, OCH2), 4.35 t (1H, OH, J = 5.2 Hz),
6.48 s (1H, 5-H), 7.13 m and 7.22 m (4H, AA′BB′,
Harom, J = 8.3 Hz), 7.17 s (1H, OH). Found, %:
C 51.99; H 4.49; S 21.59. C13H14O4S2. Calculated, %:
C 52.33; H 4.73; S 21.49.
1
1624 (C=C). H NMR spectrum, δ, ppm: 2.9–3.1 m
(2H, SCH2), 4.0–4.2 m (2H, OCH2), 6.23 s and 6.24 s
(1H, 5′-H), 6.58 s and 6.58 s (1H, 5-H). 13C NMR
spectrum, δC, ppm: 29.70, 29.72 (SCH2); 70.07, 70.11
(OCH2); 87.07 (C5′); 101.75 (C5); 123.13, 123.18,
124.00, 124.05 (C3, C3′); 148.27, 148.35, 150.81,
150.91 (C4, C4′); 163.50, 164.46 (C2, C2′). Found, %:
C 31.45; H 1.88; Cl 37.66; S 8.68. C10H6Cl4O5S. Cal-
culated, %: C 31.60; H 1.59; Cl 37.32; S 8.44.
3-Chloro-4-(2-hydroxyethylsulfanyl)-5-methoxy-
furan-2(5H)-one (X) was synthesized in a similar way
from 0.74 g (4.04 mmol) of compound VI and 0.28 ml
(4.04 mmol) of 2-sulfanylethanol in the presence of
0.57 ml (4.04 mmol) of triethylamine. Reaction time
60 h. The oily residue obtained after evaporation of the
filtrate under reduced pressure was purified by column
chromatography using hexane–diethyl ether (1:3) as
eluent. The light yellow oily product did not crystal-
7-Chloro-2,3,4a,6-tetrahydrofuro[2,3-b][1,4]oxa-
thiin-6-one (IV). Concentrated sulfuric acid, 0.01 ml
(20 mol %), was added to a solution of 0.214 g
(0.102 mmol) of compound II in 25 ml of benzene.
The mixture was heated for 3 h under reflux, cooled,
and washed with water until neutral washings. The
benzene solution was dried over MgSO4 and evaporat-
ed to dryness, and the residue was recrystallized from
petroleum ether–benzene. Yield 52%, colorless needles,
mp 81°C, Rf 0.63. IR spectrum, ν, cm–1: 1773 (C=O),
1
lize. Yield 58%. H NMR spectrum, δ, ppm: 3.29 m
(1H, SCHA, JAB = 13.6, JAX = 5.2, JAY = 4.6, JAM
0.0 Hz), 3.46 m (1H, SCHB, JAB = 13.6, JBX = 7.6, JBY
=
=
5.1, JBM = 0.0 Hz), 3.56 s (3H, CH3), 3.81 m (1H,
OCHX, JAX = 5.2, JBX = 7.6, JXY = 11.5, JXM = 5.3 Hz),
3.92 m (1H, OCHY, JAY = 4.6, JBY = 5.1, JXY = 11.5,
1
1602 (C=C). H NMR spectrum, δ, ppm: 3.28 m (1H,
SCHA, JAB = 13.1, JAX = 9.4, JAY = 2.6 Hz), 3.29 m (1H,
SCHB, JAB = 13.1, JBX = 1.7, JBY = 7.2 Hz), 4.32 m (1H,
SCHX, JAX = 9.4, JBX = 1.7, JXY = 12.4 Hz), 4.45 m (1H,
SCHY, JAY = 2.6, JBY = 7.2, JXY = 12.4 Hz), 6.11 s (1H,
5-H). 13C NMR spectrum, δC, ppm: 28.66 (SCH2),
67.13 (OCH2), 97.73 (C5), 119.12 (C3), 154.31 (C4),
164.19 (C2). Found, %: C 37.15; H 2.68; Cl 18.41;
S 16.61. C6H5ClO3S. Calculated, %: C 37.41; H 2.62;
Cl 18.41; S 16.65.
JYM = 5.3 Hz), 4.38 t (1H, OHM, JAM = JBM = 0.0, JXM
JYM = 5.3 Hz), 6.31 s (1H, 5-H). Recrystallization of
liquid compound X from water gave furanone II.
=
3-Chloro-5-ethoxy-4-(2-hydroxyethylsulfanyl)-
furan-2(5H)-one (XI) was synthesized in a similar
way from 1.66 g (8.43 mmol) of compound VII and
0.59 ml (8.43 mmol) of 2-sulfanylethanol in the pres-
ence of 1.17 ml (8.43 mmol) of triethylamine. Reac-
tion time 10 h. Recrystallization of the yellow oily
product from carbon tetrachloride–acetone gave white
powder. Yield 65%, mp 45°C, Rf 0.40. IR spectrum, ν,
cm–1: 3100–3300 br (OH), 1770 (C=O), 1596 (C=C).
