Synthesis and properties of β-oxo sulfides of the dioxothiolane series

Article abstract of DOI:10.1007/s10593-005-0232-2

It was shown that the hydroxy group in β-hydroxy sulfides of the dioxothiolane series can be oxidized selectively to a carbonyl group in the presence of a sulfide group. A sequence of transformations leading to the final β-oxo sulfides was proposed and wa

Full text of DOI:10.1007/s10593-005-0232-2

Chemistry of Heterocyclic Compounds, Vol. 41, No. 7, 2005
SYNTHESIS AND PROPERTIES OF β-OXO
SULFIDES OF THE DIOXOTHIOLANE SERIES
S. N. Gaydamaka, O. A. Shantaliy, and I. A. Raltshuk
It was shown that the hydroxy group in β-hydroxy sulfides of the dioxothiolane series can be oxidized
selectively to a carbonyl group in the presence of a sulfide group. A sequence of transformations leading
to the final β-oxo sulfides was proposed and was confirmed experimentally. A new original method was
developed for the production of β-oxo sulfides. Some characteristics of the synthesized compounds were
studied.
Keywords: β-hydroxy sulfides, β-oxo sulfides, five-membered cyclic sulfones, selective oxidation,
chemical properties.
Five-membered cyclic sulfones are extremely reactive compounds and are of interest both in synthetic
chemistry and in the design of substances with useful properties [1]. A notable position among such compounds
is occupied by the carbonyl derivatives. The presence of the carbonyl group in conjunction with the thiolane ring
significantly extends the synthetic possibilities of this type of compound. They have found use in peptide
synthesis [2] and in the synthesis of hormonal products [3], heterocyclic analogs of steroids [4, 5],
insectoacaricides [6], and herbicides [7]. In addition, they can be used as convenient intermediates for the
production of various types of cyclic sulfones [8].
Earlier [9] we demonstrated the basic possibility of selectively oxidizing a hydroxyl group to a carbonyl
group in the presence of a sulfide group in the β-hydroxy sulfide 1 (R = Me) of the dioxothiolane series using
chlorinating agents (elemental chlorine, sulfuryl chloride) with the formation of the keto sulfides 2 [9].
O
OH
RS
RS
S
S
O
O
O
O
1
2 a–d
1, 2a R = Me; 2 b R = Et, c R = p-MeC6H4, d R = p-BrC6H4
Further investigation of this reaction showed that direct oxidation of the hydroxyl group does not occur
[10]. Initially, substitutive chlorination occurs at the C(4) atom with the formation of the chloride 3,
accompanied by elimination of hydrogen chloride and the formation of the sulfolene 4. Migration of the double
bond then occurs in the acidic medium, and this leads to the enol 5 and to the ketone 2 as final product.
__________________________________________________________________________________________
Institute of Biochemistry and Petrochemistry, National Academy of Sciences of Ukraine, Kiev 02094;
e-mail: users@bpci.kiev.ua. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 974-985, July,
2005. Original article submitted April 30, 2003; revision submitted March 14, 2005.
820
0009-3122/05/4107-0820©2005 Springer Science+Business Media, Inc.

OH
O
OH
O
OH
O
RS
RS
RS
Cl
+
H
–HCl
Cl
1
2
a
S
S
S
c
b
d
O
O
O
3
5
4
Isomerization at the double bond in compound 4 (R = p-C6H4), which was isolated by fractional
crystallization from the crude product of the reaction of the hydroxy sulfide 1 with SO2Cl2, was established by
IR spectroscopy from the disappearance of the absorption band of the hydroxyl group and the appearance of the
carbonyl group in a methylene chloride solution saturated with hydrogen chloride.
As a rule, migration of the double bond in a dioxothiolane ring is carbanionic in nature, i.e., takes place
in an alkaline medium [11]. There are isolated examples of isomerization in an acidic medium, e.g., [12], but
their nature was not studied. It was noticed that the double bond in 4-hydroxy-2-thiolene 1,1-dioxide does not
isomerize either in an alkaline or in an acidic medium [13].
