Halo derivatives of 2,4-dinitrothiolene 1,1-dioxides: Synthesis and structure

Article abstract of DOI:10.1023/A:1020763118667

Procedures were developed for preparing representatives of a new type of halonitrothiolene 1,1-dioxides: mono- and dihalo derivatives of 2,2,4-tri- and 2,4-dinitro-3-thiolene 1,1-dioxides. An X-ray diffraction study showed that 2,5-dinitro-2,3-dichloro-3-thiolene 1,1-dioxide molecules exist in the crystal as enantiomeric pairs; the five-membered rings have the envelope conformation, with deviation of the sulfur atom from the ring plane; the halogen atom and nitro group at the multiple bond are essentially coplanar with the ring.

Full text of DOI:10.1023/A:1020763118667

Russian Journal of General Chemistry, Vol. 72, No. 7, 2002, pp. 1111 1118. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 7, 2002,
pp. 1189 1197.
Original Russian Text Copyright
2002 by Berestovitskaya, Litvinov, Efremova, Lapshina, Krivolapov, Gubaidullin.
Halo Derivatives of 2,4-Dinitrothiolene 1,1-Dioxides:
Synthesis and Structure
V. M. Berestovitskaya, I. A. Litvinov, I. E. Efremova, L. V. Lapshina,
D. B. Krivolapov, and A. T. Gubaidullin
Herzen Russian State Pedagogical University, St. Petersburg, Russia
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received February 14, 2001
Abstract Procedures were developed for preparing representatives of a new type of halonitrothiolene
1,1-dioxides: mono- and dihalo derivatives of 2,2,4-tri- and 2,4-dinitro-3-thiolene 1,1-dioxides. An X-ray
diffraction study showed that 2,5-dinitro-2,3-dichloro-3-thiolene 1,1-dioxide molecules exist in the crystal
as enantiomeric pairs; the five-membered rings have the envelope conformation, with deviation of the sulfur
atom from the ring plane; the halogen atom and nitro group at the multiple bond are essentially coplanar
with the ring.
2,2,4-Trinitrothiolene 1,1-dioxides [1] containing
fragments of polynitroalkanes, CH acids, nitroethenes,
and five-membered heterocycles are interesting poly-
functional objects. Owing to the presence in their
molecules of several reaction centers, diverse reaction
pathways are possible, allowing synthesis of previous-
ly unknown or difficultly accessible groups of com-
pounds: dinitrothiolene 1,1-dioxides [2], arylaminodi-
nitrobutadienes [3], substituted nitroquinoxalines [4],
and also stable molecular complexes of dinitrothio-
phene 1,1-dioxides with pyridine ad its derivatives [5].
In view of the fact that introduction of a halogen atom
into a nitrothiolene 1,1-dioxide ring considerably
expands the synthetic potential of this class of com-
pounds [1], it seemed interesting to prepare halo de-
rivatives of di- and trinitrothiolene 1,1-dioxides and to
reveal their structural features.
With the aim to prepare halogenated polynitrothio-
lene 1,1-dioxides, we studied nitration of 4-nitro-3-
chloro-2- and -3-thiolene 1,1-dioxides I and II, and
also of 2-hydroximino-3-chloro-3-thiolene 1,1-dioxide
III. Nitration of I III with 55% HNO3 yielded 2,2,4-
trinitro-3-chloro-3-thiolene 1,1-dioxide IV, but its yield
did not exceed 8%. Along with the desired product
IV, we obtained large amounts ( 40%) of oxalic acid
crystal hydrate, the well-known product of oxidative
cleavage of haloethenes in nitration reactions [6, 7].
Cl
NO2
Cl
O2N
NO2
55% HNO3
100% HNO3
SO2
I
H
SO2
V
Cl
NO2
Cl
NO2
O2N
55% HNO3
O2N SO2
IV
SO2
Cl
NO2
Cl
NO2
II (1) 55% HNO ;
3
O2N
55% HNO3
(2) 100% HNO3
HON
SO2
III
Cl SO2
VI
1070-3632/02/7207-1111$27.00 2002 MAIK Nauka/Interperiodica

1112
BERESTOVITSKAYA et al.
When varying the conditions of nitration of II with
A convenient route to dichlorodinitrothiolene
1,1-dioxide VI and to its structural analogs, 2-chloro-
and 2-bromo-3-methyl-2,4-dinitro-3-thiolene 1,1-diox-
ides XI and XII, is halogenation of thiolenylnitro-
nates [11]. Chlorination and bromination of 4(2)-ni-
the aim to increase the yield of the desired product IV,
we obtained unexpected results. With 100% nitric acid
as nitrating agent (under these conditions, apparently,
radical nitration is inhibited), we obtained a precursor
of IV, 2,4-dinitro-3-chloro-3-thiolene 1,1-dioxide V.