1H NMR spectrum, δ, ppm: 1.28 t (3H, CH3, J =
5-Hydroxy-4-(2-hydroxyethylsulfanyl)-3-(4-
methylphenylsulfanyl)furan-2(5H)-one (IX). A solu-
tion of 0.18 ml (2.65 mmol) of 2-sulfanylethanol in
8 ml of acetone was added dropwise under vigorous
stirring to a solution of 0.68 g (2.65 mmol) of com-
pound V in 10 ml of acetone, and a solution of 0.36 ml
(2.65 mmol) of triethylamine in 4 ml of acetone was
7.1 Hz), 3.30 m (1H, SCHA, JAB = 13.6, JAX = 5.2, JAY
5.2, JAM = 0.0 Hz), 3.47 m (1H, SCHB, JAB = 13.6,
JBX = 7.6, JBY = 5.3, JBM = 0.0 Hz), 3.75–3.97 m (4H,
=
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 8 2008

REACTIONS OF 2-SULFANYLETHANOL WITH MUCOCHLORIC ACID
1231
OCH2, OCHXHY), 4.38 t (1H, OHM, J = 5.1 Hz), 6.36 s
REFERENCES
(1H, 5-H). Found, %: C 40.13; H 4.47; Cl 15.12;
S 13.74. C8H11ClO4S. Calculated, %: C 40.26; H 4.65;
Cl 14.85; S 13.43. Recrystallization of solid compound
XI from water gave furanone II.
1. Rao, Y.S., Chem. Rev., 1964, vol. 64, p. 353.
2. Rao, Y.S., Chem. Rev., 1976, vol. 76, p. 625.
3. Avetisyan, A.A., Usp. Khim., 1977, vol. 46, p. 1250.
4. Knight, D.W., Contemp. Org. Synth., 1994, vol. 1,
3-Chloro-4-(2-hydroxyethylsulfanyl)-5-isopro-
poxyfuran-2(5H)-one (XII) was synthesized as de-
scribed above for compound II from 1.0 g (4.74 mmol)
of isopropoxyfuranone VIII and 0.33 ml (4.74 mmol)
of 2-sulfanylethanol in the presence of 0.66 ml
(4.74 mmol) of triethylamine. Evaporation of the
filtrate under reduced pressure gave a solid which was
recrystallized from carbon tetrachloride. Yield 83%,
colorless crystals, mp 72°C, Rf 0.43. IR spectrum, ν,
p. 287.
5. Bellina, F., Anselmi, C., Martina, F., and Rossi, R., Eur.
J. Org. Chem., 2003, p. 2290.
6. Bellina, F. and Rossi, R., Curr. Org. Chem., 2004,
vol. 8, p. 1089.
7. Zhang, J., Das Sarma, K., Curran, T.T., Belmont, D.T.,
and Davidson, J.G., J. Org. Chem., 2005, vol. 70,
p. 5890.
1
cm–1: 3509 (OH), 1748 (C=O), 1591 (C=C). H NMR
8. Zhang, J., Morton, H.E., and Ji, J., Tetrahedron Lett.,
2006, vol. 47, p. 8733.
spectrum, δ, ppm: 1.28 d (3H, CH3, J = 6.1 Hz), 1.32 d
(3H, CH3, J = 6.1 Hz), 3.30 m (1H, SCHA, JAB = –13.5,
JAX = JAY = 5.3, JAM = 0.0 Hz), 3.47 m (1H, SCHB,
9. Buu-Hoi, N.P., Bull. Soc. Chim. Fr., 1971, no. 8,
p. 2999.
10. Simonov, V.D., Shitova, E.N., Yasman, Ya.B., Galie-
va, A.F., and Estrina, V.Z., Zh. Org. Khim., 1978,
vol. 14, p. 152.
J
AB = –13.5, JBX = 7.7, JBY = 5.3, JBM = 0.0 Hz), 3.82 m
(1H, OCHX, JAX = 5.3, JBX = 7.7, JXY = –11.5, JXM
5.0 Hz), 3.92 m (1H, OCHY, JAY = JBY = 5.3, JXY
=
=
3
11. Kurbangalieva, A.R., Devyatova, N.F., Bogdanov, A.V.,
Berdnikov, E.A., Mannafov, T.G., Krivolapov, D.B., Lit-
vinov, I.A., and Chmutova, G.A., Phosphorus, Sulfur
Silicon Relat. Elem., 2007, vol. 182, p. 607.
–11.5, JYM = 5.0 Hz), 4.21 m (1H, OCH, J = 6.1 Hz),
4.39 t (1H, OHM, JAM = JBM = 0.0, JXM = JYM = 5.0 Hz),
6.42 s (1H, 5-H). Found, %: C 42.41; H 4.96;
Cl 14.32; S 12.52. C9H13ClO4S. Calculated, %:
C 42.77; H 5.18; Cl 14.03; S 12.69.
