A simple synthesis of some new arylsulfonylnitromethanes

Article abstract of DOI:10.1080/10426500903348005

Arylsulfonylnitromethanes were obtained by a nucleophilic substitution reaction. The suggested method of obtaining arylsulfonylnitromethanes has some important advantages over the methods known so far: It is a relatively short, one-stage process; no byproducts are obtained, so there is no need for further procedures to separate the main products from thereaction mixture; and the final compounds possess a good degree of purity. The structure of the new products were confirmed by ¹H NMR, IR, and elemental analysis. The solid state structure of 6 was established by X-ray analysis. Copyright

Full text of DOI:10.1080/10426500903348005

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Phosphorus, Sulfur, and Silicon and the
Related Elements
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A Simple Synthesis of Some New
Arylsulfonylnitromethanes
D. Aleksiev a , S. Ivanova a & R. Valeva a
a Department of Organic Chemistry , University Prof. Dr. A.
Zlatarov , Bourgas , Bulgaria
Published online: 05 Apr 2012.
To cite this article: D. Aleksiev , S. Ivanova & R. Valeva (2012) A Simple Synthesis of Some New
Arylsulfonylnitromethanes, Phosphorus, Sulfur, and Silicon and the Related Elements, 187:6, 743-747,
DOI: 10.1080/10426500903348005
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Phosphorus, Sulfur, and Silicon, 187:743–747, 2012
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500903348005
A SIMPLE SYNTHESIS OF SOME NEW
ARYLSULFONYLNITROMETHANES
D. Aleksiev, S. Ivanova, and R. Valeva
Department of Organic Chemistry, University Prof. Dr. A. Zlatarov, Bourgas,
Bulgaria
Arylsulfonylnitromethanes were obtained by a nucleophilic substitution reaction. The sug-
gested method of obtaining arylsulfonylnitromethanes has some important advantages over the
methods known so far: It is a relatively short, one-stage process; no byproducts are obtained,
so there is no need for further procedures to separate the main products from the reaction
mixture; and the final compounds possess a good degree of purity. The structure of the new
products were confirmed by 1H NMR, IR, and elemental analysis. The solid state structure of
6 was established by X-ray analysis.
Keywords Arylsulfonylnitromethanes; structure; synthesis
INTRODUCTION
α–Nitrosulfones were obtained by the oxidation of α–nitrosulfides,1–4 an interaction
between sulfonylcarbanion and organic nitrate,5 or a reaction of metal sulfides and sulfinic
acids with α–chloro-, α–bromo-, α–iodonitroalkanes.2,6–10 In one particular case alone, a
direct nitration of arylsulfone was made resulting in α–nitrosulfone. Zeilstra and Engberts
suggested a method of obtaining α–nitrosulfones based on the reaction between potassium
nitronate and p-toluene sulfonylbromide.11 Publications describing a method of obtaining
α–nitrosulfones by nitration in the presence of bases are also available.12 Studies on the
chemical behavior of α–nitrosulfones show that they readily take part in reactions of
nucleophilic addition.13 As a result, α–nitroesters, nitroacetonitriles, bis(phenylsulfonyl)
methane, and bis(alkylsulfonyl)methanes are obtained. They react readily with aldehydes
and alcohols to give alkenes or bioadducts. Arylnitromethylethylsulfones can also be used to
obtained bis(arylsulfonyl)furans.14 Wade et al. found out that phenylsulfonylnitromethane
takes part in C-alkylation reactions resulting in a series of α–nitrosulfones.15 Studies on the
conformation of aromatic α–nitrosulfones were also made.16
The present work proposes a modified method of obtaining arylsulfonylni-
tromethanes. Their chemical composition and crystalline structure were studied, and the
main crystallographic parameters were determined.
Received 7 April 2009; accepted 18 September 2009.
Address correspondence to R. Valeva, Department of Organic Chemistry, University Prof. Dr. A. Zlatarov,
Bul. Prof. Jakimov 1, 8000 Bourgas, Bulgaria. E-mail: r.valeva@mail.bg
743