The composition of the products of the investigated reaction depends on the ratio of the rates of the
individual stages, which in turn depend to a considerable degree on the electronic and steric characteristics of the
substituent at the sulfur atom. The process takes place sufficiently smoothly if the rates of the first two stages (a
and b) are higher than the rates of the last two stages (c and d). Otherwise, difficultly separated mixtures, from
which compounds 3, 4, and 6 can be isolated together with the initial and final products, are formed.
O
RS
SO2Cl2
1, 2
S
O
O
6a,b
6 a R = Me, b R = Ph
Thus, in the reaction of the hydroxy sulfide 1c (R = Ph) with sulfuryl chloride the unsaturated ketone 6b
was isolated from the mixture of compounds with a 17% yield instead of the expected ketone 2. The rate of
stages a and b is clearly lower than the rate of the concluding stages, and the unreacted chlorinating agent reacts
with the saturated ketone that forms, giving the unsaturated ketone. This is confirmed by the fact that the oxo
sulfide 6a is readily produced during chlorination of the oxo sulfide 2a.
From the established sequence of reactions, leading to transformation of the hydroxyl group into a
carbonyl group, we proposed a new original approach to the synthesis of β-oxo sulfides of the dioxothiolane
series making it possible to avoid the formation of side products and to increase considerably the yield of the
final products. The method involves prior protection of the hydroxyl group with the formation of the acetate 7
(a), its oxidative chlorination to the sulfolene 8 (b), removal of the protection, and isomerization at the double
bond (c and d) (Table 1).
OAc
RS
OAc
RS
SO2Cl2
H+
H+
AcCl
1
5
2
a
S
c
b
d
S
O
O
O
O
8a–e
7a–e
7,8 a R = Me, b R = Et, c R = Ph, d R = p-MeC6H4, e R = p-BrC6H4
821

TABLE 1. The Physicochemical Characteristics of Compounds 2a-d, 7a,c-e,
and 8a-e
Found, %
——————
Com
pound*
Empirical
formula
Calculated, %
mp, °C*2
Yield, %
C
H
S
2а
C5H8O3S2
33.00
33.30
37.56
37.10
4.50
4.48
5.21
5.19
35.50
35.58
32.71
33.01
80-82
87-88
70
80
2b
C6H10O3S2
2c
2d
7а
7c
7d
7e
C11H12O3S2
C12H13BrO4S2
C7H12O4S2
51.75
51.54
5.08
4.72
24.68
25.01
129-132
146-147.5
53-56*3
92-93.5
84-85
89
70
86
95
89
70
37.58
37.39
3.13
2.82
19.91
19.56
37.84
37.49
5.47
5.39
28.26
28.59
C12H14O4S2
C13H16O4S2
C12H13BrO4S2
50.29
50.33
4.94
4.93
22.14
22.39
51.73
51.98
5.35
5.37
21.25
21.35
39.54
39.46
3.57
3,59
17.15
17.56
123-125
(21.77)
(21.87)*4
8а
8b
8c
8d
8e
C7H10O4S2
C8H12O4S2
C12H14O4S2
C13H16O4S2
C12H13BrO4S2
37.98
37.83
4.54
4.54
28.79
28.75
121-122
109-111
125-127
94-97
68.5
84.6
88
41.02
40.66
5.19
5.12
27.08
27.13
50.17
50.69
4.16
4.25
22.35
22.55
52.42
52.33
4.78
4.73
21.69
21.49
60.7
70.7
40.01
39.67
3.25
3.05
(21.38)
117-118
(21.72)*4
_______
* Compound 7b: bp 144-146°C (0.03 mm Hg), yield 80%.
*2 Solvents: isopropyl alcohol (compounds 2a-c, 7c,d, and 8b,e), benzene
(compounds 2d and 8a,c), and methanol (compounds 7e and 8d).
*3 bp 126-128°C (0.05 mm Hg), solidifies on storage. Crystallized by
introducing a seed into the freshly distilled product.
*4 Data from analysis for bromine.
Preparatively, the last two processes are carried out in one stage. The protecting group is removed first,
and the rearrangement then occurs, as confirmed by the fact that as the hydrochloric acid concentration at stage
(c) decreases the unsaturated hydroxy sulfide 4 is also found in the reaction products together with the final
product.