Under conditions of gradual increase in the nitrating
agent concentration (the reaction was started in 55%
HNO3, and then 100% HNO3 was added), we isolated
2,4-dinitro-2,3-dichloro-3-thiolene 1,1-dioxide VI in
6% yield, and also oxalic acid crystal hydrate. Appar-
ently, compound VI formed under these conditions is
a product of destructive nitration [8] associated with
the effect of halogenating agents arising under the
action of concentrated HNO3 as oxidant on halogen-
ated alkenes [9, 10].
6
tro-1,1-dioxo-1 -thiolenyl-2(4)-nitronates IX and X,
which are prepared from di- and trinitro-containing
precursors V, VII, and VIII [2], occurs under mild
conditions and gives halo derivatives VI, XI, and
XII in 25 34% yields as final products. The selec-
tivity of the electrophilic attack of the C2 position
of IX and X, observed in these reactions, is charac-
teristic of ambident thiolenylnitronate anions [11]
and is probably due to the electron-withdrawing ef-
fect of the sulfonyl group on the electron density dis-
tribution:
R
NO2
R
NO2
O2N
O2N
CH3ONa (KOH)
KOH, H2O2
H
SO2
V, VII
NO2
SO2
VIII
O2N
R
O2N
R
NO2
R
NO2
.
.
.
.
.... ..
.
O2N
Cl2
MeCl
Br2
MeBr
.
.
.... ..
O2N
Kat+
Cl SO2
Br SO2
SO2
IX, X
VI, XI
XII
R = Cl (V, VI, IX), CH3 (VII, VIII, X XII); Kat = Na (IX), K (X).
The spectral characteristics of 2,2,4-trinitro-3-clo-
The spectral characteristics of sodium 4(2)-nitro-3-
chloro-1,1-dioxo-1 -thiolenyl-2(4)-nitronate IX agree
with those of the previously described potassium salt
of 3-methyl-2,4-dinitrothiolene 1,1-dioxide X [2]. The
electronic absorption spectrum of IX in aqueous solu-
6
ro-3-thiolene 1,1-dioxide IV prepared by nitration of
I and III are in agreement with published data [12]
for the sample prepared by us from chloronitrothio-
lene 1,1-dioxide II; compounds VII and X were char-
acterized in part in [2]. The structure of previously
unknown compounds V, VI, IX, XI, and XII was de-
termined spectroscopically (Table 1).
tion is characterized by a long-wave absorption band
1
at
360 nm ( 6000 l mol 1 cm ) corresponding
max
to the conjugated heterocyclic dinitro anion. The IR
spectrum contains absorption bands belonging to the
2,4-Dinitro-3-chloro-3-thiolene 1,1-dioxide V is
a colorless crystalline substance; its 1H NMR spectrum
in DMSO-d6 contains signals of the methylene
(4.44 ppm) and nitromethine (8.39 ppm) protons. The
downfield location of the latter signal is typical of
similar dinitro compounds [13], including previously
described 3-methyl-2,4-dinitro-3-thiolene 1,1-dioxide
VII (8.50 ppm) [2], and is indicative of the increased
CH acidity of dinitrothiolene 1,1-dioxides. The IR
spectrun of V contains, along with the absorption
bands of conjugated and nonconjugated nitro groups,
also the bands of the ionized nitro group, indicating
that the ionic structure contributes to the ground state
of V (Table 1).
1
ionized nitro group (1590, 1510, 1230, 1180 cm )
1
[14], sulfonyl group (1350, 1130 cm ), and multiple
1
bond (1610 cm ).
