Reactions of 2-butylsulfanyl-2-alkenals with alcohols and water

Article abstract of DOI:10.1007/s11178-005-0249-0

2-Butylsulfanyl-2-alkenals react with alcohols at room temperature in the presence of acid catalysts to give 45-90% of the corresponding acetals. Acetals derived from 2-butylsulfanylpropenal readily undergo hydrolysis at the vinylsulfanyl group (20°C, catalysis by HCl or TsOH) with formation of 2-oxopropionaldehyde O,O- or O,S-acetals in 70-90% yield. Unlike 2-butylsulfanyl-2-propenal O,O-dialkyl acetals, the initial aldehydes and 2,4-dinitrophenylhydrazones derived therefrom are stable to hydrolysis under analogous conditions: the vinyl sulfide moiety remains unchanged even under considerably more severe conditions (100°C, 3 h; HCl, H₂SO ₄, CF₃SO₂OH, or TiCl₄).

Full text of DOI:10.1007/s11178-005-0249-0

Russian Journal of Organic Chemistry, Vol. 41, No. 6, 2005, pp. 811–815. Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 6, 2005,
pp. 832–836.
Original Russian Text Copyright © 2005 by Keiko, Chuvashev, Stepanova, Larina.
Reactions of 2-Butylsulfanyl-2-alkenals with Alcohols and Water
N. A. Keiko, Yu. A. Chuvashev, L. G. Stepanova, and L. I. Larina
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: keiko@irioch.irk.ru
Received July 3, 2004
Abstract—2-Butylsulfanyl-2-alkenals react with alcohols at room temperature in the presence of acid catalysts
to give 45–90% of the corresponding acetals. Acetals derived from 2-butylsulfanylpropenal readily undergo
hydrolysis at the vinylsulfanyl group (20°C, catalysis by HCl or TsOH) with formation of 2-oxopropion-
aldehyde O,O- or O,S-acetals in 70–90% yield. Unlike 2-butylsulfanyl-2-propenal O,O-dialkyl acetals, the
initial aldehydes and 2,4-dinitrophenylhydrazones derived therefrom are stable to hydrolysis under analogous
conditions: the vinyl sulfide moiety remains unchanged even under considerably more severe conditions
(100°C, 3 h; HCl, H2SO4, CF3SO2OH, or TiCl4).
2-Alkenals are known to take up alcohols at the
carbonyl group in the presence of acid catalysts [1].
These reactions often occur at room temperature [2, 3].
When a small amount of a solvent immiscible with
water is used, the liberated water separates from
the mixture, and no azeotropic removal of water is
necessary [3]. However, it was proposed to synthesize
acetals from high-boiling alcohols with removal of
water by azeotropic distillation [4]. In this case, the
reaction can be accompanied by formation of an ap-
preciable amount of the corresponding 1,1,3-trialkoxy-
propane [4, 5].
2-alkylsulfanyl-2-alkenal dialkyl acetals IIIa–IIId
(Scheme 1). Compounds III undergo appreciable de-
composition during vacuum distillation (at 1 mm);
however, they can be isolated by molecular distillation.
Acetals IV, V, and dibutyl disulfide are often
formed as by-products (5–6, 7–14, and 5–8 wt %,
respectively, according to the GC–MS data), regardless
of the mode of water removal from the reaction
mixture (azeotropic distillation or trapping with 3- or
4-Å molecular sieves). Compounds IV and V are
likely to result from hydrolysis of the vinylsulfanyl
group in III. Facile hydrolysis of the vinylsulfanyl
fragment in III was demonstrated by carrying out
the reaction of 2-butylsulfanylpropenal dibutyl acetal
(IIIc) with water at 20°C in the presence of p-tolu-
enesulfonic acid (Scheme 2). After 9 days, the yield of
Vc reached 89% (1H NMR data).
The goal of the present work was to examine the
regioselectivity in reactions of 2-butylsulfanyl-2-al-
kenals with alcohols and water. These substrates may
be regarded as a combination of acrylic and vinyl
sulfide moieties. The presence of the latter leads us to
expect that addition of alcohols will follow the Mar-
kownikoff rule [6]. This pattern is typical of reactions
of 2-alkoxypropenals with equimolar amounts of
alcohols, where regioselective attack on the C=C bond
occurs [7]. Provided that polarization of the C=C bond
is determined mainly by electron-acceptor effect of the
carbonyl group, nucleophilic attack on the latter might
be expected.