The synthesis of the analogous oxo sulfides 2 (R = Alk, C4, C6, C8) by the reaction of the corresponding
hydroxy sulfoxides with thionyl chloride was described in [12]. The authors state that the process can be realized
in sulfoxides with the trans arrangement of the substituents at positions 3 and 4 of the dioxothiolane ring; in the
case of the cis isomers the final product is the hydroxy sulfide 4. In view of our discovered transformation of the
hydroxy sulfide 4 into the oxo sulfide 2 it is difficult to agree with such statements.
According to data in [14], the 3-oxosulfolane is present to a significant degree in the enolic form. There
are no signs of the enolic form in the IR and NMR spectra of freshly obtained compounds 2. However, the oxo
sulfide 2c probably isomerizes gradually into the enolic form during prolonged storage. (Absorption bands
characteristic of the hydroxyl group and the C=C bond appear in the IR spectra.)
822

The obtained substances are polyfunctional compounds with many reaction centers. It can be assumed
that during the action of bases the anion can form at any of the carbon atoms and also at the oxygen atom. The
products from O- or C-alkylation or acylation can therefore be expected to form during their reaction with alkyl
or acyl halides.
We studied the reaction of some β-oxo sulfides with acid chlorides in the presence of triethylamine. The
reactions were conducted under mild conditions at room temperature in an inert solvent. The O-acylation
products 9a-j were formed (Table 2).
OAc
OAc
RS
RS
R1COCl, Et3N
2
S
S
O
O
O
O
9 a–j
10
9 a-e R = Me, f-i R = Et, j R = p-C6H4Br; a, f, j R1 = Me, b R1 = Et, c, g R1 = Pr,
d, h R1= Ph, e, i R1 = C2H4COOMe
The position of the double bond is confirmed by the data from the IR spectra. In the spectra of the
investigated compounds there is fairly strong absorption at 1610-1630 cm-1. This favors structure 9, in which the
double bond occupies position 2 of the dioxothiolane ring. In compounds 8, which we obtained by the action of
SO2Cl2 on the acylated hydroxy sulfides 7 where the double bond occupies position 4, the νC=C absorption bands
are significantly lower (1570-1580 cm-1) while those in the 3-sulfolenes 10 are weak.
TABLE 2. 4-Alkyl(aryl)thio-3-carboxy-1,1-thiolene 1,1-Dioxides 9a-j
Found, %
Calculated, %
H
IR, ν, cm-1
——————
Com-
pound
Empirical
formula
mp, °С*
Yield, %
C
S
νC=C
νC=O
1788
1783
1783
1750
9a
9b
9c
9d
9e
C7H10O4S2
C8H12O4S2
C9H14O4S2
C12H22O4S2
C10H14O6S2
37.91
37.83
40.67
40.66
43.15
43.18
50.78
48.95
4.56
4.54
5.17
5.12
5.60
5.64
4.54
4.79
29.26
28.85
27.20
27.14
25.61
25.61
22.44
21.78
90-92
84-85
76-78
94-96
85-86
1626
1610
1610
1624
1620
66.0
76.1
71.4
49.4
89
40.90
40.81
4.74
4.79
21.80
21.78
1725
1760
9f
9g
9h
9i
C8H12O4S2
C10H16 O4S2
C13H14O4S2
C11H16O6S
40.82
40.66
45.51
45.43
52.37
52.33
42.85
42.85
5.13
5.12
6.10
6.10
4.76
4.73
5.06
5.23
27.16
27.14
24.27
24.25
21.41
21.47
20.78
20.79
81-83
70-71
1626
1620
1782
1782
1750
66.7
58.9
71.4
76
116-117.5 1612
69.5-70.5
114-117
1621
77.4
1730
1780
9j*2
C12H11BrO4S 39.69
39.67
3.04
3.05
17.54
17.65
1780
77.4
_______
* Solvents: methanol (compounds 9a,b,e-g,i), isopropyl alcohol (compound
9c), benzene (compounds 9d,h), and carbon tetrachloride (compound 9j).
*2 Found, %: Br 22.70. Calculated, %: Br 21.99.