2-Halo-2,4-dinitro-3-thiolene 1,1-dioxides VI, XI,
and XII are light yellow crystalline substances with
similar IR spectra (Table 1) containing bands of the
C=C bond and nitro and sulfonyl groups. According
to published data [14 16], the bands at 1590 1580
1
and 1310 1300 cm can be assigned to vibrations of
the gem-halonitromethyl group, the bands at 1540
1
1530 and 1360 1350 cm , to vibrations of the con-
jugated nitro group, and the absorption in the range
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 7 2002

HALO DERIVATIVES OF 2,4-DINITROTHIOLENE 1,1-DIOXIDES: SYNTHESIS AND STRUCTURE 1113
Table 1. Physicochemical and spectral characteristics of substituted 2,4-dinitro-3-thiolene 1,1-dioxides IV VII, XI, and XII
R
NO2
O2N
X
SO2
IR spectrum,a , cm
=CNO2, C=NO2, C(NO2)X
1H NMR spectrum,b
, ppm
1
mp,
C
R
X
SO2
C=C CH3 CH2 CHNO2
IV
V
VI
Cl
Cl
Cl
NO2
H
Cl
H
Cl
Br
8
83 84
1600, 1590, 1550, 1390, 1330, 1320 1330, 1170 1640
4.93
4.44
4.93
25 141 142 1590, 1520, 1350, 1310, 1240, 1160 1350, 1130 1620
34c 84 85
1590, 1540, 1350, 1310, 1200, 1160 1340, 1130 1620
50 76 77
30 101 102 1590, 1530, 1350, 1300, 1220, 1200 1350, 1150 1600 2.20 4.27
25 103 105 1580, 1540, 1360, 1300, 1210, 1170 1360, 1130 1610 2.40 4.30
8.39
8.50
VII CH3
XI
XII CH3
1580, 1500, 1340, 1320, 1220, 1180 1340, 1120 1630 2.30 4.24
CH3
a
For measuring the IR spectra, samples of IV and VII were prepared as Nujol mulls, and samples of V, VI, XI, and XII, as KBr
b
1
c
pellets. The H NMR spectra of V and VII were taken in DMSO-d , and those of IV, VI, XI, and XII, in acetonitrile-d . The
6
3
yield of IV is given for the synthesis by halogenation of IX.
Table 2. Atomic coordinates in the structure of VI, equivalent isotropic temperature factors of nonhydrogen atoms
3
B = 4/33
(ai aj)B(i, j) ( 2), and isotropic temperature factors of hydrogen atoms Biso
(
)
2
i = 1 j = 1
VIa
VIb
Atom
x
y
z
B, Biso
x
y
z
B, Biso
Cl2
Cl3
S1
0.3489(4)
0.2600(3)
0.2238(3)
0.3010(8)
0.1522(8)
0.4089(9)
0.5257(8)
0.0421(7)
0.061(1)
0.4330(9)
0.0482(8)
0.314(1)
0.229(1)
0.140(1)
0.127(1)
0.0183
0.0556(8)
0.3894(8)
0.1194(7)
0.129(2)
0.081(2)
0.485(2)
0.223(2)
0.614(2)
0.664(2)
0.305(2)
0.580(2)
0.189(3)
0.341(2)
0.421(2)
0.373(3)
0.3279
0.1443(2)
0.0922(1)
0.2288(1)
0.2676(4)
0.2182(3)
0.2091(5)
0.1847(5)
0.1820(4)
0.1207(4)
0.1897(4)
0.1582(4)
0.1756(5)
0.1488(5)
0.1754(5)
0.2241(5)
0.2380
4.8(1)
4.26(9)
3.05(8)
3.7(2)
3.6(2)
6.7(4)
7.9(5)
3.9(3)
4.4(3)
3.6(3)
2.2(3)
3.7(4)
1.7(3)
2.6(3)
2.8(3)
6
0.2597(4)
0.1098(3)
0.3470(3)
0.4730(8)
0.2671(9)
0.4430(9)
0.4516(9)
0.135(1)
0.0216(9)
0.414(1)
0.110(1)
0.298(1)
0.198(1)
0.197(1)
0.292(1)
0.2373
0.3793(8)
0.0689(8)
0.3662(7)
0.393(2)
0.560(2)
0.080(2)
0.080(3)
0.115(2)
0.164(2)
0.061(2)
0.098(2)
0.204(2)
0.065(2)
0.039(3)
0.172(3)
0.2135
0.0086(2)
0.0157(2)
0.0892(2)
0.0905(4)
0.0909(5)
0.0508(4)
0.0163(3)
0.1684(4)
0.1100(5)
0.0215(5)
0.1262(5)
0.0367(4)
0.0544(5)
0.1017(5)
0.1296(5)
0.1631
4.7(1)
4.1(1)
3.30(9)
3.7(2)
5.7(3)
6.1(3)
5.4(3)
7.0(3)
5.9(4)
3.4(3)
4.0(3)
2.0(3)
2.1(3)
3.1(4)
3.2(4)
6
O1
O2
O3
O4
O5
O6
N2
N4
C2
C3
C4
C5
H51
H52
0.1449
0.5027
0.2430
3
0.3656
0.0999
0.1436
4
1
1540 1530 and 1220 1160 cm , apparently, to
vibrations of the ionized nitro group.