Likewise, acetal Vc is readily formed in the reac-
tion of 2-butylsulfanylpropenal (Ib) with butanol,
catalyzed by concentrated hydrochloric acid, unless
liberated water is trapped. After 24 h, the weight
fraction of Vc in the reaction mixture reaches 70%
(GC–MS). In this experiment, one fraction isolated by
distillation contained about 50% of acetal IVc. Usual-
ly, the concentration of IVc in the reaction mixture is
low, so that it cannot be determined by 1H NMR spec-
troscopy or isolated by distillation (it can be detected
only by GC–MS). Accumulation of a considerable
amount of 2-oxopropanal dialkyl acetal in the reaction
mixture led us to presume that this compound is
a precursor of mixed O,S-acetal V; as a rule, the
Experiments showed that, unlike 2-alkoxypropen-
als, 2-butylsulfanyl-2-alkenals Ia and Ib take up
alcohols in the presence of a catalytic amount of
a Brønsted or Lewis acid (TsOH, HBr, BF3 ·OEt2,
HgCl2) at room temperature exclusively at the car-
bonyl group to give 52–100% of the corresponding
1070-4280/05/4106-0811 © 2005 Pleiades Publishing, Inc.

KEIKO et al.
812
Scheme 1.
BuS
SBu
R = H
O
CHO
VI
OBu
SBu
RCH
C
CH
R'OH
IIa, IIb
SBu
OBu
SBu
RCH
C
CHO
RCH
C
CH(OR')2
RCH2
C
O
CH
A
a
SBu
SBu
RCH2
C
CH(OR')2
Ia, Ib
IIIa–IIId
Va, Vc, Vd
b
c
O
IVa, IVc
BuSH
R
CH CH CHO
R
CH CH CH(OR')2
BuS
SBu
BuS
SBu
B
VII
I, R = Me (a), H (b); II, R' = Bu (a), Et (b); III, R = Me, R' = Bu (a), Et (b); R = H, R' = Bu (c), Et (d); IV, R = Me, R' = Bu (a),
R = H, R' = Bu (c); V, R = Me, R' = OBu (a); R = H, R' = Bu (c), Et (d); VII, R = Me, R' = Et.
concentration of IV is twice as low as that of V.
Alternatively, compound V may be formed by hydrol-
ysis of intermediate acetal A (Scheme 1). Presumably,
the latter was detected in up to 4% yield by GC–MS
(m/z 304) in the reaction of aldehyde Ia with butanol.
corresponding dimer, 2,5-bis(butylsulfanyl)-2,3-dihy-
dro-4H-pyran-2-carbaldehyde (VI) (28–60%, accord-
ing to the 1H NMR data). As shown in [9], aldehyde Ib
is capable of undergoing cyclodimerization at a high
rate. In order to minimize this process, the reactions
were performed using a 10–20-fold excess of alcohols,
and the initial aldehyde was diluted with ether. Under
these conditions, the yield of acetal IIIc reached 80%,
while the yield of IIId was as low as 30–45%. Among
other reasons, the low yield of IIId is explained by the
fact that initial aldehyde Ib (which is prepared by
retro-Diels–Alder reaction from dimer VI [10]) usually
contains 20–30% of the dimer. As with crotonaldehyde
derivative Ia, the reaction of aldehyde Ib with ethanol
gives up to 8% of monothioacetal Vd as by-product.
Another side reaction is nucleophilic 1,4-addition of
thiol formed by decomposition of butyl vinyl sulfide in
acid medium, as well as by hydrolysis of dimer VI.
Intermediate formation of 2,3-bis(butyl-sulfanyl)pro-
The reaction sequence a–b–c operating in the
absence of water acceptors and reaction d (Scheme 2)
may be regarded as a new preparative route to 2-oxo-
propanal O,S-acetals. Alkylsulfanyl group may be
introduced into molecules of O,O-acetals IV via nucle-
ophilic replacement of the RO group by butanethiol
which could be formed by partial decomposition of the
initial aldehyde or acetal III. An analogous process
was observed previously in the reaction of 2-oxopro-
panal diethyl acetal with EtSH [8]. However, such
a reaction seems to be surprising, taking into account
20–40-fold excess of alcohol used in our experiments.
These data convincingly demonstrate predominating
activity of the RS nucleophile and a fairly high stabil-
ity of monothioacetals V to disproportionation.
1
panal B was detected by H NMR and GC–MS; the
spectral data were compared with those reported in
[11]. Diethyl acetal VII was isolated by distillation
(yield up to 6%).
Scheme 2.