823

In the reaction of the ketones 2a and 11 with unsymmetrical dimethylhydrazine the enehydrazines 12 are
formed instead of the expected hydrazones.
NHNMe2
R
O
R
H2NNMe2
+
S
S
O
O
O
O
2a, 11
12a,b
2a, 12a R = SMe; 11, 12b R = H
The structure of these compounds was established by IR and 13C NMR spectroscopy. The presence of an
absorption band at 3240 cm-1 (νNH) favors the enehydrazine structure and makes it possible to assign the band at
1628 cm-1 to the vibrations of the C=C bond and not the C=N bond. In addition, the 13C NMR spectrum contains
signals for two sp2-hybridized C(2) and C(3) atoms and not one as in the supposed hydrazone.
Unlike dimethylhydrazine, hydroxylamine and O-alkylhydroxylamines react with the oxo sulfide 2a to
form the respective oximes 13a-g (Table 3).
NOR
MeS
H2NOR
2a
S
O
O
13a–g
13 a R = H, b R = Me, c R = Et, d R = Pr, e R = Bu, f R = CH2−CH=CH2;
g R = CH2Ph
The structure of the oximes 13 is confirmed by data from the 13C NMR spectra and chemical
transformations. The IR spectra do not contradict the proposed structure, but they do not contain absorption
characteristic of the C=N bond. Since, according to the selection rules, vibrations accompanied by change in
dipole moment do not appear in the IR spectra, it can be supposed that change in the electronic nature of
substituents close to the above-mentioned bond will affect the character of its vibrations, and it will appear in the
spectrum. In fact, although the spectrum of the oxidized substance 14 also does not contain the relevant
absorption, in the spectrum of the acetyl derivative 15 there is a weak band at 1640 cm-1.
NOAc
MeS
NOH
MeSO2
S
S
O
O
O
O
14
15
Oxidation of the methylthio group in the oxime 13a with hydrogen peroxide takes place readily without
complications. Oxidation of this group in the oxo sulfide 2a under analogous conditions leads to a complex
mixture of compounds, from which 2-(methylsulfonyl)ethylsulfonylacetic acid 16 was isolated with a 26% yield.
At first sight this unusual opening of the sulfothiolane ring in an acidic medium is reminiscent of
Baeyer–Villiger oxidation [15], in which the corresponding lactones or ω-hydroxy acids are formed from cyclic
ketones. We suppose that in the investigated case sulfide group is initially oxidized, thereby facilitating
subsequent nucleophilic substitution at the carbonyl carbon atom with cleavage of the C=C bond. This is
supported by the fact that compound 17 is formed during oxidation under anhydrous conditions.
824

825

O
O
O
O
MeSO2
MeSO2
OH
HOH
H2O2
2a
S
AcOH
S
O
O
17
16
The reverse reaction to the production of the oxime (acid hydrolysis) is accompanied by
dehydrogenation with the formation of the unsaturated oxo sulfide 6. The nitrogen-containing part was identified
in the form of ammonium chloride.