The UV spectrum of bromodinitrothiolene 1,1-dioxide
XII contains an absorption band at
370 nm
max
1
( 6000 l mol 1 cm ) characteristic of the 3-methyl-
1
The H NMR spectrum of 2,4-dinitro-2,3-dichloro-
2,4-dinitro-3-thiolene 1,1-dioxide anion ( max 370 nm,
3-thiolene 1,1-dioxide VI cosists of a single signal of
methylene protons at 4.93 ppm. The spectra of 2-chlo-
ro- and 2-bromo-3-methyl-2,4-dinitro-3-thiolene 1,1-
dioxides XI and XII contain signals of methyl (2.20,
2.40 ppm) and methylene (4.27, 4.30 ppm) protons.
1
8000 l mol 1 cm [2]). This fact suggests ready
heterolytic rupture of the C Br bond, which is consis-
tent with published data for bromotrinitromethane [15]
and for other gem-bromonitro derivatives [14, 16].
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 7 2002

1114
BERESTOVITSKAYA et al.
Table 3. Bond lengths (d, ) in VIa and VIb
Bond
VIa
VIb
Bond
VIa
VIb
Bond
VIa
VIb
Cl2 C2
Cl3 C3
S1 O1
S1 O2
S1 C2
1.77(2)
1.68(1)
1.40(1)
1.47(1)
1.86(2)
1.72(1)
1.68(1)
1.388(9)
1.46(1)
1.87(1)
S1 C5
O3 N2
O4 N2
O5 N4
O6 N4
1.87(2)
1.25(2)
1.14(1)
1.22(1)
1.20(2)
1.75(2)
1.23(2)
1.17(2)
1.24(2)
1.14(2)
N2 C2
N4 C4
C2 C3
C3 C4
C4 C5
1.53(2)
1.47(2)
1.52(2)
1.33(2)
1.43(2)
1.59(2)
1.44(2)
1.47(2)
1.36(2)
1.54(2)
Table 4. Bond angles ( , deg) in VIa and VIb
Angle
VIa
VIb
Angle
VIa
VIb
Angle
VIa
VIb
O1S1O2
O1S1C2
O1S1C5
O2S1C2
O2S1C5
C2S1C5
O3N2O4
O3N2C2
O4N2C2
121.2(6)
108.7(6)
111.5(6)
107.4(7)
110.9(6)
93.3(7)
128.0(1)
110.0(1)
122.0(1)
119.9(7)
111.6(6)
113.5(7)
105.9(7)
108.0(7)
94.8(7)
128.0(1)
113.0(1)
119.0(1)
O5N4O6
O5N4C4
O6N4C4
Cl2C2S1
Cl2C2N2
Cl2C2C3
S1C2N2
S1C2C3
122.0(1)
118.0(1)
120.0(1)
109.9(9)
109.5(9)
112.0(1)
110.0(1)
102.8(9)
123.0(1)
112.0(1)
124.0(1)
110.8(8)
108.8(9)
115.5(9)
105.9(8)
103.5(9)
N2C2C3
Cl3C3C2
Cl3C3C4
C2C3C4
N4C4C3
N4C4C5
C3C4C5
S1C5C4
112.0(1)
118.0(9)
130.0(1)
112.0(1)
123.0(1)
113.0(1)
124.0(1)
100.3(9)
112.0(1)
118.0(1)
126.0(1)
115.0(1)
124.0(1)
119.0(1)
117.0(1)
104.0(1)
Table 5. Torsion angles ( , deg) in VIa and VIb
Angle
VIa
VIb
Angle
VIa
VIb
O1S1C2Cl2
O1S1C2N2
O1S1C2C3
O2S1C2Cl2
O2S1C2N2
O2S1C2C3
C5S1C2Cl2
C5S1C2N2
C5S1C2C3
O1S1C5C4
O2S1C5C4
C2S1C5C4
O3N2C2Cl2
O3N2C2S1
O3N2C2C3
O4N2C2Cl2
O4N2C2S1
103.0(8)
18(1)
137.4(9)
29.9(9)
150(1)
90(1)
143.0(8)
96(1)
23(1)
134.6(9)
87(1)
23(1)
176(1)
64(1)
50(2)
94.0(8)
24(1)
141.6(9)
38.1(8)
155.9(8)
86(1)
148.5(7)
93.8(9)
24(1)
137.4(9)
87(1)
21(1)
176(1)
65(1)
47(2)
4(2)
O4N2C2C3
O5N4C4C3
O5N4C4C5
O6N4C4C3
O6N4C4C5
Cl2C2C3Cl3
Cl2C2C3C4
S1C2C3Cl3
S1C2C3C4
N2C2C3Cl3
N2C2C3C4
Cl3C3C4N4
Cl3C3C4C5
C2C3C4N4
C2C3C4C5
N4C4C5S1
C3C4C5S1
134(2)
167(1)
17(2)
10(2)
167(1)
46(1)
135(1)
164.5(7)
17(1)
78(1)
101(1)
1(2)
177(1)
177(1)
1(2)
165.0(9)
19(2)
125(1)
172(1)
9(2)
16(2)
163(1)
46(1)
141(1)
167.7(8)
19(1)
79(1)
94(1)
5(2)
177(1)
177(1)
4(2)
164(1)
14(2)
9(2)
112(2)
123(1)
Reliable information on the structure of 2,4-dinitro-
2,3-dichloro-3-thiolene 1,1-dioxide VI, formed by this
unusual pathway, is furnished by single crystal X-ray