H+, 20°C
OBu
IIIc
+
H2O
Me
C
CH
d
Thus 2-butylsulfanyl-2-enals take up alcohols only
at the carbonyl group. No Markownikoff addition of
alcohols or thiols at the C=C bond, which is typical of
2-alkoxypropenals [7, 8] or vinyl sulfides [6], was
observed.
SBu
O
Vc
Apart from the above products resulting from hy-
drolytic cleavage of acetals IV and V of both crotonic
and acrylic series, reactions of 2-butylsulfanylpropenal
(Ib) with alcohols give rise to a large amount of the
Unlike acetals III, hydrolysis of the vinyl sulfide
moiety in initial 2-butylsulfanyl-2-alkenals I is con-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 6 2005

REACTIONS OF 2-BUTYLSULFANYL-2-ALKENALS WITH ALCOHOLS AND WATER
813
siderably more difficult. We previously showed that
aldehyde Ib reacts with 2,4-dinitrophenylhydrazine in
aqueous ethanol in the presence of a large amount of
concentrated sulfuric acid to afford 2-butylsulfanyl-
2-propenal 2,4-dinitrophenyl-hydrazone as the only
product (yield 35%) [12]. Likewise, the reaction of
2-butylsulfanyl-2-butenal (Ia) with 2,4-dinitrophenyl-
hydrazine in the presence of concentrated hydrochloric
acid (100°C, 3 h) gave only the corresponding hydra-
zone VIIIa (yield 50%, Scheme 3) [13].
(CH2, Bu), 31.86 (SCH2), 32.20 (CH2, Bu), 139.50
(C=), 155.44 (CH=), 191.10 (CHO); the signals were
13
assigned using standard JMOD technique. C NMR
spectrum of 2-butylsulfanylpropenal (Ib), δC, ppm:
13.57 (CH3), 22.1 (CH2), 29.65 (CH2), 29.82 (CH2),
126.44 (H2C=), 147.89 (=CSBu), 190.60 (CHO); the
signals were assigned from the proton-coupled
spectrum.
1,1-Dibutoxy-2-butylsulfanyl-2-butene (IIIa).
a. A mixture of 2.76 g (0.017 mol) of 2-butenal (Ia),
23.7 g (0.37 mol) of butyl alcohol, 51.4 g of diethyl
ether, 0.3 g (0.0017 mol, 10 mol %) of p-toluene-
sulfonic acid, and 5.8 g of 4-Å molecular sieves was
kept for 13 days at room temperature. An additional
portion of 4-Å molecular sieves, 8.83 g, was then
added, the mixture was kept for 3 days and neutralized
with dry potassium carbonate, and diethyl ether and
excess butyl alcohol were removed under reduced
pressure. According to the NMR data, the residue con-
tained 94.9% of acetal IIIa. By triple vacuum distilla-
tion we isolated 1.3 g (26%) of dibutyl acetal IIIa,
bp 125–127°C (6 mm). The still residue contained a lot
Scheme 3.
Ia, Ib
H+/H2O
+
H2NNHC6H3(NO2)2-2,4
RCH
C
CH NNHC6H3(NO2)2-2,4
SBu
VIIIa, VIIIb
R = Me (a), H (b).
Hydrolysis of substituted vinyl sulfides usually
requires severe conditions, e.g., catalysis by HgCl2
(2 equiv, 50–80°C, 20–40 h) [14], 70% perchloric acid
(6 equiv)–benzenethiol (2 equiv) [15], or TiCl4
(2 equiv) [16]. Our attempts to effect hydrolysis of
2-butylsulfanylpropenal (Ib) in the presence of TiCl4
under analogous conditions were unsuccessful: only
tarry material was obtained. The hydrolysis of alde-
hyde Ib in the presence of a catalytic amount of
CF3SO2OH was also accompanied by tarring. No
expected 2-oxopropanal was detected by spectral
methods (1H NMR, IR). We can conclude that, if
a molecule possesses an acrylic bond system (or its
imino analog), the vinylsulfanyl moiety therein (alde-
hydes I) or in the corresponding 2,4-dinitrophenyl-
hydrazones (compounds VIII) is stable to hydrolysis.