H2O, HCl
–NH4Cl
SO2Cl2
13a
2a
6a
With aliphatic and aromatic isocyanates in the presence of dibutyldiacetyltin the oxime 13a is converted
into the corresponding carbamoyloximes 18a-n (Table 4). Aliphatic carbamoyloximes 18a-g, unlike the aromatic
compounds, are thermally unstable, and they cannot therefore be purified by recrystallization. They
TABLE 4. 3-Carbamoyloxyimino-4-methylthiothiolane 1,1-Dioxides 18a-n
Found, %
Calculated, %
——————
Com-
pound
Empirical
formula
mp, °С*
Yield, %
76.9
C
H
N
S
18а
C7 H12N2O4 S2
33.10
33.31
4.71
4.79
11.15
11.10
25.11
25.40
99-100
18b
18c
18d
18e
18f
18g
18h
18i
C8H14N2O4S2
C9H16N2O4S2
C9H16N2O4S2
C10H18N2O4S2
C12H20N2O4S2
C13H16N2O4S2
C12H14N2O4S2
C12H13ClN2O4S2
C13H16N2O4S2
C12H13ClN2O4S2
35.92
36.08
38.55
38.56
5.36
5.30
5.79
5.75
10.45
10.52
10.00
9.99
24.05
24.08
22.93
22.87
23.03
22.87
21.86
21.78
20.01
20.01
19.50
19.52
20.59
20.39
90-92
85-86
86.6
85
—
—
—
70-73
69.4
22
40.89
40.80
44.85
44.98
47.04
47.55
6.10
6.16
6.35
6.29
4.85
4.90
9.67
9.52
8.33
8.74
8.06
8.53
8.94
8.95
72-74
84-86
67
105-106
122-124
67.8
80
(10.39)*2 128-130
(10.16)
(10.18)*2 123-125
(10.16)
84
18j
18k
8.50
8.53
—
19.50
19.53
—
74
126-127
22
18l
C12H13FN2O4S2
C12H13N3O6S2
—
—
—
—
—
19.15
19.29
17.51
17.84
131-133
141-142
38
87
18m
11.41
11.69
18n
C12H13N3O6S2
—
—
—
17.50
17.84
136-137
67.4
_______
* Solvents: benzene (compounds 18h,j,k), benzene + isopropyl alcohol
(compound 18i), dichloroethane (compound 18l,n).
*2 Data from analysis for Cl.
826

can be obtained in the analytically pure state with the use of pure starting compounds, accurate proportioning of
the reagents, and treatment under mild conditions. With the exception of 18g these compounds are converted
into dark-red resinous substances after storage for 2-3 months.
NOCONHR
MeS
RNCO
13a
Bu2Sn(OAc)2
S
O
O
18a–n
18 a R = Me, b R = Et, c R = Pr, d R = i-Pr, e R = sec-Bu, f R = cyclo-C6H11, g R = CH2Ph, h R = Ph, i R = p-ClC6H4,
j R = p-MeC6H4, k R = o-ClC6H4, l R = m-FC6H4, m R = p-NO2C6H4, n R = m-NO2C6H4
EXPERIMENTAL
The IR spectra of the synthesized compounds were recorded on a Specord M-80 spectrometer in tablets
with potassium bromide. The 13C NMR spectra were recorded on a Bruker SXR-200 instrument at 50 MHz in
acetone-d6. The signal of the CD3 group was taken as 29.2 ppm. The 1H NMR spectrum for 6b was recorded on a
Bruker SXR-200 instrument at 200 MHz in acetone-d6 with TMS as internal standard.
The initial β-hydroxy sulfides 1 were obtained by the described methods from 3-chloro-4-
hydroxythiolane 1,1-dioxide 1a [16] or 3,4-epoxythiolane 1,1-dioxide 1b [17] and the corresponding sodium
thiolates, using mixtures of the cis and trans isomers.
3-Hydroxy-4-methylthiothiolane 1,1-Dioxide (1a). Yield 85%; mp 152-154°C (0.05 mm Hg).
3-Hydroxy-4-(p-tolylthio)thiolane 1,1-Dioxide (1c). To a solution of sodium (0.130 g) in absolute
methanol (400 ml) we added 3,4-epoxythiolane 1,1-dioxide (14 g, 104.4 mmol) and p-methylthiophenol (13 g,
104.4 mmol). The mixture was boiled with stirring for 2 h and neutralized with hydrochloric acid solution, and
the volatile products were removed under vacuum. A small amount of water was added to the residue (a
yellowish oily liquid). The precipitate was filtered off, dried, and recrystallized from 2-propanol. The product
formed colorless prisms, yield 16.9 g (63%); mp 93-96°C. Found, %: С 50.98; H 5.60; S 24.96. C11H14O3S2.
Calculated, %: C 51.16; H 5.43; S 24.80.