diffraction (Tables 2 5). We found that compound VI
exists in the crystal as an enantiomeric pair of mole-
cules VIa and VIb (Fig. 1) with the R and S configu-
ration of C2, respectively. The respective bond lengths
and bond angles in crystallographically independent
molecules VIa and VIb are equal within experimental
error (Tables 3, 4).1
1
Because of the small size of the available crystal of VI, the
number of the measured intensities was insufficient for full
structure refinement, and the molecular geometries were de-
termined with large errors. Therefore, we discuss only the
molecular conformations.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 7 2002

HALO DERIVATIVES OF 2,4-DINITROTHIOLENE 1,1-DIOXIDES: SYNTHESIS AND STRUCTURE 1115
Fig. 1. Geometry of independent molecules (a) VIa and (b) VIb in the crystal.
Fig. 2. Molecular packing of VI in the crystal (projection along the 0x axis). The C H O hydrogen bonds are shown.
The five-membered rings in VIa and VIb have the
envelope conformation: The C2C3C4C5 fragments are
VIb]. There are short intramolecularr contacts between
Cl3 and O6 [2.85(1) in VIa and 2.92(1) in VIb;
sum of the van der Waals radii 3.27 ]. The C3 Cl3
and C4 N4 bonds are appreciably shorter than
the corresponding bonds at C2, which is consistent
with variation of the carbon covalent radius depend-
ing on the carbon valence state.
planar within 0.005(14) (in VIa) and 0.02(2)
VIb), and the sulfur atom deviates from this plane by
0.560(4) (in VIa) and 0.510(4) (in VIb). The
(in
O2 atoms at sulfur and the nitro groups at C2 are axial,
and the O1 and Cl2 atoms are equatorial. The double
bond in the rings of VIa and VIb has a usual planar
structure, despite the eclipsed location of such bulky
substituents as Cl and NO2 [torsion angle Cl3C3C4N4
1(2) in VIa and 5(2) in VIb] (Table 5). The nitro
group at C4 is also virtually coplanar with the double
bond [torsion angle C3C4N4O6 10(2) in VIa and
16(2) in VIb; dihedral angle between the C2C3C4C5
and C4N4O5O6 planes 12(2) in VIa and 14(2) in
The molecular packing in the crystal (Fig. 2) is
determined by C H O hydrogen bonds:
(1) C5a H51a O2a ( x, 1/2 + y, 1/2 z), C5a H51a
1.28, H51a O2a 2.31, C5a O2a 3.481(15) , angle
C5a H51a O2a 150 ;
(2) C5b H51b O1a, C5b H51b 1.16, H51b O1a 2.31,
C5b O1a 3.181(19) , angle C5b H51b O1a 130 ;
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 7 2002

1116
BERESTOVITSKAYA et al.
1812 had I 3 , were measured on an Enraf-Nonius
(3) C5b H51b O5a ( x, 1/2 + y, 1/2 z), C5b H51b
1.16, H51b O5a 2.43, C5b O5a 3.377(16) , angle
C5b H51b O5a 137 ;
CAD-4 automatic four-circle diffractometer at 20 C
in the reciprocal space quadrant (CuK radiation,
graphite monochromator, /2 scanning,
70 ).
(4) C5b H52b O4a (1
x, 1/2 + y, 1/2
z),
,
The intensities of three check reflections did not de-
crease in the course of the experiment. The absorption
C5b H52b 1.00, H52b O4a 2.57, C5b O4a 3.481(19)
angle C5b H52b O4a 153 .