1
of tars. H NMR spectrum, δ, ppm: 0.89 t (6H,
3
CH3CH2, J = 7.1 Hz), 0.91 t (3H, CH3CH2), 1.38 m
(6H, CH2CH3), 1.54 m (6H, CH2CH2CH3), 1.87 d (3H,
3
CH3CH, J = 6.8 Hz), 2.68 t (2H, SCH2), 3.38 d.t and
3.57 d.t (4H, OCH2, 3J = 6.5 Hz), 4.78 s (1H, OCHO),
6.18 q (1H, CH3CH, 3J = 6.8 Hz). Mass spectrum, m/z
(Irel, %): 288 (9) [M]+, 216 (40) [M – C3H7CHO]+, 215
(19) [M – C3H7CH2O]+, 159 (50) [C4H9OCHOC4H9]+,
103 (75) [C4H9OCHOC4H9 – C4H8]+, 57 (100) [C4H9]+.
Found, %: C 66.18; H 11.10; S 11.20. C16H32O2S. Cal-
culated, %: C 66.67; H 11.10; S 11.12.
b. The reaction was carried out as described above
in a with the difference that 5 mol % of HBr was used
as catalyst. After 3 days, the mixture contained the
following products (wt %, GC–MS): initial aldehyde
Ia (18), acetal IIIa (38), acetal Va (12), dibutyl disul-
fide (6). Compounds Ia and IIIa were identified by
comparing their GC–MS parameters with those of
authentic samples. Mass spectrum of Va, m/z (Irel, %):
175 (30) [BuOCHSBu]+, 119 (62) [BuOCHSBu –
C4H8]+, 57 (80) [CH3CH2CO]+, 29 (100) [CH3CH2]+.
Mass spectrum of Bu2S2, m/z (Irel, %): 178 (30) [M]+,
122 (25), 87 (10), 79 (8), 57 (98) [Bu]+, 45 (20), 41
(80), 29 (100) [Et]+.
EXPERIMENTAL
1
The H and 13C NMR spectra were recorded on
a Bruker DPX-400 spectrometer (400 MHz for 1H and
13
100.61 MHz of C), respectively, using CDCl3 as sol-
vent and HMDS as internal reference. Gas chromato-
graphic–mass spectrometric analysis was performed on
a Hewlett–Packard HP 5971A mass-selective detector
(electron impact, 70 eV) coupled with an HP 5890
chromatograph (Ultra-2 column, 5% of phenylmethyl-
silicone, injector temperature 250°C, oven temperature
programming from 70 to 280°C at 20 deg/min).
2-Butylsulfanyl-1,1-diethoxy-2-butene (IIIb).
A mixture of 0.8 g (0.005 mol) of aldehyde Ia, 11.58 g
(0.25 mol) of ethyl alcohol, 0.04 g of HBr in 1.25 ml
of CHCl3 (10 mol %), and 1.1 g of 3-Å molecular
2-Butylsulfanyl-2-butenal (Ia) was synthesized by
the procedure described in [13]. 13C NMR spectrum,
δC, ppm: 13.74 (CH3, Bu), 16.85 (CH3CH=), 21.73
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 6 2005

KEIKO et al.
814
neutralized with dry potassium carbonate. According
to the H NMR spectrum, the yield of acetal IIId was
sieves was kept for 6 days at room temperature. The
mixture was neutralized with potassium carbonate, and
the solvent was evaporated. According to the NMR
data, the residue was 100% of acetal IIIb. Vacuum
distillation afforded 0.38 g (32%) of IIIb with bp 125–
127°C (3 mm). 1H NMR spectrum, δ, ppm: 0.88 t (3H,
CH3 in Bu), 1.21 t (6H, CH3 in Et, 3J = 7.0 Hz), 1.38 m
(2H, CH2CH3 in Bu), 1.52 m (2H, SCH2CH2), 1.88 d
1
30%, of aldehyde VII, 12%, and of acetal Vd, 13%.
The 1H NMR spectrum and GC–MS parameters of Vd
were consistent with those reported in [8]. By vacuum
distillation we isolated 1 g (12.65%) of 2-butylsul-
fanyl-3,3-diethoxy-1-propene (IIId), bp 98–100°C
1
(5 mm). H NMR spectrum, δ, ppm: 0.9 t (3H, CH3 in
3
3
Bu), 1.2 t (6H, CH3 in Et), 1.38 m (2H, CH2 in Bu),
1.60 m [2H, CH2 in Bu), 2.65 m (2H, SCH2), 3.47 d.q
and 3.59 d.q (4H, OCH2), 4.90 s (1H, =CH2), 4.87 s
(1H, =CH2), 5.44 s (1H, OCHO). Mass spectrum, m/z
(Irel, %): 218 (2) [M]+, 189 (1) [M – C2H5]+, 174 (40)
[M – CH3CHO]+, 173 (8) [M – CH3CH2O]+, 145 (3),
117 (16), 103 (100) [C2H5OCHOC2H5]+, 89 (24)
[C4H9S]+, 75 (83) [C2H5OCHOC2H5 – C2H4]+, 47 (73)
[C2H5OCHOC2H5 – 2C2H4]+. Found, %: C 60.12;
H 10.27; S 14.68. C11H22O2S. Calculated, %: C 60.55;
H 10.08; S 14.69. In addition, vacuum distillation gave
(third fraction) 1.25 g (11.3%) of 2,3-bis(butylsul-
fanyl)-1,1-diethoxypropane (VII), bp 155°C (5 mm).