4-(p-Bromophenylthio)-3-hydroxythiolane 1,1-Dioxide (1d). To a solution of sodium hydroxide
(2.33 g, 52.9 mmol) in water (34 ml) we added in portions with stirring over 45 min p-bromothiophenol (10 g,
52.9 mmol) and then dioxane (34 ml). After this over 2 h at room temperature we added 3-hydroxy-4-thiolene
1,1-dioxide (9.02 g, 52.9 mmol). The mixture was stirred for 2 h and was then concentrated to a third of the
initial volume under vacuum. The precipitate was filtered off, washed with water (2×30 ml), and dried. The yield
of the crude product was 15.68 g (92%); mp after threefold recrystallization from benzene, isopropyl alcohol,
and trichloroethylene 122-124.5°C. The product formed colorless plates. Found, %: C 37.48; H 3.41; Br 24.36 S
19.64. C11H14BrO3S2. Calculated, %: C 37.16; H 3.43; Br 24.72; S 19.84.
3-Acetoxy-4-alkyl(aryl)thiothiolane 1,1-Dioxides 7a-e. We dissolved the respective hydroxy sulfide
(20-30 mmol) in ten times the amount of acetyl chloride and left the solution at room temperature for 10-15 h.
The excess of acetyl chloride was removed under vacuum, and the residue was purified either by
recrystallization or by distillation at reduced pressure.
3-Acetoxy-4-alkyl(aryl)thio-2-thiolene 1,1-Dioxides 8a-e. To a 20-30% solution of the respective
compound 7a-e in methylene chloride we added dropwise with stirring an equimolar amount (up to a 10%
excess) of sulfuryl chloride. The mixture was stirred at room temperature until the release of gas had stopped
(2-3 h). The volatile products were removed under vacuum, and the residue was recrystallized. During storage
without protection against atmospheric moisture the substances were converted into oily products of
undetermined structure.
827

4-Alkyl(aryl)thio-3-oxothiolane 1,1-Dioxides 2. A. To a solution of the hydroxy sulfide 1a,b
(80 mmol) in methylene chloride (400 ml) with stirring and cooling (-10°C) we added sulfuryl chloride
(80 mmol) in methylene chloride (90 ml) over 2 h 30 min. The mixture was stirred without cooling for a further
1 h, most of the solvent was removed at atmospheric pressure, the residue and the gaseous products were
removed under vacuum (15 mm Hg), and the product was left overnight. The mixture was then again treated
under vacuum until the heating had stopped and the gaseous products were released. A 30-ml portion of
isopropyl alcohol was added to the residue, and the precipitate was separated, dried, and recrystallized. The yield
was ~70%. An additional quantity of the product can be obtained by partial evaporation of the mother solution.
B. A sample of the acetate 8 was boiled with 10-20 times the amount of hydrochloric acid until the
mixture was completely homogeneous (2-3 h). The product separated in the form of an oily liquid, which
solidified with time. The solid substance was filtered off, washed with water, dried, and recrystallized from a
suitable solvent.
4-Methylthio-3-oxo-4-thiolene 1,1-Dioxide (6a). To a solution of the oxo sulfide 2a (5.4 g, 30 mmol)
in methylene chloride (25 ml) with stirring and cooling (-10°C) we added sulfuryl chloride (4.05 g, 30 mmol) in
methylene chloride (8 ml) over 45 min, after which the mixture was stirred without cooling for 3 h. The volatile
products were removed under vacuum, and the residue was recrystallized from dichloroethane and then from
isopropyl alcohol. Yield 0.34 g (63%); mp 174-176°C, and the product formed colorless prisms. IR spectrum,
ν, cm-1: 1152, 1316 (νSO2); 1556 (νC=C); 1720 (νC=O). 13C NMR spectrum, δ, ppm (J, Hz): 13.89 (CH3, q,
1
1
1JCH = 142.9); 56.29 (CH2, t, JCH = 149.5); 137.44 (CH, d, JCH = 191.2); 153.0 (s, C–S); 187.7 (s, C=O).
Found, %: S 35.55. C5H6O3S2. Calculated, %: S 35.98.
3-Oxo-4-phenylthio-4-thiolene 1,1-Dioxide (6b). To a solution of compound 1c (3 g, 12.3 mmol) in
methylene chloride (150 ml) at room temperature with cooling we added dropwise sulfuryl chloride (1.66 g) in
methylene chloride (15 ml) over 2 h. The mixture was stirred for 2 h and left overnight. The next day isopropyl
alcohol (15 ml) was added to the mixture, and the precipitate was filtered off, washed with the same solvent, and
dried. After recrystallization from isopropyl alcohol 0.5 g of compound 6b (17%) was obtained; mp 127-147°C.