12. Kurbangalieva, A.R., Bogdanov, A.V., Movchan, A.I.,
and Chmutova, G.A., Russ. J. Org. Chem., 2004,
vol. 40, p. 1216.
2-Chloro-3-(2-hydroxyethylsulfanyl)prop-
2-enoic acid (XIII). 2-Sulfanylethanol, 0.42 ml
(5.9 mmol), was added dropwise under vigorous stir-
ring to a solution of 1 g (5.9 mmol) of mucochloric
acid (I) and 1.33 g (23.7 mmol) of potassium hydrox-
ide in 10 ml of water. The mixture was stirred for 2 h,
acidified with dilute hydrochloric acid to pH 1, and
evaporated to dryness under reduced pressure. The
semisolid residue was purified by column chromatog-
raphy using acetone–benzene (1:5) as eluent to obtain
a solid which was additionally recrystallized from
hexane–benzene. Yield 51%, colorless crystals,
mp 147°C, Rf 0.16. IR spectrum, ν, cm–1: 3353 (OH);
2527, 2612, 2682, 2787 m (COOH); 1686 (C=O);
13. Zanker, F. and Reicheneder, F., FRG Patent Appl.
no. 2032709, 1972; Chem. Abstr., 1972, vol. 76,
no. 140252c.
14. Gumulka, W. and Kokosinski, J., Pol. Organika, 1976,
p. 45.
15. Hartke, K. and Rauschen, F., J. Prakt. Chem., 1997,
vol. 339, p. 15.
16. Bellamy, L.J., The Infra-red Spectra of Complex Mole-
cules, London: Methuen, 1958.
17. Vlasov, O.N., Rybakov, B.N., and Kogan, L.M.,
Zh. Prikl. Khim., 1968, vol. 41, p. 373.
18. Mowry, D.T., J. Am. Chem. Soc., 1950, vol. 72, p. 2535.
19. Fishbein, P.L. and Moore, H.W., Synth. Commun., 1989,
1
1569 (C=C). H NMR spectrum, δ, ppm: 3.14 t (2H,
vol. 19, p. 3283.
SCH2, 3J = 6.00 Hz), 3.84 t (2H, OCH2, 3J = 6.00 Hz),
4.0–4.5 br (1H, OH), 8.14 s (1H, 5-H). Found, %:
C 33.00; H 3.74; Cl 19.67; S 17.86. C5H7ClO3S. Cal-
culated, %: C 32.88; H 3.86; Cl 19.41; S 17.56.
20. Altomare, A., Cascarano, G., Giacovazzo, C., and
Virerbo, D., Acta Crystallogr., Sect. A, 1991, vol. 47,
p. 744.
21. Sheldrick, G.M., SHELXL97. V. 5.10, Madison, WI,
USA: Bruker AXS, 1997.
This study was performed under financial support
by the joint program of CRDF and Ministry of Educa-
tion and Science of the Russian Federation (program
“Fundamental Research and Higher Education,” NOTs
KGU 007, no. Y2-C-07-17).
22. Farrugia, L.J., J. Appl. Crystallogr., 1999, vol. 32,
p. 837.
23. Spek, A.L., Acta Crystallogr., Sect. A, 1990, vol. 46,
p. 34.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 8 2008

DEVYATOVA et al.
1232
24. Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuse-
ria, G.E., Robb, M.A., Cheeseman, J.R., Zakrzew-
ski, V.G., Montgomery, J.A., Stratmann, R.E., Bur-
ant, J.C., Dapprich, S., Millam, J.M., Daniels, A.D.,
Kudin, K.N., Strain, M.C., Farkas, O., Tomasi, J.,
Barone, V., Cossi, M., Cammi, R., Mennucci, B.,
Pomelli, C., Adamo, C., Clifford, S., Ochterski, J.,
Petersson, G.A., Ayala, P.Y., Cui, Q., Morokuma, K.,
Malick, D.K., Rabuck, A.D., Raghavachari, K., Fores-
man, J.B., Cioslowski, J., Ortiz, J.V., Baboul, A.G., Ste-
fanov, B.B., Liu, G., Liashenko, A., Piskorz, P., Koma-
romi, I., Gomperts, R., Martin, R.L., Fox, D.J.,
Keith, T., Al-Laham, M.A., Peng, C.Y., Nanayak-
kara, A., Gonzalez, C., Challacombe, M., Gill, P.M.W.,
Johnson, B.G., Chen, W., Wong, M.W., Andres, J.L.,
Head-Gordon, M., Replogle, E.S., and Pople, J.A.,
Gaussian 98, Rev. A.7, Pittsburgh PA: Gaussian Inc.,
1998.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 8 2008