744
D. ALEKSIEV ET AL.
RESULTS AND DISCUSSION
Preparation of the Title Compounds
Arylsulfonylnitromethanes were preparated by a nucleophilic substitution reaction
(Scheme 1). The suggested method of obtaining arylsulfonylnitromethanes has some im-
portant advantages over the methods known so far: It is a relatively short, one-stage process;
no byproducts are obtained, so there is no need for further procedures to separate the main
products from the reaction mixture; and the final compounds possess a good degree of
purity.
O
S
O
S
ClCH2NO2
Z
Na
Z
CH2 NO2
+
O
O
Z = H (1); Z = 4-Me (2); Z = 4-MeO (3);
Z = 4- Cl (4); Z = 4-Br (5); Z = 4-I (6).
Scheme 1
Arylsulfonylnitromethanes 1–6 were synthesized by mixing equimolar quantities of the
corresponding reagents in ethanol at 18–20◦C during 12 to 72 h. These compounds are
colorless, crystalline substances, and very soluble in chloroform, acetone, and dioxane.
They are stable for long storage periods and melt without decomposing. The compounds
obtained were identified by TLC.
The Structures of the Title Compounds
All the products 1–6 were purified by recrystallization or flash column chromatogra-
phy on silica gel with benzene as the eluent. The structure of compounds 1–6 was confirmed
by 1H NMR and IR spectra, as well as by elemental analysis (Tables I and II).
Table 1 Characterization data of the new synthesized compounds
Calcd/found%
Compound
no.
Mp, ◦C
solvent
Color
Yield%
Mol. Formula
Mol.wt.
C
H
N
S
1
2
3
4
5
6
76–77
EtOH
73–74
EtOH
79–80
EtOH
138–139
EtOH/dioxane
159
EtOH/dioxane
186–187
EtOH/dioxane
White
81
White
78
White
75
White
82
White
74
White
86
C7H7NO4S
201.14
C8H9NO4S
215.16
C8H9NO5S
231.13
C7H6ClNO4S
235.58
C7H6BrNO4S
280.12
C7H6INO4S
327.03
43.60
43.26
44.20
44.66
41.57
40.80
35.55
35.69
29.75
30.01
25.50
25.71
3.71
3.48
3.95
4.18
3.65
3.89
2.40
2.55
2.45
2.14
1.56
1.83
7.06
6.96
6.72
6.51
5.80
6.06
5.76
5.95
5.38
5.00
4.38
4.28
15.60
15.94
14.58
14.90
13.95
13.87
13.45
13.67
11.65
11.45
9.70
9.80

NEW ARYLSULFONYLNITROMETHANES
745
Table 2 Spectral data of some new synthesized compounds
Spectral data
Compound no.
1
2
3
4
5
6
1H NMR: 5.52 (d, J = 5.8 Hz, 2H), 7.24–7.80 (m, 5H)
IR: 1550, 1340 (NO2), 1310,1150 (SO2), 2930, 2850, 1450 (CH2)
1H NMR: 2.42 (s, CH3), 5.50 (d, J = 5.6 Hz, 2H), 7.20–7.85 (m, 4H)
IR: 1545, 1345 (NO2), 1305,1140 (SO2), 2920, 2845, 1450 (CH2)
1H NMR: 2.40 (s, CH3), 5.51 (d, J = 5.6 Hz, 2H), 7.25–7.75 (m, 4H)
IR: 1550, 1340 (NO2), 1310,1145 (SO2), 2920, 2845, 1470 (CH2)
1H NMR: 5.53 (d, J = 5.8 Hz, 2H), 7.20–7.85 (m, 4H)
IR: 1560, 1345 (NO2), 1305,1150 (SO2), 2925, 2855, 1455 (CH2)
1H NMR: 5.51 (d, J = 5.8 Hz, 2H), 7.23–7.84 (m, 4H)
IR: 1555, 1340 (NO2), 1300,1140 (SO2), 2930, 2860, 1460 (CH2)
1H NMR: 5.52 (d, J = 5.8 Hz, 2H), 7.20–7.78 (m, 4H)
IR: 1550, 1335 (NO2), 1305,1145 (SO2), 2920, 2850, 1460 (CH2)
1
The H NMR spectra of arylsulfonylnitromethanes contain an aromatic multiplet
at 7.24–7.85 ppm. The signals of methylene protons can be seen at 5.50–5.53 ppm. The
chemical shift of the methyl group at the benzene nucleus is at 2.40 ppm. The presence of
a methyl group does not affect substantially the position of the aromatic multiplet.
The IR spectra of the compounds obtained contain intensive absorption bands of
nitro and sulfonyl groups. Asymmetric and symmetric valence vibrations of nitro groups
can be seen at 1560–1545 and 1345–1335 cm−1, while the asymmetric and symmetric
vibrations of sulfonyl groups are at 1310–1300 and 1150–1140 cm−1. These bands are
highly intensive since the sulfonyl groups are not situated at the same plane as the other
substituents. The absorption bands at 3100–3000 cm−1 are assigned to valence C H aryl
vibration. A triplet characterized by a decreasing intensity of the high-frequency bands can
be seen in this interval because the molecules of the compounds under study contain mono-
substituted benzene nuclei. The skeletal vibrations of the arene nucleus are at 1640–1600
and 1480–1450 cm−1. There is an absorption band of a monosubstituted benzene nucleus at
700 cm−1, and an absorption band of a p-disubstituted nucleus at 810–800 cm−1. A charac-
teristic band of valence C N vibration can be seen at 850–840 cm−1. The methylene group
is identified by the absorption maxima of valence asymmetric and symmetric vibrations
at 2930–2845 cm−1 and deformation vibrations at 1470–1450 cm−1. The absorption band
of asymmetric and symmetric valence vibrations at 2950–2850 cm−1 is due to the methyl
group in p-position in the arene nucleus. The presence of a methoxy group in the benzene
nucleus is proved by the absorption bands of valence vibrations of the methyl group at
2840 cm−1 and the valence asymmetric and symmetric vibrations of C O C bond at 1270
and 1030 cm−1. The presence of a halogen atom in the phenylsulfonyl group results in
a characteristic band at 800–580 cm−1. An absorption band of medium intensity corre-
sponding to valence S-aryl vibrations is characteristic of all arylsulfonylnitromethanes at
1090–1080 cm−1
.
The structure of 4-iodophenylsulfonylnitromethane was confirmed by a single crystal
X-ray diffraction (Figure 1). Compound 6 crystallizes in the triclinic space group P-1
(Table III). Selected bond lengths are as follows: S1–C1 1.3438(5) Å, C1–N1 1.2547(5) Å,
C6–I 1.5071 Å.