1H NMR spectrum, δ, ppm: 0.85 t (6H, CH3 in Bu),
1.2 t (6H, CH3 in Et), 1.35 m (4H, CH2 in Bu), 1.50 m
(4H, CH2 in Bu), 2.4 m (4H, SCH2), 2.67 m (1H, CH),
(3H, CH3CH, J = 6.8 Hz), 2.70 t (2H, SCH2, J =
3
7.4 Hz), 3.46 d.q and 3.60 d.q (4H, OCH2, J =
3
7.0 Hz), 4.82 s (1H, OCHO), 6.24 q (1H, CH, J =
6.8 Hz). Mass spectrum, m/z (Irel, %): 232 (5) [M]+,
188 (9) [M – CH3CHO]+, 187 (9) [M – C2H5O]+, 159
(2), 143 (1) [M – SC4H9], 131 (4), 103 (100) [C2H5O-
CHOC2H5]+, 75 (58) [C2H5OCHOC2H5 – C2H4]+, 47
(42) [C2H5OCHOC2H5 – 2C2H4]+. Found, %: S 13.92.
1
C12H24O2S. Calculated, %: S 13.80. The H NMR
spectrum of IIIb coincided with that reported in [13]
for a sample prepared by reaction of Ia with Si(OEt)4.
3,3-Dibutoxy-2-butylsulfanyl-1-propene (IIIc).
A mixture of 5.76 g (0.04 mol) of 2-butylsulfanyl-
2-propenal (Ib), 37 g (0.5 mol) of butanol, 77.9 g
(1.05 mol) of diethyl ether, 0.24 g (0.0014 mol,
3.5 mol %) of p-toluenesulfonic acid, and 6.84 g of
4-Å molecular sieves was kept for 10 days at room
temperature. The mixture was neutralized with dry
potassium carbonate, and the solvent was distilled off
under reduced pressure. According to the NMR data,
the residue contained 73% of acetal IIIc, 20% of dimer
VI, and 7% of acetal Vc. The mass spectrum of the
latter was identical to that of an authentic sample (see
below). By double vacuum distillation we isolated
3.8 g (32.5%) of acetal IIIc, bp 117–120°C (2 mm).
1H NMR spectrum, δ, ppm: 0.87 t (6H, CH3 in OBu),
0.88 t (3H, CH3 in SBu), 1.38 m (6H, CH2CH3),
1.56 m (6H, CH2CH2CH3), 2.67 t (2H, SCH2), 3.40 d.t
and 3.52 d.t (4H, OCH2), 4.84 s (1H, =CH2), 4.89 s
(1H, =CH2), 5.43 s (1H, OCHO). Mass spectrum, m/z
(Irel, %): 274 (2) [M]+, 217 (1) [M – C4H9]+, 202 (30)
[M – C3H7CHO]+, 201 (8) [M – C4H9O]+, 159 (22)
[C4H9OCHOC4H9]+, 146 (7), 145 (11), 103 [C4H9O-
CHOC4H9 – C4H9]+, 89 (24) [C4H9S]+, 73 (7), 57 (100)
[C4H9]+. Found, %: C 65.60; H 11.09; S 11.42.
C15H2O2S. Calculated, %: C 65.14; H 11.02; S 11.68.
3
2
2.80 d.d and 2.87 d.d (2H, CH2CH, J = 5.3, J =
3
12.4 Hz), 3.53 d.q and 3.67 d.q (4H, OCH2, J =
3
7.0 Hz), 4.56 d (1H, OCHO, J = 5.0 Hz). Mass spec-
trum, m/z (Irel, %): 308 (1) [M]+, 263 (3) [M – OC2H5]+,
219 (1) [M – SC4H9]+, 205 (1) [M – CH2SC4H9]+, 173
(2), 154 (2), 103 (100) [C2H5OCHOC2H5]+, 75 (33)
[C2H5OCHOC2H5 – C2H4]+, 47 (4) [C2H5OCHOC2H5 –
2C2H4]+. Found, %: C 58.54; H 10.40; S 20.88.