1
( Cu 85.66 cm ) was not taken into account empiri-
cally, because we found no sufficiently strong reflec-
Along with these hydrogen bonds, in the crystal of
VI there are numerous short contacts (shorter than the
sum of the van der Waals radii) between the Cl, O,
and N atoms. As a result, the molecular packing is
fairly close, which is manifested in the high density
tions with
80 . The structure was solved by the
direct method using SIR program [21] and refined
first in the isotropic and then in the anisotropic
approximation. All the hydrogen atoms were subse-
quently revealed from the differential electron density
series, and their contribution to the structural ampli-
tudes was taken into account with fixed positional and
isotropic temperature parameters. To elucidate the
absolute structure, we refined the direct and inverted
structures. For the direct structure, R 0.07276, RW
0.07388; for the inverted structure, R 0.07523, RW
0.07839. A total of 271 parameters were refined from
1322 reflections. According to the Hamilton test [22],
the direct structure corresponds to the absolute struc-
ture with 90% probability. The final divergence fac-
tors are R 0.073, RW 0.074 for 1322 unique reflec-
tions with F2 3 . All calculations were performed
on an Alpha Station 200 computer using MolEN pro-
gram package [23]. The figures were plotted and the
intermolecular contacts analyzed using PLATON
program [24].
3
of VI, 1.95 g cm .
Thus, we have developed new procedures for pre-
paring mono- and dihalo derivatives of 2,2,4-trinitro-
and 2,4-dinitro-3-thiolene 1,1-dioxides and character-
ized their structure by UV, 1H NMR, and IR spectros-
copy. The molecular geometry and structural param-
eters of 2,4-dinitro-2,3-dichloro-3-thiolene 1,1-dioxide
have been determined by single crystal X-ray diffrac-
tion.
EXPERIMENTAL
The IR spectra were taken on Specord IR-75 and
UR-20 spectrophotometers (LiF and NaCl prisms).
Samples of IV and VII were prepared as Nujol mulls,
and samples of V, VI, XI, and XII, as KBr pellets.
The electronic absorption spectra were taken on a
Specord M-40 double-beam spectrophotometer (dis-
mountable quartz cells) with automatic recording of
the spectrum and on an SF-46 spectrophotometer
(quartz cells). The solvents were water (for IX) and
acetonitrile (for XII).
2,2,4-Trinitro-3-chloro-3-thiolene 1,1-dioxide IV.
a. Dinitrogen tetroxide (1 ml) was added to a solution
of 1 g of 4-nitro-3-chloro-2-thiolene 1,1-dioxide I in
6 ml of 55% HNO3. The mixture was left for 70 h,
after which the solution was evaporated in the cold
until light yellow crystals of IV formed; these crystals
were filtered off and dried. Yield 0.11 g (7%), mp 83
84 C (from chloroform). Mixing with an authentic
sample prepared according to [12]2 gave no melting
point depression. Found, %: C 16.92, 16.91; H 0.90,
0.89; N 14.56, 14.56. C4H2ClN3O8S. Calculated, %:
C 16.70; H 0.70; N 14.61. The mother liquor was fur-
ther evaporated in the cold, and the residue was dried
in a vacuum desiccator. Oxalic acid crystal hydrate
was obtained; yield 0.53 g (42%), mp 100 102 C
(from methanol) {mp 101.5 C (from water) [25]}.
1
The H NMR spectra were measured on a Tesla
BS-487C spectrometer (80 MHz). The solvents were
acetonitrile-d3 for IV, VI, VII, IX, and XII, and
DMSO-d6 for V. The chemical shifts were determined
relative to internal and external HMDS (accuracy
0.5 Hz,
scale).
4-Nitro-3-chloro-2-thiolene 1,1-dioxide
I
[17],
4-nitro-3-chloro-3-thiolene 1,1-dioxide II [18], 4-ni-
tro-2-hydroximino-3-chloro-3-thiolene 1,1-dioxide III
[19], and 3-methyl-2,2,4-trinitro-3-thiolene 1,1-diox-
ide VIII [20] were prepared by published procedures.
b. Compound IV was prepared from 4-nitro-3-chlo-
ro-3-thiolene 1,1-dioxide II according to [12] in the
absence of paraform. Yield 8%, mp 83 84 C (from
chloroform).
Light yellow crystals of VI were grown from the
reaction solution. Rhombic system; at 20 C: a
3
10.930(5), b 6.030(5), c 28.642(8) ; V 1888(1)
,
3
2
dcalc 1.95 g cm , Z 8, space group P212121 (two inde-
pendent molecules VIa and VIb). The unit cell param-
eters and intensities of 4307 reflections, of which
The melting point of 2,2,4-trinitro-3-chloro-3-thiolene 1,1-di-
oxide IV prepared according to [12] is also 83 84 C and
not 108 C as erroneously indicated in [12].