It gradually decomposed during storage. IR spectrum (0.1 M in methylene chloride), ν, cm-1: 1146, 1328 (νSO2);
1
1558 (νC=C); 1732 (νC=O). H NMR spectrum (solution in acetone-d6), δ, ppm: 4.30 (2Н); 6.99 (1Н); 7.59-7.64
(5Н). 13C NMR spectrum, δ, ppm: 57.285 (CH2); 128.350, 132.000, 132.144, 176.120 (Carom); 139.890, 139.926
(=CH); 153.534 (C–S); 188.572 (C=O).
3-O-Acyl-4-alkyl(aryl)thio-2-thiolene 1,1-Dioxides (9a-j). To a solution of the oxo sulfide 2
(~30 mmol) and an equimolar amount of acyl chloride in dioxane (15 ml) we added dropwise with stirring and
without cooling an equivalent amount of triethylamine in dioxane (5 ml). The mixture was stirred at room
temperature for 2 h and filtered, and the filtrate was evaporated under vacuum. The residue was recrystallized
from a suitable solvent.
3-(N,N-Dimethylhydrazino)-2-thiolene 1,1-Dioxide (12b). To a solution of 3-oxothiolane 1,1-dioxide
(5 g, 37.3 mmol) in methylene chloride (50 ml) with stirring at room temperature we added dropwise a solution
of N,N-dimethylhydrazine (2.24 g, 37.3 mmol) in methylene chloride (10 ml). The mixture was stirred for 1 h
and filtered. The filtrate was evaporated under vacuum, and the residue was recrystallized from dichloroethane.
The product formed colorless prisms; mp 131-135°C. Yield 4.72 g (71.8%). An additional quantity of the
product can be extracted by partial evaporation of the mother solution. 13C NMR spectrum, δ, ppm: 98.35 (C-2);
152.353 (C-3); 39.979 (C-4); 57.03 (C-5); 10.457 (SCH3); 6.522 (N(CH3)2). Found, %: S 17.94. C6H12N2O2S.
Calculated, %: S 18.19.
3-(N,N-Dimethylhydrazino)-4-methylthio-2-thiolene 1,1-Dioxide (12a). Similarly to the previous
method from the oxo sulfide 2a (1.0 g) and N,N-dimethylhydrazine (0.36 g) we obtained the corresponding
enehydrazine (0.2 g). The product formed slightly yellowish prisms; mp 111-114°C. 13C NMR spectrum, δ, ppm:
95.133 (C-2); 154.389 (C-3); 24.752 (C-4); 49.632 (C-5); 48.712 (N(CH3)2). Found, %: S 28.46. C7H14N2O2S2.
Calculated, %: S 28.84. After prolonged storage the substance decomposes.
828

(2-Methylsulfonylethylsulfonyl)acetic Acid (16). A mixture of compound 2a (0.27 g, 1.5 mmol) and
30% hydrogen peroxide (0.7 ml, 7.5 mmol) in glacial acetic acid (5 ml) was kept at room temperature for 3 days.
The mixture was evaporated under vacuum, filtered, and washed with isopropyl alcohol. Yield 0.09 g; mp 164-
165°C. IR spectrum, ν, cm-1: 1120, 1304 (νSO2), 1712 (νC=O), 3108 (νOH). Found, %: C 26.59; H 4.00; S 27.50.
C5H10O6S2. Calculated, %: C 26.08; H 4.38; S 27.85.
4-Methylsulfonyl-3-oxothiolane 1,1-Dioxide (17). To a solution of compound 2a (0.5 g, 2.7 mmol) in
anhydrous methylene chloride (10 ml) while stirring and cooling with iced water we added dropwise
m-chloroperbenzoic acid (1.0 g, 5.8 mmol) in methylene chloride (17 ml) over 1 h. The mixture was stirred
without cooling for 3 h 30 min. The precipitate was separated, washed with methylene chloride, dried, and
recrystallized from dichloroethane. Yield 0.2 g (34%); mp 164-166°C. IR spectrum, cm-1: 1123, 1145, 1308,
1332 (νSO2); 1750 (νC=O). 13C NMR spectrum (acetone-d6), δ, ppm: 42.00 (СН3); 50.85, 59.23 (С2, С6); 70.13
(С3); 193.81 (С4). Found, %: C 28.26; H 4.07; S 30.28. C5H8O5S2. Calculated, %: C 28.30; H 3.80; S 30.21.