746
D. ALEKSIEV ET AL.
Figure 1 X-ray structure of 4-iodophenylsulfonylnitromethane.
EXPERIMENTAL
Instrumentation
Melting points were determined on a Kofler hot stage apparatus and are uncorrected.
The elemental analyses were carried out in the Microanalytical Center at University Prof.
A. Zlatarov. The infrared spectra were recorded on a Specord spectrometer using KBr
discs in the range 4000 to 400 cm−1. 1H NMR (chemical shifts measured in the deuterated
solvent are given in ppm from TMS) spectra were recorded with a Bruker 250 MHz
spectrometer using CDCl3 solution. X-ray data were collected on a Bruker Nonius Kappa
Table 3 Crystal structure and data refinement parameters
Compound
6
Empirical formula
Formula weight
C7H6INO4S
327.03
Crystal system / space group
a / Å
b / Å
Triclinic / P-1
11.3415 (12)
12.2310 (11)
6.8823 (7)
102.6410
101.2200
93.9650
906.7 (1)
1
c / Å
α / ◦
β / ◦
γ / ◦
V / Å3
Z
D calc (g/cm3)
1.320
0.873
µ (mm−1
)
Crystal size (mm)
0.567
Color / Shape
White
Temp (K)
298
Theta range for collection
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness of fit on F2
Final R indices [I > 2σ(I)]
R indices (all data)
3–60
4538
1850
12
1.380
0.0305 / 0.0975
0.0350
0.320 / 0.316 e/ Å3
Largest difference peak/hole

NEW ARYLSULFONYLNITROMETHANES
747
CDD diffractometer at 150 K. The structure was solved using the WINGX package,17 by
direct methods (SHELXS–97), and refined by least-squares against F2 (SHELXS–97).18 All
non-hydrogen atoms were anisotropically refined, while the hydrogen atoms were located
in the difference Fourier map and isotropically refined with a fixed thermal factor of 0,03.
Preparation of 1–6
An equimolar quantity of chloronitromethane dissolved in ethanol (25 mL) was
added to the sodium salt of sulfinic acid (0.01 mol). The reaction mixture was rapidly
stirred and then allowed to stay during 12 to 72 h at room temperature. The crystals
obtained were separated from the reaction mixture and were recrystallized from ethanol
and ethanol/dioxane.
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