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HALO DERIVATIVES OF 2,4-DINITROTHIOLENE 1,1-DIOXIDES: SYNTHESIS AND STRUCTURE 1117
c. Dinitrogen tetroxide (1 ml) was added with stir-
ring to a solution of 2.0 g of 4-nitro-2-hydroximino-
3-chloro-3-thiolene 1,1-dioxide III in 10 ml of 55%
HNO3. The mixture was left for 1 h, after which the
solution was evaporated in the cold until light yellow
crystals of IV formed; these crystals were filtered off
and dried. Yield 0.23 g (8%), mp 83 84 C (from
chloroform). Mixing with the samples prepared by
procedures a and b gave no melting point depression.
The mother liquor was further evaporated in the cold,
and the residue was dried in a vacuum desiccator.
Oxalic acid crystal hydrate was obtained; yield 0.98 g
(44%), mp 100 102 C (from methanol).
residue was dried in a vacuum desiccator. Oxalic acid
crystal hydrate was obtained; yield 0.56 g (22%),
mp 100 102 C (from methanol).
b. Chlorine was passed through 0.79 g of a suspen-
sion of IX in 25 ml of absolute methanol. The salt
gradually dissolved, and a white precipitate formed.
After keeping for 30 min, the NaCl precipitate was
filtered off, and the mother liquor was evaporated on
a rotary evaporator. The light yellow oily residue
was treated with chloroform to induce crystallization
of VI. The light yellow crystals were filtered off and
dried. Yield of VI 0.25 g (34%), mp 84 85 C (dec.).
Mixing with the sample prepared by procedure a gives
no melting point depression.
2,4-Dinitro-3-chloro-3-thiolene 1,1-dioxide V.
A 2-g portion of II was dissolved in 20 ml of 100%
HNO3. The solution was left for 10 days, after which
it was evaporated in the cold until colorless crystals
of the initial 4-nitro-3-chloro-3-thiolene 1,1-dioxide II
started to form; these crystals were filtered off and
dried. A 0.26-g portion of II (13%) was recovered;
mp 159 160 C. Mixing with the initial sample gave
no depression of the melting point. The filtrate was
further evaporated in the cold until light yellow plates
of V formed; these were filtered off and dried in a
vacuum desiccator. Yield of V 0.62 g (25%), mp 140
142 C. Found, %: C 19.89, 19.90; H 1.35, 1.40; N
9.69, 9.73. C4H3ClN2O6S. Calculated, %: C 19.79;
H 1.24; N 9.90. The mother liquor was further evap-
orated in the cold, and the residue was dried in a
vacuum desiccator. Oxalic acid crystal hydrate was
obtained; yield 0.30 g (12%), mp 100 102 C (from
methanol).
3-Methyl-2,4-dinitro-3-thiolene 1,1-dioxide VII.
A 1-ml portion of 30% H2O2 was added to a suspen-
sion of 0.53 g of 3-methyl-2,2,4-trinitro-3-thiolene
1,1-dioxide VIII. The resulting mixture was cooled to
10 C, after which a solution of 0.27 g of sodium
ethylate in 10 ml of absolute ethanol was added drop-
wise. After keeping for 20 min, the solvent was evap-
orated in the cold, and the residue was dried in a
vacuum desiccator. The resulting colorless precipitate
was treated with 5 ml of anhydrous acetonitrile; the
sodium nitrite precipitate was separated by decanting,
and the solution was evaporated on a rotary evapora-
tor. The resulting colorless crystals were dried in a
vacuum desiccator. Yield of crystal hydrate of VII
0.32 g (73%), mp 76 77 C (dec.). Compound VII is
unstable; therefore, it was purified by reprecipitation
with dry chloroform from absolute acetone. Found, %:
C 20.72, 20.70; H 4.94, 4.91; N 10.01, 10.10.
C5H6N2O6S 4H2O. Calculated, %: C 20.41; H 4.80;
N 9.52.
6
Sodium 4(2)-nitro-3-chloro-1,1-dioxo-1 -thiolen-
yl-2(4)-nitronate IX. A solution of 0.33 g of sodium
methylate in 5 ml of absolute methanol was added
dropwise to a suspension of 0.72 g of 2,4-dinitro-
3-chloro-3-thiolene 1,1-dioxide V in 25 ml of absolute
ether. The solution was stirred for 15 min, after which
the precipitate was filtered off, washed with absolute
ether, and dried in a vacuum desiccator over alkali.