4-Hydroxyimino-3-methylthiothiolane 1,1-Dioxide (13a). A mixture of compound 17 (5.4 g,
30 mmol), hydroxylamine hydrochloride (6.25 g, 90 mmol), and sodium acetate (7.38 g, 90 mmol) in 2-propanol
(125 ml) was boiled for 5 h. After cooling the reaction mixture was evaporated to dryness under vacuum, water
(5 ml) was added to the residue, the mixture was filtered, and the product was dried and recrystallized from
2-propanol. Yield 3.4 g. A further 0.5 g of the substance was isolated by extraction of the aqueous filtrate with
ethyl acetate. The total yield 67%. IR spectrum, cm-1: 1140, 1320 (νSO2), 32.60 (νOH). Found, %: C 31.17;
H 4.66; N 7.32; S 32.73. C5H9NO3S2. Calculated, %: C 30.80; H 4.60; N 7.20; S 32.80.
3-Hydroxyimino-4-methylsulfonylthiolane 1,1-Dioxide (14). A mixture of the oxime 13a (2 g,
10 mmol), 30% hydrogen peroxide (2.5 ml, 25 mmol), and acetic acid (30 ml) was stirred at 70°C for 3 h. The
reaction mixture was evaporated to dryness under vacuum, and the residue was recrystallized from ethanol.
Yield 1.0 g (43%); mp 193-196°C (decomp.). 13C NMR spectrum (DMSO-d6), δ, ppm (J, Hz): 46.62 (СН3,
1
1
1
1JCH = 136.7); 53.42 (C2, JCH = 147.6); 52.54 (C5, JCH = 146.3); 64.74 (C3, JCH = 144.9); 146.32 (C4).
Found, %: N 6.06; S 27.93. C5H9NO5S2. Calculated, %: N 6.16; S 27.92.
3-Acetoxyimino-4-methylthiothiolane 1,1-Dioxide (15). To a solution of the oxime 13a (2.0 g,
10 mmol) and acetyl chloride (0.83 g, 11 mmol) in dioxane (40 ml) with stirring and cooling with iced water we
added triethylamine (1.06 g, 11 mmol) in dioxane (15 ml) over 30 min. The mixture was stirred at room
temperature for 2 h and filtered. the filtrate was evaporated under vacuum, and the residue was recrystallized
from methanol. Yield 1.56 g (64%); mp 103-105°C, and the product formed colorless prisms. Found, %: N 6.28;
S 26.85. Calculated, %: N 6.90; S 27.02.
3-Alkoxyimino-4-methylthiothiolane 1,1-Dioxides (13b-g). A mixture of compound 2a (12.0 mmol),
the respective O-alkylhydroxylamine hydrochloride (15.0 mmol), and sodium acetate (15.0 mmol) in 2-propanol
(30 ml) was boiled for 5 h. The solvent was distilled under vacuum, and water (15 ml) was added to the residue.
The mixture was filtered, and the product was washed with water, dried, and recrystallized from alcohol.
3-[N-Alkyl(aryl)carbamoyloxyimino-4-methylthiothiolane 1,1-Dioxide (18). To a solution of the
oxime 13a (1.0 g) in dioxane (15 ml) we added an equimolar amount of the respective isocyanate and 2-3 drops
of tin dibutyldiacetate, and we left the mixture overnight. The residue in the form of a slightly colored viscous
mass was crystallized by rubbing with 2-propanol or ether. The aromatic carbamoyloximes were purified by
recrystallization, and the aliphatic compounds were obtained in the analytically pure state after washing with
ether. The latter decompose after prolonged storage.
The work was carried out with support from the Ukrainian Fundamental Research Fund (grant 3/328).
829

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