C15H32O2S2. Calculated, %: C 58.39; H 10.38; S 20.80.
1-Butoxy-1-butylsulfanyl-2-propanone (Vc).
A mixture of 7.33 g (0.05 mol) of 2-butylsulfanyl-2-
propenal (Ib), 22.24 g (0.3 mol) of butyl alcohol, and
0.5 ml of concentrated hydrochloric acid was kept for
24 h at room temperature. The mixture was neutralized
with K2CO3 and evaporated, and the residue was sub-
jected to double vacuum distillation to isolate 3.05 g
(28%) of compound Vc with bp 175–180°C (1 mm),
1
nD20 = 1.4690. H NMR spectrum, δ, ppm: 4.81 s (1H,
SCHO), 3.8 m (2H, CH2S), 3.4 m (2H, CH2O), 2.24 s
(3H, CH3CO), 1.45 m (4H, CH2), 1.49 m (4H, CH2),
0.91 m (6H, CH3). Mass spectrum, m/z (Irel, %): 175
(33) [C4H9SCHOC4H9]+, 119 (100) [C4H9SCHOC4H9 –
C4H8]+, 63 (23) [C4H9SCHOH – C4H8]+, 57 (79)
[C4H9]+, 43 (26) [CH3CO]+. Found, %: C 60.60;
H 10.20; S 14.75. C11H22O2S. Calculated, %: C 60.55;
H 10.09; S 14.68. The preceding fraction contained
Reaction of 2-butylsulfanyl-2-propenal with
ethyl alcohol. A mixture of 5.22 g (0.036 mol) of
aldehyde Ib, 32.26 g (0.7 mol) of ethyl alcohol, 0.41 g
(6.4 mol %) of p-toluenesulfonic acid, 121.47 g of
diethyl ether, and 7.43 g of 3-Å molecular sieves was
kept for two weeks at room temperature and was then
1
acetals Vc and IVc at a ratio of 1:1. The H NMR
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 6 2005

REACTIONS OF 2-BUTYLSULFANYL-2-ALKENALS WITH ALCOHOLS AND WATER
815
Bull. Acad. Serbe Sci., Arts., Clas. Sci. Mathem. Nat.,
1973, vol. 51, p. 85.
spectrum of IVc was in agreement with the data given
in [17]. Mass spectrum of IVc, m/z (Irel, %): 159 (6)
[BuOCHOBu]+, 129 (2), 103 (14) [M – C4H8]+, 57
(100) [Bu]+, 47 (4), 43 (22) [CH3CO]+, 41 (40).
6. Trofimov, B.A. and Shainyan, B.A., The Chemistry of
Functional Groups. Suppl. S: The Chemistry of Sulphur-
Containing Functional Groups, Patai, S. and Rappo-
port, Z., Eds., New York: Wiley, 1993, p. 755.
7. Keiko, N.A., Chuvashev, Yu.A., Stepanova, L.G., and
Voronkov, M.G., Izv. Ross. Akad. Nauk, Ser. Khim.,
1998, p. 2504.
8. Keiko, N.A., Funtikova, E.A., Stepanova, L.G., Chuva-
shev, Yu.A., and Larina, L.I., Russ. J. Org. Chem., 2002,
vol. 38, p. 970.
9. Keiko, N.A., Stepanova, L.G., Sarapulova, G.I.,
Vashchenko, A.V., Larina, L.I., Funtikova, E.A., and
Voronkov, M.G., Izv. Ross. Akad. Nauk, Ser. Khim.,
2000, p. 2009.
Reaction of 3,3-dibutoxy-2-butylsulfanyl-1-pro-
pene (IIIc) with water. A mixture of 2.97 g (0.01 mol)
of acetal IIIc, 0.2 g (0.1 mol) of water, and 0.19 g
(0.001 mol, 10 mol %) of p-toluenesulfonic acid was
kept for 9 days at room temperature. According to the
NMR data, the mixture contained 89% of acetal Vc;
the GC–MS data of Vc coincided with those given
above.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 03-03-33143).
10. Keiko, N.A., Chuvashev, Yu.A., Stepanova, L.G., Lari-
na, L.I., Sarapulova, G.I., and Voronkov, M.G., Russ. J.
Org. Chem., 1999, vol. 35, p. 34.
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