Yield of sodium nitronate IX 0.63 g (78%), mp 165
168 C (dec.).
6
Potassium 3-methyl-4(2)-nitro-1,1-dioxo-1 -thio-
lenyl-2(4)-nitronate X. a. A 3-ml portion of 30%
H2O2 was added to a solution of 0.53 g of VIII in
20 ml of methanol. The mixture was cooled to 10 C,
and a solution of 0.80 g of KOH in 10 ml of methanol
was added dropwise. After keeping for 10 min, the
orange precipitate of nitronate X was filtered off.
Yield 0.42 g (80%), decomposition point 170 C.
2,4-Dinitro-2,3-dichloro-3-thiolene 1,1-dioxide VI.
a. A 2-g portion of II was dissolved in 15 ml of 55%
HNO3. After 24 h, 5 ml of 100% HNO3 was added,
and the mixture was left for 10 days. After that, the
mixture was evaporated in the cold until yellow nee-
dles of VI formed, which were filtered off and dried.
Yield 0.17 g (6%), mp 84 85 C. Found, %: C 17.22,
17.25; H 0.70, 0.69; N 9.63, 9.88. C4H2Cl2N2O6S.
Calculated, %: C 17.33; H 0.72; N 10.14. The mother
liquor was further evaporated in the cold, and the
b. A solution of 0.17 g of KOH in 10 ml of meth-
anol was added to a suspension of 0.88 g of crystal
hydrate of VII in 10 ml of methanol. After keeping
for 10 min, nitronate X was subjected to halogenation
without intermediate isolation.
3-Methyl-2,4-dinitro-2-chloro-3-thiolene 1,1-di-
oxide XI. Chlorine was passed through a suspension
of 0.78 g of X in 25 ml of absolute methanol. The red
precipitate of the salt gradually dissolved, and a white
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 7 2002

1118
BERESTOVITSKAYA et al.
precipitate formed. After keeping for 30 min, the KCl
precipitate was filtered off, and the mother liquor was
treated with chloroform, after which colorless crystals
of XI were separated and air-dried. Yield 0.23 g
(30%), 101 102 C (dec.). Found, %: C 23.06, 23.09;
H 2.27, 2.27; N 11.09, 11.06. C5H5ClN2O6S. Calcu-
lated, %: C 23.39; H 1.95; N 10.92.
9. Zakharkin, L.I., Izv. Akad. Nauk SSSR, Otd. Khim.
Nauk, 1957, no. 9, p. 1064.
10. Martynov, I.V., Kruglyak, Yu.L., and Makarov, S.P.,
Zh. Obshch. Khim., 1963, vol. 33, no. 10, p. 3382.
11. Efremova, I.E., Abzianidze, V.V., Berkova, G.A., and
Berestovitskaya, V.M., Zh. Obshch. Khim., 2000,
vol. 70, no. 6, p. 1037.
12. Berestovitskaya, V.M., Efremova, I.E., Pivovarov, A.B.,
Lapshina, L.V., and Nepomnyashchaya, N.B., Zh. Org.
Khim., 1998, vol. 34, no. 7, p. 1119.
13. Terpigorev, A.N., Tselinskii, I.V., Makarevich, A.V.,
Frolova, G.M., and Mel’nikov, A.A., Zh. Org. Khim.,
1987, vol. 23, no. 2, p. 244.
14. Novikov, S.S., Shvekhgeimer, G.A., Sevost’yano-
va, V.V., and Shlyapochnikov, V.A., Khimiya alifa-
ticheskikh i alitsiklicheskikh nitrosoedinenii (Chem-
istry of Aliphatic and Alicyclic Nitro Compounds),
Moscow: Khimiya, 1974.
2-Bromo-3-methyl-2,4-dinitro-3-thiolene 1,1-di-
oxide XII. A solution of 0.21 ml of bromine in 5 ml
of absolute methanol was added dropwise to a suspen-
sion of 0.78 g of X in 25 ml of absolute methanol,
cooled to a temperature from 10 to 5 C. The mix-
ture was stirred for an additional 30 min at the same
temperature, after which the KBr precipitate was fil-
tered off, and the mother liquor was evaporated in the
cold. Light yellow crystals of XII formed, which were
filtered off and dried in a vacuum desiccator over
CaCl2. Yield 0.48 g (54%), mp 103 105 C (dec.).
Found, %: C 20.00, 20.04; H 2.00, 2.00; N 9.37, 9.40.
C5H5BrN2O6S. Calculated, %: C 19.93; H 1.66;
N 9.30.
15. Altukhov, K.V. and Perekalin, V.V., Usp. Khim.,
1976, vol. 45, no. 11, p. 2050.
16. The Chemistry of the Nitro and Nitroso Groups,
Feuer, H., Ed., New York: Interscience, 1969.
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